JP2003226818A - Flame retardant resin composition - Google Patents

Abstract

(57) [Problem] To provide a flame-retardant resin composition which is flame-retarded without using a halogen-based flame retardant. SOLUTION: Base resin, (A1) double salt of amino group-containing nitrogen compound and polyphosphoric acid, (A2) salt of amino group-containing nitrogen compound and polymetaphosphoric acid, (A3) polyphosphoric acid amide, (A4) amino Group-containing nitrogen compound, sulfuric acid,
(A5) at least one flame retardant (A) selected from a salt with an organic sulfonic acid, an organic phosphonic acid or an organic phosphinic acid, and (A5) a cyclic urea compound; (B1) a phosphorus-containing compound; A flame-retardant resin composition is composed of a group III resin and at least one kind of a flame retardant aid (B) selected from metal salts of inorganic acids (B3). (A) Flame retardants include melamine polyphosphate, melam, melem double salt, melamine polymetaphosphate, polyphosphamide, melamine sulfate,
It may be melam pyrosulfate, melam organic sulfonate, melamine organic phosphonate, melamine organic phosphinate and the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant composed of a base resin, a specific nitrogen-containing compound, and a specific flame-retardant aid (phosphorus-containing compound, aromatic resin, metal salt of inorganic acid). A flame-retardant resin composition containing and a method for producing the same,
It also relates to a molded product formed from this flame-retardant resin composition.

[0002]

2. Description of the Related Art Among thermoplastic resins, polyester resins such as polybutylene terephthalate and styrene resins have excellent mechanical properties, electrical properties, weather resistance, water resistance, chemical resistance and solvent resistance. Since it has, it is used for various purposes such as electric / electronic parts and automobile parts. On the other hand, as the fields of use expand, improvements in flame retardant properties are being studied.

In Japanese Patent Laid-Open No. 61-287960, by adding a polyester resin having a butylene naphthalate unit to a polyamide resin having a xylylene adipamide unit, the moldability of the polyamide resin is improved and injection is performed. A method of molding is disclosed. JP 62-2
No. 01963 discloses a thermoplastic polyester resin,
A polyester resin composition is disclosed in which a gas-barrier property and transparency are improved by adding a metaxylylene group-containing polyamide resin and a compatibilizer. Furthermore, JP-A-6
JP-A-3-92667 discloses a stretch blow molding resin composition obtained by adding a metaxylylene group-containing polyamide resin, a specific thermoplastic resin, and mica powder to a polyester resin having an ethylene terephthalate unit. . In these documents, the moldability, gas barrier property and transparency of the resin are improved, but the flame retardancy is not sufficient.

Therefore, there has been proposed a method of making a thermoplastic resin flame-retardant by adding a flame retardant containing a halogen compound or an antimony compound. For example, JP-A-6
JP-A 3-150349 discloses a flame retardant composition in which glass fiber, an organic halogen-based flame retardant, antimony trioxide, and a hydroxide of an alkali metal or an alkaline earth metal are mixed with a mixed resin composed of a polyamide resin and nylon 66. There is disclosed a resin composition that has been converted into a resin. However, a halogen-based flame retardant may generate a dioxin-based compound during combustion decomposition, which is not preferable in terms of environmental problems. Therefore, there has been proposed a flame-retardant method using a phosphorus-based compound, a nitrogen-containing compound, or the like as the non-halogen flame retardant.

Japanese Unexamined Patent Publication (Kokai) No. 6-25506 discloses a thermoplastic resin comprising a copolymer of an aromatic vinyl compound and a vinyl monomer, a graft copolymer of a rubbery polymer, and a novolac resin. A flame-retardant resin composition containing a compound is disclosed. Japanese Unexamined Patent Publication No. 9-111059 discloses a flame-retardant resin composition obtained by mixing a polyolefin resin with a specific amount of a phenol resin, a phosphorus-containing compound (red phosphorus), and expandable graphite. Further, JP-A-10-195283 discloses a flame-retardant polyester obtained by combining a phosphoric acid ester having a specific structure with an appropriate amount of a specific compound (a novolac-type phenol resin and an oxide of iron, cobalt, nickel or copper). Resin compositions are disclosed. JP-A-11-152402
Japanese Patent Laid-Open Publication No. 2003-242242 discloses a composition containing polybutylene terephthalate, a reinforcing component, and a flame retardant composed of a melamine pyrophosphate and an aromatic phosphate oligomer, wherein the ratio of the flame retardant to the polymer component is about 35 to 35. 55
A flame retarded polyester composition is disclosed that is in weight percent. Furthermore, WO98 / 45363 and WO98 /
Japanese Patent No. 45364 discloses a composition containing a polyester resin, a polyphenylene oxide resin, melamine pyro or polyphosphate, zinc borate and the like, wherein the proportion of melamine pyro or polyphosphate is 15 with respect to the composition.
A flame-retardant resin composition is disclosed which is at least wt%.

Although the non-halogen flame retardant does not contain harmful halogen, the flame retardant effect is inferior to that of the halogen flame retardant, so that a large amount of flame retardant is required. Addition of a large amount of flame retardant causes bleed-out (blooming), deterioration of moldability (generation of mold deposit), and deterioration of mechanical properties of resin. Therefore, it is not possible to improve the flame retardancy and mechanical properties. For example, when expansive graphite is used in combination, the appearance during molding remarkably deteriorates. In particular, when a large amount of phosphoric acid ester is used as the phosphorus-containing compound, bleed-out, heat resistance and moldability are deteriorated.

As described above, according to the conventional method, it is difficult to impart high flame retardancy without deteriorating the moldability and the characteristics of the resin. Further, in the above flame retardant,
Although it is possible to make a specific resin flame-retardant, it is not possible to impart high flame retardancy to a wide range of thermoplastic resins.

[0008]

Therefore, an object of the present invention is to provide a non-halogen flame-retardant resin composition which is flame-retarded to a high level even with a small amount of flame-retardant, and a method for producing the same. Especially.

Another object of the present invention is to provide a flame-retardant flame-retardant resin composition and a method for producing the same, without deteriorating moldability and resin characteristics.

Still another object of the present invention is to provide a molded article having improved flame retardancy.

[0011]

Means for Solving the Problems The inventors of the present invention have made earnest studies to achieve the above object, and as a result, by adding a specific non-halogen flame retardant to the base resin, it has been found that flame retardation can be achieved at a high level. Found and completed the present invention.

That is, the flame-retardant resin composition of the present invention is
A flame-retardant resin composition comprising a base resin, (A) a flame retardant and (B) a flame retardant auxiliary, wherein the (A) flame retardant comprises:
(A1) Double salt of amino group-containing nitrogen compound and polyphosphoric acid, (A2) Salt of amino group-containing nitrogen compound and polymetaphosphoric acid, (A3) Polyphosphoric acid amide, (A4) Amino group-containing nitrogen compound, sulfuric acid, Pyrosulfuric acid, organic sulfonic acid,
Salts with organic phosphonic acids or organic phosphinic acids, and (A
5) At least one flame retardant selected from cyclic urea compounds, wherein (B) flame retardant aid is (B1) phosphorus-containing compound, (B2) aromatic resin, and (B3) inorganic acid metal salt. And at least one flame retardant aid selected from. Base resin includes polyester resin, styrene resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, vinyl resin,
It includes olefin resins and acrylic resins. The flame retardant (A) is melamine / melam / melem double salt of polyphosphate, melamine polymetaphosphate, polyphosphoric acid amide, melamine sulfate, melam pyrosulfate, melam organic sulfonate, melamine organic phosphonate, melamine organic phosphinate, etc. Good. The phosphorus-containing compound (B1) is a phosphoric acid ester, a phosphoric acid ester amide, a phosphonitrile compound,
It may be an organic phosphonic acid compound, an organic phosphinic acid compound or the like. The aromatic resin (B2) is mainly a polyphenylene sulfide resin, a polyphenylene oxide resin, a polycarbonate resin, an aromatic nylon, a polyarylate resin, an aromatic epoxy resin, an aromatic ring having a hydroxyl group and / or an amino group. It may be a resin having a chain or a side chain, particularly a polyphenylene sulfide resin, a novolac resin, an aralkyl resin, a hydroxyl group-containing aromatic vinyl resin, or the like.

Further, according to the present invention, there is provided a flame-retardant resin composition comprising a polyester resin, a styrene resin and a flame retardant, wherein the flame retardant comprises a nitrogen-containing compound and a phosphorus-containing compound. The flame-retardant resin composition is also included.
The nitrogen-containing compound is melamine polyphosphate melam.
It may be composed of melem double salt, melamine polymetaphosphate, polyphosphoric acid amide, melamine sulfate, melam pyrosulfate, melam organic sulfonate, melamine organic phosphonate, melamine organic phosphinate, and the like. The phosphorus-containing compound may be composed of a phosphoric acid ester, a phosphoric acid ester amide, a phosphonitrile compound, a phosphinic acid compound, or the like.

Further, the flame-retardant resin composition of the present invention comprises a hindered phenolic antioxidant, a phosphorus stabilizer, an inorganic stabilizer, a compound having a functional group reactive with an active hydrogen atom (reaction (Stability stabilizer), a fluororesin, a filler, etc. may be contained.

Further, according to the present invention, a method for producing a flame-retardant resin composition by mixing a base resin, a flame retardant, and a flame retardant auxiliary agent, and a molded article formed from the flame-retardant resin composition. Is also included.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION As a base resin, various resins used for molding, for example, polyester resin, styrene resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, vinyl resin, olefin Examples of the resin include acrylic resin and acrylic resin.

(1) Polyester Resin Polyester resin is a homopolyester or copolyester obtained by polycondensation of dicarboxylic acid component and diol component, polycondensation of oxycarboxylic acid or lactone, or polycondensation of these components. Is. A preferred polyester resin is usually a saturated polyester resin,
In particular, aromatic saturated polyester resins are included.

Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids (eg, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid). , Dimer acids and other dicarboxylic acids having about 4 to 40 carbon atoms, preferably 4 to 4 carbon atoms.
14 dicarboxylic acids), alicyclic dicarboxylic acids (for example, dihydrocarboxylic acids having about 8 to 12 carbon atoms such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and hymic acid), aromatic dicarboxylic acids ( For example, phthalic acid, isophthalic acid, terephthalic acid,
Naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,
4'-diphenoxy ether dicarboxylic acid, 4,4'-
Oxydibenzoic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylketonedicarboxylic acid and other dicarboxylic acids having about 8 to 16 carbon atoms, or derivatives thereof (eg lower alkyl ester, aryl ester, acid) Ester-formable derivatives such as anhydrides). These dicarboxylic acid components may be used alone or in combination of two or more. Furthermore, if necessary, a polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid may be used in combination.

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

Examples of the diol component include aliphatic alkylene diols (eg, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butane diol, 1,3-butane diol, neopentyl glycol, hexane diol, octane diol). , An aliphatic glycol having about 2 to 12 carbon atoms, such as decanediol, preferably an aliphatic glycol having about 2 to 10 carbon atoms), polyoxyalkylene glycol [wherein the alkylene group has about 2 to 4 carbon atoms, and A glycol having an oxyalkylene unit, for example, diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol, etc.], an alicyclic diol (for example, 1 4-cyclohexanediol,
1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.) and the like. Also, hydroquinone, resorcinol, biphenol, 2,2-bis (4
-Hydroxyphenyl) propane, 2,2-bis- (4
Aromatic diols such as-(2-hydroxyethoxy) phenyl) propane and xylylene glycol may be used in combination. You may use these diol components individually or in combination of 2 or more types. Furthermore, if necessary, a polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol may be used in combination.

Preferred diol components are C _2-6 alkylene glycols (linear alkylene glycols such as ethylene glycol, trimethylene glycol, propylene glycol and 1,4-butanediol), and oxy compounds having a repeating number of about 2-4. Examples thereof include polyoxyalkylene glycol having an alkylene unit [poly (oxy-C _2-4 alkylene) -containing glycol such as diethylene glycol and polytetramethylene glycol] and 1,4-cyclohexanedimethanol.

Examples of the oxycarboxylic acid include oxybenzoic acid, oxynaphthoic acid, hydroxyphenylacetic acid,
An oxycarboxylic acid such as glycolic acid or oxycaproic acid, or a derivative thereof is included.

The lactone includes propiolactone, butyrolactone, valerolactone, caprolactone (for example,
ε- caprolactone) and the like C _3-12 lactones such as.

Preferred polyester resins are homopolyesters or copolyesters containing alkylene arylate such as alkylene terephthalate and alkylene naphthalate as a main component (for example, 50 to 100% by weight, preferably about 75 to 100% by weight) [for example, , Polyalkylene terephthalates (for example, poly (1,4-cyclohexanedimethylene terephthalate) (PCT), polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT) and other poly C _2-4 alkylene terephthalates) , polyalkylene naphthalate (e.g., polyethylene naphthalate, poly C _2-4 alkylene naphthalate and polybutylene naphthalate) homopolymer polyesters such as; alkylene terephthalamide Mainly of rate and / or alkylene naphthalate unit (e.g., more than 50% by weight)
As a copolyester]. Particularly preferred polyester-based resins include polybutylene terephthalate-based resins containing butylene terephthalate units as a main component (for example, polybutylene terephthalate, polybutylene terephthalate copolyester) and polyethylene terephthalate-based resins containing ethylene terephthalate units as a main component (for example, ,polyethylene terephthalate,
Polyethylene terephthalate copolyester). These polyester resins can be used alone or in combination of two or more.

In the copolyester, as the copolymerizable monomer, C _2-6 alkylene glycol (such as linear alkylene glycols such as ethylene glycol, propylene glycol and 1,4-butanediol), the number of repetitions Has an oxyalkylene unit of about 2 to 4 (eg, a glycol containing a poly (oxy-C _2-4 alkylene) unit such as diethylene glycol or polytetramethylene glycol), a C _6-12 aliphatic dicarboxylic acid ( Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.),
Examples thereof include aromatic dicarboxylic acids (phthalic acid, isophthalic acid, diphenyldicarboxylic acid, etc.) and oxycarboxylic acids (oxybenzoic acid, oxynaphthoic acid, etc.). The polyester resin may have not only a straight chain structure but also a branched chain structure and may be cross-linked as long as the melt moldability and the like are not impaired. It may also be liquid crystal polyester.

The polyester resin can be produced by a conventional method such as transesterification or direct esterification.

(2) Styrene-based resin Examples of the styrene-based resin include homopolymers or copolymers of styrene-based monomers (for example, styrene, vinyltoluene, α-methylstyrene, etc.); styrene-based monomers and vinyl. Monomers (eg, unsaturated nitriles such as acrylonitrile, (meth) acrylic acid esters, (meth) acrylic acid, α, β-monoolefinic unsaturated carboxylic acids such as maleic anhydride or acid anhydrides or esters thereof, etc. And a styrene-based graft copolymer, a styrene-based block copolymer, and the like.

Preferred styrene resins include polystyrene [GPPS, SPS (syndiotactic polystyrene)], styrene-methyl methacrylate copolymer,
Styrene- (meth) acrylic acid copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile- (meth) acrylic acid glycidyl copolymer, styrene-based rubber component High impact polystyrene (HIP)
S), polystyrene-based graft or block copolymers and the like. As the polystyrene-based graft copolymer, a copolymer obtained by graft-polymerizing at least a styrene-based monomer and a copolymerizable monomer into a rubber component [for example, ABS resin obtained by graft-polymerizing styrene and acrylonitrile onto polybutadiene, acrylic rubber AAS resin graft polymerized with styrene and acrylonitrile, ACS resin graft polymerized with styrene and acrylonitrile on chlorinated polyethylene, polymer polymerized with styrene and acrylonitrile on ethylene-vinyl acetate copolymer, styrene and acrylonitrile on ethylene-propylene rubber MB grafted with styrene and methyl methacrylate on polybutadiene
S resin, a resin in which styrene and acrylonitrile are graft-polymerized on a styrene-butadiene copolymer rubber] and the like. As the block copolymer, a copolymer composed of a polystyrene block and a diene or an olefin block [eg, styrene-butadiene-styrene (SBS) block copolymer, styrene-isoprene block copolymer, styrene-isoprene-block copolymer). Styrene (S
IS) block copolymer, hydrogenated styrene-butadiene-styrene (SEBS) block copolymer, hydrogenated styrene-isoprene-styrene (SEPS) block copolymer, epoxidized SBS, epoxidized SIS] and the like. These styrene resins can be used alone or in combination of two or more.

(3) Polyamide Resins Polyamides include polyamides derived from diamines and dicarboxylic acids; aminocarboxylic acids; polyamides obtained by using diamines and / or dicarboxylic acids in combination, if necessary; lactams. Correspondingly included are polyamides derived by combination with diamines and / or dicarboxylic acids. Polyamides also include copolyamides formed by at least two different polyamide forming components.

Examples of diamines include trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, octamethylenediamine. , Aliphatic diamines such as nonamethylenediamine; bis (4-
Aminocyclohexyl) methane, bis (4-amino-3)
Alicyclic diamines such as -methylcyclohexyl) methane. Further, aromatic diamines such as phenylenediamine and metaxylylenediamine may be used in combination.
These diamines may be used alone or in combination of two or more.

Examples of the dicarboxylic acid include C _4-20 aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and octadecanedioic acid; dimerized fatty acid (dimer acid ); Cyclohexane-1,4-dicarboxylic acid or cyclohexane-
Alicyclic dicarboxylic acids such as 1,3-dicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and naphthalenecarboxylic acid.

Examples of the aminocarboxylic acid include C _4-20 aminocarboxylic acid such as aminoheptanoic acid, aminononanoic acid and aminoundecanoic acid. Aminocarboxylic acids may be used alone or in combination of two or more.

Examples of lactams include C _4-20 lactams such as butyrolactam, pivalolalactam, caprolactam, capryllactam, enantolactam, undecanolactam, dodecaractam and the like. These lactams may be used alone or in combination of two or more.

As the polyamide resin, nylon 4 is used.
6, Nylon 6, Nylon 66, Nylon 610, Nylon 612, Nylon 11, Nylon 12 and other aliphatic polyamides, aromatic dicarboxylic acids (eg terephthalic acid and / or isophthalic acid) and aliphatic diamines (eg hexamethylene diamine) , Nonamethylenediamine, etc.), polyamides obtained from aromatic and aliphatic dicarboxylic acids (eg terephthalic acid and adipic acid) and aliphatic diamines (eg hexamethylenediamine), and the like. These polyamides can be used alone or as a mixture. Preferred polyamides include non-aromatic and aliphatic polyamides (nylon 6, nylon 66, nylon 610, nylon 612,
Nylon 11, nylon 12, etc.), semi-aromatic polyamide (nylon MXD6, nylon 9T, etc.), semi-aromatic copolyamide (nylon 6T / 6, nylon 6T /
66, nylon 6T / 12, nylon 6I / 6, nylon 6I / 66, nylon 6T / 6I, nylon 6T / 6
I / 6, Nylon 6T / 6I / 66, Nylon 6T / M
5T) etc. are included. The polyamide resins can be used alone or in combination of two or more.

(4) Polycarbonate Resin Polycarbonate resin includes a dihydroxy compound and
Included are polymers obtained by reaction with carbonic acid esters such as phosgene or diphenyl carbonate. The dihydroxy compound may be an alicyclic compound or the like, but is preferably a bisphenol compound.

As the bisphenol compound, bis (4
-Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,
2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis ( 4-hydroxyphenyl)
Hexane, 2,2-bis (4-hydroxyphenyl)-
Bis (hydroxyaryl) such as 4-methylpentane
C _1-6 alkane; 1,1-bis (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) C _4-10 cycloalkane such as 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4 ′ -Dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl sulfone; 4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxydiphenyl ketone and the like.

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

(5) Polyphenylene oxide resin The polyphenylene oxide resin (polyphenylene ether resin) includes homopolymers and copolymers. As a homopolymer, poly (2,6-dimethyl-
1,4-phenylene) oxide, poly (2,5-dimethyl-1,4-phenylene) oxide, poly (2,5-diethyl-1,4-phenylene) oxide, poly (2-methyl-6-ethyl-) 1,4-phenylene) oxide, poly (2,6-di-n-propyl-1,4-phenylene)
Oxide, poly (2-ethyl-6-isopropyl-1,
4-phenylene) oxide, poly (2-methyl-6-methoxy-1,4-phenylene) oxide, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) oxide, poly (2,3,6) -Trimethyl-1,4-phenylene) oxide, poly (2,6-diphenyl-1,4)
-Phenylene) oxide, poly (2-methyl-6-phenyl-1,4-phenylene) oxide, and other poly (mono,
Di- or tri-C _1-6 alkyl - phenylene) oxide, poly (mono- or di-C _{6 -20} aryl - phenylene) oxide, poly (mono C _1-6 alkyl - mono C _6-20 aryl -
Phenylene) oxide and the like.

As the polyphenylene oxide copolymer, a copolymer having two or more monomer units of the above homopolymer (for example, 2,6-dimethyl-1,4-phenylene oxide units and 2,3,6 -Trimethyl-1,
Random copolymers containing 4-phenylene oxide units, etc.), benzene formaldehyde resin (formaldehyde condensate of benzene ring-containing compound such as phenol resin) and alkylbenzene formaldehyde resin are reacted with alkylphenols such as cresol and p-tert-butylphenol. A modified polyphenylene oxide copolymer composed of an alkylphenol-modified benzene-formaldehyde resin block thus obtained and a polyphenylene oxide block as a main structure, a polyphenylene oxide or a copolymer thereof and a styrene-based polymer and / or
Alternatively, a modified graft copolymer in which an unsaturated carboxylic acid or an anhydride ((meth) acrylic acid, maleic anhydride, etc.) is grafted may be used. The polyphenylene oxide resins can be used alone or in combination of two or more.

(6) Vinyl Resin As vinyl resins, vinyl monomers (for example, vinyl acetate, vinyl propionate, vinyl crotonate, vinyl benzoate, etc.); chlorine-containing vinyl monomers (for example, , Vinyl chloride, chloroprene, etc.); Fluorine-containing vinyl monomers (eg, fluoroethylene, etc.);
Vinyl ketones such as methyl vinyl ketone and methyl isopropenyl ketone; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinylamines such as N-vinylcarbazole and N-vinylpyrrolidone) homopolymers or copolymers, or other A copolymer with a copolymerizable monomer and the like are included.

Derivatives of the above vinyl resins (for example, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral and other polyvinyl acetals, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, etc.) can also be used. These vinyl resins may be used alone or in combination of two or more.

(7) Olefin Resin Examples of the olefin resin include homo- or copolymers of α-C _2-10 olefins such as ethylene and propylene,
Cyclic olefin-based resin (C _3-10 cyclic olefin homopolymer, α-C _2-10 olefin-cyclic olefin copolymer, etc.), particularly propylene-based resin and ethylene-based resin (for example, propylene-ethylene copolymer) , A propylene- (meth) acrylic acid copolymer, an ethylene-ethyl (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid glycidyl copolymer, and the like).

(8) Acrylic resin The acrylic resin includes, for example, homopolymers or copolymers of (meth) acrylic monomers ((meth) acrylic acid or esters thereof), and (meth) acrylic acid. -Styrene copolymers, methyl (meth) acrylate-styrene copolymers and the like are included.

(9) Other resins Other resins include polyacetal resins, aliphatic polyketone resins (ketone resins); polysulfones (eg, thermoplastic polysulfones, poly (ether sulfones), poly (4,4'-bisphenols). Ether sulfone); polyetherketone; poly (etheretherketone); polyetherimide; thermoplastic polyurethane-based resin (for example, obtained by reacting a diisocyanate compound such as tolylene diisocyanate with the glycol and / or the diamine) Examples thereof include polymers and polyurethane elastomers that may have a segment such as polytetramethylene glycol); thermoplastic polyimides; polyoxybenzylenes; thermoplastic elastomers.

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

Preferred base resins include polyester resins which may be liquid crystal polyesters, styrene resins, polyamide resins, polycarbonate resins, polyphenylene oxide resins, vinyl resins and the like, and more preferably polyester. Resins, polycarbonate resins and styrene resins are mentioned, especially polyester resins (PBT resins, PET resins, etc.)
Is preferred.

From the viewpoint of preventing blooming, a polyester resin and a styrene resin may be used in combination. The ratio (weight ratio) of polyester resin and styrene resin is
The former / the latter = 99/1 to 50/50, preferably 95 /
5-60 / 40, more preferably 90 / 10-70 /
It is about 30.

The number average molecular weight of the base resin is not particularly limited and may be appropriately selected depending on the type and application of the resin. For example, 5 × 10 ³ to 200 × 10 ⁴ , preferably 1 × 10 ⁴ .
^{4 to} 150 × 10 ⁴ , more preferably 1 × 10 ⁴ to 10
It can be selected from the range of about 0 × 10 ⁴ . When the base resin is a polyester resin, the number average molecular weight is, for example, 5 × 10 ^{3 to} 100 × 10 ⁴ , preferably 1 × 10 ^4.
˜70 × 10 ⁴ , more preferably 1.2 × 10 ⁴ ˜30
It may be about 10 ⁴ .

[(A) Flame Retardant] In the present invention, the (A) flame retardant comprises (A1) a double salt of an amino group-containing nitrogen compound and polyphosphoric acid, and (A2) an amino group-containing nitrogen compound and polymetaphosphoric acid. Salt, (A3) polyphosphoric acid amide, (A4) salt of amino group-containing nitrogen compound with sulfuric acid, pyrosulfuric acid, organic sulfonic acid, organic phosphonic acid or organic phosphinic acid, (A
5) It is composed of a cyclic urea compound or the like. These flame retardants can be used alone or in combination of two or more.

(A1) Double salt of amino group-containing nitrogen compound and polyphosphoric acid The amino group-containing nitrogen compound includes a heterocyclic compound having at least one amino group and at least one nitrogen atom as a ring heteroatom. In addition to nitrogen, the heterocycle may have other heteroatoms such as sulfur and oxygen. Such a nitrogen-containing heterocycle has a 5- or 6-membered unsaturated group having a plurality of nitrogen atoms such as imidazole, thiadiazole, thiadiazoline, furazan, triazole, thiadiazine, pyrazine, pyrimidine, pyridazine, triazine and purine as a ring-constituting atom. And nitrogen-containing heterocycles and the like. Of such nitrogen-containing rings, 5- or 6-membered unsaturated nitrogen-containing rings having a plurality of nitrogen atoms as ring-constituting atoms are preferable, and triazole and triazine are particularly preferable.

Examples of triazole compounds include 1,2,3
-Triazoles (1H-1,2,3-triazoles; 2H-1,2,3-triazoles and the like), and 1,2,4-triazoles (1H such as guanazole
-1,2,4-triazoles; 4H such as guanazine
-1,2,4-triazoles and the like), and the amino group may be substituted at an appropriate site (nitrogen atom and carbon atom, particularly carbon atom) of the triazole ring. The number of amino groups is not particularly limited and is 1 to 3, particularly 1 to 2.

As the triazine compound, 1,3,5-
Triazines [melamine, substituted melamine (alkyl melamine such as 2-methyl melamine, guanyl melamine etc.), melamine condensate (melam, melem, melon etc.), co-condensation resin of melamine (melamine-formaldehyde resin, phenol-melamine resin, Benzoguanamine-melamine resin, aromatic polyamine-melamine resin, etc.) or a derivative thereof; cyanuric acid amides such as ammeline and ammelide; guanamine, methylguanamine, acetoguanamine, benzoguanamine,
Succinoguanamine, guanamine such as CTU-guanamine or derivatives thereof, etc., amino group-containing 1,2,3-
Triazines (1,2,3-triazine in which amino group is substituted at 5-position, 4,5-position, 4,5,6-position, etc., 4-
Amino-benzo-1,2,3-triazine, etc.), amino group-containing 1,2,4-triazines (3-position, 5-position,
Examples include various aminotriazines such as 1,2,4-triazine having an amino group substituted at the 3,5-position and the like. The amino group may be substituted at an appropriate site (nitrogen atom and carbon atom, particularly carbon atom) of the triazine ring.
The number of amino groups is not particularly limited, and is 1 to 4, particularly 1 to
It is about 3 (for example, 1 to 2).

Of these, amino group-containing triazine compounds, particularly amino group-containing 1,3,5-triazines are preferable.

The nitrogen-containing cyclic compound having an amino group is
A plurality of the same or different nitrogen-containing compounds (the nitrogen-containing cyclic compound and other amino group-containing nitrogen-containing compounds) form a salt with one polyphosphoric acid to form a double salt of polyphosphoric acid. In addition, the nitrogen atom part (imino group) that constitutes the ring
Although a salt may be formed with polyphosphoric acid, it is usually preferable to form a salt with at least one amino group substituted on the ring and polyphosphoric acid. When it has a plurality of amino groups, all the amino groups may form a salt with polyphosphoric acid.

Polyphosphoric acid includes polymetaphosphoric acid (HPO
₃ ) _q (wherein q represents an integer of 2 or more), hypophosphoric acid,
Condensed phosphoric acid (polyphosphoric acid) such as phosphoric anhydride (diphosphorus pentaoxide) is included. The polyphosphoric acid also includes condensed phosphoric acids represented by the following formula (1).

[0056]

[Chemical 1]

(In the formula, u represents an integer of 3 or more).

In the above formula, u represents the condensation degree of polyphosphoric acid, and is preferably an integer of 3 to 200, more preferably an integer of 3 to 100.

The polyphosphoric acid also includes triphosphoric acid and tetraphosphoric acid.

Phosphoric acid having a plurality of salt-forming sites has at least a part of other amino group-containing compounds, such as amine and urea, and partial salts (ammonium polyphosphate,
Partial salts of condensed acids such as urea polyphosphate; partial salts of non-condensed acids such as urea orthophosphate may also be formed.

The double salt of the amino group-containing nitrogen compound and polyphosphoric acid includes melamine / melam / melem double salt of polyphosphoric acid,
Also included are melamine / melam / melem double salts of metaphosphate and melamine / melam / melem double salts of polyacids containing the sulfur atom (polyacids containing sulfur atom, oxygen atom, etc. in addition to phosphorus atom). Details of these double salts are disclosed in Japanese Patent Laid-Open No. Hei 10
Reference can be made to JP-A-306081 and JP-A-10-306082. The polyphosphoric acid double salt may contain a sulfur atom derived from sulfuric acid. A triazole salt corresponding to the above triazine salt can also be used.

The ratio of the nitrogen-containing cyclic compound having an amino group and the polyphosphoric acid is not particularly limited, but for example, the former / the latter (molar ratio) = 1/20 to 20/1, preferably 1/10 to 10 /. 1 (for example, 1/5 to 10/1), particularly about 1/2 to 8/1. The equivalent ratio between the amino group of the nitrogen-containing cyclic compound and the site capable of forming a salt of oxyacid is not particularly limited, and is, for example, 10/1 to 1/2, preferably 5
It is about 1/1 to 1/1, especially about 4/1 to 1/1.

These double salts of amino group-containing nitrogen compounds and polyphosphoric acid can be used alone or in combination of two or more kinds.

(A2) Salt of amino group-containing nitrogen compound and polymetaphosphoric acid As the amino group-containing nitrogen compound and polymetaphosphoric acid,
The amino group-containing nitrogen-containing cyclic compound and polymetaphosphoric acid similar to the above (A1) can be used.

The nitrogen-containing cyclic compound having an amino group is
The ring may form a salt with polymetaphosphoric acid at a nitrogen atom site (imino group), but it is usually preferable to form a salt with at least one amino group substituted on the ring and polymetaphosphoric acid. When it has a plurality of amino groups, all the amino groups may form a salt with polymetaphosphoric acid.

Examples of salts of amino group-containing nitrogen compounds and polymetaphosphoric acid include polymetaphosphate salts of amino group-containing triazine compounds such as melamine polymetaphosphate, melem polymetaphosphate, melam polymetaphosphate, melon polymetaphosphate and guanamine polymetaphosphate. It can be illustrated. Moreover, the polyphosphate may contain a sulfur atom derived from sulfuric acid. A triazole salt corresponding to the above triazine salt can also be used.

The ratio of the nitrogen-containing cyclic compound having an amino group and the polymetaphosphoric acid is the same as in the above-mentioned (A1) polyphosphate.

These salts of amino group-containing nitrogen compounds and polymetaphosphoric acid can be used alone or in combination of two or more kinds.

(A3) Polyphosphoric acid amide As polyphosphoric acid amide, phosphoric acid and -N = C = N
It is a condensate with a compound having a unit represented by -or -N = C (-N <) ₂ (such as a cyanamide derivative), and is a polymer compound containing amide nitrogen. Such a polyphosphoric acid amide is usually obtained by heating (calcining or the like) the phosphoric acid and the cyanamide derivative in the presence of at least one (binding agent) selected from urea and phosphoric acid urea.

Examples of the phosphoric acids include non-condensed phosphoric acid (orthophosphoric acid, metaphosphoric acid, etc.), partial esters of phosphoric acid (ammonium polyphosphate, urea phosphate, etc.) in addition to the polyphosphoric acid exemplified in the item (A1). ) Etc. can be preferably used. The phosphoric acids can be used alone or in combination of two or more kinds.

Examples of the cyanamide derivative include amino group-containing triazines (amino group-containing 1,3,5-triazines such as melamine, melam, melem, melon, guanamine, acetoguanamine, and benzoguanamine), 3-amino-1,2. , Containing amino groups such as 4-triazine 1,
2,4-triazines), amino group-containing triazoles (amino group-containing 1,3,4-triazoles such as 2,5-diamino-1,3,4-triazole), and other cyclic cyanamide derivatives; guanidine Examples thereof include acyclic cyanamide derivatives such as the types [guanidine, guanidine derivatives (dicyandiamide, guanylurea, etc.)] and the like. Preferred cyanamide derivatives are amino group-containing 1,3,5-triazines, guanidine or its derivatives, especially melamine. Such cyanamide derivatives can be used alone or in combination of two or more.

The polyphosphoric acid amide can be used alone or in combination of two or more kinds. Regarding polyphosphoric acid amide, for example, JP-A-7-138463 can be referred to. Such polyphosphoric acid amide is disclosed in JP-B-53-21.
70, Japanese Patent Publication No. 53-15478, Japanese Patent Publication No. 5
5-49004, JP 61-126091, JP 10-81691, and US Pat. No. 404.
It can be produced by the method described in the specification of 3987 and the like. Polyphosphoric acid amide is available in "Sumisafe PM" [manufactured by Sumitomo Chemical Co., Ltd.], "Taien S" [manufactured by Taihei Chemical Co., Ltd.], "Melapur" [manufactured by DSM], "E".
xolit "[made by Clariant]," AMGARD "
It is commercially available as [Albright & Wilson].

These polyphosphoric acid amides can be used alone or in combination of two or more kinds.

(A4) Salt of Amino Group-Containing Nitrogen Compound with Specific Oxygen Acid As the amino group-containing nitrogen compound, the same amino group-containing nitrogen-containing cyclic compound as described in (A1) above can be used. The nitrogen-containing cyclic compound having an amino group may form a salt with an oxygen acid at a nitrogen atom site (imino group) constituting a ring, but usually, at least one amino group substituted on the ring and an oxygen acid are combined. It is preferable to form a salt. When it has a plurality of amino groups, all the amino groups may form a salt with an oxygen acid.

The specific oxygen acid is composed of sulfuric acid, pyrosulfuric acid, organic sulfonic acid, organic phosphonic acid or organic phosphinic acid.

Examples of the salt of an amino group-containing nitrogen compound and sulfuric acid include melamine sulfates (melamine sulfate, dimelamine sulfate, guanylmelamine sulfate, etc.), non-condensed melamine sulfates such as melamine sulfite corresponding to melamine sulfate, Examples thereof include melem salt, melam salt, melon salt and guanamine salt corresponding to the non-condensed melamine sulfate salt.

Examples of salts of amino group-containing nitrogen compounds with pyrosulfate include melamine pyrosulfates (melamine pyrosulfate, dimelamine pyrosulfate, etc.), melem salts corresponding to melamine pyrosulfates, melam salts, melon salts, guanamine salts. Can be exemplified.

It should be noted that melamine sulfate is described in, for example, Japanese Unexamined Patent Publication No. Hei 8
It can be obtained by the method described in JP-A-231517. Dimelam pyrosulfate is commercially available, for example, from ACS Sympo
siumSeries No. 425 "Fire and Polymers", Chapter 15,
211-238 (American Chemical Society, Washi
ngton DC, 1990) and the method described in JP-A-10-306082.

Examples of the organic sulfonic acid include C _1-10 alkane sulfonic acid (eg, methane sulfonic acid, ethane sulfonic acid, ethane disulfonic acid, etc.), C _6-20 aryl sulfonic acid (eg, benzene sulfonic acid, toluene sulfonic acid). Etc.).

As the salt of the amino group-containing nitrogen compound and the organic sulfonic acid, melamine sulfonates (melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine.melam.melem double salt methanesulfonate, methane Examples thereof include guanamine sulfonate).

The organic phosphonic acid includes a phosphonic acid monoester, a hydrogen atom directly bonded to a phosphorus atom of the phosphonic acid, such as an organic group such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. And a substituted organic phosphonic acid monoester and the like.

The phosphonic acid monoester includes alcohol
Class (monohydric or polyhydric alcohol, monohydric or polyhydric phenol
Phosphonic acid monoester). Said al
Coals include aliphatic monools [methanol, ethanol
, Propanol, isopropanol, butanol,
C such as hexanol and stearyl alcohol_1-20(In particular
C_1-10) Aliphatic monools], aliphatic polyols (eth
Len glycol, propylene glycol, butanedio
Le, pentanediol, hexanediol, neo-plier
Luglycol, glycerol, pentaerythritol, etc.
C_1-10Aliphatic polyols), fats with heteroatoms
Group polyols (hetero-sources such as nitrilotrimethanol
C with children_2-10Aliphatic polyol), alicyclic mono-o
Le [cyclopentanol, cyclohexanol, etc. C
_5-8Alicyclic monools (preferably C_5-6Cycloalkano
A), alicyclic diol [cyclohexanediol, etc.
Which C_5-8Alicyclic diol (preferably C_5-6Cycloal
Candiol)], monovalent phenols [phenol,
Alkylphenols (eg p- or m-cresol)
3,5-xylenol, trimethylphenol, t
-Butylphenol, p-octylphenol, nonyl
Mono or tri C such as phenol_1-20Alkylpheno
), Arylphenols (eg phenylpheno)
, Benzylphenol, cumylphenol), naphtho
, Hydroxybiphenyl, etc.], monovalent aralkyl
Alcohol (benzyl alcohol, phenethyl alcohol
C such as le _7-20Aralkyl alcohol, etc.), aromatic ring di
All (bisphenols (bisphenol A, bisphenol
Enol AD, bisphenol F, etc.) and the like.

Examples of such phosphonic acid monoesters include phosphonic acid mono C _1-10 alkyl esters such as phosphonic acid methyl ester and phosphonic acid butyl ester, phosphonic acid ethylene glycol monophosphonic acid ester, pentaerythritol bisphosphonic acid ester and the like. C _2-10
Mono- or tetraphosphonic acid esters of aliphatic polyhydric alcohols, phosphonic acid esters of monohydric phenols which may have a substituent (such as a C _1-4 alkyl group) (particularly C
_1-4 Phosphonic acid mono C which may have an alkyl group
_6-14 aryl ester) [eg, phosphonic acid phenyl ester, phosphonic acid cresyl ester, phosphonic acid xylenyl ester, etc.], phenylene bisphosphonic acid ester, or the like, which may have a substituent (C _1-4 alkyl group, etc.) Good polyhydric phenol phosphonates (for example, C _6-14 arylene phosphonates _optionally having C _1-4 alkyl groups), alkyl-aryl phosphonates [methyl phenyl phosphonates, etc. (preferably C _1-6 alkyl C _6-10 aryl phosphonic acid ester) of C _1-10 alkyl C _{6- 14} aryl phosphonic acid esters, and the like etc.].

The substituted organic phosphonic acids include aliphatic phosphonic acids [alkylphosphonic acids such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid and butylphosphonic acid; 1-hydroxyethylidene-1-phosphonic acid, 1-hydroxyphosphoric acid
Mono- or diphosphonic acid esters of aliphatic polyols such as hydroxyethylidene-1,1-diphosphonic acid; phosphono C such as phosphonoacetic acid and 3-phosphonopropionic acid
_1-10 Aliphatic carboxylic acid or carboxylic acid ester thereof (carboxylic acid esters of phosphonocarboxylic acid such as ethyl phosphonoacetate and ethyl 3-phosphonopropionate)
Substituents such as phosphonocarboxylic acids, such as (a hydroxyl group, a carboxyl group, an ester group, etc.) phosphonate (preferably substituted by optionally C _1-10 alkyl group optionally having the C _1-6 alkyl substituted phosphonic Acid); C _1-10 alkylenediphosphonic acid such as ethylenebisphosphonic acid; substituted with an aliphatic polyvalent group having a hetero atom such as nitrilotris (methylphosphonic acid) ([nitrilotris (methylene)] trisphosphonic acid) Phosphonic acid, etc., aromatic phosphonic acid [ _C6-10 arylphosphonic acid such as phenylphosphonic acid, tolylphosphonic acid; phosphono _C7-15 aromatic carboxylic acid such as phosphonobenzoic acid or its carboxylic acid ester (phosphonobenzoic acid Phosphonocarboxylic acids such as carboxylic acid esters of phosphonoaromatic carboxylic acids such as ethyl); And phosphonic acid substituted with an aromatic polyvalent group which may have a substituent such as enylene bisphosphonic acid (C _1-4 alkyl group etc.) and the like. Further, the organic phosphonic acid may be a phosphonic acid bonded to a polymer (polyvinylphosphonic acid or the like).

Substituted organic phosphonic acid monoesters have been previously described
Of the substituted organic phosphonic acid and the phosphonic acid monoester
Monoesters with alcohols exemplified in the section, for example,
C such as tylphosphonic acid monomethyl ester_1-10Archi
Luphosphonic acid mono C_1-6Alkyl ester; phosphonoca
Rubonic acid diester (ethoxycarbonylmethylphosphine
Monoethyl phosphonate, ethoxycarbonylethylphosphone
C such as monoethyl acid _2-6Alkoxycarbonyl C_1-6A
Lucylphosphonic acid Mono C_1-6Alkyl ester etc.);
C such as methylphosphonic acid monophenyl ester_1-10A
Lucylphosphonic acid Mono C_6-10Aryl ester; Pheny
C such as luphosphonic acid monomethyl ester_6-10Aryl
Phosphonic acid C_1-6Alkyl ester; Phenylphosphone
C such as acid monophenyl ester_6-10Aryl phosphone
Acid Mono C_6-10Aryl esters and the like are included. In addition,
The phosphonate is a cyclic phosphonate
(9,10-dihydro-10-hydroxy-10-oxy
So-9-oxa-10-phosphaphenanthrene, etc.)
May be

As the salt of the amino group-containing nitrogen compound and the organic phosphonic acid, a melamine salt of C _1-6 alkyl-substituted phosphonic acid, a melamine salt of mono- or diphosphonic acid ester of C _1-6 aliphatic diol (1-hydroxy). Ethylidene
1,1-diphosphonic acid / dimelamine, 1-hydroxyethylidene-1,1-diphosphonic acid / tetramelamine, etc.), melamine salt of phosphonic acid substituted with an aliphatic polyvalent group having a hetero atom [nitrilotris (methylphosphonic acid ). Tetramelamine salt, nitrilotris (methylphosphonic acid), hexamelamine salt, etc.], and C _6-10 arylphosphonic acid / melamine (phenylphosphonic acid / melamine, phenylphosphonic acid / dimelamine, etc.) and the like.

The organic phosphinic acid includes an organic phosphinic acid in which an organic group (a hydrocarbon group such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group) is bonded to a phosphorus atom of phosphinic acid. Be done. Examples of such an organic phosphinic acid include substituted phosphinic acids corresponding to the above-mentioned substituted phosphonic acids, for example, mono- or di-C _1-10 alkylphosphinic acids such as methylethylphosphinic acid and diethylphosphinic acid; and C such as methylphenylphosphinic acid. Hosufinikoji C, such as phosphinyl co carboxylic acid [Hosufinikoji acetate; C _6-10 aryl phosphinic acids such as phenyl phosphinic acid; _1-10 alkyl C _6-10 aryl phosphinic acid
_1-6 aliphatic carboxylic acid; C _1-6 alkylphosphinico-mono C such as 3- (methylphosphinico) propionic acid
_1-6 aliphatic carboxylic acid, 3- (phenylphosphinico)
C _6-10 arylphosphinico-mono C _1-6 aliphatic carboxylic acids such as propionic acid, carboxylic acid esters of these phosphinicocarboxylic acids, and the like; phosphinicomono or di C _6-10 arylcarboxylic acids or thereof Carboxylic acid ester]; hydroxyphosphine oxide (1-hydroxydihydrophosphonyl oxide, 1-hydroxyphosphorane oxide, etc.) and the like.

Examples of salts of amino group-containing nitrogen compounds and organic phosphinic acids include phosphinicocarboxylic acid / melamine salts [3- (phenylphosphinico) propionic acid / melamine, 3- (phenylphosphinico) propionic acid. -Arylphosphinicocarboxylic acid / melamine salt such as dimelamine; melem salt, melam salt, melon salt, guanamine salt corresponding to the melamine salt; and to the melamine salt such as pentaerythritol bisphosphate-melamine melam / melem Corresponding double salts and the like can be mentioned.

The method for producing an organic phosphonate or phosphinate of a nitrogen-containing compound having such an amino group (particularly, an amino group-containing triazine compound) is not particularly limited. For example, the nitrogen-containing compound and the organic phosphonate can be used. A solution or dispersion containing an acid or phosphinic acid (water-acetone mixed system, water-alcohol mixed system or other aqueous solution or suspension, etc.) at an appropriate temperature (eg, about 50 to 100 ° C.)
It can be produced by a method such as stirring and mixing with, separating the resulting precipitate, and drying.

A triazole salt corresponding to the above triazine salt can also be used. These salts of the amino group-containing nitrogen compound and the specific oxygen acid can be used alone or in combination of two or more kinds.

The ratio of the nitrogen-containing cyclic compound having an amino group and the oxygen acid is the same as that of the (A1) polyphosphate.

The salts of the nitrogen compounds containing amino groups with the oxygen acids can be used alone or in combination of two or more kinds.

(A5) Cyclic urea compound The cyclic urea compound comprises at least one urea unit-N
It is not particularly limited as long as it has HCONH- as a ring-constituting unit, and may be a monocyclic compound, a condensed ring with an aromatic hydrocarbon ring, a bridged ring, or the like. Examples of such a cyclic urea compound include cyclic monoureide and cyclic diureide. These cyclic urea compounds can be used alone or in combination of two or more.

Examples of the cyclic monoureide include alkylene urea [C _1-10 alkylene urea such as methylene urea, ethylene urea, and crotonylidene urea (CDU) (preferably C _1-6 alkylene urea)], alkenylene urea (vinylene urea). , C _2-10 alkenylene ureas such as cytosine), alkynylene ureas [C _2-10 alkynylene ureas (preferably C _2-6 alkynylene ureas)], arylene ureas (such as imesatin), ureides of dicarboxylic acids (paravanic acid, Dimethylparabanic acid, barbituric acid,
5,5-diethylbarbituric acid, dirituric acid, dialuric acid, alloxan, alloxanic acid, isocyanuric acid, uramil, etc.), β-aldehyde acid ureido [uracil,
5-methyluracil (thymine), dihydrouracil, urazole, benzylene urea, etc.], α-oxy acid ureido [hydantoin, 5,5-dimethylhydantoin,
1,1-methylenebis (5,5-dimethylhydantoin), hydantoins such as allantoin, and the like, or derivatives thereof.

Examples of the cyclic diureide include uric acid,
3-methyluric acid, pseudouric acid, acetylene urea (glycoluril), diureide of α-oxy acid [1,1-
Examples thereof include methylenebis (5,5-dimethylhydantoin), allantoin, etc.], diurea such as p-urazine, dicarboxylic acid diureide (alloxanthin, purpuric acid, etc.), and derivatives thereof.

Of these cyclic urea compounds, cyclic diureides having two urea units as ring constitutional units (including cyclic thioureas having two urea units), particularly acetylene urea, uric acid and their derivatives are preferable. .

These cyclic urea compounds may be used alone or in combination of two or more.

Among these flame retardants, melamine polymeline / melam / melem complex salt, melamine polymetaphosphate,
Preferred are polyphosphoric acid amide, melamine sulfate, melam pyrosulfate, melam organic sulfonate, melamine organic phosphonate, and melamine organic phosphinate.

These (A) flame retardants may be treated with a surface modifier such as an epoxy compound, a coupling agent (silane compound, titanate compound, aluminum compound, etc.), chromium compound, etc. The flame retardant (A) is metal, glass, cyanuric acid salt of triazine derivative, thermosetting resin (for example, phenol resin, urea resin, melamine resin, aniline resin, furan resin, xylene resin, or co-condensation resin thereof). , Unsaturated polyester resin, alkyd resin, vinyl ester resin, diallyl phthalate resin, epoxy resin, polyurethane resin, silicon resin, polyimide, etc.), thermoplastic resin or the like. Of these treatments, a thermosetting resin (for example, phenol resin or epoxy resin) is usually used for coating. For example, as a coating treatment method of (A) flame retardant, JP-A-52-125489 and JP-A-62-2
1704, JP-A-63-110254, JP-A-8-53569, JP-A-8-53574, JP-A-2000-169120, and JP-A-2001.
Reference can be made to, for example, JP-A-131293.
The ratio of the (A) flame retardant to the coating component is not particularly limited, but for example, the coating component is 0.1 to 20% by weight, preferably 0.1 to 10% by weight (e.g. ~
8% by weight).

[(B) Flame retardant aid] The flame retardant aid (B) is
(B1) phosphorus-containing compound, (B2) aromatic resin, and (B
3) Includes metal salts of inorganic acids. These flame retardant aids are
They can be used alone or in combination of two or more.

(B1) Phosphorus-containing compound Examples of the phosphorus-containing compound include organic phosphorus compounds (monomer type organic phosphorus compounds, polymer type organic phosphorus compounds, etc.), inorganic phosphorus compounds and the like.

Among the above-mentioned organic phosphorus compounds, monomeric organic phosphorus compounds include phosphoric acid esters, phosphoric acid ester amides, phosphonitrile compounds, organic phosphonic acid compounds (phosphonic acid esters, metal salts, etc.), organic phosphinic acid compounds, Examples include phosphine oxide (triphenylphosphine oxide, tricresylphosphine oxide, etc.).

(Phosphate ester) Examples of the phosphate ester include aliphatic phosphate esters [trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triisobutyl phosphate, pentaphosphate] Erythritol (eg, Great Lake)
NH-1197 manufactured by Chemicals, Inc.
Phosphoric acid tri C _1-10 alkyl esters such as Bishikurorin such esters) described in 1-106889 JP; phosphoric acid di C _1-10 alkyl ester and phosphoric acid mono C _1-10 corresponding to the phosphate triester Alkyl ester, etc.], aromatic phosphate ester [triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, diphenyl cresyl phosphate, tri (isopropylphenyl) phosphate,
Tri-C phosphate such as diphenylethyl cresyl phosphate
_6-20 aryl ester, etc.], aliphatic-aromatic phosphate ester [methyl diphenyl phosphate, phenyl diethyl phosphate, polyphenol (cyclic alkylene glycol phosphate) [resorcinol bis (neopenpentylene glycol phosphate), hydroquinone bis (neopentyl) Ren glycol phosphate), biphenol bis (neopenpentylene glycol phosphate), bisphenol-A bis (neopenylene glycol phosphate), etc.], spiro cyclic aromatic phosphate ester (diphenyl pentaerythritol diphosphate, dicresyl pentaerythritol diphosphate, Dixylyl pentaerythritol diphosphate, etc.)] and the like.

(Phosphoric acid ester amide) As the phosphoric acid ester amide, there can be used a phosphoric acid ester amide represented by the following formula (2) including a bonding mode of phosphoric acid ester and phosphoric acid amide.

[0105]

[Chemical 2]

[In the formula, R¹~ R^FourAre the same or different,
-OR^Five(R^FiveIs an alkyl group, a cycloalkyl group or an ari
Group, which may have a substituent
I) or -NR⁶R⁷(R⁶And R⁷Are the same or different
A hydrogen atom, an alkyl group, a cycloalkyl group or an ari
Group, which may have a substituent
R ¹And R², R³And R^Four, And R⁶And R⁷Are each other
And optionally form a ring).¹Is
Indicates an amine residue or arylenedioxy group, and m is 0 or less.
Indicates the upper integer. However, R¹~ R^FourAt the same time-OR^Fiveof
If A¹Is a diamine residue].

In the formula (2), the alkyl group represented by R ^{5 to} R ⁷ is C such as methyl, ethyl, butyl, t-butyl, hexyl, octyl, nonyl and dodecyl.
_{A 1-20} alkyl group, preferably a C _1-12 alkyl group, and more preferably a C _1-6 alkyl group are mentioned. Examples of the cycloalkyl group include C _5-20 cycloalkyl groups such as cyclohexyl, preferably C _6-12 cycloalkyl groups. Examples of the aryl group represented by R ^{5 to} R ⁷ include C _6-20 aryl groups such as phenyl and naphthyl, substituted aryl groups (alkyl-substituted aryl groups such as methylphenyl group and ethylphenyl group, and hydroxyphenyl group). Can be mentioned. R ⁶ and R ⁷ may combine with each other to form a ring (for example, a 4- to 10-membered heterocycle having adjacent nitrogen atoms as hetero atoms). In addition, these groups are
It may have a substituent (for example, a C _1-4 alkyl group, particularly a C _1-3 alkyl group; a hydroxyl group, etc.).

The —OR ⁵ group is a monovalent organic group such as phenyloxy, mono-, di- or tri-C _1-4 alkylphenyloxy (eg tolyloxy, xylyloxy, trimethylphenyloxy, diethylphenyloxy, etc.) and the like. have a substituent (such as C _1-3 alkyl group) phenyl group also.

-NR⁶R⁷As the group, a monovalent amino group, eg,
For example, mono or di such as methylamino and dibutylamino.
C_1-4Alkylamino group; such as cyclohexylamino
Mono or di C_4-12Cycloalkyl-substituted amino group; phenyl
Mono or di C such as luamino _6-20Arylamino group;
C such as tylphenylamino_1-4Alkyl C_6-20Ally
Luamino group; pyrrolidino, 2-methylpyrrolidino, pipet
Lysino, 2-Methylpiperidino (Pipecorino), 3-Me
Tilpiperidino, 4-methylpiperidino, piperazino,
Heteroatoms containing at least one nitrogen atom such as morpholino
4- to 10-membered (preferably 5 to 8-membered) heterocyclic group as a child
And so on.

R ¹ and R ² adjacent to each other and R ³ and R ⁴ adjacent to each other are bonded to each other to form a ring, for example, an alkylenedioxy group (eg methylenedioxy, dimethylenedioxy). , Trimethylenedioxy, 2,2-dimethyl-1,3-trimethylenedioxy, 2-ethyl-2-methyl-1,3-trimethylenedioxy, 2,2-diethyl-1,3-trimethylene C _2-10 alkylenedioxy such as dioxy) may be formed.

In the formula (2), A ¹ is the following formula (3)
Alternatively, it may be a divalent group represented by (4).

[0112]

[Chemical 3]

(In the formula, R ⁸ and R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group or a cycloalkyl group,
R ⁸ and R ⁹ may combine with each other to form a ring. Z ¹
Represents an alkylene group, a cycloalkylene group or a divalent aromatic group. Z ² represents a divalent aromatic group).

The alkyl group and cycloalkyl group represented by R ⁸ and R ⁹ include the alkyl groups (methyl,
C _1-6 alkyl group such as ethyl), cycloalkyl groups (such as C _4-10 cycloalkyl group such as cyclohexyl), and the like. R ⁸ and R ⁹ may be bonded to each other to form a C _1-6 alkylene group such as ethylene, propylene, tetramethylene and hexamethylene.

Z¹The alkylene group represented by
Tylene, ethylene, propylene, tetramethylene, hex
C such as sumethylene_1-6An alkylene group, preferably C_1-4
Examples of the alkylene group include cycloalkylene groups.
Is C such as cyclohexylene _4-20Cycloalkylene
A group, preferably C_6-12And cycloalkylene groups
It Z¹And Z²As the divalent aromatic group represented by,
Arylene groups (eg phenylene, naphthylene groups, etc.
C_6-20Arylene groups, etc.), a plurality of the above arylene groups
A group having a [bisphenol (bisphenol A, biphenol
Sphenol D, bisphenol AD, 2,2-bis
(3,5-Dimethyl-4-hydroxyphenyl) propa
1,1-bis (4-hydroxyphenyl) butane,
2,2'-dihydroxydiphenylmethane, 2,2'-
Diethyl-4,4'-dihydroxydiphenylmethane
Which bis (hydroxydiaryl) alkanes; 1,1
-Bis (4-hydroxyphenyl) cyclohexane, etc.
Bis (hydroxydiaryl) cycloalkanes;
1,4-bis (4-hydroxyphenylisopropyl)
Bis (hydroxyarylalkyl) such as benzene
Benzene; bis (4-hydroxyphenyl) sulfone,
Bis (3,5-dimethyl-4-hydroxyphenyl) s
Bis (hydroxydiaryl) sulfone such as Rufone
Kinds; bis (4-hydroxyphenyl) ether, bis
(3,5-dimethyl-4-hydroxyphenyl) ether
Such as 4,4'-dihydroxydiphenyl ether
Bis (hydroxyaryl) ethers; 4,4'-di
Hydroxybenzophenone, 3,3 ', 5,5'-teto
Lamethyl-4,4'-dihydroxybenzophenone, etc.
Bis (hydroxyaryl) ketones; bis (4-hi)
Droxyphenyl) sulfide, bis (3-methyl-4)
-Hydroxy (phenyl) sulfide and other bis (hydro)
Xyaryl) sulfides; bis (4-hydroxy group)
Bis (hydroxy aryl) such as phenyl) sulfoxide
Le) sulfoxides; 4,4'-dihydroxydipheny
Bispheno) such as dihydroxydiphenyls
Biphenylene, a group from which hydroxyl groups have been removed
Group, etc.].

As the diamine residue represented by A ¹ ,
Diamine [eg C _2-4 such as ethylenediamine, diethylenediamine, N, N-dimethylethylenediamine, etc.
Alkylenediamine; 1,3-piperazine, 1,4-piperazine, 2-methyl-1,4-piperazine, 2,5-
Piperazines such as dimethyl-1,4-piperazine;
C _4-8 cycloalkyldiamine such as 1,4-cyclohexanediamine; phenylenediamine (eg, 1,4
-Phenylenediamine and the like); toluenediamine (eg 2,4-diaminotoluene, 3,5-diethyl-
2,4-diaminotoluene, etc.); xylylenediamine (eg, 1,3-xylylenediamine, 1,4-xylylenediamine, etc.); diaminodiphenylmethane (eg, 4,4′-diaminodiphenylmethane, 2,2 ′)
-Diethyl-4,4'-diaminodiphenylmethane,
3,3′-diethyl-4,4′-diaminodiphenylmethane and the like); diaminodiphenyl ether (eg,
4,4'-diaminodiphenyl ether, 2,2'-dimethyl-4,4'-diaminodiphenyl ether and the like); diaminodiphenyl sulfone (eg 4,4 '
-Diaminodiphenyl sulfone, 3,3-dimethyl-
4,4′-diaminodiphenyl sulfone and the like); diaminodiphenyl sulfide (eg, 4,4′-diaminodiphenyl sulfide and the like) residues.

In addition, A¹Ally Range Oki represented by
Hydroquinone residue and resorcinol residue
Phenylenedioxy groups such as groups, bisphenols (previous
Note Z ¹And Z²Bisphenols exemplified in the section, for example
For example, dihydroxydiarylalkanes, dihydroxy
Diaryl ethers, dihydroxydiaryl sulf
And dihydroxydiaryl sulfones)
Examples include residues.

Preferred phosphoric acid ester amides include compounds of the formula (2) wherein m is 0 or 1, especially m is 1. The compound in which m is 1 is represented by the following formula (5).

[0119]

[Chemical 4]

(In the formula, R ¹ , R ² , R ³ , R ⁴ and A ¹ are
Same as above).

Examples of the phosphoric acid ester amide include, for example,
C _2-6 alkylenediaminediyltetraarylphosphate (piperazindiyltetraarylphosphate in which aryl is phenyl, cresyl, xylyl, etc.,
Ethylenediaminediyltetra C _6-10 arylphosphate, N, N′-dimethylethylenediaminediyltetra C _6-10 arylphosphate, etc.); _optionally substituted C _6-10 arylenediaminediyltetra C
_6-10 Aryl phosphate (arylene is o-phenylene, m-phenylene, p-phenylene, etc., and aryl is phenyl, cresyl, xylyl, etc., phenylenediaminediyl tetraphenyl phosphate, resorcinol triphenyl phosphate diphenylamide, hydroquinone triphenyl Phosphate diphenylamide, etc.); C _8-20 aralkylene diamine tetra C _6-10 aryl phosphate which may have a substituent (aralkylene is xylylene, etc., and aryl is phenyl, cresyl, xylyl, etc.) Aminediyltetraarylphosphate etc.); C
_2-15 Alkylenediaminediylbis (cyclic alkyleneglycol phosphate) [Piperazinediylbis (neopenpentyleneglycolphosphate) in which alkylenediamine is piperazine and alkylene is neopentylene
Etc.]; C _6-20 arylenediamine diyl bis (cyclic alkylene glycol phosphate) which may have a substituent [phenylene diamine diyl bis (neopentylene glycol phosphate) in which arylene is phenylene and alkylene is neopentylene, etc. ] C _8-20 aralkylenediaminediylbis (cyclic alkylene glycol phosphate) which may have a substituent
[Xylylenediaminediylbis (neopenthylene glycol phosphate) where aralkylene is xylylene and alkylene is neopentylene, etc.]; bisphenol A triphenyl phosphate dibutylamide and other bisphenol phosphate di C _1-6 alkylamides; bisphenol A triphenyl diphenyl phosphate closed C _1-6 alkyl amide such as diphenyl phosphate closed butyl amide; phosphate bisphenol phosphates C _6-10 aryl amide, such as diphenyl amide diphenyl phosphate methylphenyl amide, diphenyl phosphate C _6-10 aryl amide, such as diphenyl phosphate diphenylamide A piperidinodi C in which aryl is phenyl, cresyl, xylyl, etc.
_6-10 aryl phosphate and pipecoline di C _6-10 aryl phosphate and the like. These phosphoric acid ester amides can be used alone or in combination of two or more kinds.

The method for producing the phosphoric acid ester amide is as follows:
Although not particularly limited, JP-A-2002-226547, JP-A-2001-354684, and JP-A-2000
-327834, JP-A-2000-154277, JP-A-10-175985, Journal
of Chem. Soc. C, 3614 (197)
1), JP-A-8-59888, JP-A-63-23
It can be produced with reference to JP-A-5363, JP-A-54-19919 and the like. For example, (1) a method in which a phenol is reacted with phosphorus oxyhalide and then an amine is reacted, and (2) a method in which an amine is reacted with phosphorus oxyhalogenated and then a phenol is reacted,
(3) A method for reacting amines with phenyl dihalophosphate, (4) A method for reacting amines with halophosphate diphenyl ester, (5) A method for reacting amines with diphenylphosphite, etc. Alternatively, it can be obtained in the presence of a metal chloride.

Preferred phosphoric acid ester amides include the compounds and high molecular weight condensed phosphoric acid ester amides described in the above-mentioned patent publications. Examples of such phosphoric acid ester amide include, for example, N- (diaryloxyphosphinyl) -substituted alkylene amines [for example,
N, N'-bis (diphenoxyphosphinyl) piperazine, N, N'-bis (ditoluyloxyphosphinyl)
Piperazine, N, N'-bis (dixylyloxyphosphinyl) piperazine, N, N'-bis (di or trimethylphenyloxyphosphinyl) piperazine, etc.], bis to tetrakis [(diaryloxyphosphinyl)]
Amino] -substituted aromatic compounds {eg, 1,3- or 1,4-bis [(diphenoxyphosphinyl) amino]
Benzene, 1,3- or 1,4-bis [(ditoluyloxyphosphinyl) amino] benzene, 1,3- or 1,4-bis [(dixylyloxyphosphinyl) amino] benzene, 1, 3- or 1,4-bis [(di or trimethylphenyloxyphosphinyl) amino] benzene, 1,3- or 1,4-bis [(diphenoxyphosphinyl) aminomethyl] benzene, 1,3- Or 1,4
-Bis [(ditoluyloxyphosphinyl) aminomethyl] benzene, 1,3- or 1,4-bis [(dixylyloxyphosphinyl) aminomethyl] benzene, 1,
3- or 1,4-bis [(di-trimethylphenyloxyphosphinyl) aminomethyl] benzene etc.}, N-
(Cyclic alkylenedioxyphosphinyl) -substituted alkyleneamines [eg, N, N′-bis (neopentylenedioxyphosphinyl) piperazine, etc.], bis or tetrakis [(cyclic alkylenedioxyphosphinyl) amino] Substituted aromatic compounds {eg 1,3- or 1,
4-bis [(neopentylenedioxyphosphinyl) amino] benzene, 1,3- or 1,4-bis [(neopentylenedioxyphosphinyl) aminomethyl] benzene, etc.}, N- (cyclic arylene diene Oxyphosphinyl) -substituted alkylene amines [eg, N, N′-bis (phenylene-1,2-dioxyphosphinyl) piperazine, 1,3- or 1,4-bis [(biphenylene-
2,2'-dioxyphosphinyl) aminomethyl] piperazine and the like], bis to tetrakis [(cyclic arylenedioxyphosphinyl) amino] substituted aromatic compounds {for example, 1,3- or 1,4- Bis [(phenylene-
1,2-dioxyphosphinyl) amino] benzene,
1,3- or 1,4-bis [(biphenylene-2,2 '
-Dioxyphosphinyl) aminomethyl] benzene etc., 3,9-bis (N-substituted amino) -2,4,8,
10-Tetraoxa-3,9-diphosphaspiro [5.
5] -undecane-3,9-dioxides [eg N
-Substituted amino group is a dialkylamino group (diethylamino group, etc.), cyclic amino group (piperidino group, pipecorino group, dimethylpiperidino group, morpholino group, etc.), arylamino group (phenylamino group, etc.), alkylarylamino group (Eg, methylphenylamino group) and the like] and the like.

Phosphoric acid ester amide is a trade name of "phosphoric acid ester amide flame retardant SP series (for example, SP-
601, SP-670, SP-703, SP-720, etc.) ”(manufactured by Shikoku Chemicals Co., Ltd.).

(Phosphonitrile Compound) As the phosphonitrile compound, a compound having a repeating unit represented by the following formula (6) can be used. The phosphonitrile compound may be linear or cyclic.

[0126]

[Chemical 5]

(In the formula, R ¹⁰ and R ¹¹ are the same or different and each represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, a substituted oxy group, a substituted amino group or a thiocyanato group, and n is an integer of 3 or more. Indicates).

The alkyl group and aryl group represented by R ¹⁰ and R ¹¹ include the alkyl group (especially C _1-4 alkyl group etc.) and the aryl group (especially C _1-4 alkyl group) exemplified in the item of R ⁵ of the above formula (1). C _6-10 aryl group). As the aralkyl group, a C _6-14 aryl-C _1-6 alkyl group such as benzyl or phenethyl group (in particular, C _6-10 aryl-C _1-4
Alkyl group) and the like. As the substituted oxy group, an alkoxy group such as methoxy group (C _1-4 alkoxy group etc.), an aryloxy group such as phenoxy group, tolyloxy group, xylyloxy group (C _6-10 aryloxy group etc.), C _6-10 An aryl-C _1-4 alkyloxy group and the like can be mentioned. The substituted amino group includes the alkyl group,
An amino group substituted with an aryl group, di-C _1-4 alkylamino group, especially disubstituted amino group (dimethylamino group; and methylphenylamino group; di- C _{6-1 0} aryl amino groups such as diphenylamino group C _1-4 alkyl C
_6-10 arylamino groups, etc.) are included.

The phosphonitrile compound also includes a branched and / or crosslinked derivative modified with a polyhydric phenol (for example, phenoxyphosphazene modified with hydroquinone, resorcinol, biphenol, bisphenol, phloroglucin, etc.). .

N is preferably an integer of about 3 to 100.

(Organic Phosphonic Acid Compound) Examples of the organic phosphonic acid (phosphorous acid) compound include aromatic phosphite (tri C _6-20 aryl phosphite in which aryl is phenyl, cresyl, xylyl, etc.). Such),
Aliphatic phosphite (tri-C _1-10 alkyl phosphite whose alkyl is the alkyl exemplified in the above R ^{5 to} R ⁷ ; diphosphite corresponding to the trialkyl phosphite or Mono C _1-10 alkyl ester, etc.), organic phosphite ester [for example, C _1-6 alkylphosphonic acid di C _{1-6 in which} alkyl is the alkyl exemplified above]
Alkyl (spirocyclic alkylphosphonate ester such as pentaerythritol bis (methylphosphonate), pentaerythritol bis (ethylphosphonate), pentaerythritol bis (propylphosphonate), pentaerythritol bis (butylphosphonate)),
Alkyl is the above-exemplified alkyl, aryl is phenyl, cresyl, xylyl is a C _1-6 alkylphosphonic di C _6-10 aryl and C _1-6 alkyl phosphonic acid C _1-6 alkyl C _6-10 aryl Alkylphosphonic acid diesters such as C _6-10 aryl-phosphonic acid diesters corresponding to said alkylphosphonic acid diesters (spirocyclic C _6-10 arylphosphones such as pentaerythritol bis (phenylphosphonate), pentaerythritol bis (tolylphosphonate) Acid ester, etc.); C
_6-10 arylphosphonic acid monoester (for example, 10-
Hydroxy-9,10-dihydro-9-oxa-10-
Phospha such phenanthrene-10-oxide); phosphonocarboxylic acid ester (C _1-4 alkoxycarbonyloxy C _1-4 corresponding to the alkyl phosphonic acid diester, such as methoxycarbonylmethyl acid dimethyl
Phosphonocarboxylic acid triesters such as alkylphosphonic acid diesters) and various phosphonic acid esters such as Further, phosphorous acid which may be substituted with an alkyl or aryl group, (cyclic) phosphorous acid monoester, or phosphonocarboxylic acid (for example, alkylphosphonic acid,
Alkylphosphonic acid monoalkyl ester, alkylphosphonic acid monoaryl ester, arylphosphonic acid,
Arylphosphonic acid monoalkyl ester, arylphosphonic acid monoaryl ester, etc.) metal salts (Ca,
Mg, Zn, Ba, Al salts, etc.) are also included. Regarding typical compounds of such organic phosphonic acid metal salts, for example, JP-A-63-22866 and JP-A-1 are available.
-226891, JP-A-4-243993, JP-A-8-245659, JP-A-9-272
No. 759, etc. can be referred to.

(Organic Phosphinic Acid Compound) The organic phosphinic acid compound includes an alkyl group (C _1-4 alkyl group, etc.)
Alternatively, a phosphinic acid ester (C _1-6 alkyl such as methyl phosphinate such as methyl phosphinate) and phosphinic acid such as phenyl phosphinate, which may be substituted (mono- or di-substituted) with an aryl group (such as C _6-10 aryl group) _C6-10 aryl, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- _C1-30 alkyl or _C6-20 aryl substituted-9,10-dihydro-
Cyclic phosphinic acid esters such as 9-oxa-10-phosphaphenanthrene-10-oxide) and the like. In addition, a phosphinicocarboxylic acid ester which may be substituted with an alkyl group or an aryl group (for example, 3
-Methylphosphinicopropionate, 3-phenylphosphinicopropionate, etc.), and homopolymers and copolymers thereof.

Further, a phosphinic acid which may be mono- or di-substituted with an alkyl group (C _1-10 alkyl group or the like) or an aryl group [eg, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, ethylbutyl] Phosphinic acid, dipropylphosphinic acid, dibutylphosphinic acid, dioctylphosphinic acid, ethane-1,
Dialkylphosphinic acid such as 2-di (methylphosphinic acid), alkylarylphosphinic acid such as methylphenylphosphinic acid, diarylphosphinic acid such as diphenylphosphinic acid, 1-hydroxydihydrophosphonyl oxide, 1-hydroxyphosphorane oxide, etc.] And a metal salt of the phosphinicocarboxylic acid (Ca,
Mg, Zn, Ba, Al salts, etc.) are also included. Representative compounds of these organic metal salts of organic phosphinates include, for example, JP-A-55-5979 and JP-A-11-1999.
-60924, JP-A-11-140228, JP-A-11-236392, JP-A-2001
2686, JP 2001-513784 A,
Special table 2001-513784 gazette, special table 2001-5
13786, US5973194, US6
Reference can be made to Japanese Patent No. 011172, US Pat.

(Polymer-Type Organic Phosphorus Compound) As the polymer-type organic phosphorus compound, a condensate of a monomer-type organic phosphorus compound can be used. The condensate may be a compound represented by the following formula (7).

[0135]

[Chemical 6]

(In the formula, R ^{12 to} R ¹⁵ each represent an aryl group which may have a substituent, and Z ³ represents a divalent aromatic group.
p represents an integer of 1 or more).

Examples of the aryl group represented by R ^{12 to} R ¹⁵ in the formula (7) include the C _6-20 aryl group and the substituted aryl group exemplified in the item of R ^{5 to} R ^{7 in} the above formula (1). To be Further, as the divalent aromatic group represented by Z ³ ,
In addition to the C _6-20 arylene group exemplified in the above Z ¹ and Z ² , biphenylene group, bisphenol residue [bis (hydroxyaryl) alkane residue such as bisphenol A, bisphenol D, bisphenol AD, bisphenol S, etc.] And so on.

Examples of the condensate represented by the formula (7) (particularly, condensed phosphoric acid ester) include resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dixyl phosphate), etc. Resorcinol phosphates; and hydroquinone phosphates corresponding to these resorcinol phosphates, biphenol phosphates and bisphenol-A phosphates.

The above-mentioned polymer type organic phosphorus compound is
It may be a phosphoric acid ester of a polymer having a hydroxyl group (such as a phenol resin). Examples of the phosphoric acid ester of such a polymer include those represented by the following formula (8).
A polymer having a structural unit represented by

[0140]

[Chemical 7]

(In the formula, R ¹⁶ and R ¹⁷ represent an aryl group).

Examples of the aryl group include the aryl groups exemplified above (for example, C _6-20 aryl groups, especially phenyl) and substituted aryl groups (for example, alkyl-substituted aryl groups).
Is mentioned.

Further, the polymer type organic phosphorus compound also includes polyphosphinicocarboxylic acid ester and polyphosphonic acid amide. Examples of the polyphosphonic acid amide include polymers having a structural unit represented by the following formula (9).

[0144]

[Chemical 8]

(In the formula, Z ⁴ represents an alkylene group, an arylene group or an aralkylene group. R ¹⁸ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R
¹⁹ and R ²⁰ are the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R ¹⁹ and R ²⁰ may be directly connected to each other to form a ring).

Examples of the alkylene group and arylene group represented by Z ⁴ include an alkylene group and an arylene group exemplified in the above-mentioned items of Z ¹ and Z ² , as well as a biphenyl and a bisphenol residue [the above-mentioned item of Z ¹ or Z ² And the like, the residue of the bis (hydroxyaryl) alkane, etc., which is exemplified in 1.), and the aralkylene group is a group in which these alkylene groups and arylene groups are linked (in particular, C _1-4 alkylene-C _6-10 arylene groups, etc.). Is mentioned. R ¹⁹ and R ²⁰ may be bonded to each other to form the alkylene group exemplified in the item of R ⁸ and R ⁹ .

(Inorganic phosphorus compound) Examples of the inorganic phosphorus compound include red phosphorus, (poly) phosphate [orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid (metaphosphoric acid,
Non-condensed or condensed (sub) phosphorous acid salts such as polyphosphorous acid (metaphosphorous acid, pyrophosphorous acid, etc.) and the like] and the like.

As salts, ammonium salts, alkali metal salts (Li, Na, K salts, etc.), alkaline earth metal salts (Mg, Ca salts, etc.), Group 2B metal salts (Zn salt, etc.), Periodic table Examples thereof include Group 3B metal salts (such as Al salts).

Red phosphorus has a high flame retarding effect and can impart flame retardancy to the resin even in a small amount. Further, since the effect can be obtained with a small amount, flame retardance can be achieved without impairing the resin characteristics (for example, mechanical characteristics and electrical characteristics). For red phosphorus,
Usually, red phosphorus which has been subjected to a stabilizing treatment (stabilized red phosphorus) is preferably used. In particular, without crushing red phosphorus, red phosphorus obtained by a method of forming fine particles without forming a crushed surface having high reactivity with water or oxygen on the surface of red phosphorus, and further, the surface of red phosphorus, Red phosphorus coated with a resin (for example, a thermosetting resin or a thermoplastic resin), a metal, a metal compound (for example, a metal hydroxide, a metal oxide, etc.) alone or in combination of two or more can be used. .

Examples of the thermosetting resin for coating the surface of red phosphorus include phenol resin, melamine resin, urea resin, alkyd resin, unsaturated polyester resin, epoxy resin, silicone resin, and the like. Examples of the plastic resin include polyester resin, polyamide resin, acrylic resin, olefin resin and the like. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, titanium hydroxide and the like, and examples of the metal oxide include aluminum oxide, magnesium oxide, zinc oxide, Examples thereof include titanium oxide, zirconium oxide, copper oxide, iron oxide, molybdenum oxide, tungsten oxide, manganese oxide, tin oxide and the like.

Further, as a method of coating the surface of red phosphorus with a metal to stabilize it, for example, an electroless plating method is used.
Examples of the method include coating with a metal (iron, nickel, copper, aluminum, zinc, manganese, tin, titanium, zirconium, etc.) or an alloy thereof. As another method for coating the surface of red phosphorus, red phosphorus is treated with a solution of a metal salt (a salt of aluminum, magnesium, zinc, titanium, copper, silver, iron, nickel, etc.), and a metal phosphorus compound is added to the surface of the red phosphorus. It also includes a method of stabilizing by forming a.

In particular, a method of atomizing red phosphorus into fine particles without forming a crushed surface on the surface of red phosphorus is used, and a coating of a metal component (metal hydroxide or metal oxide) and a coating of a resin are combined to form a plurality of layers. A coating treatment, in particular, a coating of a metal component may be performed, and then a resin coating may be multiple-coated. These stabilized red phosphorus is excellent in heat resistance stability and hydrolysis resistance, remarkably little phosphine is formed by the decomposition reaction in the presence of water or at high temperature, and when producing the resin composition of the present invention. , And from the viewpoint of safety when manufacturing a molded product.

As the red phosphorus, generally, stabilized red phosphorus can be used in the form of powder. The particle size of the stabilized red phosphorus is, for example, 0.01 to 100 μm, preferably 0.1 to 70.
μm, and more preferably about 0.1 to 50 μm.

Preferred phosphorus-containing compounds include phosphoric acid esters (aliphatic phosphoric acid esters, aromatic phosphoric acid esters and condensed phosphoric acid esters, especially condensed phosphoric acid esters), phosphoric acid ester amides, phosphonitrile compounds,
Examples include organic phosphonic acid compounds, organic phosphinic acid compounds, inorganic phosphorus compounds ((poly) phosphate salts, etc.),
In particular, monomer type or oligomer type phosphoric acid ester (for example, oligomer type phosphoric acid ester) is preferable.

(B2) Aromatic Resin Aromatic resin includes polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, polyarylate resin, aromatic nylon, aromatic epoxy resin, novolac resin, aralkyl resin, aromatic resin. Group vinyl resins are included. As the polyphenylene oxide-based resin and the polycarbonate-based resin, the same resins as the resins exemplified in the section of the base resin can be used, and the base resin and the aromatic resin are usually different kinds of resins.

(Polyphenylene sulfide-based resin) As the polyphenylene sulfide-based resin (polyphenylene thioether-based resin), a polyphenylene sulfide skeleton-(Ar-S-)-[in the formula, Ar represents a phenylene group]
Homopolymers and copolymers having Examples of the phenylene group (-Ar-) include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group (for example, alkylphenylene group having a substituent such as C _1-5 alkyl group, and Arylphenylene group having a substituent such as phenyl group), p, p'-diphenylenesulfone group, p, p'-biphenylene group, p, p'diphenylene ether group, p, p'-diphenylenecarbonyl group, etc. Can be illustrated. The polyphenylene sulfide-based resin may be a homopolymer using the same repeating unit among the phenylene sulfide groups composed of such a phenylene group, and contains a different repeating unit from the viewpoint of processability of the composition. It may be a copolymer.

As the homopolymer, a substantially linear one having a repeating unit of p-phenylene sulfide group is preferably used. The copolymer may be used in combination of two or more different phenylene sulfide groups. Among these, the copolymer is preferably a combination containing a p-phenylene sulfide group as a main repeating unit and an m-phenylene sulfide group, and p-phenylene is preferable in terms of physical properties such as heat resistance, moldability and mechanical properties. A substantially linear copolymer containing 60 mol% or more (preferably 70 mol%) of sulfide groups is particularly preferable.

The polyphenylene sulfide-based resin may be a polymer having a relatively low molecular weight linear polymer whose melt viscosity is increased by oxidative crosslinking or thermal crosslinking to improve the moldability, and may be mainly composed of a bifunctional monomer. It may be a high molecular weight polymer having a substantially linear structure obtained by polycondensation from the monomer. From the viewpoint of the physical properties of the obtained molded product, the substantially linear structure polymer obtained by polycondensation is preferred. Further, as the polyphenylene sulfide resin, a branched or crosslinked polyphenylene sulfide resin obtained by combining and polymerizing a monomer having three or more functional groups in addition to the above polymer, and a resin composition obtained by blending this resin with the above linear polymer Objects can also be used.

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

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

(Aromatic Nylon) As the aromatic nylon constituting the flame retardant, a resin different from the polyamide resin of the base resin is used. As such a resin, a compound having a unit represented by the following formula (10) can be used.

[0162]

[Chemical 9]

(In the formula, Z ⁵ and Z ⁶ are the same or different and are selected from an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and at least one of them is an aromatic hydrocarbon group. And R ²¹ and R ²² are the same or different and are selected from a hydrogen atom, an alkyl group and an aryl group, and R ²¹ and R ²² may be directly bonded to form a ring).

Such an aromatic nylon is a polyamide derived from a diamine and a dicarboxylic acid,
A polyamide in which at least one of the diamine component and the dicarboxylic acid component is an aromatic compound; an aromatic aminocarboxylic acid, and a polyamide obtained by using a diamine and / or dicarboxylic acid in combination, if necessary.
Aromatic nylons also include copolyamides formed by at least two different polyamide forming components.

As the diamine, for example, phenylenediamine, diaminotoluene, 2,4-diaminomesitylene, 3,5-diethyl-2,6-diaminotoluene, xylylenediamine (particularly metaxylylenediamine, paraxylylenediamine). ), Bis (2-aminoethyl) benzene, biphenylenediamine, diamine having a biphenyl skeleton (for example, 4,4-diamino-3,3′-ethylbiphenyl), diamine having a diphenylalkane skeleton [for example, diaminodiphenylmethane, bis. (4
-Amino-3-ethyl) diphenylmethane, bis (4-
Amino-3-methylphenyl) methane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 '
-Bis (4-aminophenyl) propane etc.], bis (4-aminophenyl) ketone, bis (4-aminophenyl) sulfone, 1,4-naphthalenediamine and other aromatic diamines and N-substituted aromatic diamines thereof Is mentioned. Also, 1,3-cyclopentanediamine,
1,4-cyclohexanediamine, bis (4-amino-
Alicyclic diamine such as 3-methylcyclohexyl) methane; trimethylenediamine, tetramethylenediamine,
Pentamethylenediamine, hexamethylenediamine,
2,2,4-trimethylhexamethylenediamine, 2,
Aliphatic amines such as 4,4-trimethylhexamethylenediamine and octamethylenediamine and their N-
You may use substituted aliphatic diamine etc. together. These diamines can be used alone or in combination of two or more.
As the diamine, it is preferable to use an aromatic diamine (in particular, xylylenediamine, N, N'-dialkyl-substituted xylylenediamine).

Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid and octadecane. C _2-20 aliphatic dicarboxylic acid such as diacid; aromatic dicarboxylic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid; cyclohexane-1,4-dicarboxylic acid or cyclohexane-
Alicyclic dicarboxylic acids such as 1,3-dicarboxylic acid; dimerized fatty acids (for example, dimer acid) and the like.
These dicarboxylic acids can be used alone or in combination of two or more. As the dicarboxylic acid, it is preferable to use an aliphatic dicarboxylic acid (particularly, a C _6-20 aliphatic dicarboxylic acid such as adipic acid).

Examples of the aromatic or alicyclic aminocarboxylic acid include phenylalanine, tyrosine, anthranilic acid, aminobenzoic acid and the like. Aminocarboxylic acids can also be used alone or in combination of two or more.

As aromatic nylon, lactam and / or α, ω can be used as long as the characteristics as a flame retardant are not impaired.
-A condensate with an aminocarboxylic acid may also be used. Examples of lactams include C _3-12 lactams such as propiolactam, butyrolactam, valerolactam, and caprolactam (ε-caprolactam). Α, ω-aminocarboxylic acids include 7-aminoheptanoic acid and 10-aminodecanoic acid. Is mentioned.

As an auxiliary component of other aromatic nylon,
Monobasic acids (eg, acetic acid, propionic acid, caproic acid, nicotinic acid, etc.), monoamines (eg, ethylamine, butylamine, benzylamine, etc.), dibasic acids (eg, adipic acid, sebacic acid, terephthalic acid, isophthalic acid) , Cinchomeronic acid, etc.), diamines (eg, tetramethylenediamine, hexamethylenediamine, etc.), lactams and the like can be used as a viscosity modifier.

As the aromatic nylon, a polyamide whose diamine component is an aromatic compound (for example, a polyamide or copolyamide containing xylylenediamine as a diamine component), preferably an aromatic diamine and α, ω-C _2-12.
Polyamide obtained from dicarboxylic acid [for example, polyamide obtained from adipic acid and metaxylylenediamine (MXD6), polyamide obtained from suberic acid and metaxylylenediamine, obtained from adipic acid and paraxylylenediamine] Polyamide (PMD6),
Polyamides obtained from suberic acid and paraxylylenediamine, polyamides obtained from adipic acid and N, N'-dimethylmetaxylylenediamine, polyamides obtained from suberic acid and N, N'-dimethylmetaxylylenediamine , A polyamide obtained from adipic acid and 1,3-phenylenediamine, adipic acid and 4,4 '
-A polyamide obtained from diaminodiphenylmethane, a copolyamide obtained from adipic acid and metaxylylenediamine and paraxylylenediamine, obtained from adipic acid and metaxylylenediamine and N, N'-dimethylmethaxylylenediamine Copolyamide, etc.] and the like. Particularly preferred aromatic nylons are aromatic diamines (especially xylylenediamine).
And a polyamide obtained from α, ω-C _2-12 aliphatic dicarboxylic acid (especially MXD6). These polyamides can be used alone or in combination of two or more.

These aromatic nylons are described, for example, in JP-B-44-22510, JP-B-47-51480, JP-A-57-200420, and JP-A-58-2004.
111829, JP 62-283179, and Industrial Chemistry Magazine Vol. 74 No. 4 (1971) 786.
Page, Journal of Industrial Chemistry, Vol. 74, No. 10, (1971), 218.
5 page, Engineering Plastics Dictionary (Gihodo Publishing Co., Ltd., 1998), page 74, and the references described therein, by the atmospheric direct method or the melt polymerization method.

The number average molecular weight of the aromatic nylon is not particularly limited, and can be selected from the range of, for example, 300 to 10 × 10 ⁴ , preferably 500 to 5 × 10 ⁴ .

(Polyarylate Resin) The polyarylate resin has the following formula (11) [-O-Ar-OC (O) -A ² -C (O)-] (11) (wherein Ar is A compound having a structural unit represented by an aromatic group and A ² represents an aromatic, alicyclic, or aliphatic group can be used.

Such a polyarylate resin can be prepared by a melt polymerization method, a solution method, etc. by a transesterification method (eg, an acetate method, a phenyl ester method, etc.), an acid chloride method, a direct method or a polyaddition method as a polyesterification reaction. It can be produced using a polymerization method or an interfacial polymerization method.

The polyarylate resin can be obtained by reacting an aromatic polyol component with a polycarboxylic acid component (aromatic polycarboxylic acid component, aliphatic polycarboxylic acid component, alicyclic polycarboxylic acid component, etc.). . The polycarboxylic acid component usually contains at least an aromatic polycarboxylic acid component.

As the aromatic polyol (monomer),
Usually, a diol such as a monocyclic aromatic diol or a polycyclic aromatic diol, or a reactive derivative thereof [eg, a salt of an aromatic polyol (sodium salt, potassium salt, etc.), an ester of an aromatic polyol (acetic acid ester, etc. Etc.), silyl-protected aromatic polyols (trimethylsilylated products, etc.)] are used.

Examples of the monocyclic aromatic diol include:
Benzenediol (resorcinol, hydroquinone,
m-xylylene glycol, p-xylylene glycol, etc.), and aromatic ring diols having about 6 to 20 carbon atoms such as naphthalene diol.

As the polycyclic aromatic diol, bis (hydroxyaryl) s (bisphenols), for example,
4,4′-dihydroxybiphenyl, 2,2′-biphenol, dihydroxydiarylalkanes exemplified in the above Z ¹ and Z ² , and bis (hydroxyaryl) C _1-6 alkane such as bisphenol F; bis (Hydroxyaryl) cycloalkane [eg, bis (hydroxyaryl) C _3-12 cycloalkane such as bis (hydroxyphenyl) cyclohexane]; bis (hydroxyaryl) carboxylic acid [eg, bis-4,4
Bis (hydroxyaryl) C _2-6 carboxylic acid such as-(hydroxyphenyl) butanoic acid] and the like. In addition, other polycyclic aromatic diols include compounds having a bis (hydroxyaryl) skeleton, for example,
Di (hydroxyphenyl) exemplified in the section of Z ¹ and Z ²
Besides ether, di (hydroxyphenyl) ketone, di (hydroxyphenyl) sulfoxide, di (hydroxyphenyl) thioether, bis (C _1-4 alkyl-substituted hydroxyphenyl) alkane [eg, bis (3-methyl-4-hydroxyphenyl) ) Methane, bis (3-methyl-4-hydroxyphenyl) propane, bis (3,5-
Dimethyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.], terpene diphenols (for example, 1,4-
Di (C _1-4 alkyl-substituted hydroxyphenyl) -p-menthane) and the like are also included.

These aromatic polyols can be used alone or in combination of two or more kinds.

Preferred aromatic polyols include bisphenols such as bis (hydroxyaryl) C _1-6.
Alkanes (eg, bisphenol A, bisphenol F, bisphenol AD, etc.) and the like are included.

The aromatic polyol may be used in combination with an aliphatic or alicyclic polyol. Examples of the aliphatic polyol include C _1-10 aliphatic polyols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and neopentyl glycol. Further, the aliphatic polyol includes C _3-10 such as 1,4-cyclohexanedimethanol.
Also included are aliphatic polyols having an aliphatic ring. Examples of cycloaliphatic polyols include C such as cyclohexanediol
_3-10 alicyclic polyols can be mentioned.

Examples of the aromatic polycarboxylic acid include:
Dicarboxylic acids such as monocyclic aromatic dicarboxylic acids and polycyclic aromatic dicarboxylic acids, or reactive derivatives thereof [eg aromatic polycarboxylic acid halides (aromatic polycarboxylic acid chlorides etc.), aromatic polycarboxylic acids Ester (alkyl ester, aryl ester, etc.), aromatic polycarboxylic acid anhydride, etc.].

As the monocyclic aromatic ring dicarboxylic acid, for example, the aromatic carboxylic acids exemplified in the above-mentioned aromatic nylon (benzenedicarboxylic acid, naphthalenedicarboxylic acid and other aryldicarboxylic acids having about 8 to 20 carbon atoms) can be used. Is mentioned. The benzenedicarboxylic acid and naphthalenedicarboxylic acid (particularly benzenedicarboxylic acid) include
It may be substituted by 1 or 2 C _1-4 alkyl groups.

Examples of the polycyclic aromatic dicarboxylic acid include bis (arylcarboxylic acids), for example, bis (carboxyaryl) C _1-6 alkanes such as biphenyldicarboxylic acid and bis (carboxyphenyl) methane; bis (carboxyphenyl) ) Bis (carboxyaryl) C _3-12 cycloalkane such as cyclohexane; Bis (carboxyaryl) ketone such as bis (carboxyphenyl) ketone; Bis (carboxyaryl) sulfoxide such as bis (carboxyphenyl) sulfoxide; Bis (carboxyphenyl) ) Bis (carboxyaryl) ethers such as ethers; bis (carboxyaryl) thioethers such as bis (carboxyphenyl) thioethers, and the like.

Preferred aromatic polycarboxylic acid components include
Monocyclic aromatic dicarboxylic acids (particularly benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid) and bis (carboxyaryl) C _1-6 alkanes are included.

Examples of the aliphatic polycarboxylic acid (monomer) include the aliphatic dicarboxylic acids (particularly C _2-20 aliphatic dicarboxylic acid) exemplified in the above-mentioned aromatic nylon, and C ₃ such as dicarboxymethylcyclohexane. _It may be a dicarboxylic acid having an _-10 aliphatic ring. The alicyclic polycarboxylic acid includes the alicyclic dicarboxylic acids exemplified in the above-mentioned aromatic nylon (particularly C _3-20 alicyclic dicarboxylic acid).

Preferred polyarylate resins are polyarylate resins in which the aromatic polyol is benzenediols and / or bisphenols, for example, benzenediols (hydroquinone, resorcinol, etc.) and / or bisphenols (bisphenol A, bisphenol). AD, bisphenol F, biphenol, etc.)
Polyester with benzenedicarboxylic acid (isophthalic acid, terephthalic acid, etc.), benzenediols and / or bisphenols and bis (arylcarboxylic acids) [eg, bis (carboxyphenyl) methane, bis (carboxyphenyl) ethane, bis Bis (carboxyaryl) C such as (carboxyphenyl) propane
_1-4 Alkane] and polyester. These polyarylate resins can be used alone or in combination of two or more.

In addition to the aromatic diol and the aromatic dicarboxylic acid, the polyarylate-based resin may further contain an aromatic triol or an aromatic tetraol [eg,
1,1,2,2-tetrakis (hydroxyphenyl) ethane, etc.], aromatic tricarboxylic acid, aromatic tetracarboxylic acid, etc. may be used in combination.

The end of the polyarylate resin may be blocked (bonded) with an alcohol, a carboxylic acid or the like (particularly, a monohydric alcohol or a monovalent carboxylic acid). Examples of monohydric alcohols that block the ends of the polyarylate-based resin include monohydric aryl alcohols (monohydric groups that may be substituted with a C _1-10 alkyl group and / or a C _6-10 aryl group). Phenols, for example, phenol, alkylphenols having 1 to 2 C _1-4 alkyl groups such as methyl groups at the o, m, or p positions; o,
C such as phenyl, benzyl, arylphenol having a phenyl, benzyl, cumyl group, etc. at the m or p position, monovalent alkyl alcohols (methanol, ethanol, propanol, butanol, hexanol, stearyl alcohol, etc.)
_1-20 alkyl monoalcohols), monovalent aralkyl alcohols (C _7-20 aralkyl monoalcohols such as benzyl alcohol and phenethyl alcohol), and the like.

Examples of the monovalent carboxylic acids for blocking (bonding) the ends of the polyarylate resin include monovalent aliphatic carboxylic acids (C such as acetic acid, propionic acid, octanoic acid, etc.).
_1-20 aliphatic monocarboxylic acid), monovalent alicyclic carboxylic acid (C _4-20 alicyclic monocarboxylic acid such as cyclohexanecarboxylic acid), monovalent aromatic carboxylic acid (benzoic acid, toluic acid, o, m, or p-tert-butylbenzoic acid,
C _7-20 aromatic monocarboxylic acid such as p-methoxyphenylacetic acid) and the like are included. Further, the carboxylic acid is a monovalent aliphatic carboxylic acids of aromatic groups is substituted, such as phenyl acetic acid (particularly, C _1-10 aliphatic monocarboxylic acids C _{6- 20} aromatic group-substituted) Good.

The polyarylate resin may form a polymer alloy with a resin other than the polyarylate resin, such as polyamide. The polymer alloy includes not only a simple mixture but also a polymer alloy obtained by transesterification reaction or a polymer alloy containing a compatibilizer.

The number average molecular weight of the polyarylate resin is
For example, 300 to 30 × 10 ⁴ , preferably 500 to 1
It is about 0 × 10 ⁴ .

(Aromatic Epoxy Resin) The aromatic epoxy resin includes an ether type epoxy resin (for example, a bisphenol type epoxy resin, a novolac type epoxy resin, etc.) and an amine type epoxy resin using an aromatic amine component. .

The bisphenol constituting the bisphenol type epoxy resin is the same as the bis (hydroxyaryl) s. Preferred bisphenol type epoxy resins include glycidyl ethers such as bis (hydroxyaryl) C _1-6 alkanes, especially bisphenol A, bisphenol AD and bisphenol F.
The bisphenol type epoxy resin also includes the above-mentioned bisphenol glycidyl ether having a large molecular weight (that is, phenoxy resin).

Novolac comprising novolac type epoxy resin
As the rack resin, an alkyl group (for example,
C_1-20Alkyl group, preferably methyl group, ethyl group, etc.
C _1-4Novolak optionally substituted with an alkyl group)
Resin (eg phenol novolac resin, cresol
Novolak resin). preferable
For novolac type epoxy resin, C_1-2Alkyl group is placed
Glycidyl ether of novolak resin which may be replaced
Is included.

The aromatic amine component constituting the amine epoxy resin includes monocyclic aromatic amines (aniline, toluidine, etc.), monocyclic aromatic diamines (diaminobenzene, xylylenediamine, etc.), monocyclic aromatics. Group amino alcohols (such as aminohydroxybenzene), polycyclic aromatic diamines (such as diaminodiphenylmethane), and polycyclic aromatic amines.

The number average molecular weight of the aromatic epoxy resin is, for example, 200 to 5 × 10 ⁴ , preferably 300 to 1 × 1.
0 ⁴ , more preferably about 400 to 6,000. The number average molecular weight of the phenoxy resin is, for example,
500 to 5 × 10 ⁴ , preferably 1,000 to ⁴ × 10 ^4.
It is a degree.

Aromatic epoxy resins include amine type curing agents (for example, aliphatic amines such as ethylenediamine, aromatic amines such as metaphenylenediamine and xylylenediamine), polyaminoamide type curing agents, acids and acid anhydrides. It may be used after being cured with a curing agent such as a curing agent.

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

(Resin Having Aromatic Ring Containing Hydroxyl Group and / or Amino Group) The resin having an aromatic ring having a hydroxyl group and / or an amino group is a resin having the aromatic ring in the main chain or side chain. Is mentioned. Among these resins, as the resin having an aromatic ring in the main chain,
For example, novolac resin and aralkyl resin can be exemplified.
Examples of the resin having an aromatic ring as a side chain include aromatic vinyl resins.

(1) Novolac resin The novolac resin has a repeating unit represented by the following formula (12).

[0202]

[Chemical 10]

(In the formula, R ^{23 to} R ²⁵ are the same or different and each represents a hydrogen atom, an alkyl group or an aryl group, and r represents an integer of 1 or more).

Examples of the alkyl group and the aryl group include the C _1-20 alkyl group (especially C _1-20 ) exemplified in the section of R ^{5 to} R ^7.
_1-12 alkyl group), C _6-20 aryl group and substituted aryl group (particularly C _1-4 alkyl substituted aryl group).

The novolac resin (particularly the random novolac resin) is generally obtained by the reaction of phenols with aldehydes. Examples of the phenols include phenol, p- or m-cresol, 3,5-xylenol, alkylphenol (for example, C _1-20 alkylphenol such as t-butylphenol, p-octylphenol, and nonylphenol), arylphenol (for example, phenyl). Phenol, benzylphenol, cumylphenol) and the like. You may use these phenols by 1 type or in combination of 2 or more types.

Examples of the aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde and propionaldehyde, and aromatic aldehydes such as phenylacetaldehyde. Formaldehyde etc. are mentioned as a preferable aldehyde.
Further, condensates of formaldehyde such as trioxane and paraformaldehyde can also be used. The ratio of phenols and aldehydes is the former / latter = 1 / 0.5 to 1 /
It is about 1 (molar ratio).

The condensation reaction between phenols and aldehydes is usually carried out in the presence of an acid catalyst. Examples of acid catalysts include inorganic catalysts (eg, hydrochloric acid, sulfuric acid, phosphoric acid, etc.), organic catalysts (p-toluenesulfonic acid, oxalic acid, etc.), and the like.

Particularly, a phenol novolac resin having a reduced number of 1 to 2 nuclides is preferably used. Examples of such a phenol novolac resin include Sumitomo Dures Co., Ltd. under the trade names "Sumilite Resin PR-53647", "Sumilite Resin PR-NMD-100 Series", and "Sumilite Resin PR-NMD-200 Series". ) Available from

As the novolak resin, a high ortho novolak resin having an ortho / para ratio of 1 or more may be used.

Particularly, as the novolac resin, ortho /
Para ratio is 1 or more, for example, 1 to 20 (especially 1 to 15)
A novolac resin having a certain degree, that is, a so-called high ortho novolac resin is preferably used. Such a high ortho novolac resin can be obtained from Sumitomo Dures Co., Ltd. under the trade name "Sumilite Resin HPN Series".

Methods for producing these novolac resins are described in JP-A 2001-172348 and 2000.
-273133, JP-A-2000-273132, JP-A-2000-226423, JP-A-10
Reference can be made to JP-A-204139, JP-A-10-195158 and the like.

The above-mentioned phenols, dioxybenzenes, naphthols and bisphenols (for example,
Bisphenols exemplified in the section of Z ¹ and Z ² , alkylbenzenes (for example, toluene, ethylbenzene,
Xylene, mesitylene, etc.), anilines, furfurals, ureas and triazines (eg, urea, cyanuric acid, isocyanuric acid, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), terpenes, cashew nuts, rosins, etc. A cocondensation product with a cocondensation component can also be used. In particular, aminotriazine novolac modified with triazines is a preferred cocondensate. Such an aminotriazine novolak is capable of co-catalyzing phenols, triazines, and formaldehydes in the presence or absence of a basic catalyst (such as ammonia, triethylamine, triethanolamine) and / or an acidic catalyst (such as oxalic acid). Condensation method [eg DIC Te
mechanical Review No. 3, p47 (1
997), JP-A-8-253557 and JP-A-10-35757.
-279657, etc.]. Aminotriazine novolak is available from Dainippon Ink and Chemicals, Inc. under the trade name "Phenolite".

Further, some or all of the phenolic hydroxyl groups of the novolac resin (random novolac resin and high ortho novolac resin) are converted to phosphorus compounds (for example, phosphoric acid, phosphorous acid, organic phosphonic acid, organic phosphinic acid, and other phosphorus compounds). Acids and their anhydrides, halides, salts,
Or an ester (particularly, an aliphatic ester) and a boron compound (eg, boric acid such as boric acid, organic boronic acid, organic boric acid, and their anhydrides, halides, salts, or esters). Modified novolac resin modified with at least one of
Phosphoric acid-modified novolac resin, boric acid-modified novolac resin, etc.) can also be used. The hydroxyl group of the novolak resin is usually modified as a phosphoric acid ester or a boric acid ester.

Further, some or all of the hydrogen atoms of the phenolic hydroxyl group of the novolak resin (random novolac resin and high ortho novolac resin) are metal ions, silyl groups or organic groups (alkyl group, alkanoyl group,
A modified novolak resin modified (or substituted) with a benzoyl group) can also be used.

Preferred novolac resins include phenol formaldehyde novolac resins, alkylphenol formaldehyde resins (eg t-butylphenol formaldehyde novolac resins, p-octylphenol formaldehyde resins), and their co-condensates (aminotriazine novolac resins), and their derivatives. A mixture may be mentioned.

The number average molecular weight of the novolac resin (random novolac resin and high ortho novolac resin) is not particularly limited, and can be selected from the range of, for example, 300 to 5 × 10 ⁴ , preferably 300 to 1 × 10 ⁴ .

(2) Aralkyl Resin The aralkyl resin has a structural unit represented by the following formula (13).

[0218]

[Chemical 11]

(Wherein Ar represents an aromatic group, Z ⁷ and Z ⁸ are the same or different and represent an alkylene group, R ²⁶ represents a hydrogen atom or an alkyl group, X represents a hydroxyl group, an amino group, or Shows an N-substituted amino group).

The aromatic group represented by Ar is preferably an aromatic group having 6 to 20 carbon atoms, for example, a phenylene group (o-phenylene group, m-phenylene group, p-phenylene group, etc.), naphthylene group and the like. Can include a phenylene group (particularly a p-phenylene group).

Z⁷And Z⁸As an alkylene group represented by
Is the above Z¹And Z²The alkylene group (C
_1-4Alkylene groups, especially C_1-2Alkylene group)
It R ²⁶The alkyl group represented by^Five~ R⁷
C exemplified in section_1-20Alkyl group (especially C_1-4Alkyl
Group).

The N-substituted amino group represented by X includes a mono- or di-C _1-4 alkylamino group such as dimethylamino group and diethylamino group.

As the aralkyl resin, a phenol aralkyl resin in which X is a hydroxyl group is often used. A preferable phenol aralkyl resin is a resin in which Z ⁷ and Z ⁸ are methylene groups, Ar is a phenylene group, R ²⁶ is a hydrogen atom, and p-xylene-substituted phenol represented by the following formula (14) is a repeating unit. included.

[0224]

[Chemical 12]

Aralkyl resins are generally represented by the following formula (1
It can be obtained by reacting the compound represented by 5) with phenols or anilines. When phenols are used, a phenol aralkyl resin can be obtained, and when anilines are used, an aniline aralkyl resin can be obtained.

YZ ⁷ -Ar-Z ⁸ -Y (15) (In the formula, Y represents an alkoxy group, an acyloxy group, a hydroxyl group or a halogen atom. Ar, Z ⁷ and Z ⁸ are the same as the above).

In formula (15), the alkoxy group represented by Y includes C _1-4 alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups. The acyloxy group includes an acyloxy group having a carbon number of about 2 to 5, such as acetoxy group. In addition, the halogen atom includes chlorine, bromine, iodine and the like.

As the compound represented by the above formula (15)
Is, for example, xylylene glycol C _1-4Alkyla
Ter (p-xylylene glycol dimethyl ether, p
-Xylylene glycol diethyl ether, etc.)
Aralkyl ethers, p-xylylene-α, α'-di
Acyloxyaralkyls such as acetate, p-xy
Aralkyldiols such as rylene-α, α'-diols
, P-xylylene-α, α'-dichloride, p-key
Aralkylha such as silylene-α, α'-dibromide
Rides are included.

Examples of the phenols include the phenols and alkylphenols exemplified in the section of the novolak resin. You may use these phenols by 1 type or in combination of 2 or more types.

Examples of anilines include aniline,
Alkylaniline (eg, toluidine, xylidine,
C _1-20 alkylaniline such as _{octylaniline and} nonylaniline), and N-alkylaniline (eg,
And N—C _1-4 alkylaniline such as N, N-dimethylaniline and N, N-diethylaniline). These anilines may be used alone or in combination of two or more.

The ratio of the compound represented by the above formula (15) to the phenols or anilines is, for example, the former / the latter = 1/1 to 1/3 (molar ratio), preferably 1/1.
It is about 1 / 2.5 (molar ratio).

The softening point of the aralkyl resin thus obtained is, for example, about 40 to 160 ° C., preferably 5
It is about 0 to 150 ° C, and more preferably about 55 to 140 ° C. In addition, as another aralkyl resin, Japanese Patent Application Laid-Open No.
The aralkyl resin described in 0-351822 can also be used.

The aralkyl resin may be cured or modified as required. Curing or modification can be usually carried out by a conventional method such as methylene crosslinking with a polyamine (hexamethylenetetramine, etc.) and epoxy modification with an epoxy compound (epichlorohydrin, etc.).

(3) Aromatic Vinyl Resin As the aromatic vinyl resin, for example, a resin having a structural unit represented by the following formula (16) can be used.

[0235]

[Chemical 13]

(In the formula, R ²⁷ represents a hydrogen atom or a C _1-3 alkyl group, R ²⁸ represents an aromatic ring, and s is an integer of 1 to 3.)

In the formula (16), a preferable C _1-3 alkyl group is a methyl group. Examples of the aromatic ring include C such as benzene and naphthalene ring.
_6-20 aromatic rings. In addition, the aromatic ring may have a substituent (for example, a hydroxyl group; an alkyl group exemplified in the above R ^{5 to} R ⁷ ; an alkoxy group exemplified in the above Y).

In the formula (16), the hydrogen atom of the hydroxyl group is a metal ion, a silyl group or an alkyl group,
Organic groups (protecting groups) such as alkanoyl group and benzoyl group
May be protected by.

The resin obtained from such a derivative has, for example, a structural unit represented by the following formula (17).

[0240]

[Chemical 14]

[In the formula, R ²⁷ is the same as defined above. R ²⁹ is -O
H, -OSi (R ³⁰⁾ ₃ and -OM (M is a metal cation, O
An R ³⁰ and OCOR ^30, R ³⁰ is a radical selected from the group consisting of a a) alkyl group or an aryl group having 1 to 5 carbon atoms. Also, t is an integer of 1 to 3].

In the above formula, M may be either a monovalent alkali metal cation (sodium, lithium, potassium, etc.), or a divalent alkaline earth metal cation (magnesium, calcium, etc.) or a transition metal cation. Good.

The substituent R ^{29 in the} above formula may be located at any one of the ortho position, the meta position and the para position. Further, in addition to the substituent R ²⁹ , the pendant aromatic ring has C _1-4.
It may be substituted with an alkyl group.

The aromatic vinyl resin includes a homopolymer or copolymer of an aromatic vinyl monomer having a hydroxyl group corresponding to the structural unit (16), or a copolymer with another copolymerizable monomer. Be done.

The aromatic vinyl monomer is, for example,
Examples include hydroxyl group-containing aromatic vinyl monomers such as vinylphenol, dihydroxystyrene, and vinylnaphthol. These aromatic vinyl monomers can be used alone or in combination of two or more.

Other copolymerizable monomers include, for example,
(Meth) acrylic monomer [(meth) acrylic acid,
(Meth) acrylic acid ester (for example, (meth) acrylic acid C _1- such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate) ₁₈ alkyl ester,
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, etc., (meth) acrylamide, (meth) acrylonitrile, etc.], styrene-based monomers (eg, styrene,
Vinyltoluene, α-methylstyrene, chlorostyrene, vinylnaphthalene, vinylcyclohexane, etc.),
Polymerizable polycarboxylic acid (fumaric acid, maleic acid, etc.),
Maleimide-based monomers (maleimide, N-alkylmaleimide, N-phenylmaleimide, etc.), diene-based monomers (isoprene, 1,3-butadiene, 1,4-hexadiene, dicyclopentadiene, etc.), vinyl-based monomers (eg vinyl acetate) , Vinyl esters such as vinyl propionate; vinyl ketones such as methyl vinyl ketone and methyl isopropenyl ketone; vinyl ethers such as vinyl isobutyl ether and vinyl methyl ether; N-vinylcarbazole, N-vinylpyrrolidone, N-vinylimidazole, etc. Nitrogen-containing vinyl monomers, etc.) and the like. These copolymerizable monomers can be used alone or in combination of two or more.

The ratio of the vinyl monomer to the copolymerizable monomer is, for example, 10/90 to 100/0 (% by weight), preferably 30/70 to 100/0 (% by weight), and more preferably 50/50 to. It is about 100/0 (% by weight).

A preferred aromatic vinyl resin is a vinylphenol homopolymer (polyhydroxystyrene), especially p.
A vinylphenol homopolymer.

The number average molecular weight of the aromatic vinyl resin is not particularly limited and can be selected from the range of, for example, 300 to 50 × 10 ⁴ , preferably 400 to 30 × 10 ⁴ .

Of these aromatic resins, polyphenylene sulfide resins, novolac resins, aralkyl resins, aromatic vinyl resins, and particularly polyphenylene sulfide resins are preferred.

Various inorganic acids such as phosphoric acid, boric acid and stannic acid can be used as the inorganic acid constituting the metal salt salt of the inorganic acid (B3).

Metals that form salts with inorganic acids include alkali metals (potassium, sodium, etc.); alkaline earth metals (magnesium, calcium, barium, etc.); transition metals (Group 3A metals, such as scandium; titanium, etc.). Group 4A metal; Group 5A metal such as vanadium; chromium;
Group 6A metals such as molybdenum; 7A such as manganese
Group metals; Group 8 metals such as iron, cobalt, nickel, and palladium; and Group 1B metals such as copper and silver), Group 2B metals (such as zinc), Group 3B metals (such as aluminum), Group 4B Metals (tin, lead, etc.), Group 5B metals (antimony, bismuth, etc.) and the like are included. These metals can be used alone or in combination of two or more.

(Metal salt of phosphoric acid) As phosphoric acid, non-condensed phosphoric acid such as orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid; hypophosphoric acid salt, pyrophosphoric acid salt, polyphosphoric acid salt (triphosphoric acid) Phosphate, tetraphosphate, etc.), polymetaphosphate (Ca ₃ (P ₃ O ₉ ) _2, etc.), anhydrous phosphates (Ca ₂ (P ₄
O ₁₂ ), Ca ₅ (P ₃ O ₁₀ ) _{2 and the} like) are preferred, and non-condensed phosphoric acid is particularly preferred.

The metal is preferably a polyvalent metal, for example, an alkaline earth metal, a transition metal, a metal of Group 2B to 3B of the periodic table, and particularly an alkaline earth metal.

Examples of the metal salt of phosphoric acid include salts of the phosphoric acid with polyvalent metals, and hydrogen phosphate corresponding to the polyvalent metal phosphates. The metal salts include coordination salts. A child (eg, hydroxo, halogen, etc.) may be coordinated.

Examples of the metal salt of phosphoric acid include pyrophosphate (Ca ₂ P ₂ O ₇ etc.), polymetaphosphate [Ca ₃
Such as _{(P 3 O 9) 2]} , phosphates anhydride _{(Ca 2 (P 4 O 12} ),
In addition to Ca ₅ (P ₃ O ₁₀ ) ₂ ), Ca ₅ (PO ₄ ) ₃ (OH), C
A condensed phosphate such as a ₅ (PO ₄ ) ₃ (F, Cl) may be used, but it is preferable to use a hydrogen phosphate.

Examples of such hydrogen phosphates include magnesium hydrogen orthophosphate (magnesium hydrogen phosphate, magnesium dihydrogen phosphate, etc.), calcium hydrogen orthophosphate (calcium dihydrogen phosphate, dicalcium phosphate, etc.) and the like. Alkaline earth metal hydrogen phosphates of manganese; transition metal hydrogen phosphates such as manganese hydrogen phosphate (manganese hydrogen phosphate (III) etc.), iron hydrogen phosphate [Fe (H ₂ PO ₄ ) ₃ etc.]; phosphorus Periodic table Group 2B metal hydrogen phosphate such as zinc hydrogen phosphate and cadmium hydrogen phosphate; Periodic table Group 3B metal hydrogen phosphate such as aluminum hydrogen phosphate; Periodic table 4B such as tin hydrogen phosphate Examples include non-condensed hydrogen phosphates such as hydrogen phosphates of group metals. Of these, substantially anhydrous metal hydrogen phosphates, especially alkaline earth metal hydrogen phosphates [magnesium dihydrogen phosphate,
Calcium dihydrogen phosphate, dicalcium phosphate (Ca
HPO ₄ ) etc.] are preferred.

(Metal salt of boric acid) Examples of boric acid include non-condensed boric acid such as orthoboric acid and metaboric acid; condensed boric acid such as pyroboric acid, tetraboric acid, pentaboric acid and octaboric acid, and basic boric acid. Boric acid and the like are preferable.

As the metal, an alkali metal or the like may be used, but an alkaline earth metal, a transition metal and a polyvalent metal of Group 2B metal of the periodic table are preferable.

The boric acid metal salt is usually a hydrous salt, for example, non-condensed borate [alkaline earth metal non-condensed borate such as calcium orthoborate, calcium metaborate; manganese orthoborate, copper metaborate]. Such as transition metal non-condensed borate; zinc metaborate, cadmium metaborate and other non-condensed borates of Group 2B metals (especially metaborate)], condensed borates (trimagnesium tetraborate) , Alkaline earth metal condensed borates such as calcium pyroborate; transition metal condensed borates such as manganese tetraborate and nickel diborate; of Group 2B metals of the periodic table such as zinc tetraborate and cadmium tetraborate Condensed borate, etc.); basic borate (basic zinc borate, basic cadmium borate, etc.), etc. That. Further, hydrogen borate salts corresponding to these borate salts (for example, manganese hydrogen orthoborate) can be used. In particular, alkaline earth metal or Group 2B metal borate of the periodic table (non-condensed or condensed borate), particularly (hydrous) zinc borate and (hydrous) calcium borate are preferable.

(Metal salt of stannic acid) Examples of stannic acid include stannic acid, metastannic acid, orthostannic acid, and hexahydrooxostannic acid. As the metal, alkali metal,
Examples are polyvalent metals such as alkaline earth metals, transition metals, and metals in Group 2B of the periodic table. The metal salt of stannic acid is usually a hydrous salt, for example, an alkali metal salt of stannic acid (for example, sodium stannate or potassium stannate), an alkaline earth metal salt of stannic acid (for example, magnesium stannate, etc.). ), A transition metal salt of stannic acid (for example, cobalt stannate, etc.), a metal salt of Group 2B of the periodic table for stannic acid (for example, zinc stannate, etc.)
Can be illustrated. Of these metal salts of stannic acid, metal salts of Group 2B of the periodic table of stannic acid, particularly zinc stannate, are preferable.
The metal salts of stannic acid can be used alone or in combination of two or more.

As the metal salt of an inorganic acid (oxygen acid) other than phosphoric acid, boric acid and stannic acid, various metal salts corresponding to the above metal salts of phosphoric acid and metal salts of boric acid can be used.

[Proportion of Use of Flame Retardant and Flame Retardant Auxiliary] The flame retardant (A) of the present invention contains a specific nitrogen-containing compound, so that even a small amount of it can be added to a wide range of base resins. Flame resistance can be imparted. The ratio of the (A) flame retardant to the resin component composed of the base resin and the aromatic resin (B2) is 0.1 to 30 parts by weight with respect to 100 parts by weight of the resin component.
It can be selected from the range of 0 parts by weight, but usually the resin component 10
200 parts by weight or less with respect to 0 parts by weight (for example, 1-2
00 parts by weight), preferably 3 to 150 parts by weight, more preferably 5 to 100 parts by weight.

Usually, different resins are used as the base resin and the aromatic resin (B2). In this case, the ratio (weight ratio) of the base resin and the aromatic resin (B2) is such that Resin = 50 / 50-100 / 0, preferably 55 /
45-100 / 0, more preferably 60 / 40-10
It is about 0/0.

The ratio (weight ratio) of the flame retardant to the flame retardant auxiliary is
Flame retardant / flame retardant aid = 99/1 to 1/99, preferably 9
8/2 to 2/98, more preferably 97/3 to 3/9
It is about 7.

Aromatic resin (B) in flame retardant aid (B)
The ratio of 2) can be appropriately selected within a range capable of imparting flame retardancy, and is 0 with respect to 100 parts by weight of the phosphorus-containing compound (B1).
To 500 parts by weight (for example, 0 to 500 parts by weight), preferably 0 to 400 parts by weight, and more preferably 10 to 300 parts by weight.
It is a degree. The proportion of the inorganic acid metal salt (B3) in the flame retardant aid is 0 to 200 parts by weight, preferably 0 to 150 parts by weight, relative to 100 parts by weight of the phosphorus-containing compound (B1).
Parts by weight, more preferably about 0 to 100.

[Additive] The flame-retardant resin composition of the present invention comprises
If desired, various additives (eg, other flame retardants, anti-dripping agents, antioxidants, stabilizers, etc.) may be included. The total content of additives is 100% base resin.
0.01 to 50 parts by weight, preferably,
The amount is 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight.

(Other Flame Retardants) The flame retardant resin composition of the present invention further contains other flame retardants in order to impart flame retardancy.
For example, a nitrogen-containing flame retardant, a sulfur-containing flame retardant, a silicon-containing flame retardant, an alcohol flame retardant, an inorganic flame retardant (metal oxide, metal hydroxide, metal sulfide, etc.) may be contained.

As the nitrogen-containing flame retardant, the nitrogen-containing cyclic compound having an amino group exemplified in the paragraph (A) above, the nitrogen-containing cyclic compound having an amino group and an oxygen acid [nitric acid, chloric acid (peroxide) Chloric acid, chloric acid, chlorous acid, hypochlorous acid, etc.), phosphoric acid (peroxophosphoric acid, orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, etc.), boric acid (orthoboric acid, metaboric acid, etc.) Non-condensed boric acid; condensed boric acid such as tetraboric acid and boric anhydride), antimonic acid, molybdic acid, tungstic acid, stannic acid, silicic acid, etc.], a nitrogen-containing cyclic compound having an amino group and an organic compound Phosphoric acid [phosphoric acid mono- or diesters corresponding to the phosphonates exemplified in the section (A) Flame retardant]
And a salt, a nitrogen-containing cyclic compound having an amino group and a nitrogen-containing cyclic compound having a hydroxyl group (hydroxyl group-containing 1,3,5-triazines, particularly cyanuric acid such as cyanuric acid, ammeline and ammelide or derivatives thereof) And salt and the like.

As the sulfur-containing flame retardant, organic sulfonic acid (alkane sulfonic acid, perfluoroalkane sulfonic acid, aryl sulfonic acid, sulfonated polystyrene, etc.), sulfamic acid, organic sulfamic acid, organic sulfonic acid amide salt (ammonium salt) , Alkali metal salt,
Alkaline earth metal salts, etc.) and the like.

Silicon-containing flame retardants include (poly) organosiloxanes. As the (poly) organosiloxane, a homopolymer such as a dialkylsiloxane (for example, dimethylsiloxane), an alkylarylsiloxane (for example, phenylmethylsiloxane), a diarylsiloxane, a monoorganosiloxane (for example, polydimethylsiloxane, polyphenylmethylsiloxane). Etc.) or a copolymer or the like. As the (poly) organosiloxane, a branched organosiloxane [trade name “XC99-B566 of Toshiba Silicone Co., Ltd.] is used.
4 ”, trade name“ X-40-924 ”of Shin-Etsu Chemical Co., Ltd.
3 "," X-40-9244 "," X-40-980 "
5 ", compounds described in JP-A-10-139964], modified (poly) organosiloxanes having a substituent such as an epoxy group, a hydroxyl group, a carboxyl group, an amino group or an ether group at the molecular end or main chain (for example, , Modified silicone, etc.) can also be used.

Examples of alcohol flame retardants include polyhydric alcohols (pentaerythritol, etc.), oligomeric polyhydric alcohols (dipentaerythritol, tripentaerythritol, etc.), esterified polyhydric alcohols,
Substituted alcohols, celluloses (cellulose, hemicellulose, lignocellulose, pectocellulose,
Adipocellulose, etc.), saccharides (monosaccharides, polysaccharides, etc.)
And so on.

Among the inorganic flame retardants, examples of metal oxides include molybdenum oxide, tungsten oxide, titanium oxide, zirconium oxide, tin oxide, copper oxide, zinc oxide, aluminum oxide, nickel oxide, iron oxide and manganese oxide. , Antimony trioxide, antimony tetraoxide, antimony pentoxide and the like. As metal hydroxide,
Examples thereof include aluminum hydroxide, magnesium hydroxide, tin hydroxide and zirconium hydroxide. Examples of metal sulfides include zinc sulfide, molybdenum sulfide, and tungsten sulfide. The inorganic flame retardant also includes expandable graphite.

These other flame retardants can be used alone or in combination of two or more.

The content of the other flame retardant is, for example, about 0.01 to 50 parts by weight with respect to 100 parts by weight of the base resin,
Preferably about 0.05 to 30 parts by weight, particularly 0.1 to 2
It can be selected from the range of about 0 parts by weight.

Further, the flame-retardant resin composition of the present invention may contain an antioxidant or a stabilizer in order to maintain stable heat resistance for a long period of time. Antioxidants or stabilizers include, for example, phenol-based (hindered phenols, etc.), amine-based (hindered amines, etc.), phosphorus-based, sulfur-based, hydroquinone-based, quinoline-based antioxidants (or stabilizers), inorganic A system stabilizer, a compound having a functional group reactive with an active hydrogen atom (reactive stabilizer), and the like are included.

Phenolic antioxidants include hindered phenols (hindered phenol antioxidants),
For example, 1,6-hexanediol-bis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate] and other C _2-10 alkylenediol-bis [3
-(3,5-di-branched _C3-6 alkyl-4-hydroxyphenyl) propionate]; for example triethylene glycol-bis [3- (3-t-butyl-5-methyl-
4-hydroxyphenyl) propionate] or other di- or trioxy C _2-4 alkylenediol-bis [3-
(3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate]; for example, C such as glycerin tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] _3-8 alkylenetriol-bis [3- (3,5-di-branched C _3-6 alkyl-
4-hydroxyphenyl) propionate];
Pentaerythritol tetrakis [3- (3,5-di-
C _4-8 alkylenetetraol tetrakis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate] such as t-butyl-4-hydroxyphenyl) propionate] is preferable.

[0278] The amine-series antioxidant, a hindered amine, for example, tri- or tetra-C _1-3 alkyl piperidine or methoxy derivative thereof (4-position, benzoyloxy, phenoxy and the like may be substituted 2,2 , 6,
6-tetramethylpiperidine, etc.), bis (tri, tetra or penta C _1-3 alkylpiperidine) C _2-20 alkylene dicarboxylic acid ester [eg bis (2,2,2
6,6-tetramethyl-4-piperidyl) oxalate, malonate corresponding to oxalate, adipate,
Sebacate, terephthalate, etc .; bis (1, 2, 2,
6,6-Pentamethyl-4-piperidyl) sebacate], 1,2-bis (2,2,6,6-tetramethyl-
4-piperidyloxy) ethane, phenylnaphthylamine, N, N'-diphenyl-1,4-phenylenediamine, N-phenyl-N'-cyclohexyl-1,4-phenylenediamine and the like are included.

Examples of the phosphorus (organic phosphorus) stabilizer (or antioxidant) include triisodecylphosphite, trisnonylphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite,
2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) ditridecylphosphite, tris (branched C _{3- 6} alkylphenyl)
Phosphite [eg, tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-
4-methylphenyl) phosphite, tris (2,4-
Di-t-amylphenyl) phosphite, etc.], (branched C _3-6 alkylphenyl) phenylphosphite [eg, bis (2-t-butylphenyl) phenylphosphite, 2-t-butylphenyldiphenylphosphite, etc. ], Tris (2-cyclohexylphenyl) phosphite, bis (C _1-9 alkylaryl) pentaerythritol diphosphite [for example, bis (2,4-di-
t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) ) Pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, etc.], triphenyl phosphate stabilizers (for example, 4-phenoxy-9-α- (4-hydroxyphenyl) -p-cumenyloxy-3, 5,8,10-Tetraoxa-4,9-
Diphosphapyro [5.5] undecane, tris (2,4-
Di-t-butylphenyl) phosphate, etc., diphosphonite stabilizers (eg, tetrakis (2,4-di-t-butyl) -4,4′-biphenylene diphosphonate, etc.) and the like. The phosphorus-based stabilizer usually has a branched C _3-6 alkylphenyl group (particularly, t-butylphenyl group).

Hydroquinone antioxidants include, for example:
2,5-di-t-butylhydroquinone and the like are included, and examples of the quinoline antioxidant include 6-ethoxy-2,
2,4-trimethyl-1,2-dihydroquinoline and the like are included, and the sulfur antioxidant includes, for example, dilauryl thiodipropionate and distearyl thiodipropionate.

The inorganic stabilizer (inorganic metal or mineral stabilizer) includes hydrotalcite, zeolite, alkaline earth metal compounds and the like. As the hydrotalcite, hydrotalcites described in JP-A-60-1241 and JP-A-9-59475, for example, a hydrotalcite compound represented by the following formula can be used. .

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] ^{x +} [A ^n- _{x / n} · mH ₂ O] ^x- (In the formula, M ²⁺ is Mg ²⁺ , Mn ²⁺ , It shows divalent metal ions such as Fe ²⁺ and Co ²⁺ , and M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ³⁺
Indicates a trivalent metal ion such as. A ^n- is CO ₃ ^2-, OH ^-,
An n-valent (particularly monovalent or divalent) anion such as HPO ₄ ²⁻ or SO ₄ ²⁻ is shown. x is 0 <x <0.5, and m is
0 ≦ m <1).

The hydrotalcite is "DHT-
4A ”,“ DHT-4A-2 ”,“ Alcamizer ”and the like are available from Kyowa Chemical Industry Co., Ltd.

The zeolite is not particularly limited, but for example, the zeolite described in JP-A-7-62142 [a zeolite whose minimum unit cell is a crystalline aluminosilicate of an alkali and / or alkaline earth metal] (A-type, X-type, Y-type, L-type and ZSM-type zeolites, mordenite-type zeolites; chabazite, mordenite-type, natural zeolites such as faujasite), and the like] and the like can be used.

[0285] The A-type zeolite includes "Zeolam series (A-3, A-4, A-5)" and "Zeostar series (KA100P, NA-100P, CA-100.
P) ”, and the X-type zeolite is“ Zeolam series (F-9) ”,“ Zeostar series (NX
-100P) "etc., Y-type zeolite is" HS
Z series (320NAA) "and the like are available from Tosoh Corporation and Nippon Kagaku Kogyo.

Examples of the alkaline earth metal compound include oxides (magnesium oxide, etc.), hydroxides (magnesium hydroxide, calcium hydroxide, etc.), carbonates [magnesium carbonate, (soft / colloid / heavy) Calcium carbonate], organic carboxylic acid salts (magnesium acetate, calcium acetate, magnesium stearate, calcium stearate, calcium 12-hydroxystearate, etc.) and the like can be used.

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

The reactive stabilizer includes a compound having a functional group reactive with an active hydrogen atom. The compound having a functional group reactive with an active hydrogen atom is at least one selected from a cyclic ether group, an acid anhydride group, an isocyanate group, an oxazoline group (ring), an oxazine group (ring), a carbodiimide group, and the like. The compound having the functional group of can be exemplified.

The compound having a cyclic ether group includes a compound having an epoxy group or an oxetane group.
Examples of the compound having an epoxy group include alicyclic compounds such as vinylcyclohexene dioxide, glycidyl ester compounds such as versatic acid glycidyl ester, glycidyl ether compounds (hydroquinone diglycidyl ether, biphenol diglycidyl ether, bisphenol-A diester). Glycidyl ether, etc.),
Examples thereof include glycidyl amine compounds, epoxy group-containing vinyl copolymers, epoxidized polybutadiene, epoxidized diene monomer-styrene copolymers, triglycidyl isocyanurate, and epoxy-modified (poly) organosiloxane.

Examples of the compound having an oxetane group include oxetanyl ester compounds such as isophthalic acid di [1-ethyl (3-oxetanyl)] methyl ester and terephthalic acid di [1-ethyl (3-oxetanyl)] methyl ester. Oxetanyl ether compounds {for example, alkyl oxetanyl compounds such as di [1-ethyl (3-oxetanyl)] methyl ether and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane,
Aryl oxetanyl compounds such as 3-ethyl-3- (phenoxymethyl) oxetane, 1,4-bis {[(3
Aralkyl oxetanyl ether compounds such as -ethyl-3-oxetanyl) methoxy] methyl} benzene, bisphenol-type oxetane resins such as bisphenol-A di [1-ethyl (3-oxetanyl)] methyl ether, mono to poly [1-ethyl ( 3-oxetanyl)] methyl etherified phenol novolac and novolac type oxetane resins such as mono- or poly [1-ethyl (3-oxetanyl)] methyl etherified cresol novolac}, 3-ethyl-3-{[3- (tri Oxetane-modified (poly) organosiloxanes such as ethoxysilyl) propoxy] methyloxetane, and alkyloxetanylmethyl derivatives corresponding to the derivatives having the oxetanyl unit {eg, [1-ethyl (3-oxetanyl)] methyl derivative} Body {e.g., [1-methyl (3-oxetanyl)] methyl derivatives}, and the like.

Examples of the compound having an acid anhydride group include an olefin resin having a maleic anhydride group (eg, ethylene-maleic anhydride copolymer, maleic anhydride modified polypropylene).

Examples of the compound having an isocyanate group include aliphatic isocyanates such as hexamethylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aromatic isocyanates such as diphenylmethane isocyanate, and modified products of these isocyanates (eg, isophorone diisocyanate). Trimer) and the like.

As the compound having an oxazoline group,
For example, 2,2 '-(1,3-phenylene) -bis (2
-Oxazoline) and 2,2 '-(1,4-phenylene)
Examples thereof include bisoxazoline compounds such as bis (2-oxazoline) and vinyl resins having an oxazoline group (for example, vinyloxazoline-modified styrene resin).

Examples of the compound having an oxazine group include 2,2'-bis (5,6-dihydro-4H-1,
3-oxazine) and other bisoxazine compounds.

As the compound having a carbodiimide group, for example, poly (phenylcarbodiimide), poly (naphthylcarbodiimide) and other polyarylcarbodiimides, poly (2-methyldiphenylcarbodiimide), poly (2,6-diethyldiphenylcarbodiimide), Poly (2,6-diisopropyldiphenylcarbodiimide), poly (2,4,6-triisopropyldiphenylcarbodiimide), poly (2,4,6-tri-t-
Butyldiphenylcarbodiimide) and other polyalkylarylcarbodiimides, poly [4,4′-methylenebis (2,6-diethylphenyl) carbodiimide], poly [4,4′-methylenebis (2-ethyl-6-methylphenyl) carbodiimide] , Poly [4,4'-methylenebis (2,6-diisopropylphenyl) carbodiimide], poly [4,4'-methylenebis (2-ethyl-
6-Methylcyclohexylphenyl) carbodiimide]
And poly [alkylenebis (alkyl or cycloalkylaryl) carbodiimide] and the like.

These reactive stabilizers can be used alone or in combination of two or more kinds.

These antioxidants and / or stabilizers may be used alone or in combination of two or more. The content of the antioxidant and / or the stabilizer is, for example, 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, particularly 0.1 to 2 parts by weight, relative to 100 parts by weight of the base resin. You can choose from a range of degrees.

When a polyester resin or a polycarbonate resin is used as the base resin, the phosphoric acids (for example, phosphoric acid, etc.) exemplified in the section of the above specific flame retardant aid are used.
Addition of inorganic phosphoric acid such as phosphorous acid, phosphonic acid, phosphinic acid and polyphosphoric acid; organic phosphoric acid such as phosphonocarboxylic acid and nitrogen-containing phosphoric acid further improves the thermal stability.

Further, the flame-retardant resin composition of the present invention may contain a dripping inhibitor such as a fluorine resin. The anti-dripping agent can suppress fire species and dripping of the melt during combustion. Fluorine resin,
Homogeneous or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene and perfluoroalkyl vinyl ether; copolymerizable monomers such as the fluorine-containing monomers described above with ethylene, propylene and acrylate And copolymers thereof are included. Examples of such a fluorine-based resin (fluorine-containing resin) include homopolymers of polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride and the like;
Examples of the copolymer include tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene-chlorotrifluoroethylene copolymer. . These fluororesins can be used alone or in combination of two or more.

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

The content of the fluorinated resin is, for example, 0.1% by weight based on 100 parts by weight of the total of the base resin and the aromatic resin.
The amount is about 01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, and more preferably about 0.1 to 3 parts by weight.

Further, the flame-retardant resin composition of the present invention may contain other additives depending on the purpose. Other additives include stabilizers (UV absorbers, heat resistance stabilizers, weather resistance stabilizers, etc.), lubricants, release agents, colorants, plasticizers, nucleating agents, impact modifiers, sliding agents, etc. .

[Filler] The flame-retardant resin composition of the present invention comprises
It may be modified with a filler in order to further improve mechanical strength, rigidity, heat resistance, electrical properties and the like.
The fillers include fibrous fillers and non-fibrous fillers (plate-like fillers, powdery and granular fillers, etc.).

As the fibrous filler, glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, potassium titanate fiber, metal fiber, high melting point organic fiber (for example, aliphatic or aromatic) is used. Examples thereof include polyamide, aromatic polyester, fluororesin, acrylic resin such as polyacrylonitrile, etc.).

Among the non-fibrous fillers, the plate-like filler is
For example, glass flakes, mica, graphite, various metal foils and the like can be exemplified.

Examples of the powdery or granular filler include carbon black, silicon carbide, silica, quartz powder, glass beads, glass powder, milled fiber (eg milled glass fiber), calcium silicate, aluminum silicate, kaolin, talc, Silicates such as clay, diatomaceous earth and wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; calcium sulfate, barium sulfate etc. Includes metal sulfates, metal powders, and the like.

Preferred fibrous fillers include glass fibers and carbon fibers, and preferred non-fibrous fillers are powdery or plate-like fillers, particularly glass beads, milled fibers, kaolin, talc and mica. , And glass flakes.

Particularly preferred fillers include glass fibers, such as glass fibers having high strength and rigidity (chopped strands, etc.).

When a filler is used, the proportion of the filler in the flame-retardant resin composition is, for example, about 1 to 60% by weight, preferably about 1 to 50% by weight, more preferably 1 to 45% by weight.
It is about% by weight.

In using these fillers, it is desirable to use a sizing agent or a surface treating agent, if necessary. As such a sizing agent or surface treatment agent, a functional compound is included. Examples of the functional compound include epoxy compounds, silane compounds, titanate compounds, preferably epoxy compounds, particularly bisphenol A type epoxy resins and novolac type epoxy resins.

The filler may be subjected to a converging treatment or a surface treatment with the converging agent or the surface treating agent. Regarding the timing of the treatment, the treatment may be performed simultaneously with the addition of the filler,
You may pre-process before addition.

The amount of the functional surface treating agent or sizing agent used in combination is 5% by weight or less, preferably about 0.05 to 2% by weight, based on the filler.

The flame retardant of the present invention can highly flame retard the resin, probably because it promotes carbonization of the resin surface during combustion. Further, by combining a specific amino group-containing nitrogen compound and a specific flame retardant aid, the base resin can be effectively flame-retarded even in a small amount, and bleed-out and heat resistance are not deteriorated. .

[Method for producing flame-retardant resin composition] The flame-retardant resin composition of the present invention may be a mixture of powder and granules, a melt mixture, a base resin, a flame retardant, and a flame retardant aid. And, if necessary, an anti-dripping agent and other additives can be prepared by mixing in a conventional manner. For example, (1)
(2) A method in which the components are mixed, kneaded by a uniaxial or biaxial extruder and extruded to prepare pellets, and then molded, (2)
A method of once preparing pellets (masterbatch) having different compositions, mixing (diluting) a predetermined amount of the pellets and subjecting to molding to obtain a molded article of a predetermined composition, (3) 1 or 1 of each component in a molding machine A method of directly charging two or more can be adopted. Further, as a method for manufacturing pellets by an extruder, (1) a manufacturing method in which components excluding the brittle filler (such as a glass-based filler) are first melt-mixed and then the brittle filler components are mixed, (2) phosphorus A manufacturing method in which the brittle filler and the phosphorus-containing compound are simultaneously mixed (at the same feed position) after the components other than the containing compound and the brittle filler are melt-mixed first, and (3) the phosphorus-containing compound and the component excluding the brittle filler The method may be employed in which the brittle filler and the phosphorus-containing compound are sequentially mixed (at separate feed positions) after first melt-mixing. In pellet production by this extruder,
A small amount of an aromatic compound or a halogen compound (benzene, toluene, xylene, chlorobenzene, trichlorobenzene, chloroform, trichloroethylene, etc.) may be added as a dispersion aid at the time of extrusion. This dispersion aid is removed from the kneading resin through the vent port of the extruder. Further, in the preparation of a composition used for a molded article, a powdery material of a base resin (for example, a powdery material obtained by crushing a part or all of a polyester resin) and other components (flame retardant, etc.) are mixed. Then, melt kneading is advantageous for improving the dispersion of other components.

From the viewpoint of handling, the non-resinous component (phosphorus-containing compound, nitrogen-containing compound, inorganic acid metal salt, etc.) and the resinous component (base resin, aromatic resin, etc.) are once melt mixed. By doing so, it is convenient to prepare a masterbatch. In particular, when red phosphorus is used together as a phosphorus-containing compound, a masterbatch is often prepared. Further, when the master batch is composed of resinous components, a part of the base resin is often used for the master batch.

Examples of the masterbatch include (a) a masterbatch composed of a part of a base resin and a non-resinous component, (b) a masterbatch composed of an aromatic resin and a non-resinous component, (C) A masterbatch composed of an aromatic resin, a resinous flame retardant and a non-resinous component, (d) a masterbatch composed of a part of the base resin, an aromatic resin and a non-resinous component, ( e) a masterbatch composed of a part of the base resin, a resinous component and a non-resinous component,
(F) A masterbatch composed of a part of the base resin, an aromatic resin, a resinous component and a non-resinous component may be used.

The masterbatch may contain various additives such as fluororesins, antioxidants, phosphorus stabilizers, inorganic stabilizers, reactive stabilizers and fillers, if necessary. You may have.

A flame-retardant resin composition can be produced by melt-mixing the masterbatch thus obtained, the base resin and, if necessary, the remaining components.

Further, the flame-retardant resin composition of the present invention can be melt-kneaded and molded by a conventional method such as extrusion molding, injection molding or compression molding, and the molded product formed has flame retardancy and molding processability. It has excellent properties and can be used for various purposes. For example, it can be suitably used for electric / electronic parts, home electric appliance parts, office automation (OA) equipment parts, machine mechanism parts, automobile parts, packaging materials, cases and the like.

[0320]

In the present invention, since the base resin is combined with the specific amino group-containing nitrogen compound and the flame retardant aid, it is possible to make the flame retardant even in a small amount without using a halogen-based flame retardant. It is possible to suppress deterioration of moldability and resin properties. Further, such a resin composition makes it possible to obtain a molded article having improved flame retardancy.

[0321]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

The flame retardancy, blooming property and moldability of the resin composition were evaluated by the following tests.

(Flammability test) According to UL94, the flammability was evaluated with a test piece having a thickness of 1.6 mm.

(Evaluation of Blooming Property) A 1.6 mm burning test piece was heated at 150 ° C. for 5 hours, and the exudation state on the surface of the test piece was visually observed, and the blooming property was evaluated according to the following criteria.

[0325] ◎: No bleeding is seen ◯: Almost no seeping Δ: Some bleeding is seen X: Marked bleeding is observed.

(Evaluation of Moldability) A molded product having a predetermined shape was molded by an injection molding machine for 500 shots, and a mold deposit (mold deposit MD) after molding was visually observed, and the moldability was evaluated according to the following criteria. did.

[0327] ◯: MD is hardly seen △: Some MD is seen X: Remarkable MD is seen.

[Base resin R] R-1: Polybutylene terephthalate [Duranex, intrinsic viscosity = 1.0, manufactured by Polyplastics Co., Ltd.] R-2: 12 mol% isophthalic acid modified polybutylene terephthalate copolymer [specific Viscosity = 1.0] R-3: Polyethylene terephthalate [Belpet EF
G10, manufactured by Kanebo Synthetic Fibers Co., Ltd.] R-4: Nylon-6, 6 [Ceranese nylon 66,
Chicona] R-5: Nylon-6 [UBE Nylon 6, Ube Industries, Ltd.] R-6: Polycarbonate [Panlite L1225, Teijin Chemicals] R-7: Acrylonitrile-styrene copolymer [Sebian N JD, manufactured by Daicel Chemical Industries, Ltd.].

[Flame Retardant A] A-1: Melamine / Melam / Melem double salt of polyphosphate [PM
P200, manufactured by Nissan Chemical Industries, Ltd.] A-2: melamine polymetaphosphate A-3: polyphosphoric acid amide [prepared according to Example 1 described in JP-A-10-81619] A-4: melamine sulfate [ Apinone 901, manufactured by Sanwa Chemical Co., Ltd.] A-5: Melame methanesulfonate [MMS-200, manufactured by Nissan Chemical Industries, Ltd.] A-6: Organic phosphonic acid melamine salt [10% of nitrilotris (methylphosphonic acid)] To the aqueous solution, a 4-fold molar amount of a 10% melamine suspension aqueous solution was added, and the mixture was stirred at 80 ° C. for 3 hours, the formed precipitate was separated by filtration, dried, and pulverized with a lab mill.] A-7: Organophosphonic acid melamine salt [ To a 10% aqueous solution of phenylphosphonic acid, an equimolar amount of a 10% melamine suspension aqueous solution was added, and the mixture was stirred at 80 ° C. for 6 hours. -8: acetyleneurea A-9: uric acid A-10: melamine pyrophosphate A-11: melamine phosphate.

[Flame retardant aid B1] B1-1: Resorcinol bis (di-2,6-xylyl phosphate) [PX200, manufactured by Daihachi Chemical Industry Co., Ltd.] B1-2: Hydroquinone bis (di-2, 6-xylyl phosphate) [PX201, manufactured by Daihachi Chemical Industry Co., Ltd.] B1-3: biphenol bis (di-2,6-xylyl phosphate) [PX202, manufactured by Daihachi Chemical Industry Co., Ltd.] B1-4 : Bisphenol-A bis (diphenyl phosphate) [CR741, manufactured by Daihachi Chemical Industry Co., Ltd.] B1-5: N, N'-bis (diphenoxyphosphinyl) piperazine [1,4-piperazinediyltetraphenyl phosphate] B1-6: N, N'-bis (di-2,6-xylyloxyphosphinyl) piperazine [1,4-piperazinediyltetra-2,6-xylyl Phosphate] B1-7: Phosphonitrile compound [phenoxyphosphazene] B1-8: Red phosphorus [Nova Excel 140, manufactured by Rin Kagaku Kogyo Co., Ltd.] B1-9: Aluminum ethylmethylphosphinate [JP-A-11-60924] Prepared according to the example] B1-10: N, N'-bis (neopentylenedioxyphosphinyl) piperazine B1-11: 10- (2,5-dihydroxyphenyl)
-10H-9-oxa-10-phosphaphenanthrene-10-oxide.

[Flame retardant aid B2] B2-1: Polycarbonate [Panlite L1225,
Teijin Chemicals Ltd.] B2-2: Polyarylate [Polyarylate U100,
Unitika Co., Ltd.] B2-3: Nylon MXD6 [Renny 6002, Mitsubishi Engineering Plastics Co., Ltd.] B2-4: Phenoxy resin [Phenothote YP-50,
Toto Kasei Co., Ltd.] B2-5: Novolac-type phenol resin [Sumilite Resin PR-53647, Sumitomo Dures Co., Ltd.].

[Flame Retardant Aid B3] B3-1: Zinc borate [Fire Break ZB, manufactured by Borax Japan KK] B3-2: Anhydrous calcium monohydrogen phosphate [Average particle size =
About 30 μm, manufactured by Taihei Chemical Industry Co., Ltd.].

[Antioxidant C] C-1: Pentaerythritol-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] [Irganox 1010, manufactured by Ciba Geigy].

[Phosphorus Stabilizer D1] D1-1: Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite [Adeka Stab PEP36, manufactured by ADEKA ARGUS CORPORATION] D1-2 : Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite [Sand Stub P-EPQ, manufactured by Sand Corp.].

[Inorganic stabilizer D2] D2-1: Hydrotalcite [DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.] D2-2: Zeolite [Zeoramu A-3, Tosoh Corporation]
Manufacturing] D2-3: calcium carbonate D2-4: magnesium hydroxide.

[Reactive Stabilizer D3] D3-1: Bisphenol-A diglycidyl ether D3-2: 1,4-bis {[3-ethyl-3-oxetanyl) methoxy] methyl} benzene [OXT-121,
Toagosei Co., Ltd.] D3-3: Polycarbodiimide [Carbodilite HMV
-8CA, manufactured by Nisshinbo Industries, Inc.] D3-4: Oxazoline group-containing vinyl polymer [Epocros RAS-1020, manufactured by Nippon Shokubai Co., Ltd.].

[Dripping Prevention Agent E] E-1: Polytetrafluoroethylene [Filler F] F-1: Glass chopped strand having a diameter of 10 μm and a length of 3 mm.

Examples 1 to 59 and Comparative Examples 1 to 17 The above components were mixed in the proportions (parts by weight) shown in Tables 1 to 5 and kneaded and extruded with an extruder to prepare resin compositions. This resin composition was injection-molded to prepare a test molded article, and its characteristics were evaluated. The results are shown in Tables 1 to 5.

[0339]

[Table 1]

[0340]

[Table 2]

[0341]

[Table 3]

[0342]

[Table 4]

[0343]

[Table 5]

As is clear from the table, all of the examples using the flame retardant (A) composed of the specific nitrogen-containing compound and the specific flame retardant auxiliary (B) were found to have any of these components. It was excellent in flame retardancy, blooming property and moldability, as compared with the comparative example lacking such a point.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA22 AA43 AA45 AA46 AA50                       AA54 AB19 AC12 AC15 AE07                       AF47 BA01 BB03 BB05 BB06                 4J002 BB001 BC021 BC022 BG001                       CF001 CF041 CF051 CF061                       CF071 CF081 CG001 CH071                       CL001 DE187 EW006 EW007                       EW137 EW157 FD136 FD137

Claims (17)

[Claims] 1. A flame-retardant resin composition comprising a base resin, (A) a flame retardant, and (B) a flame retardant auxiliary, wherein the (A) flame retardant contains (A1) an amino group. Double salt of nitrogen compound and polyphosphoric acid, (A2) salt of amino group-containing nitrogen compound and polymetaphosphoric acid, (A3) polyphosphoric acid amide,
(A4) Amino group-containing nitrogen compound, sulfuric acid, pyrosulfuric acid,
A salt with an organic sulfonic acid, an organic phosphonic acid or an organic phosphinic acid, and (A5) at least one flame retardant selected from cyclic urea compounds, and (B) a flame retardant aid,
A flame-retardant resin composition comprising (B1) a phosphorus-containing compound, (B2) an aromatic resin, and (B3) at least one flame-retardant aid selected from a metal salt of an inorganic acid. 2. The base resin is a polyester resin, a styrene resin, a polyamide resin, a polycarbonate resin, a polyphenylene oxide resin, a vinyl resin,
The flame-retardant resin composition according to claim 1, which is at least one kind of thermoplastic resin selected from an olefin resin and an acrylic resin. 3. The base resin is a homo- or copolyester having at least one unit selected from 1,4-cyclohexanedimethylene terephthalate, C _2-4 alkylene terephthalate and C _2-4 alkylene naphthalate. Item 1. The flame-retardant resin composition according to item 1. 4. The difficulty according to claim 1, wherein the base resin is at least one selected from polybutylene terephthalate, butylene terephthalate-based copolyester, polyethylene terephthalate, and ethylene terephthalate-based copolyester. Flammable resin composition. 5. The base resin is composed of a polyester resin and a styrene resin, and the ratio (weight ratio) of the former to the latter is former / latter = 99/1 to 50/50. Flame-retardant resin composition. 6. The flame retardant (A) is melamine polyphosphate.
The at least one flame retardant selected from melam / melem double salt, polymetaphosphoric acid melamine, polyphosphoric acid amide, melamine sulfate, melam pyrosulfate, melam organic sulfonate, melamine organic phosphonate and melamine organic phosphinate. Flame-retardant resin composition. 7. The phosphorus-containing compound (B1) is a phosphoric acid ester, a phosphoric acid ester amide, a phosphonitrile compound,
The flame-retardant resin composition according to claim 1, which is at least one selected from an organic phosphonic acid compound and an organic phosphinic acid compound. 8. The flame-retardant resin composition according to claim 1, wherein the phosphorus-containing compound (B1) is a condensed phosphoric acid ester and / or a condensed phosphoric acid ester amide. 9. The aromatic resin (B2) contains a polyphenylene sulfide resin, a polyphenylene oxide resin, a polycarbonate resin, an aromatic nylon, a polyarylate resin, an aromatic epoxy resin, and a hydroxyl group and / or an amino group. The flame-retardant resin composition according to claim 1, wherein the flame-retardant resin composition is at least one selected from resins having an aromatic ring in a main chain or a side chain. 10. (B3) The metal salt of an inorganic acid is phosphoric acid,
The flame-retardant resin composition according to claim 1, which is a salt of a polyvalent metal with at least one oxygen acid selected from boric acid and stannic acid. 11. A flame-retardant resin composition comprising a polyester resin, a styrene resin and a flame retardant, wherein the flame retardant is composed of a nitrogen-containing compound and a phosphorus-containing compound. Composition. 12. The nitrogen-containing compound is selected from melamine / melam / melem double salts of polyphosphate, melamine polymetaphosphate, polyphosphoric acid amide, melamine sulfate, melam pyrosulfate, melam organic sulfonate, melamine organic phosphonate and melamine organic phosphinate. The flame-retardant resin composition according to claim 11, which is composed of at least one selected. 13. The phosphorus-containing compound is a phosphoric acid ester,
The flame-retardant resin composition according to claim 11, which is composed of at least one selected from phosphoric acid ester amides, phosphonitrile compounds and phosphinic acid compounds. 14. A hindered phenol antioxidant, a phosphorus stabilizer, an inorganic stabilizer, a compound having a functional group reactive with an active hydrogen atom, a fluorine resin and a filler. Claim 1 containing at least 1 type
The flame-retardant resin composition described. 15. A method for producing a flame-retardant resin composition by mixing a base resin with the flame-retardant agent and the flame-retardant auxiliary agent according to claim 1. 16. A molded product formed from the flame-retardant resin composition according to claim 1. 17. The molded product according to claim 16, which is an electric / electronic component, an office automation device component, a home electric appliance component, an automobile component, or a machine mechanism component.