JP2001207053A - Flame-retardant polyamide-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop an additive of a more excellent metal-preventive effect to a flame-retardant polyamide-based resin composition because a conventional flame-retardant polyamide-based resin composition has not satisfactorily been capable of preventing such metal corrosion in a molding machine and a metal mold as is caused at the time of the molding. SOLUTION: This flame-retardant, polyamide-based resin composition having the excellent metal preventive effect can be obtained by adding, to a flame- retardant polyamide-based resin composition consisting of a polyamide-based resin and a bromine-based flame retarder, specified amounts of zinc oxide and zinc borate, or further a specified amount of a hydrotalcite compound or a zeolite compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyamide having a low metal corrosion and comprising a specific amount of a specific additive added to a flame-retardant polyamide resin comprising a polyamide resin and a bromo flame retardant. The present invention relates to a resin composition, and can be widely used in fields requiring little metal corrosion and requiring flame retardancy.

[0002]

2. Description of the Related Art In general, a method of adding a flame retardant or a flame retardant such as a halogen compound, a phosphorus compound, antimony trioxide or the like to a polyamide resin has been conventionally carried out. Among flame retardants, halogen compounds, particularly bromo compounds, are frequently used.

[0003] However, in general, when a bromo-based flame retardant is added to a polyamide-based resin, a problem often arises that the molding machine and its mold are corroded when the flame-retarded polyamide-based resin is molded. In order to solve these problems, the following techniques have already been disclosed. (1) A method in which at least one compound selected from boric acid or boric anhydride, a borate ester compound, an organic tin maleate compound and an organic tin mercaptide compound is added to a halogen-based flame retardant-containing synthetic resin composition (Japanese Patent Laid-Open No. 4
No. 239059) to improve the metal corrosion of the halogen-based flame retardant-containing synthetic resin composition. Boric acid or boric anhydride, borate compound used in the art,
Organotin maleate compounds and organotin mercaptide compounds are distinctly different from zinc oxide and zinc borate used in the present invention. In addition, there is no description or suggestion in the art regarding the combined use of zinc oxide and zinc borate. Furthermore, the art relates to zinc oxide and zinc borate, hydrotalcite, zinc-substituted hydrotalcite compounds, 4A
There is no description or suggestion of addition in combination with at least one compound selected from a zeolite containing a type zeolite, a metal belonging to Group II or Group IV of the periodic table, or potassium. (2) A method of adding a halogen-based flame retardant, a boric acid-based inorganic compound, or an organic or inorganic antimony-containing compound to a thermoplastic polyester (JP-A-59-202253) to obtain a flame-retardant polyester resin composition Technology to improve flammability. The boric acid-based inorganic compound used for the purpose of improving flame retardancy in this technique is the same as the zinc borate used in the present invention, but in this technique, zinc oxide and zinc borate are added in combination. There is no description or suggestion of a method for improving the metal corrosivity. In addition, the art is directed to zinc oxide and zinc borate as well as hydrotalcites, zinc-substituted hydrotalcite compounds, zeolites of type 4A, and zeolites containing metals or potassium of Group II or IV of the Periodic Table. At least one of the compounds
There is no description or suggestion of a method for improving metal corrosion by adding a seed in combination. (3) The flame-retardant thermoplastic polyester resin is obtained by adding an organic halogen compound, antimony trioxide, zinc borate hydrate and a reinforcing filler to a thermoplastic aromatic polyester (JP-A-55-34209). Technology to improve the prevention of dripping of the composition during flame retardancy. The zinc borate hydrate used as a flame retardant aid in the art is the same as the zinc borate used in the present invention, but in the art, zinc oxide and zinc borate are added in combination. There is no description or suggestion about a method for improving metal corrosion. In addition, the art is directed to zinc oxide and zinc borate as well as hydrotalcites, zinc-substituted hydrotalcite compounds, zeolites of type 4A, and zeolites containing metals or potassium of Group II or IV of the Periodic Table. There is no description or suggestion about a method of improving the metal corrosivity by adding at least one of the above compounds in combination. (4) A reinforced polyamide composition comprising a polyamide, a reinforcing agent, and a halogenated flame retardant, zinc borate, antimony oxide, zinc oxide, lead oxide,
A method of adding an oxide selected from the group consisting of ferrous oxide, ferric oxide, stannous oxide, stannic oxide and cadmium oxide or a mixture of the above oxides (Japanese Patent Application Laid-Open No. 52-102)
364), a technique for improving the anti-carbonization property and the flame retardancy. The zinc borate and zinc oxide used as a surplus agent for a flame retardant in the art are the same as the zinc borate and zinc oxide used in the present invention. There is no description or suggestion of a method for improving the property, and the amount of zinc borate used as a phase-retaining agent for a flame retardant in the art is significantly larger than that of the present invention. Further, zinc oxide and zinc borate, hydrotalcite, zinc-substituted hydrotalcite compounds,
Description and suggestion of a method for improving metal corrosivity by co-adding with zeolite A, at least one compound selected from the group II or IV metals of the periodic table, or a zeolite containing potassium. There is no. (5) The polyolefin is a zinc salt of mercaptoimidazole, a di-t-butylphenol-based antioxidant, and at least one selected from zinc oxide, zinc sulfide, and zinc borate.
A method of adding a kind of inorganic zinc compound, a mixture of an organic halogen compound and an antimony oxide, and further, if necessary, a small amount of a crosslinking agent and a crosslinking assistant (Japanese Patent Application Laid-Open No. 57-1451).
No. 36) to improve heat aging resistance and corrosiveness to metals. The zinc oxide and zinc borate used in the technology are the same as the zinc oxide and zinc borate used in the present invention, but the technology is for a polyolefin composition and the flame-retardant polyamide of the present invention is used. It is different from the base resin composition. Also, zinc oxide and zinc borate and hydrotalcite, zinc-substituted hydrotalcite compounds,
Description and suggestion of a method for improving metal corrosivity by co-adding 4A type zeolite, at least one compound selected from metals of group II or IV of the periodic table or a zeolite containing potassium There is no. (6) A method of adding at least one kind of zinc borate or a zinc compound and at least one kind of a boron compound to a styrene-based resin composition containing a bromine-based flame retardant (Japanese Patent Application Laid-Open No.
264652), a technique for improving thermal stability. The zinc borate and zinc compound used in the technology are the same as the zinc borate and zinc oxide used in the present invention, but the technology is directed to a brominated flame retardant-containing styrenic resin composition. It is different from the flame retarded polyamide resin composition of the invention. In addition, the technique includes zinc borate and zinc oxide, hydrotalcite, zinc-substituted hydrotalcite compounds, zeolite of type 4A, and zeolite containing a metal of Group II or Group IV of the periodic table or potassium. There is no description or suggestion of a method for improving metal corrosion by adding at least one of the above compounds in combination. (7) The flame-retardant resin composition is prepared by adding a halogen-containing organic flame retardant, a hydrotalcite stabilizer and a flame retardant aid to a thermoplastic or thermosetting resin (JP-A-60-1241). Corrosion during molding, yellowing of molded products,
Technology to improve heat resistance and weather resistance. The hydrotalcite stabilizer used in this technique is the same as the hydrotalcite of the component (b) used in the present invention, but the technique includes zinc borate and zinc oxide, and furthermore, zinc borate and zinc oxide. At least one selected from the group consisting of zinc and hydrotalcite, a zinc-substituted hydrotalcite compound, a zeolite of type 4A, and a zeolite containing a metal or potassium of Group II or Group IV of the periodic table;
There is no description or suggestion about a method for improving metal corrosion by adding a seed in combination. (8) A method of adding a hydrotalcite-based solid solution to a synthetic resin containing a halogen and / or an acidic substance (JP-A-61
No. 174270) to improve the rust resistance or coloring resistance of the resin composition. The hydrotalcite-based solid solution used in the technique is the same as the zinc-substituted hydrotalcite compound of the component (c) used in the present invention, but the technique includes zinc borate and zinc oxide, and furthermore, boric acid. There is no description or suggestion of a method for improving metal corrosion by adding zinc and zinc oxide, and at least one compound selected from hydrotalcite and zinc-substituted hydrotalcite compounds.

[0004]

Problems to be Solved by the Invention
No. 9, boric acid or boric anhydride, a boric ester compound, an organic tin maleate compound, an organic tin mercaptide compound as described in JP-A-59-2022.
No. 53, or a zinc borate hydrate described in JP-A-55-34209 alone may be added.
A large amount of zinc borate and zinc oxide as described in No. 2364 may be added, or a zinc salt of mercaptoimidazole and a di-t-butylphenol antioxidant as described in JP-A-57-145136. And zinc oxide and zinc borate, or zinc borate or a zinc compound and a boron compound as described in JP-A-63-264652, and JP-A-60-1241. Hydrotalcite, and JP-A-61-
In the conventional technique of adding a zinc-substituted hydrotalcite compound alone as described in JP-A-174270, all of them are sufficient for a flame-retardant polyamide resin composed of a polyamide resin and a bromo flame retardant. The development of an additive which does not provide a metal corrosion preventing effect and further has an excellent metal corrosion preventing effect has been awaited.

[0005]

In view of the above, the present inventors have conducted intensive studies on a flame retardant polyamide resin composed of a polyamide resin and a bromo flame retardant with respect to an additive having low metal corrosivity. As a result, the polyamide resin 1
(A) zinc oxide and zinc borate in a ratio of 40 to 60% by weight to 90 to 10% by weight in a flame-retardant polyamide resin comprising 00 parts by weight and 1 to 50 parts by weight of a bromo flame retardant. The flame retardant polyamide-based resin composition obtained by adding 0.5 to 1.0 part by weight was found to have extremely low metal corrosiveness, and further, 100 parts by weight of a polyamide-based resin and 1 to 50 parts by weight of a bromo-based flame retardant. (A) component zinc oxide and zinc borate are added to a flame-retardant polyamide resin composed of
0.05 to 1.0 at a ratio of 0% to 90% by weight.
Parts by weight, and (b) component hydrotalcite,
(C) component zinc-substituted hydrotalcite compound,
(D) Component 4A type zeolite, (e) Component 0.05 to 2.0 parts by weight of at least one compound selected from zeolites containing a metal or potassium belonging to Group II or Group IV of the periodic table. It has been found that a flame-retardant polyamide-based resin composition obtained by adding the compound has much lower metal corrosiveness, and has completed the present invention.

The polyamide resin used in the present invention is a polymer having an amide bond (-NHCO-), (1) a polymer obtained by polycondensation of a diamine and a dicarboxylic acid, and (2) a polymer of an aminocarboxylic acid. Polymers obtained from polycondensation (3) Polymers obtained from ring-opening polymerization of lactams.

Examples of diamines include aliphatic diamines, aromatic diamines and alicyclic diamines.

[0008] Aliphatic diamines are those having 3 to 18 carbon atoms.
And specific examples thereof include 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, and , 7-heptamethylenediamine, 1,8-octamethylenediamine,
1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine,
1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine,
16-hexadecamethylenediamine, 1,17-heptadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and the like. Can be.

The aromatic diamines are diamines having 6 to 8 carbon atoms in which two amino groups are bonded to a phenylene group, diamines having 12 to 27 carbon atoms in which at least one amino group is bonded to a phenylene group, and naphthylene diamine. It is an isomer of an amine and specific examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 3,4 -Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-
Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-di (m-aminophenoxy) diphenylsulfone, 4,4'-di (p-aminophenoxy) diphenyl Sulfone, benzidine, 2,2'-dimethylbenzidine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 4,4'-bis (4
-Aminophenoxy) biphenyl, 2,2-bis [4-
(4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene,
1,3-bis (3-aminophenoxy) benzene, 4,
4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,
3 ′, 5,5′-tetramethyldiphenylmethane,
Examples thereof include 1,5-naphthylenediamine and 1,8-naphthylenediamine.

[0010] The alicyclic diamines are those having at least one amino group bonded to a cyclohexylene group having 6 to 6 carbon atoms.
15 is a diamine, and specific examples thereof are 4,4 ′
-Diamino-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, 4,4'-diamino-3,3'-dimethyl-dicyclohexylenemethane, 1,4-diaminocyclohexane and the like. it can.

Examples of dicarboxylic acids include aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alicyclic dicarboxylic acids.

The aliphatic dicarboxylic acids are those having 2 to 2 carbon atoms.
18 saturated or unsaturated dicarboxylic acids, specific examples of which include oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid,
Tridecane dicarboxylic acid, hexadecane dicarboxylic acid,
Maleic acid and fumaric acid can be mentioned.

Aromatic dicarboxylic acids are dicarboxylic acids having 8 to 15 carbon atoms in which two carboxyl groups are bonded to a phenylene group, dicarboxylic acids having 8 to 15 carbon atoms in which at least one carboxyl group is bonded to a phenylene group, and It is an isomer of naphthalene dicarboxylic acid, and specific examples thereof include isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and diphenylmethane-
4,4′-dicarboxylic acid, diphenyl ether-4,
4'-dicarboxylic acid, diphenylsulfone-4,4 '
-Dicarboxylic acid, naphthalene-1,2-dicarboxylic acid,
Naphthalene-1,4-dicarboxylic acid, naphthalene-2,
Examples thereof include 6-dicarboxylic acid and naphthalene-2,7-dicarboxylic acid.

The alicyclic dicarboxylic acids are those having 6 to 6 carbon atoms.
14 dicarboxylic acids, specific examples of which are 1,
2-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 4,4 ′
-Dicyclohexyldicarboxylic acid and the like.

Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid and the like can be used within a range in which melt molding is possible.

The aminocarboxylic acid is an aliphatic aminocarboxylic acid having 4 to 18 carbon atoms, and specific examples thereof include:
4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 14-aminotetradecanoic acid , 16-aminohexadecanoic acid and 18-aminooctadecanoic acid.

Specific examples of lactams include ε-caprolactam, ω-laurolactam, ζ-enantholactam, η-caprylactam and the like.

The polyamide resin used in the present invention comprises:
Generally available polyamide resins can be used. Specific examples of commercially available polyamide resins include poly (tetramethylene adipamide) [nylon 4,6], poly (hexamethylene adipamide) [nylon 6,6], and poly (hexamethylene sebacamide). ) [Nylon 6,10], poly (hexamethylene dodecamide)
[Nylon 6,12], poly (heptamethylenepimelamide) [nylon 7,7], poly (octamethylenesuberamide) [nylon 8,8], poly (nonamethyleneazeramid) [nylon 9,9], Poly (decamethylene azeramid) [nylon 10, 9], poly (decamethylene sebacamide) [nylon 10, 10], poly (hexamethylene isophthalamide), poly (hexamethylene terephthalamide), poly (m-xylene) Adipamide), poly (p-xylenesebacamide), poly (p-phenyleneterephthalamide), poly (m-phenyleneisophthalamide), poly [bis (4-aminocyclohexyl) methane-1,10-decanecarboxylate Amide)], poly (2,2,2-trimethylhexamethylene terephthalamide), poly (pipe Jinsebakamido), poly (4-aminobutyric acid) [nylon 4], poly (6-aminohexanoic acid) [nylon 6], poly (7-amino heptanoic acid)
[Nylon 7], poly (8-aminooctanoic acid) [nylon 8], poly (9-aminononanoic acid) [nylon 9], poly (10-aminodecanoic acid) [nylon 1
0], poly (11-aminoundecanoic acid) [nylon 1
1] and poly (12-aminododecanoic acid) [nylon 1
2] and the like. A polyamide resin in which the acid component is terephthalic acid and the amine components are 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine; and the acid components are adipic acid and azelaic acid. A polyamide resin wherein the amine component is 4,4′-diamino-dicyclohexylenepropane, the acid component is isophthalic acid, and the amine component is
4'-diamino-3,3'-dimethyl-dicyclohexylenemethane, polyamide resin copolymerized with ε-caprolactam, acid components terephthalic acid and isophthalic acid, and amine component 4,4'- Diamino-dicyclohexylene methane polyamide resin, hexamethylene terephthalamide and hexamethylene isophthalamide copolymerized polyamide resin, hexamethylene terephthalamide and hexamethylene adipamide copolymerized polyamide resin and hexamethylene terephthalamide and ε And-a copolymerized polyamide resin comprising caprolactam.

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

As the bromo flame retardant used in the present invention, bromo flame retardants usually used in this field can be used without any limitation. Among them, brominated phenyl ethers, Brominated bisphenol A-based carbonate oligomers, brominated bisphenol A-based epoxy resins, brominated styrene-based, brominated phthalimide-based, and brominated benzenes can be mentioned.

Brominated phenyl ethers are compounds in which one or more bromine atoms are bonded to a phenyl ether group, for example, 2,3-dibromopropylpentabromophenyl ether, bis (tribromophenoxy) ethane, Examples thereof include pentabromophenylpropyl ether, pentabromodiphenyl ether, hexabromodiphenylether, octabromodiphenylether, decabromodiphenylether, and polydibromophenylene oxide. Commercially available brominated phenyl ether flame retardants include Bromochem Far East Co., Ltd.'s "FR-1205" and "FR-12".
08 "and" FR-1210 ", Great Lakes
Chemical Co., Ltd. “Great Lakes FF-6”
80 "," Great Lakes DE-83 ",
"Great Lakes DE-83R" and "Gr
eat Lakes DE-79 ", Albemarle Corporation" Saytex 102E "and" Sayte "
x 111 ".

The brominated bisphenol A-based carbonate oligomer has the following formula

[0023]

Embedded image Wherein the oligomer is a polymer having a degree of polymerization (n) of 1 to 10. For example, a flame retardant represented by the following formula can be given.

[0024]

Embedded image Examples of commercially available flame retardants of the above formula include "Fireguard 7000" and "Fireguard 7500" manufactured by Teijin Chemicals Limited.

[0025]

Embedded image The commercially available flame retardants of the above formula include Great Lake Chemical's "Great Lake".
s BC-52 "and" Great Lakes BC
-58 "and the like.

The brominated bisphenol A epoxy resin has the following formula

[0027]

Embedded image The terminal of the polymer represented by the following formula

[0028]

Embedded image And a resin having a degree of polymerization (n) of 1 to 100. Examples of the resin include a flame retardant represented by the following formula. it can.

[0029]

Embedded image Commercially available flame retardants of the above formula include various products depending on the degree of polymerization. Bromochem Far East Co., Ltd.'s "F-2300", "F-2300H", "F-2300H"
-2400 "and" F-2400H ", Dainippon Ink and Chemicals, Inc." Prasam EP-16 "," Prasam EP-30 "," Prasam EP-100 "and" Prasam EP-500 ", Sakamoto Pharmaceutical "SR"
-T1000 "," SR-T2000 "," SR-T5
000 "and" SR-T20000 ".

Examples of the brominated bisphenol A-based epoxy resin include compounds in which the epoxy groups at both ends of the above formula are blocked with a blocking agent and compounds in which one terminal epoxy group is blocked with a blocking agent. be able to. The blocking agent is not limited as long as it is a compound capable of ring-opening addition of an epoxy group, and examples thereof include phenols, alcohols, carboxylic acids, amines and isocyanates containing a bromine atom. Among them, brominated phenols are preferable in terms of improving the flame-retardant effect, and examples thereof include dibromophenol, tribromophenol, pentabromophenol, dibromoethylphenol, dibromopropylphenol, dibromobutylphenol, and dibromocresol. Can be.

Examples of the flame retardant in which the epoxy groups at both ends of the polymer are blocked with a blocking agent include a flame retardant represented by the following formula.

[0032]

Embedded image Commercially available flame retardants of the above formula include “Prasam EC-14”, “Prasam EC-20” and “Prasam EC-30” of Dainippon Ink and Chemicals, Inc., and “TB” of Toto Kasei Co., Ltd. -60 "and" TB-62 "," SR-T3040 "and" SR-T "of Sakamoto Pharmaceutical Co., Ltd.
7040 "and the like.

Examples of the flame retardant in which the terminal epoxy group on one side of the polymer is blocked with a blocking agent include a flame retardant represented by the following formula.

[0034]

Embedded image Examples of commercially available flame retardants of the above formula include "Prasam EPC-15F" manufactured by Dainippon Ink and Chemicals, Inc., and "E5354" manufactured by Yuka Shell Epoxy Co., Ltd.

The brominated styrene-based flame retardant has the following formula

[0036]

Embedded image The following formula in which 1 to 5 bromine atoms are bonded to a benzene ring of a styrene skeleton represented by

[0037]

Embedded image A brominated styrene monomer represented by the following formula and

[0038]

Embedded image And preferably a polymer. For example, brominated styrene and brominated polystyrene can be mentioned, and as a commercially available brominated polystyrene-based flame retardant, "Great Lakes PD" of Great Lakes Chemical Co., Ltd.
BS-10 "and" Great Lakes PDBS "
-80 "and the like. Further, although the manufacturing method is different from that of the above-mentioned flame retardant, "Pyrocheck 68" manufactured by Ferro Co., Ltd.
"PB" can also be mentioned as an example of a brominated polystyrene-based flame retardant.

The brominated phthalimide-based flame retardant comprises 1 to 8
Is a compound in which one or more bromo atoms are bonded to a benzene ring of one or two phthalimide groups, for example, monobromophthalimide, dibromophthalimide, tribromophthalimide, tetrabromophthalimide, ethylenebis (monobromophthalimide), Ethylene bis (dibromophthalimide), ethylene bis (tribromophthalimide)
And ethylenebis (tetrabromophthalimide) of the following formula

[0040]

Embedded image Examples of commercially available flame retardants include:
Albemarle's "Saytex BT-93" and "Saytex BT-93W" can be mentioned.

Brominated benzenes are compounds comprising a group in which one or more bromine atoms are bonded to a benzene ring, such as monobromobenzene, dibromobenzene, tribromobenzene, tetrabromobenzene, pentabromobenzene, and hexabromobenzene. Brominebenzene, bromophenyl allyl ether, pentabromotoluene, bis (pentabromophenyl) ethane, poly (pentabromobenzyl acrylate) and the like can be mentioned. As a commercially available flame retardant, “Saytex 801” manufactured by Albemarle Ltd.
0 ".

In the examples, a typical bromo-based flame retardant widely used among them is used, but the same effect can be obtained by using other bromo-based flame retardants. Be expected.

In addition to the bromo flame retardants commonly used as described above, of course, those described in the literature and in catalogs of bromo flame retardant manufacturers can also be used. It is fully expected that the flame retardant polyamide-based resin composition composed of a flame retardant can also achieve the effects of the present invention. These brominated flame retardants include brominated phenols, brominated phenoxytriazines, brominated cycloalkanes, brominated alkanes, brominated isocyanurates, brominated maleimides, brominated phthalic acids and brominated bisphenols A or brominated bisphenol S can be mentioned.

The brominated phenols are compounds in which 1 to 5 bromine atoms are bonded to a phenol group, and include, for example, monobromophenol, dibromophenol, tribromophenol, tetrabromophenol and pentabromophenol. Can be mentioned.

The brominated phenoxytriazine flame retardant is a compound in which 1 to 5 bromine atoms are bonded to a phenoxy group, and 1 to 3 of the brominated phenoxy groups are bonded to a triazine ring. (Monobromophenoxy) triazine, mono (dibromophenoxy) triazine, mono (tribromophenoxy) triazine, mono (pentabromophenoxy) triazine, bis (monobromophenoxy) triazine, bis (dibromophenoxy) triazine, bis (tri Bromphenoxy) triazine, bis (pentabromophenoxy) triazine,
Tris (monobromophenoxy) triazine, tris (dibromophenoxy) triazine, tris (pentabromophenoxy) triazine and tris (tribromophenoxy) triazine of the following formula

[0046]

Embedded image And the like.

The brominated cycloalkanes are hydrocarbons in which 1 to 6 bromine atoms are bonded to a cycloalkane (cycloaliphatic hydrocarbon) having 6 to 12 carbon atoms. Examples of the cycloalkane include cyclohexane and cyclododecane, and examples of the brominated cycloalkane include monobromocyclohexane, dibromocyclohexane, tribromocyclohexane, tetrabromocyclohexane, pentabromocyclohexane, and hexabromocyclohexane. , Monobromocyclododecane, dibromocyclododecane, tribromocyclododecane, tetrabromocyclododecane, pentabromocyclododecane and hexabromocyclododecane.

The brominated alkane system is an alkane having 1 to 8 brom atoms having 2 to 6 carbon atoms (chain aliphatic hydrocarbon).
Is a compound bound to Examples of the alkane include ethane, propane, butane, pentane and hexane, and examples of the brominated alkane include monobromoethane, dibromoethane, tetrabromoethane, monobromopropane, dibromopropane, and tribromo. Propane, pentabrompropane, hexabrompropane,
Octabromopropane, monobromobutane, dibromobutane, tetrabromobutane, hexabromobutane, octabromobutane, monobromopentane, dibromopentane, tribromopentane, pentabromopentane, octabromopentane, monobromohexane, dibromohexane, Examples thereof include tribromohexane, tetrabromohexane, pentabromohexane, hexabromohexane, and octabromohexane.

Brominated isocyanurates are compounds in which an alkyl residue and a isocyanuric acid residue of the above-mentioned brominated alkane are bonded, and a brominated phenoxy group in which 1 to 5 brom atoms are bonded to a phenoxy group and an isocyanuric acid residue. Compounds having attached groups can be mentioned. Specific examples thereof include tris (monobromoethyl) isocyanurate, tris (dibromoethyl) isocyanurate, tris (tetrabromoethyl) isocyanurate, tris (monobromopropyl) isocyanurate, and tris (2,3-dibromopropyl). Isocyanurate, tris (tribromopropyl) isocyanurate, tris (tetrabromopropyl) isocyanurate, tris (pentabromopropyl) isocyanurate, tris (heptabromopropyl) isocyanurate, tris (monobromobutyl) isocyanurate, tris ( Dibromobutyl) isocyanurate, tris (pentabromobutyl) isocyanurate, tris (octabromobutyl) isocyanurate, tris (monobromopentyl)
Isocyanurate, tris (dibromopentyl) isocyanurate, tris (pentabromopentyl) isocyanurate, tris (octabromopentyl) isocyanurate, tris (monobromohexyl) isocyanurate, tris (dibromohexyl) isocyanurate, tris ( Tribromohexyl) isocyanurate, Tris (pentabromohexyl) isocyanurate, Tris (monobromophenoxy) isocyanurate, Tris (dibromophenoxy) isocyanurate, Tris (tribromophenoxy) isocyanurate, Tris (pentabromophenoxy) isocyanate Nurate, tris (monobromoethylphenoxy) isocyanurate, tris (dibromoethylphenoxy) isocyanurate, tris (tetrabromoethyl) Phenoxy) isocyanurate, may be mentioned tris (mono-bromopropyl phenoxy) isocyanurate, tris (dibromopropyl phenoxy) isocyanurate and tris (tetrabromo propylphenoxy) isocyanurate.

The brominated maleimide system is a compound in which 1 to 5 brom atoms are bonded to a phenylmaleimide group, such as monobromophenylmaleimide, dibromophenylmaleimide, tribromophenylmaleimide and pentabromophenylmaleimide. Can be mentioned.

The brominated phthalic acids include compounds in which 1 to 4 brom atoms are bonded to phthalic anhydride. Examples thereof include monobromophthalic anhydride, dibromophthalic anhydride, tribromophthalic anhydride and tribromophthalic anhydride. Tetrabromophthalic anhydride and the like can be mentioned.

Examples of the brominated bisphenol A or brominated bisphenol S include compounds in which 1 to 8 bromo atoms are bonded to the benzene ring of a bisphenol A residue or a bisphenol S residue. , Monobromobisphenol A, dibromobisphenol A, tribromobisphenol A, tetrabromobisphenol A, pentabromobisphenol A, hexabromobisphenol A, octabromobisphenol A, tetrabromobisphenol A bis (2-hydroxyethyl ether), tetra Brombisphenol A
Bis (2-bromoethyl ether), tetrabromobisphenol A bis (1,2-dibromoethyl ether), tetrabromobisphenol A bis (propyl ether), tetrabromobisphenol A bis (3-bromopropyl ether), tetrabromo Bisphenol A bis (2,3-dibromopropyl ether), monobromobisphenol S, dibromobisphenol S, tribromobisphenol S, tetrabromobisphenol S, pentabromobisphenol S, hexabromobisphenol S, octabromobisphenol S, tetra Brom bisphenol S bis (2-hydroxyethyl ether), tetrabromobisphenol S bis (2-
Bromoethyl ether), tetrabromobisphenol S bis (1,2-dibromoethyl ether), tetrabromobisphenol S bis (propyl ether), tetrabromobisphenol S bis (3-bromopropyl ether) and tetrabromobisphenol S bis ( 2,
3-dibromopropyl ether).

The amount of the bromo flame retardant used in the present invention varies depending on the relationship between the degree of flame retardancy required for the polyamide resin and the physical properties. It is used in an amount of 1 to 50 parts by weight based on parts by weight. If the amount is less than 1 part by weight, the desired flame retardancy cannot be imparted. If the amount exceeds 50 parts by weight, even if the flame retardancy is sufficient, the physical properties of the molded article of the resin composition are unfavorably deteriorated. However, in view of the balance between flame retardancy and physical properties, it is practically used in the range of 3 to 30 parts by weight.

Further, depending on the purpose, a bromo-based flame retardant may be used.
More than one kind can be used in combination, but usually one kind is sufficient.

It is common practice to use a flame retardant aid such as antimony trioxide for the purpose of further enhancing the flame retardant effect. However, the addition of this flame retardant aid has no effect on the effect of the present invention. It has no effect. The amount of the flame-retardant aid is usually 1 to 20 parts by weight based on 100 parts by weight of the polyamide resin.
The preferred amount is 2 to 5 parts by weight.

As the zinc oxide (a) used in the present invention, commercially available zinc oxide can be used.

Specific examples of the zinc borate (a) used in the present invention include zinc orthoborate [Zn ₃ B ₂ O].
₆ ], zinc diborate [Zn ₂ B ₂ O ₅ ], zinc metaborate [Zn (BO ₂ ) ₂ ], zinc tetraborate [ZnB ₄ O ₇ ],
Zinc pentaborate [Zn ₂ B ₁₀ O ₁₇ ], zinc octaborate [ZnB ₈
O ₁₃ ], Zn ₂ B ₆ O ₁₁ and their hydrates. Preferred are zinc metaborate [Zn
(BO ₂ ) ₂ ], zinc tetraborate [ZnB ₄ O ₇ ] or Zn ₂
B ₆ O ₁₁ and hydrates thereof can be mentioned.

The hydrotalcite of the component (b) used in the present invention is a compound composed of magnesium and aluminum. For example, the following general formula (1): Mg _1-x Al _x (OH) ₂ (A ^q- ) _{X / q} · aH ₂ O (1).

The zinc-substituted hydrotalcite compound of the component (c) is, for example, a compound in which a part of Mg in the general formula (1) is replaced with Zn, and the following general formula (2) _y1 Zn _y2 Al _X (OH) may be mentioned compounds of the ^{_{2 (a q-) X / q}} · aH 2 O (2). The substitution ratio of Zn is 1 mol% to 50 mol%, preferably 15 mol% to 30 mol% with respect to Mg. [In the formulas (1) and (2), q is 1 or 2, and A ^q- is a q-valent anion, ie, (CO ₃ ) ^2- or (ClO ₄ ) ^- , and X
, Y1, y2 and a are real numbers satisfying the following conditions.

0 <X ≦ 0.5, y1 + y2 = 1−X, y1 ≧
y2, 0 ≦ a <1] Typical examples of the general formula (1) include the following. No. 1: Mg _0.750 Al _0.250 (OH) ₂ (CO
₃ ) _0.125・ 0.5 H ₂ O No. 2: Mg _0.692 Al _0.308 (OH) ₂ (CO
₃ ) _0.154 · 0.1 H ₂ O No. _{3: Mg 0.683 Al 0.317 (OH} ) 2 (CO
₃ ) _0.159 · 0.5 H ₂ O No. 4: Mg _0.667 Al _0.333 (OH) ₂ (CO
₃ ) _0.167 · 0.1 H ₂ O No. 5: Mg _0.750 Al _0.250 (OH) ₂ (ClO
₄ ) _0.250・ 0.5 H ₂ O No. 6: Mg _0.692 Al _0.308 (OH) ₂ (ClO
₄ ) _0.308・ 0.1 H ₂ O No. 7: Mg _0.667 Al _0.333 (OH) ₂ (ClO
₄ ) _0.333 · 0.1 H ₂ O The following are typical examples of the general formula (2). No. 8: Mg _0.625 Zn _0.125 Al _0.250 (OH)
₂ (CO ₃ ) _0.125・ 0.45H ₂ O No. 9: Mg _0.538 Zn _0.154 Al _0.308 (OH)
₂ (CO ₃ ) _0.154 No. 10: Mg _0.500 Zn _0.167 Al _0.333 (OH)
₂ (CO ₃ ) _0.167 · 0.54 H ₂ O No. 11: Mg _0.625 Zn _0.125 Al _0.250 (OH)
₂ (ClO ₄ ) _0.250 · 0.3 H ₂ O No. 12: Mg _0.538 Zn _0.154 Al _0.308 (OH)
₂ (ClO ₄ ) _0.308 · 0.5 H ₂ O No. 13: Mg _0.500 Zn _0.167 Al _0.333 (OH)
₂ (ClO ₄ ) _0.333 · 0.1 H ₂ O In the present invention, in order to improve the compatibility and dispersibility of the hydrotalcite and zinc-substituted hydrotalcite compounds with the flame-retardant polyamide resin, A hydrotalcite and a zinc-substituted hydrotalcite compound that has been surface-treated with a surface treating agent, for example, a higher fatty acid, can also be used. Specific examples of the surface-treated hydrotalcite include Alkamizer 2, Alkamizer 3, DHT-4A and DHT-4A-2 manufactured by Kyowa Chemical Industry Co., Ltd. Specific examples of the surface-treated zinc-substituted hydrotalcite compounds include Alkamizer 4, Alkamizer 4-2, and Alkamizer 7 manufactured by Kyowa Chemical Industry Co., Ltd.

Such surface treating agents can be used in addition to the above-mentioned higher fatty acids, as well as known literature, for example, JP-A-60-1241.
No. 4, page 4 and the like.

The surface treatment agents described in the above-mentioned known documents include:
Those generally used in this field, for example, anionic surfactants, silane coupling agents, titanium coupling agents, higher fatty acid esters and the like,
Specific examples thereof include, for example, anionic surfactants such as sodium stearate, sodium oleate, and sodium laurylbenzenesulfonate, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, isopropyltriisostearoyl titanate, There are disclosed silane-based or titanium-based coupling agents such as isopropyltridecylbenzenesulfonyl titanate, and higher fatty acid esters such as glycerin monostearate and glycerin monooleate.

The 4A zeolite of the component (d) used in the present invention includes the following general formula (3): Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ .bH ₂ O (3) [wherein b in the formula (3) Represents a real number satisfying 0 ≦ b ≦ 36. ]
4A zeolite represented by

Specific examples of the 4A-type zeolite include:
For example, Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ , Na ₁₂ Al ₁₂ Si _{12
O 48 · 6H 2 O, Na} 12 Al 12 Si 12 O 48 · 12H 2
O, Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ · 21H ₂ O, Na ₁₂ Al
₁₂ Si ₁₂ O ₄₈ · 27H ₂ O, Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ ·
36H ₂ O and the like.

The zeolite containing a metal of Group II or Group IV of the Periodic Table or potassium as the component (e) is
A zeolite in which Na in the 4A-type zeolite is partially substituted with a metal or potassium of Group II or Group IV of the periodic table (hereinafter, referred to as "metal-substituted zeolite"), and the metal is not particularly limited. However, from the viewpoint of effect, toxicity and availability, magnesium, calcium, zinc, strontium, barium, zirconium, tin and potassium can be mentioned, and preferred metals are calcium, zinc, magnesium, Barium and potassium can be mentioned.

The metal-substituted zeolite is generally obtained industrially as a 4A-type zeolite having a metal substitution ratio of 10 mol% to 70 mol%.

Specific examples of the metal-substituted zeolite include synthetic zeolites such as magnesium-substituted zeolite, calcium-substituted zeolite, zinc-substituted zeolite, strontium-substituted zeolite, barium-substituted zeolite, zirconium-substituted zeolite, tin-substituted zeolite, and potassium-substituted zeolite. Can be mentioned. The method for producing the metal-substituted zeolite may be a known method, for example, a method described in JP-A-57-28145.

The component (d) used in the present invention, 4A
The zeolite containing a type zeolite and a metal or potassium of Group II or IV of the Periodic Table of the component (e),
Higher fatty acids, for example, alkali metal salts of higher fatty acids such as alkali metal salts such as stearic acid and oleic acid, and organic sulfonic acids, for example, alkali metal salts of organic sulfonic acids such as alkali metal salts such as dodecylbenzenesulfonic acid. May be surface-treated.

The amount of zinc oxide and zinc borate of component (a) used in the present invention is 40 to 60% by weight to 90% by weight based on 100 parts by weight of the polyamide resin.
0.05 to 1.0 parts by weight with respect to 10% by weight,
Preferably, zinc oxide and zinc borate are present in an amount of 50 to 50% by weight.
It is 0.1 to 0.8 parts by weight at a ratio of 80 to 20% by weight.

The combination ratio of zinc oxide and zinc borate as the component (a) is 40 to 60% by weight, which is the combination ratio according to the present invention.
If the amount is out of the range of 0 to 10% by weight, no remarkable metal corrosion preventing effect is obtained by the combined use. If the amount of component (a) is less than 0.05 parts by weight, a sufficient metal corrosion preventing effect cannot be obtained. The prevention effect cannot be obtained.

Also, hydrotalcite of the component (b),
(C) a zinc-substituted hydrotalcite compound as a component,
The amount of at least one compound selected from the group consisting of a 4A zeolite as the component (d) and a zeolite containing a metal or potassium belonging to Group II or IV of the Periodic Table as the component (e) is a polyamide resin. For 100 parts by weight,
0.05 to 2.0 parts by weight, preferably 0.1 to
1.5 parts by weight.

The hydrotalcite of the component (b)
(C) a zinc-substituted hydrotalcite compound as a component,
The addition amount of at least one compound selected from the group consisting of a 4A zeolite as the component (d) and a zeolite containing a metal or potassium belonging to Group II or Group IV of the periodic table as the component (e) is 0.05% by weight. When the amount is less than 1 part, metal corrosion is prevented by the combined addition of at least one compound selected from component (a) and component (b), component (c), component (d) or component (e). If the effect is not obtained, and if it exceeds 2.0 parts by weight, the expected effect of preventing metal corrosion by increasing the amount cannot be obtained.

Further, zinc oxide and zinc borate of the component (a)
Component (b) hydrotalcite, component (c) zinc-substituted hydrotalcite compound, component (d) 4A zeolite or component (e) Group II or IV metal or potassium The combination ratio of at least one compound selected from zeolites containing is not particularly limited, and may be an arbitrary ratio.

Even if a filler such as glass fiber, carbon fiber, or inorganic substance is added to the flame retardant polyamide resin composition of the present invention, the metal corrosion preventing effect of the present invention is not affected at all.

The flame-retardant polyamide resin composition of the present invention can be obtained by kneading using a calender roll, an extruder, an injection molding machine, a Banbury mixer, a kneader or the like. When kneading, each component may be kneaded at once, or may be separately added and kneaded.

In carrying out the present invention, the following embodiments can be mentioned. (1) A flame-retardant polyamide resin comprising 100 parts by weight of a polyamide resin and 1 to 50 parts by weight of a bromo-based flame retardant,
(A) Component: zinc oxide and zinc borate are 40 to 60% by weight.
A flame-retardant polyamide resin composition comprising 0.05 to 1.0 parts by weight in a ratio of 90 to 10% by weight. (2) A flame-retardant polyamide resin comprising 100 parts by weight of a polyamide-based resin and 3 to 30 parts by weight of a bromo-based flame retardant,
(A) Component 50 to 50% by weight of zinc oxide and zinc borate
A flame-retardant polyamide-based resin composition comprising 0.1 to 0.8 parts by weight at a ratio of 80 to 20% by weight. (3) A flame-retardant polyamide resin comprising 100 parts by weight of a polyamide resin and 3 to 30 parts by weight of a bromo flame retardant,
(A) component zinc oxide and zinc metaborate [Zn (BO ₂ )
₂ ], zinc tetraborate [ZnB ₄ O ₇ ], Zn ₂ B ₆ O ₁₁ and hydrates thereof at a ratio of 50 to 50% by weight to 80 to 20% by weight of zinc borate. .1 to 0.8
A flame-retardant polyamide-based resin composition obtained by adding parts by weight. (4) A flame retardant polyamide resin consisting of 100 parts by weight of a polyamide resin and 1 to 50 parts by weight of a bromo flame retardant, (a) component zinc oxide and zinc borate are added in an amount of 40 to 60% by weight.
(B) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component 4A zeolite (e) component Period Flame retardant polyamide resin composition comprising 0.05 to 2.0 parts by weight of at least one compound selected from zeolites containing Group II or Group IV metals or potassium . (5) A flame-retardant polyamide resin comprising 100 parts by weight of a polyamide resin and 3 to 30 parts by weight of a bromo-based flame retardant, wherein (a) component zinc oxide and zinc borate are 50 to 50% by weight.
(B) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component 4A zeolite (e) component Flame retardant polyamide-based resin composition comprising 0.1 to 1.5 parts by weight of at least one compound selected from zeolites containing metals or potassium of Group II or IV . (6) A flame-retardant polyamide resin comprising 100 parts by weight of a polyamide-based resin and 3 to 30 parts by weight of a bromo-based flame retardant, (a) component zinc oxide and zinc metaborate [Zn (BO ₂ )
₂ ], zinc tetraborate [ZnB ₄ O ₇ ], Zn ₂ B ₆ O ₁₁ and hydrates thereof at a ratio of 50 to 50% by weight to 80 to 20% by weight of zinc borate. .1 to 0.8
Parts by weight and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component 4A zeolite (e) component zeolite containing a metal of Group II or Group IV of the periodic table or potassium A flame-retardant polyamide resin composition comprising 0.1 to 1.5 parts by weight of at least one compound selected from the group consisting of: (7) A flame-retardant polyamide resin comprising 100 parts by weight of a polyamide resin and 1 to 50 parts by weight of a bromo-based flame retardant,
(A) Component: zinc oxide and zinc borate are 40 to 60% by weight.
Flame-retardant polyamide based on the addition of 0.05 to 1.0 parts by weight at a ratio of 90 to 10% by weight and 0.05 to 2.0 parts by weight of component (c) zinc-substituted hydrotalcite compound. Resin composition. (8) A flame-retardant polyamide resin comprising 100 parts by weight of a polyamide resin and 3 to 30 parts by weight of a bromo flame retardant,
(A) Component 50 to 50% by weight of zinc oxide and zinc borate
A flame-retardant polyamide system comprising 0.1 to 0.8 parts by weight in a ratio of 80 to 20% by weight and 0.1 to 1.5 parts by weight of a zinc-substituted hydrotalcite compound (c). Resin composition. (9) A flame-retardant polyamide resin comprising 100 parts by weight of a polyamide resin and 3 to 30 parts by weight of a bromo-based flame retardant,
(A) component zinc oxide and zinc metaborate [Zn (BO ₂ )
₂ ], zinc tetraborate [ZnB ₄ O ₇ ], Zn ₂ B ₆ O ₁₁ and hydrates thereof at a ratio of 50 to 50% by weight to 80 to 20% by weight of zinc borate. .1 to 0.8
A flame-retardant polyamide resin composition comprising 0.1 parts by weight and 1.5 parts by weight of a zinc-substituted hydrotalcite compound as component (c).

[0077]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention include the above-mentioned embodiments (2), (3), (5) to (9).
More preferred embodiments include Embodiments (3), (6), (8) and (9), and the most preferred embodiments are Embodiments (8) and (9). Is mentioned.

[0078]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In these examples, parts means parts by weight.

[Additive used in the present invention: component (a)] A-1: zinc oxide A-2: zinc metaborate trihydrate [Zn (BO ₂ ) _2.
3H 2 O] A-3: zinc tetraborate 3.5 hydrate [ZnB ₄ O _7.
3.5 H ₂ O] _{A-4: Zn 2 B 6} O 11 · 3.5H 2 O A-5: ortho zinc borate [Zn ₃ B ₂ O _6] A-6: two zinc borate 3.5 hydrate [Zn ₂ B ₂ O _5.
3.5H ₂ O] A-7: zinc pentaborate [Zn ₂ B ₁₀ O ₁₇ ] A-8: zinc octaborate 3.5 hydrate [ZnB ₈ O _13.
3.5H ₂ O] [Additive used in the present invention: component (b)] B-1: No. in the specification. Hydrotalcite B-2: No. 1 in the description. Hydrotalcite B-3: No. 3 in the description Hydrotalcite represented by No. 6 [Additive used in the present invention: component (c)] C-1: No. 6 in the specification. No. 9 of zinc-substituted hydrotalcite compound C-2: No. 9 in the specification. Zinc-substituted hydrotalcite compounds represented by C-10: No. 10 in the specification. Zinc-substituted hydrotalcite compound represented by the 13 [additives used in the present invention: (d) Component] _{D-1: Na 12 Al 12} Si 12 O 48 · 27H 2 O D-2: Na 12 Al 12 Si ₁₂ O ₄₈ [additive used in the present invention: component (e)] E-1: calcium-substituted zeolite E-2: magnesium-substituted zeolite E-3: zinc-substituted zeolite E-4: barium-substituted zeolite E-5 : Potassium-substituted zeolite (The metal substitution ratio of each of E-1 to E-5 is 70 mol%.) [Additives other than the present invention] F-1: orthoboric acid [H ₃ BO ₃ ] F-2: diboron trioxide [B ₂ O _3] F-3: aluminum borate F-4: magnesium borate F-5: calcium borate F-6: lead borate F-7: metaborate ammonium 2.5 hydrate [(NH
₄ ) ₂ O.B ₂ O ₃ .2.5H ₂ O] F-8: ammonium tetraborate tetrahydrate [(NH ₄ ) _{2
O · 2B 2 O 3 · 4H} 2 O ] F-9: lead oxide F-10: ferrous oxide F-11: ferric oxide F-12: cadmium oxide F-13: tristearyl borate F-14: Irganox 1010 [manufactured by Ciba Geigy: tetrakis- [methylene-3- (3 ′, 5′-di-
t-15-butyl-4'-hydroxyphenyl) -propionate] -methane] F-15: Nocrack MBZ [manufactured by Ouchi Shinko Chemical Co., Ltd .: zinc salt of 2-mercaptobenzimidazole] F-16: zinc sulfide F- 17: zinc chloride F-18: zinc hydroxide F-19: zinc carbonate F-20: zinc silicate F-21: zinc polyphosphate F-22: zinc pyrophosphate F-23: zinc stearate F-24: dibutyl Tin maleate F-25: dibutyltin-3-mercaptopropionate F-26: sodium antimonate [Example 1] Polyamide resin [manufactured by Asahi Chemical Industry Co., Ltd.]
100 parts of nylon 66 Leona 1500], 20 parts of brominated bisphenol A-based epoxy resin [Platherm EP-100 manufactured by Dainippon Ink and Chemicals, Inc.], 3 parts of antimony trioxide, polyethylene wax [manufactured by Mitsui Petrochemical Industries, Ltd.] [HI-WAX 400PF] 0.5 part,
The additives shown in Tables 1 to 17 were mixed, mixed with a Henschel mixer, and then melt-kneaded at 280 ° C. using an extruder.
A pellet was obtained. Further, an appropriate amount of the pellet was put in a test tube, placed in a heating block set at 300 ° C., covered with a SUS plate [SUS304], and the corrosion state of the SUS plate after a certain time was visually observed.

Incidentally, the corrosion state of the SUS plate is visually determined.
Judgment was made based on the following criteria.

A: The SUS plate is not corroded at all.

：: A part of the SUS plate is slightly corroded.

Δ: About half of the SUS plate is corroded.

×: The entire surface of the SUS plate is corroded.

XX: The entire surface of the SUS plate is severely corroded.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

[0092]

[Table 7]

[0093]

[Table 8]

[0094]

[Table 9]

[0095]

[Table 10]

[0096]

[Table 11]

[0097]

[Table 12]

[0098]

[Table 13]

[0099]

[Table 14]

[0100]

[Table 15]

[0101]

[Table 16]

[0102]

[Table 17] Sample numbers 1 to 110 are working examples, and sample numbers 111 to 213 are comparative examples. As is clear from the comparison of the results in Tables 1 to 17, the flame-retardant polyamide-based resin composition of the present invention comprises:
It can be seen that the metal corrosion prevention effect is extremely excellent.
As shown in Sample Nos. 32 to 110, when zinc oxide and zinc borate as the component (a) and at least one of the components (b) to (e) are used in combination, the zinc oxide as in the same numbers 1 to 31 is used. It can be seen that the metal corrosion preventing effect is much better than when only the component (a) of zinc borate is added. When zinc oxide or zinc borate as the component (a) is added alone, as in sample numbers 111 to 122, and when only component (b) is added, as in samples 123 to 125, the same numbers 126 to 128 are used. When only the component (c) is added, like the reference numbers 129 and 130, and when only the component (d) is added, like the reference numbers 131 to 134,
When only the component (e) is added, the same numbers 135 to 139 are used.
When the combination ratio of zinc oxide and zinc borate as the component (a) is out of the range of the present invention, the same numbers 140 and 141 are used.
When the addition amount of the component (a) is out of the range of the present invention, as in the case of the same number 142 to 149, the addition amount of the components (b) to (e) is out of the range of the present invention. When the component (a) is only zinc oxide or zinc borate as in the same numbers 150 to 158, when the additive other than the present invention is added as in the same numbers 159 to 212, and in the same number 2
In the case where no additive is added, as in the case of 13, no sufficient metal corrosion preventing effect can be obtained. [Example 2] Polyamide resin [manufactured by Asahi Chemical Industry Co., Ltd.]
Nylon 66 Leona 1500] 100 parts, brominated polystyrene [Pyro Check 68PB manufactured by Ferro Corporation]
(Brominated styrene type)]
After mixing the additives shown in, and mixing with a Henschel mixer,
The mixture was melt-kneaded at 280 ° C. using an extruder to obtain pellets. Further, an appropriate amount of the pellet is put into a test tube, and 290
The sample was placed in a heating block set to ° C., covered with a SUS plate [SUS304], and the corrosion state of the SUS plate after a certain time was visually observed.

Incidentally, the corrosion state of the SUS plate was as follows [Example 1]
Judgment was made based on the same criteria as described above.

[0104]

[Table 18]

[0105]

[Table 19]

[0106]

[Table 20]

[0107]

[Table 21]

[0108]

[Table 22]

[0109]

[Table 23]

[0110]

[Table 24]

[0111]

[Table 25]

[0112]

[Table 26]

[0113]

[Table 27]

[0114]

[Table 28]

[0115]

[Table 29]

[0116]

[Table 30]

[0117]

[Table 31]

[0118]

[Table 32]

[0119]

[Table 33]

[0120]

[Table 34]

[0121]

[Table 35]

[0122]

[Table 36]

[0123]

[Table 37]

[0124]

[Table 38]

[0125]

[Table 39]

[0126]

[Table 40]

[0127]

[Table 41]

[0128]

[Table 42]

[0129]

[Table 43]

[0130]

[Table 44] Sample numbers 1 to 175 are working examples, and sample numbers 176 to 292 are comparative examples. As is clear from the comparison of the results in Tables 18 to 44, the flame-retardant polyamide-based resin composition of the present invention has an extremely excellent metal corrosion prevention effect. In addition, sample number 6-105, same number 111-140,
When zinc oxide and zinc borate as the component (a) and at least one of the components (b) to (e) are used in combination as in the same numbers 146 to 175, the same numbers 1 to 5 and the same numbers 106 to 1 are used.
10, it can be seen that the metal corrosion prevention effect is much more excellent than the case where only the component (a) of zinc oxide and zinc borate as in the case of the same numbers 141 to 145 are added. When the zinc oxide or zinc borate of the component (a) is added alone, as in sample numbers 176 to 181, and when only the component (b) is added, as in samples 182 and 183, the same numbers 184 and 185 are added. When only the component (c) is added, like the numbers 186 and 187, and when only the component (d) is added, like the numbers 188 and 189, (e)
When only the components are added, as in the case of the same numbers 190 to 192, and when the combination ratio of zinc oxide and zinc borate as the component (a) is out of the range of the present invention, as in the case of the same numbers 193 to 198, (a) If the amount of the component is outside the scope of the present invention,
When the added amount of the components (b) to (e) is out of the range of the present invention as in the same numbers 199 to 230, the same number 231 is used.
271, when the component (a) is only zinc oxide or zinc borate, when an additive other than the present invention is added, as in 272 to 291, and when no additive is added, as in 292. In each case, a sufficient effect of preventing metal corrosion cannot be obtained. [Example 3] Polyamide resin [Nylon 6 Novamid 10 manufactured by Mitsubishi Engineering-Plastics Corporation]
20CA2] 100 parts, ethylenebis (tetrabromophthalimide) [Saytex manufactured by Albemarle Co., Ltd.]
BT-93W (brominated phthalimide type)], 3 parts, polyethylene wax [HI-, manufactured by Mitsui Chemicals, Inc.
[WAX 400PF] 0.5 part was mixed with the additives shown in Tables 45 to 50, mixed with a Henschel mixer, and melt-kneaded at 250 ° C. using an extruder to obtain pellets.
Further, an appropriate amount of the pellet is put in a test tube, put into a heating block set at 280 ° C., and a SUS plate [S
US304], and the corrosion state of the SUS plate after a certain time was visually observed.

[0131] The corrosion state of the SUS plate was determined according to [Example 1].
Judgment was made based on the same criteria as described above.

[0132]

[Table 45]

[0133]

[Table 46]

[0134]

[Table 47]

[0135]

[Table 48]

[0136]

[Table 49]

[0137]

[Table 50] Sample numbers 1 to 31 are working examples, and sample numbers 32 to 66 are comparative examples. As is clear from the comparison of the results in Tables 45 to 50, the flame-retardant polyamide-based resin composition of the present invention has an extremely excellent metal corrosion prevention effect. As shown in Sample Nos. 6 to 31, when zinc oxide and zinc borate of component (a) are used in combination with at least one of components (b) to (e), zinc oxides of the same numbers 1 to 5 are used. It can be seen that the metal corrosion preventing effect is much better than when only the component (a) of zinc borate is added. When zinc oxide or zinc borate as the component (a) is added alone, as in sample numbers 32 to 35, and when only component (b) is added, as in samples 36 and 37, the same numbers 38 and 39 are used. When only the component (c) is added,
When only the component (d) is added, as in 0 and 41, the zinc oxide of the component (a) is added, as in the same numbers 44 and 45, when only the component (e) is added, as in the same numbers 42 and 43. When the combination ratio with zinc borate is out of the range of the present invention,
When the added amount of the component (b) is out of the range of the present invention as in the same numbers 46 and 47, as in the same numbers 48 and 49,
(A) When the component is only zinc oxide or zinc borate,
In the case where additives other than the present invention are added as in Nos. 50 to 65 and in the case where no additives are added as in No. 66, no sufficient metal corrosion preventing effect can be obtained. [Example 4] Polyamide resin [Nylon 12 diamide L1640 manufactured by Daicel Huls Co., Ltd.] 10
0 parts, decabromodiphenyl ether [FR-1210 (brominated phenyl ethers) manufactured by Bromochem Far East Co., Ltd.] 15 parts, antimony trioxide 2 parts, polyethylene wax [HI manufactured by Mitsui Chemicals Petroleum Industry Co., Ltd.]
-WAX 400PF] in 0.5 parts, Tables 51 to 56
After mixing the additives shown in, and mixing with a Henschel mixer,
The mixture was melt-kneaded at 230 ° C. using an extruder to obtain pellets. Further, an appropriate amount of the pellet is placed in a test tube, and 280
The sample was placed in a heating block set to ° C., covered with a SUS plate [SUS304], and the corrosion state of the SUS plate after a certain time was visually observed.

[0138] The corrosion state of the SUS plate was determined according to [Example 1].
Judgment was made based on the same criteria as described above.

[0139]

[Table 51]

[0140]

[Table 52]

[0141]

[Table 53]

[0142]

[Table 54]

[0143]

[Table 55]

[0144]

[Table 56] Sample numbers 1 to 31 are working examples, and sample numbers 32 to 65 are comparative examples. As is clear from the comparison of the results in Tables 51 to 56, it is understood that the flame-retardant polyamide resin composition of the present invention has an extremely excellent metal corrosion prevention effect. As shown in Sample Nos. 6 to 31, when zinc oxide and zinc borate of component (a) are used in combination with at least one of components (b) to (e), zinc oxides of the same numbers 1 to 5 are used. It can be seen that the metal corrosion preventing effect is much better than when only the component (a) of zinc borate is added. When zinc oxide or zinc borate as the component (a) is added alone, as in sample numbers 32 to 35, and when only component (b) is added, as in samples 36 and 37, the same numbers 38 and 39 are used. When only the component (c) is added,
When only the component (d) is added, as in 0 and 41, the zinc oxide of the component (a) is added, as in the same numbers 44 and 45, when only the component (e) is added, as in the same numbers 42 and 43. When the combination ratio with zinc borate is out of the range of the present invention,
When the added amount of the component (c) is out of the range of the present invention as in the same numbers 46 and 47, as in the same numbers 48 and 49,
(A) When the component is only zinc oxide or zinc borate,
In the case where additives other than the present invention are added as in Nos. 50 to 64, and in the case where no additive is added as in No. 65, no sufficient metal corrosion preventing effect can be obtained. [Example 5] Polyamide resin [Nylon 6 Novamid 10 manufactured by Mitsubishi Engineering-Plastics Corporation]
20CA2] 100 parts, bis (pentabromophenyl)
Ethane [Saytex 801 manufactured by Albemarle Co., Ltd.
0 (brominated benzenes)], 30 parts of antimony trioxide, polyethylene wax [Mitsui Chemical Oil Co., Ltd.]
HI-WAX 400PF] (1.0 part), the additives shown in Tables 57 to 62 were mixed, mixed with a Henschel mixer, and melt-kneaded at 250 ° C. using an extruder to obtain pellets. Furthermore, put an appropriate amount of this pellet in a test tube,
Put in a heating block set at 300 ° C,
Cover with a US plate [SUS304]
The corrosion state of the S plate was visually observed.

[0145] The corrosion state of the SUS plate was determined according to [Example 1].
Judgment was made based on the same criteria as described above.

[0146]

[Table 57]

[0147]

[Table 58]

[0148]

[Table 59]

[0149]

[Table 60]

[0150]

[Table 61]

[0151]

[Table 62] Sample numbers 1 to 31 are working examples, and sample numbers 32 to 67 are comparative examples. As is clear from comparison of the results in Tables 57 to 62, it is understood that the flame-retardant polyamide-based resin composition of the present invention has an extremely excellent metal corrosion prevention effect. As shown in Sample Nos. 6 to 31, when zinc oxide and zinc borate of component (a) are used in combination with at least one of components (b) to (e), zinc oxides of the same numbers 1 to 5 are used. It can be seen that the metal corrosion preventing effect is much better than when only the component (a) of zinc borate is added. When zinc oxide or zinc borate as the component (a) is added alone, as in sample numbers 32 to 35, and when only component (b) is added, as in samples 36 and 37, the same numbers 38 and 39 are used. When only the component (c) is added,
When only the component (d) is added, as in 0 and 41, the zinc oxide of the component (a) is added, as in the same numbers 44 and 45, when only the component (e) is added, as in the same numbers 42 and 43. When the combination ratio with zinc borate is out of the range of the present invention,
When the added amount of the component (d) is out of the range of the present invention as in the same numbers 46 and 47, as in the same numbers 48 and 49,
(A) When the component is only zinc oxide or zinc borate,
When the addition amount of the component (a) is out of the range of the present invention as in the same numbers 50 and 51, when the additive other than the present invention is added as in the same numbers 52 to 66, and as in the same number 67, In the case where no additive is added, no sufficient metal corrosion preventing effect can be obtained. [Example 6] 100 parts of a polyamide resin [Polyamide MXD6 resin Reny 2041 manufactured by Mitsubishi Engineering-Plastics Co., Ltd.], tetrabromobisphenol A carbonate oligomer [Fireguard 7500 manufactured by Teijin Chemicals Ltd. (brominated bisphenol A-based carbonate oligomer) )] 50 parts, antimony trioxide 3 parts,
Polyethylene wax [M made by Mitsui Chemicals, Inc. H
I-WAX 400PF] 1.0 part, Table 63 to Table 6
The additives shown in No. 8 were mixed, mixed with a Henschel mixer, and then melt-kneaded at 320 ° C. using an extruder to obtain pellets. Further, put an appropriate amount of the pellet in a test tube,
Put in a heating block set at 0 ° C, and place SUS
The plate was covered with [SUS304], and the corrosion state of the SUS plate after a certain time was visually observed.

Incidentally, the corrosion state of the SUS plate was determined according to [Example 1].
Judgment was made based on the same criteria as described above.

[0153]

[Table 63]

[0154]

[Table 64]

[0155]

[Table 65]

[0156]

[Table 66]

[0157]

[Table 67]

[0158]

[Table 68] Sample numbers 1 to 31 are working examples, and sample numbers 32 to 64 are comparative examples. As is clear from the comparison of the results in Tables 63 to 68, it is understood that the flame-retardant polyamide resin composition of the present invention has an extremely excellent metal corrosion prevention effect. As shown in Sample Nos. 6 to 31, when zinc oxide and zinc borate of component (a) are used in combination with at least one of components (b) to (e), zinc oxides of the same numbers 1 to 5 are used. It can be seen that the metal corrosion preventing effect is much better than when only the component (a) of zinc borate is added. When zinc oxide or zinc borate as the component (a) is added alone, as in sample numbers 32 to 35, and when only component (b) is added, as in samples 36 and 37, the same numbers 38 and 39 are used. When only the component (c) is added,
When only the component (d) is added, as in 0 and 41, the zinc oxide of the component (a) is added, as in the same numbers 44 and 45, when only the component (e) is added, as in the same numbers 42 and 43. When the combination ratio with zinc borate is out of the range of the present invention,
When the added amount of the component (e) is out of the range of the present invention as in the same numbers 46 and 47, as in the same numbers 48 and 49,
(A) When the component is only zinc oxide or zinc borate,
When the addition amount of the component (a) is out of the range of the present invention as in the same numbers 50 and 51, when the additive other than the present invention is added as in the same numbers 52 to 63, and as in the same number 64, In the case where no additive is added, no sufficient metal corrosion preventing effect can be obtained.

[0159]

The flame-retardant polyamide resin composition of the present invention is much more effective in preventing metal corrosion than conventional flame-retardant polyamide resin compositions.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/02 C08K 5/02 (72) Inventor Masaharu Akitsu 788 Kuji, Takatsu-ku, Kawasaki-shi, Kanagawa Sankyo Organic Synthesis F term in reference (reference) 4J002 BC112 CD122 CG032 CL011 CL031 CL041 CL051 CL061 CN021 CN031 DE107 DE289 DJ009 DK008 EB136 EU056 FB079 FB089 FD010 FD132

Claims (2)

[Claims] 1. A flame retardant polyamide resin comprising 100 parts by weight of a polyamide resin and 1 to 50 parts by weight of a bromo flame retardant is added with (a) component zinc oxide and zinc borate in a ratio of 40 to 60.
A flame-retardant polyamide-based resin composition comprising 0.05 to 1.0 part by weight in a ratio of 90 to 10% by weight. 2. A flame retardant polyamide resin comprising 100 parts by weight of a polyamide resin and 1 to 50 parts by weight of a bromo flame retardant, wherein (a) component zinc oxide and zinc borate are added in an amount of 40 to 60% by weight.
(B) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component 4A zeolite (e) component Period Flame retardant polyamide resin composition comprising 0.05 to 2.0 parts by weight of at least one compound selected from zeolites containing Group II or Group IV metals or potassium .