JP2008050509A - Flame retardant polyamide-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant polyamide-based resin composition without containing a chlorine compound and bromine compound, and capable of highly balancing mechanical characteristics, processability, workability and flame retardance. <P>SOLUTION: This flame retardant polyamide-based resin composition comprises based on (A) 100 pts.mass of a polyamide-based resin, (B) 5 to 70 pts.mass of an at least one kind selected from a phosphazene compound and phosphinic acid salt, and (C) 1 pt.mass to 20 pts.mass of a polycarbonate-based resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyamide resin composition which does not contain chlorine, bromine and antimony compounds, has a low environmental load, is highly flame-retardant, and has excellent workability and appearance of a molded product.

Among engineering resins, polyamide resins are widely used in electronic / electrical applications, OA equipment applications, automotive applications, etc. due to their high heat resistance and extremely good molding fluidity. Is required, and a flame-retardant polyamide resin composition is frequently used.
As a technique for making a polyamide resin flame retardant, a melamine cyanurate is used as a flame retardant for a polyamide resin without a filler, and brominated polystyrene and antimony oxide are used as a flame retardant for a polyamide resin added with glass fiber or an inorganic filler. Is the mainstream. The flame retardant polyamide resin with no filler does not use halogen, so the environmental impact is small. In this respect, it can be said to be an excellent flame retardant method, but the flame retardancy of melamine cyanurate may be insufficient, resulting in improved performance. In some cases, it may be required.

  Polyamide resins are subject to cracking in the dry state immediately after molding in winter, and the change in water absorption due to humidity changes corresponding to seasonal changes throughout the year becomes a problem. In order to improve the cracking, it is considered effective to add an impact strength imparting agent such as an elastomer, and it is considered to add a resin that does not absorb water such as polypropylene to change the water absorption dimension. When a resin such as an elastomer or polypropylene is added, it is difficult to make the polyamide resin flame-retardant. With the current melamine cyanurate, it is difficult to improve the flame retardancy to a level that achieves UL94V-0.

  In the filler-added polyamide resin, since the filler acts as a candle core and accelerates combustion, melamine cyanurate still has a shortage of flame retardancy and must use a halogen-based flame retardant. Non-halogen flame retardants other than melamine cyanurate also have practical problems such as bleed out due to thermal decomposition, hydrolysis, etc. because they do not have sufficient flame resistance, and a more advanced flame retardant method is required. It was done.

Patent Document 1 discloses a resin flame-retardant method in which a phosphazene compound and an aromatic resin are added to a base resin. However, when a polyamide-based resin is used as the base resin, there are problems such as poor flame retardant and other component dispersion in the polyamide-based resin, bleeding during melt-kneading, and poor mold release during molding. There was a possibility.
JP 2003-342482 A

  An object of the present invention is to provide a flame retardant polyamide-based resin composition which does not contain chlorine, bromine and antimony compounds and is excellent in various properties such as flame retardancy, mechanical properties and processability.

As a result of intensive studies to solve the above problems, the present inventors have greatly promoted the formation of a carbonized layer during high-temperature heating by adding a phosphorus-based flame retardant and a polycarbonate-based resin to a polyamide-based resin. The inventors have found that a flame-retardant polyamide-based resin composition having excellent flame retardancy and excellent mechanical properties and processability can be obtained, and the present invention has been achieved.
That is, the present invention
1. (A) The total of at least one compound selected from the group consisting of a phosphazene compound and a phosphinate is 5 to 70 parts by mass with respect to 100 parts by mass of the polyamide resin, and (C) 1 to 20 parts by mass of the polycarbonate resin. A flame-retardant polyamide resin composition comprising three parts of a component,
2. (B) The flame-retardant polyamide-based resin composition according to 1 above, wherein the component is a phosphazene compound,
3. (D) The flame-retardant polyamide resin according to the above 1 or 2, further comprising 10 to 150 parts by mass in total of at least one resin selected from the group consisting of a polyphenylene ether resin and a phenol resin Composition,
4). (E) The flame retardant polyamide resin composition according to any one of 1 to 3 above, further comprising 10 to 200 parts by mass of a filler,
5. The molded object which consists of a resin composition in any one of said 1-4,
It is.

  The flame-retardant polyamide-based resin composition of the present invention is a polyamide-based resin composition that does not contain chlorine, bromine, and antimony compounds, has excellent mechanical properties, workability, and processability, and has high flame retardancy.

The present invention is described in detail below.
In the present invention, (A) the polyamide-based resin is not limited to at least one selected from (B) a phosphazene compound and a phosphinate, and (C) a polycarbonate-based resin is combined to generate bleed during extrusion. It was found that it was possible to suppress, further improve the releasability at the time of molding, and to impart excellent flame retardancy, thereby completing the present invention.
Hereinafter, various components used in the present invention will be described.
(A) Polyamide-based resin The polyamide-based resin used in the present invention is composed of an amine and a dicarboxylic acid, and conventionally known ones are suitably used and are not particularly limited.

  Examples of amines include hexamethylene diamine, pentamethylene diamine, 2-methylpentamethylene diamine, octamethylene diamine, 2-methyl octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylylene. Range amine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2- Dimethyl-1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5-dimethyl-1,7-heptanediamine, 2- Methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanedia 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8 -Octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1 , 8-octanediamine, 5-methyl-1,9-nonanediamine, isophoronediamine, norbornanedimethylamine, tricyclodecanedimethylamine, etc., and one or more of these can be used.

  Dicarboxylic acids include adipic acid, octamethylene dicarboxylic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 3,3-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4′-biphenyldicarboxylic acid, 4,4 '-Oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4 Examples of amino acids such as' -dicarboxylic acid, decamethylene dicarboxylic acid, undecamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid, pentamethyleneaminocarboxylic acid, decamethyleneaminocarboxylic acid, undecamethyleneaminocarboxylic acid, These can be used alone or in combination of two or more.

Moreover, as a lactam which synthesize | combines a polyamide-type resin, a caprolactam, a laurolactam, etc. can be used conveniently, These can use 1 type, or 2 or more types.
Examples of the resulting polyamide-based resin include polyamide 6, polyamide 66, polyamide 66/6, polyamide 46, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 6I, polyamide 6T, polyamide 9T, polyamide MXD6, polyamide 66. / 6I, polyamide 66 / 6T, polyamide 6T / 6I, polyamide 66 / 6I / 6, polyamide 66 / 6I / 11, polyamide 66 / 6I / 12, polyamide 66 / 6I / 610, polyamide 66 / 6I / 612, polyamide M5T , Polyamide 9T, polyamide 10T, polyamide 12T, and the like. These can be used alone or as a mixture of two or more.

  The polymerization reaction method of the polyamide resin of the present invention is not particularly limited as long as it is a general polyamide polymerization method. Usually, when polymerizing from a diamine and a dicarboxylic acid, an equivalent salt of an amine and an acid is made, or an equivalent equivalent is added separately to carry out a polycondensation reaction. When polymerizing from a lactam, a small amount of water, an amino acid, a mineral acid, etc. are added as a ring-opening catalyst, and a condensation polymerization reaction is carried out. Melt polymerization in which a monomer or an aqueous monomer solution is heated and polymerization is carried out while removing water is widely used industrially. Here, it is well known to add an amine or an acid as a polymerization degree control agent. There is also a method in which the monomer is heated in the presence of water in a closed container to prepolymerize the oligomer, and this is post-polymerized with a kneader or an extruder. Depending on the type of monomer, there is also a method of polymerizing from the monomer stage with a kneader or an extruder.

  In producing the polyamide of the present invention, phosphoric acid, phosphorous acid, hypophosphorous acid, their salts or esters can be added as a catalyst. Examples of the salt or ester include phosphoric acid, phosphorous acid or hypophosphorous acid and metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. Salt; ammonium salt of phosphoric acid, phosphorous acid or hypophosphorous acid; ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester of phosphoric acid, phosphorous acid or hypophosphorous acid , Stearyl ester, phenyl ester and the like.

In the present invention, when a polyamide-based resin having an aromatic ring is used, the aromatic ring component content in the main chain is preferably 5 to 75% by mass, more preferably 25 to 65% by mass, and still more preferably 31 to 55% by mass. A polyamide-based resin is preferably used. The aromatic ring component content in the main chain is represented by the formula (1).
Aromatic ring component content (φ) = (total atomic weight of carbon and hydrogen constituting the aromatic ring) / (total atomic weight of repeating units of polyamide) × 100 (%) (1)
In the case of copolyamide, it is obtained by the formula (2).
Aromatic ring component content (φ) = Σφi × αi × 100 (%) (2)
φi: aromatic ring component content of the i-th copolyamide component αi: mass fraction of the i-th copolyamide component with respect to the total amount of polyamide

  Specifically, polyamide 6I, polyamide 6T, polyamide 9T, polyamide MXD6, polyamide 66 / 6I, polyamide 66 / 6T, polyamide 6T / 6I, polyamide 66 / 6I / 6, polyamide 66 / 6I / 11, polyamide 66 / 6I / 12, polyamide 66 / 6I / 610, polyamide 66 / 6I / 612, polyamide 9T, polyamide 10T, polyamide 12T, and the like. These can be used singly or as a mixture of two or more.

  As the polyamide resin used in the present invention, a polyamide resin having a polymerization degree within a specific range, that is, a relative viscosity is preferable. A preferred relative viscosity is 1.5 to 4.0, more preferably 1.8 to 3 for a semi-aromatic polyamide as measured at a concentration of 1% in 98% sulfuric acid and a temperature of 25 ° C. according to JIS K 6810. .0 range. In view of material strength, fluidity, moldability, product appearance, etc., it is preferable to have an appropriate relative viscosity.

  The end of the polyamide of the present invention may be capped, and the end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide. Acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, etc. can be used. Carboxylic acid or monoamine is preferable, and monocarboxylic acid is more preferable from the viewpoint of easy handling.

  The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Aliphatic monocarboxylic acids such as pelargonic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, pivalic acid, isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid Carboxylic acids; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. These can be used alone or in combination of two or more. Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, tridecylic acid, myristic acid, in terms of reactivity, stability of the sealing end, price, etc. Palmitic acid, isopalmitic acid, stearic acid, isostearic acid and benzoic acid are preferred.

  The monoamine used as a terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, Aliphatic monoamines such as stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine . These 1 type or 2 types or more can be used. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, high boiling point, stability of the sealing end and price.

(B) component In this invention, a phosphazene compound and a phosphinate can be used suitably, These can be used individually by 1 type or in mixture of 2 or more types.
(B-1) Phosphazene Compound As the phosphazene compound that can be used in the present invention, conventionally known compounds can be widely used. The structure of the phosphazene compound preferably used in the present invention is described in, for example, “Inorganic Polymers” Pretice-Hall International, Inc., 1992, p61-p140, by James E. Mark, Harry R. Allcock, Robert West. . For example, a cyclic phosphazene compound represented by the following general formula (1) and / or a chain phosphazene compound represented by the following general formula (2) can be mentioned, and among them, 95% by mass or more of a phosphazene compound having these structures is contained. Those are preferred.

(In the formula, n is an integer of 3 to 25, m is an integer of 3 to 10,000, and the substituent X is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 11 carbon atoms, a fluorine atom, A substituent selected from an aryloxy group having a substituent represented by the following general formula (3), a naphthyloxy group, an alkoxy group having 1 to 6 carbon atoms and an alkoxy-substituted alkoxy group, The hydrogen on the substituent may be partially or entirely substituted with fluorine, a hydroxyl group, or a cyano group, and Y in the formula is —N═P (O) ( X) or -N = P (X) ₃ and Z represents -P (X) ₄ or -P (O) (X) ₂ )

(In the formula, Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, a phenyl group, or a hetero-element-containing group. Represents a substituent selected from the group consisting of the inside.)
These compounds may be used alone or as a mixture of two or more.
One factor that determines flame retardancy is the concentration of phosphorus atoms contained in the molecule. In the phosphazene compound, the chain phosphazene having a chain structure has a substituent at the molecular end, so that the phosphorus content is lower than that of the cyclic phosphazene compound, and when the same amount is added, the cyclic phosphazene than the chain phosphazene compound. Since the compound is considered to have a higher flame retardancy-imparting effect, the use of a phosphazene compound having a cyclic structure is preferred in the present invention, and a compound containing 95% by mass or more of a cyclic phosphazene compound is preferred.

  The substituent X in the phosphazene compound is not particularly limited, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, tert-butyl group, n-amyl group, Alkyl group such as isoamyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,5-dimethylphenyl Group, aryl group such as 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-tertiarybutylphenyl group, 2-methyl-4-tertiarybutylphenyl group, methoxy group, ethoxy group, n- Propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, s-butyloxy group, n-amyloxy group, isoamido Alkoxy groups such as ruoxy group, tert-amyloxy group, n-hexyloxy group, alkoxy substituted alkoxy groups such as methoxymethoxy group, methoxyethoxy group, methoxyethoxymethoxy group, methoxyethoxyethoxy group, methoxypropyloxy group, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 3,4-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2, 4,5-trimethylphenoxy group, 3,4,5-trimethyl Enoxy group, 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2,6-diethylphenoxy group, 2,5-diethylphenoxy group, 2,4-diethylphenoxy group, 3,5-diethyl Phenoxy group, 3,4-diethylphenoxy group, 4-n-propylphenoxy group, 4-isopropylphenoxy group, 4-tertiarybutylphenoxy group, 2-methyl-4-tertiarybutylphenoxy group, 2-phenylphenoxy group , Alkyl-substituted phenoxy groups such as 3-phenylphenoxy group, 4-phenylphenoxy group, aryl-substituted phenoxy groups, naphthyl groups, naphthyloxy groups, etc., and part or all of hydrogen of these groups is fluorine and / or hetero It may be replaced with a group containing an element. Here, the group containing a hetero element is a group containing B, N, O, Si, P, and S atoms. For example, an amino group, an amide group, an aldehyde group, a glycidyl group, a carboxyl group , Groups containing a hydroxyl group, a cyano group, a mercapto group, a silyl group, and the like.

  Further, these compounds may be cross-linked by a cross-linking group selected from the group consisting of a phenylene group, a biphenylene group and a group (4) shown below by the technique disclosed in International Publication No. WO 00/09518. .

(In the formula, X represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and y represents 0 or 1).
The phosphazene compound having such a crosslinked structure is specifically produced by reacting a dichlorophosphazene oligomer with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound. These alkali metal salts are added to the dichlorophosphazene oligomer slightly in excess of the theoretical amount.
These phosphazene compounds may be used alone or as a mixture of two or more.

  The phosphazene compound is a mixture of different structures such as cyclic trimers and cyclic tetramers and chain phosphazenes, but the processability when added to the resin is cyclic trimer and tetramer content. Is higher, more specifically, a phosphazene compound containing 80% by mass or more of a cyclic trimer and / or tetramer compound, more preferably 85% by mass or more of a trimer and / or tetramer compound. More preferred is a phosphazene compound containing 93% by mass or more.

In the present invention, the trimer is preferably 70% by mass or more, more preferably the trimer is 76% by mass or more, still more preferably the trimer is 80% by mass or more, and particularly preferably the trimer is 85% by mass or more. When the phosphazene compound contained is used, a particularly excellent flame retardancy imparting effect can be obtained, and an excellent mechanical property improving effect can be obtained.
The phosphazene compound varies depending on the type and structure of the substituent, but can take various forms such as liquid, waxy, solid, etc., as long as it does not impair the effects of the present invention. It does not matter in shape. If the solid state, the bulk density is preferably 0.45 g / cm ³ or more, more preferably 0.45 g / cm ³ or more and 0.75 g / cm ³ or less.
The alkali metal components such as sodium and potassium contained in the phosphazene compound are each preferably 200 ppm or less, more preferably 50 ppm or less, and still more preferably the total alkali metal component is 50 ppm or less.

In addition, the content of the phosphazene compound in which at least one of the substituents X in the general formula (1) is a hydroxyl group, that is, the phosphazene compound containing a P—OH bond is preferably less than 1% by mass, and chlorine The content is preferably 1000 ppm or less, more preferably 500 ppm or less, and still more preferably 300 ppm or less.
A phosphazene compound in which at least one of the substituents X is a hydroxyl group may have an oxo-form structure represented by the following general formula (5), and such an oxo-form compound is also 1 like a hydroxyl group-containing phosphazene compound. It is desirable that it is less than mass%. The same applies to phosphazene compounds having a chain structure represented by the general formula (2).

(In the formula, a + b = n, n is an integer of 3 or more, and X in the formula represents an aryloxy group and / or an alkoxy group which may be the same or different.)
The water content contained in the phosphazene compound suitably used in the present invention is preferably 1000 ppm or less, more preferably 800 ppm or less, more preferably 650 ppm or less, and further 500 ppm, considering electric characteristics, hydrolysis resistance and the like. Hereinafter, it is particularly preferably 300 ppm or less, and the acid value measured based on JIS K6751 is preferably 1.0 or less, more preferably 0.5 or less.
In the phosphazene compound preferably used in the present invention, from the viewpoint of hydrolysis resistance and moisture absorption resistance, solubility in water (mixed sample with distilled water at a concentration of 0.1 g / mL, and 1 hour at room temperature) The amount of the sample dissolved in water after stirring) is preferably 100 ppm or less, more preferably 50 ppm, and still more preferably 25 ppm or less.

In the phosphazene compound used in the present invention, in consideration of flame retardancy, low smoke generation during combustion, low volatility, etc. when used in combination with the component (A), ascending in an inert gas atmosphere by TGA. The difference in temperature when the mass is reduced by 50% by mass and when the mass is reduced by 5% by mass when heated from room temperature to 600 ° C. at a temperature rate of 10 ° C./min is preferably 20 to 150 ° C., more preferably 20 to 120 ° C. ° C. Moreover, when it uses with respect to resin, when the flame retardance efficiency by the carbonization layer formation promotion effect at the time of combustion is considered, the temperature at the time of 50 mass% mass reduction is 320-500 degreeC, More preferably, 350 ~ 460 ° C.
The phosphazene compound suitably used in the present invention can take various forms such as liquid, waxy, solid, etc., depending on the type and structure of the substituents contained, and the effects of the present invention can be achieved. Any shape can be used as long as it is not damaged. When it is necessary to consider handleability, workability, etc., a solid state is preferable.

(B-2) Phosphinic acid salt The phosphinic acid salt that can be used in the present invention is at least one selected from phosphinic acid salts represented by the following general formula (6) and / or (7) and / or polymers thereof. It is.

(Wherein Q ₁ , Q ₂ , Q ₃ , and Q ₄ represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group, and an aryloxy group, ₅ represents a group selected from alkylene having 1 to 18 carbon atoms, arylalkylene, arylene, alkylarylene, and diarylene, wherein n and m are each an integer of 1 to 3, and x is 1 or 2. M represents a group selected from a metal atom, an amide, an ammonium group, and a melamine derivative after the fourth period of the periodic table, and when x is 2, it may be the same group or a different group.
Among the phosphinic acid salts used in the present invention, the phosphinic acid metal salt is produced in an aqueous solution using phosphinic acid and metal carbonate, metal hydroxide or metal oxide, and is essentially a monomeric compound. Depending on the reaction conditions, polymeric phosphinates with a degree of condensation of 1-3 are also included depending on the environment.

As phosphinic acid, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methylphenylphosphinic acid and And diphenylphosphinic acid.
The metal component is not particularly limited as long as it is a metal atom after the fourth period of the periodic table, but is preferably a metal element after the fourth period of the periodic table excluding alkali metals such as potassium and cesium. More preferably, a metal carbonate, a metal hydroxide, or a metal oxide containing magnesium, calcium, aluminum, tin, germanium, titanium, iron, zirconium, zinc, bismuth, strontium, or manganese is used. Particularly preferred is a metal carbonate, metal hydroxide or metal oxide containing calcium, magnesium, aluminum, titanium and / or zinc.

  Examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, Examples thereof include calcium diethylphosphinate.

  Further, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, titanium diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methylmethyln-propylphosphinate, methyl -Zinc n-propylphosphinate, titanium methyl-n-propylphosphinate, methandi (methylphosphinic acid) calcium, methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, methane (Methylphosphinic acid) titanium, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, benzene- 4- (dimethyl phosphinic acid) aluminum, benzene-1,4 (dimethyl phosphinic acid), zinc benzene-1,4 (dimethyl phosphinic acid) and titanium.

Also, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, titanium methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, diphenylphosphinic acid Examples thereof include zinc and titanium diphenylphosphinate. In particular, aluminum diethylphosphinate and zinc diethylphosphinate are preferable from the viewpoint of flame retardancy and electrical characteristics.
From the viewpoint of the mechanical strength of the molded product obtained by molding the composition of the present invention and the appearance of the molded product, the phosphinic acid salt particle size is preferably 100 μm or less, more preferably 50 μm or less. Use of a powder of 0.5 to 20 μm is particularly preferable because it not only exhibits high flame retardancy but also significantly increases the strength of the molded product.
Among the component (B) preferably used in the present invention, a phosphazene compound is particularly preferably used when it is necessary to consider hydrolysis resistance, handleability and processing fluidity.

(C) Polycarbonate resin The polycarbonate resin that can be suitably used in the present invention is preferably a polymer having a repeating unit represented by the following general formula (8).

(Ar in the formula is a divalent aromatic group having 4 to 200 carbon atoms. For example, phenylene, biphenylene, terphenylene, naphthylene, or a group represented by the following general formula (9): )

(In the formula, X is represented by -O-, -S-, -C (O)-, -C (O) O-, -C (O) NH-, the following general formula (10) or (11)). Group.)

(In the formula, R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, and the hydrogen atom on the substituent may be substituted with a fluorine atom.)

(Wherein R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, and the hydrogen atom on the substituent is substituted with a fluorine atom) May be.)
The polycarbonate resin that can be suitably used in the present invention may have a branched structure. Polyorganosiloxane-modified polycarbonate resins modified with organosiloxane can also be suitably used (for example, resins described in JP-A Nos. 6-100684 and 10-182832, etc.).
These may be used alone or in combination of two or more.

The terminal group of the polycarbonate resin is not particularly defined as long as the effects of the present invention can be obtained. Illustrative examples include alkyl groups, alkyl carbonate groups, aryl groups, aryl carbonate groups, and the like, and one or more groups can be bonded as terminal groups.
The molecular weight of the polycarbonate resin that can be suitably used in the present invention is not limited as long as it does not impair the effects of the present invention. Specifically, those having a polystyrene-reduced number average molecular weight of preferably 1000 to 100,000, more preferably 2000 to 70000, and still more preferably 5000 to 25000 can be suitably used. A polycarbonate resin having an appropriate molecular weight may be used as appropriate in accordance with characteristics particularly required when a resin composition is used.
A conventionally known method can be widely used as a method for producing a polycarbonate resin which can be suitably used in the present invention, and is not defined at all. If an example is given, what was manufactured by the phosgene method, the transesterification method, etc. can be used conveniently.

Component (D) In the present invention, polyphenylene ether resins and phenol resins can be added for the purpose of improving flame retardancy. These resins may be used alone or in combination of two or more. It may be used.
(D-1) Polyphenylene ether-based resin The polyphenylene ether resin that can be suitably used in the present invention is a homopolymer having a repeating unit represented by the following general formula (12) and / or (13), or a copolymer It is preferably a coalescence.

(Here, R ₁ and R ₂ independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen.)

(Here, R ₃ , R ₄ , R ₅ and R ₆ independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group and hydrogen. However, R ₅ and R ₆ are not hydrogen at the same time.)
Representative examples of polyphenylene ether-based homopolymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2, 6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) Ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl) And homopolymers such as -1,4-phenylene) ether.

Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methylphenylene ether described in JP-A-63-301222 and the like is preferable. A polyphenylene ether containing a unit or a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit as a partial structure is particularly preferred.
Here, the polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main monomer unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2 , 3,6-trimethylphenol and a copolymer of o-cresol, a copolymer of 2,6-dimethylphenol and bisphenol represented by the following general formula (14), and the like.

(Here, R ₇ , R ₈ , R ₉ , and R ₁₀ each independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen. In the formula, X represents —C (CH ₃ ) _{2. -, - SO 2 -, -} S-, or -O-, y is 0 or 1, z is 1 or 2).
In the present invention, a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a mercapto group, a silyl group, a hydroxyl group, or an anhydrous dicarboxyl group is grafted or copolymerized on part or all of the polyphenylene ether resin. A modified polyphenylene ether resin introduced by any method can be used as long as the object of the present invention is not impaired. These may be used alone or in combination of two or more.

  Modified polyphenylene ether resins obtained by modifying part or all of polyphenylene ether resins with unsaturated carboxylic acids or functional derivatives thereof are disclosed in JP-A-2-276823, JP-A-63-108059, JP-A-59. For example, it is produced by melt-kneading and reacting an unsaturated carboxylic acid or a functional derivative thereof with a polyphenylene ether resin in the presence or absence of a radical initiator. Alternatively, it is produced by dissolving polyphenylene ether and an unsaturated carboxylic acid or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in a solution.

  Examples of unsaturated carboxylic acids or functional derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene 1,2-dicarboxylic acid, and endo-cis-bicyclo (2.2.1). ) -5-heptene-2,3-dicarboxylic acid, etc., acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., esters of these monocarboxylic acids, amides, etc. Can be mentioned. In addition, a compound which is a saturated carboxylic acid but can be thermally decomposed itself at the reaction temperature when producing the modified polyphenylene ether to become a functional derivative used in the present invention can be used. An acid etc. are mentioned. These may be used alone or in combination of two or more.

  The molecular weight of the polyphenylene ether that can be used in the present invention is not limited as long as the effects of the present invention are not impaired. Specifically, those having a number average molecular weight of 500 to 30,000 can be suitably used. When it is necessary to obtain a composition particularly excellent in moldability, the number average molecular weight of the polyphenylene ether is preferably 500 or more and 5000 or less, more preferably 1200 or more and 4000 or less. When it is necessary to obtain a composition having particularly excellent heat resistance, it is preferable to use a polyphenylene ether having a number average molecular weight exceeding 5000. Polyphenylene ether having an appropriate molecular weight may be used as appropriate in accordance with characteristics particularly required when a resin composition is used.

(D-2) Phenolic Resin Conventionally known resins can be widely used as the phenolic resin used in the present invention. For example, a resol type phenol resin obtained by adding and condensing phenols and aldehydes with a basic catalyst, a novolak type phenol resin obtained by adding and condensing phenols and aldehydes with an acid catalyst, etc. Examples include phenol aralkyl resins and polyvinyl phenol resins. Among these, novolac type phenol resins are preferably used.

Preferable phenols include phenols having 1 to 4 alkyl groups having 1 to 10 carbon atoms as substituents, such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, etc. Examples of aldehydes used in the method include formaldehyde, acetaldehyde, and benzenes having a formyl group.
These phenolic resins may be used alone or in combination of two or more. These phenolic resins may be modified with cashew, oil, rubber or the like.
Phenol novolac resins include high-orthophenol novolac resins, in which many methylene bonds are bonded to the phenolic hydroxyl group at the ortho position, and random phenol novolac resins in which the ortho and para positions are mixed. Also included are triazine-modified phenol novolac resins copolymerized with triazines (melamine, benzoguanamine, etc.).

The polystyrene-reduced mass average molecular weight of the phenolic resin used in the present invention is not particularly limited, but in view of the balance between flame retardancy imparting effect, improvement of mechanical properties and workability, 2000-100000 are preferred. More preferably 2000 to 80000, still more preferably 2000 to 50000, and particularly preferably 3000 to 30000.
The phenolic resin used in the present invention has a total content of free monomers and dinuclears of 15% by mass of the total phenolic resin, considering the balance of flame retardancy, process fluidity, mechanical properties, low smoke generation, etc. Or less, more preferably 11% by mass or less. Further, those having a trinuclear component content of preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 7% by mass or less are suitably used.

In addition, when low volatility is particularly required, a reduced mass at 350 ° C. when heated from room temperature to 700 ° C. at an increase rate of 20 ° C./min in an inert gas atmosphere by TGA is preferably 15% by mass or less, More preferably, it is 12 mass% or less, More preferably, it is 10 mass% or less.
The method for producing such a phenol resin is not defined at all, but examples thereof include the methods described in JP-A No. 2004-323822 and JP-A No. 11-246643.

(E) Filler The flame retardant polyamide resin composition of the present invention can be blended with conventionally known fillers for the purpose of improving various properties such as mechanical properties. For example, titanium oxide, glass beads, glass flakes, glass fibers, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, potassium titanate, aluminum borate, magnesium borate, kenaf fiber, carbon fiber, alumina fiber, quartz fiber, etc. Examples include fibrous reinforcing agents and non-fibrous reinforcing agents. These may be used individually by 1 type, or may use 2 or more types together. Moreover, these may be coat | covered with organic substance, an inorganic substance, etc.

When glass fiber is used as the filler, it can be selected from long fiber type roving, short fiber type chopped strand, milled fiber, and the like. It is preferable to use a glass fiber that has been surface-treated for the resin used.
By blending the filler, the strength of the incombustible layer (or carbonized layer) generated during combustion can be further improved. The incombustible layer (or carbonized layer) once generated during combustion is less likely to be damaged, can exhibit stable heat insulation ability, and a greater flame retardant effect can be obtained. Further, high rigidity can be imparted to the material.

(Mixing ratio)
The blending ratio of each component in the flame-retardant polyamide resin composition of the present invention is (A) with respect to 100 parts by mass of the polyamide-based resin, considering the balance between flame retardancy imparting effect, mechanical properties, processability, and the like ( B) A total of at least one compound selected from the group consisting of a phosphazene compound and a phosphinate is 5 to 70 parts by mass, preferably 7 to 60 parts by mass, more preferably 10 to 50 parts by mass, (C) a polycarbonate resin. 1 to 20 parts by mass, preferably 2 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 2 to 10 parts by mass.

Further, the blending ratio in the case of using at least one resin selected from the group consisting of (D) polyphenylene ether resin and phenol resin is preferably 10 in total with respect to 100 parts by mass of (A) polyamide resin. -150 mass parts, More preferably, it is 10-120 mass parts, More preferably, it is 10-100 mass parts. When component (D) is a phenolic resin, the amount is particularly preferably 15 to 50 parts by mass.
Furthermore, the blending amount in the case of using the (E) filler is not particularly specified as long as the effect of the present invention can be exhibited. The blending amount for efficiently obtaining the above-mentioned effects by blending the filler is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, and still more preferably 100 parts by weight of the polyamide-based resin. It is 20-120 mass parts, Most preferably, it is 20-100 mass parts.

(Nitrogen compounds)
In the present invention, a nitrogen-containing compound may be added for the purpose of further enhancing the flame retardant effect.
f For example, tertiary amines such as triarylamine, dialkylarylamine, alkyldiarylamine, and quaternary ammonium salts, melamine, melam, melem, melon, methylene dimelamine, ethylene dimelamine, decamethylene dimelamine, 1,3-cyclohexyl dimelamine, 4,4′-diethylene dimelamine, diethylene trimelamine, benzoguanamine, dibenzoguanamine, succinoguanamine, methylguanamine, acetoguanamine, melamine resin, and the like, cyanuric acid salts and sulfates of the above compounds , Phosphate, borate, 2-dibutylamino-4,6-dimercapto-S-triazine, 2-N-phenylamino-4,6-dimercapto-S-triazine, 2,4,6-trimercapto-S -Triazine, triallyl cyanurate, And Li methallyl isocyanurate triazine compounds include polyphosphates and the like.

When heat resistance is particularly required, triazine compounds and polyphosphates are preferably used. Furthermore, when heat stability, volatility resistance, etc. are required, melamine condensates such as melam, melem, melon, etc., reaction products of the above triazine compounds with cyanuric acid, polyphosphates, especially the reaction of melamine with cyanuric acid Melamine cyanurate and polyphosphate which are products are preferably used. Further, a part or all of the hydroxyl group and / or amino group of the reaction product of the triazine compound and cyanuric acid may be substituted with another substituent.
The method for producing a melamine condensate such as melem, melam, melon and the like suitably used in the present invention is not particularly limited. As an example, melamine or a melamine salt can be obtained by self-condensation by heating to about 280 to 320 ° C. in an inert gas atmosphere or in a vacuum, without a catalyst or under an organic acid catalyst.

Melamine cyanurate preferably used in the present invention is an equimolar reaction product of melamine and cyanuric acid. For example, by stirring and mixing a melamine aqueous solution and a cyanuric acid aqueous solution at a temperature of about 90 to 100 ° C., and precipitating and filtering the product obtained by the reaction, it can be obtained as a white solid, and pulverized. It is preferable to use it in the form of fine powder. The said nitrogen-containing compound may be used individually by 1 type, and may be used as a 2 or more types of mixture. Moreover, these compounds do not necessarily need to be completely pure products, and some unreacted materials may remain.
Examples of the polyphosphate that is preferably used in the present invention include ammonium polyphosphate, melamine polyphosphate, and the like.

  For example, industrially available ammonium polyphosphates include THYEN S [manufactured by Taihei Chemical Sangyo Co., Ltd.], SUMISEPH P, SUMISEPH made by treating ammonium polyphosphate with melamine resin or the like to make it insoluble in water. PM [above, manufactured by Sumitomo Chemical Co., Ltd.], Exolit 462 (manufactured by Hoechst), AMGARD MC (manufactured by Albright and Wilson), FR CROS (manufactured by Budenheim Iberica), TERRAJU (Budenheim Iberica) Manufactured) and the like. Furthermore, Exolit VP IFR-23 (manufactured by Hoechst), SPINFLAM MF80 / PP, SPINFLAM MF82 / PP, SPINFLAM MF82 / PS (above, Montecati-) And the like).

Moreover, the polyphosphoric acid which comprises ammonium polyphosphate is what is called condensed phosphoric acid, and chain | strand-shaped polyphosphoric acid, cyclic | annular polymetaphosphoric acid, etc. are mentioned. In the present invention, the degree of condensation is not particularly defined as long as the effects of the present application can be obtained, but the degree of condensation is preferably 5 or more particularly when heat resistance is required.
The polyphosphoric melamine that can be used in the present invention means a melamine adduct formed from substantially equimolar amounts of melamine and the above-mentioned phosphoric acid, pyrophosphoric acid or polyphosphoric acid, and part of the acid functional group is free. You may be in the state.

  The melamine polyphosphate used in the present invention means a product obtained from a substantially equimolar reaction product of melamine and phosphoric acid, pyrophosphoric acid or polyphosphoric acid, and the production method is not particularly limited. Usually, melamine polyphosphate obtained by heat condensing melamine phosphate under nitrogen atmosphere can be mentioned. Specific examples of phosphoric acid constituting melamine phosphate include orthophosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid. Melamine polyphosphate obtained by condensing an adduct with acid and melamine using pyrophosphoric acid has a high effect as a flame retardant and is preferable. In particular, the degree of condensation n of melamine polyphosphate is preferably 5 or more from the viewpoint of heat resistance.

  Melamine polyphosphate may be an equimolar addition salt of polyphosphoric acid and melamine. Examples of polyphosphoric acid that form an addition salt with melamine include chain polyphosphoric acid called cyclic phosphoric acid and cyclic polymetaphosphoric acid. Can be mentioned. The degree of condensation n of these polyphosphoric acids is not particularly limited, but the degree of condensation n of the polyphosphoric acid used here is preferably 5 or more from the viewpoint of the heat resistance of the melamine polyphosphate addition salt. Such a melamine polyphosphate addition salt forms a mixture of melamine and polyphosphoric acid, for example, as an aqueous slurry, and mixes them well to form both reaction products in the form of fine particles. Then, the slurry is filtered, washed, dried, If necessary, it is a powder obtained by firing and pulverizing the obtained solid.

From the viewpoint of the mechanical strength of the molded product obtained by molding the composition of the present invention and the appearance of the molded product, the particle size of the melamine polyphosphate is preferably 100 μm or less, more preferably 50 μm or less. Use of a powder of 0.5 to 20 μm is particularly preferable because it not only exhibits high flame retardancy but also significantly increases the strength of the molded product.
The melamine polyphosphate is not necessarily completely pure, and some unreacted melamine, phosphoric acid, or polyphosphoric acid may remain. What contains 10-18 mass% as a phosphorus atom in a melamine polyphosphate has the phenomenon that a contaminating substance adheres to a shaping | molding die at the time of a shaping | molding process, and is especially preferable.
These nitrogen compounds may be used alone or in combination of two or more.
The addition amount of the nitrogen-based compound is not specified as long as the effect of the present invention can be exerted, but is preferably 1 to 150 parts by mass, more preferably 5 to 100 parts by mass of the (A) polyamide-based resin. 100 parts by mass, more preferably 10 to 80 parts by mass.

(Other flame retardants, flame retardant aids)
In the present invention, conventionally known non-halogen, non-antimony flame retardants, flame retardant aids and the like can be used in combination as long as the effects of the present invention can be achieved. Illustrative examples include metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, calcium aluminate, metal oxides such as copper oxide, iron oxide, zinc oxide, magnesium oxide, boric acid, zinc borate compounds, etc. Boron-containing compounds, silica, coal ash (fly ash), zeolite, silicate, polyorganosiloxane, silsesquioxane, silicon-containing compounds such as silicon resin, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, phenyl Phosphate esters such as cresyl phosphate, phenylxylenyl phosphate, cresyl xylenyl phosphate, condensed phosphates crosslinked with bisphenol A, bisphenol S, resorcin, hydroquinone, triarylphosphine, trialkylphosphine, etc. Was added to a tertiary phosphine or their oxides or sulfides such as fins or the like, to further improve the flame retardancy is also possible.

(Other resins)
The flame-retardant polyamide resin of the present invention can be used in combination with a conventionally known resin as long as the effects of the present invention are not impaired. The resin to be used is not limited at all, and a known curable resin, thermoplastic resin or the like is preferably used. For example, polypropylene resin, polyethylene resin, polystyrene resin, syndiotactic polystyrene resin, ABS resin, AS resin, biodegradable resin, polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polytrimethylene Polyalkylene arylate resins such as terephthalate and polyethylene naphthalate, unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, epoxy resins, cyanate resins, xylene resins, triazine resins, urea resins, melamine resins, benzoguanamine resins, urethane resins, Examples include oxetane resins, ketone resins, alkyd resins, furan resins, styrylpyridine resins, silicone resins, and synthetic rubbers.
Other resins that can be used in the present invention may be used singly or in combination of two or more resins.

(Additive)
In order to impart other characteristics such as rigidity and dimensional stability to the flame-retardant polyamide resin composition of the present invention, other additives such as plasticizers and antioxidants are within the range not impairing the effects of the present invention. , Stabilizers such as UV absorbers, light stabilizers, curing agents, curing accelerators, antistatic agents, conductivity imparting agents, stress relaxation agents, mold release agents, crystallization accelerators, hydrolysis inhibitors, lubricants, Impact imparting agent, slidability improver, compatibilizer, nucleating agent, reinforcing agent, reinforcing agent, flow modifier, dye, sensitizer, coloring pigment, rubbery polymer, thickener, anti-settling agent, An anti-sagging agent, an antifoaming agent, a coupling agent, an antirust agent, an antibacterial / antifungal agent, an antifouling agent, a conductive polymer and the like can be added.

(Mixing order)
The blending order of each component in the flame-retardant polyamide resin composition of the present invention is not particularly defined as long as the effect of the present invention can be achieved. All the components may be mixed and used in advance, or may be mixed and used in order as appropriate.

(Mixing method)
The blending method of the flame retardant polyamide resin composition of the present invention is not particularly defined as long as the effect of the present invention can be achieved. For example, it can be kneaded and produced using a kneader such as an extruder, a heating roll, a kneader, a roller mixer, a Banbury mixer and the like. Among these, kneading with an extruder is preferable in terms of productivity. The kneading temperature may be according to the preferred processing temperature of the base resin, and as a guideline, it is preferably in the range of 140 to 340 ° C, more preferably in the range of 180 to 330 ° C.

  In addition, the molded product of the composition of the present invention has a plate shape, a rod shape, a spherical shape, a sheet shape, a film shape, a hollow shape, a gas fine dispersion shape, a foam shape, a fiber shape, a pellet shape, etc. Can be widely used. These moldings can be molded by known methods such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, press molding, extrusion molding, foam molding, film molding, and the like. Secondary processing molding methods such as pressure forming and vacuum forming can also be used, and preferred methods can be used depending on the appropriateness of each resin.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following examples.
(1) Flame retardance Based on UL-94 vertical combustion test, measured using an injection molded test piece with a thickness of about 0.8 mm. Evaluate the presence or absence of absorbent cotton ignition by droppings. Moreover, the average burning time at the time of the 1st flame contact in five test pieces and the presence or absence of cotton ignition at the time of the first flame contact are evaluated.
(2) Bleed at the time of extrusion Using a ZSK-25 twin screw extruder (manufactured by Werner & Frederer), melt-kneading under the conditions of the following examples, and cooling the resulting strand in a water bath Visually observe the amount of oil film coming out and evaluate.
○: No oil film is observed ×: Oil film is seen

(3) Releasability Molding test of length 128mm x width 12.8mm x thickness 0.79mm using PS-40E molding machine manufactured by Nissei Plastic Industry Co., Ltd. Molded a piece, ○ when there was no problem with mold separation of the runner part during 20 shot molding, △ when there was a molded piece with bad mold separation, △ with a bad mold separation with all molded pieces Observe and evaluate visually.
Examples 1-5, Example 7, Comparative Example 1: Cylinder temperature 270 ° C., mold temperature 80 ° C.
Example 6: Cylinder temperature 315 ° C, mold temperature 90 ° C.
Example 8: Cylinder temperature 280 ° C, mold temperature 80 ° C.

Each component used in Examples and Comparative Examples is as follows.
(A) Polyamide resin (A-1)
Polyamide 66 resin (Leona 1300; manufactured by Asahi Kasei Chemicals Corporation)
(A-2)
664 g (4.0 mol) terephthalic acid, 633 g (4.0 mol) 1,9-nonanediamine, 2.92 g (0.024 mol) benzoic acid, 0.13 g (0.0012 mol) sodium hypophosphite monohydrate and 1400 g of distilled water was placed in an autoclave having an internal volume of 5.0 liters and purged with nitrogen. The internal temperature was raised to 260 ° C. over 1 hour 30 minutes with stirring. At this time, the autoclave was pressurized to 4.0 MPa. Thereafter, water vapor was gradually extracted up to 320 ° C., and the reaction was carried out while maintaining the pressure at 4.0 MPa. Next, the pressure was reduced to normal pressure over 90 minutes, and the polymer was collected from the autoclave discharge valve. The obtained pulverized polymer was dried at 90 ° C. for 24 hours under a nitrogen stream. ηr = 2.7.

（Ｂ−２）ホスファゼン化合物
２，６−キシレノールのカリウム塩及びフェノールのカリウム塩をクロロホスファゼン（下記一般式（１）においてＸ＝Ｃｌであり、ｎ＝３が９４．２ｗｔ％、ｎ＝４が４．４ｗｔ％、ｎ≧５が１．４ｗｔ％）と反応させて得られたフェノキシキシレノキシホスファゼン。推定組成が［Ｎ＝Ｐ（ＯＸｙ−２，６）_0.6（ＯＣ₆Ｈ₅）_0.4］。酸価０．１２
（Ｂ−３）ホスファゼン化合物
クレゾールのカリウム塩及びフェノールのカリウム塩をクロロホスファゼン（上記一般式（１）においてＸ＝Ｃｌであり、ｎ＝３が９４．２ｗｔ％、ｎ＝４が４．４ｗｔ％、ｎ≧５が１．４ｗｔ％）と反応させて得られたフェノキシトリルオキシホスファゼン。推定組成が［Ｎ＝Ｐ（ＯＣ₆Ｈ₄Ｍｅ）_0.4（ＯＣ₆Ｈ₅）_0.6］。酸価０．１９ (B) Component (B-1) Phosphazene Compound Phenoxyphosphazene in which n = 3 is 93.6% by mass, n = 4 is 4.0% by mass, and n ≧ 5 is 2.4% by mass in the following chemical formula (15) . 5% weight loss temperature: 336 ° C., 50% weight loss temperature: 398 ° C., 500 ° C. Residue amount: 4.7 mass%, acid value: 0.17, water content: 182 ppm.

(B-2) Phosphazene Compound A potassium salt of 2,6-xylenol and a potassium salt of phenol are chlorophosphazene (in the following general formula (1), X = Cl, n = 3 is 94.2 wt%, and n = 4 is 4.4 wt%, n ≧ 5 is 1.4 wt%), and obtained by reaction with phenoxylenoxyphosphazene. The estimated composition is [N = P (OXy-2,6) _0.6 (OC ₆ H ₅ ) _0.4 ]. Acid value 0.12
(B-3) Phosphazene Compound A potassium salt of cresol and a potassium salt of phenol are chlorophosphazene (in the above general formula (1), X = Cl, n = 3 is 94.2 wt%, and n = 4 is 4.4 wt%. Phenoxytolyloxyphosphazene obtained by reacting with n ≧ 5 of 1.4 wt%. The estimated composition is [N = P (OC ₆ H ₄ Me) _0.4 (OC ₆ H ₅ ) _0.6 ]. Acid value 0.19

(C) Polycarbonate resin Caliber 301-10 (manufactured by Sumitomo Dow Co., Ltd.)
(D) Component (D-1)
Phenol novolac resin (PR-50731; manufactured by Sumitomo Bakelite Co., Ltd.)
(D-2)
Phenol novolac resin (PR-55307; manufactured by Sumitomo Bakelite Co., Ltd.)
(D-3)
Phenol aralkyl resin (XL-225; manufactured by Mitsui Chemicals, Inc.)
(D-4)
Biaxial extrusion by blending 0.5 parts by weight of maleic anhydride with 100 parts by weight of poly (2,6-dimethyl-1,4-phenylene ether) having a ηsp / c of 0.41 measured with a chloroform solution at 30 ° C. Maleic anhydride-modified polyphenylene ether obtained by kneading and extruding at 330 ° C. and 300 rpm in a machine.

(E) Filler Glass fiber (GF) T-275 (manufactured by Nippon Electric Glass Co., Ltd.)
(Other ingredients)
・ Melamine cyanurate (MCA) MCA C-0 (Mitsubishi Chemical Corporation)
-Anti-drip agent PTFE 6C-J (Mitsui DuPont Fluorochemical Co., Ltd.)

[Examples 1 to 8, Comparative Example 1]
Using a ZSK-25 twin-screw rotary extruder (manufactured by Werner & Frederer) with one supply port on each of the upstream side and the downstream side, the set temperature of the heating cylinder was 275 ° C. (Examples 1 to 5 and Examples) Set to Example 7, Comparative Example 1) or 315 ° C. (Example 6), 280 ° C. (Example 8), and mix and feed each component other than GF from the upstream supply port at the ratio shown in Table 1, GF was supplied from the downstream supply port in the amount shown in Table 1, melt-kneaded at a screw speed of 300 rpm, and the strand was cooled and cut to obtain resin composition pellets.
Next, the obtained resin composition pellets were molded into physical property test pieces with an injection molding machine, and subjected to physical property tests according to the above test methods. The results shown in Table 1 were obtained.

  The flame-retardant polyamide-based resin composition according to the present invention includes an electrical / electronic device component such as a coil bobbin, a flyback transformer, a connector, and a polarization yoke, a printed wiring board, a printed board, a sealant, an electrical insulating material, and an electrical coating agent. , Laminates, high-speed computing varnishes, advanced composite materials, electric wires, antenna agents, cables, high-performance molding materials and other electrical and electronic materials, paints, adhesives, coating materials, tableware, buttons, textile and paper treatment agents, Decorative plate, UV curable ink, sealant, synthetic leather, heat insulating buffer material, waterproof coating material, anti-corrosion lining, mold binder, lacquer, paint, ink modifier, resin modifier, aircraft interior agent, composite material Most suitable for matrix, household goods, OA equipment, AV equipment, battery electrical equipment, lighting equipment, automotive parts use, housing use, ETC, ITC, mobile phone etc. They are used to.

Claims (5)

  (A) 5 to 70 parts by mass in total of at least one compound selected from the group consisting of (B) phosphazene compounds and phosphinates with respect to 100 parts by mass of the polyamide resin, and (C) 1 to 20 parts by mass of the polycarbonate resin. A flame-retardant polyamide resin composition comprising three parts of the component.   The flame retardant polyamide resin composition according to claim 1, wherein the component (B) is a phosphazene compound.   The flame retardant polyamide system according to claim 1 or 2, further comprising (D) 10 to 150 parts by mass in total of at least one resin selected from the group consisting of a polyphenylene ether resin and a phenol resin. Resin composition.   Furthermore, (E) 10-200 mass parts of fillers are contained, The flame-retardant polyamide-type resin composition as described in any one of Claims 1-3 characterized by the above-mentioned.   The molded object which consists of a resin composition as described in any one of Claims 1-4.