JP2014024946A - Flame-retardant polyamide resin composition and moldings of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polyamide resin composition excellent in terms of workability and realizing excellent flame retardances of thin-flesh portions or thin-film portions of thin-flesh moldings or thin-film moldings obtained therefrom.SOLUTION: The composition includes a polyamide resin (A) and a phosphorus atom-containing oligomer (B) expressed by the following structural formula (1).

Description

  The present invention relates to a polyamide resin composition excellent in flame retardancy, heat resistance and molding processability of the resulting cured product, and a molded product thereof.

Polyamide resins are widely used in electrical and electronic materials, OA equipment, automobile members and the like because of their high heat resistance and extremely good molding fluidity. Since flame retardancy is often required for these applications, flame retardant polyamide resin compositions are generally used. In addition, due to the recent trend of thinning and thinning, it is expected that flame retardancy will be efficiently obtained even for thin-walled molded products.
As a technique for flame-retarding a polyamide resin, a technique using melamine cyanurate as a flame retardant (see Patent Document 1 below), or a technique using a phosphorous compound phosphazene or phosphinic acid flame retardant (described below) Patent Document 2) is known.
The method using melamine cyanurate represented by Patent Document 1 does not use halogen, and therefore has a low environmental load. In this respect, it can be said to be an excellent flame retardant method. However, the flame retardancy is not sufficient, and with conventional melamine cyanurate, it is difficult to improve the flame retardancy to the level that achieves UL94V-0, and also causes a bleed out due to thermal decomposition, hydrolysis, etc. There are many problems in practical use.
Further, the technique using a phosphazene-based or phosphinic acid-based flame retardant described in Patent Document 2 relates to a method for flame-retarding a resin in which a phosphazene compound and an aromatic resin are added to a base resin. However, while workability such as bleed at the time of melt kneading and releasability at the time of molding is good and a certain flame retardancy is obtained, in recent years, as molded products are becoming smaller and thinner, The current situation is that the flame retardancy of the thin-walled parts of molded products is still insufficient.

JP 2003-342482 A JP 2008-50509 A

  Accordingly, the problem to be solved by the present invention is a flame-retardant polyamide resin composition that is excellent in workability at the time of molding, and has excellent flame retardancy in a thin-walled molded product, a thin-walled portion of the molded product, and a thin-film portion, And providing a molded body thereof.

  As a result of intensive investigations to solve the above-mentioned problems, the present inventors have reacted a phosphorus atom-containing compound typified by HCA with an o-hydroxybenzaldehyde compound and oligomerized the phosphorus atom-containing phenolic oligomer obtained from polyamide. It has been found that by using it as a flame retardant for resin, it exhibits excellent heat resistance and processability, and also exhibits excellent flame retardancy even in thin-walled molded products, thin-walled parts of molded products, or thin-film parts. The present invention has been completed.

That is, the present invention provides a polyamide resin (A), and
The following structural formula (1)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表し、ｎは繰り返し単位で１以上の整数であり、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit and is an integer of 1 or more, and X is Structural formula (x1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、また、該構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表されるリン原子含有オリゴマー（Ｂ）を必須成分とすることを特徴とする難燃性ポリアミド樹脂組成物に関する。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. It is related with the flame-retardant polyamide resin composition characterized by making the phosphorus atom containing oligomer (B) represented by this into an essential component.

  The present invention further relates to a molded article obtained by molding the flame retardant polyamide resin composition.

  According to the present invention, a flame-retardant polyamide resin composition that is excellent in heat resistance and processability, and that has excellent flame retardancy in a thin-walled molded product, a thin-walled portion of a molded product, or a thin-film portion, and a molded body thereof Can be provided.

1 is a GPC chart of the phosphorus atom-containing oligomer (A-1) obtained in Synthesis Example 1. FIG.

  Hereinafter, the present invention will be described in detail.

  Examples of the polyamide resin (A) used in the present invention include an amino acid polymer (a1), a lactam ring-opening polymer (a2), and a diamine-dicarboxylic acid polymer (a3).

  Here, examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like. Examples of the lactam include ε-caprolactam and ω-laurolactam.

Examples of the amine constituting the polymer (a3) include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2. , 4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1 -Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane,
Various aliphatic, alicyclic, and aromatic diamines such as bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, su (aminopropyl) piperazine, and aminoethylpiperazine Is mentioned.

  On the other hand, the dicarboxylic acid constituting the polymer (a3) includes adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5 -Aliphatic, alicyclic and aromatic dicarboxylic acids such as methyl isophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid and hexahydroisophthalic acid.

  In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

  Specific examples of the polyamide resin (A) include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide ( Nylon 610), polyhexamethylene dodecanamide (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycapro Amide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide / Ricaproamide copolymer (nylon 66 / 6I / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I) ), Polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene Adipamide (nylon XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polynonamethylene terephthalate Taruamido (nylon 9T), and the like and mixtures thereof or copolymers.

  Among these, polyhexamethylene adipamide (nylon 66) (melting point 265 ° C.) and polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T) (melting point 300 ° C.) are excellent in heat resistance. In view of strength, etc., polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6) and polycaproamide (nylon 6) are high in inorganic fillers. This is preferable in terms of excellent appearance when filling.

  The degree of polymerization of the polyamide resin is not particularly limited, but 1 g of polyamide resin is dissolved in 100 mL of 98% concentrated sulfuric acid solution according to JISK6810, and the relative viscosity measured at 25 ° C. is in the range of 1.7 to 4.0. A range of 1.8 to 3.5 is particularly preferable. A relative viscosity within this range is preferable from the viewpoint of excellent moldability and mechanical properties.

  Moreover, when using the polyamide resin which has an aromatic ring for the said polyamide resin, it is preferable that the aromatic ring content rate in a principal chain is the range of 5-75 mass%, especially 25-65 mass%, Furthermore, 31-31 The range is preferably 55% by mass. Here, the aromatic ring content can be calculated as the total atomic weight of carbon and hydrogen constituting the aromatic ring in the total atomic weight of the repeating unit of the polyamide resin (A).

  Next, as described above, the phosphorus atom-containing oligomer (B) used in the present invention is a polyamide resin (A) and the following structural formula (1).

（構造式（１）中、Ｒ^１〜Ｒ^５は、それぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、又はフェニル基であり、Ｘは水素原子又は下記構造式（ｘ１）、

(In Structural Formula (1), R ^{1 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and X is A hydrogen atom or the following structural formula (x1),

で表される構造部位であり、また、該構造式（ｘ１）中、Ｒ^２〜Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基であり、かつ、構造式（１）中のｎは繰り返し単位で０以上の整数である。）で表されるものである。本発明では、斯かるリン原子含有オリゴマー（Ｂ）を難燃剤成分として用いることにより、溶融混練時のブリードを抑えかつ金型からの離型性を良好に維持しながらも、薄肉成型品、成型品の薄肉部、薄膜部における難燃性能を飛躍的に高めることができるものである。また、前記リン原子含有オリゴマー（Ｂ）は、特に前記構造式（１）においてｎが０であるリン原子含有化合物と、ｎが１以上であるリン原子含有オリゴマーとの混合物であることが、溶融混練時のブリードや成型時の離型性などに優れると共に、薄肉成型品、成型品の薄肉部、薄膜部における難燃性能が一層向上する点から好ましい。

In the structural formula (x1), R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. And n in the structural formula (1) is a repeating unit and is an integer of 0 or more. ). In the present invention, by using such a phosphorus atom-containing oligomer (B) as a flame retardant component, a thin-walled molded product, a molded product can be obtained while suppressing bleeding at the time of melt-kneading and maintaining good releasability from the mold. The flame retardancy in the thin-walled part and the thin-film part of the product can be dramatically improved. Further, the phosphorus atom-containing oligomer (B) is a mixture of a phosphorus atom-containing compound in which n is 0 in the structural formula (1) and a phosphorus atom-containing oligomer in which n is 1 or more. It is preferable from the viewpoints of excellent bleed at the time of kneading and releasability at the time of molding, and further improving the flame retardancy performance in the thin molded product, the thin portion of the molded product, and the thin film portion.

  Such a phosphorus atom-containing oligomer (B) is, for example, a chemical structure represented by the structural formula (1) wherein X is a hydrogen atom, specifically, the following structural formula (1-1) ) To (1-4).

  On the other hand, among the chemical structures represented in the structural formula (1), those in which X is represented by the structural formula (x1)

  In the present invention, X in the structural formula (1) is the structural formula (x1) or a hydrogen atom, and is particularly preferably the structural formula (x1) from the viewpoint of flame retardancy. Represented by the formulas (1-5) to (1-8), it is a mixture of a component of n = 0 and a component in which n is 1 or more, processability, a thin molded product, a thin portion of a molded product, It is preferable from the point which is excellent in the flame retardance performance in a thin film part.

In addition, R ^{1 to} R ⁵ in the structural formula (1) and R ^{2 to} R ⁵ in the structural formula (x1) are each independently a hydrogen atom or an alkyl having 1 to 4 carbon atoms, as described above. Group, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a t-butyl group, and examples of the alkoxy group having 1 to 4 carbon atoms include , A methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, and a t-butoxy group.

In the present invention, R ^{1 to} R ⁵ in the structural formula (1) and R ^{2 to} R ⁵ in the structural formula (x1) are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In particular, R ^{1 to} R ⁵ in the structural formula (1) and R ^{2 to} R ⁵ in the structural formula (x1) are all hydrogen atoms are preferable from the viewpoint of flame retardancy.

  In addition, as described above, the phosphorus atom-containing oligomer (B) includes a compound in which n is 0 in the above structural formula (1) (hereinafter, abbreviated as “component where n is 0”), n Is a mixture with a phosphorus atom-containing oligomer (hereinafter, abbreviated as “component having 1 or more”), wherein n is 1 or more. It is preferable that the ratio is in the range of 5 to 90% on the basis of the peak area in GPC measurement from the viewpoint of excellent workability and flame retardancy in a thin molded product, a thin portion of a molded product, and a thin film portion.

  Here, the phosphorus atom-containing oligomer (B) has a phosphorus atom-containing oligomer content of 40 to 85% on the basis of the peak area in GPC measurement, in the structural formula (1) above, where n is 1 or more. What exists in a range is preferable from the point which is excellent in the flame retardance in a thin molded article, the thin part of a molded article, and a thin film part especially.

  Here, the content of the component having n of 1 or more in the structural formula (1) in the phosphorus atom-containing oligomer (B) is a peak of less than 36.0 minutes in the GPC chart measured under the following conditions. This is the area ratio.

<GPC measurement conditions>
4) GPC: The measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml / min standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  In the present invention, that is, the content of the component having n of 1 or more is preferably 5% to 90% on the basis of the peak area in the GPC measurement. In particular, compatibility with the polyamide resin (A) and workability The content of the component having n of 1 or more in the phosphorus atom-containing oligomer (B) is 40 from the viewpoint that the flame-retardant performance in the thin-walled molded product, the thin-walled portion of the molded product, and the thin-film portion is good. It is preferable that the content of the component having n of 0 is 60 to 25%.

  More specifically, the content of the component with n = 0 is 95 to 10% and the content of the phosphorus atom-containing oligomer with n = 1 (hereinafter abbreviated as “component with n = 1”) is 3-3. The balance of workability and flame retardancy is 50% and the content of the phosphorus atom-containing oligomer having n of 2 or more (hereinafter abbreviated as “component having n of 2 or more”) is 2 to 45%. In particular, the content of the component with n = 0 is 60 to 25%, the content of the component with n = 1 is 10 to 45%, and the content of the component with n is 2 or more is 10%. It is preferable that it is ˜40% from the point that the flame retardancy in the thin molded article, the thin part of the molded article, and the thin film part becomes remarkable.

  The phosphorus atom-containing oligomer (B) described above preferably has a phosphorus atom content in the range of 9 to 12% by mass from the viewpoint of flame retardancy. The phosphorus atom content is a value measured according to “JIS standard K010246”.

  The phosphorus atom-containing oligomer (B) detailed above is, for example, the following structural formula (a1)

（式中、Ｒ^２〜Ｒ^５は、それぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表す。）で表される化合物（ａ１）と、
下記構造式（ａ２）

(Wherein R ^{2 to} R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group). a1)
The following structural formula (a2)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表す。）
で表される化合物（ａ２）とを、モル比［化合物（ａ１）／化合物（ａ２）］が０．０１／１．０〜０．９９／１．０となる割合で配合し、酸触媒の存在下或いは無触媒下に、１００〜２００℃で反応を行い、次いで、前記化合物（ａ２）の仕込み量に対して、モル基準で合計１．０１〜３．０倍量となる前記化合物（ａ１）を加え、１４０〜２２０℃にて反応を行うことにより目的とするリン原子含有オリゴマー組成物を得ることができる。

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group.)
The compound (a2) represented by formula (I) is blended at a molar ratio of [compound (a1) / compound (a2)] of 0.01 / 1.0 to 0.99 / 1.0. In the presence or in the absence of a catalyst, the reaction is performed at 100 to 200 ° C., and then the total amount of the compound (a1) is 1.01 to 3.0 times on a molar basis with respect to the charged amount of the compound (a2). ) And the reaction is carried out at 140 to 220 ° C. to obtain the intended phosphorus atom-containing oligomer composition.

  In this invention, when manufacturing a phosphorus atom containing oligomer (B) by this method, precipitation of a reaction intermediate can be suppressed favorably and it becomes easy to make it high molecular weight.

Here, as the alkyl group having 1 to 4 carbon atoms constituting R ² , R ³ , R ⁴ and R ⁵ in the structural formula (a1), a methyl group, an ethyl group, an n-propyl group, i -Propyl group and t-butyl group are mentioned, and examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, and t-butoxy group. In the present invention, the compound (a1) is preferably a compound in which all of R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms from the viewpoint of flame retardancy. On the other hand, R ¹ in the structural formula (a2) in the compound (a2) is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group. Examples of the alkyl group of 4 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a t-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n -Propyloxy group, i-propyloxy group, t-butoxy group can be mentioned. Among these, R ¹ is preferably a hydrogen atom from the viewpoint of excellent reactivity with the compound (a1) and flame retardancy of the cured product.

  As described above, a catalyst may or may not be used in the above method, but the reaction is preferably carried out in the absence of a catalyst from the viewpoint of excellent selectivity and yield of the finally obtained compound. Here, when a catalyst is used, examples of catalysts that can be used include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, Examples include Lewis acids such as anhydrous aluminum chloride and zinc chloride. The amount used is in the range of 0.1 to 5.0% by mass with respect to the total weight of the charged raw materials from the viewpoint of preventing the electrical insulation of the cured product from decreasing.

  In the reaction, since the compound (a2) is in a liquid state, it can be used as an organic solvent, but another organic solvent may be used from the viewpoint of improving workability and the like. Here, examples of the organic solvent used include non-ketone organic solvents such as alcohol-based organic solvents and hydrocarbon-based organic solvents. Specifically, examples of the alcohol-based organic solvent include propylene glycol monomethyl ether. Examples of the hydrocarbon organic solvent include toluene, xylene and the like.

  After completion of the reaction, the desired product can be obtained by drying under reduced pressure.

  In the present invention, in addition to the above-mentioned polyamide resin (A) and the phosphorus atom-containing oligomer (B), the polycarbonate resin (C) is further blended, so that even when the thickness of the molded product is further reduced, it is excellent. Flame retardancy can be expressed.

  The polycarbonate resin (C) used here is, for example, a polymer obtained by polymerizing a polycondensation product of a divalent or bifunctional phenol and a carbonyl halide, or a divalent or bifunctional phenol and a carbonic acid diester. Can be mentioned.

  Here, examples of the divalent or bifunctional phenol as a raw material for the polycarbonate resin (C) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxy). Phenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) ) Propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Sulfoxide, bis (4-hydroxyphenyl) ketone, hydroquinone, resorcin Catechol, and the like. Among these divalent phenols, bis (hydroxyphenyl) alkanes are preferable, and those using 2,2-bis (4-hydroxyphenyl) propane as the main raw material are particularly preferable.

  On the other hand, examples of the carbonyl halide or carbonic acid diester to be reacted with a divalent or bifunctional phenol include, for example, phosgene; dihaloformate of dihydric phenol, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, and m-cresyl carbonate. And diaryl carbonates such as: aliphatic carbonate compounds such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, diamyl carbonate, and dioctyl carbonate.

  The polycarbonate resin (C) may have a branched structure in addition to the polymer chain having a linear molecular structure. Such a branched structure includes 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene as a raw material component. , Phloroglucin, trimellitic acid, isatin bis (o-cresol) and the like.

  In the reaction, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, or the like can be used as a molecular weight regulator.

  The polycarbonate resin (C) preferably has a weight average molecular weight (Mw) in the range of 10,000 to 200,000 from the viewpoint of excellent heat resistance and flame retardancy. Here, the weight average molecular weight (Mw) can be measured under the GPC measurement conditions described above.

  Furthermore, in the present invention, in addition to the above components, polyphenylene ether resin and phenol resin can be added for the purpose of improving flame retardancy.

  Here, the polyphenylene ether resin includes, for example, 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-1,4) -Phenylene) ether and the like.

Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methylphenylene ether unit or 2- (N-alkyl-N-phenylaminomethyl) is preferable. Polyphenylene ether containing a -6-methylphenylene ether unit as a partial structure may be used.

  In the polyphenylene ether resin, 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 introduced into the resin structure by any method such as graft reaction or copolymerization. Modified polyphenylene ether resins can also be used as long as the object of the present invention is not impaired.

  The molecular weight of the polyphenylene ether is not limited as long as it does not impair the effects of the present invention. 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.

  Examples of the phenol resin include a resol type phenol resin and a novolac type phenol resin, and a phenol aralkyl resin, a polyvinyl phenol resin, a triazine-modified phenol novolak resin modified with melamine or benzoguanamine, and the like. Among these, a novolac type phenol resin is particularly preferable from the viewpoint of excellent molded product strength.

The phenol resin preferably has a weight average molecular weight (Mw) in the range of 2000 to 100000, particularly 3000 to 30000, considering the effect of imparting flame retardancy, improvement in mechanical properties and processability. A range is preferable.

  The phenol resin used in the present invention has a total content of free monomers and dinuclears of 15% by mass or less of the entire phenol resin, considering the balance of flame retardancy, process fluidity, mechanical properties, low smoke generation, etc. It is preferable that there is, 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.

  A conventionally known filler (E) can be blended with the flame retardant polyamide resin composition of the present invention 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.

  The blending ratio of each component in the flame retardant polyamide resin composition of the present invention includes phosphorus atoms with respect to 100 parts by mass of the polyamide resin (A), considering the balance between flame retardancy imparting effect, mechanical properties, workability, and the like. 5 to 70 parts by mass of the oligomer (B) in total, preferably 7 to 60 parts by mass, more preferably 10 to 50 parts by mass, (C) 1 to 20 parts by mass of the polycarbonate resin, preferably 2 to 20 parts by mass, More preferably, it is 2-15 mass parts, More preferably, it is 2-10 mass parts.

  Further, the blending ratio in the case of using at least one resin (D) selected from the group consisting of polyphenylene ether resin and phenol resin is preferably 10 to 150 mass in total with respect to 100 mass parts of polyamide resin (A). Parts, more preferably 10 to 120 parts by mass, and still more preferably 10 to 100 parts by mass. When the component (D) is a phenol resin, the amount is particularly preferably 15 to 50 parts by mass.

  Furthermore, the blending amount when using the filler (E) is not particularly defined as long as the effect of the present invention can be exhibited. The blending amount for efficiently obtaining the above effect by blending the filler is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, and still more preferably 20 parts by weight with respect to 100 parts by weight of the polyamide resin. To 120 parts by mass, particularly preferably 20 to 100 parts by mass.

  In the present invention, a nitrogen-containing compound may be added for the purpose of further enhancing the flame retardant effect. Such nitrogen-containing compounds include tertiary amines such as triarylamines, dialkylarylamines, alkyldiarylamines, 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, etc., cyanuric acid salts of the above compounds, sulfuric acid Salt, phosphate, borate, 2-dibutylamino-4,6-dimercapto-S-triazine, 2-N-phenylamino-4,6-dimercapto-S-triazine, 2,4,6-trimercapto- S-triazine, triallyl cyanure DOO, triazine compounds such as tri methallyl isocyanurate and include polyphosphate salts and the like.

  When heat resistance is particularly required, a triazine compound or a polyphosphate can be 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 It is preferable to use melamine cyanurate or polyphosphate which is a product. In addition, in the reaction product of the triazine compound and cyanuric acid, part or all of the hydroxyl group and / or amino group may be substituted with another substituent.

  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. Examples of the polyphosphate include ammonium polyphosphate and melamine polyphosphate.

  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), AMGARDMC (manufactured by Albright and Wilson), FRCROS (manufactured by Budenheim Iberica), TERRAJU (manufactured by Budenheim Iberica), etc. Is mentioned. Furthermore, Exolip VPIFR-23 (manufactured by Hoechst), SPINFLAMMF80 / PP, SPINFLAMMMF82 / PP, SPINFLAMMMF82 / PS (above, manufactured by Montecatini) etc., in which other auxiliary components are added to ammonium polyphosphate to further improve the flame retardant effect Can also be mentioned.

  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.
Although the addition amount of a nitrogen-type compound will not be prescribed | regulated if it is the quantity which can exhibit the effect of this invention, 1-150 mass parts suitably with respect to 100 mass parts of polyamide resins (A), More preferably, it is 5-100. Part by mass, more preferably 10 to 80 parts by mass.

  In the present invention, non-halogen, non-antimony flame retardants, flame retardant aids and the like other than the phosphorus atom-containing oligomer (B) may be used in combination as long as the effects of the present invention can be achieved. Non-halogen and non-antimony flame retardants and flame retardant aids include, for example, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, calcium aluminate, copper oxide, iron oxide, zinc oxide, magnesium oxide. Boron-containing compounds such as boric acid and zinc borate compounds, silica, coal ash (fly ash), zeolite, silicate, polyorganosiloxane, silsesquioxane, silicon-containing compounds such as silicon resin, Crosslinked with phosphates such as phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, phenyl cresyl phosphate, phenyl xylenyl phosphate, cresyl xylenyl phosphate, bisphenol A, bisphenol S, resorcin, hydroquinone, etc. Condensation Ester, by addition of a tertiary phosphine or their oxides or sulfides such as triarylphosphine or trialkyl phosphine, it is also possible to further improve the flame retardancy.

The flame-retardant polyamide resin composition of the present invention can be used in combination with conventionally known resins 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.

  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 a plasticizer, an antioxidant, Stabilizers such as UV absorbers and light stabilizers, curing agents, curing accelerators, antistatic agents, conductivity imparting agents, stress relaxation agents, mold release agents, crystallization accelerators, hydrolysis inhibitors, lubricants, impacts Giving agent, slidability improver, compatibilizer, nucleating agent, reinforcing agent, reinforcing agent, flow modifier, dye, sensitizer, coloring pigment, rubbery polymer, thickener, anti-settling agent, sauce It is also possible to add an inhibitor, an antifoaming agent, a coupling agent, a rust inhibitor, an antibacterial / antifungal agent, an antifouling agent, a conductive polymer, and the like.

  The blending order of each component when producing 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. Moreover, the compounding method can knead | mix and manufacture using kneading machines, such as an extruder, a heating roll, a kneader, a roller mixer, a Banbury mixer, for example. 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.

  The molded body of the flame retardant polyamide resin composition of the present invention can be used in various forms such as plate, rod, sphere, sheet, film, hollow, finely dispersed gas, foam, fiber, pellet, 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.

  Specific uses of the molded body include, for example, an air flow meter, an air pump, a thermostat housing, an engine mount, an ignition hobbin, an ignition case, a clutch bobbin, a sensor housing, an idle speed control valve, a vacuum switching valve, an ECU housing, and a vacuum pump. Case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter , Fuel cap, fuel strainer, distributor cap, bell Percanister housing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes such as automobile under hood parts, torque control lever, safety belt Parts, register blades, washer levers, window regulator handles, window regulator handle knobs, passing light levers, sun visor brackets, motor interior parts such as various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hoods Louver, wheel cover, wheel cap, grill apron cover frame, lamp reflector, lamp bezel, door Automotive exterior parts such as handles, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors and other automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings and Internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers, handheld mobiles, recording media (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings And electric / electronic parts represented by internal parts, facsimile housings and internal parts, parabolic antennas, and the like. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Electrical and electronic parts such as transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related parts, gears, screws, springs, bearings, levers, key stems, cams , Ratchet, roller, water supply parts, toy parts, cable ties, clips, fans, tegus, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, prevention Bird sheet, Non-woven fabric for vegetation protection, Pot for seedling, Vegetation pile, Seed string tape, Germination sheet, House lining sheet, Agricultural fastener, Slow-release fertilizer, Agricultural materials such as root sheets, garden nets, insect nets, infant tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage nets, inducement strings, windproof nets, paper diapers, sanitary wrapping materials, cotton swabs, towels , Hygiene items such as toilet seat wipes, medical non-woven fabric (stitching reinforcement, anti-adhesion membrane, prosthetic repair material), wound dressing, wound tape bandage, sticker base fabric, surgical suture, fracture reinforcement, medical Medical supplies such as film, calendar, stationery, clothing, food packaging film, tray, blister, knife, fork, spoon, tube, plastic can, pouch, container, tank, basket, etc. Fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, Containers such as shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, wrapping films for electrical and electronic parts, etc. Packaging, natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tape, Print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric hot melt binder, magnetic material, zinc sulfide, electrode Powder binders for materials, optical elements, Electric embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag , Chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. The melt viscosity at 150 ° C. and GPC, NMR and MS spectra were measured under the following conditions.

1) Melt viscosity at 180 ° C .: conforms to ASTM D4287 2) Softening point measurement method: JIS K7234
3) Phosphorus content measurement method: compliant with JIS K0102-46

4) GPC: The measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
The component ratio of n = 2 or more was calculated based on the peak area of less than 36.0 minutes on the GPC chart.

であらわされるリン原子含有オリゴマー物（Ａ−１）を４１０重量部得た。得られたフェノール樹脂の水酸基当量は４２８グラム/当量、軟化点１４０℃、燐含有量は１０．５％であり、ｎ＝１以上の成分比率は４６．７％であった。得られたリン含有オリゴマーのＧＰＣチャートを図１に示す。 Synthesis example 1
In a flask equipped with a thermometer, a condenser tube, a fractionating tube and a stirrer, 324.0 parts by mass (1.5 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 122 parts by mass (1.0 mol) of o-hydroxybenzaldehyde was charged and stirred at 40 ° C. while blowing nitrogen. The mixture was heated to 140 ° C. and stirred for 4 hours, then heated to 180 ° C. and stirred for 8 hours. Thereafter, water is removed under reduced pressure by heating, and the following structural formula

410 parts by weight of the phosphorus atom-containing oligomer (A-1) represented by The obtained phenol resin had a hydroxyl group equivalent of 428 g / equivalent, a softening point of 140 ° C., a phosphorus content of 10.5%, and a component ratio of n = 1 or more was 46.7%. A GPC chart of the obtained phosphorus-containing oligomer is shown in FIG.

ｎ＝３が９４質量％、ｎ＝４が４質量％、ｎ≧５が２質量％であるフェノキシホスファゼン５％重量減少温度；３３６℃、５０％重量減少温度；３９８℃、５００℃残渣量；４．７質量％
（Ｃ）成分：ポリカーボネート樹脂
（Ｃ−１） カリバー３０１−１０（住友ダウ（株）製）
（Ｄ）成分
（Ｄ−１） フェノールノボラック樹脂 フェノライトＴＤ−２１３１（ＤＩＣ（株）製）
（Ｄ−２） ２，６ジメチル−１，４−フェニレンエーテル１００質量部に無水マレイン酸０．５質量部を配合し、２軸押出機で３３０℃、３００ｒｐｍで混練押出しして得られた無水マレイン酸変性ポリフェニレンエーテル
その他
（Ｅ−１） ガラス繊維（ＧＦ） Ｔ−２７５（日本電気硝子（株）製）
メラミンシアヌレート（ＭＣＡ） ＭＣＡ Ｃ−０（三菱化学（株）製）
滴下防止剤（ＰＴＦＥ） ６Ｃ−Ｊ （三井デュポンフロロケミカル（株）製） [Examples 1 to 4, Comparative Example 1]
Examples 1-4, Comparative Example 1
Using a twin-screw rotary extruder equipped with one supply port on each of the upstream side and the downstream side, the set temperature of the heating cylinder is set to 280 ° C., and each component other than GF is listed in Table 1 from the upstream supply port. The mixture was added at the indicated ratio, and GF was supplied from the downstream supply port in the amount shown in Table 1, melted and kneaded at a screw rotation speed of 300 rpm, and the strand was cooled and cut to obtain a resin composition pellet.
(Each component in Table 1 is as follows.)
Component (A): Polyamide resin (A-1) Polyamide 66 resin (Leona 1300; manufactured by Asahi Kasei Chemicals Corporation)
(B) component: phosphazene compound (B-2) In the following chemical formula,

5% weight loss temperature of phenoxyphosphazene in which n = 3 is 94% by mass, n = 4 is 4% by mass, and n ≧ 5 is 2% by mass; 336 ° C., 50% weight loss temperature; 398 ° C., 500 ° C. residue amount; 4.7% by mass
(C) component: Polycarbonate resin (C-1) Caliber 301-10 (manufactured by Sumitomo Dow Co., Ltd.)
(D) Component (D-1) Phenol novolac resin Phenolite TD-2131 (manufactured by DIC Corporation)
(D-2) Anhydrous anhydride obtained by blending 0.5 parts by mass of maleic anhydride with 100 parts by mass of 2,6 dimethyl-1,4-phenylene ether and kneading and extruding at 330 ° C. and 300 rpm with a twin screw extruder. Maleic acid-modified polyphenylene ether and others (E-1) Glass fiber (GF) T-275 (manufactured by Nippon Electric Glass Co., Ltd.)
Melamine cyanurate (MCA) MCA C-0 (Mitsubishi Chemical Corporation)
Anti-dripping agent (PTFE) 6C-J (Mitsui DuPont Fluorochemical Co., Ltd.)

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.
[Physical property test conditions]
(1) Flame retardance Compliant with UL-94 vertical combustion test (2) Melting and kneading using a bleed twin screw rotary extruder at the time of extrusion, and when the obtained strand is cooled in a water bath, it comes out on the water bath The amount of oil film is visually observed and evaluated.

○: No oil film is observed ×: Oil film is seen (3) Releasability Using an injection molding machine set to a specified temperature, a molding test piece of length 128 mm × width 12.8 mm × thickness 0.79 mm was obtained. When molding, 20 shots with mold removal of the runner part had no problem ○, mold with bad mold separation △, with all molds with poor mold separation X, visually Were observed and evaluated.

Claims (9)

Polyamide resin (A) and the following structural formula (1)

(In Structural Formula (1), R ^{1 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and X is A hydrogen atom or the following structural formula (x1),

In the structural formula (x1), R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. And n in the structural formula (1) is a repeating unit and is an integer of 0 or more. A flame retardant polyamide resin composition comprising a phosphorus atom-containing oligomer (B) represented by The phosphorus atom-containing oligomer (B) is a mixture of a component in which n is 0 in the structural formula (1) and a component in which n is 1 or more in the structural formula (1), and n is one component The flame-retardant polyamide resin composition according to claim 1, which is used as a phosphorus atom-containing oligomer composition having a content of the above components in a range of 5 to 90% on the basis of a peak area in GPC measurement. The flame-retardant polyamide resin composition according to claim 1, wherein the phosphorus atom-containing oligomer (B) has a phosphorus atom content of 9 to 12% by mass. The phosphorus atom-containing oligomer (B) is represented by the following structural formula (b1-1) or (b1-2)

(Wherein R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group) b1)
The following structural formula (b2)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group.)
The flame retardant polyamide resin composition according to claim 1, which is obtained by reacting the compound (b2) represented by the formula: The phosphorous atom-containing oligomer (B) is contained in a proportion of 5 to 70 parts by mass and the polycarbonate resin (C) is contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polyamide resin (A). The flame-retardant polyamide resin composition described in 1. The polycarbonate resin (C) is further contained in a proportion of 10 to 150 parts by mass with respect to 100 parts by mass of the polyamide resin (A) in addition to the components (A) and (B). Flame retardant polyamide resin composition. In addition to the components (A) and (B), at least one resin selected from the group consisting of polyphenylene ether and phenol resin is further added in an amount of 10 to 150 parts by mass with respect to 100 parts by mass of the polyamide resin (A). The flame retardant polyamide resin composition according to claim 1, wherein the flame retardant polyamide resin composition is contained. In addition to the components (A) and (B), the filler is further contained at a ratio of 10 to 200 parts by mass with respect to 100 parts by mass of the polyamide resin (A). The flame-retardant polyamide resin composition according to any one of 5. The molded object formed by shape | molding the flame-retardant polyamide resin composition of Claim 1.

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