JP5388165B2 - Flame retardant resin composition - Google Patents

Description

  The present invention relates to a flame retardant resin composition that is excellent in mechanical properties and heat resistance, has high flame retardancy in thin-walled parts, and further has significantly reduced corrosiveness to metals.

Conventionally, crystalline polyamides represented by polyamide 6, polyamide 66, etc. are used for automotive parts, electrical and electronic applications such as connectors, clothing, and textile materials for industrial materials because of their excellent properties and ease of melt molding. Has been.
Recently, semi-aromatic polyamides such as polyamide 9T, which has higher heat resistance than polyamide 6 and polyamide 66, have begun to be used for applications requiring high heat resistance such as parts for surface mount technology (SMT). Yes.
In recent years, as an environmental measure, there has been an increasing demand for substitution of halogen-based compounds and antimony-based compounds that have been conventionally used as flame retardants for polyamides.

Based on these market demands, technology development for non-halogen flame-retardant of polyamide has been actively conducted.
As a conventional technology for flame-retarding polyamide, a technology for flame-retarding hexamethylene adipamide with melamine phosphate (Patent Document 1), a technology for flame-retardant aromatic polyamide with a halogen-based flame retardant (Patent Document) 2) Technology for flame-retarding polyamides with phosphinates, which are non-halogen flame retardants (Patent Document 3), Technology for adding resins having aromatic rings to polyamides and phosphinates (Patent Document 4), high melting point A technique of adding phosphinates to a resin composition composed of polyamide and polyphenylene ether (Patent Document 5) has been proposed. Among these, a non-halogen flame retardant technology is finally being put into practical use in a system in which phosphinate is combined as a flame retardant for polyamide.

However, when phosphinates are used as flame retardants, it has been found that they have metal corrosivity depending on the processing conditions. Especially as polyamide species, in the combination of semi-aromatic polyamide and phosphinate flame retardant at the processing temperature. Has recently been found to have very high metal corrosivity.
In order to respond to this, it is becoming necessary to use expensive corrosion-resistant and wear-resistant steel for the processing equipment to be used. This rapid solution and the development of materials that have high flame resistance even in thin-walled products It is desired.
JP 2001-279091 A JP-A-7-228775 JP 2004-263188 A Special table 2007-536401 gazette Japanese Patent Application No. 2007-197444

  An object of the present invention is to provide a flame retardant resin composition of polyamide / polyphenylene ether that has a high degree of flame retardance in a thin-walled part, which has been difficult to achieve with the prior art, and a metal corrosion resistance is remarkably suppressed.

  As a result of repeated studies to solve the above-described problems, the present inventors have made a specific phosphinic acid salt as a flame retardant and include it in a polyamide / polyphenylene ether / inorganic filler composition to form a resin composition. As a result, the inventors have found that the above-described problems can be solved by using calcium hydroxide and / or calcium oxide, and further using a specific amount of particulate inorganic filler with respect to the fibrous inorganic filler, thereby completing the present invention.

That is, the present invention is as follows.
1. (A) polyamide, (B) polyphenylene ether, (C) a phosphinic acid salt represented by the following formula (I), a diphosphinic acid salt represented by the following formula (II), and a condensate thereof: one phosphinates, (D) an inorganic filler, and (E) calcium hydroxide, an a comprising at flame-retardant resin composition, (D) an inorganic filler, fibrous inorganic filler And a particulate inorganic filler, wherein the inorganic inorganic filler is 1 to 15% by mass when the total amount of inorganic fillers is 100% by mass.

［式中、Ｒ¹及びＲ²は、同一か又は異なり、直鎖状もしくは分岐状のＣ₁〜Ｃ₆−アルキル及び／又はアリールであり、Ｒ³は、直鎖状もしくは分岐状のＣ₁〜Ｃ₁₀−アルキレン、Ｃ₆〜Ｃ₁₀−アリーレン、Ｃ₆〜Ｃ₁₀−アルキルアリーレン又はＣ₆〜Ｃ₁₀−アリールアルキレンであり、Ｍはカルシウム（イオン）、マグネシウム（イオン）、アルミニウム（イオン）、亜鉛（イオン）、ビスマス（イオン）、マンガン（イオン）、ナトリウム（イオン）、カリウム（イオン）及びプロトン化された窒素塩基から選ばれる１種以上であり、ｍは１〜３であり、ｎは１〜３であり、ｘは１又は２である。］

[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and R ³ is linear or branched C ₁ -C ₁₀ - alkylene, C ₆ -C ₁₀ - arylene, C ₆ -C ₁₀ - alkylarylene or C ₆ -C ₁₀ - aryl alkylene, M is calcium (ion), magnesium (ion), aluminum (ion) , Zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and one or more protonated nitrogen bases, m is 1 to 3, n Is 1 to 3, and x is 1 or 2. ]

2. 1 above, wherein the amount ratio of the particulate inorganic filler and the fibrous inorganic filler is 3.0 to 12.0% by mass when the total of both is 100% by mass. The flame-retardant resin composition as described in 2.
3. (C) 0.05-10 mass parts of (E) calcium hydroxide is included with respect to 100 mass parts of phosphinates, The flame-retardant resin composition of said 1 or 2 characterized by the above-mentioned.

［式中、Ｒ¹及びＲ²は、同一か又は異なり、直鎖状もしくは分岐状のＣ₁〜Ｃ₆−アルキル及び／又はアリールであり、Ｍはカルシウム（イオン）、マグネシウム（イオン）、アルミニウム（イオン）、亜鉛（イオン）、ビスマス（イオン）、マンガン（イオン）、ナトリウム（イオン）、カリウム（イオン）及びプロトン化された窒素塩基から選ばれる１種以上であり、ｍは１〜３である。］ 4). The flame retardant according to any one of 1 to 3 above, wherein the phosphinic acid salt of component (C) comprises 90% by mass or more of the phosphinic acid salt represented by the following formula (I): Resin composition.

[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and M is calcium (ion), magnesium (ion), aluminum (Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and one or more protonated nitrogen bases, and m is 1 to 3. is there. ]

5. The particulate inorganic filler of component (D) is at least one selected from glass beads, talc, mica, wollastonite, kaolin and calcium carbonate having an aspect ratio of 1 to 10. 5. The flame retardant resin composition according to any one of 1 to 4 above.
6). (D) The fibrous inorganic filler as component is at least one selected from glass fiber, carbon fiber, wollastonite, and potassium titanate whisker having an aspect ratio exceeding 10. The flame-retardant resin composition according to any one of 1 to 5.

7). 7. The average particle diameter of the particulate inorganic filler is in the range of 0.03 to 3.5 times the average fiber diameter of the fibrous inorganic filler. Flame retardant resin composition.
8). 8. The average particle diameter of the particulate inorganic filler is in the range of 0.1 to 2.0 times the average fiber diameter of the fibrous inorganic filler. Flame retardant resin composition.

9. (D) The flame-retardant resin composition according to any one of 1 to 8 above, wherein the blending amount of the inorganic filler is 1 to 60% by mass in the entire flame-retardant resin composition.
10. (A) The polyamide comprises an aromatic ring-containing monomer as a monomer component constituting the polymer, and comprises a semi-aromatic polyamide in which the amount of the aromatic ring-containing monomer is 20 mol% or more in the monomer component. 10. The flame retardant resin composition according to any one of 1 to 9 above.
11. (A) 60-100 mol of dicarboxylic acid unit (a) in which the polyamide contains 60-100 mol% of terephthalic acid units, 1,9-nonanediamine units and / or 2-methyl-1,8-octanediamine units 11. The flame retardant resin composition according to any one of 1 to 10 above, which is a semi-aromatic polyamide resin comprising a diamine unit (b) contained in an amount of 1%.

12 When (A) polyamide and (B) polyphenylene ether have a total amount of 100 parts by mass, (A) polyamide is 40 to 90 parts by mass, and (B) polyphenylene ether is 60 to 10 parts by mass. The flame-retardant resin composition according to any one of 1 to 11 above, wherein
13. (C) The compounding quantity of phosphinic acid salts is 1-80 mass parts with respect to a total of 100 mass parts of (A) polyamide and (B) polyphenylene ether, Any one of said 1-12 characterized by the above-mentioned. The flame-retardant resin composition according to item.

14 (F) The flame retardant according to any one of 1 to 13 above, which contains one or more compatibilizers selected from citric acid, maleic acid, itaconic acid and anhydrides thereof as component (F) Resin composition.
15. 15. The difficulty according to 14 above, wherein the compatibilizer of component (F) is contained in an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass in total of (A) polyamide and (B) polyphenylene ether. A flammable resin composition.

16. (A) polyamide, (B) polyphenylene ether, (C) a phosphinic acid salt represented by the following formula (I), a diphosphinic acid salt represented by the following formula (II), and a condensate thereof: one phosphinates, (D) an inorganic filler, and (E) comprises calcium hydroxide, a, (D) an inorganic filler, a mixture of fibrous inorganic filler and particulate inorganic filler A method for producing a flame-retardant resin composition in which the amount of the inorganic inorganic filler is 1 to 15% by mass when the total amount of the inorganic fillers is 100% by mass, and includes (A) polyamide and (B) polyphenylene ether in advance. After melt-kneading and adding the fibrous inorganic filler of (D) inorganic filler to the molten resin component and melt-kneading, (C) phosphinic acid salts and (D) of inorganic filler Inorganic filler, (E) hydroxylation Method for producing a flame-retardant resin composition characterized by melt-kneading added Rushiu beam.

［式中、Ｒ¹及びＲ²は、同一か又は異なり、直鎖状もしくは分岐状のＣ₁〜Ｃ₆−アルキル及び／又はアリールであり、Ｒ³は、直鎖状もしくは分岐状のＣ₁〜Ｃ₁₀−アルキレン、Ｃ₆〜Ｃ₁₀−アリーレン、Ｃ₆〜Ｃ₁₀−アルキルアリーレン又はＣ₆〜Ｃ₁₀−アリールアルキレンであり、Ｍはカルシウム（イオン）、マグネシウム（イオン）、アルミニウム（イオン）、亜鉛（イオン）、ビスマス（イオン）、マンガン（イオン）、ナトリウム（イオン）、カリウム（イオン）及びプロトン化された窒素塩基から選ばれる１種以上であり、ｍは１〜３であり、ｎは１〜３であり、ｘは１又は２である。］

[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and R ³ is linear or branched C ₁ -C ₁₀ - alkylene, C ₆ -C ₁₀ - arylene, C ₆ -C ₁₀ - alkylarylene or C ₆ -C ₁₀ - aryl alkylene, M is calcium (ion), magnesium (ion), aluminum (ion) , Zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and one or more protonated nitrogen bases, m is 1 to 3, n Is 1 to 3, and x is 1 or 2. ]

17. The pellet obtained from the flame-retardant resin composition of any one of said 1-15.
18. A molded article obtained from the flame retardant resin composition according to any one of 1 to 15 above.

  According to the present invention, it is possible to provide a flame retardant resin composition having high flame retardance in thin-walled parts, which has been difficult to achieve with the prior art, and further having significantly reduced corrosiveness to metals.

Hereinafter, the contents of the present invention will be described in detail.
As the type of the component (A) polyamide that can be used in the present invention, any polyamide having an amide bond {—NH—C (═O) —} in the repeating unit of the polymer main chain may be used. can do.
In general, polyamides are obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but are not limited thereto.

The diamine is roughly classified into aliphatic, alicyclic and aromatic diamines. Specific examples include tetramethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine, 1,9-nonamethylene diamine, 2- Methyl-1,8-octamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnona One or more types selected from methylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine are listed. It is done.
Among these, preferable diamines are exemplified by 1 selected from tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, 1,9-nonamethylenediamine, and 2-methyl-1,8-octamethylenediamine. Species or higher diamines can be mentioned. Particularly preferred are hexamethylenediamine, 1,9-nonamethylenediamine, and a mixture of 1,9-nonamethylenediamine and 2-methyl-1,8-octamethylenediamine.

  Dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids, and specific examples include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyl. Aliphatic dicarboxylic acids such as adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid; 1,3-cyclopentanedicarboxylic acid, 1,4- Cycloaliphatic dicarboxylic acids such as 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, diphenylmethane-4,4′-dicarboxylic acid Examples include units derived from aromatic dicarboxylic acids such as diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and the use of one or more of these units. Can do.

Specific examples of lactams include ε-caprolactam, enantolactam, and ω laurolactam.
Specific examples of aminocarboxylic acids include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminonanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecane. An acid etc. are mentioned.

In the present invention, any of these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids can be used alone or as a copolymerized polyamide obtained by polycondensation in a mixture of two or more.
Also, those obtained by polymerizing these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids up to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight in an extruder or the like can be suitably used.

  Particularly, polyamides that can be usefully used in the present invention include polyamide 6, polyamide 6,6, polyamide 6, T, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, polyamide 6 / 6,12, polyamide MXD (m-xylylenediamine), 6, polyamide 9, T, polyamide 12, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6 , I, polyamide 6,6 / 6, T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12 / 6, T, polyamide 6,6 / 12/6, T, polyamide 6/12/6, I, polyamide 6,6 / 12/6, I, etc. Copolymerized polyamides such may also be used. Preferred polyamides are polyamide 6, polyamide 6,6, polyamide 6,6 / 6, T, polyamide 9, T, polyamide 6,6 / 9, T, polyamide 6,6 / 6, I, polyamide MXD, 6, polyamide One or more selected from 4,6, polyamide 11, and polyamide 12. Among these, the most preferable polyamide is at least one selected from polyamide 6, polyamide 6,6, polyamide 6,6 / 6, T, polyamide 9, T, and polyamide 12.

  The polyamide that can be more preferably used in the present invention is a semi-aromatic polyamide that contains an aromatic ring-containing monomer as a monomer component constituting the polymer, and the amount of the aromatic ring-containing monomer is 20 mol% or more in the monomer component. . Among them, polyamide contains 60 to 100 mol% of dicarboxylic acid unit (a) containing 60 to 100 mol% of terephthalic acid units, 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit. It is a semi-aromatic polyamide resin comprising a diamine unit (b) to be contained.

  The viscosity number of the polyamide used in the present invention is not particularly limited as long as the characteristics of the present invention are not impaired. However, as a preferable range of the polyamide viscosity number measured with 96% sulfuric acid according to ISO 307: 1994. For example, for use in injection molding, 50 ml / g to 100 ml / g or 50 ml / g to 150 ml / g is preferable. For example, in applications such as blow molding, sheet molding and film molding, 50 ml / g to 250 ml / g. g or a range of 100 ml / g to 250 ml / g is preferred.

  The polyamide that can be used in the resin composition of the present invention may be a mixture of a plurality of polyamides having different viscosity numbers. When a plurality of polyamides are used, the viscosity number of the polyamide mixture is preferably within the above-mentioned range. In order to confirm that the polyamide mixture is within the above-mentioned range of the viscosity number, it can be easily confirmed by actually measuring the viscosity number of the polyamide mixture mixed at a desired mixing ratio.

The end groups of the polyamide are involved in the reaction with the polyphenylene ether. Polyamide generally has an amino group or a carboxyl group as a terminal group. However, when the carboxyl group concentration is generally increased, impact resistance is decreased, fluidity is improved, and conversely, the amino group concentration is increased. Impact resistance improves and fluidity decreases.
In the present invention, a preferred ratio of these terminal groups is an amino group / carboxyl group concentration ratio of 9/1 to 1/9, more preferably 6/4 to 1/9, still more preferably 5/5 to 1. / 9.
The terminal amino group concentration is preferably 10 to 80 μmol / g. More preferably, it is 15-65 micromol / g, Most preferably, it is 20-40 micromol / g. By making the concentration of the terminal amino group within these ranges, it is possible to prevent a significant decrease in the fluidity of the composition within the mold.

As a method for adjusting the end groups of these polyamide resins, a known method that will be apparent to those skilled in the art can be used. For example, there may be mentioned a method of adding one or more selected from diamine compounds, monoamine compounds, dicarboxylic acid compounds, monocarboxylic acid compounds and the like so that a predetermined terminal concentration is obtained during polymerization of the polyamide resin.
Examples of the monoamine compound include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine, cyclohexylamine, and dicyclohexylamine. Examples thereof include alicyclic monoamines such as amines, aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, and arbitrary mixtures thereof. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, sealing end stability, price, and the like.

  Examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3, 3 Aliphatic dicarboxylic acids such as diethyl succinic acid, azelaic acid, sebacic acid and suberic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic 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, diphenylmethane-4,4 ' -Dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldi Can be mentioned units derived from aromatic dicarboxylic acids such as carboxylic acids, it can be used one or two or more of them.

  Examples of the monocarboxylic acid compound include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Examples include alicyclic monocarboxylic acids such as carboxylic acid and cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and aromatic monocarboxylic acid such as phenylacetic acid. be able to. In the present invention, these carboxylic acid compounds may be used alone or in combination of two or more.

In the present invention, a transition metal and / or a halogen may be present in the resin composition for the purpose of further improving the heat stability imparted to the resin composition by the polyamide resin. Although there is no restriction | limiting in particular regarding the kind of transition metal, Copper, cerium, nickel, and cobalt are preferable, and copper is especially preferable. Of the halogens, bromine or iodine can be preferably used.
A preferable amount of the transition metal is 10 ppm or more and less than 300 ppm in the resin composition. More preferably, it is 10 ppm or more and less than 250 ppm. Moreover, the preferable amount of halogen is 500 ppm or more and less than 1500 ppm, More preferably, it is 700 ppm or more and less than 1200 ppm.

Examples of the method for adding these transition metals and / or halogens to the resin composition include, for example, a method of adding a polyamide / polyphenylene ether composition as a powder when melt-kneading, a method of adding a polyamide during polymerization, Although the method etc. which add this master pellet to a resin composition after producing the master pellet added at high concentration are mentioned, any method may be taken. Among these methods, a preferable method is a method of adding at the time of polymerization of polyamide, or a method of adding after preparing master pellets added to polyamide at a high concentration.
Furthermore, in addition to the above, known additives that can be added to the polyamide may be added in an amount of less than 10 parts by mass with respect to 100 parts by mass of the polyamide.

〔式中、Ｏは酸素原子、Ｒは、それぞれ独立して、水素、ハロゲン、第一級もしくは第二級の低級アルキル、フェニル、ハロアルキル、アミノアルキル、炭化水素オキシ、又はハロ炭化水素オキシ（但し、少なくとも２個の炭素原子がハロゲン原子と酸素原子を隔てている）を表わす。〕 The polyphenylene ether of component (B) that can be used in the present invention is a homopolymer and / or copolymer composed of structural units of the following formula.

[Wherein O is an oxygen atom, R is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that At least two carbon atoms separating the halogen atom and the oxygen atom). ]

  Specific examples of the polyphenylene ether of the present invention include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2 -Methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and further, co-use of 2,6-dimethylphenol with other phenols. Polyphenylene ether such as a polymer (for example, a copolymer with 2,3,6-trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in JP-B-52-17880) A copolymer is also mentioned.

Among these, particularly preferred polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these It is a mixture.
The preferred amount of 2,3,6-trimethylphenol when using a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol as polyphenylene ether is 5 to 40 mol%, Preferably it exists in the range of 10-25 mol%.

  The method for producing the polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method. For example, U.S. Pat. Nos. 3,306,874, 3,306,875, and 3,257,357 are disclosed. And the production methods described in JP-A-3257358, JP-A-50-51197, JP-B52-17880, and 63-152628.

The preferred range of the reduced viscosity (measured with a 0.5 g / dl chloroform solution, 30 ° C., Ubbelohde viscosity tube) of the polyphenylene ether constituting the resin composition of the present invention is 0.35 dl / g to 0.65 dl / g. Within range. More preferably, it is the range of 0.40 dl / g-0.60 dl / g.
In the present invention, a blend of two or more polyphenylene ethers having different reduced viscosities can be preferably used.

  In addition, the polyphenylene ether that can be used in the present invention may be a polyphenylene ether modified in whole or in part. The modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group. And polyphenylene ether modified with at least one modifying compound.

  The modified polyphenylene ether is produced by the following: (1) a modified compound without melting the polyphenylene ether in the temperature range of 100 ° C. or higher and lower than the glass transition temperature of the polyphenylene ether in the presence or absence of a radical initiator. (2) A method in which the compound is melt-kneaded and reacted with the modifying compound in a temperature range of not less than the glass transition temperature of the polyphenylene ether and not more than 360 ° C., and (3) a modification with the polyphenylene ether at a temperature lower than the glass transition temperature of the polyphenylene ether. Examples thereof include a method of reacting a compound in a solution, and any of these methods may be used, but the method (1) or (2) is preferred.

Next, at least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group in the molecular structure. This will be specifically described.
Examples of the modified compound having a carbon-carbon double bond and a carboxylic acid group or an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and These acid anhydrides are mentioned. Fumaric acid, maleic acid, and maleic anhydride are particularly preferable, and fumaric acid and maleic anhydride are particularly preferable. In addition, one in which one or two of the two carboxyl groups of the unsaturated dicarboxylic acid is an ester can be used.

Examples of the modified compound having a carbon-carbon double bond and a glycidyl group in the molecule include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural oil and fat, and the like. Among these, glycidyl acrylate and glycidyl methacrylate are particularly preferable.
Examples of the modified compound having a carbon-carbon double bond and a hydroxyl group in the molecule include general formula C _n H _2n-3 OH such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadien-3-ol. (N is a positive integer) unsaturated alcohol, and unsaturated alcohols such as general formulas C _n H _2n-5 OH and C _n H _2n-7 OH (n is a positive integer).

The above-described modifying compounds may be used alone or in combination of two or more.
The amount of the modifying compound added when producing the modified polyphenylene ether is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether.

A preferable amount of the radical initiator when producing the modified polyphenylene ether using the radical initiator is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyphenylene ether.
Further, the addition ratio of the modifying compound to the modified polyphenylene ether is preferably 0.01 to 5% by weight. More preferably, it is 0.1 to 3% by weight.
In the modified polyphenylene ether, the unreacted modified compound and / or polymer of the modified compound may remain if the amount is less than 1% by weight.
Furthermore, you may add the well-known additive etc. which can be added to polyphenylene ether in the quantity of less than 10 mass parts with respect to 100 mass parts of polyphenylene ether.

  In this invention, (A) polyamide and the preferable quantity ratio of (B) polyphenylene ether are (A) 10-90 mass parts of polyamide, (B) polyphenylene ether 90-10 when the sum total of both is 100 mass parts. Within the range of parts by mass. More preferably, (A) 40-90 parts by mass of polyamide, (B) within the range of 60-10 parts by mass of polyphenylene ether, most preferably (A) 50-85 parts by mass of polyamide, (B) 50-15 parts by mass of polyphenylene ether. Within the range of the part.

Moreover, in the flame-retardant resin composition of this invention, a well-known organic and inorganic stabilizer other than what was mentioned above can also be used without a problem. Examples of organic stabilizers include hindered phenolic antioxidants typified by Irganox 1098 (manufactured by Ciba Japan), phosphorus processing heat stabilizers typified by Irgaphos 168 (manufactured by Ciba Japan), Examples include lactone-based processing heat stabilizers represented by HP-136 (manufactured by Ciba Japan), sulfur-based heat stabilizers, hindered amine-based light stabilizers, and the like. Among these organic stabilizers, a hindered phenol antioxidant, a phosphorus processing heat stabilizer, or a combination thereof is more preferable.
Examples of the inorganic stabilizer include metal stabilizers such as zinc oxide and zinc sulfide.
The preferable compounding quantity of these stabilizers is 0.001-5 mass parts with respect to 100 mass parts of the total amount of polyamide and polyphenylene ether, More preferably, it is 0.01-3 mass parts.

Moreover, in this invention, you may mix | blend a styrene-type thermoplastic resin if it is the quantity of less than 50 mass parts with respect to a total of 100 mass parts of polyamide and polyphenylene ether.
Examples of the styrenic thermoplastic resin in the present invention include homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin). Etc.

［式中、Ｒ¹及びＲ²は、同一か又は異なり、直鎖状もしくは分岐状のＣ₁〜Ｃ₆−アルキル及び／又はアリールであり、Ｒ³は、直鎖状もしくは分岐状のＣ₁〜Ｃ₁₀−アルキレン、Ｃ₆〜Ｃ₁₀−アリーレン、Ｃ₆〜Ｃ₁₀−アルキルアリーレン又はＣ₆〜Ｃ₁₀−アリールアルキレンであり、Ｍはカルシウム（イオン）、マグネシウム（イオン）、アルミニウム（イオン）、亜鉛（イオン）、ビスマス（イオン）、マンガン（イオン）、ナトリウム（イオン）、カリウム（イオン）及びプロトン化された窒素塩基から選ばれる１種以上であり、ｍは、１〜３であり、ｎは、１〜３であり、ｘは、１又は２である。］
について説明する。 Component (C) of the present invention, at least one selected from phosphinic acid salts represented by the following formula (I), diphosphinic acid salts represented by the following formula (II), and condensates thereof: Phosphinates

[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and R ³ is linear or branched C ₁ -C ₁₀ - alkylene, C ₆ -C ₁₀ - arylene, C ₆ -C ₁₀ - alkylarylene or C ₆ -C ₁₀ - aryl alkylene, M is calcium (ion), magnesium (ion), aluminum (ion) , Zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and one or more protonated nitrogen bases, m is 1 to 3, n is 1 to 3, and x is 1 or 2. ]
Will be described.

The phosphinic acid salts in the present invention use phosphinic acid and metal carbonate, metal hydroxide or metal oxide as described in, for example, European Patent Application Publication No. 699708 and Japanese Patent Application Laid-Open No. 08-73720. Those manufactured in an aqueous solution can be used effectively.
Although these are essentially monomeric compounds, depending on the reaction conditions, polymeric phosphinates that are condensates having a degree of condensation of 1 to 3 are also included depending on the environment.

［式中、Ｒ¹及びＲ²は、同一か又は異なり、直鎖状もしくは分岐状のＣ_１〜Ｃ₆−アルキル及び／又はアリールであり、Ｍはカルシウム（イオン）、マグネシウム（イオン）、アルミニウム（イオン）、亜鉛（イオン）、ビスマス（イオン）、マンガン（イオン）、ナトリウム（イオン）、カリウム（イオン）及びプロトン化された窒素塩基から選ばれる１種以上であり、ｍは、１〜３である。］ The phosphinic acid salts of the present invention may be mixed in any composition as long as the effects of the present invention are not impaired, but are represented by the following formula (I) from the viewpoint of flame retardancy and suppression of mold deposits. The phosphinic acid salt is preferably contained in an amount of 90% by mass or more, more preferably 95% by mass or more, and most preferably 98% by mass or more.

[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and M is calcium (ion), magnesium (ion), aluminum (Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion), and protonated nitrogen base, and m is 1 to 3 It is. ]

  Examples of preferred phosphinic acids for forming the phosphinic acid salts of the present invention include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene- One or more selected from 1,4- (dimethylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid and mixtures thereof are mentioned, and among them, phosphine selected from dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid One or more selected from acids and mixtures thereof are preferred.

  The preferred metal component for forming the phosphinic acid salts of the present invention is selected from calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base. One or more selected from calcium ions, magnesium ions, aluminum ions, and zinc ions are more preferable.

  Preferred examples of formed phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, Zinc ethyl methylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphine Acid aluminum, methyl n-propyl phosphinate zinc, methandi (methylphosphinic acid) calcium, methandi Methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, benzene- 1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, diphenylphosphine Examples thereof include at least one selected from calcium acid, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

Especially from the viewpoint of flame retardancy and mold deposit suppression, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate , One or more selected from aluminum diethylphosphinate and zinc diethylphosphinate are preferable, and aluminum diethylphosphinate is particularly preferable.
The phosphinic acid salts in the present invention may contain unreacted substances or by-products as long as the effects of the present invention are not impaired.

  In this invention, the quantity of a preferable phosphinic acid salt is 1-80 mass parts with respect to a total of 100 mass parts of (A) polyamide and (B) polyphenylene ether. More preferably, it is 2 to 40 parts by mass, particularly preferably 2 to 35 parts by mass, and most preferably 4 to 30 parts by mass. The amount of phosphinates is preferably 1 part by mass or more in order to develop sufficient flame retardancy, and the amount of phosphinates is 80 parts by mass or less in order to obtain a melt viscosity suitable for extrusion and molding processes. preferable.

The particle diameter of the phosphinates may be any size as long as the characteristics of the present invention are not impaired, but the lower limit of the number average particle diameter of the preferred phosphinates is 0.1 μm, and more preferable lower limit. Is 0.5 μm. The upper limit value of the number average particle diameter of the preferred phosphinic acid salts is 200 μm, and the more preferable upper limit value is 45 μm.
When the lower limit of the number average particle diameter of the phosphinic acid salt is 0.1 or 0.5 μm or more, handling property and biting into an extruder are improved during processing such as melt kneading, and the number average particle size is preferable. When the upper limit of the diameter is 45 or 200 μm or less, it is preferable from the viewpoint of the mechanical strength expression of the resin composition and the good surface appearance of the molded product.

The average particle size of the phosphinates can be measured and analyzed by dispersing the phosphinates in water using a laser diffraction particle size distribution analyzer (for example, trade name: SALD-2000, manufactured by Shimadzu Corporation).
Dispersion of phosphinates in water can be achieved by adding water and phosphinates to an ultrasonic diffuser and / or a stirrer equipped with a stirrer. This dispersion is sent to a measurement cell via a pump, and the particle diameter is measured by laser diffraction. The number average particle size can be calculated from the particle size and the frequency distribution of the number of particles obtained by measurement.

  Among the inorganic fillers (D) of the present invention, the particulate inorganic filler is an average particle having an aspect ratio of 10 or less, which is a ratio of major axis to minor axis having a plate shape, rod shape, spherical shape, or the like. An inorganic filler having a diameter of 1 to 100 μm.

  Non-swelling silicic acid such as talc, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, asbestos, aluminosilicate, calcium silicate, and the like that meet the above conditions Metal oxides such as salt, alumina, silica, diatomaceous earth, zinc oxide, magnesium oxide, tin oxide, antimony oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dolomite, hydrotal Carbonate such as site, sulfate such as calcium sulfate and barium sulfate, hydroxide such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, glass beads, glass flakes, ceramic beads, boron nitride, aluminum nitride, carbonized Silicon etc. Are, Among these particulate inorganic fillers, those having an average particle diameter and a specific aspect ratio of the present invention. These may be hollow, and two or more of these inorganic fillers may be used. These inorganic fillers may be used after being treated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound.

  Of these particulate inorganic fillers, glass beads, talc, mica, wollastonite, kaolin, and calcium carbonate are preferable from the viewpoint of excellent rigidity, surface appearance, and dimensional stability as well as flame retardancy.

Even if the kind of these particulate inorganic fillers is the same, the effect of the present invention cannot be obtained unless the aspect ratio and the average particle diameter are satisfied. The upper limit of the preferred aspect ratio is 10 or less, more preferably 5 or less, and most preferably 3 or less. A preferred lower limit of the aspect ratio is 1.
When the aspect ratio exceeds 10, even if the average particle size is 100 μm or less, the flame retardancy is inferior, which is not preferable.

Moreover, the upper limit of a preferable average particle diameter is 100 micrometers. More preferably, it is 50 micrometers, Most preferably, it is 20 micrometers. A preferred lower limit of the average particle diameter is 1 μm, a more preferred lower limit is 5 μm, and a most preferred lower limit is 7 μm.
When the average particle size is within the preferred upper limit, it is preferable to exhibit a high degree of thin-wall flame retardancy.

  The aspect ratio was determined by observing an arbitrary 300 or more particles using a scanning electron microscope, measuring the minor axis and major axis of the particle from an image of the particle group that was appropriately enlarged and photographed, and obtaining the average minor axis and major axis. The aspect ratio is defined as the ratio. Here, the minor axis and the major axis in the plate shape refer to the minor axis and the major axis in the plate-like plane, and do not refer to the plate thickness. The minor axis and the major axis in the form of a rod and a sphere indicate the shortest part and the longest part in the shape.

The average particle diameter refers to a volume average particle diameter (median diameter) measured using a laser diffraction particle size distribution meter (manufactured by Shimadzu Corporation, trade name: SALD-7000). In the measurement, it is necessary to set the refractive index value appropriate for the type of the particulate inorganic filler, and the value of the refractive index data provided by the manufacturer (Shimadzu Corporation) was used.
The average particle size is measured by a wet method in which a particulate inorganic filler is dispersed in water or an alcohol aqueous solution.

  The amount of the particulate inorganic filler of the present invention is 1 to 100% by mass of the total of 100% by mass of the fibrous inorganic filler and the particulate inorganic filler from the viewpoint of simultaneously expressing high flame retardancy and thin-wall fluidity. It is 15 mass%, More preferably, it is 3.0-12.0 mass%.

Next, the fibrous inorganic filler preferably has an aspect ratio exceeding 10 and an average fiber length exceeding 100 μm. More preferably, the average fiber length is greater than 200 μm, and most preferably greater than 250 μm.
Moreover, the range of the preferable fiber diameter (diameter) of a fibrous inorganic filler is 1.0 micrometer-20.0 micrometers, More preferably, it is 2.0-18.0 micrometers, Most preferably, it is 5.0-15. The range is 0.0 μm.

  Examples of fibrous inorganic fillers that satisfy these conditions include glass fibers, carbon fibers, potassium titanate whiskers, gypsum fibers, brass fibers, stainless fibers, steel fibers, ceramic fibers, boron whiskers, wollastonite, or other fibrous or needles. In the form of an inorganic filler. These fibrous inorganic fillers may be used in combination of two or more. Among these, more preferable fibrous inorganic fillers include glass fibers. Further, the fibrous inorganic filler may be a surface-treated product by a known method using a surface treatment agent such as a silane coupling agent.

  (D) Although the compounding quantity of an inorganic filler can be selected according to a use purpose from a viewpoint of the mechanical strength of a molded object, the minimum value of a preferable usage-amount is 1 in a flame-retardant resin composition. It is preferably at least 5% by mass, more preferably at least 5% by mass, most preferably at least 10% by mass. The upper limit of the preferred amount used is preferably 60% by mass or less, more preferably 55% by mass or less, and most preferably 50% by mass or less.

  In order to achieve the high flame retardancy of the present invention, the average particle diameter of the particulate inorganic filler should be in the range of 0.03 to 3.5 times the average fiber diameter of the fibrous inorganic filler. Is preferred. More preferably, it is the range of 0.1 to 2.0 times.

The purity of calcium hydroxide [Ca (OH) ₂ ] that can be used as the component (E) in the present invention may be any purity as long as it does not impair the characteristics of the present invention.
When calcium hydroxide is to be obtained, slaked lime is an example of what is generally distributed. Various characteristics of slaked lime are defined as industrial lime (JIS R9001: 2006) in Japanese Industrial Standards.
When using industrial lime as calcium hydroxide, the preferred purity of calcium oxide in the slaked lime is that of industrial slaked lime No. 2 or higher.

  Since calcium hydroxide is obtained by the reaction of calcium oxide and water, the purity of calcium hydroxide is expressed by the content of calcium oxide in JIS R9001: 2006. A specific preferable purity is 65 mass% or more as calcium oxide in slaked lime. More preferably, it is 70 mass% or more, More preferably, it is 72.5 mass% or more, Most preferably, it is 75 mass% or more.

Other components contained in industrial slaked lime include CO ₂ , SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , MgO, etc. Among these components, SiO ₂ , Al ₂ O ₃ , Fe ₂ The total content of O ₃ and MgO is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less. In order to suppress the deterioration of the mechanical properties of the flame retardant resin composition, it is desirable to suppress the concentration of these inorganic impurities.

  As the particle diameter of calcium hydroxide, those having substantially no fineness residue at 590 μm as defined by JIS R9001: 2006 are preferable. More preferably, the fineness residue of 149 μm is 15% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. The specific preferable average particle diameter is desirably 100 μm or less, more preferably 50 μm or less, and most preferably 20 μm or less. As a minimum, if it is 0.5 micrometer or more, it can be used without a problem in particular. In order to exhibit a high corrosion-inhibiting effect and maintain the high mechanical strength of the flame retardant resin composition, the average particle size is preferably 100 μm or less. In order not to deteriorate the handleability, the average particle size is preferably 0.5 μm or more. However, for example, when the handleability is improved by granulation treatment or the like, those having an average particle size of 0.5 μm or less can be preferably used.

The purity of calcium oxide [CaO] that can be used in the present invention may be any purity as long as the characteristics of the present invention are not impaired.
When trying to obtain calcium oxide, quick lime is mentioned as an example of what is generally circulating. Various characteristics of quick lime are defined as industrial lime (JIS R9001: 2006) in Japanese Industrial Standards.
The preferred purity of calcium oxide in quicklime when industrial quicklime is used as calcium oxide is that of industrial slaked lime No. 2 or higher.
A specific preferable purity is 80 mass% or more as calcium oxide in slaked lime. More preferably, it is 90 mass% or more, More preferably, it is 93 mass% or more, Most preferably, it is 95 mass% or more.
Other components contained in industrial quicklime include CO ₂ , SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , MgO, etc. Among these components, SiO ₂ , Al ₂ O ₃ , Fe ₂ The total content of O ₃ and MgO is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less. In order to suppress the mechanical properties of the flame retardant resin composition and the decrease in flame retardancy, it is desirable to suppress the concentration of these inorganic impurities.

  Next, the average particle diameter of calcium oxide is preferably 500 μm or less, more preferably 100 μm or less, and most preferably 20 μm or less. As a minimum, if it is 0.5 micrometer or more, it can be used without a problem in particular. In order to exhibit a high corrosion-inhibiting effect and maintain the high mechanical strength of the flame retardant resin composition, the average particle size is preferably 100 μm or less. In order not to deteriorate the handleability, the average particle size is preferably 0.5 μm or more. However, for example, when the handleability is improved by granulation treatment or the like, those having an average particle size of 0.5 μm or less can be preferably used.

  The average particle diameter of calcium hydroxide and / or calcium oxide (hereinafter sometimes abbreviated as calcium salts) in the present invention can be measured using a laser diffraction particle size distribution analyzer, as in the measurement of phosphinates. . However, at this time, it is necessary to appropriately select a solvent in which calcium salts and other components contained therein do not dissolve or swell.

  In this invention, the preferable quantity of these calcium salts is the range of 0.05-10 mass parts with respect to 100 mass parts of (C) phosphinic acid salts. More preferably, it is 0.08-7 mass parts, Most preferably, it is the range of 0.10-5 mass parts. The amount of these calcium salts is preferably 0.05 parts by mass or more in order not to reduce the corrosive suppression effect, and in order not to deteriorate the mechanical properties and flame retardancy, the amount of these calcium salts is It is desirable to be 10% by mass or less.

In the present invention, it is more preferable to add a compatibilizing agent in order to improve the compatibility between polyamide and polyphenylene ether. The main purpose of using the compatibilizer is to improve the physical properties of the polyamide-polyphenylene ether mixture.
The compatibilizing agent that can be used in the present invention refers to a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both. This interaction may be chemical (eg, grafting) or physical (eg, changing the surface properties of the dispersed phase). In any case, the resulting polyamide-polyphenylene ether mixture exhibits improved compatibility.

Examples of the compatibilizer of the component (F) that can be used in the present invention are described in detail in JP-A-8-48869 and JP-A-9-124926, and these known compatibilizing agents. All agents can be used and can be used in combination.
Among these various compatibilizers, the particularly preferred compatibilizer for component (F) is at least one selected from citric acid, maleic acid, itaconic acid, and anhydrides thereof. Of these, maleic anhydride and citric acid are most preferred.
The preferable amount of the compatibilizing agent in the present invention is 0.01 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, and most preferably 0.1 to 100 parts by mass of the mixture of polyamide and polyphenylene ether. ˜2 parts by mass.

Next, in the present invention, for the purpose of improving the appearance of the molded product, an appearance improving agent can be used within a range not impairing the effects of the present invention.
The appearance improving agent is at least one selected from mineral oil and wax.
First, mineral oil is at least one selected from aromatic compounds, naphthene ring compounds, and paraffinic compounds, and is generally a mixture of three types. When the mineral oil is a mixture, those called paraffinic mineral oil and naphthenic mineral oil with an aromatic compound of less than 30% are particularly preferred from the viewpoint of dispersibility and solubility when using an impact modifier.
The properties of these mineral oils are preferably those having a kinematic viscosity at 37.8 ° C. of 20 to 500 cst, a pour point of −10 to −15 ° C. and a flash point of 170 to 300 ° C.

Next, examples of the wax include paraffin wax, polyethylene wax, polyolefin wax, fatty acid ester, aliphatic dibasic acid ester, phthalic acid ester, and aromatic carboxylic acid ester. Of these, paraffin wax and polyethylene wax are particularly preferably used.
These appearance improving agents may be used alone or in combination of two or more.
The amount of these appearance modifiers used is the lower limit of the amount used with respect to a total of 100 parts by mass of (A) polyamide and (B) polyphenylene ether from the viewpoint of improving the surface appearance and preventing bleeding out to the surface of the molded product. Is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more. The upper limit of the amount used is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

Furthermore, an impact improving material can be used in the present invention as long as the effect is not impaired.
An impact modifier is a block copolymer comprising at least one block mainly composed of an aromatic vinyl compound and at least one block mainly composed of a conjugated diene compound, and / or a hydrogenated product of the block copolymer. Is mentioned.

  A block copolymer comprising a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound, which can be used in the present invention, Specific examples of the aromatic vinyl compound constituting a part of the copolymer include styrene, α-methylstyrene, vinyltoluene and the like. Two or more of these aromatic vinyl compounds may be used in combination. Styrene is particularly preferred.

  Specific examples of the conjugated diene compound constituting a part of the block copolymer include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, but are not limited thereto. Two or more of these conjugated diene compounds may be used in combination.

  In the impact-improving material, “mainly” in the block mainly composed of an aromatic vinyl compound and the block mainly composed of a conjugated diene compound means that at least 50% by mass of the block is an aromatic vinyl compound or conjugated diene compound. Means something. More preferably, it is 70 mass% or more.

  When butadiene is used as the conjugated diene compound of the block copolymer, the microstructure of the polybutadiene block part is that the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 5 to 80%. It is preferably 10 to 50%, more preferably 15 to 40%. Usually, there are 1,2-vinyl bond, 3,4-vinyl bond, and 1,4-vinyl bond as the bond form of the conjugated diene compound. The vinyl bond amount referred to here is the conjugated diene compound at the time of polymerization. The ratio of the bonding form is shown. For example, the amount of 1,2-vinyl bond means the ratio of 1,2-vinyl bond in the above three bond forms and can be easily known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like. be able to.

  A block copolymer comprising a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound is a polymer block mainly composed of an aromatic vinyl compound. (S) and a polymer block (B) mainly composed of a conjugated diene compound is a block copolymer having a bond type selected from SB type, SBS type and SSB type. A polymer is preferred. Among these, the SBS type and the SBS type are more preferable, and the SBS type is most preferable. Of course, these may be a mixture.

  In the present invention, a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound can be used. In other words, this hydrogenated block copolymer is obtained by hydrogenating an aliphatic double bond in the above-mentioned block copolymer of an aromatic vinyl compound and a conjugated diene compound to exceed 100%. Controlled by the hydrogenation treatment ratio for the double bond within the range up to. A preferable hydrogenation rate of the hydrogenated block copolymer is 50% or more, more preferably 80% or more, and most preferably 95% or more.

In the present invention, the block copolymer (optionally hydrogenated) of an aromatic vinyl compound and a conjugated diene compound is preferably a block copolymer having a number average molecular weight of 100,000 or more. More preferably, it is a block copolymer of 150,000 or more.
The number average molecular weight as used in the field of this invention means the number average molecular weight measured with the ultraviolet spectroscopic detector using the gel permeation chromatography measuring apparatus, and converted with standard polystyrene. At this time, a low molecular weight component resulting from catalyst deactivation during polymerization may be detected. In this case, the low molecular weight component is not included in the molecular weight calculation. Usually, the calculated correct molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.0 to 1.1.

  In the present invention, the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound is preferably 15,000 or more. More preferably, it is 30,000 or more and 400,000 or less. By setting the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound to 15,000 or more and 400,000 or less, variation in impact resistance (surface impact strength) of the resin composition can be suppressed. it can.

In addition, the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound can be obtained by the following equation using the number average molecular weight of the block copolymer described above.
Mn (a) = {Mn × a / (a + b)} / N
[In the above formula, Mn (a) is the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound, and Mn is at least one polymer block composed mainly of at least one aromatic vinyl compound. The number average molecular weight of a block copolymer comprising a polymer block mainly composed of a conjugated diene compound, a is the weight percent of the polymer block mainly composed of all aromatic vinyl compounds in the block copolymer, b is The weight% of the polymer block mainly composed of all conjugated diene compounds in the block copolymer, and N represents the number of polymer blocks mainly composed of the aromatic vinyl compound in the block copolymer. ]

  These block copolymers that can be used in the present invention are those having different bond types, different aromatic vinyl compound types, different conjugated diene compound types, unless contrary to the spirit of the present invention. , 2-bond vinyl content or 1,2-bond vinyl content and 3,4-bond vinyl content different, aromatic vinyl compound component content different, hydrogenation rate different, etc. You may mix and use 2 or more types.

In addition, these block copolymers used in the present invention may be block copolymers in which all or part of them are modified.
The modified block copolymer here means at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or It refers to a block copolymer modified with at least one modifying compound having a glycidyl group.

  The modified block copolymer can be produced by (1) melt-kneading with the modified compound at a temperature in the range of the softening point temperature of the block copolymer to 250 ° C. in the presence or absence of a radical initiator. (2) a method of reacting the block copolymer and the modifying compound in a solution at a temperature below the softening point of the block copolymer, and (3) a temperature below the softening point of the block copolymer, Examples include a method of reacting the block copolymer and the modifying compound without melting them, and any of these methods may be used, but the method (1) is preferable, and among the methods (1), in the presence of a radical initiator. The method of performing is most preferred.

  At least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group in the molecular structure referred to herein. Can be the same as the modified compound described for the modified polyphenylene ether.

  The preferable amount of the impact modifier in the present invention is 5 to 25 parts by mass when the total amount of polyamide and polyphenylene ether is 100 parts by mass. More preferably, it is 7-15 mass parts.

In the present invention, an adduct formed from melamine and phosphoric acid can be used as long as the characteristics of the present invention are not impaired.
Specific examples of adducts formed from melamine and phosphoric acid include reaction products of melamine and polyphosphoric acid and / or reaction products of condensate of melamine and polyphosphoric acid, formula (NH ₄ ) _y H _{3 -y} PO ₄ or (NH ₄ PO ₃ ) _z [wherein y is 1 to 3, and z is 1 to 10,000], a nitrogen-containing phosphate, ammonium hydrogen phosphate, phosphoric acid 1 or more types chosen from ammonium dihydrogen and / or ammonium polyphosphate are mentioned. In particular, it is represented by the following chemical formula (C ₃ H ₆ N ₆ · HPO ₃ ) _n (where n represents the degree of condensation), and is substantially the same between melamine and phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. Those obtained from molar reaction products are preferably usable. More specifically, at least one selected from dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, and mixed polysalts thereof can be used. Of these, melamine polyphosphate is most preferable.

There is no restriction | limiting in particular in these manufacturing methods, For example, the method etc. which heat-condensate melamine phosphate in nitrogen atmosphere will 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 is preferable because of its high effect as a flame retardant.

Moreover, since heat resistance becomes high by making the condensation degree n of melamine polyphosphate into 5 or more, it is a preferable direction.
Melamine polyphosphate may be an equimolar addition salt of polyphosphoric acid and melamine. Examples of polyphosphoric acid forming an addition salt with melamine include linear polyphosphoric acid called cyclic phosphoric acid and cyclic polymetaphosphoric acid. . The condensation degree n of these polyphosphoric acids is not particularly limited and is usually from 3 to 50. However, the condensation degree n of the polyphosphoric acid used here is preferably 5 or more from the viewpoint of the heat resistance of the resulting melamine addition salt.

A method for producing such a melamine polyphosphate addition salt is, for example, a slurry in which a mixture of melamine and polyphosphoric acid is dispersed in water, which is mixed well to form both reaction products in the form of fine particles. There is a method of filtering, washing and drying, further baking if necessary, and pulverizing the obtained solid to obtain a powder.
In the adduct formed from melamine and phosphoric acid, an unreacted product or a by-product may remain or be mixed as long as the effects of the present invention are not impaired.
A preferable amount of the adduct formed from melamine and phosphoric acid is 0.3 to 30 parts by mass with respect to a total of 100 parts by mass of (A) polyamide and (B) polyphenylene ether. More preferably, it is 0.5-15 mass parts, Most preferably, it is 1-10 mass parts, Most preferably, it is 1-8 mass parts.

When an adduct formed from melamine and phosphoric acid is used, the following zinc-containing compounds can also be used for the purpose of stabilization without departing from the characteristics of the present invention.
The zinc-containing compound includes all organic zinc-containing compounds such as zinc stearate and inorganic zinc-containing compounds such as zinc oxide. Among these, preferred zinc-containing compounds are inorganic zinc-containing compounds. Among these, at least one selected from zinc oxide, zinc sulfide, zinc borate, and zinc stannate is more preferable, and xZnO.yB ₂ O ₃ .zH ₂ O (x> 0, y> 0, z ≧ 0). Most preferred is zinc borate represented by
Specific examples thereof include one or more selected from 2ZnO · 3B ₂ O ₃ · 3.5H ₂ O, 4ZnO · B ₂ O ₃ · H ₂ O, and zinc borate represented by 2ZnO · 3B ₂ O _3. It is.

Zinc-containing compounds increase the flame retardancy by suppressing the generation of gas as fuel in the decomposition of the resin by blocking the heat from the flame that is the heat source during combustion as a flame retardant aid (heat insulation ability) It plays the role of forming a non-combustible layer (or carbonized layer) necessary for this.
Furthermore, these zinc-containing compounds may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent.
A preferable amount of these zinc-containing compounds is 0.01 to 15 parts by mass with respect to a total of 100 parts by mass of (A) polyamide and (B) polyphenylene ether. More preferably, it is 0.1-10 mass parts, 0.2-5 mass parts is more preferable, 0.2-3 mass parts is the most preferable. In order to increase the stability of the flame retardant, it is desirable that the zinc-containing compound is within the above-described range.

Furthermore, various conductive fillers can be used in the resin composition of the present invention.
Examples thereof include conductive carbon black, carbon nanotubes (carbon fibrils), graphite, and carbon fibers. These may be used in a mixture of two or more. Of these, carbon black for electrical conduction and carbon nanotubes (carbon fibrils) can be preferably used.
The amount of the conductive filler used is in the range of 0.5 to 20% by mass when the resin composition is 100% by mass. Preferably it is 1-10 mass%, More preferably, it is 1-5 mass%. Most preferably, it is 1-3 mass%.

In the present invention, the method for adding the conductive filler is not particularly limited, but a preferable method includes a method in which the conductive filler is added in the form of a conductive masterbatch obtained by melt-kneading in polyamide in advance. At this time, the preferable amount of the conductive filler in the master batch is generally 5 to 30% by mass (when the conductive master batch is 100% by mass). When conductive carbon black is used as the conductive filler, 5 to 15% by mass is more preferable, and 8 to 12% by mass is most preferable. When a conductive filler other than conductive carbon black containing carbon nanotubes (carbon fibrils), graphite, and carbon fibers is used as the conductive filler, it is preferably 10 to 30% by mass, and most preferably 15 to 25% by mass.
As a manufacturing method of the conductive master batch, a method of manufacturing using a twin screw extruder is preferable. In particular, a method in which a conductive filler is added to molten polyamide and further melt-kneaded is preferable.

Moreover, the resin composition of the present invention may further contain a flame retardant other than the component (C). As the flame retardant in this case, an inorganic or organic flame retardant containing substantially no halogen is more preferable.
In the present invention, “substantially free of halogen” means that the halogen concentration in the resin composition containing a flame retardant is less than 1% by weight. More preferably, it is less than 5000 ppm, and most preferably less than 1000 ppm. In this case, the lower limit is zero.
Examples of flame retardants that can be used are known inorganic flame retardants represented by magnesium hydroxide, aluminum hydroxide, and the like, triphenyl phosphate, triphenyl phosphate, bisphenol A bis (diphenyl phosphate) and the like. Organophosphates, phosphoric acid nitrogen-containing compounds represented by ammonium polyphosphate, polymelamine melamine, etc., phosphazene compounds as described in JP-A-11-181429, silicone oils, red phosphorus And other known flame retardants.

Moreover, in this invention, the fluorine-type polymer represented by the tetrafluoroethylene etc. which are known as a dripping prevention agent can also be used if it is the quantity below 2 mass% in a resin composition.
In the present invention, in addition to the above-described components, additional components may be added at any stage as necessary within the range not impairing the effects of the present invention.
Examples of additional components include other thermoplastic resins such as polyester and polyolefin, plasticizers (low molecular weight polyolefin, polyethylene glycol, fatty acid esters, etc.), antistatic agents, nucleating agents, fluidity improvers, fillers , Reinforcing agents, various peroxides, spreading agents, copper heat stabilizers, organic heat stabilizers typified by hindered phenolic antioxidants, antioxidants, UV absorbers, light stabilizers, etc. is there.
The specific preferable addition amount of these components is 10 weight% or less in a resin composition, respectively. A more preferred amount is less than 5% by weight and most preferred is 3% by weight or less.

  Specific processing machines for obtaining the flame retardant resin composition of the present invention include, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. Among these, a twin screw extruder is preferable, and a twin screw extruder having an upstream supply port and one or more downstream supply ports is most preferable.

The production method of the present invention is not particularly limited as long as the effects of the present invention are exhibited, but preferred examples will be described below.
(1) Using a twin screw extruder having one supply port on the upstream side and one on the downstream side, supply at least polyamide and polyphenylene ether from the upstream supply port, and if necessary, impact modifiers, compatibilizers, etc. A method of melt-kneading, supplying phosphinates, fibrous inorganic fillers and particulate inorganic fillers as inorganic fillers, calcium salts and other additives from a downstream supply port, and further melt-kneading.
(2) Using a twin screw extruder having one supply port on the upstream side and one on the downstream side, polyphenylene ether and polyamide, phosphinates from the upstream supply port, if necessary, other additives, impact modifiers, A method in which a compatibilizing agent is supplied and melt-kneaded, and a fibrous inorganic filler and particulate inorganic filler, calcium salts, and other additives are supplied from a downstream supply port, and further melt-kneaded.

(3) Using a twin screw extruder having one supply port on the upstream side and two supply ports on the downstream side, at least polyphenylene ether from the upstream supply port, if necessary, other additives, impact modifiers, compatibilizing agents And melt-kneading, supplying polyamide and, if necessary, other additives from the downstream first supply port (downstream supply port located upstream), melt-kneading, and phosphine from the downstream second supply port Method of supplying acid salts, inorganic fillers, calcium salts, other additives as required, and further melt-kneading (4) Using a twin-screw extruder having one supply port on the upstream side and two supply ports on the downstream side, At least polyphenylene ether and polyamide from the upstream supply port, if necessary, impact modifiers and compatibilizers are supplied and melt kneaded, and inorganic from the downstream first supply port (downstream supply port located upstream) Of Hama material was melt-kneaded by supplying a fibrous inorganic filler, downstream second feed port than phosphinates, particulate inorganic fillers, to supply calcium salts, and further a method in which melt kneading. Among the above, the methods (3) and (4) are preferable.

The melt-kneading temperature for obtaining the flame-retardant resin composition of the present invention (the melt-kneading temperature referred to in the present invention is a set temperature of a cylinder such as an extruder) is not particularly limited. In consideration of the conditions, a condition in which a suitable composition can be obtained can be arbitrarily selected from 240 to 360 ° C. Preferably it is the range of 280 degreeC-330 degreeC.
150-800 rpm is preferable and, as for the rotation speed of the extruder at the time of a process, 250-700 rpm is more preferable. In order to increase the dispersibility of phosphinates efficiently, the rotation speed is preferably 150 rpm or more, and in order to suppress the decomposition of the resin, it is desirable to set it to 800 rpm or less.
The flame retardant resin composition of the present invention thus obtained can be used as a molded body for various parts by various conventionally known methods such as injection molding.

The flame retardant resin composition of the present invention is a composition having an average burning time of 5 seconds or less measured by vertical flame contact according to UL94 in a 1.6 mm thickness test piece or more preferably in a 0.8 mm thickness test piece. A thing can be used suitably for various uses, and is preferable.
The flame-retardant resin composition of the present invention can be suitably used particularly for electrical and electronic parts and automotive electrical and electronic parts. In particular, there are many thin-walled parts, and they can be suitably used as materials for parts for surface mounting technology in the electronic field, where high heat resistance is required.
Hereinafter, the embodiments of the present invention will be described in more detail by way of examples.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to this Example.
The raw materials and measurement methods used in Examples and Comparative Examples are shown below.

[raw materials]
(A) Polyamide (A-1) PA9T-1: Semi-aromatic polyamide composed of terephthalic acid, nonamethylenediamine and 2-methyl-1,8-octamethylenediamine Melting point: 308 ° C., viscosity number (specified by ISO307: 1997) Measured in 96% sulfuric acid) 70 ml / g, end-capping rate: 90%,
Terminal amino group concentration: 19 μmol / g
Prepared according to the production of polyamide 9T in the examples of WO2007 / 058169.

(A-2) PA6T / 66: Semi-aromatic polyamide consisting of hexamethylenediamine, terephthalic acid and adipic acid Melting point: 314 ° C
Product name: Amodel A-4000 (manufactured by Solvay Advanced Polymers)

(A-3) PA66: aliphatic polyamide consisting of hexamethylenediamine and adipic acid Melting point: 257 ° C
Obtained as Leona 1200S (Asahi Kasei Chemicals)

(B-1) Polyphenylene ether (hereinafter referred to as PPE-1)
Poly (2,6-dimethyl-1,4-phenylene ether)
Reduced viscosity [ηsp / c]: 0.42 dl / g

(C) Phosphinic acid salts Aluminum diethylphosphinate (hereinafter referred to as DEP).
Purity: 95% or more Particle size: Average particle size 5 μm
Product name: Exolit OP930 (manufactured by Clariant)

(D) Calcium salt Calcium hydroxide: [hereinafter Ca (OH) ₂ ]
Uses reagent (Wako Pure Chemical Industries, Ltd.)

(E) Inorganic filler (E-1) Fibrous inorganic filler Glass fiber (hereinafter referred to as GF)
Product name: ECS03-T747 Nippon Electric Glass Co., Ltd. Chop fiber length: 3 mm
Fiber diameter: 13 μm

(E-2) Particulate inorganic filler Microcrystalline talc (hereinafter referred to as Talc)
Average particle size: 11 μm
Aspect ratio: 1.2

(E-3) Particulate inorganic filler wollastonite (hereinafter, wollastonite-1)
Average particle size: 3 μm
Aspect ratio: 3

(E-4) Fibrous inorganic filler wollastonite (hereinafter, wollastonite-2)
Average particle size: 8μm
Aspect ratio: 14

(E-5) Particulate inorganic filler Calcium carbonate (hereinafter referred to as CaCO ₃ )
Average particle size: 150 nm
Aspect ratio: 1.0

(F) Compatibilizer Maleic anhydride (hereinafter MAH)
Product name: Crystal MAN Nippon Oil & Fats Co., Ltd.

[Measuring method]
(1) Flame retardancy (UL-94VB)
Using the method of UL94 (standard defined by Under Writers Laboratories Inc., USA), five samples were measured per sample. In addition, the test piece (length 127mm, width 12.7mm, thickness 0.8mm) was shape | molded using the injection molding machine (Toshiba machine Co., Ltd. product: IS-80EPN). Molding was performed at a cylinder temperature of 330 ° C and a mold temperature of 120 ° C.
In the flame retardancy class, the flame retardance class classified by UL94 vertical flame test is shown. However, all the samples were judged by performing five tests. The outline of the classification method is as follows. Other details conform to the UL94 standard.

V-0: Total combustion time of 50 seconds or less Maximum combustion time per bottle of 10 seconds or less No flaming dripping V-1: Total combustion time of 250 seconds or less Maximum combustion time per bottle of 30 seconds or less
V-2: Total burning time 250 seconds or less Maximum burning time per bottle 30 seconds or less
Non-standard: burns up to those that do not correspond to the above three items and clamps that hold the specimen
The total burning time (seconds) is the total burning time of the time required to extinguish after 10 times of flame contact with each sample 5 specimens 5 times in total. The time (seconds) represents the time that took the longest to extinguish.

(2) Corrosion test Carbon steel obtained by putting 20 g in an SUS314 autoclave having a pressure resistance of 2.0 MPa and an internal volume of 100 ml, and polishing the surface by # 2000 in size length x width x thickness 10 mm x 20 mm x 2.0 mm. (Material: SS400) A test piece is put, 20 g of pellets are further put, and a carbon steel test piece is buried. After the inside of the autoclave was replaced with nitrogen, it was sealed and left in a thermostatic bath set at 330 ° C. for 5 hours. The autoclave was taken out under running water, cooled to room temperature, and the autoclave was opened.
The carbon steel test piece was taken out from the melted and solidified pellet, and the resin adhering to the carbon steel test piece was dissolved and removed by HFIP (hexafluoroisopropanol).
The carbon steel test piece was air-dried, weighed to the nearest 0.1 mg, and divided in advance by the weight of the carbon steel test piece before the corrosion test, and the weight loss rate before and after the test was determined in mass ppm.

(3) Reflow test Create the same test piece as molded in the combustion test, absorb moisture for 168 hours at 23 ° C and 50% relative humidity, and then heat for 10 seconds at a maximum temperature of 265 ° C and 260 ° C or higher. Through the set reflow furnace, the change of the test piece in the reflow environment was observed.
Since the surface of the test piece that swells and has a melt mark is not suitable for surface mount technology (SMT) compatible parts, the presence or absence was visually observed.

[Examples 1 to 10 and Comparative Examples 1 to 9]
Two on the upstream side and two supply ports on the downstream side (one at the 0.4 position and one at the 0.8 position when the total length of the extruder cylinder is 1.0) The cylinder temperature of the shaft extruder [ZSK-26MC: manufactured by Coperion (Germany)] from the upstream supply port (hereinafter referred to as upstream supply port) to the supply port at L = 0.4 (hereinafter referred to as central supply port). 320 degreeC and the downstream side from the center supply port were set to 300 degreeC.
According to the ratio of Tables 1-2, each raw material was supplied, and it melt-kneaded and obtained the pellet. In order to adjust the moisture content of the obtained pellets, after extrusion, the pellets were dried in a dehumidifying dryer set at 80 ° C., and then put in an aluminum-coated moisture-proof bag. The moisture content of the pellets at this time was approximately 250 to 500 ppm.
The screw speed at this time was 250 rpm, and the discharge rate was 15 kg / h. Further, openings were provided in the block immediately before the cylinder block having the central supply port and the cylinder block immediately before the die, and the remaining volatile components and oligomers were removed by vacuum suction. The degree of vacuum (absolute pressure) at this time was 60 Torr.
Various evaluations described above were performed using the obtained pellets. The results are shown in Tables 1 and 2 together with the composition.

  In Examples 1 to 4, metal corrosiveness is suppressed, and the flame retardancy and reflow resistance of a 0.8 mm-thick test piece are excellent. In Example 5, although the reflow resistance is weak, the metal corrosiveness is suppressed, and the flame retardancy of the 0.8 mm thick test piece is excellent. In Comparative Examples 1 to 3, the metal corrosivity is large. In Comparative Examples 4 to 6, in the combustion test, the maximum combustion time exceeds 10 seconds and does not become V-0, and the combustibility is not sufficient.

According to the comparison between Examples 6 to 9 and Comparative Examples 7 to 8, only when a specific amount of the particulate inorganic filler is included, the flame retardancy in the 0.8 mm-thick test piece is excellent and the corrosivity is suppressed. You can see that
Comparison between Example 10 and Comparative Example 9 shows that even if the inorganic fillers are of the same type, if their aspect ratios are different, they are excellent in flame retardancy only within the scope of the present invention.

[Example 11]
The flame retardant resin composition was produced and evaluated in the same manner except that Talc in Example 2 was replaced with CaCO _3. As a result, as in Example 2, the flame retardancy was excellent and the corrosivity was remarkably suppressed. It was.

  The present invention relates to a flame retardant resin composition of polyamide / polyphenylene ether which has high flame resistance in thin-walled parts, which is difficult to achieve with the prior art, and high heat resistance, and has a significantly reduced corrosiveness to metals. In particular, it can be suitably used for electrical and electronic parts and automotive parts. In particular, it can be suitably used for electrical and electronic parts that can cope with surface mounting technology (SMT).

Claims (18)

(A) polyamide, (B) polyphenylene ether, (C) a phosphinic acid salt represented by the following formula (I), a diphosphinic acid salt represented by the following formula (II), and a condensate thereof: A flame-retardant resin composition comprising one phosphinate, (D) inorganic filler, and (E) calcium hydroxide, wherein (D) the inorganic filler is a fibrous inorganic filler A flame retardant resin composition, which is a mixture of particulate inorganic fillers, wherein the inorganic particulate filler is 1 to 15% by mass when the total amount of inorganic fillers is 100% by mass.

[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and R ³ is linear or branched C ₁ -C ₁₀ - alkylene, C ₆ -C ₁₀ - arylene, C ₆ -C ₁₀ - alkylarylene or C ₆ -C ₁₀ - aryl alkylene, M is calcium (ion), magnesium (ion), aluminum (ion) , Zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and one or more protonated nitrogen bases, m is 1 to 3, n Is 1 to 3, and x is 1 or 2. ]   The particulate inorganic filler is 3.0 to 12.0 mass% when the amount ratio of the particulate inorganic filler and the fibrous inorganic filler is 100 mass% in total. The flame retardant resin composition according to 1. (C) 0.05-10 mass parts of (E) calcium hydroxide is included with respect to 100 mass parts of phosphinates, The flame-retardant resin composition of Claim 1 or 2 characterized by the above-mentioned. The flame retardant according to any one of claims 1 to 3, wherein the phosphinic acid salt of component (C) comprises 90% by mass or more of the phosphinic acid salt represented by the following formula (I). Resin composition.

[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and M is calcium (ion), magnesium (ion), aluminum (Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and one or more protonated nitrogen bases, and m is 1 to 3. is there. ]   The particulate inorganic filler of component (D) is at least one selected from glass beads, talc, mica, wollastonite, kaolin and calcium carbonate having an aspect ratio of 1 to 10. The flame-retardant resin composition according to any one of claims 1 to 4.   The fibrous inorganic filler of component (D) is at least one or more selected from glass fibers, carbon fibers, wollastonite, and potassium titanate whiskers having an aspect ratio exceeding 10. Item 6. The flame retardant resin composition according to any one of Items 1 to 5.   The average particle diameter of the particulate inorganic filler is in the range of 0.03 to 3.5 times the average fiber diameter of the fibrous inorganic filler. Flame retardant resin composition.   The average particle diameter of the particulate inorganic filler is in the range of 0.1 to 2.0 times the average fiber diameter of the fibrous inorganic filler. Flame retardant resin composition.   (D) The flame retardant resin composition according to any one of claims 1 to 8, wherein the blending amount of the inorganic filler is 1 to 60% by mass in the entire flame retardant resin composition. .   (A) The polyamide comprises an aromatic ring-containing monomer as a monomer component constituting the polymer, and comprises a semi-aromatic polyamide in which the amount of the aromatic ring-containing monomer is 20 mol% or more in the monomer component. The flame-retardant resin composition according to any one of claims 1 to 9.   (A) 60-100 mol of dicarboxylic acid unit (a) in which the polyamide contains 60-100 mol% of terephthalic acid units, 1,9-nonanediamine units and / or 2-methyl-1,8-octanediamine units The flame-retardant resin composition according to any one of claims 1 to 10, which is a semi-aromatic polyamide resin comprising a diamine unit (b) contained in%.   When (A) polyamide and (B) polyphenylene ether have a total amount of 100 parts by mass, (A) polyamide is 40 to 90 parts by mass, and (B) polyphenylene ether is 60 to 10 parts by mass. The flame-retardant resin composition according to any one of claims 1 to 11, wherein   (C) The compounding quantity of phosphinic acid salt is 1-80 mass parts with respect to a total of 100 mass parts of (A) polyamide and (B) polyphenylene ether, The any one of Claims 1-12 characterized by the above-mentioned. The flame retardant resin composition according to Item 1.   The difficulty according to any one of claims 1 to 13, wherein the component (F) includes one or more compatibilizers selected from citric acid, maleic acid, itaconic acid and anhydrides thereof. A flammable resin composition.   The compatibilizer for component (F) is contained in an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass in total of (A) polyamide and (B) polyphenylene ether. Flame retardant resin composition. It is selected from (A) polyamide, (B) polyphenylene ether, (C) phosphinic acid salt represented by the following formula (I), diphosphinic acid salt represented by the following formula (II), and condensates thereof. at least one phosphinic acid salts, (D) an inorganic filler, and (E) calcium hydroxide, comprises a, (D) an inorganic filler, a mixture of fibrous inorganic filler and particulate inorganic filler A method for producing a flame retardant resin composition in which the amount of the inorganic inorganic filler is 1 to 15% by mass when the total amount of the inorganic fillers is 100% by mass, and includes (A) polyamide and (B) polyphenylene in advance. Ether is melt-kneaded, and after adding the fibrous inorganic filler of (D) inorganic filler to the molten resin component and melt-kneading, (C) phosphinates and (D) particles of inorganic filler Inorganic filler, (E) Hydroxic acid Method for producing a flame-retardant resin composition characterized by melt-kneading addition of calcium.

[Wherein, R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and R ³ is linear or branched C ₁ -C ₁₀ - alkylene, C ₆ -C ₁₀ - arylene, C ₆ -C ₁₀ - alkylarylene or C ₆ -C ₁₀ - aryl alkylene, M is calcium (ion), magnesium (ion), aluminum (ion) , Zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion) and one or more protonated nitrogen bases, m is 1 to 3, n Is 1-3 and x is 1 or 2. ]   The pellet obtained from the flame-retardant resin composition of any one of Claims 1-15.   A molded product obtained from the flame retardant resin composition according to any one of claims 1 to 15.