JP5402628B2 - Flame retardant polyamide resin composition and molded body using the same - Google Patents

Description

  The present invention relates to a flame retardant polyamide resin composition and a molded body using the same, and in particular, a polyamide resin composition having excellent flame retardancy and excellent mechanical properties such as rigidity and toughness, and the resin composition The present invention relates to a molded body formed by molding.

Polyamide resins have excellent mechanical properties, heat resistance, and chemical resistance, and are therefore useful as engineering plastics as molding materials for electronic / electrical applications, OA equipment applications, automotive applications, and the like. In these uses, when flame retardancy, particularly flame retardancy at the V-0 level in the UL94 standard, is required, a polyamide resin composition to which a flame retardant is added is used.
As a flame retardant for a polyamide resin, a combination of brominated polystyrene and antimony oxide is mainly used for a polyamide resin blended with a triazine compound such as melamine cyanurate and a glass fiber in a polyamide resin without a filler. Flame retardant methods that do not use halogen compounds are superior in that they have a low environmental impact, but the flame retardant effect of triazine compounds and the like is not sufficient, and it is necessary to add them in large quantities to impart a high level of flame retardant properties. . In addition, a flame retardant polyamide resin molded product containing a triazine compound has a problem that when the flame retardant elapses for a long time, the flame retardant is bled to the surface of the molded product and the surface of the molded product is whitened.

Phosphorus flame retardants, on the other hand, are considered to exhibit higher flame retardancy as the phosphorus element concentration is higher, but substances with a high phosphorus concentration, such as red phosphorus, will hydrolyze and corrode metals, or toxic phosphine. Gas is generated and there is a risk of ignition due to friction during kneading with the polyamide resin composition. Further, since the phosphorus-based flame retardant has a relatively large particle size distribution, the physical properties of the resin composition are greatly reduced, and the toughness inherent to the polyamide resin is impaired.
Then, the composite flame retardant which combined the phosphinate and the nitrogen-type base etc. is proposed (refer patent documents 1 and 2). However, when these composite flame retardants are added, the strength, elongation at break, impact strength, etc. are reduced compared to the additive-free polyamide resin composition, the toughness inherent to the polyamide resin is impaired, and the molded product is brittle. Is often a problem.
In order to improve the rigidity and toughness of the flame retardant polyamide resin composition, an inorganic filler such as glass fiber may be added. However, the rigidity increases but the toughness is insufficient, and talc-like However, there is a problem that it is difficult to exhibit toughness with the use of a plate-like inorganic filler.

Special table 2000-508365 JP 2004-18857 A

  The present invention solves the above problems, has a flame retardancy of V-0 level according to the UL94 standard, and is excellent in mechanical properties such as rigidity and toughness, and molding the resin composition It aims at providing the molded object which becomes.

That is, the present invention provides the following (1) and (2).
(1) A flame retardant polyamide resin composition comprising a polyamide resin (A), an acicular inorganic filler (B), a flame retardant (C), and a polyfluoroolefin resin (D).
(2) A molded article obtained by molding the flame retardant polyamide resin composition of (1).

  According to the present invention, a polyamide resin composition having flame retardancy of V-0 level according to UL94 standard and excellent in mechanical properties such as rigidity and toughness, and a molded body formed by molding the resin composition are provided. Can be provided.

The flame-retardant polyamide resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) includes a polyamide resin (A), an acicular inorganic filler (B), a flame retardant (C), and a polyfluoroolefin. System resin (D) is included.
[Polyamide resin (A)]
There is no restriction | limiting in particular as a polyamide resin (A) used for this invention, From the well-known aliphatic polyamide resin and aromatic polyamide resin, 1 type (s) or 2 or more types can be selected arbitrarily. Here, the aliphatic polyamide resin refers to a polyamide having no aromatic ring in the molecular chain, and the aromatic polyamide resin refers to a polyamide having an aromatic ring in the molecular chain.
Examples of such a polyamide resin include polyamides mainly composed of aminocarboxylic acid, lactam or diamine and dicarboxylic acid.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 6 to 12 carbon atoms, such as 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. It is done.
Examples of the lactam include lactams having 4 to 12 carbon atoms, such as α-pyrrolidone, ε-caprolactam, ω-laurolactam, and ε-enantolactam.

Examples of diamines include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethyl. Hexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane Bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, metaxylylene Amines, aliphatic such as p-xylylenediamine, alicyclic, and a diamine of the aromatic and the like.
Dicarboxylic acids include fats such as adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc. Aromatic, alicyclic and aromatic dicarboxylic acids.

In the present invention, polyamide 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 used in the present invention include polyamide 6, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 6/66, polynonamethylene terephthalamide (polyamide 9T), poly Hexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene terephthalamide / polycaproamide copolymer (polyamide 6T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer ( Polyamide 66 / 6I), polyhexamethylene isophthalamide / polycaproamide copolymer (polyamide 6I / 6), polydodecamide / polyhexamethylene terephthalamide copolymer ( Lyamide 12 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene terephthalamide) copolymer (polyamide 6T / M5T), polyxylylene adipamide (polyamide MXD6), and mixtures or copolymer resins thereof. Among these, polyamide 6, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12 or polyamide 6/66 are preferable, and polyamide 6/66 (copolymer resin) is particularly preferable from the viewpoint of toughness. .

30-80 mass% is preferable based on the resin composition whole quantity, and, as for the mixture ratio of the polyamide resin (A) used by this invention, 40-70 mass% is more preferable. When the blending ratio of the polyamide resin (A) is less than 30% by mass, the molding processability is poor and sufficient material properties may not be obtained. When it exceeds 80% by mass, sufficient flame retardancy is not obtained. There is.
The polyamide resin (A) used in the present invention is preferably one having a polymerization degree within a specific range, that is, a relative viscosity within a specific range. A preferable relative viscosity is a value measured according to JIS K 6920, and is usually about 1.8 to 5.0, particularly preferably 2.0 to 4.5. If the relative viscosity is low, the material strength becomes small. On the other hand, if the relative viscosity is too high, the fluidity is lowered and the moldability and the product appearance may be impaired.

[Acicular inorganic filler (B)]
Examples of the needle-like inorganic filler (B) used in the present invention include aluminum hydroxide, asbestos, wollastonite, potassium titanate, zonotlite, capiolite, phosphate fiber, gypsum fiber, magnesium oxysulfate, and carbon fiber. It is done. These acicular inorganic fillers can be used singly or in combination of two or more.
The acicular inorganic filler (B) is used for imparting excellent rigidity and toughness mechanical properties to the polyamide resin composition of the present invention. From the viewpoint of the effect of imparting mechanical properties, the shape has an average diameter of usually about 3 to 20 μm, preferably 5 to 15 μm, and an average length of usually about 20 to 300 μm, preferably 20 to 100 μm. The aspect ratio (average length / average diameter) is preferably 3 to 100, and more preferably 3 to 20.
In the present invention, wollastonite is particularly preferable as the acicular inorganic filler (B) from the viewpoints of mechanical properties of the resin composition and safety to the human body. This wollastonite is a natural white mineral having needle-like crystals, the chemical formula is represented by CaSiO ₃ , usually SiO ₂ is about 50 mass%, CaO is about 47 mass%, other Fe ₂ O ₃ , Al ₂ O ₃ etc. and specific gravity is about 2.9.

In the present invention, the needle-shaped inorganic filler (B) is used for the purpose of increasing the affinity for the resin component and preventing aggregation of the needle-shaped inorganic fillers during melt kneading of the resin component and the needle-shaped inorganic filler. It is preferable to process. Examples of the surface treating agent include known organic treating agents and inorganic dispersing agents. For example, various coupling agents such as silane coupling agents, titanate coupling agents, aluminate coupling agents, fatty acids such as oleic acid and stearic acid, fatty acid esters, phosphate esters, alkyl phosphate esters, fatty acid metals Examples thereof include salts, silicates such as methyl silicate and ethyl silicate, alcohols and the like. Of these, silane coupling agents and fatty acids are preferred. There is no restriction | limiting in particular in the surface treatment method, A well-known method can be used.
When using wollastonite as the acicular inorganic filler (B), a silane coupling agent is particularly preferable as the surface treatment agent.

  Examples of the silane coupling agent include triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxy. (Cyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are preferable.

As a method of using the silane coupling agent, a method of surface-treating wollastonite in advance according to a conventional method and then melt-kneading with the polyamide resin (A) or the like is preferably used. A so-called integral blend method in which a silane coupling agent is added simultaneously with melt-kneading with the polyamide resin (A) or the like can also be used.
In the resin composition of the present invention, the blending ratio of the needle-like inorganic filler (B) is usually 5 to 5 based on the total amount of the resin composition from the viewpoint of the balance of the mechanical properties and moldability, surface state, etc. of the resin composition. 40% by mass, preferably 10 to 30% by mass.

[Flame Retardant (C)]
There is no restriction | limiting in particular as a flame retardant (C) used for this invention, From a well-known flame retardant, 1 type (s) or 2 or more types can be selected arbitrarily.
The flame retardant (C) can be broadly classified into organic flame retardants and inorganic flame retardants such as bromine-containing flame retardants, nitrogen-containing flame retardants, phosphorus-containing flame retardants and nitrogen-phosphorus-containing flame retardants.
(Bromine-containing flame retardant)
As the bromine-containing flame retardant, a brominated flame retardant containing bromine, preferably 40 to 80% by mass, more preferably 50 to 70% by mass, is suitable, such as brominated polystyrene, polybrominated styrene, brominated polyphenylene ether, etc. Is mentioned.
Examples of brominated polystyrene include polydibromostyrene, polytribromostyrene, polypentabromostyrene, polytribromo α-methylstyrene, and the like. Brominated polystyrene is produced by brominating polystyrene or poly α-methylstyrene, and polybrominated styrene is produced by polymerizing brominated styrene or brominated α-methylstyrene. Further, copolymerization of brominated styrene and an olefin having an epoxy group, or unsaturated carboxylic acid or a derivative thereof may be graft copolymerized.

Specific examples of bromine-containing flame retardants include hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenyl oxide, tetrabromobisphenol A and tetrabromobisphenol A. Tetrabromo such as -bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether) Bisphenol A derivatives, tetrabromobisphenol S and tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol Tetrabromobisphenol S derivatives such as bis S-bis (2,3-dibromopropyl ether), tetrabromophthalic anhydride derivatives such as tetrabromophthalic anhydride, tetrabromophthalimide, ethylenebistetrabromophthalimide, ethylene bis (5,6- Dibromonorbornane-2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, Diels-Alder adduct of hexabromocyclopentadiene, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylene Bistribromophenyl ether, ethylenebispentabromophenyl, ethylenebispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polyphenylene oxide, brominated Epoxy resins, brominated polycarbonate, poly pentabromobenzyl acrylate, octa-bromonaphthalene, pentabromodiphenyl cyclohexane, hexabromocyclododecane, bis (tribromophenyl) fumaramide, N- methyl hexabromoiridium diphenylamine and the like.
These bromine-containing flame retardants can be used in combination with flame retardant aids such as antimony oxide.

(Nitrogen-containing flame retardant)
An example of the nitrogen-containing flame retardant is a triazine flame retardant. Examples of triazine flame retardants include cyanuric acids, isocyanuric acids, melamines, and melamine cyanurates.
Examples of cyanuric acids include cyanuric acid, trimethylcyanurate, triethylcyanurate, tri (n-propyl) cyanurate, methyl cyanurate, diethyl cyanurate and the like. Examples of isocyanuric acids include isocyanuric acid, trimethylisocyanurate, and triethyl. Examples include isocyanurate, tri (n-propyl) isocyanurate, diethyl isocyanurate, and methyl isocyanurate.
Examples of melamines include melamine, melamine derivatives, compounds having a structure similar to melamine, and melamine condensates. Specific examples of melamines include melamine, ammelide, ammelin, formoguanamine, guanylmelamine, cyanomelamine, arylguanamine, melam, melem, melon, etc., and melamine and aromatic dicarboxylic acids such as phthalic acid, terephthalate Examples include adducts with acids, isophthalic acid and the like.
Examples of the melamine cyanurate include an equimolar reaction product of cyanuric acid and melamine. Moreover, some of the amino groups or hydroxyl groups in melamine cyanurate may be substituted with other substituents. Melamine cyanurate can be obtained, for example, by mixing an aqueous solution of cyanuric acid and an aqueous solution of melamine, reacting with stirring at about 90 to 100 ° C., and filtering the generated precipitate, and is a white solid. It is preferable to use it after pulverizing it into a fine powder. Of course, a commercially available product can be used as it is or after being pulverized.
Preferable examples of the nitrogen-containing flame retardant include cyanuric acid, isocyanuric acid, melamine, melamine cyanuric acid, melem cyanuric acid, and cyanuric acid because there is no inconvenience such as blooming in which the decomposition product is raised on the surface of the molded product. An equimolar reaction product of cyanuric acid represented by acid melamine and melamine is more preferable.

(Phosphorus-containing flame retardant)
Examples of the phosphorus-containing flame retardant include (a) phosphoric ester compounds, (b) phosphinates and diphosphinates, (c) phosphines and oxides thereof.
(A) Phosphate ester compound As a phosphate ester compound, the phosphate ester compound represented, for example by the following general formula (I) is mentioned.

(In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or an organic group, X represents a divalent or higher organic group, p is 0 or 1, and q is an integer of 1 or higher. R represents an integer of 0 or more.)
In the general formula (I), examples of the organic group represented by R ^{1 to} R ⁴ include a substituted or unsubstituted alkyl group, a cycloalkyl group, and an aryl group. In addition, examples of the substituent when substituted include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an arylthio group. Furthermore, an arylalkoxyalkyl group that is a combination of these substituents, or an arylsulfonylaryl group that is a combination of these substituents bonded together by oxygen, nitrogen, sulfur, etc. There is.

In the general formula (I), the divalent or higher valent organic group represented by X is a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the organic group described above. Is mentioned. Examples thereof include an alkylene group, a (substituted) phenylene group, and a group derived from bisphenols that are polynuclear phenols.
The phosphate ester compound may be a monomer, oligomer, polymer, or a mixture thereof. Specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (2-ethylhexyl) phosphate, diisopropyl Phenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, or a substitution product thereof, condensation Examples can be given.

  Among these, in general formula (I), those in which r is a phosphoric acid ester compound having 1 or more, or those in which a phenyl group is partially substituted with an alkyl group or the like are attached to the mold during molding. May be preferable in terms of heat resistance, heat resistance of molded products, moisture resistance, and the like. Here, as a commercially available phosphoric ester compound, for example, TPP [triphenyl phosphate], TXP [trixylenyl phosphate], CR-733S [resorcinol bis (diphenyl phosphate)] manufactured by Daihachi Chemical Industry Co., Ltd., PX200 [1,3-phenylene-teslakis (2,6-dimethylphenyl) phosphate, PX201 [1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, PX202 [4,4′-biphenylene -Teslakis 2,6-dimethylphenyl] phosphate and the like.

(B) Phosphinic acid salt and diphosphinic acid salt Examples of the phosphinic acid salt and diphosphinic acid salt include compounds represented by the following general formula (II) and general formula (III), respectively.

(In the formula, R ⁵ and R ⁶ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ⁷ is an alkylene group having 1 to 10 carbon atoms, and 6 to 10 carbon atoms. And M ^{m +} represents calcium ion, magnesium ion, aluminum ion or zinc ion, m represents 2 or 3, and n represents 1 or 2.)
In the general formulas (II) and (III), the alkyl group having 1 to 6 carbon atoms of R ⁵ and R ⁶ may be linear or branched, and may be a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups and the like. The aryl group having 6 to 10 carbon atoms of R ⁵ and R ^6, a phenyl group, a tolyl group, a xylyl group, a naphthyl group.
The alkylene group having 1 to 10 carbon atoms in R ⁷ may be linear or branched, and is a methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, 1-methyltrimethylene. Group, pentamethylene group, octamethylene group, decamethylene group and the like. Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group. Examples of the aralkylene group having 7 to 10 carbon atoms include a benzylene group, a phenethylene group, and a phenylpropylene group. Is mentioned.

The term “phosphinic acid salt” as used below includes phosphinic acid and diphosphinic acid salts and polymers thereof.
This phosphinate is produced in an aqueous medium and is essentially a monomeric compound. Depending on the reaction conditions, polymeric phosphinic acid salts having a degree of condensation of 1 to 3 are also included in some cases.
Examples of phosphinic acids suitable as components of phosphinates are dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, isobutylmethylphosphinic acid, hexylmethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid) ) -1,2- (dimethylphosphinic acid), hexane-1,6-di (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methylphenylphosphinic acid and diphenylphosphinic acid. .
Examples of the phosphinic acid salts include calcium salts, magnesium salts, aluminum salts, and zinc salts, with aluminum salts and zinc salts being preferred.

(C) Phosphines and their oxides Examples of phosphines include tertiary phosphines such as triarylphosphine, trialkylphosphine, bis (diarylphosphino) benzene, and tris (diarylphosphino) benzene.
Examples of phosphine oxides include oxides of the phosphines and compounds represented by the following general formula (IV).

(In formula, R < ⁸ > -R < ¹¹ > is a C1-C10 aliphatic hydrocarbon group which may have a substituent each independently, or C6-C14 which may have a substituent. R ¹² represents an aromatic hydrocarbon group, and R ¹² may have a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or may have a substituent and has 6 to 30 carbon atoms. Represents a divalent aromatic hydrocarbon group.)
In the general formula (IV), the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ^{8 to} R ¹¹ is methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s -Butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group and other alkyl groups; cyclopentyl group, cyclohexyl group, cyclooctyl group and other cycloalkyl groups; From this point, those having 1 to 6 carbon atoms are preferred. Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ^{8 to} R ¹¹ include a phenyl group, a naphthyl group, a toluyl group, a 4-t-butylphenyl group, a biphenyl group, a phenanthryl group, an anthranyl group, Aryl groups such as mesityl group; aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, biphenylmethyl group and the like. Examples of the substituent that these aliphatic hydrocarbon groups and aromatic hydrocarbon groups may have include alkoxy groups such as methoxy group and ethoxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; And dialkylamino groups such as N, N-dimethylamino group; cyano groups and the like. In the general formula (IV), R ^{8 to} R ¹¹ may all be the same group, or different groups may be mixed.

The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent represented by R ¹² in the general formula (IV) may be linear, branched or cyclic. Methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, nonamethylene group, decamethylene group, isopropylidene group, 3-methyl-1,5-pentamethylene group, 2-methyl-1,8 -Octamethylene group, 1,4-cyclohexylene group, 2,6-dimethyl-1,5-cyclooctylene group and the like can be mentioned.
Also, represented by R ^12, examples of the divalent aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a substituent such as a lower alkyl group on an aromatic ring having one or more Arylene groups such as various phenylene groups, various naphthylene groups, various diphenylene groups, various diphenylmethanediyl groups, various 2,2-diphenylpropanediyl groups, various anthrylene groups, etc .; substitution of lower alkyl groups on the aromatic ring Aralkylene groups such as various benzylene groups, various phenethylene groups, various naphthylmethylene groups, various bisbenzylene groups, various bisphenethylene groups, various diphenyldimethylene groups, various naphthyldimethylene groups, etc., which may have one or more groups. Can be mentioned.

  Specific examples of the phosphine oxides represented by the general formula (IV) include methylene bis (diphenyl) phosphine oxide, ethylene bis (diphenyl) phosphine oxide, propylene bis (diphenyl) phosphine oxide, butylene bis (diphenyl) phosphine oxide, isopropylidene. Bis (diphenyl) phosphine oxide, 1,9-nonamethylenebis (diphenyl) phosphine oxide, 2-methyl-1,8-octamethylenebis (diphenyl) phosphine oxide, 1,10-decamethylenebis (diphenyl) phosphine oxide, Ethylene bis (dinaphthyl) phosphine oxide, butylene bis (diethyl) phosphine oxide, ethylene bis (di-2-ethylhexyl) phosphine oxide, butylene bis (di-cyanomethyl) Examples include phosphine oxide, 1,4-bis [di (2-cyanoethyl) phosphorylmethyl] benzene, and ethylene bis (sio-methoxyphenyl) phosphine oxide.

(Nitrogen-phosphorus containing flame retardant)
Examples of the nitrogen-phosphorus-containing flame retardant include adducts (melamine adducts) formed from melamine or a condensation product thereof and phosphoric acid. Examples of phosphoric acid constituting this melamine adduct include orthophosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid.
Specific examples of the melamine adduct include melamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, etc. Among these, longer than 2, particularly more than 10. Melamine polyphosphate with a long chain length is preferred.
Furthermore, a phosphazene compound, for example, a cyclic phosphazene compound represented by the following general formula (V) is preferably exemplified.

(In the formula, R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a represents an integer of 3 to 15)
In general formula (V), the alkyl group having 1 to 10 carbon atoms of R ¹³ and R ¹⁴ may be linear, branched or cyclic, and may be a methyl group, an ethyl group, or n-propyl. Group, isopropyl group, various butyl groups, various hexyl groups, various octyl groups, cyclopentyl groups, cyclohexyl groups and the like. Examples of the aryl group having 6 to 15 carbon atoms include phenyl and the like, to which a substituent such as an alkyl group, an aryl group, and an alkoxy group may be introduced on the ring.
R ¹³ and R ¹⁴ are preferably both aryl groups, particularly preferably both phenyl groups. Furthermore, the cyclic phosphazene compound which contains 80 mass% or more of 6-membered ring and 8-membered ring whose n is 3 and 4 in all the phosphazene compounds is suitable.

(Inorganic flame retardant)
Examples of inorganic flame retardants include inorganic flame retardants such as metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and calcium aluminate, zinc borate, and a mixture of zinc borate and other zinc salts. In particular, magnesium hydroxide and a mixture of zinc borate and zinc phosphate are suitable.
As magnesium hydroxide, granular, plate-like, needle-like or the like can be used. When using a granular or plate-like material, the average particle diameter is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm. Moreover, when using a needle-shaped thing, it is preferable that the average diameter is 0.01-10 micrometers, It is more preferable that it is 0.1-5 micrometers, It is preferable that average length is 5-2000 micrometers. 10 to 1000 μm is more preferable.
Magnesium hydroxide preferably has a low content of impurities such as chlorine, calcium, iron, aluminum and sulfur from the viewpoint of heat resistance. Furthermore, the surface of magnesium hydroxide is used for the purpose of improving the dispersibility in the polyamide resin (A) and improving the thermal stability of the flame retardant polyamide resin composition, and a silane coupling agent and a titanium coupling agent. It is preferable that the surface treatment is performed with a fatty acid and a derivative thereof, other polymer or low molecular surface treatment agent, a solid solution of a metal such as nickel.
The zinc _{borate, 2ZnO · 3B 2 O 3,} 4ZnO · B 2 O 3 · H 2 O, include _{2ZnO · 3B 2 O 3 · 3.5H} 2 O and the like. Other zinc salts may be selected from zinc phosphates such as Zn ₃ (PO ₄ ) ₂ .ZnO, zinc stannates such as ZnSn (OH) ₆ and ZnSnO ₃ , and other calcium zinc molybdates. Is possible.
As other zinc salts used in combination with zinc borate, zinc phosphate is preferable. In this case, the ratio of zinc borate to zinc phosphate based on mass is preferably 1: 0.1 to 1: 5, more preferably. Is 1: 2 to 1: 4, more preferably 1: 2.5 to 1: 3.5.

In the present invention, the flame retardant (C) can be used singly or in combination of two or more, but from the viewpoint of environmental hygiene, non-halogen-containing nitrogen-containing flame retardant, phosphorus-containing flame retardant and Nitrogen-phosphorus containing flame retardants are preferred.
The content of the flame retardant (C) in the resin composition of the present invention depends on the type of the flame retardant, but is provided with a flame retardancy of V-0 level according to the UL94 standard, and suppresses other performance degradation. Therefore, 5-40 mass% is preferable and 10-30 mass% is more preferable.

[Polyfluoroolefin resin (D)]
The polyfluoroolefin-based resin (D) used in the present invention is used for the purpose of preventing melt dripping during dripping.
The polyfluoroolefin-based resin is usually a polymer or copolymer containing a fluoroethylene structure, such as a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, or a tetrafluoroethylene. And a copolymer of ethylene monomer not containing fluorine.
Polytetrafluoroethylene (PTFE) is preferable, and the average molecular weight is preferably 500,000 or more, particularly preferably 500,000 to 10,000,000, and a known one can be used. it can.
Use of a polyfluoroolefin-based resin having a fibril-forming ability can impart even higher melt drip prevention. Here, the “fibril forming ability” means a property showing a tendency that the resins are bonded to each other by an external action such as a shearing force to form a fiber.

The polytetrafluoroethylene (PTFE) resin having fibril forming ability is not particularly limited, and examples thereof include Teflon 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon. F-201 (manufactured by Daikin Industries), CD076 (manufactured by Asahi IC Fluoropolymers), Argoflon F5 (manufactured by Montefluos), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.), acrylic resin modified poly Tetrafluoroethylene such as Methbrene A3000, Methbrene A3700 (manufactured by Mitsubishi Rayon Co., Ltd.) or the like can be used.
The PTFE resin having fibril-forming ability is, for example, PTFE in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide and the like, under a pressure of about 7 to 700 kPa, at a temperature of about 0 to 200 ° C., preferably 20 It can be obtained by polymerization at -100 ° C or by modification with an acrylic resin. These PTFE resins can be used singly or in combination of two or more.
The content of the polyfluoroolefin-based resin (D) in the resin composition of the present invention is preferably 0.05 to 8% by mass from the viewpoint of sufficient melt-drip prevention and impact resistance and suppression of deterioration in appearance. 0.1-5 mass% is more preferable, and 0.5-3 mass% is further more preferable.

[Optional ingredients]
In the resin composition of the present invention, a flame retardant aid, an antioxidant, an ultraviolet absorber, a light stabilizer, a release agent, an antistatic agent, and the like are appropriately added as desired without departing from the object of the present invention. It can be included.
(Flame retardant aid)
Examples of the flame retardant aid include the above-described antimony oxide, silicone powder, and low melting point glass having a softening point of 800 ° C. or less. Among these, antimony oxide is preferable from the viewpoint of improving flame retardancy. One or more of these flame retardant aids can be used.
The average particle size of the flame retardant aid is preferably 0.05 to 200 μm, and more preferably 0.1 to 100 μm. Further, the flame retardant aid is a silane coupling agent, titanium coupling agent, fatty acid and derivatives thereof, other polymer or low molecular surface treatment agent for the purpose of enhancing dispersibility in the polyamide resin (A). A surface treatment is preferred.
The antimony oxide is preferably selected from antimony trioxide, antimony pentoxide, and sodium antimonate.
1-15 mass% is preferable from a viewpoint of a flame retardance improvement effect, and, as for content of the flame retardant adjuvant in the resin composition of this invention, 3-10 mass% is more preferable.

(Antioxidant)
As the antioxidant, phenol-based and phosphorus-based antioxidants are preferable.
Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate]. 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di) -Tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert- Til-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxa Spiro (5,5) undecane and the like can be mentioned.

Examples of phosphorus antioxidants include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4 -Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite , Bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.
These antioxidants can be used singly or in combination of two or more. The content is usually about 0.05 to 3% by mass based on the total amount of the resin composition.

(UV absorber)
Examples of the ultraviolet absorber include benzotriazole-based, triazine-based, benzoxazine-based, and benzophenone-based ultraviolet absorbers.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidomethyl). -5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) Benzotriazole, 2- (3′-tert-butyl-5′-methyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis (4- (1,1,3,3-tetra Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) Enyl) -2H-benzotriazole, 2- (3 ′, 5′-di-tert-amyl-2′-hydroxyphenyl) benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-3- (4- Methoxy-α-cumyl) -5-tert-butylphenyl) -2H-benzotriazole and the like.

Examples of triazine-based ultraviolet absorbers include Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 1577, CGL-479, CGL-777 (all manufactured by Ciba Specialty Chemicals).
Examples of the benzoxazine-based ultraviolet absorber include 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazine-4-one, 2-phenyl-3,1-benzoxazine -4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2,2 ′ -Bis (3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (3,1 -Benzoxazin-4-one), 2,2 '-(4,4'-diphenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2,6 or 1,5- Naphthalene) bis (3,1-benzoxazin-4-one), 1, , 5- tris (3,1-benzoxazin-4-one-2-yl) benzene.

Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and the like can be mentioned.
These ultraviolet absorbers can be used alone or in combination of two or more. The content is usually about 0.05 to 3% by mass based on the total amount of the resin composition.

(Light stabilizer)
Examples of the light stabilizer include a hindered amine light stabilizer (HALS) as a radical scavenger. Examples of the hindered amine light stabilizer include dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [6- (1,1,3 , 3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2, 6,6-tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2 , 6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1,1 ′-(1,2-ethanediyl) ) Screw (3, 3, 5 , 5-tetramethylpiperazinone), (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, N, N′-bis (3-Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensation Poly [6-N-monophoryl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2 , 6,6-Tetramethyl-4-piperidyl) imide], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane Product, [N- (2,2 6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide and the like.
These light stabilizers can be used alone or in combination of two or more. The content is usually about 0.1 to 3% by mass based on the total amount of the resin composition.

(Release agent)
Examples of the mold release agent include zinc stearate, calcium stearate, and higher fatty acid esters of mono- or polyhydric alcohols. The higher fatty acid ester is preferably a partial ester or complete ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of partial esters or complete esters of mono- or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol monostearate Examples thereof include rate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate and the like. Among these, stearic acid monoglyceride and pentaerythritol tetrastearate are preferable.
These release agents can be used alone or in combination of two or more. Moreover, the content is about 0.01-5.0 mass% normally based on the resin composition whole quantity of this invention.
(Antistatic agent)
As the antistatic agent, for example, monoglycerides of fatty acids having 14 to 30 carbon atoms, specifically stearic acid monoglyceride, palmitic acid monoglyceride, or polyamide polyether block copolymers can be used.

[Characteristics of flame retardant polyamide resin composition]
The resin composition of the present invention is UL94 (Underwriters Laboratory Subject 94) for test pieces having a thickness of 1/16 inch (1.58 mm) and 1/32 inch (0.79 mm) obtained by injection molding. The flame retardancy measured according to the above is V-0 level.
Further, the flexural modulus measured according to ISO 178 can be 3.5 GPa or more, preferably 4.0 GPa or more, and the tensile fracture strain measured according to ISO 527 is 4% or more, preferably 5 % Or more.

  There is no restriction | limiting in particular in the preparation method of the flame-retardant polyamide resin composition of this invention. For example, a polyamide resin (A), an acicular inorganic filler (B), a flame retardant (C), a polyfluoroolefin-based resin (D), and various additive components that are used as desired, such as a Henschel mixer, a tumbler, and a ribbon blender It can be obtained by dry blending in advance using a mixer and kneading using a known melt kneader such as a single or twin screw extruder, a Banbury mixer, a kneader, or a mixing roll. More specifically, for example, by using a twin-screw kneading extruder, after blending all the raw materials, melt kneading, blending some raw materials, melt kneading, further blend the remaining raw materials and melt Any method such as a method of kneading, or a method of mixing a part of raw materials and then mixing the remaining raw materials using a side feeder during melt kneading can be employed.

[Molded body]
The flame retardant polyamide resin composition prepared as described above is formed into molded products having various shapes by known molding methods such as injection molding, extrusion molding, press molding, blow molding, calendar molding, and casting. Can be processed. For example, it is melted in a cylinder of an injection molding machine set to a temperature equal to or higher than the melting point of the flame retardant polyamide resin composition, and processed into a predetermined shape by injection into a mold having a desired shape. be able to. Moreover, it can be processed into a fiber by melting in an extruder and spinning from a nozzle nozzle, and can be processed into a film or a sheet-like molded body by extrusion from a T die. Moreover, it can also be used in the form which formed the coating layer which consists of a coating material, a metal, another kind polymer, etc. on the surface of the molded object manufactured by such a method.
Furthermore, the flame-retardant polyamide resin composition of the present invention can be formed into a composite molded body with other materials. Examples of such other materials include various plastic polymers other than the flame retardant polyamide resin composition of the present invention or a composition thereof, thermosetting resin, paper, fabric, metal, wood, ceramics, and the like.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these examples.
In addition, the physical property of the resin composition obtained by the Example and the comparative example was evaluated by the method shown below.
<Before heat treatment>
(1) Flame retardancy Measured according to the method of UL94 (standard established by Under Writers Laboratories Inc., USA). The thicknesses of the test pieces are 1/16 inch (1.58 mm) and 1/32 inch (0.79 mm).
(2) Flexural modulus Measured by a method based on ISO 178.
(3) Tensile fracture strain Measured by a method based on ISO 527.
<After heat treatment>
After heat-treating the test piece under the following conditions, the tensile fracture strain was measured in the same manner as in the above (1) to (3).
Heat-resistant treatment conditions: in a hot air circulating thermostatic dryer (model 41-S5, manufactured by Satake Chemical Machinery Co., Ltd.), after 30 days treatment at 120 ° C. setting, in a 23 ° C. desiccator (humidity <20% RH) And then evaluated after curing for 1 week.

Examples 1 to 3, Reference Examples 1 to 3 and Comparative Examples 1 to 6
After dry blending the components of the types and amounts shown in Table 1, they were melt kneaded with a twin screw extruder (“TEX44HCT” manufactured by Nippon Steel Co., Ltd.) at a temperature of 240 to 280 ° C. and cooled in a water bath. Resin composition pellets were prepared.
After drying the resin composition pellets, the pellets were supplied to an injection molding machine [manufactured by Sumitomo Heavy Industries, Ltd., “SE100D”], test pieces were prepared at a melting temperature of 250 to 290 ° C., and the physical properties were evaluated. The results are shown in Table 1.

In addition, the detail of the component shown in Table 1 is as follows.
Polyamide 6/66: “5023B” manufactured by Ube Industries, Ltd.
Polyamide 6: Ube Industries, Ltd. “1013B”
Wollastonite: Kinsei Matec Co., Ltd., “FPW # 400”, average diameter 8 μm, average length 40 μm, aspect ratio 5
Glass fiber: manufactured by Nippon Electric Glass Co., Ltd., “ECSO3T-249H”, average diameter 10 μm, average length 3 mm, aspect ratio 300
・ Talc: Ube Materials Co., Ltd., “LS-408”, average diameter 12 μm
・ Phosphorus flame retardant: “Exolit OP1312” manufactured by Clariant Japan
Melamine cyanurate: “MCA-C1” manufactured by Mitsubishi Chemical Corporation
Polytetrafluoroethylene (PTFE): “Metbrene A3700” manufactured by Mitsubishi Rayon Co., Ltd.
Other additives: The following four types of additives were blended at a ratio of 0.1: 0.3: 0.1: 0.1 (0.6 parts in total).
(1) Phenol antioxidant: “Tominox 917” manufactured by Yoshitomi Fine Chemical Co., Ltd.
(2) Phosphorus antioxidant: “Irgaphos 168” manufactured by Ciba Specialty Chemicals Co., Ltd.
(3) Ultraviolet absorber: “Chinubin 234” manufactured by Ciba Specialty Chemicals Co., Ltd.
(4) Light stabilizer: “Kimasorb 944” manufactured by Ciba Specialty Chemicals Co., Ltd.

  From Table 1, it can be seen that the flame-retardant polyamide resin composition of the present invention has flame retardancy of V-0 level according to UL94 standard, and excellent mechanical properties such as rigidity and toughness.

  The flame-retardant polyamide resin composition of the present invention has a flame retardancy of V-0 level according to the UL94 standard, and has good rigidity and toughness, so that it can be used for automobile parts, electrical / electronic parts, home appliances, and building materials. It can be used effectively in a wide range of fields such as sanitary goods, sporting goods, miscellaneous goods, textiles, and films. Specific examples include fuel tanks for general-purpose engines, hoses for automobile piping, connectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, resistors, terminal blocks, IC and LED housings, gears, Examples include bearing retainers, spring holders, chain tensioners, washers, various housings, weight rollers, breaker parts, and clutch parts.

Claims (6)

Polyamide resin (A), needle-like inorganic filler (B), flame retardant (C), and polyfluoro olefin resin (D) look-containing polyamide resin (A), and characterized in that a polyamide 6/66 A flame retardant polyamide resin composition. The flame-retardant polyamide resin composition according to claim 1, wherein the needle-like inorganic filler (B) has an average diameter of 3 to 20 µm and an average length of 20 to 300 µm. The flame-retardant polyamide resin composition according to claim 1 or 2 , wherein the needle-like inorganic filler (B) is wollastonite. The flame-retardant polyamide resin composition according to any one of claims 1 to 3 , wherein the polyfluoroolefin-based resin (D) is a polytetrafluoroethylene-based resin having a fibril-forming ability. Needle-like inorganic filler (B) 5 to 40 wt%, organic flame retardant (C) 5 to 40 wt%, and polyfluoro olefin resin (D) according to claim 1-4 containing 0.05-8 wt% The flame-retardant polyamide resin composition according to any one of the above. The molded object formed by shape | molding the flame-retardant polyamide resin composition in any one of Claims 1-5 .