WO2009107514A1 - Procédé de fabrication de pastilles de composition de polyamide présentant une propriété de corrosion de métal réduite et procédé de fabrication d'un article moulé - Google Patents

Procédé de fabrication de pastilles de composition de polyamide présentant une propriété de corrosion de métal réduite et procédé de fabrication d'un article moulé Download PDF

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WO2009107514A1
WO2009107514A1 PCT/JP2009/052669 JP2009052669W WO2009107514A1 WO 2009107514 A1 WO2009107514 A1 WO 2009107514A1 JP 2009052669 W JP2009052669 W JP 2009052669W WO 2009107514 A1 WO2009107514 A1 WO 2009107514A1
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polyamide
polyamide composition
unit
acid
group
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PCT/JP2009/052669
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English (en)
Japanese (ja)
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秀治 松岡
宇治 重松
興造 田村
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株式会社クラレ
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Priority to JP2009521474A priority Critical patent/JP5638242B2/ja
Publication of WO2009107514A1 publication Critical patent/WO2009107514A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a method for producing a flame-retardant polyamide composition pellet, a method for producing a molded article, and a polyamide composition.
  • Polyamide resins are widely used in the field of automotive parts and electrical / electronic parts because of their excellent mechanical properties and heat resistance.
  • polyamide resins semi-aromatic polyamides with higher heat resistance are commercialized, and the performance of these parts Contributes to improvement.
  • surface mounting processes with high component mounting efficiency are widespread, and semi-aromatic polyamides with small dimensional change and excellent appearance are prevalent as suitable materials for forming these components.
  • lead-free solder has been adopted as the solder used in the surface mounting process from the viewpoint of reducing the environmental load.
  • lead-free solder has a relatively high melting temperature, the temperature in the reflow process of the surface mounting process is reduced. It is necessary to set it high (about 260 ° C.). Therefore, among semi-aromatic polyamides, those having a relatively high melting point are employed.
  • the flame retardant blended with the semi-aromatic polyamide having a relatively high melting point as described above includes, in addition to high flame retardant performance, at the time of melt-kneading when a polyamide composition is produced and a molded product. High heat resistance that can withstand the high temperature conditions during the molding process is required. Therefore, the flame retardant which can be mix
  • Phosphinate is known as a flame retardant having high flame resistance and heat resistance and containing no halogen.
  • a flame retardant polyamide molding material containing a specific polyamide having a diamine unit mainly composed of an alicyclic diamine unit and a phosphinate is known (see Patent Document 1).
  • a molding material containing an aliphatic polyamide such as nylon 66 and a specific phosphinate is known (see Patent Document 2).
  • specific resin compositions containing specific semi-aromatic polyamides, polyphenylene ethers and phosphinates are known (see Patent Documents 3 and 4).
  • the polyamide composition is usually produced and distributed in the form of pellets, and a molded product is produced by molding it using an injection molding machine or the like.
  • the cylinder temperature of the extruder when producing the polyamide composition In order to sufficiently melt the polyamide, the cylinder temperature of the molding machine such as an injection molding machine when the pellet is used as a molded product is usually set to a temperature equal to or higher than the melting point of the polyamide. Therefore, when using a semi-aromatic polyamide having a relatively high melting point, the above temperature is set to be high, and this tendency is particularly observed when a large amount of semi-aromatic polyamide is blended from the viewpoint of the quality of the obtained molded product. Become stronger.
  • the phosphinic acid salt is used as a flame retardant
  • a molding machine such as an extruder or an injection molding machine is used.
  • the metal parts such as the cylinder, the screw disposed in the cylinder, and the metal mold used during the injection molding are significantly corroded or worn. It was unexpected that such a problem would occur when using a phosphinic acid salt that has high heat resistance.
  • the present invention can provide a pellet of a polyamide composition that can withstand a high reflow process temperature in which lead-free solder is used and that is a molded product that hardly changes in appearance such as blister. Despite containing phosphinate as a flame retardant, reduce the corrosion and wear of metal parts such as extruder cylinders and screws installed in the cylinders, and produce pellets efficiently at low cost. It is an object of the present invention to provide a method for producing pellets that can be processed.
  • the present invention includes a cylinder of a molding machine such as an injection molding machine, a screw disposed in the cylinder, a mold used at the time of injection molding, etc., despite containing phosphinate as a flame retardant. It is an object of the present invention to provide a method for manufacturing a molded product that can reduce the corrosion and wear of metal parts and can manufacture a molded product at low cost and efficiently. Furthermore, this invention makes it a subject to provide the polyamide composition used for the manufacturing method of the said molded article.
  • the present inventors have extruded a semi-aromatic polyamide having a specific melting point and a phosphinic acid salt under specific extrusion conditions into pellets, which are arranged in an extruder cylinder and in the cylinder. It has been found that the corrosion and wear of metal parts such as installed screws can be significantly reduced. Moreover, by molding a polyamide composition containing a semi-aromatic polyamide having a specific melting point and a phosphinate under specific injection molding conditions, a cylinder of an injection molding machine, a screw disposed in the cylinder, and an injection It has been found that corrosion and wear of metal parts such as molds used during molding can be significantly reduced. The present inventors have further studied based on these findings and completed the present invention.
  • a method for producing pellets of a polyamide composition comprising 15 to 95% by mass of polyamide (I) having a melting point of 270 to 300 ° C. and 5 to 25% by mass of phosphinate (II), comprising: A method for producing pellets of a polyamide composition, wherein at least the polyamide (I) and the phosphinate (II) are melt-kneaded and then pelletized under a condition where the cylinder temperature does not exceed 310 ° C; [2] The above-mentioned [1], wherein the polyamide (I) has a dicarboxylic acid unit containing 40 to 100 mol% of a terephthalic acid unit and a diamine unit containing 60 to 100 mol% of an aliphatic diamine unit having 4 to 18 carbon atoms.
  • the diamine unit contains 60 to 100 mol% of 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit, and the 1,9-nonanediamine unit and 2-methyl-1,8-octane
  • the production method of the above [2], wherein the molar ratio of diamine units is 1,9-nonanediamine unit: 2-methyl-1,8-octanediamine unit 60: 40 to 80:20, [4]
  • R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group, and a plurality of R 1 are identical to each other. May be different.
  • R 2 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group, or an aryl alkylene group, and a plurality of R 2 may be the same or different from each other.
  • M represents magnesium, aluminum, calcium, or zinc, and a plurality of M may be the same as or different from each other.
  • m is 2 or 3
  • n is 1 or 3
  • x is 1 or 2.
  • the polyamide composition contains at least one metal compound (III) selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal borate and hydrotalcite or derivatives thereof.
  • the diamine unit contains 60 to 100 mol% of 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit, and the 1,9-nonanediamine unit and 2-methyl-1,8-octane
  • the production method of [9] above, wherein the molar ratio of diamine units is 1,9-nonanediamine unit: 2-methyl-1,8-octanediamine unit 60: 40 to 80:20, [11]
  • the production method of any one of [8] to [10] above, wherein the intrinsic viscosity of polyamide (I) measured in concentrated sulfuric acid at 30 ° C. is 0.6 to 0.95 dl / g.
  • phosphinic acid salt (II) is a monophosphinic acid salt represented by the following formula (1) and / or a diphosphinic acid salt represented by the following formula (2): Manufacturing method,
  • R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group, and a plurality of R 1 are identical to each other. May be different.
  • R 2 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group, or an aryl alkylene group, and a plurality of R 2 may be the same or different from each other.
  • M represents magnesium, aluminum, calcium, or zinc, and a plurality of M may be the same as or different from each other.
  • m is 2 or 3
  • n is 1 or 3
  • x is 1 or 2.
  • the polyamide composition further comprises at least one metal compound (III) selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal borate and hydrotalcite or derivatives thereof. Including the production method of any one of [8] to [13] above,
  • the diamine unit contains 60 to 100 mol% of 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit, and the 1,9-nonanediamine unit and 2-methyl-1,8-octane
  • the polyamide composition according to [16] above, wherein the molar ratio of diamine units is 1,9-nonanediamine unit: 2-methyl-1,8-octanediamine unit 60: 40 to 80:20, [18]
  • the polyamide composition according to any one of [15] to [17] above, wherein the intrinsic viscosity of the polyamide (I) measured in concentrated sulfuric acid at 30 ° C. is 0.6 to 0.95 dl / g.
  • phosphinic acid salt (II) is a monophosphinic acid salt represented by the following formula (1) and / or a diphosphinic acid salt represented by the following formula (2):
  • R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group, and a plurality of R 1 are identical to each other. May be different.
  • R 2 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group, or an aryl alkylene group, and a plurality of R 2 may be the same or different from each other.
  • M represents magnesium, aluminum, calcium, or zinc, and a plurality of M may be the same as or different from each other.
  • m is 2 or 3
  • n is 1 or 3
  • x is 1 or 2.
  • the polyamide composition further comprises at least one metal compound (III) selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, borate metal salts and hydrotalcite or derivatives thereof. Containing the polyamide composition of any one of the above [15] to [20], [22] The polyamide composition according to any one of [15] to [21], wherein the polyamide composition further comprises an anti-dripping agent (IV), About.
  • a polyamide composition that can withstand a high reflow process temperature (for example, a temperature of about 260 ° C.) in which lead-free solder is used, and that is a molded product that hardly changes in appearance such as blisters. It is possible to give pellets, and despite containing phosphinate as a flame retardant, it reduces corrosion and wear of extruder parts and metal parts such as screws installed in the cylinder, reducing the Provided is a method for producing pellets, which can produce pellets at low cost and efficiently.
  • a cylinder of a molding machine such as an injection molding machine, a screw disposed in the cylinder, and a mold used at the time of injection molding despite containing phosphinate as a flame retardant
  • a method for producing a molded product which can reduce the corrosion and wear of metal parts such as the above, and can efficiently produce a molded product at low cost.
  • the polyamide composition used for the manufacturing method of the said molded article is provided.
  • the polyamide (I) used in the present invention has a melting point of 270 to 300 ° C.
  • examples of the polyamide (I) used in the present invention include aliphatic polyamides such as PA46, dicarboxylic acid units containing 40 to 100 mol% of terephthalic acid units, and aliphatic diamine units having 4 to 18 carbon atoms.
  • examples thereof include semi-aromatic polyamide having a diamine unit contained in mol%. Of these, semi-aromatic polyamides are preferred in terms of heat resistance and low water absorption.
  • the dicarboxylic acid unit constituting the semi-aromatic polyamide contains terephthalic acid in an amount of 40 to 100 mol%, pellets that give a molded product having high heat resistance or a molded product having high heat resistance can be obtained.
  • the content of the terephthalic acid unit in the dicarboxylic acid unit is more preferably in the range of 60 to 100 mol%, further preferably in the range of 75 to 100 mol%, and particularly preferably in the range of 90 to 100 mol%.
  • Said dicarboxylic acid unit may contain other dicarboxylic acid units other than a terephthalic acid unit.
  • the other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2, Aliphatic dicarboxylic acids such as 2-diethylsuccinic 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-phenylenedioxydi
  • the content of these other dicarboxylic acid units in the dicarboxylic acid unit is preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 25 mol% or less, and more preferably 10 mol%. % Or less is particularly preferable.
  • the semi-aromatic polyamide may contain a unit derived from a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid as long as melt molding is possible.
  • the diamine unit constituting the semi-aromatic polyamide preferably contains 60 to 100 mol% of an aliphatic diamine unit having 4 to 18 carbon atoms.
  • the content of the aliphatic diamine unit having 4 to 18 carbon atoms in the diamine unit is more preferably in the range of 75 to 100 mol%, and further preferably in the range of 90 to 100 mol%.
  • Examples of the aliphatic diamine unit having 4 to 18 carbon atoms include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, and 1,8-octane.
  • Linear aliphatic diamines such as diamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine; 1-butyl-1,2-ethanediamine, 1, 1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1, 4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-penta Diamine, 2,5-dimethyl-1,6-hexanediamine, 2,
  • the above diamine unit is used to obtain pellets that give molded products with excellent physical properties such as heat resistance, low water absorption, and chemical resistance, and molded products with excellent physical properties such as heat resistance, low water absorption, and chemical resistance.
  • 1,6-hexanediamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, , 12-dodecanediamine is preferably contained in an amount of 60 to 100 mol%, and 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit is contained in an amount of 60 to 100 mol%. It is more preferable.
  • the melting point of the polyamide (I) can be easily within the range described later.
  • the above diamine unit may contain a diamine unit other than the aliphatic diamine unit having 4 to 18 carbon atoms.
  • the other diamine units include aliphatic diamines such as ethylenediamine, 1,2-propanediamine, and 1,3-propanediamine; cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, norbornanedimethylamine, and tricyclodecanedimethylamine.
  • Alicyclic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4 ′ -Units derived from aromatic diamines such as diaminodiphenyl ether can be mentioned, and one or more of these can be included.
  • the content of these other diamine units in the diamine unit is preferably 40 mol% or less, more preferably 25 mol% or less, and even more preferably 10 mol% or less.
  • the above semi-aromatic polyamide may contain an aminocarboxylic acid unit.
  • the aminocarboxylic acid unit include units derived from lactams such as caprolactam and lauryllactam; aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid.
  • the content of aminocarboxylic acid units in the semiaromatic polyamide is preferably 40 mol% or less, more preferably 20 mol% or less, based on 100 mol% of all dicarboxylic acid units of the semiaromatic polyamide. preferable.
  • 10% or more of the end groups of the molecular chain of the semi-aromatic polyamide is sealed with an end-capping agent.
  • the ratio of the end groups of the molecular chain being sealed with the end-capping agent (end-capping rate) is more preferably 40% or more, and even more preferably 70% or more.
  • Use of semi-aromatic polyamide with a terminal sealing ratio of 10% or more gives pellets that give molded products with better physical properties such as melt moldability and surface aesthetics, and physical properties such as melt moldability and surface aesthetics. A molded product can be obtained.
  • the end-capping rate was determined by measuring the number of carboxyl group ends and amino group ends present in the semi-aromatic polyamide, and the number of end groups blocked with a terminal blocking agent, respectively, according to the following formula: Can be sought.
  • the number of each terminal group can be determined by 1 H-NMR based on the integral value of the characteristic signal corresponding to each terminal group.
  • End sealing rate (%) [(Y ⁇ Z) / Y] ⁇ 100 [Wherein Y represents the total number of end groups of the molecular chain of the semi-aromatic polyamide (this is usually equal to twice the number of polyamide molecules), Z is the remaining carboxyl group ends and amino Represents the total number of base ends. ]
  • a monofunctional compound having reactivity with a terminal amino group or terminal carboxyl group can be used. Specific examples include acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like.
  • the stopper monocarboxylic acid is preferable, and as the terminal blocking agent for the terminal carboxyl group, monoamine is preferable. Moreover, monocarboxylic acid is more preferable as a terminal blocker from the viewpoint of easy handling.
  • the monocarboxylic acid used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group.
  • acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, laurin Aliphatic monocarboxylic acids such as acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid , ⁇ -naphthalene carboxylic acid, methyl naphthalene carboxylic acid, aromatic monocarboxylic acid such as phenyl acetic acid; any mixtures thereof.
  • acetic acid propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearin, etc. Acid and benzoic acid are preferred.
  • the monoamine used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group.
  • Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine and dibutylamine
  • Cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine
  • Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; any mixtures thereof Can be mentioned.
  • butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, high boiling point, stability of the capped end, and price.
  • the polyamide (I) used in the present invention can be produced using any method known as a method for producing crystalline polyamide.
  • it can be produced by a solution polymerization method or interfacial polymerization method using acid chloride and diamine as raw materials, a melt polymerization method using dicarboxylic acid and diamine as raw materials, a solid phase polymerization method, a melt extrusion polymerization method, or the like.
  • Polyamide (I) is prepared by, for example, first adding a diamine, a dicarboxylic acid, and, if necessary, a catalyst and a terminal blocking agent in a lump to produce a nylon salt, followed by heat polymerization at a temperature of 200 to 250 ° C. It can be produced by preparing a prepolymer having an intrinsic viscosity [ ⁇ ] at 30 ° C. of 0.1 to 0.6 dl / g in concentrated sulfuric acid and further performing solid phase polymerization or polymerization using a melt extruder. .
  • the intrinsic viscosity [ ⁇ ] of the prepolymer is in the range of 0.1 to 0.6 dl / g, there is little shift in the molar balance of carboxyl groups and amino groups and a decrease in polymerization rate in the post-polymerization stage, and the molecular weight Polyamide (I) that gives a polyamide composition having a small distribution and excellent in various physical properties and moldability is obtained.
  • the final stage of the polymerization is carried out by solid phase polymerization, it is preferably carried out under reduced pressure or under an inert gas flow. If the polymerization temperature is in the range of 200 to 280 ° C., the polymerization rate is high and the productivity is excellent. Coloring and gelation can be effectively suppressed.
  • the polymerization temperature when the final stage of the polymerization is carried out by a melt extruder is preferably 370 ° C. or less.
  • the polyamide resin is hardly decomposed and polyamide (I) with little deterioration is obtained. .
  • Examples of the catalyst that can be used in producing the polyamide (I) include phosphoric acid, phosphorous acid, hypophosphorous acid, salts thereof and esters thereof.
  • Examples of the salt or ester include phosphoric acid, phosphorous acid or hypophosphorous acid and metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony.
  • Salt ammonium salt of phosphoric acid, phosphorous acid or hypophosphorous acid; ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester of phosphoric acid, phosphorous acid or hypophosphorous acid , Stearyl ester, phenyl ester and the like.
  • the melting point of the polyamide (I) used in the present invention is required to be 270 to 300 ° C, preferably 275 to 295 ° C, and more preferably 285 to 293 ° C. Since the polyamide (I) has a melting point in the above range, even when a large amount of the polyamide (I) is blended in the polyamide composition, melt-kneading is sufficiently performed at the cylinder temperature of the extruder or molding machine described later. In addition, it is possible to produce a pellet that gives a molded product having sufficient solder heat resistance or a molded product having sufficient solder heat resistance.
  • the melting point in the present specification is a value measured by a differential scanning calorimeter (DSC) as will be described later in Examples.
  • the polyamide (I) used in the present invention preferably has an intrinsic viscosity [ ⁇ ] measured in concentrated sulfuric acid at 30 ° C. of 0.6 to 0.95 dl / g, and 0.65 to 0.93 dl / g. More preferred.
  • an intrinsic viscosity [ ⁇ ] measured in concentrated sulfuric acid at 30 ° C.
  • a material having an intrinsic viscosity [ ⁇ ] within the above range is used, a polyamide composition having excellent moldability can be obtained, and a molded product having excellent mechanical properties and heat resistance can be obtained.
  • the intrinsic viscosity exceeds 0.95 dl / g, the molten resin temperature is greatly increased by shearing heat generation of the extruder or the molding machine, and the metal parts tend to be easily corroded and worn.
  • phosphinic acid salt (II) used in the present invention a monophosphinic acid salt represented by the following formula (1) and / or a diphosphinic acid salt represented by the following formula (2) can be preferably used.
  • R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group, and a plurality of R 1 are identical to each other. May be different.
  • R 2 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group, or an aryl alkylene group, and a plurality of R 2 may be the same or different from each other.
  • M represents magnesium, aluminum, calcium, or zinc, and a plurality of M may be the same as or different from each other.
  • m is 2 or 3
  • n is 1 or 3
  • x is 1 or 2.
  • examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -Butyl group, sec-butyl group, n-pentyl group, neopentyl group, n-hexyl group and the like.
  • examples of the aryl group represented by R 1 include aryl groups having 6 to 10 carbon atoms such as phenyl group, tolyl group, dimethylphenyl group, t-butylphenyl group, 1-naphthyl group and 2-naphthyl group. It is done.
  • examples of the linear or branched alkylene group having 1 to 10 carbon atoms represented by R 2 include a methylene group, 1,2-ethylene group, 1,3-propylene group, 2 -Methyl-1,3-propylene group, 2,2-dimethyl-1,3-propylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,7-heptylene Group, 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group and the like.
  • Examples of the arylene group represented by R 2 include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, tolylene group, xylylene group, t-butylphenylene group, and 1,4-naphthylene group. And arylene groups having 6 to 10 carbon atoms such as 1,5-naphthylene group, 1,8-naphthylene group, 2,6-naphthylene group and 2,7-naphthylene group. Examples of the arylalkylene group represented by R 2 include arylalkylene groups having 6 to 10 carbon atoms such as phenylethylene group and 2-phenyl-1,3-propylene group.
  • the phosphinic acid salt represented by the above formula (1) or (2) includes, for example, a phosphinic acid compound and a metal such as a metal carbonate, a metal hydroxide, and a metal oxide as described in Patent Document 5. It can be produced by reacting the components in an aqueous solution.
  • the phosphinic acid compound include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methylenebis (methylphosphinic acid), 1,4-phenylenebis (methylphosphinic acid), Examples thereof include methylphenylphosphinic acid and diphenylphosphinic acid.
  • the metal component include metal carbonates, metal hydroxides, and metal oxides containing calcium ions, magnesium ions, aluminum ions, and zinc ions.
  • monophosphinic acid salt represented by the above formula (1) include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethylmethylphosphinic acid.
  • Um magnesium methylphenyl phosphinate, aluminum methylphenyl phosphinate, methyl phenyl phosphinate, zinc, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinic acid, diphenyl phosphinic acid zinc.
  • diphosphinic acid salt represented by the above formula (2) include, for example, methylene bis (methylphosphinic acid) calcium, methylenebis (methylphosphinic acid) magnesium, methylenebis (methylphosphinic acid) aluminum, and methylenebis (methylphosphinic acid).
  • Zinc 1,4-phenylenebis (methylphosphinic acid) calcium, 1,4-phenylenebis (methylphosphinic acid) magnesium, 1,4-phenylenebis (methylphosphinic acid) aluminum, 1,4-phenylenebis (methylphosphine) Acid) zinc.
  • phosphinic acid salts (II) include calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate.
  • Aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate are preferred, especially industrially commercially available aluminum diethylphosphinate in terms of heat resistance and mass productivity Can be used more preferably.
  • the phosphinic acid salt (II) is preferably used in the form of a powder having an average particle diameter of preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 0.5 to 40 ⁇ m.
  • the average particle diameter of the phosphinate (II) in this specification is a laser diffraction particle size distribution analyzer using a dispersion of the phosphinate (II) dispersed in a medium such as water as a measurement sample. It means the number average particle diameter determined from the frequency distribution of particle diameter and particle number measured by use.
  • the phosphinate (II) is not necessarily completely pure, and a small amount of unreacted product or by-product may remain.
  • the polyamide composition constituting the pellets produced in the method for producing pellets of the present invention and the polyamide composition used in the method for producing molded articles of the present invention comprise 15 to 95% by mass of the above polyamide (I) and 5 to 25% by mass of the above phosphinate (II) is contained.
  • the content of the polyamide (I) in the above polyamide composition is preferably 35 to 70% by mass, and more preferably 40 to 60% by mass.
  • the content of the phosphinic acid salt (II) in the polyamide composition is preferably 10 to 20% by mass, more preferably 10 to 17% by mass.
  • the polyamide composition described above is blended with at least one metal compound (III) selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal borate and hydrotalcite or derivatives thereof. can do.
  • metal compound (III) selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal borate and hydrotalcite or derivatives thereof. can do.
  • the metal compound (III) is blended, it is possible to further reduce the corrosion and wear of the metal parts used when producing the polyamide composition pellets or molding the polyamide composition.
  • the metal oxide include zinc oxide, iron oxide, calcium oxide, aluminum oxide (alumina), magnesium oxide, and silicon oxide (silica).
  • metal hydroxide include magnesium hydroxide, aluminum hydroxide, alumina hydrate and the like.
  • metal carbonate include calcium carbonate and magnesium carbonate.
  • boric acid metal salt include zinc borate, magnesium borate, calcium borate, and aluminum borate.
  • hydrotalcite or derivatives thereof examples include basic aluminum magnesium carbonate hydrate (hydrotalcite), hydrotalcite calcined and crystal water dehydrated.
  • these metal compounds (III) calcium oxide, zinc borate, alumina hydrate, and hydrotalcite are preferable because they have a great effect of capturing acidic substances.
  • the compounding amount of these metal compounds (III) in the polyamide composition if the amount is too small, a sufficient effect cannot be expected. If the amount is too large, the fluidity of the polyamide composition after compounding may decrease.
  • It is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass.
  • an anti-dripping agent (IV) may be added to the above polyamide composition in order to increase the flame retardancy efficiency.
  • the anti-dripping agent (IV) include: fluorine-based resins such as fiberized polytetrafluoroethylene; modified aromatic vinyl-based polymers such as maleic anhydride-modified polystyrene; modified polyolefins such as maleic anhydride-modified ethylene-propylene copolymer; Examples include ionomers.
  • fiberized polytetrafluoroethylene and maleic anhydride-modified polystyrene are preferable because of a high anti-dripping effect, and maleic anhydride-modified polystyrene is more preferable because it does not contain halogen. If the blending amount of the anti-dripping agent (IV) in the polyamide composition is too small, a sufficient effect cannot be expected, and if it is too large, the resulting molded product may have poor appearance and the like. % By mass is preferable, and 0.05 to 1% by mass is more preferable.
  • a flame retardant aid formed from a melamine compound such as melamine, melam, melem, melon and a phosphoric acid compound such as phosphoric acid or polyphosphoric acid ( V) may be blended.
  • a flame retardant aid (V) When such a flame retardant aid (V) is blended, carbonization is promoted at the time of flame retardancy evaluation, so that the blending amount of the phosphinate (II) can be reduced.
  • Specific examples of such a flame retardant aid (V) include, for example, melamine polyphosphate “Melapur 200” or “Melapur 200 70” manufactured by Ciba Specialty Chemicals, and melamine polyphosphate “Phosmel-200” manufactured by Nissan Chemical Industries, Ltd. Or the like.
  • the blending amount of the flame retardant aid (V) in the polyamide composition is too large, the mold may be contaminated when a molded product is produced by injection molding. It is preferably 0 to 1% by mass.
  • the above polyamide composition may contain a filler (VI).
  • filler (VI) what has various forms, such as fibrous form, flat form, needle shape, powder form, cloth form, can be used. Specifically, fibrous fillers such as glass fibers, carbon fibers, aramid fibers, liquid crystal polymer (LCP) fibers, and metal fibers; flat fillers such as mica and talc; potassium titanate whiskers, aluminum borate whiskers, Needle-like fillers such as calcium carbonate whisker, magnesium sulfate whisker, wollastonite, sepiolite, zonotlite, zinc oxide whisker; silica alumina, titanium oxide, boron nitride, potassium titanate, calcium silicate, magnesium sulfate, asbestos, glass beads And powdery fillers such as carbon black, graphite, molybdenum disulfide, phenol resin particles, crosslinked styrene resin particles, and crosslinked acrylic resin particles.
  • fibrous fillers such as glass fibers, carbon
  • fillers (VI) may be used alone or in combination of two or more.
  • the surface of these fillers (VI) is surface-treated with a silane coupling agent, a titanium coupling agent, other high-molecular or low-molecular compounds for the purpose of enhancing the dispersibility in polyamide (I). It is preferable.
  • fillers fibrous fillers or needle-like fillers are preferable, and glass fibers are particularly preferable because a molded product with low cost, excellent productivity, and high mechanical strength can be obtained.
  • glass fibers include chopped strands, milled fibers, cut fibers, etc., and depending on the shape of the molded product and desired properties, one of these may be used alone or in combination of two or more. be able to.
  • the cross-sectional shape of the glass fiber include a round shape, a saddle shape, and a flat shape.
  • the content of the filler (VI) in the polyamide composition is preferably 0 to 60% by mass, and more preferably 0 to 45% by mass.
  • Amide compound (VII) may be blended with the above polyamide composition.
  • the amide compound (VII) include amide oligomers, aliphatic amides, bisamides of aliphatic dicarboxylic acids, aromatic carboxylic acid amides, bisamides of aromatic dicarboxylic acids, and bisamides of aliphatic diamines.
  • an amide compound obtained by a reaction of a mixture of monocarboxylic acid and dicarboxylic acid and diamine is preferable.
  • the amide compound (VII) preferably has a melting point of 80 to 260 ° C. from the viewpoint of fluidity and moldability of the polyamide composition.
  • the molecular weight of the amide compound (VII) is preferably 300 to 3000.
  • the blending amount of the amide compound (VII) in the polyamide composition is preferably 0.1 to 5% by mass.
  • the above polyamide composition includes modified elastomers (maleic anhydride modified ethylene propylene copolymer, maleic anhydride modified ethylene butene copolymer, maleic anhydride modified styrene-ethylene / butene-styrene block copolymer) for improving toughness.
  • modified elastomers maleic anhydride modified ethylene propylene copolymer, maleic anhydride modified ethylene butene copolymer, maleic anhydride modified styrene-ethylene / butene-styrene block copolymer
  • Other polymers such as polymers), aliphatic polyamides other than polyamide (I) (PA612, PA11, PA12, PA66, PA6, etc.), polyphenylene sulfide, liquid crystal polymer, polyphenylene oxide, and the like.
  • the blending amount of these other polymers in the polyamide composition is preferably 0 to 40% by mass.
  • blend reflective materials such as titanium dioxide and a zinc oxide
  • the blending amount of the reflective material (pigment) in the polyamide composition is preferably 0 to 20% by mass.
  • the above polyamide composition includes a colorant; an ultraviolet absorber such as benzophenone, benzotriazole, and triazine; a light stabilizer such as a hindered amine; phosphorous acid, phosphoric acid, phosphonous acid, and esters thereof.
  • Hindered phenol, thio, phosphorus, hindered amine and other antioxidants include Antistatic agents; Crystal nucleating agents; Plasticizers; Waxes such as polyolefin waxes and higher fatty acid esters; Silicone oils, etc.
  • Other components such as a mold release agent and a lubricant can be further blended.
  • the blending amount of other components in the polyamide composition is preferably 0 to 1% by mass.
  • the cylinder temperature of the above extruder means a set temperature in the cylinder.
  • the cylinder temperature of the extruder does not exceed 305 ° C, and does not exceed 300 ° C. Is more preferable.
  • the cylinder temperature of the portion where the polyamide (I) and the phosphinate (II) are melt-kneaded does not exceed the above temperature.
  • the phosphinate (II) is downstream from the portion where the side feed is performed. It is sufficient that the cylinder temperature of the part does not exceed the above temperature throughout.
  • the lower limit of the cylinder temperature of the extruder is not particularly limited as long as it is a temperature at which components such as polyamide (I) and phosphinate (II) can be melt-kneaded. it can.
  • the temperature of the molten resin in the extruder is preferably the above cylinder temperature + 10 ° C. or less, more preferably the cylinder temperature + 5 ° C. or less in consideration of the shear heat generation in the extruder.
  • the extruder used in the method for producing pellets of the present invention is not particularly limited, and examples thereof include a single-screw extruder and a twin-screw extruder, but they are self-cleaning and excellent in productivity.
  • a screw extruder is preferable, and a vented twin screw extruder is more preferable.
  • the ratio (L / D) between the cylinder length (L) and the cylinder diameter (D) of the extruder is preferably 40 or less, and the cylinder diameter (single diameter) is preferably 20 to 100 mm.
  • the steel material of the metal parts that contact the molten resin such as the cylinder and screw forming the extruder, or the die attached to the extruder
  • a nitriding steel material or an alloy such as Cr, Mo, Ni, or W
  • Cr, Mo, Ni, or W it is possible to use a double boride-based hard sintered alloy containing components, and it is preferable to use a double boride-based hard sintered alloy because of its excellent corrosion resistance and oxidation resistance when exposed to high temperatures.
  • an extruder using metal parts that do not use a double boride type hard sintered alloy is sufficient. Can be used.
  • each of the above-mentioned components to be blended in the obtained pellets uses a mixer such as a tumbler, V-type blender, Henschel mixer, Nauta mixer, ribbon mixer, mechanochemical apparatus, extrusion mixer, etc.
  • a mixer such as a tumbler, V-type blender, Henschel mixer, Nauta mixer, ribbon mixer, mechanochemical apparatus, extrusion mixer, etc.
  • a master batch consisting of some components is formed and premixed, and then the resulting mixture is supplied from the supply port at the most upstream part of the extruder and melt-kneaded.
  • Pellets of polyamide composition can be produced.
  • some components can be side-fed from the middle to the downstream of the extruder. Examples of components that are preferably side-fed include phosphinate (II) and fibrous filler.
  • Pellets can be produced by extruding the polyamide composition melt-kneaded as described above into strands and cutting with a pelletizer. Prior to cutting with a pelletizer, it is preferable to cool the strand-like polyamide composition by passing it in water. There is no particular limitation on the size of the pellets to be obtained, but since it is also assumed that the molded product is formed by injection molding with a small injection molding machine having a screw diameter of 18 mm ⁇ or less, the pellet diameter is preferably 1 mm to 3 mm. The pellet length is preferably 1 mm to 3.5 mm.
  • the polyamide composition is extruded, injection molded or blow molded under the condition that the cylinder temperature of the molding machine does not exceed 310 ° C.
  • the cylinder temperature of the molding machine means a set temperature in the cylinder. When the cylinder temperature of the molding machine is too high, corrosion and wear of metal parts are likely to occur. Therefore, it is preferable that the cylinder temperature of the molding machine does not exceed 305 ° C, and it does not exceed 300 ° C. Is more preferable.
  • the cylinder temperature of the portion where the polyamide composition is melt-kneaded in the extruder, injection molding machine or blow molding machine does not exceed the above temperature throughout. .
  • the lower limit value of the cylinder temperature of the molding machine is not particularly limited as long as it is a temperature at which the polyamide composition can be melt-kneaded. For example, 270 ° C. can be exemplified.
  • the temperature of the molten resin in the molding machine is preferably the above cylinder temperature + 10 ° C. or less, more preferably the cylinder temperature + 5 ° C. or less in consideration of shear heat generation in the molding machine.
  • the injection molding machine used for injection molding is not particularly limited, and is a plunger type injection molding machine, a pre-plastic injection molding machine, a screw-in-line type injection. Although a molding machine etc. can be mentioned, a pre-plastic injection molding machine and a screw-in-line injection molding machine are preferable.
  • the cylinder diameter of the injection molding machine is preferably 10 to 40 mm.
  • a fixed quantity supply device for example, “Hungry Feeder” manufactured by Nippon Oil Machinery Co., Ltd.
  • a fixed quantity supply device can eliminate the supply of polyamide composition (pellet) due to free fall and effectively remove moisture and gas.
  • ”Or“ Ecomac ”manufactured by Haruna Co., Ltd. is preferably used in combination.
  • the supply of pellets to the molding machine is controlled to an arbitrary degree, excessive shearing heat generation due to screw rotation in the molding machine is suppressed, and excessive temperature rise of the molten resin is suppressed. Can do.
  • it is preferable to purge with nitrogen by introducing nitrogen from a nitrogen line. By purging with nitrogen, it is possible to prevent deterioration of the resin or the like due to oxygen in the cylinder of the molding machine.
  • the cylinder and screw steel materials forming the molding machine there are no particular limitations on the cylinder and screw steel materials forming the molding machine, and commonly used steel materials such as SCM440 or SACM645 can be mentioned, but a double boride system containing alloy components such as Cr, Mo, Ni, W, etc. This is preferable because the hard sintered alloy (for example, “KH V50” manufactured by Toyo Steel Co., Ltd.) is excellent in corrosion resistance and oxidation resistance when exposed to high temperatures. According to the present invention, since corrosion and wear of metal parts can be reduced, even a molding machine using metal parts that do not use a double boride type hard sintered alloy is sufficient. Can be used.
  • KH V50 manufactured by Toyo Steel Co., Ltd.
  • the thing excellent in corrosion resistance and abrasion resistance such as SKD11 and "ELMAX” (SUS420C), is preferable. Among these, “ELMAX” is more preferable, and continuous productivity can be improved.
  • the mold surface may be coated.
  • the coating material is not particularly limited, but TiN (nitride) and DLC (amorphous carbon film having a carbon bond) are preferable because they can be applied to high temperature durability and fine molds.
  • the polyamide composition supplied to the molding machine is preferably in the form of pellets.
  • the polyamide composition used in the method for producing a molded article of the present invention may be a pellet produced in the method for producing a pellet of the present invention, and as long as the composition of the polyamide composition satisfies the provisions of the present invention, The pellet which is not the pellet manufactured in the manufacturing method of the pellet of this invention may be sufficient.
  • the polyamide composition may be a recycled material obtained by pulverizing sprues, runners, molding defects and the like generated in injection molding.
  • the polyamide composition used is excellent in electrical properties such as tracking resistance, has flame resistance of V-0 class, and is used at a temperature at which it is practically used. Since the amount of generated gas is small, various electronic parts, automobile parts, home appliances, building materials, sanitary goods, sports goods, miscellaneous goods and the like that require flame retardancy can be preferably exemplified. More specifically, connectors, switches, sensors, sockets, capacitors, hard disk components, jacks, fuse holders, relays, coil bobbins, resistors, IC and LED housings, gears, bearing retainers, spring holders, chain tensioners, washers, Various housings, weight rollers, breaker parts, clutch parts and the like can be mentioned.
  • connectors, sockets, card connectors, jacks, power supply parts, switches, sensors, capacitor seats, hard disk parts, relays, resistors, fuse holders Particularly preferable examples include a coil bobbin, an IC housing, an LED housing, and the like.
  • the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
  • the melting point of polyamide, the intrinsic viscosity of polyamide, the molten resin temperature in a twin-screw extruder, the molten resin temperature in an injection molding machine, flame retardancy of test pieces, solder heat resistance of test pieces, pellets The copper plate corrosion test using was measured or evaluated by the following method.
  • polyamide (sample weight 10 mg) was heated in a DSC furnace under a nitrogen atmosphere at 330 ° C. for 2 minutes to completely melt, ⁇ The crystal was cooled to 50 ° C. at a rate of 50 ° C./min, and the position of the melting peak of the crystal that appeared when the temperature was raised again at a rate of 10 ° C./min was measured. When there were a plurality of peaks, the melting point on the high temperature side was adopted.
  • DSC polyamide melting point differential scanning calorimeter
  • Polyamide concentrated sulfuric acid solutions having polyamide intrinsic viscosity concentrations of 0.05 g / dl, 0.1 g / dl, 0.2 g / dl and 0.4 g / dl were prepared, and for each concentrated sulfuric acid solution, an Ubbelohde viscometer was prepared.
  • An Ubbelohde viscometer was prepared.
  • Solution viscosity at 30 ° C From the relationship between the obtained concentration and the solution viscosity, the solution viscosity when extrapolated to a concentration of 0 g / dl was determined, and this was defined as the intrinsic viscosity [ ⁇ ].
  • molten resin temperature (Twin screw extruder) In the following Example 1 and Comparative Example 1, the temperature of the extruded molten resin was measured using a thermometer (“HA-” manufactured by Anritsu Keiki Co., Ltd.) equipped with a needle-like thermocouple (BS-21E-010, 2.1 mm ⁇ ). 100E "). The measured temperature was measured when the temperature increased and maintained at a constant temperature for 5 seconds or more.
  • molten resin temperature injection molding machine
  • injection molding machine “ ⁇ -15” screw diameter: 18 mm ⁇ , extended nozzle diameter: 2 mm ⁇
  • the temperature of the continuously discharged molten resin was measured using a thermometer (“HA-100E” manufactured by Anritsu Keiki Co., Ltd.) equipped with a needle-shaped thermocouple (BS-21E-010, 2.1 mm ⁇ ). Measured. The measured temperature was measured when the temperature increased and maintained at a constant temperature for 5 seconds or more.
  • T is 50 seconds or less
  • M is 10 seconds or less and does not burn up to the clamp
  • V-0 T is "V-1" if 250 seconds or less
  • M is 30 seconds or less
  • the other conditions are the same as V-0
  • T is 250 seconds or less
  • M is 30 seconds or less, and does not burn up to the clamp.
  • Copper plate corrosion test Copper foil (manufactured by Niraco Co., Ltd., purity 99.9%, thickness 0.05 mm) was prepared as a 2 cm ⁇ 2 cm test piece, and 2 g of a sample (polyamide composition pellet) and a copper foil test piece were crucibles ( 30 ml, diameter 45 mm, height 36 mm) and the lid was closed. The heating furnace was set to 300 ° C. or 320 ° C. and heat-treated for 60 minutes, and then cooled to room temperature by natural cooling. The internal copper foil was taken out and the surface condition was observed. A case where the surface state was not changed or only a change in color tone was indicated as “ ⁇ ”, and a case where a brownish brown rust-like matter was generated was indicated as “X”.
  • the phosphinate (II) and the filler (VI) were supplied from the side feeder and melt-kneaded.
  • the values in Table 1 were adopted as the cylinder temperature of the twin screw extruder.
  • the melt-kneaded polyamide composition was extruded into a strand shape, cooled and cut to obtain polyamide composition pellets.
  • the screw wear amount was quantified by subtracting the thickness of the screw after producing 25 kg of pellets from the initial thickness. The results are shown in Table 1.
  • Example 1 in which pellets of polyamide composition were produced using PA9T-1 having a melting point of 292 ° C. at a cylinder setting temperature of 295 ° C. (the temperature of the molten resin was 299 ° C.), the wear of the screw was not seen.
  • Comparative Example 1 using PA9T-2 having a melting point of 306 ° C. a cylinder setting temperature of 320 ° C. is necessary to sufficiently melt and knead the resin (the temperature of the molten resin is 325 ° C.).
  • wear of the screw of the extruder occurred, and metal corrosivity was recognized.
  • Examples 2 to 7 and Comparative Example 2 Components other than phosphinate (II) and filler (VI) are premixed (dry blended) at the ratio shown in Table 2 and supplied from the hopper at the uppermost stream of the extruder, and phosphinate (II) and A polyamide composition containing each component in the proportions shown in Table 2 in the same manner as in Example 1 except that the filler (VI) is supplied from the side feeder (however, in Comparative Example 2 the cylinder temperature was 320 ° C.). Of pellets were produced.
  • Example 2 In the copper plate corrosion test at 320 ° C. close to the molten resin temperature of Comparative Example 2, brown It was suggested that crater-like rust was generated and that significant corrosion by the molten resin occurred. Even in Example 2 using a polyamide having a melting point of 300 ° C. or less, since a brown and crater-like rust was generated in the 320 ° C. copper plate corrosion test, the cylinder temperature of the molding machine was defined within the range specified in the present invention. I know you need to do that.
  • Example 3 Each of the above-mentioned PA9T-1 (sample 1), the above-mentioned phosphinate (II) (sample 2) and the pellet obtained in Example 2 (sample 3) (sample amount of about 10 mg; in the case of pellets, cut)
  • Thermogravimetric measurement by heating from 30 ° C to 500 ° C under conditions of air flow rate of 150ml / min and temperature increase rate of 10 ° C / min using a METTLER TOLEDO thermogravimetric measuring device (TGA) Went.
  • TGA thermogravimetric measuring device
  • a polyamide composition pellet manufacturing method and molding capable of achieving halogen-free with reduced corrosion and wear of metal parts without sacrificing solder heat resistance by polyamide having a specific melting point.
  • a method of manufacturing an article is provided.
  • the manufacturing method of the molded product according to the present invention is compatible with the SMT method. Connector, socket, card connector, jack, power supply component, switch, sensor, capacitor seat plate, hard disk component, relay, resistor, fuse holder, coil bobbin, IC, etc. It is particularly useful for manufacturing LED housings and the like.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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Abstract

L'invention porte sur un procédé de fabrication de pastilles, qui permet de produire des pastilles d'une composition de polyamide qui peuvent supporter une température de procédé de refusion élevée et qui peuvent être moulées en un article provoquant moins de changement d'aspect tel que la formation de boursouflure et qui ne corrode ou n'érode guère une partie métallique, bien que les pastilles contiennent un sel d'acide phosphinique. Le procédé permet de produire les pastilles à faible coût et avec un rendement de production élevé. De façon spécifique, l'invention porte sur un procédé de fabrication de pastilles d'une composition de polyamide incluant de 15 à 95 % en masse d'un polyamide (I) présentant un point de fusion de 270 à 300 °C et 5 à 25 % en masse d'un sel d'acide phosphinique (II). Le procédé consiste à : malaxer en phase fondue au moins le polyamide (I) et le sel d'acide phosphinique (II) dans les conditions dans lesquelles la température de cylindre d'une extrudeuse ne dépasse pas 310 °C; et pastiller le produit résultant.
PCT/JP2009/052669 2008-02-29 2009-02-17 Procédé de fabrication de pastilles de composition de polyamide présentant une propriété de corrosion de métal réduite et procédé de fabrication d'un article moulé WO2009107514A1 (fr)

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JP2012523469A (ja) * 2009-04-09 2012-10-04 ソルベイ・アドバンスト・ポリマーズ・エルエルシー 改善されたハロゲンを含まない難燃性ポリアミド組成物
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JP2014523449A (ja) * 2011-04-04 2014-09-11 ローディア オペレーションズ 高い熱伝導率を有するポリアミド組成物
JP2014528013A (ja) * 2011-09-27 2014-10-23 ローディア オペレーションズ 高い熱伝導率を有するポリアミド組成物
JP5733871B2 (ja) * 2013-01-11 2015-06-10 旭化成ケミカルズ株式会社 ポリアミド組成物及び成形品
JP2018158959A (ja) * 2017-03-22 2018-10-11 大日精化工業株式会社 難燃性マスターバッチ、難燃性樹脂組成物、及び難燃性繊維
CN114591625A (zh) * 2022-03-31 2022-06-07 珠海万通特种工程塑料有限公司 一种聚酰胺复合材料及其制备方法和应用
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