JP4451130B2 - Method for producing high molecular weight polyamide resin composition - Google Patents

Description

The present invention has excellent moldability that is excellent in stability of melt viscosity at the time of molding suitable for industrial materials such as various machine industry parts and electrical and electronic parts, and reduced contamination of the mold due to thermal decomposition components. The present invention relates to a method for producing a high molecular weight polyamide resin composition having excellent slidability, abrasion resistance and appearance of a molded product obtained.

  Polyamide resins are excellent in mechanical properties, heat resistance, chemical resistance, etc., and are therefore used as engineering plastics in various applications such as automobile parts, electronic and electrical parts, and industrial parts. In recent years, the shape, thickness, and specialization of polyamide resin molded products have progressed, and a polyamide resin that can cope with this has been demanded. High durability polyamide resin material that can be used in harsh environments where excessive external force or heat is applied, and high cycle and use of recycled pellets from the perspective of economics and environmental issues There is also a strong demand for polyamide resin materials. For example, the application of a high molecular weight polyamide resin to structural parts and sliding parts around an automobile engine in a high temperature atmosphere can be exemplified.

  However, when making a molded product such as the above with a high molecular weight polyamide resin, the heat retention temperature and time increase because the molding temperature is increased or the hot runner molding method is used to increase melt fluidity. There is a problem that thermal oxidative degradation and thermal decomposition of the resin are more likely to occur than those having a molecular weight used in conventional and normal injection molding. Such thermal oxidative deterioration changes the color of the resin and lowers the color tone of the obtained molded product. In addition, the thermal decomposition generates volatile oligomers, and this volatile component adheres to the surface of the molded product, resulting in the appearance of the molded product being impaired. Furthermore, since this resin decomposition product adheres to and contaminates the mold and the nozzle, the mold and the nozzle must be frequently cleaned, which continuously inhibits stable molding. In addition, as the resin undergoes thermal degradation and thermal decomposition, the resin viscosity, ie, molecular weight, changes. Changes in the viscosity of the resin during heat retention not only cause the molding conditions to become unstable, but also cause a decrease in the mechanical properties of the resulting molded product.

As a method for preventing such thermal degradation and thermal decomposition, there is generally a method of performing molding in an inert gas environment, but it is uneconomical and not practical. Moreover, in order to prevent the thermal deterioration and thermal decomposition of polyamide, examination which mix | blends a heat stabilizer is made | formed. For example, a method of adding phosphoric acid or phosphates, or a metal salt of hypophosphorous acid or phosphorous acid (JP 2000-129119 A), a method of adding a known heat stabilizer (JP 7-118926 A). And a method of adding a terminal blocking agent (JP-A-8-3443, JP-A-2001-26647) and the like.
However, although the conventional method shows some improvement in thermal stability, it has not yet achieved a satisfactory result.

The present invention is excellent in stability of melt viscosity at the time of molding, suitable as industrial materials such as various machine industry parts and electric / electronic parts, is reduced in mold contamination due to thermal decomposition components, and has releasability, plasticity. It is an object of the present invention to provide a method for producing a heat-resistant high molecular weight polyamide resin having excellent moldability and excellent slidability, wear resistance, and appearance of the obtained molded product.

As a result of intensive studies to solve the above-mentioned problems of the present invention, the present inventors have found that a specific thermal stability is formed on the pellet surface of a thermal stabilizer masterbatch comprising a specific high molecular weight polyamide , a polyamide resin, a copper compound, and a halogen compound. In a polyamide resin composition to which a specific amount of an agent, a fatty acid ester, and a fatty acid metal salt is attached , a heat stabilizer master batch is prepared by melt-kneading a polyamide resin, components (E) and (F) previously pulverized As a result, it has been found that the above problems can be solved, and the present invention has been completed.
That is, the present invention
1. An organic heat stabilizer (B) selected from hindered phenols (B) in an amount of 0.005 to 0.1 parts by weight with respect to 100 parts by weight of the high molecular weight polyamide 66 (A) having a relative viscosity RV of 80 to 350, an acid 0.005 to 0.1 parts by weight of a higher fatty acid ester (C) having a valence of 5 to 50 (mgKOH / g) and a saponification value of 50 to 200 (mgKOH / g) and a higher fatty acid metal salt (D) of 0. 01 to 0.1 parts by weight, the total amount of the copper compound (E) and the halogen compound (F) other than the halogen copper is 0.01 to 1 part by weight, and the molar ratio of the halogen element to the copper element is 1 to 50 A method for producing a polyamide resin composition contained in a range, wherein a polyamide resin, a component (E) and a component (F) previously pulverized are melt-kneaded to obtain a heat stabilizer master batch (G), Component (A), Component (B) Manufacturing method of the component (C), mixing components (D) and the component (G), the polyamide resin composition,

2 . The method for producing a polyamide resin composition according to 1 above, wherein 0.1 to 100 parts by weight of the heat stabilizer master batch (G) is blended with 100 parts by weight of the component (A).
3 . Component (G) is 0.01 to 30 parts by weight of the total amount of component (E) and component (F) with respect to 100 parts by weight of polyamide resin, and (2) the molar ratio of halogen element to copper element is 1 to 30 parts by weight. 50. The method for producing a polyamide resin composition according to the above 1 or 2 , which is a heat stabilizer masterbatch in the range of 50,
4. The method for producing a polyamide resin composition according to any one of the above 1 to 3, wherein the polyamide resin, component (E) and component (F) are pulverized in advance to an average particle size of less than 100 μm,
It is.

The polyamide resin composition obtained by the production method of the present invention has excellent moldability such that it has excellent melt viscosity stability at the time of molding and contamination of the mold due to thermal decomposition components is reduced. Excellent slidability, wear resistance, and appearance. In particular, the improvement effect is remarkable in injection molding.

Hereinafter, the present invention will be described in detail.
The molecular weight of the polyamides 66, in the molecular weight determined by measured according to ASTM D789 (RV), abrasion resistance of the molded article is 80 or more from the viewpoint of durability, 350 or less from the viewpoint to the injection molding of It is. Preferably they are 100 or more and 250 or less, More preferably, they are 100 or more and 200 or less. The molecular weight (RV) is measured at a temperature of 25 ° C. at a concentration of 3 g sample / 30 ml formic acid using 90% formic acid as a solvent.
The polyamides 66, to the extent not to impair the object of the present invention, other than polyamide 66, polyamide 6, polyamide 610, polyamide 612, polyamide 6T (T: terephthalic acid), polyamide 6I (I: isophthalic acid) other such Polyamide components may be mixed or copolymerized.

The polyamides 66 can contain a copper compound and a halogen compound other than silver copper as a heat stabilizer. Examples of copper compounds include metal compounds of elemental copper, such as copper halides, sulfates, acetates, propionates, benzoates, adipates, terephthalates, salicates, nicotine. Examples thereof include acid salts, stearates, chelate compounds such as ethylenediamine (en) and ethylenediaminetetraacetic acid, and mixtures thereof. Among these, preferred are copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate.
The halogen compound other than the halogen copper is a salt of iodine and a metal element of Group 1 or 2 of the periodic table of elements, and preferable examples include potassium iodide, sodium iodide, and a mixture thereof. Among them, potassium iodide can be mentioned as the most preferable one.

The compounding amount of the copper compound and the halogen compound other than the halogen copper is 0.01 or more from the viewpoint of manifesting the thermal deterioration suppressing effect with respect to 100 parts by weight of the polyamide, and the metal copper is deposited in the molding machine or on the surface of the molded product. Moreover, it is preferable that it is 1 weight part from viewpoints, such as a color tone change by thermal oxidation degradation, 0.05-0.75 weight part is more preferable, 0.05-0.5 weight part is the most preferable.
In the present invention, a copper compound and a halogen compound other than copper are used in combination. From the viewpoint of improving mold contamination, the molar ratio of the halogen element to the copper element is in the range of 1 to 50. Preferably, the range of 5-30 is more preferable.

  The method of blending a polyamide compound with a halogen compound other than copper halide and halogen copper is, for example, a method of blending the compound with a polyamide raw material, a method of blending in a polyamide polymerization process, a method of adhering to a polyamide pellet surface, a melt kneading method with a polyamide. Any method may be used, such as a method of blending with polyamide, a method of blending with polyamide as a masterbatch, or a method of blending these methods in combination. In the present invention, among them, a method of blending with a polyamide raw material and a method of blending with a polyamide as a master batch can be mentioned as preferable methods.

A heat stabilizer masterbatch (hereinafter sometimes referred to as a heat-anchor masterbatch) is a high-grade powder of halogenated compounds other than copper compounds and halogenated copper, which has been refined in advance for the purpose of improving the dispersibility of the heat stabilizer. A dispersant such as a fatty acid metal salt, specifically calcium stearate, is further blended and mixed with a polyamide resin, and then subjected to mechanical pulverization such as freeze pulverization to form a finely pulverized powder mixture having an average particle size of less than 100 μm, followed by melt-kneading. Obtained. When the powder particle diameter of the halogen compound other than the copper compound and halogen copper to be blended is too large, the mechanical properties, particularly toughness, of the resulting molded article is greatly reduced.
The amount of copper compound and a halogen compound other than silver copper or heat stabilizer masterbatch, thermal stability effect is not less 0.01 parts by weight or more in terms of expression, 30 weight from difficulty in melt-kneading Or less. The amount is preferably 0.5 to 20 parts by weight, and more preferably 1 to 15 parts by weight.

A preferred polymerization process of polyamides, more specifically, to a hexamethylene adipamide polyamide 66 material, a copper compound optionally iodine compounds other than iodide Motodo, and anti-foaming agent, 40 This is a hot-melt polycondensation method in which heat condensation is performed at a temperature of 300 ° C., and the generated water vapor pressure is maintained at a pressure between normal pressure and 20 atm. . Furthermore, a solid-phase polymerization method performed at a temperature below the melting point of the diamine / dicarboxylate solid salt or polycondensate, a solution method in which a dicarboxylic acid halide component and a diamine component are polycondensed in a solution, or the like can also be used. These methods may be combined as necessary. Further, the polymerization form may be a batch type or a continuous type. The polymerization apparatus is not particularly limited, and a known apparatus such as an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, or the like can be used.

Organic based heat stabilizer is a heat stabilizer selected from hindered phenols.
Examples of the hindered phenols include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propioamide], benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol is mentioned.

Further, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexane-tert-butyl- 4-a, a ', a "-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [[[3,5-bis- (1,1-dimethylethyl) -4- Hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] Is mentioned.
Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene, 2,6-di There may be mentioned -tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol or a mixture thereof.

The amount of organic-based heat stabilizer, relative to 100 parts by weight of the polyamide of the present invention, 0.005 to 0.1 parts by weight, preferably 0.01 to 0.1 parts by weight, more preferably 0.02 ~ 0.05 parts by weight. The blending amount of the organic heat stabilizer is determined from the viewpoint of improving effects such as mold contamination, the occurrence of silver defects on the surface of the molded product, and toughness.
High grade fatty acid esters are esters of a higher alcohol and a higher fatty acid, or esters of polyhydric alcohol and a higher fatty acid, or mixtures thereof are preferably used.

(C-1) Ester of higher alcohol and higher fatty acid As the ester of higher alcohol and higher fatty acid, an ester of an aliphatic alcohol having 8 or more carbon atoms and a higher fatty acid having 8 or more carbon atoms is more preferable. Preferably, it is an ester of an aliphatic alcohol having 12 or more carbon atoms and a higher fatty acid having 12 or more carbon atoms, and most preferably an ester of an aliphatic alcohol having 12 or more carbon atoms and a higher fatty acid having 16 or more carbon atoms. .

Examples of the aliphatic alcohol having 8 or more carbon atoms include octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristic alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, Examples include stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol, and melyl alcohol.
Examples of the higher fatty acid having 8 or more carbon atoms include capric acid, uradecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid. , Serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laxeric acid.

  Any of the higher alcohol and higher fatty acid esters may be used, but more preferable higher fatty acid esters include, for example, lauryl laurate, lauryl myristate, lauryl palmitate, lauryl stearate, lauryl behenate, and lauryl. Lignocerate, lauryl meristate, myristyl laurate, myristyl myristate, myristyl stearate, myristyl behenate, myristyl lignocerate, myristyl meristate, palmityl laurate, palmityl myristate, palmityl stearate, pal Mityl behenate, palmityl lignocerate, palmityl meristate, stearyl laurate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl behene , Stearyl arachinate, stearyl lignocerate, stearyl melicate, eicosyl laurate, eicosyl palmitate, eicosyl stearate, eicosyl behenate, eicosyl lignocerate, eicosyl meristate, behenyl laurate, Behenyl myristate, behenyl palmitate, behenyl stearate, behenyl behenate, behenyl arachinate, behenyl merisate, tetracosanyl laurate, tetracosa palmitate, tetracosanyl stearate, tetracosanyl behenate, tetra Cosanyl lignocerate, tetracosanyl serotate, serotinyl stearate, serotinyl behenate, serotinyl serotinate, merisyl laurate, mesylyl stearate, merisyl behenate, merisyl Riseto or can mixtures thereof.

(C-2) Ester of polyhydric alcohol and higher fatty acid The partial ester of polyhydric alcohol and higher fatty acid is, for example, glycerin, 1,2,3-butanetriol, 1,2,3-pentanetriol as polyhydric alcohol. Erythritol, pentaerythritol, trimethylolpropane, mannitol, sorbitol and the like are preferably used, and higher fatty acids include, for example, capric acid, uradecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid , Stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid are preferably used.

  These esters of polyhydric alcohols and higher fatty acids may be monoesters, diesters or triesters. More preferred examples include higher fatty acid monoglycerides such as glycerin monolaurate, glycerin monomyristate, glycerin monostearate, glycerin monobehenate, glycerin monolignocerate, glycerin monomellate, pentaerythritol mono- or di- Laurate, pentaerythritol mono- or di-laurate, pentaerythritol mono- or di-myristate, pentaerythritol mono- or di-palmitate, pentaerythritol mono- or di-stearate, pentaerythritol mono- or Mono- or di-higher fats of pentaerythritol, such as di-behenate, pentaerythritol mono- or di-lignocerate, pentaerythritol mono- or di-melissate Esters, trimethylolpropane-mono- or di-laurate, trimethylolpropane-mono- or dimyristate, trimethylolpropane-mono- or dipalmitate, trimethylolpropane-mono- or di-stearate, trimethylol Mono- or di-higher fatty acid esters of trimethylolpropane, such as propane-mono- or di-behenate, trimethylolpropane-mono- or di-lignocerate, trimethylolpropane-mono- or di-melisate, sorbitan-mono, di Or tri-laurate, sorbitan-mono, di- or tri-myristate, sorbitan-mono, di- or tri-stearate, sorbitan-mono, di- or tri-behenate, sorbitan-mono, di- or tri-rig Sorbitan-mono, di- or tri-higher fatty acid esters such as serate, sorbitan-mono, di- or tri-melisate, mannitan-mono, di- or tri-laurate, mannitan-mono, di- or tri-myristate, mannitan-mono, Mannitan-, such as di- or tri-palmitate, mannitan-mono, di- or tri-stearate, mannitan-mono, di- or tri-behenate, mannitan-mono, di- or tri-lignocerate, mannitan-mono, di- or tri-meliselate Mention may be made of mono-, di- or tri-higher fatty acid esters or mixtures thereof.

High grade fatty acid esters, acid number as measured by ASTM D1386 is from the viewpoint of mold staining of the effect of improving the expression 5 (mgKOH / g) or more, 50 in view of preventing decrease in the molecular weight during molding (mg KOH / g), and the saponification value measured by ASTM D1387 is 50 (mgKOH / g) or more from the viewpoint of the effect of improving mold contamination, and 200 from the viewpoint of preventing contamination of the mold due to deterioration of heat resistance. (MgKOH / g) or less. The acid value is preferably 10 to 40, and more preferably 10 to 30. The saponification value is preferably 100 to 200, and more preferably 110 to 180.
The amount of high-grade fatty acid esters, to the polyamides 100 parts by weight, 0.005 to 0.1 parts by weight, preferably 0.01 to 0.1 parts by weight, more preferably 0.01 ~ 0.05 parts by weight. The blending amount of the higher fatty acid ester is determined from the viewpoint of improving the mold fouling property and generating silver on the surface of the molded product.

Fatty acid metal salt is represented by the following formula.
CH3 (CH2) nCOO (M)
Here, n = 8 to 32, and the metal element (M) is preferably a group 1, 2, 3 element of the periodic table, zinc, aluminum or the like. Among them, more preferred are, for example, capric acid, uradecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid , Heptacosanoic acid, montanic acid, mellicic acid, lithium salt of lactic acid, sodium salt, magnesium salt, calcium salt, zinc salt, aluminum salt, etc., or a mixture thereof.

The amount of fatty acid metal salt, with respect to polyamides based on 100 parts by weight of plasticizing, such as releasability improving effect 0.01 part by weight or more, of silver-like defect of the molded article surface and prevents lowering of the molecular weight From this viewpoint, it is 0.1 parts by weight or less, preferably 0.02 to 0.075 parts by weight, and more preferably 0.025 to 0.05 parts by weight.
Method for producing polyamides resin composition is not limited in particular as long as it is a method of blending an organic heat stabilizers and higher fatty acid esters, higher fatty acid metal salt to the polyamide resin, for example, organic polyamide resin pellet surface System heat stabilizer and higher fatty acid ester, surface adhesion method for adhering higher fatty acid metal salts and mixtures thereof, melting blending organic heat stabilizer, higher fatty acid ester and higher fatty acid metal salt into polyamide resin by melt kneading machine Any method such as a kneading method, a masterbatch method in which a masterbatch of an organic heat stabilizer and a higher fatty acid ester, a higher fatty acid metal salt or a mixture thereof is blended with a polyamide resin, or a combination of these methods. May be used.

The polyamides resin composition, to the extent not to impair the object of the present invention, additives conventionally used in the polyamide resin, such as pigments and dyes, flame retardants, lubricants, fluorescent bleaching agents, plasticizers, ultraviolet absorbing Agents, nucleating agents, rubbers, other polyamides, resins other than polyamides, and reinforcing agents can also be contained.
Polyamide resin composition, methods known molding, for example press molding, injection molding, gas assisted injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, such melt spinning, generally known Even if a plastic molding method is used, molding can be performed satisfactorily. Especially, it is excellent in injection moldability.
Y de moldings is not a particular limitation as long molded article obtained by injection molding, in particular, binding band, thin moldings and shapes complex molded articles in which high-cycle, such as tag pins are required, sled, These include thin flat plate and long molded products that require dimensional characteristics, and sliding parts such as gears, gears, shoes, tensioners, guide rails, and cams that require molded product surface smoothness and slidability.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded. In addition, the physical property evaluation described in the following examples and comparative examples was performed as follows.
1. Characteristics of polyamide resin composition (1-1) Molecular weight of polyamide (RV)
90% formic acid is used as a solvent at a concentration of 3 g sample / 30 ml formic acid under a temperature condition of 25 ° C.
(1-2) Acid value and saponification value of higher fatty acid ester The acid value conforms to ASTM D1386, and the saponification value conforms to ASTM D1387.

2. Properties of polyamide resin composition (2-1) Sublimation generation by thermal decomposition of pellets (visual observation)
20 g of dried pellets are put into a 50 ml glass test tube, and the opening is covered with aluminum foil, and then set on an aluminum block heater (Daiyo Scientific Industrial Co., Ltd. Dry Thermo Unit TAH-1B). And heated for 4 hours. The degree of adhesion of the sublimate adhering to the inner wall surface of the test tube at that time was visually observed.
○: Almost no adhesion △: Medium adhesion that can be clearly confirmed ×: Large amount of adhesion

(2-2) Mold Contamination Using an injection molding machine (PS40E manufactured by Nissei Resin Co., Ltd.), the cylinder temperature was set to 285 ° C., the mold temperature was set to 70 ° C., the injection speed was 35%, the injection was 8 seconds, and the cooling was 10 100 shots of cap-shaped parts were injection-molded under the injection molding conditions of 2 seconds and a molding cycle of 22 seconds, and the state of dirt on the mold gas vent was visually evaluated.
○: Almost unstained.
Δ: Slightly adhered and dirty.
X: Adherent and dirty.

(2-3) Sliding characteristics
Using an injection molding machine (FN3000 manufactured by Nissei Resin Co., Ltd.), a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. are set, and an evaluation plate (90 mm × 60 mm, 3 mm) under injection conditions of 14 seconds for injection and 15 seconds for cooling. Thick plate).
In the frictional wear test, the coefficient of friction and the amount of wear were measured under the following conditions in a room temperature atmosphere using a pin / plate tester AFT-15MS manufactured by Tohken Precision Industry Co., Ltd.
Pin material: SUS314
Reciprocating speed: 30 mm / second Reciprocating distance: 20 mm
Load: 2kg

(2-4) Mechanical properties Using an injection molding machine (FN3000 manufactured by Nissei Resin Co., Ltd.), the cylinder temperature is set to 300 ° C., the mold temperature is set to 80 ° C., and evaluation is performed under injection molding conditions of 14 seconds for injection and 15 seconds for cooling. A test piece was obtained.
(A) Flexural modulus and flexural strength (MPa)
This was performed according to ASTM D790.
(B) Tensile strength (MPa) and tensile elongation (%)
This was performed according to ASTM D638.

[Production Example 1]
Manufacture of polyamide resin (1) Using a 50 wt% aqueous solution containing 1600 kg of polyamide 66 raw material (equimolar salt of hexamethylenediamine and adipic acid), 60 g of acetic acid and 70 g of a silicone-based antifoaming agent were blended as a terminal blocking agent. The mixture was charged in an autoclave of about 4000 liters having a discharge nozzle at the bottom, mixed under a temperature condition of 50 ° C., and replaced with nitrogen. Next, the temperature was raised from 50 ° C. to about 150 ° C. over about 1 hour. At this time, in order to maintain the pressure in the autoclave at a gauge pressure of about 0.15 MPa, heating was continued while removing water out of the system. Further, the autoclave was sealed, the temperature was raised from 150 ° C. to about 220 ° C. over about 1 hour, and the pressure was increased to about 1.77 MPa by making the pressure a gauge pressure. Thereafter, the temperature was raised from about 220 ° C. to about 280 ° C. over about 1 hour, and heating was performed while removing water from the system so as to keep the pressure at about 1.77 MPa. Finally, the pressure was reduced to atmospheric pressure over about 1 hour, and after reaching atmospheric pressure, the polymer was discharged in a strand form from the lower nozzle, water-cooled and cut to obtain polyamide resin (1) pellets. The obtained pellets were dried in a nitrogen stream at 90 ° C. for 4 hours. The relative viscosity (RV) of the polyamide pellets was 45. The moisture content measured by the Karl Fischer method was 0.08% by weight.

[Production Example 2]
Production of polyamide resin (2) 50% by weight aqueous solution containing 1600 kg of polyamide 66 raw material (equimolar salt of hexamethylenediamine and adipic acid), a mixture of 0.276 kg of copper acetate and 3.17 kg of potassium iodide, 70 g of the foaming agent was blended, charged in an autoclave of about 4000 liters having a discharge nozzle at the bottom, mixed under a temperature condition of 50 ° C., and replaced with nitrogen. Next, the temperature was raised from 50 ° C. to about 150 ° C. over about 1 hour. At this time, in order to maintain the pressure in the autoclave at a gauge pressure of about 0.15 MPa, heating was continued while removing water out of the system. Further, the autoclave was sealed, the temperature was raised from 150 ° C. to about 220 ° C. over about 1 hour, and the pressure was increased to about 1.77 MPa by making the pressure a gauge pressure. Thereafter, the temperature was raised from about 220 ° C. to about 280 ° C. over about 1 hour, and heating was performed while removing water from the system so as to keep the pressure at about 1.77 MPa. Finally, the pressure was reduced to atmospheric pressure over about 1 hour, and after reaching atmospheric pressure, the polymer was discharged in a strand form from the lower nozzle, water-cooled and cut to obtain polyamide resin (2) pellets. The obtained pellets were dried in a nitrogen stream at 90 ° C. for 4 hours. The relative viscosity (RV) of the polyamide pellets was 43. The moisture content measured by the Karl Fischer method was 0.10% by weight.

[Production Example 3]
Production of Polyamide Resin (3) 5 tons of 4 batches of pellets obtained in Production Example 1 were charged into a 10000 L solid phase polymerization apparatus, and nitrogen substitution was sufficiently performed. Thereafter, the heater temperature was set to 220 ° C. using a steam line, and solid phase polymerization was performed while flowing nitrogen at 30000 L / hour.
At that time, the internal temperature changed from 190 to 200 ° C., the heating was stopped after about 15 hours, and the pellets were taken out after cooling. The relative viscosity (RV) of the obtained pellet was 265.

[Production Example 4]
Production of polyamide resin (4) The production was carried out in the same manner as in Production Example 3 except that 5 tons of 4 batches of pellets obtained in Production Example 2 were used. The molecular weight (RV) of the obtained pellet was 260.

[Production Example 5]
Production of polyamide resin (5) The production was carried out in the same manner as in Production Example 3 except that the heating time for solid phase polymerization was 20 hours. The relative viscosity (RV) of the obtained pellet was 380.

[Production Example 6]
Production of Polyamide Resin (6) Polyamide resin pellets were obtained in the same manner as in Production Example 2 except that a mixture of 0.0276 kg of copper acetate and 0.317 kg of potassium iodide was blended. This pellet was used in the same manner as in Production Example 3. The obtained pellet had a molecular weight (RV) of 280.

[Production Example 7]
Manufacture of An An master batch (1) For 100 parts by weight of Leona 9200 pellets (polyamide 66/6 copolymer manufactured by Asahi Kasei Chemicals Co., Ltd.), 1.5 parts by weight of copper iodide powder, average particle size of 20 μm refined in advance 12 parts by weight of potassium iodide powder and 0.27 part by weight of calcium stearate powder were mixed, and a mixed powder raw material refined by freeze pulverization was prepared. This raw material was melt kneaded at a melting temperature of 280 ° C. with a twin-screw extruder to obtain a hot master batch.

[Production Example 8]
Production of Hotan Masterbatch (2) The same procedure as in Production Example 7 was conducted, except that potassium iodide powder having an average particle size of 500 μm or more was freeze-pulverized and a mixed powder was not prepared in advance.

[Production Example 9]
Production of Hotan Masterbatch (3) The production was conducted in the same manner as in Production Example 7 except that 0.05 parts by weight of copper iodide powder and 3 parts by weight of potassium iodide powder were used.

[Production Example 10]
Except for using 5 parts by weight of copper iodide powder and 30 parts by weight of potassium iodide powder, an attempt was made in the same manner as in Production Example 7, but it was not possible to melt knead and obtain a heat-resistant masterbatch. .

[ Reference Example 1]
Irganox 1098 (Ciba Specialty Chemicals Co., Ltd. N, N'-hexane-1,6-diylbis [3- (3,5-diyl) with respect to 100 parts by weight of the polyamide resin (3) pellets of Production Example 3 -Tert-butyl-4-hydroxyphenyl) propioamide]), 0.05 parts by weight of Licowax-E (Montanic acid ester wax manufactured by Clariant Japan KK), SA-1500 (Sakai Chemical Industry ( (Mixed aluminum distearate) and 0.05 parts by weight of a spreading agent (PEG-400 manufactured by NOF Corporation) using a tumbler to mix the polyamide resin composition. Obtained. The evaluation results are shown in Table 1.

[ Reference Example 2]
Irganox 1098 (Ciba Specialty Chemicals Co., Ltd. N, N'-hexane-1,6-diylbis [3- (3,5-diyl) per 100 parts by weight of the polyamide resin (4) pellets of Production Example 4 -Tert-butyl-4-hydroxyphenyl) propioamide]) 0.025 parts by weight, Licowax-E (Clariant Japan Co., Ltd. montanate ester wax) 0.025 parts by weight, SA-1000 (Sakai Chemical Industry ( A polyamide resin composition was mixed by using a tumbler so that 0.05 part by weight of aluminum monostearate manufactured by Co., Ltd. and 0.03 part by weight of spreading agent (PEG-400 manufactured by Nippon Oil & Fats Co., Ltd.) were mixed. Got. The evaluation results are shown in Table 1.

[ Reference Example 3]
The same procedure as in Reference Example 2 was performed except that 5 parts by weight of a black colored master batch was added. The evaluation results are shown in Table 1.

[ Reference Example 6 ]
It implemented similarly to the reference example 1 except using the polyamide resin (1) of manufacture example 1 instead of a polyamide resin (3). The evaluation results are shown in Table 1.

[ Reference Example 7 ]
It implemented like the reference example 1 except having used the polyamide resin (5) of manufacture example 5 instead of the polyamide resin (3). The evaluation results are shown in Table 1.

[ Reference Example 8 ]
It implemented like the reference example 1 except not adding Irganox1098. The evaluation results are shown in Table 1.

[ Reference Example 9 ]
The same procedure as in Reference Example 1 was performed except that Licowax-E was not added. The evaluation results are shown in Table 1.

[ Reference Example 10 ]
It implemented like the reference example 1 except not adding SA-1500. The evaluation results are shown in Table 1.

[ Reference Example 4]
It carried out similarly to the reference example 3 except melt-kneading on 290 degreeC conditions using a twin-screw extruder (Toshiba machine Co., Ltd. TEM35) instead of using a tumbler, and obtaining a polyamide resin composition. The evaluation results are shown in Table 1.

[ Reference Example 5]
Instead of Irganox 1098, Irganox 1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] manufactured by Ciba Specialty Chemicals Co., Ltd.) In addition to Licowax-E, Licowax-OP (Montannic acid partially saponified ester wax manufactured by Clariant Japan KK) was used in the same manner as in Reference Example 4 except that 0.05 part by weight was used.

[ Reference Example 11 ]
The same operation as in Reference Example 2 was carried out except that the polyamide resin (6) pellets of Production Example 6 were used. The evaluation results are shown in Table 2.

[ Example 1 ]
The same procedure as in Reference Example 1 was carried out except that 100 parts by weight of the polyamide resin (3) pellets of Production Example 3 was further mixed with 3 parts by weight of Hotan Masterbatch (1) pellets of Production Example 7. The evaluation results are shown in Table 2.

[ Comparative Example 1 ]
The same procedure as in Reference Example 11 was carried out except that the hot-heat master batch (2) of Production Example 8 was used. The evaluation results are shown in Table 2.

[ Comparative Example 2 ]
The same procedure as in Reference Example 11 was carried out except that the heat-heated master batch (3) of Production Example 9 was used. The evaluation results are shown in Table 2.

Thin molded products that require high cycles, such as cable ties and tag pins, molded products with complex shapes, warps, thin flat or long molded products that require dimensional characteristics, molded product surface smoothness and slidability Is suitably used for sliding parts such as gears, gears, shoes, tensioners, guide rails, and cams.

Claims (4)

An organic heat stabilizer (B) selected from hindered phenols (B) in an amount of 0.005 to 0.1 parts by weight with respect to 100 parts by weight of the high molecular weight polyamide 66 (A) having a relative viscosity RV of 80 to 350, an acid 0.005 to 0.1 parts by weight of a higher fatty acid ester (C) having a valence of 5 to 50 (mgKOH / g) and a saponification value of 50 to 200 (mgKOH / g) and a higher fatty acid metal salt (D) of 0. 01 to 0.1 parts by weight, the total amount of the copper compound (E) and the halogen compound (F) other than the halogen copper is 0.01 to 1 part by weight, and the molar ratio of the halogen element to the copper element is 1 to 50 A method for producing a polyamide resin composition contained in a range, wherein a polyamide resin, a component (E) and a component (F) previously pulverized are melt-kneaded to obtain a heat stabilizer master batch (G), Component (A), Component (B) Method for manufacturing components (C), mixing components (D) and the component (G), the polyamide resin composition. 2. The method for producing a polyamide resin composition according to claim 1 , wherein 0.1 to 100 parts by weight of the heat stabilizer master batch (G) is blended with 100 parts by weight of the component (A). Component (G) is 0.01 to 30 parts by weight of the total amount of component (E) and component (F) with respect to 100 parts by weight of polyamide resin, and (2) the molar ratio of halogen element to copper element is 1 to 30 parts by weight. The method for producing a polyamide resin composition according to claim 1 or 2 , wherein the heat stabilizer master batch is in the range of 50. The method for producing a polyamide resin composition according to any one of claims 1 to 3, wherein the polyamide resin, component (E) and component (F) are pulverized in advance to an average particle size of less than 100 µm.