JP4162252B2 - Manufacturing method of polyamide masterbatch - Google Patents

Description

  The present invention relates to a polyamide masterbatch that can eliminate the problems of metal precipitation and corrosion during extrusion and molding, and can provide a polyamide molded article excellent in toughness, heat aging resistance, appearance, and color tone.

Polyamide resins are used in many applications in the automotive and electrical / electronic fields, taking advantage of their excellent mechanical properties, heat resistance, chemical resistance, flame resistance, and the like. Among them, polyamide resins are excellent in long-term heat aging resistance as not seen in other resins, and are therefore used in parts where heat at extremely high temperatures is applied, such as in an automobile engine room. In recent years, with the increase in the density of parts in the automobile engine compartment and the increase in engine output, the environmental temperature in the engine compartment has become higher and higher long-term heat aging resistance has been demanded of polyamide resins. .
In response to this, various technical improvements have been attempted so far, for example, a polyamide resin composition containing a copper halogen compound, an aromatic amine, and a polyamide resin composition containing a hindered phenol-based oxidative degradation inhibitor. Etc. Among these, in particular, the heat aging improvement technology using a mixture of a copper compound and a halogen compound is the best in terms of cost, and is still widely used today.

  As a method of blending a copper compound or a halogen compound into a polyamide resin, a method of preparing an aqueous solution containing a copper compound or a halogen compound and adding it before or during polymerization of polyamide, or any time after polymerization The method of adding to (blend with a polyamide resin, melt-kneading, etc.) is mentioned. The method of adding in the polymerization step is a desirable method for uniformly dispersing the copper compound and the halogen compound, but the production efficiency decreases such as the generation of an intermediate product at the time of switching the brand or the necessity of washing the polymerization apparatus. Cause. On the other hand, in the method of adding after polymerization, the dispersibility is lowered as compared with the method of adding in the polymerization step, which causes a problem of lowering mechanical properties. Further, there is a problem in that the appearance of the molded product is deteriorated by changing the color from white to green in the process of gradually absorbing water thereafter, and the color change increases as the copper concentration increases.

In order to improve the dispersibility of a copper compound or a halogen compound in a method of adding after polymerization, it has been proposed to use various compounds in combination (for example, see Patent Documents 1 and 2).
Patent Document 1 includes blending, as a lubricant, higher fatty acids such as lauric acid, higher fatty acid metal salts of higher fatty acids and aluminum, higher fatty acid amides such as ethylenebisstearylamide, and waxes such as polyethylene wax. ing. This technique is based on the idea that it is not preferable to add an aqueous solution to a hygroscopic polyamide resin, or it is preferable that water is not contained in a polyamide resin composition that can provide a molded product. Is proposed to be added in the form of fine powder. In addition, when halogen compounds are simply pulverized, they are very easy to agglomerate and solidify. By adding a lubricant to the halogen compound in advance, aggregation and solidification can be suppressed and added in a fine powder state to improve the appearance. is suggesting.
Patent Document 2 discloses a stabilizer 1 (CuI, CuBr, etc.) having an average particle diameter of 2 μm or less, a stabilizer 2 (CuI, CuBr, KI, KBr, etc.) having a particle diameter range of 2 to 200 μm, and a carbon number of 15 or more. There has been proposed a stabilizer tablet for polyamides, which is mixed with a wax having one or more functional groups selected from acids, amides, esters and allyls in the molecular chain. It is disclosed that this technique can provide a tablet in which powder is difficult to fall off due to friction or the like.

All of these techniques are techniques in which a copper compound or a halogen compound is blended with polyamide without using a solvent such as water, but improvement of copper precipitation, metal corrosion, and aggregation of halogen compounds is not sufficient.
Thus, in the method of adding a copper compound or a halogen compound after polyamide polymerization, a uniform and fine dispersion of the copper compound or the halogen compound has not been achieved, and a polyamide resin composition having satisfactory performance is obtained. Is not done.
JP 50-148461 A US Pat. No. 5,686,513

  In the method of adding a copper compound or a halogen compound after polyamide polymerization, the present invention improves the dispersibility of the copper compound or the halogen compound, deposits metal copper in the extruder or molding machine, metal corrosion, and decreases the mechanical properties of the product. An object of the present invention is to provide a polyamide masterbatch that has no change in appearance color due to water absorption and has improved heat aging resistance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have solved the above-mentioned problems by using a polyamide-containing material containing water and melt-kneading in the presence of a specific organic compound. The present inventors have found out that it is possible to achieve the present invention.
That is, the present invention is as follows.
a) 100 parts by weight of a polyamide having a moisture content of 0.05 to 2.0% by weight,
b) 0.1 to 10 parts by weight of an organic compound having at least one amide group,
c) 0.1 to 5 parts by weight of a copper compound having a maximum particle size of 50 μm or less, and d) 1 to 50 parts by weight of a halogen compound (excluding copper halide) having a maximum particle size of 50 μm or less by a melt-kneading method. The manufacturing method of the masterbatch to mix.

In the prior art, the improvement of the dispersibility of the copper compound and the halogen compound in the master batch has been achieved by optimizing the lubricant and adjusting the particle diameter of the copper compound and the halogen compound.
On the other hand, in the present invention, by using a polyamide in which moisture that dissolves a copper compound or a halogen compound is present in or on the surface thereof, the copper compound or the halogen compound is dissolved in the moisture. This is achieved by a completely new technical idea of finely dispersing in a polyamide and stabilizing the finely dispersed compound with an organic compound having an amide group.

The master batch containing a copper compound or a halogen compound produced by the method of the present invention has a dispersibility of a halogen compound or a copper compound as compared with a master batch produced by a method of adding a copper compound or a halogen compound after conventional polyamide polymerization. In addition to being able to suppress metal copper precipitation and metal corrosion in extruders and molding machines, it has excellent stability during processing, improved heat aging resistance, and reduced water absorption without deteriorating the mechanical properties of the product. It is possible to solve the suppression of the appearance color change due to.
Surprisingly, even when compared with a masterbatch produced by a method of adding a copper compound or a halogen compound in the polymerization step, metallic copper precipitation is suppressed, and a molded product having excellent heat aging resistance and appearance can be obtained. . Moreover, it has the effect of significantly reducing copper deposition during processing.
According to the method of the present invention, the addition of a copper compound or a halogen compound to a polyamide resin is performed by melt kneading with high production efficiency, and the production efficiency is increased, and the heat resistance is equal to or higher than the addition in the polymerization process. It became possible to obtain products with aging properties and high appearance.

The present invention will be specifically described below.
First, polyamide will be described.
The polyamide used in the present invention is a polymer having an amide bond (—NHCO—) in the main chain, and is not particularly limited. For example, polycaprolactam (nylon 6), polytetramethylene adipamide (nylon 46), Polyhexamethylene adipamide (nylon 66), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyundecalactam (nylon) 11), polydodecalactam (nylon 12), polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (nylon 6I), polynonanemethylene terephthalamide (9T), polyhexamethylene terephthalamide (6T), Po Bis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylenehexahydro And terephthalamide (nylon 11T (H)). Moreover, the polyamide copolymer containing 2 or more types of different polyamide components among these, a mixture, etc. may be sufficient. The presence or absence of an amide bond can be confirmed by an infrared absorption spectrum (IR).

  The polyamide raw material used in the present invention is not particularly limited as long as it is a known raw material used for producing a polymer having an amide bond (—NHCO—) in the main chain described above, but can be polymerized. Mention may be made of amino acids, polymerizable lactams, or salts or mixtures of polymerizable diamines and dicarboxylic acids, and polymerizable oligomers. These raw materials may be used as the raw material itself or as an aqueous solution.

The carboxyl group concentration ratio of the polyamide used in the present invention is preferably 0.55 to 0.80, more preferably 0.60 to 0.75.
The carboxyl group concentration ratio is a value calculated by [COOH] / ([COOH] + [NH ₂ ]), where the carboxyl group concentration and the amino group concentration in the polyamide are [COOH] and [NH ₂ ], respectively. . By setting the carboxyl group concentration ratio within this range, copper precipitation and metal corrosion can be suppressed in the molding machine. The carboxyl group concentration ratio can be adjusted by adding a terminal adjusting agent to the polyamide raw material.
The terminal modifier is not particularly limited as long as it is a compound containing a carboxylic acid in the molecular structure, but dicarboxylic acids and monocarboxylic acids are preferably used. Examples of the dicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, and 3,3-diethylsuccinic acid. Acid, azelaic acid, sebacic acid, suberic acid, dodecanedioic acid, eicodioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfo Examples thereof include isophthalic acid, hexahydroterephthalic acid, hexahydroterephthalic acid, and diglycolic acid. The monocarboxylic acid is an aliphatic monocarboxylic acid such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, And alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylmonoacetic acid. . These carboxylic acid compounds may be used alone or in combination of two or more.

  A known method can be used as a method for producing the polyamide. For example, a ring-opening polycondensation method using a lactam such as ε-caprolactam as a polyamide raw material, a heat melting method using a diamine / dicarboxylate such as hexamethylene adipamide or a mixture thereof as a raw material can be used. Further, a solid salt of a polyamide raw material or a solid phase polymerization method performed at a temperature below the melting point of the polyamide, a solution method using a dicarboxylic acid halide component and a diamine component, or the like can also be used. These methods may be combined as necessary. Among them, the most efficient method is a heat melting method or a method combining a heat melting method and solid phase polymerization. Moreover, as a superposition | polymerization form, a batch type or a continuous type may be sufficient. 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.

The moisture content of the polyamide is 0.05 to 2.0% by weight, more preferably 0.1 to 1.5% by weight, and still more preferably 0.1 to 1.0% by weight. The moisture content can be measured and measured by a coulometric titration method (Karl Fischer method) with 0.7 g of polyamide using a moisture vaporizer (VA-06 model manufactured by Mitsubishi Chemical Corporation).
The moisture in the polyamide may be present as moisture in the polyamide bonded to the polyamide molecule, or may be moisture adhered to the polyamide surface such as polyamide pellets or polyamide powder surface. From the viewpoint of suppression, it is better to exist as moisture in the polyamide bonded to the polyamide molecule.

By setting the moisture content of the polyamide within the range of the present invention, the dispersed particle diameter of the copper compound or halogen compound in the masterbatch can be made smaller than the particle diameter before blending and aggregation can be suppressed. As a result, mechanical properties such as toughness and heat aging resistance of the product manufactured from the master batch are improved, and copper precipitation and metal corrosion can be suppressed.
The moisture content of the polyamide can be adjusted by controlling the degree of decompression in the latter half of the polymerization, the immersion time in water at the time of cooling and discharging the polymer, the immersion length, or the amount of water spray.

  From the viewpoint of achieving the object of the present invention, the molecular weight of the polyamide is such that the relative viscosity at 25 ° C. is preferably 1.5 to 6.5, more preferably 1.5% in 98% sulfuric acid concentration measured according to JIS-K6810. It is 1.7-6.0, More preferably, it is 2.0-5.5. By making it into this range, the productivity of melt kneading when preparing a masterbatch is improved.

Next, a copper compound and a halogen compound will be described.
As the copper compound used in the present invention, copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, etc. Examples include copper complex salts coordinated to chelating agents such as ethylenediamine (en) and ethylenediaminetetraacetic acid. These copper compounds may be used independently and may mix 2 or more types. Among these, preferable examples include copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate.

  As for the compounding quantity of a copper compound, 0.1-5 weight part of copper compounds are preferable with respect to 100 weight part of polyamide, More preferably, it is 0.25-4 weight part, More preferably, it is 0.40-3 weight part. By setting it within this range, sufficient heat aging resistance is improved, and copper precipitation and corrosion inhibition can be suppressed.

  Examples of the halogen compound (excluding copper halide) used in the present invention include potassium iodide, sodium iodide, potassium bromide, potassium chloride, sodium chloride and the like. These halogen compounds may be used independently and may mix 2 or more types.

  The compounding amount of the halogen compound is preferably 1 to 50 parts by weight, more preferably 5 to 45 parts by weight, and still more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polyamide. By setting it in this range, sufficient heat aging resistance is improved, and copper precipitation and corrosion can be suppressed.

Moreover, it is preferable that both the maximum particle diameters of the copper compound and halogen compound to mix | blend are 50 micrometers or less, More preferably, it is 20 micrometers or less, More preferably, it is 10 micrometers or less.
In the present invention, the particle diameter means a biaxial average diameter, that is, an average value of a short diameter and a long diameter. Here, the minor axis and the major axis are the short side and the long side of the circumscribed rectangle that minimizes the area circumscribing the particle, respectively. The measurement of the maximum particle diameter of the copper compound and the halogen compound can be obtained by observing at least 50 particles using a scanning electron microscope (SEM).
By setting the maximum particle size to 50 μm or less, it is possible to finely disperse the copper compound and halogen compound in the polyamide even when the moisture content in the polyamide is low, and the problems of metal precipitation and corrosion are further improved and obtained. The toughness, heat resistance aging property, appearance, and color tone of the resulting polyamide resin composition are further improved.

  Although the copper compound and the halogen compound (except for the copper halide) can be blended alone, there is an effect, but both are blended in the present invention in order to improve the performance of the obtained polyamide resin composition. The molar ratio of halogen to copper (halogen / copper) in the master batch is preferably 3 to 30, more preferably 4 to 25, still more preferably 5 to 23. A molar ratio of halogen to copper of 3 or more is preferable because copper precipitation and metal corrosion can be suppressed. If the molar ratio of halogen and copper is 30 or less, the problem of corroding the screw of the molding machine can be suppressed without impairing mechanical properties such as toughness.

Next, an organic compound having at least one amide group will be described.
In the present invention, it is necessary that an organic compound having at least one amide group is present during melt kneading. This is because an organic compound having at least one amide group is complexed with a copper compound or a halogen compound dissolved in moisture in the polyamide during melt-kneading, and thereby, without adversely affecting the polyamide, This is presumed to stabilize the dispersion of the halogen compound in the polyamide and prevent precipitation and alteration.

The organic compound having at least one amide group used in the present invention is a compound having at least one amide group in the molecular chain. Specific examples include monoamides, substituted amides, methylol amides, and bisamides.
The monoamides are represented by the general formula R—CONH ₂ (wherein R is a saturated aliphatic, unsaturated aliphatic, aromatic having 8 to 30 carbon atoms, or a part of —H thereof is substituted with —OH. ) Specific examples include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide, etc., linoleic acid amide and the like.
The substituted amides are represented by the general formula R ₁ —CONH—R ₂ (where R ₁ and R ₂ are each independently a saturated aliphatic, unsaturated aliphatic or aromatic group having 8 to 30 carbon atoms). Alternatively, a part of —H is substituted with —OH). Specifically, for example, N-lauryl lauric acid amide, N-paltimyl palmitic acid amide, N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N -Stearyl erucic acid amide, N-oleyl palmitic acid amide, N-stearyl 12 hydroxystearic acid amide, N-oleyl 12 hydroxystearic acid amide and the like.
Methylolamides are represented by the general formula R—CONHCH ₂ OH (where R is a saturated aliphatic, unsaturated aliphatic, aromatic having 8 to 30 carbon atoms, or a part of —H is —OH. Has been replaced). Specific examples include methylol stearate amide and methylol behenate amide.
Bisamides are represented by the general formula (R—CONH) ₂ (CH ₂ ) _n (where R is a saturated aliphatic, unsaturated aliphatic, aromatic or part of —H having 8 to 30 carbon atoms) Is substituted with -OH, n is 1-8). Specifically, methylene bis lauric acid amide, methylene bis lauric acid amide, methylene bishydroxystearic acid amide, ethylene biscaprylic acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bisisostearic acid amide, ethylene bis Hydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bishydroxystearic acid amide, butylene bishydroxystearic acid amide, N, N'-distearyl adipic acid amide N, N'-distearyl sebacic acid amide, methylene bis oleic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid Amide, hexamethylenebisoleic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide, m-xylylene bisstearic acid amide, N, N'-distearyl isophthalic acid amide Etc.
These organic compounds having at least one amide group may be used alone or in combination of two or more. Of these, bisamides are preferred.

  The amount of the organic compound having at least one amide group is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5.0 parts by weight, based on 100 parts by weight of the polyamide. More preferably, it is 1.0-4.0 weight part. By setting it within this range, the dispersibility of the copper compound and the halogen compound in the polyamide is further improved, and sufficient heat aging resistance can be improved, and copper precipitation and corrosion inhibition can be achieved.

Next, melt kneading of a copper compound, a halogen compound, an organic compound having at least one amide group, and polyamide will be described.
In the present invention, the copper compound, the halogen compound, and the organic compound having at least one amide group may be blended alone in the polyamide, or at least two of the three types of compounds may be mixed in advance before the polyamide. It may be blended, or at least two of the three types of compounds may be premixed and pulverized before blending with the polyamide, or at least two of the three types of compounds may be premixed and pulverized before tableting And may be blended with polyamide.
Mixing for mixing the compounds may be any known method such as tumbler, Henschel, Proshear mixer, Nauter mixer, flow jet mixer and the like.
The compound may be pulverized by any known method such as a hammer mill, knife mill, ball mill, jaw crusher, cone crusher, roller mill, jet mill, or mortar.
The method for making the compound into a tablet may be any known method such as compression granulation, tableting, dry extrusion granulation, melt extrusion granulation and the like.

  The apparatus for performing melt kneading is not particularly limited, and a known apparatus can be used. For example, melt kneaders such as single-screw or twin-screw extruders, Banbury mixers, and mixing rolls are preferably used. Of these, a twin screw extruder is preferably used. The melt kneader may be equipped with a deaeration mechanism (vent) device and side feeder equipment.

The melt kneading temperature of the present invention is preferably about 1 to 100 ° C. higher than the melting point or softening point determined by differential scanning calorimetry (DSC) measurement of polyamide according to JISK7121. The shear rate in the kneader is preferably about 100 (SEC ⁻¹ ) or more, and the average residence time during kneading is preferably about 1 to 15 minutes.

Next, the masterbatch manufactured by the manufacturing method of this invention is demonstrated.
The moisture content of the masterbatch produced by the production method of the present invention is preferably 0.06 to 1.0% by weight, more preferably 0.10 to 0.75% by weight, and still more preferably 0.15 to 0.15%. 0.75% by weight. The moisture in the master batch may exist as moisture bonded to the polyamide molecules, or may be moisture attached to the master batch surface such as the master batch pellet or the master batch powder surface. By setting the moisture content within this range, aggregation of copper compounds and halogen compounds can be suppressed. As a result, the effect of improving mechanical properties such as toughness and heat aging resistance is high, and copper deposition and metal corrosiveness can be further suppressed.
The moisture content of the master batch can be adjusted by controlling the degree of decompression of the extruder, the immersion time in the strand bath during cooling, the immersion length, or the water spray amount.

Next, manufacturing a polyamide resin composition from a masterbatch will be described.
A polyamide resin composition can be produced by mixing 0.1 to 100 parts by weight, preferably 0.5 to 20 parts by weight, of the master batch with respect to 100 parts by weight of the second polyamide. By mixing within this range, the object of the present invention is to reduce metal copper precipitation and metal corrosion in the extruder and molding machine, thereby reducing the mechanical properties of the product in addition to excellent stability during processing. Thus, improvement in heat aging resistance and suppression of appearance color change due to water absorption can be solved. The method of mixing the second polyamide and the masterbatch may be a blend or a melt kneading method.
As the second polyamide, the same polyamide as exemplified as the polyamide that can be used in the production of the masterbatch can be used.

The moisture content of the polyamide resin composition thus obtained is preferably 0.01 to 1% by weight, more preferably 0.03 to 0.5% by weight, still more preferably 0.05 to 0. 0%. 30% by weight. The moisture in the polyamide resin composition may exist as moisture in a state of being bonded to the polyamide molecule, or may be moisture attached to the surface of the polyamide resin composition, for example, the pellet or powder surface. From the viewpoint of expressing the effect more remarkably, it is more preferable to make it exist as moisture bonded to the polyamide molecule. By setting the moisture content within the range, aggregation of the copper compound and the halogen compound can be suppressed. As a result, the effect of improving mechanical properties such as toughness and heat aging resistance is high, and copper deposition and metal corrosiveness can be further suppressed.
The moisture content of the polyamide resin composition can be adjusted by controlling the degree of decompression of the extruder, the dipping time in the strand bath during cooling, the dipping length, or the water spray amount.

  The polyamide resin composition has additives that are conventionally used for polyamides, such as pigments and dyes, flame retardants, lubricants, fluorescent bleaches, plasticizers, organic antioxidants, to the extent that the object of the present invention is not impaired. , Heat stabilizers, UV absorbers, nucleating agents, rubbers, and reinforcing agents.

  The polyamide resin composition obtained in this manner eliminates the problems of metal precipitation and corrosion during extrusion and molding, and has excellent toughness, heat aging resistance, appearance, and color tone. For example, various molded products can be obtained using press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, melt spinning, and the like. The obtained molded product is useful in many molding applications (automobile parts, industrial parts, electronic parts, gears, etc.) and extrusion applications (tubes, rods, filaments, films, blows, etc.).

The present invention will be described based on examples. In the examples and comparative examples, the following methods were used for measurement and evaluation.
(1) Relative viscosity of polyamide It implemented according to JIS-K6810. Specifically, a 1% concentration solution ((polyamide resin 1 g) / (98% sulfuric acid 100 ml)) was prepared using 98% sulfuric acid and measured under a temperature condition of 25 ° C.
(2) Moisture content of polyamide, masterbatch, polyamide resin composition Measured by coulometric titration method (Karl Fischer method) with 0.7 g of polyamide using a moisture vaporizer (VA-06 model, manufactured by Mitsubishi Chemical Corporation) did.

(3) Carboxyl group concentration ratio of polyamide The carboxyl group concentration was measured by dissolving pellets and pulverized molded articles in benzyl alcohol. More specifically, 50 ml of benzyl alcohol was added to about 4.0 g of a sample, heated to 170 ° C., and phenolphthalein was added. After dissolution, the solution was titrated with a 0.1 N NaOH aqueous solution to determine the carboxyl group concentration.
Carboxyl group concentration [COOH] = (f × 0.1 × A / S) × 100f
Where f = 0.1 N NaOH aqueous solution factor
A = Consumption of 0.1N NaOH aqueous solution (ml)
S = Sample mass (g)
On the other hand, the amino group concentration was measured by dissolving pellets or pulverized molded articles in a phenol aqueous solution. More specifically, about 3.0 of the sample was dissolved in 100 ml of 90% phenol aqueous solution, and 1 / 40N hydrochloric acid was added dropwise to neutralize, and the amount of hydrochloric acid required up to the neutralization point was determined. The same measurement was performed without adding a sample, and a blank was obtained.
Amino group concentration [NH ₂ ] = {F × (1/40) × (AB) / S} × 1000F
Where F = 1 / 40N Factor of hydrochloric acid
A = consumption of 1 / 40N hydrochloric acid (ml)
B = consumption of 1 / 40N hydrochloric acid (when blank) (ml)
S = Sample mass (g)
Using the thus measured [COOH] and [NH ₂ ], the carboxyl group concentration ratio = [COOH] / ([COOH] + [NH ₂ ]).

(4) Maximum particle diameter of copper compound and halogen compound Using S-5000 manufactured by Hitachi, Ltd., a bright field image was taken in accordance with the optimum magnification, 100 particles were arbitrarily selected, and the maximum The particle size was determined.
(5) Master batch copper concentration, halogen concentration, and molar ratio of halogen to copper (halogen / Cu)
The copper concentration was determined by adding sulfuric acid to the sample, dropping nitric acid while heating to decompose the organic component, measuring the decomposition solution in pure water, and quantifying it by ICP emission analysis (high frequency plasma emission analysis). As an ICP emission analyzer, Vista-Pro manufactured by SEIKO ELECTRONIC INDUSTRY CO., LTD. Was used.
Taking iodine as an example, the halogen concentration is combusted in a flask in which the sample is replaced with high-purity oxygen, and the generated gas is collected in an absorbing solution. The iodine in the collected solution is 1 / 100N silver nitrate solution. Quantification was performed using potentiometric titration.
The molar ratio of halogen to copper (halogen / Cu) was calculated by converting the molecular weight into a mole using the above quantitative values.

(6) Copper deposition, metal corrosion property and surface condition of master batch (6-1) Copper deposition property The master batch was brought into contact with the test carbon steel, placed in an autoclave apparatus and sealed, and then sufficiently substituted with nitrogen. Then, after holding at 280 ° C. for 6 hours and cooling, the copper deposition state of the part of the master batch that had been in contact with the test carbon steel was evaluated.
○ No copper precipitation or very mild.
Δ Copper deposition is mild.
× Copper precipitation is observed frequently.
(6-2) Metal Corrosivity Corrosion state was evaluated for the part in contact with the master batch of the test carbon steel of (6-1) above. In order to quantitatively indicate the degree of corrosion, the following corrosion coefficients were calculated and judged as follows. If this value is small, it will be difficult to corrode.
Corrosion coefficient = occurrence frequency of corrosion (pieces / cm ² ) x average diameter of corrosion (μm) x average depth of corrosion (μm)
○ Corrosion coefficient less than 500 △ Corrosion coefficient 500-2500
× Corrosion coefficient> 2500
(6-3) Pellet surface state The appearance of the master batch pellet surface was visually determined.
○ The surface is smooth and in good condition. △ Part of the surface has irregularities due to poor dispersion of the additive, and partly defective. × The entire surface has irregularities due to poor dispersion of the additive and is poor. Status

(7) Copper precipitation during residence of the polyamide resin composition in the molding machine The difference in copper concentration between the molded product (a) obtained by standard molding and the molded product (b) obtained by retention molding is defined as copper deposited in the molding machine. The copper precipitation during the stay in the molding machine was evaluated by the following formula.
Copper precipitation during retention in molding machine = (copper concentration of standard molded product (a) −copper concentration of retained molded product (b)) × 100 / copper concentration of standard molded product (a) Standard molded product (a) The stay molded product (b) was produced under the following conditions.
(A) Standard molded product: Nissei Plastic PS-40E was used as the injection molding machine, and ASTM-D638 type was used as the mold. Cylinder temperature was 280 ° C., mold temperature was 80 ° C., plasticizing stroke was 63 mm, screw rotation speed was 200 rpm, injection time was 10 seconds, and cooling time was 15 seconds to obtain an injection molded product. The residence time during plasticization was 1 minute.
(B) Residual molded product: Nissei Plastic PS-40E was used as the injection molding machine, and ASTM-D638 type was used as the mold. Cylinder temperature was 280 ° C., mold temperature was 80 ° C., plasticizing stroke was 63 mm, screw rotation speed was 200 rpm, injection time was 10 seconds, and cooling time was 15 seconds to obtain an injection molded product. The residence time during plasticization was 60 minutes.

(8) Long-term heat aging resistance of polyamide resin composition molded article The standard molded article (a) of (7) above was treated in a hot air oven at 180 ° C. for a predetermined time, and then the tensile strength was measured according to ASTM-D638. . And the tensile strength after the heat treatment with respect to the tensile strength measured before the heat treatment was calculated as the tensile strength retention, and the heat treatment time at which the tensile strength retention was 50% was defined as the half life.
(9) Color tone of molded product of polyamide resin composition The color tone of the standard molded product (a) of (7) above was measured with a color difference meter (ND-K6B type manufactured by Nippon Denshoku Co., Ltd.).

[ Reference Examples 1 to 13, Comparative Examples 1 to 5]
Reference Examples 1 to 13 and Comparative Examples 1 to 5 were carried out using a mixture of the polyamide produced in Production Examples 1 to 13 shown below and a copper compound, a halogen compound and an organic compound having at least one amide group.

[Production Example 1]
A known melt polymerization was carried out using an equimolar aqueous solution (50% by weight concentration) of hexamethylenediamine and adipic acid to obtain a polyamide 66 (1) in the form of pellets. The polyamide 66 (1) had a relative viscosity of 46, a moisture content of 0.25% by weight, and a carboxyl group concentration ratio of 0.625.
[Production Example 2]
A known melt polymerization was performed using an equimolar aqueous solution of hexamethylenediamine and adipic acid (concentration of 50% by weight) to obtain a pellet-like polyamide 66 (2). The polyamide 66 (2) had a relative viscosity of 46, a moisture content of 0.07% by weight, and a carboxyl group concentration ratio of 0.625.
[Production Example 3]
Using an equimolar aqueous solution (50% by weight concentration) of hexamethylenediamine and adipic acid, the end was adjusted with taste pinic acid, and a known melt polymerization was performed to obtain a pellet-like polyamide 66 (3). The relative viscosity of the polyamide 66 (3) was 36, the water content was 0.25% by weight, and the carboxyl group concentration ratio was 0.80.
[Production Example 4]
Water was uniformly sprayed onto the polyamide 66 (1) of Production Example 1 by spraying to obtain polyamide 66 (4). The polyamide 66 (4) had a relative viscosity of 46, a moisture content of 0.50% by weight, and a carboxyl group concentration ratio of 0.625.
[Production Example 5]
A terminal solution was adjusted with hexamethylenediamine using an equimolar aqueous solution of hexamethylenediamine and adipic acid (concentration of 50% by weight), and a known melt polymerization was performed to obtain a pellet-like polyamide 66 (5). The polyamide 66 (5) had a relative viscosity of 46, a moisture content of 0.25% by weight, and a carboxyl group concentration ratio of 0.522.
[Production Example 6]
Water was uniformly sprayed onto the polyamide 66 (1) of Production Example 1 by spraying to obtain polyamide 66 (6). The relative viscosity of the polyamide 66 (6) was 46, the water content was 2.50% by weight, and the carboxyl group concentration ratio was 0.625.
[Production Example 7]
Polyamide 66 (1) of Production Example 1 was dried in a nitrogen stream at about 80 ° C. to a moisture content of not more than the detection limit (0.01% by weight or less) to obtain polyamide 66 (7). The polyamide 66 (7) had a relative viscosity of 46, a moisture content of less than 0.01% by weight, and a carboxyl group concentration ratio of 0.625.

[Production Example 8]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearylamide were mixed and pulverized so that the maximum particle diameter was 20 μm or less to obtain a mixture of KI and ethylenebisstearylamide. . 5 parts by weight of CuI (average particle size 2 μm) was mixed well with the mixture and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (1).
[Production Example 9]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearyl amide were mixed and pulverized so that the maximum particle diameter was 50 μm or less to obtain a mixture of KI and ethylene bisstearyl amide. . 5 parts by weight of CuI (average particle size 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (2).
[Production Example 10]
75 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearylamide were mixed and pulverized so that the maximum particle diameter was 20 μm or less to obtain a mixture of KI and ethylenebisstearylamide. . To this mixture, 15 parts by weight of CuI (average particle size 2 μm) was mixed well and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (3).
[Production Example 11]
88 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearyl amide were mixed and pulverized so that the maximum particle diameter was 20 μm or less to obtain a mixture of KI and ethylene bisstearyl amide. . 2 parts by weight of CuI (average particle size 2 μm) was mixed well with the mixture and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (4).
[Production Example 12]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of aluminum distearate (average particle diameter of 30 μm) were mixed and pulverized so that the maximum particle diameter was 20 μm or less. A mixture was obtained. 5 parts by weight of CuI (average particle diameter 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (5).
[Production Example 13]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearylamide were mixed with 5 parts by weight of CuI (average particle diameter of 2 μm) without pulverizing and having a maximum particle diameter of 200 μm. Granules were obtained with Fuji Paudal F5-11-175) to obtain granules (6).

[ Reference Example 1]
24 parts by weight of granule (1) of Production Example 8 is blended with 100 parts by weight of polyamide 66 (1) of Production Example 1, and a twin-screw extruder (Plastic Engineering Laboratory Co., Ltd., twin screw co-directional screw) Using a rotary mold, L / D = 60 (D = 30φ)), a master batch was obtained by melt-kneading at a screw rotation speed of 100 rpm and a cylinder temperature of 280 ° C. The evaluation results are shown in Table 1.
[ Reference Example 2]
24 parts by weight of the granule (1) of Production Example 8 is blended with 100 parts by weight of polyamide 66 (2) of Production Example 2, and a master batch is obtained by melt-kneading with a twin screw extruder as in Reference Example 1. It was. The evaluation results are shown in Table 1.
[ Reference Example 3]
24 parts by weight of granule (1) of Production Example 8 is blended with 100 parts by weight of polyamide 66 (3) of Production Example 3, and melt-kneaded with a twin screw extruder as in Reference Example 1 to obtain a master batch. It was. The evaluation results are shown in Table 1.
[ Reference Example 4]
24 parts by weight of granule (1) of Production Example 8 is blended with 100 parts by weight of polyamide 66 (4) of Production Example 4, and a master batch is obtained by melt-kneading with a twin screw extruder as in Reference Example 1. It was. The evaluation results are shown in Table 1.
[ Reference Example 5]
24 parts by weight of granule (1) of Production Example 8 is blended with 100 parts by weight of polyamide 66 (5) of Production Example 5, and melt-kneaded with a twin-screw extruder as in Reference Example 1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The evaluation results are shown in Table 1.

[Comparative Example 1]
24 parts by weight of granule (1) of Production Example 8 is blended with 100 parts by weight of polyamide 66 (6) of Production Example 6, and melt-kneaded with a twin-screw extruder as in Reference Example 1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The evaluation results are shown in Table 1.
[Comparative Example 2]
24 parts by weight of granule (1) of Production Example 8 is blended with 100 parts by weight of polyamide 66 (7) of Production Example 7, and melt-kneaded with a twin-screw extruder as in Reference Example 1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The evaluation results are shown in Table 1.

From Table 1, it can be seen that the master batches produced by the production methods of Reference Examples 1 to 5 have improved copper precipitation and metal corrosivity.

[ Reference Example 6]
50 parts by weight of granules (1) of Production Example 8 are blended with 100 parts by weight of polyamide 66 (1) of Production Example 1, and melt-kneaded with a twin-screw extruder as in Reference Example 1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The evaluation results are shown in Table 2.
[ Reference Example 7]
The master batch obtained in Reference Example 1 was dried in a nitrogen stream at 80 ° C. to make the moisture content 0.10% by weight. The evaluation results are shown in Table 2.
[ Reference Example 8]
24 parts by weight of granule (2) of Production Example 9 is blended with 100 parts by weight of polyamide 66 (1) of Production Example 1, and melt-kneaded with a twin-screw extruder in the same manner as in Reference Example 1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The evaluation results are shown in Table 2.
[ Reference Example 9]
24 parts by weight of granules (3) of Production Example 10 are blended with 100 parts by weight of polyamide 66 (1) of Production Example 1, and melt-kneaded with a twin-screw extruder in the same manner as in Reference Example 1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The evaluation results are shown in Table 2.
[ Reference Example 10]
24 parts by weight of granules (4) of Production Example 11 are blended with 100 parts by weight of polyamide 66 (1) of Production Example 1, and melt-kneaded with a twin-screw extruder as in Reference Example 1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The evaluation results are shown in Table 2.
[Comparative Example 2-1]
24 parts by weight of granules (6) of Production Example 13 were blended with 100 parts by weight of polyamide 66 (1) of Production Example 1. The evaluation results of the obtained master batch are shown in Table 2.
[Comparative Example 3]
24 parts by weight of granules (5) of Production Example 12 are blended with 100 parts by weight of polyamide 66 (1) of Production Example 1, and melt-kneaded with a twin screw extruder as in Reference Example 1 to obtain a master batch. It was. The evaluation results are shown in Table 2.

From Table 2, it can be seen that the master batches produced by the production methods of Reference Examples 6 to 10 have improved copper precipitation and metal corrosivity. On the other hand, in Comparative Example 2-1, in which a halogen compound having a maximum particle size of 200 μm was used, the effect of improving copper precipitation was recognized, but the effect was insufficient. From this, it can be seen that it is more effective to use a copper compound or a halogen compound having a smaller maximum particle size in order to exhibit the effect of the present invention.

[ Reference Example 12]
2 parts by weight of the master batch of Reference Example 1 was blended with 100 parts by weight of polyamide 66 (1) of Production Example 1. It melt-kneaded with the twin-screw extruder similarly to the reference example 1, and obtained the polyamide resin composition. With respect to 100 parts by weight of polyamide 66, CuI is 0.0235 parts by weight, KI is 0.396 parts by weight, and ethylenebisstearylamide is 0.0470 parts by weight. The evaluation results are shown in Table 3.
[ Reference Example 13]
2 parts by weight of the master batch of Reference Example 8 is blended with 100 parts by weight of polyamide 66 (1) of Production Example 1, and melt-kneaded with a twin-screw extruder as in Reference Example 1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as in Reference Example 11. The evaluation results are shown in Table 3.
[Comparative Example 4]
2 parts by weight of the master batch of Comparative Example 2 is blended with 100 parts by weight of polyamide 66 (1) of Production Example 1, and melt-kneaded with a twin screw extruder in the same manner as in Reference Example 1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as in Reference Example 11. The evaluation results are shown in Table 3.
[Comparative Example 5]
A known melt polymerization was carried out using an equimolar aqueous solution (50% by weight concentration) of hexamethylenediamine and adipic acid. In the middle of the polymerization, a mixed aqueous solution of CuI and KI was added. Ethylene bisstearylamide was added to the surface of the obtained polyamide 66 pellets. The compounding amount of each compound was added so as to be the same as in Comparative Example 2-1. The relative viscosity of the polyamide 66 resin composition was 46, the water content was 0.10% by weight, and the carboxyl group concentration ratio was 0.625. The evaluation results are shown in Table 3.

From Table 3, it can be seen that the molded article of the polyamide resin composition obtained from the master batch produced by the production method of the reference example has improved copper precipitation, long-term heat aging resistance, and color tone.

[Examples A1 to A23, Comparative Examples A1 to A17]
Examples A1 to A23 and Comparative Examples A1 to A17 were carried out using a mixture of the polyamide produced according to Production Examples A1 to A28 shown below, a copper compound, a halogen compound, and an organic compound having at least one amide group.

1. Preparation of polyamide [Production Example A1]
Polymerization was carried out by a batch method to produce a polyamide.
As a raw material for polyamide 66, an equimolar salt of hexamethylenediamine and adipic acid was used. An aqueous solution containing 50% by weight of the raw material was charged into a polymerization tank, sufficiently purged with nitrogen, heated and heated at about 150 ° C. to remove water and concentrated to about 85%, and the polymerization tank was sealed. Next, while raising the temperature of the polymerization tank to about 210 ° C., the pressure of the polymerization tank was increased to about 1.77 MPa using the gauge pressure. Thereafter, the temperature was raised from about 210 ° C. to about 250 ° C. while maintaining the pressure at about 1.77 MPa while draining water from the polymerization tank. Thereafter, while raising the temperature to about 280 ° C. in about 1 hour, the pressure in the polymerization tank was returned to atmospheric pressure, and then the pressure was reduced at about 700 torr for about 10 minutes. The polymerization tank was pressurized with nitrogen, the die at the bottom of the polymerization tank was opened, the pellet-shaped polymer was discharged, cooled, and cut to obtain polyamide 66 (A1). The polyamide 66 (A1) had a relative viscosity of 2.7, a water content of 0.75% by weight, and a carboxyl group concentration ratio of 0.620.
[Production Example A2]
Polyamide 66 (A1) of Production Example A1 was dried in a nitrogen stream at about 140 ° C. for about 0.5 hours to obtain polyamide 66 (A2). The polyamide 66 (A2) had a relative viscosity of 2.8, a moisture content of 0.25% by weight, and a carboxyl group concentration ratio of 0.625.
[Production Example A3]
Polyamide 66 (A1) of Production Example A1 was dried in a nitrogen stream at about 90 ° C. for 1.5 hours to obtain polyamide 66 (A3). The relative viscosity of the polyamide 66 (A3) was 2.8, the water content was 0.10% by weight, and the carboxyl group concentration ratio was 0.625.
[Production Example A4]
Water was uniformly sprayed onto the polyamide 66 (A1) of Production Example A1 by spraying to obtain polyamide 66 (A4). The moisture content of the polyamide (A4) was adjusted to 1.45% by weight by adjusting the amount of water sprayed.
[Production Example A5]
Water was uniformly sprayed onto the polyamide 66 (A1) of Production Example A1 by spraying to obtain polyamide 66 (A5). The moisture content of the polyamide (A5) was adjusted to 1.80% by weight by adjusting the amount of water sprayed.
[Production Example A6]
Polyamide 66 (A1) of Production Example 1 was dried in a nitrogen stream at about 90 ° C. for about 30 hours to obtain polyamide 66 (A6). The polyamide 66 (A6) had a relative viscosity of 2.8, a moisture content of 0.03% by weight, and a carboxyl group concentration ratio of 0.625.
[Production Example A7]
Water was uniformly sprayed onto the polyamide 66 (A1) of Production Example A1 by spraying to obtain polyamide 66 (A7). The moisture content of the polyamide (A7) was adjusted to 2.25% by weight by adjusting the amount of water sprayed.
[Production Example A8]
Polymerization was carried out in the same manner as in Production Example A1, except that adipic acid was added as an end adjuster to an equimolar aqueous solution of hexamethylenediamine and adipic acid (50% by weight concentration), dried in the same manner as in Production Example A2, and pellets. A polyamide 66 (A8) was obtained. The polyamide 66 (A8) had a relative viscosity of 2.5, a moisture content of 0.25% by weight, and a carboxyl group concentration ratio of 0.80.
[Production Example A9]
Polymerization was conducted in the same manner as in Production Example A1, except that hexamethylene diamine was added as an end modifier to an equimolar aqueous solution of hexamethylene diamine and adipic acid (50% by weight concentration), and drying was conducted in the same manner as in Production Example A2. A pellet-like polyamide 66 (A9) was obtained. The polyamide 66 (A9) had a relative viscosity of 3.0, a moisture content of 0.25% by weight, and a carboxyl group concentration ratio of 0.522.
[Production Example A10]
Polymerization was carried out in a continuous process to produce a polyamide.
An equimolar salt of hexamethylenediamine and adipic acid was used as a raw material for polyamide 66. Acetic acid was added as an end conditioner to an aqueous solution containing 50% by weight of the raw material, poured into a concentration tank / reactor at a rate of about 3000 Kg / hr, and concentrated to about 90%. Next, the reaction solution was discharged to a flasher, and the pressure was slowly reduced to atmospheric pressure. The reaction solution was transferred to the next container, and maintained at a temperature of about 280 ° C. and under atmospheric pressure. The polyamide was extruded into strands, which were cooled and cut, and further dried in a nitrogen stream at about 140 ° C. for about 0.5 hours to obtain pellets of polyamide 66 (A10). The polyamide 66 (A10) had a relative viscosity of 2.7, a water content of 0.25% by weight, and a carboxyl group concentration ratio of 0.650.
[Production Example A11]
Polymerization and drying were carried out in the same manner as in Production Example A10 except that the amount of acetic acid as a terminal adjusting agent was increased, to obtain polyamide 66 (A11). The polyamide 66 (A11) had a relative viscosity of 2.8, a moisture content of 0.11%, and a carboxyl group concentration ratio of 0.650.
[Production Example A12]
As raw materials, an equimolar salt of hexamethylene diamine and adipic acid and an equimolar salt of hexamethylene diamine and isophthalic acid were used in a weight ratio of 80/20 as a terminal adjuster in a mixed aqueous solution containing 50% by weight of the raw material. Polymerization was carried out in the same manner as in Production Example A1 except that adipic acid was added, and drying was carried out in the same manner as in Production Example A2, to obtain a pellet-like polyamide 66 / 6I (A12). The polyamide 66 / 6I (A12) had a relative viscosity of 2.3, a moisture content of 0.25% by weight, and a carboxyl group concentration ratio of 0.735.

2. Preparation of a mixture of a copper compound, a halogen compound and an organic compound having at least one amide group [Production Example A13]
85 parts by weight of KI (having a particle size of 20 to 200 μm) and 10 parts by weight of bisamides, ethylene bisstearyl amide, are mixed and pulverized so that the maximum particle size of KI is 20 μm, and KI and ethylene bisstearyl are mixed. A mixture of amides was obtained. 5 parts by weight of CuI ( maximum particle diameter 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A1).
[Production Example A14]
75 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearyl amide are mixed and pulverized so that the maximum particle diameter of KI is 20 μm to obtain a mixture of KI and ethylene bisstearyl amide. It was. 15 parts by weight of CuI ( maximum particle diameter 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A2).
[Production Example A15]
88 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearyl amide are mixed and pulverized so that the maximum particle diameter of KI is 20 μm, thereby obtaining a mixture of KI and ethylene bisstearyl amide. It was. 2 parts by weight of CuI ( maximum particle diameter 2 μm) was mixed well with the mixture and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A3).
[Production Example A16]
70 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 20 parts by weight of ethylene bisstearyl amide are mixed and pulverized so that the maximum particle diameter of KI is 20 μm to obtain a mixture of KI and ethylene bisstearyl amide. It was. To this mixture, 10 parts by weight of CuI ( maximum particle size 2 μm) was mixed well and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A4).
[Production Example A17]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm), 10 parts by weight of ethylene bisstearyl amide (average particle diameter of 30 μm), 5 parts by weight of CuI ( maximum particle diameter of 2 μm) are mixed, and the maximum particle diameter of KI is The mixture (A1) was obtained by pulverizing well to 20 μm.
[Production Example A18]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearyl amide are mixed and pulverized so that the maximum particle diameter of KI is 50 μm to obtain a mixture of KI and ethylene bisstearyl amide. It was. 5 parts by weight of CuI ( maximum particle size 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A5).
[Production Example A19]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearyl amide are mixed and pulverized so that the maximum particle diameter of KI is 75 μm to obtain a mixture of KI and ethylene bisstearyl amide. It was. 5 parts by weight of CuI ( maximum particle diameter 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A6).
[Production Example A20]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of ethylene bisstearyl amide were mixed with 5 parts by weight of CuI ( maximum particle diameter of 2 μm) without pulverizing and having a maximum particle diameter of 200 μm. Granules were obtained with Fuji Paudal F5-11-175) to obtain granules (A7).
[Production Example A21]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm), 10 parts by weight of ethylene bisstearyl amide and 5 parts by weight of CuI ( maximum particle diameter of 2 μm) are mixed to a maximum of 100 mesh (maximum particle diameter of about 130 μm). The mixture (A2) was obtained by pulverization with a pulverizer having a screen.
[Production Example A22]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of N-stearyl erucamide (average particle diameter of 100 μm) as a substituted amide are mixed so that the maximum particle diameter of KI is 20 μm or less. To obtain a mixture of KI and N-stearyl erucic acid amide. 5 parts by weight of CuI ( maximum particle diameter 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A8).
[Production Example A23]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of stearic acid amide (average particle diameter of 20 μm) as monoamides are mixed and pulverized so that the maximum particle diameter of KI is 20 μm or less, A mixture of KI and stearic acid amide was obtained. 5 parts by weight of CuI ( maximum particle diameter 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A9).
[Production Example A24]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of methylol stearate amide (average particle diameter of 30 μm), which is a methylol amide, are mixed and pulverized so that the maximum particle diameter of KI is 20 μm or less. A mixture of KI and methylol stearate amide was obtained. 5 parts by weight of CuI ( maximum particle size 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A10).
[Production Example A25]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of stearic acid (average particle diameter of 30 μm), which is a higher fatty acid, are mixed and ground so that the maximum particle diameter of KI is 20 μm or less. And a mixture of stearic acid was obtained. 5 parts by weight of CuI ( maximum particle size 2 μm) was mixed well with the mixture and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A11).
[Production Example A26]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of stearyl stearate (average particle diameter of 30 μm), which is a higher fatty acid ester, are mixed and pulverized so that the maximum particle diameter of KI is 20 μm or less. A mixture of KI and stearyl stearate was obtained. The mixture was mixed well with 5 parts by weight of CuI ( maximum particle diameter 2 μm), and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A12).
[Production Example A27]
85 parts by weight of KI (having a particle diameter of 20 to 200 μm) and 10 parts by weight of calcium montanate (average particle diameter of 30 μm), which is a higher fatty acid metal salt, are mixed and pulverized so that the maximum particle diameter of KI is 20 μm or less. Thus, a mixture of KI and calcium montanate was obtained. 5 parts by weight of CuI ( maximum particle diameter 2 μm) was mixed well with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A13).
[Production Example A28]
85 parts by weight of KI (having a particle size of 20 to 200 μm) and 10 parts by weight of aluminum stearate (average particle size of 30 μm), which is a higher fatty acid metal salt, are mixed and pulverized so that the maximum particle size of KI is 20 μm or less. Thus, a mixture of KI and aluminum stearate was obtained. 5 parts by weight of CuI ( maximum particle diameter 2 μm) was mixed well with the mixture and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain granules (A14).

3. Examples A1 to A10, Comparative Examples A1 and A2
Masterbatches of Examples A1 to A10 and Comparative Examples A1 and A2 were manufactured by changing the type of polyamide.
[Example A1]
24 parts by weight of granule (A1) of Production Example 13 is blended with 100 parts by weight of polyamide 66 (A1) of Production Example A1, and a twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.) Using a rotary mold, L / D = 60 (D = 30φ)), a master batch was obtained by melt-kneading at a screw rotation speed of 100 rpm and a cylinder temperature of 280 ° C. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 4.
[Example A2]
The same procedure as in Example A1 was carried out except that polyamide 66 (A2) of Production Example A2 was used instead of polyamide 66 (A1). Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 4.
[Example A3]
It implemented similarly to Example A1 except having replaced with the polyamide 66 (A1) and using the polyamide 66 (A3) of manufacture example A3. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 4.
[Example A4]
The same procedure as in Example A1 was conducted except that polyamide 66 (A4) of Production Example A4 was used instead of polyamide 66 (A1). Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 4.
[Example A5]
It implemented similarly to Example A1 except having replaced with the polyamide 66 (A1) and using the polyamide 66 (A5) of manufacture example A5. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 4.
[Comparative Example A1]
The same procedure as in Example 1 was performed except that the polyamide 66 (A6) of Production Example A6 was used instead of the polyamide 66 (A1). Melt kneading with a twin screw extruder could be carried out stably. The color of the master batch changed to yellow. The evaluation results are shown in Table 4.
[Comparative Example A2]
The same procedure as in Example 1 was performed except that the polyamide 66 (A7) of Production Example A7 was used instead of the polyamide 66 (A1). Melt kneading with a twin screw extruder could be carried out stably. The color of the master batch turned slightly yellow. The evaluation results are shown in Table 4.

[Example A6]
It implemented similarly to Example A1 except having replaced with the polyamide 66 (A1) and using the polyamide 66 (A8) of manufacture example A8. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 4.
[Example A7]
The same procedure as in Example A1 was conducted except that polyamide 66 (A9) of Production Example A9 was used instead of polyamide 66 (A1). Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 5.
[Example A8]
It implemented similarly to Example A1 except having replaced with the polyamide 66 (A1) and using the polyamide 66 (A10) of manufacture example A10. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 5.
[Example A9]
This was carried out in the same manner as in Example A1, except that the polyamide 66 (A11) of Production Example A11 was used instead of the polyamide 66 (A1). Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 5.
[Example A10]
The same procedure as in Example A1 was conducted except that polyamide 66 / 6I (1) of Production Example A12 was used instead of polyamide 66 (A1). Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 5.

  From Tables 4 and 5, it can be confirmed that the color tone, copper precipitation, and metal corrosion of the masterbatch are improved by making the moisture content of the polyamide used in the production of the masterbatch within the numerical range defined in the present invention. It was.

4). Examples A11 to A19, Comparative Examples A3 to A10
Master batches of Examples A11 to A19 and Comparative Examples A3 to A10 were manufactured by changing the kind of the mixture of the copper compound, the halogen compound, and the organic compound having at least one amide group.
[Example A11]
24 parts by weight of granules (A2) of Production Example A14 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded in a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 6.
[Example A12]
24 parts by weight of granules (A3) of Production Example A15 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 6.
[Example A13]
24 parts by weight of granules (A4) of Production Example A16 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 6.
[Example A14]
50 parts by weight of granules (A4) of Production Example A16 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Although it was very rare, some strand breaks occurred, but the operation could be carried out without any problem. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 6.
[Comparative Example A3]
75 parts by weight of granules (A4) of Production Example A16 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt-kneading with a twin screw extruder could not produce much strand breakage. The evaluation results are shown in Table 6.

[Example A15]
24 parts by weight of the mixture (A1) of Production Example A17 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. Table 7 shows the evaluation results.
[Example A16]
24 parts by weight of the granules (A5) of Production Example A18 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. Table 7 shows the evaluation results.
[Comparative Example A4]
24 parts by weight of granule (A6) of Production Example A19 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and a master batch is obtained by melt-kneading with a twin screw extruder as in Example A1. It was. The melt-kneading in the twin-screw extruder was unstable because some strand breakage occurred. The color of the master batch turned slightly yellow. Table 7 shows the evaluation results.
[Comparative Example A5]
24 parts by weight of granules (A7) of Production Example A20 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example 1 to obtain a master batch. It was. Melt kneading with a twin-screw extruder could not be operated due to excessive strand breakage. Table 7 shows the evaluation results.
[Comparative Example A6]
24 parts by weight of the mixture (A2) of Production Example A21 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and a master batch is obtained by melt-kneading with a twin-screw extruder in the same manner as in Example A1. It was. Melt kneading in a twin screw extruder was unstable due to many strand breaks. Table 7 shows the evaluation results.

[Example A17]
24 parts by weight of granules (A8) of Production Example A22 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded in a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 8.
[Example A18]
24 parts by weight of the granules (A9) of Production Example A23 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 8.
[Example A19]
24 parts by weight of granules (A10) of Production Example A24 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded in a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color tone of the masterbatch was white and good. The evaluation results are shown in Table 8.
[Comparative Example A7]
24 parts by weight of granule (A11) of Production Example A25 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and a master batch is obtained by melt-kneading with a twin screw extruder as in Example A1. It was. Melt kneading with a twin screw extruder could be carried out stably. The color of the master batch turned slightly yellow. The evaluation results are shown in Table 8.
[Comparative Example A8]
24 parts by weight of granules (A12) of Production Example A26 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color of the master batch turned slightly yellow. The evaluation results are shown in Table 8.
[Comparative Example A9]
24 parts by weight of granules (A13) of Production Example A27 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color of the master batch turned slightly yellow. The evaluation results are shown in Table 8.
[Comparative Example A10]
24 parts by weight of granules (A14) of Production Example A28 are blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a master batch. It was. Melt kneading with a twin screw extruder could be carried out stably. The color of the master batch turned slightly yellow. The evaluation results are shown in Table 8.

  From Table 6 to Table 8, in the production method of a masterbatch using polyamide having a moisture content within the numerical range defined in the present invention, the master particle is optimized by optimizing the maximum particle size of the halogen compound and the type of organic compound. It was confirmed that the production stability of the batch, color tone, copper precipitation, metal corrosivity, and the surface condition of the master batch pellet were improved.

5. Examples A20 to A23, Comparative Examples A11 to A17
A polyamide resin composition formed by mixing the second polyamide and the masterbatch was produced.
[Example A20]
2 parts by weight of the master batch of Example A1 was blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2. It melt-kneaded with the twin-screw extruder similarly to Example A1, and the polyamide resin composition was obtained. In the polyamide resin composition, the polyamide 66 is 0.0235 parts by weight, the KI is 0.096 parts by weight, and the ethylene bisstearylamide is 0.0470 parts by weight with respect to 100 parts by weight of the polyamide 66. Table 9 shows the evaluation results.
[Example A21]
2 parts by weight of the master batch of Example A16 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin screw extruder in the same manner as in Example A1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as that of the polyamide resin composition of Example A20. Table 9 shows the evaluation results.
[Example A22]
2 parts by weight of the master batch of Example A1 is blended with 100 parts by weight of polyamide 66 (A1) of Production Example A1, and melt-kneaded with a twin screw extruder as in Example A1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as that of the polyamide resin composition of Example A20. Table 9 shows the evaluation results.
[Example A23]
A polyamide resin composition obtained by blending 0.67 parts by weight of the master batch of Example A11 with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneading with a twin screw extruder as in Example A1. Got. In the polyamide resin composition, the polyamide 66 is 0.0240 parts by weight, the KI is 0.120 parts by weight, and the ethylenebisstearylamide is 0.0160 parts by weight with respect to 100 parts by weight of the polyamide 66. Table 9 shows the evaluation results.

[Comparative Example A11]
2 parts by weight of the master batch of Comparative Example A1 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder in the same manner as in Example A1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as that of the polyamide resin composition of Example A20. Table 10 shows the evaluation results.
[Comparative Example A12]
2 parts by weight of the master batch of Comparative Example A2 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin screw extruder in the same manner as in Example A1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as that of the polyamide resin composition of Example A20. Table 10 shows the evaluation results.
[Comparative Example A13]
2 parts by weight of the master batch of Comparative Example A4 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder as in Example A1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as that of the polyamide resin composition of Example A20. Table 10 shows the evaluation results.
[Comparative Example A14]
2 parts by weight of the master batch of Comparative Example A6 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin screw extruder in the same manner as in Example A1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as that of the polyamide resin composition of Example A20. Table 10 shows the evaluation results.
[Comparative Example A15]
2 parts by weight of the master batch of Comparative Example A9 is blended with 100 parts by weight of polyamide 66 (A2) of Production Example A2, and melt-kneaded with a twin-screw extruder as in Example A1 to obtain a polyamide resin composition. It was. The compounding amount of each compound is the same as that of the polyamide resin composition of Example A20. Table 10 shows the evaluation results.
[Comparative Example A16]
The blend (A2) of Production Example A21 was blended with 100 parts by weight of polyamide 66 (A3) of Production Example A3, and dry blending was performed. The blending amount of each compound was blended so as to be the same as the polyamide resin composition of Example A20. Table 10 shows the evaluation results.
[Comparative Example A17]
A known melt polymerization was carried out using an equimolar aqueous solution (50% by weight concentration) of hexamethylenediamine and adipic acid. In the middle of the polymerization, a mixed aqueous solution of CuI and KI was added. Ethylene bisstearylamide was added to the surface of the obtained polyamide 66 pellets. The compounding amount of each compound was added so as to be the same as that of the polyamide resin composition of Example A20. The relative viscosity of the polyamide 66 resin composition was 2.8, the water content was 0.10% by weight, and the carboxyl group concentration ratio was 0.625. Table 10 shows the evaluation results.

  From Table 9 and Table 10, it was confirmed that the molded article of the polyamide resin composition obtained from the masterbatch produced by the production method of the present invention had improved copper precipitation, long-term heat aging resistance, and color tone. .

  The masterbatch produced by the production method of the present invention can be suitably used in the field of polyamide resins used for heat resistance.

Claims (11)

a) 100 parts by weight of a polyamide having a moisture content of 0.05 to 2.0% by weight,
b) 0.1 to 10 parts by weight of an organic compound having at least one amide group,
c) 0.1 to 5 parts by weight of a copper compound having a maximum particle size of 50 μm or less, and d) 1 to 50 parts by weight of a halogen compound (excluding copper halide) having a maximum particle size of 50 μm or less by a melt-kneading method. The manufacturing method of the masterbatch to mix.   The manufacturing method of the masterbatch of Claim 1 which mix | blends a raw material so that the molar ratio (halogen / copper) of the halogen and copper of the masterbatch manufactured may be 3-30.   The method for producing a masterbatch according to claim 1 or 2, wherein the maximum particle size of the copper compound and / or the halogen compound (excluding the copper halide) is 20 µm or less. Carboxyl group concentration ratio of the polyamide ([COOH] / ([COOH ] + [NH 2])) The method for producing a masterbatch according to any one of claims 1, which is 0.55 to 0.80 3.   The manufacturing method of the masterbatch of any one of Claim 1 to 4 whose moisture content of polyamide is 0.1 to 1.5 weight%.   6. The master according to claim 1, wherein the organic compound having at least one amide group is at least one compound selected from the group consisting of monoamides, substituted amides, methylol amides, and bisamides. Batch manufacturing method.   The masterbatch according to any one of claims 1 to 6, wherein a copper compound and / or a halogen compound (excluding copper halide) and an organic compound having at least one amide group are mixed in advance and pulverized. Method.   The masterbatch manufactured with the manufacturing method of any one of Claim 1 to 7.   The master batch according to claim 8, wherein the moisture content is 0.06 to 1% by weight.   A polyamide resin composition obtained by mixing 0.1 to 100 parts by weight of the masterbatch according to claim 8 or 9 with respect to 100 parts by weight of the second polyamide.   The polyamide resin composition according to claim 10, which has a moisture content of 0.01 to 1% by weight.