JP2015010213A - Method for producing polyamide 66 resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyamide 66 resin composition causing less reduction of the molecular weight of the polyamide 66 resin.SOLUTION: The method for producing a polyamide 66 resin composition includes an extrusion step of melting and kneading (A) a polyamide 66 resin composition, (B) a glass fiber, and (C) a copper compound and extruding a polyamide 66 resin composition by an extruder,. In the extrusion step, a vacuum degree of a vent in the extruder is 30 hPa or more and 350 hPa or less, a variation width of the vacuum degree of the vent with respect to an initial measured value of 100% is 75% or more and 125% or less, and a temperature of the polyamide 66 resin composition is 265°C or higher and 350°C or lower.

Description

  The present invention relates to a method for producing a polyamide 66 resin composition.

  Conventionally, polyamide 66 resin is excellent in mechanical strength, heat resistance, etc., and thus has been used in the fields of automobile parts, mechanical parts, electrical and electronic parts and the like. Moreover, since it is excellent also in slidability, it is widely used as a molded product for sliding parts such as gears, cams and bearings.

  In recent years, there has been an increasing demand for higher slidability than before, and materials in which the slidability of polyamide is improved are being studied. Among these, it is known that a high molecular weight polyamide 66 resin composition having a molecular weight higher than that of a normal molding polyamide 66 resin composition is excellent in strength, toughness, and wear resistance. In addition to this, addition of a slidability improving agent for the purpose of further reducing the friction resistance has been studied.

  For example, Patent Document 1 discloses a polyamide 66 resin composition comprising polyamide, glass fiber, copper compound, potassium halide, and melamine having a specific number average molecular weight, and is suitable as a gear material. Is disclosed.

  Patent Document 2 discloses a polyamide comprising (A) a polyamide resin, (B) an inorganic filler, (C) a copper compound, and (D) an alkali halide, which is obtained by melt-kneading by a specific method. A resin composition is disclosed.

  Furthermore, Patent Document 3 discloses that a specific organic heat stabilizer (B), a specific higher fatty acid ester (C), a specific specific amount are added to 100 parts by mass of the high molecular weight polyamide 66 (A) having a specific relative viscosity. A method for producing a polyamide resin composition in which a higher fatty acid metal salt (D), a copper compound (E) and a halogen compound (F) other than halogen copper are blended at a specific ratio is disclosed.

International Publication No. 2006/054774 Pamphlet Japanese Patent No. 4353565 Japanese Patent No. 4451130

  However, in the manufacturing technique disclosed in Patent Document 1, the molecular weight of the polyamide used as a raw material is lowered. This is considered to be because the decomposition of the polyamide proceeds due to the thermal history inside the extruder. In particular, when a high molecular weight polyamide and glass fiber are melt-kneaded, shear heat generation due to high viscosity increases, and as a result, the thermal decomposition of the polyamide tends to progress further. From this, the production method is inefficient because a higher molecular weight polyamide is required to obtain the target high molecular weight polyamide resin composition. In addition, a method of increasing the molecular weight by performing a post-process such as solid phase polymerization after obtaining a composition by extrusion has been proposed, but this is also inefficient because of an increase in the number of processes.

  Further, in Patent Document 2, a method for producing a polyamide resin composition is disclosed, but no consideration is given to the point that the molecular weight of the polyamide used as a raw material decreases as in the case of Patent Document 1 described above. According to the inventors' investigation, a decrease in the molecular weight of the polyamide was observed.

  Further, Patent Document 3 does not disclose details about melt kneading of high molecular weight polyamide, and of course does not disclose reduction in the molecular weight of polyamide due to melt kneading.

  Therefore, in the present invention, there is provided a method for producing a polyamide 66 resin composition, which can produce a polyamide 66 resin composition with little decrease in the molecular weight of the obtained polyamide 66 resin and having a stable molecular weight. The purpose is to do.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention, in a composition containing polyamide 66 resin, glass fiber, and copper compound, set the vent vacuum in the extruder and the resin temperature during extrusion to a specific range. By adjusting, it discovered that the said subject could be achieved and came to complete this invention.

That is, the present invention is as follows.
[1]
(A) a polyamide 66 resin, (B) glass fiber, and (C) a copper compound are melt-kneaded in an extruder to extrude the polyamide 66 resin composition,
The vent vacuum degree of the extruder in the extrusion step is 30 hPa or more and 350 hPa or less,
In the extrusion step, the fluctuation range of the vent vacuum degree with respect to the initial measured value of 100% of the vent vacuum degree is 75% or more and 125% or less,
The temperature of the polyamide 66 resin composition in the extrusion step is 265 ° C. or higher and 350 ° C. or lower,
A method for producing a polyamide 66 resin composition.
[2]
The method for producing a polyamide 66 resin composition according to item [1], wherein the (A) polyamide 66 resin contains one or more types of polyamide 66 resin (A-1) having a relative viscosity RV of 65 or more and 250 or less.
[3]
The production of the polyamide 66 resin composition according to the above item [1] or [2], wherein the (A) polyamide 66 resin contains one or more polyamide 66 resins (A-2) having a relative viscosity RV of 25 or more and less than 65. Method.
[4]
In the extrusion process,
For a total amount of 100 parts by mass of the (A) polyamide 66 resin and the (B) glass fiber,
(A) 50 parts by weight or more and 90 parts by weight or less of the polyamide 66 resin;
The method for producing a polyamide 66 resin composition according to any one of [1] to [3], wherein (B) 10 parts by mass or more and 50 parts by mass or less of glass fiber is melt-kneaded.
[5]
The method for producing a polyamide 66 resin composition according to any one of [1] to [4], wherein the obtained polyamide 66 resin composition has a relative viscosity RV of 55 or more and 240 or less.
[6]
The manufacturing method of the polyamide 66 resin composition of any one of the preceding items [1] to [5], wherein the moisture content contained in the obtained polyamide 66 resin composition is 100 ppm or more and less than 1000 ppm.
[7]
The production of the polyamide 66 resin composition according to any one of [1] to [6] above, wherein the concentration [Cu] of the copper component contained in the obtained polyamide 66 resin composition is 80 ppm or more and less than 300 ppm. Method.
[8]
Manufacture of the polyamide 66 resin composition of any one of said [1]-[7] whose density | concentration [X] of the halogen component contained in the obtained polyamide 66 resin composition is 40 ppm or more and 9000 ppm or less. Method.
[9]
The ratio ([Cu] / [X]) of the concentration [Cu] of the copper component and the concentration [X] of the halogen component contained in the obtained polyamide 66 resin composition is 0.02 or more and 0.25 or less. The method for producing a polyamide 66 resin composition according to any one of [1] to [8] above.
[10]
The (A) polyamide 66 resin and the (C) copper compound are charged from the same supply port of the extruder,
Any one of [1] to [9] above, wherein the (B) glass fiber is introduced from a supply port located downstream of the supply port into which the (A) polyamide 66 resin and the (C) copper compound are introduced. A process for producing the polyamide 66 resin composition according to claim 1.
[11]
Any one of [1] to [9] above, wherein the (A) polyamide 66 resin, the (B) glass fiber, and the (C) copper compound are introduced from the same supply port of the extruder. The manufacturing method of the polyamide 66 resin composition as described in claim | item.
[12]
(A) the polyamide 66 resin is charged from the supply port of the extruder,
Said (B) glass fiber and said (C) copper compound are thrown from the same supply port located downstream from the said supply port which injected | thrown-in said (A) polyamide 66 resin, [1]-[ [9] The process for producing a polyamide 66 resin composition as described in any one of [9].
[13]
(A) the polyamide 66 resin is charged from the supply port of the extruder,
[1] to [1] to [1] to [1] above, in which the (B) glass fiber and the (C) copper compound are introduced from different supply ports located downstream of the supply port in which the (A) polyamide 66 resin is added. [9] The process for producing a polyamide 66 resin composition as described in any one of [9].
[14]
(D) The method for producing a polyamide 66 resin composition according to any one of [1] to [13], wherein the halogen compound not containing copper is further melt-kneaded.
[15]
The method for producing a polyamide 66 resin composition according to any one of [1] to [14] above, which does not include a higher fatty acid metal salt during melt-kneading.

  According to the present invention, there is provided a method for producing a polyamide 66 resin composition, which can produce a polyamide 66 resin composition having a low molecular weight decrease and a continuously stable molecular weight. be able to.

The schematic block diagram of the twin-screw extruder which is an example of the apparatus which enforces the manufacturing method of the polyamide 66 resin composition which concerns on this embodiment is shown.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

[Production Method of Polyamide 66 Resin Composition]
The method for producing the polyamide 66 resin composition according to this embodiment is as follows:
(A) a polyamide 66 resin, (B) glass fiber, and (C) a copper compound are melt-kneaded in an extruder to extrude the polyamide 66 resin composition,
The vent vacuum degree of the extruder in the extrusion step is 30 hPa or more and 350 hPa or less,
In the extrusion step, the fluctuation range of the vent vacuum degree with respect to the initial measured value of 100% of the vent vacuum degree is 75% or more and 125% or less,
The temperature of the polyamide 66 resin composition in the extrusion step is 265 ° C. or higher and 350 ° C. or lower.
If it is the manufacturing method of the said polyamide 66 resin composition, compared with the said conventional manufacturing method, the fall of the molecular weight of a polyamide 66 resin is few, can manufacture the polyamide composition which has practically sufficient mechanical strength, and is continuous. In particular, a high molecular weight polyamide 66 resin composition having a stable molecular weight can be produced.

  First, the material used for the manufacturing method of the polyamide 66 resin composition which concerns on this embodiment is demonstrated.

((A) polyamide 66 resin)
(A) Polyamide 66 resin is a polymer having an amide bond (—NHCO—) in the main chain and comprising hexamethylene units and adipic acid units. (A) Although it does not specifically limit as polyamide 66 resin, For example, the polymer obtained by polycondensing hexamethylenediamine and adipic acid, and obtained by polycondensing 6-amino capronitrile and adipic acid Examples thereof include a polymer, a polymer obtained by polycondensation of hexamethylenediamine and adipoyl chloride, and a polymer obtained by polycondensation of 6-aminocapronitrile and adipoyl chloride. Among these, a polymer obtained by polycondensation of hexamethylenediamine and adipic acid is preferable because of the availability of raw materials. In addition, (A) polyamide 66 resin means resin which contains 95 mol% or more of polyamide 66 by making all units into 100 mol%.

  The “polyamide 66 resin” includes a homopolymer of polyamide 66 and a copolymer of a monomer copolymerizable with polyamide 66. Although it does not specifically limit as a monomer which can be copolymerized, For example, polyamide components other than the polyamide 66 component, for example, a polymerizable amino acid, a polymerizable lactam, or other polymerizable diamine or dicarboxylic acid can be mentioned. Moreover, a well-known compound can be added for molecular weight adjustment or hot water improvement. Examples of such compounds include, but are not limited to, acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like. . Among these, monocarboxylic acid or monoamine is preferable.

  (A) The polyamide 66 resin preferably contains at least one polyamide 66 resin (A-1) having a relative viscosity RV of 65 to 250, and a polyamide 66 resin (A-1) having a relative viscosity RV of 70 to 230. ) Is more preferable, and it is further preferable to include one or more types of polyamide 66 resin (A-1) having a relative viscosity RV of 75 to 200. By including such a polyamide 66 resin (A-1), it tends to be more excellent in extrudability and better in mechanical properties of the obtained polyamide 66 resin composition. Polyamide 66 resin (A-1) may be used individually by 1 type, or may use 2 or more types together. In addition, relative viscosity RV can be measured by the method as described in an Example.

  The (A) polyamide 66 resin preferably contains one or more polyamide 66 resins (A-2) having a relative viscosity RV of 25 or more and less than 65, and the polyamide 66 resin (A) having a relative viscosity RV of 27 or more and 60 or less. -2) is more preferably included, and it is further preferable that at least one polyamide 66 resin (A-2) having a relative viscosity RV of 30 to 55 is included. By including such a polyamide 66 resin (A-2), it tends to be easier to suppress a decrease in the molecular weight of the obtained polyamide 66 resin composition. Polyamide 66 resin (A-2) may be used individually by 1 type, or may use 2 or more types together. In addition, relative viscosity RV can be measured by the method as described in an Example.

  (A) The polyamide 66 resin preferably contains both the polyamide 66 resin (A-1) and the polyamide 66 resin (A-2). Thereby, it exists in the tendency which is excellent by the balance of a long-term characteristic and fluidity | liquidity.

  The relative viscosity RV of the polyamide 66 resin composition obtained by the method for producing the polyamide 66 resin composition according to this embodiment is not particularly limited, but is preferably 55 or more and 240 or less, and 57 or more and 220 or less. More preferably, it is 60 or more and 200 or less. By being in the above range, vibration fatigue characteristics and friction and wear characteristics tend to be more excellent. The relative viscosity RV of the polyamide 66 resin composition can be controlled by a method described later.

  Usually, such a polyamide 66 resin having a high relative viscosity RV has a tendency to significantly reduce the relative viscosity RV during melt-kneading with glass fibers. By the method of the present invention for controlling the viscosity, it is possible to suppress a decrease in the relative viscosity RV.

  A method for polymerizing the polyamide 66 resin is not particularly limited, and examples thereof include a hot melt polycondensation method, a solid phase polymerization method, and a solution method. In the hot melt polycondensation method, an antifoaming agent or the like is blended with the hexamethylene adipamide, which is a raw material of polyamide 66, if necessary, and heated and concentrated at a temperature of 40 to 300 ° C. This is a method of maintaining the pressure between ˜20 atm, and finally depressurizing to normal pressure or depressurizing to perform polycondensation. The solid phase polymerization method is a method performed at a temperature below the melting point of the diamine or dicarboxylate solid salt or polycondensate. Furthermore, the solution method is a method in which a dicarboxylic acid halide component and a diamine component are polycondensed in a solution. These methods may be combined as necessary. Moreover, as a superposition | polymerization form, a batch type or a continuous type may be sufficient. Also, the polymerization apparatus is not particularly limited. For example, an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, or the like can be used.

  In order to obtain a polyamide 66 resin having a predetermined relative viscosity RV, for example, a general method such as a method of adjusting the polymerization time by the above-described hot melt polycondensation method, a method of solid-phase polymerization below the melting point of the polycondensate, etc. The method can be used and is not particularly limited.

  Although the moisture content of (A) polyamide 66 resin used for this embodiment is not specifically limited, 100 ppm or more and less than 1000 ppm are preferable, 150 ppm or more and less than 900 ppm are more preferable, 200 ppm or more and less than 850 ppm are more preferable. When the moisture content is in the above range, a decrease in molecular weight tends to be further suppressed. In addition, when using several (A) polyamide 66 resin, it is preferable that the moisture content of (A) whole is the said range. Here, as a method for measuring the moisture content, a method defined in JISK6920 can be cited.

  In addition, it is preferable that the moisture content contained in the polyamide 66 resin composition obtained is 100 ppm or more and less than 1000 ppm, more preferably 200 ppm or more and less than 950 ppm, and further preferably 300 ppm or more and less than 900 ppm. When the moisture content is in the above range, a decrease in molecular weight tends to be further suppressed.

The terminal amino group concentration [NH ₂ ] of the (A) polyamide 66 resin used in this embodiment is preferably 10 meq / kg or more and 100 meq / kg or less, and 20 meq / kg or more and 90 meq / kg or less. Is more preferable, and more preferably 30 meq / kg or more and 80 meq / kg or less. When the terminal amino group concentration is within the above range, the color tone of the polyamide 66 resin composition is more excellent, and yellowing due to deterioration tends to be further suppressed. Examples of the method for measuring the terminal amino group concentration include a method in which a predetermined amount of polyamide 66 resin sample is dissolved in a 90% phenol aqueous solution and titrated with 1/50 N hydrochloric acid at 25 ° C. to calculate.

  The terminal carboxyl group concentration [COOH] of the (A) polyamide 66 resin used in this embodiment is preferably 10 meq / kg or more and 150 meq / kg or less, and 20 meq / kg or more and 140 meq / kg or less. More preferably, it is more preferably 30 meq / kg or more and 130 meq / kg or less. When the terminal carboxyl group concentration is within the above range, the appearance of the molded product of the polyamide 66 resin composition tends to be more excellent. As a method for measuring the terminal carboxyl group concentration, a predetermined amount of polyamide 66 resin sample was dissolved in benzyl alcohol at 160 ° C., 1/10 N potassium hydroxide in ethylene glycol solution, and phenolphthalein was used as an indicator. And titrating and calculating. Examples of the appearance of the molded product include, but are not limited to, roughness due to exposure of glass fibers, smoothness, silver streak, and the like.

The terminal carboxyl group ratio is preferably 55 to 85%, more preferably 57 to 80%, and still more preferably 60 to 75%. When the terminal carboxyl group ratio is within the above range, it tends to be excellent in long-term color stability with little yellowing. Here, the “terminal carboxyl group ratio” refers to a ratio of the terminal carboxyl group concentration to the sum of the terminal carboxyl group concentration [COOH] and the terminal amino group concentration [NH ₂ ] expressed as a percentage.

  In the extrusion step, (A) 50 parts by mass to 90 parts by mass of polyamide 66 resin and (B) 10 parts by mass of glass fiber with respect to 100 parts by mass of the total amount of (A) polyamide 66 resin and (B) glass fiber. It is preferable to melt-knead the above and 50 parts by mass or less, and (A) 55 to 87 parts by mass of polyamide 66 resin and (B) 13 to 45 parts by mass of glass fiber are melt-kneaded. It is more preferable that (A) 65 to 85 parts by mass of polyamide 66 resin and (B) 15 to 35 parts by mass of glass fiber be melt-kneaded. When the amount of (A) polyamide 66 resin and (B) glass fiber used is within the above range, a polyamide 66 resin composition that is superior in molding processability and mechanical properties tends to be obtained.

((B) Glass fiber)
(B) The glass fiber has a function of imparting excellent mechanical strength, rigidity and moldability to the polyamide 66 resin composition. (B) There is no restriction | limiting in particular as glass fiber, if it is generally used for the polyamide resin.

  (B) Although it does not specifically limit about the average fiber diameter of glass fiber, For example, 5-30 micrometers is preferable. When the average fiber diameter is within the above range, the polyamide 66 resin composition tends to be provided with excellent mechanical strength, rigidity, and moldability. Moreover, it does not restrict | limit especially as a form of glass fiber, For example, a chopped strand, roving, a milled fiber, etc. can be used. In addition, the average fiber length of (b) glass fiber is not particularly limited, but when chopped strand is used, it may be appropriately selected within a range of 0.1 to 6 mm. In addition, the average fiber diameter and average fiber length in this specification are the average value of the value obtained by measuring the diameter and length of 500 fibers extracted at random.

  (B) A conventionally known sizing agent may be attached to the surface of the glass fiber. The sizing agent is not particularly limited. For example, the main component is, for example, a copolymer of maleic anhydride and an unsaturated monomer, a silane coupling agent, an acrylic acid copolymer, and / or a urethane polymer. Are listed. Among these, those containing a copolymer of maleic anhydride and an unsaturated monomer or an amino group-containing silane coupling agent as a main constituent are preferable. By using such a sizing agent, there is a tendency to obtain a polyamide 66 resin composition that is more excellent in improving vibration fatigue properties.

  The copolymer of the maleic anhydride and the unsaturated monomer is not particularly limited. Specifically, styrene, α-methylstyrene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1, A copolymer of an unsaturated monomer such as 3-pentadiene or cyclooctadiene and maleic anhydride is exemplified. Among these, a copolymer of butadiene, styrene, and maleic anhydride is preferable. These monomers may be used alone or in combination of two or more. The sizing agent may be used as a blend such as a mixture of a maleic anhydride / butadiene copolymer and a maleic anhydride / styrene copolymer. The copolymer of maleic anhydride and unsaturated monomer preferably has an average molecular weight of 2,000 or more. Further, the ratio of maleic anhydride and unsaturated monomer is not particularly limited. Furthermore, in addition to the maleic anhydride copolymer, an acrylic acid copolymer or a urethane polymer may be used in combination.

  Although it does not specifically limit as said silane coupling agent, All the silane coupling agents normally used for the surface treatment of glass fiber can be used. Such a silane coupling agent is not particularly limited, and specific examples include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxy. Aminosilane coupling agents such as silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane; γ-glycidoxypropylmethyldiethoxysilane, Epoxysilane coupling agents such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldiethoxysilane, Examples include methacryloxysilane coupling agents such as γ-methacryloxypropyltriethoxysilane; vinylsilane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (βmethoxyethoxy) silane. Of these, aminosilane coupling agents are preferred because of their affinity for polyamide resin, and among them, γ-aminopropyltriethoxysilane and N-β (aminoethyl) γ-aminopropyltriethoxysilane are more preferred. These coupling agents may be used alone or in combination of two or more.

  (B) The usage-amount of glass fiber has the preferable range of 10 mass parts or more and 50 mass parts or less when the sum total of (A) component and (B) component is 100 mass parts, and is 13 mass parts or more and 45 mass parts or less. Is more preferable, and 15 mass parts or more and 35 mass parts or less are still more preferable. When the amount used is within the above range, a polyamide 66 resin composition having better mechanical properties tends to be obtained.

((C) Copper compound)
(C) A copper compound has a function which suppresses the molecular weight fall at the time of the melt-kneading of the polyamide 66 resin composition. (C) The copper compound is not particularly limited, for example, copper halide, sulfate, acetate, propionate, benzoate, adipate, terephthalate, salicylate, nicotinate, Examples include stearates, chelate compounds such as ethylenediamine and ethylenediaminetetraacetic acid, and mixtures thereof. Among these, copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate are preferable. By using such a copper compound, a decrease in molecular weight during melt-kneading tends to be further suppressed.

  (C) The amount of the copper compound used is preferably such that the copper concentration [Cu] in the obtained polyamide 66 resin composition is 80 ppm to 300 ppm, more preferably 90 ppm to 275 ppm, more preferably 100 ppm to 250 ppm. More preferred is an amount of When the amount used is within the above range, a decrease in molecular weight during melt-kneading can be further suppressed, and a polyamide 66 resin composition excellent in mechanical properties tends to be obtained.

((D) Halogen compound not containing copper)
In the method for producing the polyamide 66 resin composition according to the present embodiment, (D) a halogen compound not containing copper can be used in order to increase the molecular weight reduction suppressing effect. (D) Although it does not specifically limit as a halogen compound which does not contain copper, For example, the salt of bromine or iodine and the 1st or 2nd group metal element of an element periodic table is mentioned. Among these, potassium bromide, sodium bromide, potassium iodide, sodium iodide, or a mixture thereof is preferable. Among these, potassium iodide is more preferable. By using such a component (D), the molecular weight reduction tends to be further suppressed.

  (D) The amount of the halogen compound not containing copper is preferably added so that the concentration [X] of the halogen component in the polyamide 66 resin composition is 40 ppm or more and 9000 ppm or less, and 70 ppm or more and 7000 ppm or less. More preferably, it is more preferably added so that it may become 100 ppm or more and 5000 ppm or less. When the amount used is within the above range, a decrease in molecular weight during melt-kneading can be further suppressed, and a polyamide 66 resin composition excellent in mechanical properties tends to be obtained. Here, the halogen component concentration [X] includes a halogen component that may be contained in the (C) copper compound.

  The concentration ratio ([Cu] / [X]) between the copper concentration [Cu] and the halogen component concentration [X] in the polyamide 66 resin composition is preferably 0.020 or more and 0.25 or less. 0.022 to 0.23, more preferably 0.025 to 0.20. When the amount used is within the above range, a decrease in molecular weight during melt kneading can be further suppressed, and a polyamide 66 resin composition excellent in heat resistance tends to be obtained.

((E) Polyamide resin other than polyamide 66 resin)
In the method for producing a polyamide 66 resin composition according to this embodiment, a polyamide resin (E) other than the polyamide 66 resin may be used in combination with the polyamide 66 resin. The polyamide resin (E) other than the polyamide 66 resin is not particularly limited, and examples thereof include a polycondensate of dicarboxylic acid and diamine, a ring-opening polymer of cyclic lactam, and a polycondensate of aminocarboxylic acid. The polyamide resin (E) is not particularly limited. Specifically, poly (caprolactam) (hereinafter abbreviated as “polyamide 6”), poly (hexamethylene adipamide) (hereinafter “polyamide”). 66 ”), poly (tetramethylene adipamide) (hereinafter abbreviated as“ polyamide 46 ”), poly (hexamethylene sebacamide) (hereinafter abbreviated as“ polyamide 610 ”), poly (hexa Methylene dodecamide) (hereinafter abbreviated as “polyamide 612”), poly (undecamethylene adipamide) (hereinafter abbreviated as “polyamide 116”), poly (undecalactam) (hereinafter “polyamide 11”) An aliphatic polyamide such as poly (dodecalactam) (hereinafter abbreviated as “polyamide 12”); poly (metaxylylene adipamide) (hereinafter abbreviated as “polyamide 12”). , “Polyamide MXD6”), poly (hexamethylene terephthalamide) (hereinafter abbreviated as “polyamide 6T”), poly (hexamethylene isophthalamide) (hereinafter abbreviated as “polyamide 6I”), poly (nona). Methylene terephthalamide) (hereinafter abbreviated as “polyamide 9T”), poly (tetramethylene isophthalamide) (hereinafter abbreviated as “polyamide 4I”) and other polyamides containing aromatic components; Copolymers of polyamides containing aromatic components and copolymers of aliphatic polyamides and polyamides containing aromatic components; Among these mixtures, (A) those other than polyamide 66 resin may be mentioned. Among these, (A) polyamide 6, a copolymer of polyamide 6 and polyamide 66, or a mixture thereof is preferable from the viewpoint of compatibility with the polyamide 66 resin. The polyamide resin (E) other than the polyamide 66 resin means a resin containing less than 5 mol% of polyamide 66 with the total unit being 100 mol%.

(Other ingredients)
In the method for producing a polyamide 66 resin composition according to the present embodiment, other components such as flame retardants, elastomers, fibrillating agents, colorants such as pigments and dyes, and general polyamide 66 resin are used as necessary. Heat stabilizers and organic heat stabilizers typified by hindered phenolic oxidative degradation inhibitors, lubricants such as higher fatty acid esters and higher fatty acid amides, weather resistance improvers, nucleating agents, plasticizers, antistatic agents, flow A property improving agent, a filler, a reinforcing agent, a spreading agent, a sliding property improving agent, another polymer, and the like can be added at an arbitrary stage.

(Process for producing polyamide 66 resin composition)
The manufacturing method of the polyamide 66 resin composition according to the present embodiment is as follows. (A) polyamide 66 resin, (B) glass fiber, and (C) copper compound are melt-kneaded by an extruder and the polyamide 66 resin composition is used. An extrusion process for extruding the product.

(Extrusion process)
In the extrusion step, (A) polyamide 66 resin, (B) glass fiber, and (C) copper compound are melt-kneaded in an extruder.

  Although it does not specifically limit as an extruder which can be used, For example, the extruder generally utilized is applicable. For example, a uniaxial or multiaxial kneading extruder may be used. In particular, a twin screw extruder is preferable from the viewpoint of processing stability and productivity. Examples of the twin screw extruder include a ZSK series manufactured by COPERIION, a TEM series manufactured by Toshiba Machine Co., Ltd., and a TEX series manufactured by Nippon Steel Works.

  In the extrusion step, the vent vacuum degree of the extruder is 30 hPa to 350 hPa, preferably 50 hPa to 300 hPa, more preferably 70 hPa to 270 hPa, further preferably 100 hPa to 250 hPa. preferable. When the degree of vacuum is in the above range, it tends to be more excellent in suppressing the decrease in molecular weight.

  Here, the “venting degree of vacuum” means an absolute pressure when the pressure is reduced by a vacuum source from a vacuum vent port which is a vacuum devolatilization unit. Although a vacuum source is not specifically limited, For example, all the vacuum sources which can be generally used can be used individually or in combination. Typical examples include an oil rotary vacuum pump, a roots vacuum pump, a liquid ring vacuum pump, an ejector, and the like. As a method of controlling the degree of vent vacuum, for example, a method of adjusting the opening degree of the inlet valve of the vacuum source, a method of adjusting the amount of inert gas or air blown immediately before the vacuum source, and the like can be considered. There is no particular limitation, and any of these control methods can be used. The controlled absolute pressure is measured by installing a conventional vacuum gauge between the vacuum vent port and the vent vacuum degree control unit.

  In the extrusion process, the fluctuation range of the vent vacuum with respect to the initial measured value of 100% of the vent vacuum is 75% to 125% of the set value, preferably 80% to 120%, preferably 85% to 115%. Is more preferable. By continuously controlling the fluctuation range to be in the above range, a polyamide 66 resin composition having a continuously stable quality tends to be obtained.

  The “initially measured value” refers to a value measured 3 minutes after the vent vacuum reaches a set value (target value). The set value is preferably 30 to 350 hPa, more preferably 50 to 300 hPa, and still more preferably 100 to 250 hPa.

  "Continuous control" means to check the vent vacuum at intervals of 1 to 120 minutes, preferably 30 to 90 minutes, and adjust it within a predetermined range in order to follow the change in vent vacuum over time. However, this series of operations can be performed either by an automated device or by manual operation.

  The extrusion process is a process of extruding the melt-kneaded polyamide 66 resin composition. The temperature of the polyamide 66 resin composition in the extrusion step is 265 ° C. or higher and 350 ° C. or lower, preferably 290 ° C. or higher and 345 ° C. or lower, more preferably 300 ° C. or higher and 340 ° C. or lower, and 310 ° C. or higher and 335 ° C. or lower. More preferably, it is not higher than ° C. When the temperature is in the above range, it tends to be more excellent in suppressing the decrease in molecular weight. The resin temperature is measured as follows. When the polyamide resin composition is melt-kneaded, the temperature of the resin discharged from the spinning nozzle is measured with a conventional thermometer, and the measured maximum temperature is taken as the resin temperature during extrusion.

  As described above, by keeping the degree of vent vacuum low and within a certain range and lowering the resin temperature at the time of extrusion, a decrease in the molecular weight of the raw polyamide 66 resin is suppressed, and it has a suitable molecular weight and is practically sufficient. A composition having mechanical strength can be obtained.

  In FIG. 1, the schematic block diagram of a twin-screw extruder is shown as an example of the compounding apparatus used for the manufacturing method of the polyamide 66 resin composition which concerns on this embodiment.

  The twin-screw extruder has a screw 6 in the exterior 1, and the first supply port 2 on the upstream side and the second supply port on the downstream side sequentially from the flow direction of the raw material indicated by the arrow 7. 3, a third supply port 4 is provided, and a vacuum vent port 5, which is a vacuum devolatilization unit, is provided downstream of the third supply port 4.

  In the twin-screw extruder used in the method for producing the polyamide 66 resin composition according to this embodiment, the L / D (screw effective length / screw outer diameter) of the twin-screw extruder is preferably in the range of 20 or more and 60 or less. More preferably, it is in the range of 25 to 55, more preferably in the range of 30 to 50. The screw effective length L is the length of the screw 6 in the resin flow direction 8 of the screw 6 from the upstream end with respect to the raw material flow direction of the first supply port 2 of the twin screw extruder 1. The length to the tip. The screw outer diameter D is a rotational diameter (screw diameter). The rotation diameter (screw diameter D) means the maximum circular diameter when a cross section is taken perpendicular to the length direction of the effective screw length when the screw 6 is rotated.

  Although it does not specifically limit about the raw material supply apparatus for supplying a raw material to a twin-screw extruder, For example, a single screw feeder, a twin screw feeder, a table feeder, a rotary feeder, a liquid supply pump etc. can be used. In particular, the loss-in-weight feeder is preferable because it has a small fluctuation error in raw material supply.

  In the method for producing the polyamide 66 resin composition according to the present embodiment, the method for supplying (C) the copper compound is not particularly limited, but a method for supplying powder, granular or lump (C) a single copper compound, (C) A method of supplying a copper compound in a state of being included in (A) polyamide 66 resin, a method of supplying (C) a copper compound in a state of being included in a polyamide resin other than (E) polyamide 66 resin, and (C) a copper compound And other compounds are preferably mixed and supplied in powder, granular or bulk form, or a combination of these forms.

  Although it does not specifically limit as a method of supplying powder, a granular form, or a lump (C) copper compound single-piece | unit, For example, (C) A copper compound is used by the arbitrary forms which acquired the copper compound etc. (C) The copper compound is used in the form of granules in a granulator such as a disk pelleter, and (C) the copper compound is used in the form of a lump using a compression molding machine or the like.

  The method of supplying the (C) copper compound in a state of being included in the (A) polyamide 66 resin is not particularly limited. For example, the (C) copper compound is contained in the polycondensation raw material or polycondensation. Examples thereof include a method using a polyamide 66 resin, a method (A) using a polyamide 66 resin and (C) a copper compound previously melt-kneaded by a compounding apparatus such as an extruder. The above two methods may be used in combination. In the latter method, it is preferable that (A) polyamide 66 resin contains polyamide 66 resin (A-2). In any method, it is more preferable that (D) a halogen compound not containing copper is contained in the polyamide 66 resin together with (C) the copper compound.

  (C) Although it does not specifically limit as a method to supply in the state which contained the copper compound in polyamide resins other than (E) polyamide 66 resin, For example, (C) copper compound is used during the polycondensation raw material or polycondensation Examples thereof include a method of using the contained (E) polyamide resin, a method of using (E) the polyamide resin and (C) a copper compound in advance by melt-kneading with a compounding device such as an extruder. The above two methods may be used in combination. In any method, it is more preferable that (D) a halogen compound not containing copper is contained in the polyamide resin together with (C) the copper compound.

  (C) Although it does not specifically limit as a method of mixing a copper compound and another compound and supplying with powder, a granular form, or a lump form, For example, (C) The copper compound and the other compound were mixed and grind | pulverized (mixing) And the order of pulverization, whichever comes first) (Powder may be pulverized in advance) (C) A copper compound and other compounds are mixed and granulated with a granulator such as a disk pelleter And (C) a method using a mixture of a copper compound and another compound and making it agglomerated with a compression molding machine or the like. In any method, it is more preferable that the other compound is (D) a halogen compound not containing copper, or (D) a halogen compound not containing copper and another compound other than that.

  There are no particular restrictions on the method of adding each component, and a method in which each component is charged from a separate raw material supply device, or all components, or any multiple components are mixed with a mixer, cone blender, etc., and then added with the raw material supply device. Conventional methods such as methods can be used. Hereinafter, the addition method of each component is demonstrated.

(Method A)
As one form of the manufacturing method of the polyamide 66 resin composition which concerns on this embodiment, (A) polyamide 66 resin and (C) copper compound are thrown in from the same 1st supply port 2 of a twin-screw extruder, ( B) A method in which glass fibers are introduced from the second supply port 3 and / or the third supply port 4 located downstream from the first supply port 2 is preferably used. By such a method, the mechanical properties of the obtained polyamide 66 resin composition tend to be more excellent.

(Method B)
Moreover, as one form of the manufacturing method of the polyamide 66 resin composition which concerns on this embodiment, (A) polyamide 66 resin, (B) glass fiber, and (C) copper compound are the same 1st of a twin-screw extruder. A method of charging from the supply port 2 is preferably used. By such a method, the productivity of the obtained polyamide 66 resin composition tends to be more excellent.

(Method C)
Furthermore, as another form of the manufacturing method of the polyamide 66 resin composition according to this embodiment, (A) the polyamide 66 resin is introduced from the first supply port 2 of the twin-screw extruder, and (b) glass fiber ( C) A method in which the copper compound and the same supply port (either one of the second supply port 3 or the third supply port 4) located downstream from the first supply port 2 are used is preferably used. By such a method, the productivity of the obtained polyamide 66 resin composition tends to be more excellent.

(Method D)
Furthermore, as another form of the manufacturing method of the polyamide 66 resin composition according to the present embodiment, from the viewpoint of productivity, (A) the polyamide 66 resin is charged from the first supply port 2 of the twin-screw extruder, (B) Glass fiber and (C) copper compound, (A) Different supply ports located downstream from the supply port charged with polyamide 66 resin (either the second supply port 3 or the third supply port 4 1) is preferably used. By such a method, the productivity of the obtained polyamide 66 resin composition tends to be more excellent.

  In the above method A to method D, from the viewpoint of productivity, a part of the (A) polyamide 66 resin charged from the first supply port 2 is separately supplied from the second supply port 3 and / or the third supply port 4. More preferably, the charging method is also used.

(Use of polyamide 66 resin composition)
The polyamide 66 resin composition obtained by the method for producing a polyamide 66 resin composition according to this embodiment can be molded into a molded body by a known method such as injection molding, extrusion molding, blow molding or the like.

  The molded product of the polyamide 66 resin composition is suitable in the fields of automobile parts, machine parts, electrical and electronic parts, and the like. Furthermore, it is more suitable for sliding application parts such as gears, cams, and bearings.

  Hereinafter, the present embodiment will be specifically described with reference to examples and comparative examples, but the present embodiment is not limited to the following examples.

First, the raw materials and measurement methods used in Examples and Comparative Examples are shown below [Raw materials]
(A) Polyamide 66 resin (a-1): Polyamide 66 resin of Production Example 1 below, relative viscosity RV: 90, moisture content: 300 ppm
(A-2): Polyamide 66 resin of Production Example 2 below, relative viscosity RV: 130, moisture content: 260 ppm
(A-3): Polyamide 66 resin, manufactured by Asahi Kasei Chemicals Corporation, trade name 1300, relative viscosity RV: 45, moisture content: 1700 ppm
(A-4): Polyamide 66 resin of Production Example 1 below, relative viscosity RV: 45, Cu concentration: 131 ppm, moisture content: 1900 ppm
(A-5): Polyamide 66 resin of Production Example 1 below, relative viscosity RV: 88, Cu concentration: 131 ppm, moisture content: 350 ppm
(A-6): Polyamide 66 resin of Production Example 1 below, relative viscosity RV: 130, Cu concentration: 131 ppm, moisture content: 210 ppm
(B) Glass fiber (b-1): Glass fiber (GF) Product name manufactured by Nippon Electric Glass Co., Ltd. ECS03T275H / PL (average fiber diameter: 10.5 μm)
(C) Copper compound (c-1): Copper iodide, manufactured by Wako Pure Chemical Industries, Ltd., special grade.
(C-2): Copper bromide, Wako Pure Chemical Industries, Ltd., special grade.
(D) Halogen compound not containing copper (d-1): Potassium iodide, manufactured by Wako Pure Chemical Industries, Ltd., special grade.
(F) Other components (f-1): Ethylene bisstearylamide, product name Kao Wax EB-P manufactured by Kao Corporation
(G) Copper granule (g-1): Copper granule of the following manufacture example 6 Cu content 3.3%
(H) Copper master batch (h-1): Copper master batch of Production Example 7 below Cu content 0.67%

[Production Example 1] Production of a-1 15 kg of an aqueous solution containing 50 parts by mass of an equimolar salt of hexamethylenediamine and adipic acid was prepared. Next, the above aqueous solution was charged in a 40 L autoclave having a stirring device and having a nozzle extracted at the bottom, and the aqueous solution was sufficiently stirred at 50 ° C. After sufficiently replacing the interior of the autoclave with nitrogen, the temperature in the autoclave was increased from 50 ° C. to about 270 ° C. while stirring the aqueous solution. At that time, the pressure in the autoclave was about 1.8 MPa in terms of gauge pressure, but water was discharged from the system as needed so that the pressure did not exceed 1.8 MPa. The polymerization time was adjusted so that the relative viscosity of the polyamide 66 resin (measured by a method according to RV, ASTM D789) was about 45. After the polymerization in the autoclave was completed, the polyamide 66 resin was sent out in a strand form from the lower nozzle, and after cooling with water and cutting, a pellet-like polyamide 66 resin was obtained.

  This polyamide 66 resin was put into a 10,000 L solid phase polymerization apparatus, and sufficient nitrogen substitution was performed. Thereafter, solid state polymerization is performed for a predetermined time while flowing an internal temperature of the apparatus of 180 ° C. to 190 ° C. and nitrogen at 500 L / min, to obtain a polyamide 66 resin having the relative viscosity RV of 90, which is (a-1). It was.

  It was 300 ppm when the moisture content of the obtained polyamide 66 resin was measured by the method prescribed | regulated to JISK6920.

[Production Example 2] Production of a-2 Polyamide having a relative viscosity RV of 130 in the same manner as in Production Example 1 except that the time for solid phase polymerization was extended so that the relative viscosity RV was 130. 66 resin was obtained. It was 260 ppm when the moisture content of the obtained polyamide 66 resin was measured by the method prescribed | regulated to JISK6920.

[Production Example 3] Production of a-4 15 kg of an aqueous solution containing 50 parts by mass of hexamethylenediamine and equimolar salts of adipic acid, and further containing 0.15 parts by mass of potassium iodide and 0.02 parts by mass of copper iodide Was prepared. Next, the above aqueous solution was charged in a 40 L autoclave having a stirring device and having a nozzle extracted at the bottom, and the aqueous solution was sufficiently stirred at 50 ° C. After sufficiently replacing the interior of the autoclave with nitrogen, the temperature in the autoclave was increased from 50 ° C. to about 270 ° C. while stirring the aqueous solution. At that time, the pressure in the autoclave was about 1.8 MPa in terms of gauge pressure, but water was discharged from the system as needed so that the pressure did not exceed 1.8 MPa. The polymerization time was adjusted so that the relative viscosity of the polyamide 66 resin (measured by a method according to RV, ASTM D789) was about 43. After completion of the polymerization in the autoclave, the polyamide 66 resin was sent out in a strand form from the lower nozzle, and after water cooling and cutting, the above-mentioned (a-4) pellet-like polyamide 66 polymer was obtained.

  The moisture content of the obtained polyamide 66 resin was measured by the method specified in JIS K6920 and found to be 1900 ppm.

[Production Example 4] Production of a-5 The (a-4) polyamide 66 polymer obtained in Production Example 3 was charged into a 10000 L solid-phase polymerization apparatus, followed by sufficient nitrogen substitution. Thereafter, solid state polymerization was carried out for a predetermined time while flowing the apparatus at an internal temperature of 180 ° C. to 190 ° C. and nitrogen at a rate of 500 L / min. It was.
It was 350 ppm when the moisture content of the obtained polyamide 66 resin was measured by the method prescribed | regulated to JISK6920.

[Production Example 5] Production of a-6 Polyamide having a relative viscosity RV of 130 in the same manner as in Production Example 4 except that the time for solid phase polymerization was extended so that the relative viscosity RV was 130. 66 resin was obtained. It was 210 ppm when the moisture content of the obtained polyamide 66 resin was measured by the method prescribed | regulated to JISK6920.

[Production Example 6] Production of copper granule g-1 (d-1) 80 parts by mass of potassium iodide and (f-1) 10 parts by mass of ethylenebisstearylamide are mixed so that the maximum particle size is 20 μm or less. By grinding, a mixture of potassium iodide and ethylene bisstearylamide was obtained. (C-1) 10 parts by mass of CuI was thoroughly mixed with the mixture, and granulated with a disk pelleter (F5-11-175 manufactured by Fuji Powder Co., Ltd.) to obtain copper granules g-1.

[Production Example 7] Production of copper masterbatch h-1 20 parts by mass of copper granule (g-1) of Production Example 6 is blended with 80 parts by mass of polyamide 66 resin (a-3), and a twin-screw extruder. Using a (TEM35φ twin screw extruder manufactured by Toshiba Machine Co., Ltd.), a master batch h-1 was obtained by melt kneading under the conditions of a screw rotation speed of 200 rpm and a discharge rate of 90 kg / h. Melt kneading with a twin screw extruder could be carried out stably.

〔Measuring method〕
<(1) Relative viscosity>
The relative viscosity RV of the polyamide 66 resin composition was measured according to ASTM D789. Specifically, 90% formic acid was used as a solvent, and measurement was performed at a concentration of 3 g sample / 30 ml formic acid under a temperature condition of 25 ° C. In addition, relative viscosity is the average value of the measured relative viscosity by extracting the pellets every hour from the start of production to the end of production from the pellets continuously produced in the working examples and comparative examples. The maximum and minimum values were obtained. The evaluation results are shown in Table 1.

<(2) Tensile strength and tensile modulus>
Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), cylinder temperature 290 ° C., mold temperature 80 ° C., injection pressure 65 MPa, injection time 25 seconds, cooling time 20 seconds, and A multi-purpose test piece A type conforming to ISO 3167 was molded from a polyamide 66 resin composition under molding conditions of a screw rotation speed of 200 rpm to obtain a test piece.

  The obtained test piece was subjected to a tensile test using an autograph (AG-5000D type, manufactured by Shimadzu Corporation) in accordance with ISO 527, and the tensile strength and the tensile modulus were measured.

<(3) Vibration fatigue characteristics>
For the multi-purpose specimen A type obtained by the above measuring method (2), using a hydraulic servo fatigue tester EHF-50-10-3 manufactured by Kinomiya Manufacturing Co., Ltd. A tensile load of 55 MPa was applied with a wave, and the number of times of fracture was determined.

<(4) Strength half-life>
The multipurpose test specimen A obtained by the measurement method (2) was treated in a hot air oven at 180 ° C. for a predetermined time, and then the tensile strength was measured in the same manner as the measurement method (2). The tensile strength after heat treatment relative to the tensile strength before heat treatment was calculated as the tensile strength retention, and the heat treatment time (hour) at which the tensile strength retention was 50% was defined as the strength half-life.

<(5) Friction coefficient and wear depth>
Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), cylinder temperature 290 ° C., mold temperature 80 ° C., injection pressure 65 MPa, injection time 15 seconds, cooling time 15 seconds, and A flat plate having a width of 80 mm, a length of 120 mm, and a thickness of 8 mm was molded from the polyamide 66 resin composition under molding conditions of a screw rotational speed of 200 rpm. Cutting was performed in the direction perpendicular to the molding flow direction from the center of the flat plate to obtain a test piece having a width of 8 mm, a length of 80 mm, and a thickness of 4 mm.

  The test piece thus obtained was subjected to a load of 1 kg, a linear velocity of 50 mm / sec, a reciprocating distance of 20 mm, an environmental temperature of 23 ° C., an environment using a reciprocating friction and wear tester “AFT-15MS type” manufactured by Toyo Seimitsu The coefficient of friction was measured by reciprocating 5000 times at a humidity of 50%. Moreover, the abrasion depth of the test piece after a test was measured using the Tokyo Seimitsu Co., Ltd. surface roughness measuring machine (Surfcom), and the largest value was set to the abrasion depth among three places measurement. As a counterpart material used for the evaluation of the sliding properties of the test piece, a SUS304 test piece (sphere having a diameter of 5 mm) was used.

[Example 1]
A polyamide 66 resin composition was prepared using a TEM35φ twin-screw extruder manufactured by Toshiba Machine Co., Ltd. A schematic configuration of the twin screw extruder is shown in FIG. In addition, a digital vacuum gauge (manufactured by Vacuum Brand, model number DVR2) for measuring the degree of vacuum was installed at the vacuum vent port.
A specific manufacturing method will be described below. The set temperature of each barrel of the extruder was set to 310 degrees. Further, the screw rotation speed was adjusted to 200 rpm and the discharge amount was 90 kg / h. Further, the set value of the degree of vent vacuum was set to 200 hPa, and the degree of vacuum was adjusted so that the digital vacuum gauge became 200 hpa. The value 3 minutes after the vent vacuum reached the set value was measured as the initial measured value of the vent vacuum. Further, the vent vacuum was confirmed at 45 minute intervals in order to follow the change in vent vacuum over time. Under these conditions, after dry blending (A) 79.97% by mass of (a-1) as polyamide 66 resin and (C) 0.03% by mass of (c-1) as a copper compound, It was supplied from the main feed port provided in the most upstream part. From the second supply port 3, (b-1) was supplied as 20% by mass as (b) glass fiber.

  And the strand extruded from the die head nozzle (4 mm (PHI) x15 hole) provided in the most downstream part was cooled with water, and it cut with the strand cutter, and obtained the pellet of the polyamide 66 resin composition. This operation was performed continuously for 8 hours. During this period, the degree of vacuum was controlled and recorded so as to be 180 to 240 hpa, and adjustments were made. The obtained polyamide 66 resin composition pellets were used for evaluation by the above evaluation method.

[Example 2]
Other conditions were used, except that (a-1) was used instead of 79.97% by mass, (a-2) was used at 39.985% by mass, and (a-3) was used at 39.985% by mass. As in Example 1, polyamide 66 resin composition pellets were obtained and evaluated. The evaluation results are shown in Table 1.

[Comparative Example 1]
Except that (c-1) was not added and the addition amount of (a-1) was 80% by mass, other conditions were obtained in the same manner as in Example 1 to obtain a polyamide 66 resin composition pellet. Evaluated. The evaluation results are shown in Table 1.

[Comparative Example 2]
Polyamide 66 was prepared in the same manner as in Example 2 except that (c-1) was not added and the amount of (a-2) added was 40 mass% and (a-3) was 40 mass%. Resin composition pellets were obtained and evaluated. The evaluation results are shown in Table 1.

[Comparative Example 3]
Except for setting the screw rotation speed to 300 rpm, other conditions were the same as in Example 1 to obtain a polyamide 66 resin composition pellet, and this was evaluated. The evaluation results are shown in Table 1.

[Comparative Example 4]
Except that the degree of vent vacuum was set to 400 hPa, pellets of a polyamide 66 resin composition were obtained in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 1.

[Comparative Example 5]
Except for managing the upper limit of the vent vacuum so as to be 180 to 300 hpa, pellets of a polyamide 66 resin composition were obtained in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 1.

Example 3
Except that the amount of (c-1) added was 0.005% by mass, a polyamide 66 resin composition pellet was obtained in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 1.

Example 4
Except that the amount of (c-1) added was 0.1% by mass, a polyamide 66 resin composition pellet was obtained and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 5
Except that (c-2) was used instead of (c-1), a polyamide 66 resin composition pellet was obtained in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 1.

Example 6
Except that the supply port of (b-1) was changed to the first supply port 2, a polyamide 66 resin composition pellet was obtained and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 7
The polyamide 66 resin composition was prepared in the same manner as in Example 1 except that the dry blending of (a-1) and (c-1) was not performed and the supply port of (c-1) was changed to the second supply port 3. Pellets were obtained and evaluated. The evaluation results are shown in Table 1.

Example 8
Except that the supply port of (b-1) was changed to the third supply port 4, pellets of polyamide 66 resin composition were obtained in the same manner as in Example 7, and this was evaluated. The evaluation results are shown in Table 1.

Example 9
Except that the supply port of (c-1) was changed to the third supply port 4, pellets of polyamide 66 resin composition were obtained in the same manner as in Example 7 and evaluated. The evaluation results are shown in Table 1.

Example 10
Polyamide in the same manner as in Example 8 except that 69.97% by mass of (a-1) was charged from the first supply port 2 and 10% by mass of (a-1) was charged from the second supply port 3. 66 resin composition pellets were obtained and evaluated. The evaluation results are shown in Table 1.

  As shown in Table 1 above, Examples 1 and 2 both have practically sufficient tensile strength and tensile elastic modulus (also referred to as “mechanical strength”), and are obtained by melt kneading based on the result of relative viscosity. A polyamide 66 resin composition having a small decrease in molecular weight and showing more stable quality was obtained.

  In Comparative Examples 1 and 2, since the copper component was not added, a decrease in molecular weight was observed, indicating that the tensile properties and friction and wear properties were inferior.

  In Comparative Example 3, since the resin temperature was high, an excessive decrease in molecular weight was observed, indicating that the tensile physical properties and friction and wear properties were inferior.

  In Comparative Example 4, since the vent vacuum was low, an excessive decrease in molecular weight was observed, indicating that the tensile properties and friction and wear properties were inferior.

  In Comparative Example 5, since the maximum value of the degree of vent vacuum was large, stable molecular weight pellets could not be obtained continuously, indicating that the tensile properties and frictional wear characteristics were inferior.

  In Examples 3 and 4, it was shown that pellets were obtained in which a decrease in molecular weight could be suppressed compared to Comparative Example 1 depending on the amount of (c-1) added.

  In Example 5, it was shown that the addition of (c-2) yielded pellets in which the decrease in molecular weight was suppressed as compared with Comparative Example 1.

In Examples 6-9, it was shown that the effect of an Example of this application is exhibited irrespective of the supply position of (b-1) glass fiber and (c-1) copper component.

  In Example 10, it was shown that by dividing and supplying the (A) polyamide 66 resin, the resin temperature was reduced, the molecular weight suppression effect was further improved, and various physical properties were superior to Example 1. .

Example 11
(A) 79.73 mass% of (a-1) as polyamide 66 resin, 0.03 mass% of (c-1) as (C) copper compound, and (D) halogen compound not containing copper In the same manner as in Example 1 except that 0.24% by mass of (d-1) was dry blended, pellets of a polyamide 66 resin composition were obtained and evaluated. The evaluation results are shown in Table 2.

Example 12
Other conditions were used, except that (a-1) was used instead of 79.73% by mass, (a-2) was used at 39.865% by mass, and (a-3) was used at 39.865% by mass. As in Example 11, polyamide 66 resin composition pellets were obtained and evaluated. The evaluation results are shown in Table 2.

[Comparative Example 6]
Except for setting the screw rotation speed to 300 rpm, other conditions were the same as in Example 11 to obtain a polyamide 66 resin composition pellet, which was evaluated. The evaluation results are shown in Table 2.

[Comparative Example 7]
Except that the degree of vent vacuum was 400 hPa, pellets of a polyamide 66 resin composition were obtained under the same conditions as in Example 11 and evaluated. The evaluation results are shown in Table 2.

[Comparative Example 8]
Except for managing the upper limit of the vent vacuum so as to be 180 to 320 hpa, pellets of the polyamide 66 resin composition were obtained in the same manner as in Example 11 and evaluated. The evaluation results are shown in Table 2.

  As shown in Table 2 above, in Examples 11 and 12, both have practically sufficient mechanical strength, less molecular weight decrease due to melt-kneading than the result of relative viscosity, and exhibit more stable quality. A polyamide 66 resin composition was obtained.

  In Comparative Example 6, since the resin temperature was high, an excessive decrease in molecular weight was observed, indicating that the tensile physical properties and friction and wear properties were inferior.

  In Comparative Example 7, since the vent vacuum was low, an excessive decrease in molecular weight was observed, indicating that the tensile properties and friction and wear properties were inferior.

  In Comparative Example 8, since the maximum value of the vent vacuum was large, stable molecular weight pellets could not be obtained continuously, indicating that the tensile properties and frictional wear properties were inferior.

Example 13
(C) Example 1 except that (a) 80% by mass of (a-5) polyamide 66 resin containing a copper compound and (D) a halogen compound not containing copper was used instead of the dry blend product. Similarly, pellets of a polyamide 66 resin composition were obtained and evaluated. The evaluation results are shown in Table 3.

Example 14
The other conditions were the same as in Example 13 except that (a-5) was replaced by 80% by mass and (a-4) was used by 40% by mass and (a-6) was by 40% by mass. Polyamide 66 resin composition pellets were obtained and evaluated. The evaluation results are shown in Table 3.

[Comparative Example 9]
Except for setting the screw rotation speed to 300 rpm, the other conditions were the same as in Example 13 to obtain a polyamide 66 resin composition pellet, which was evaluated. The evaluation results are shown in Table 3.

[Comparative Example 10]
Except that the degree of vent vacuum was set to 400 hPa, pellets of a polyamide 66 resin composition were obtained in the same manner as in Example 13 and evaluated. The evaluation results are shown in Table 3.

[Comparative Example 11]
Except for controlling the control range of the upper limit of the vent vacuum so as to be 180 to 300 hpa, other conditions were obtained in the same manner as in Example 13 to obtain polyamide 66 resin composition pellets, which were evaluated. The evaluation results are shown in Table 3.

  As shown in Table 3 above, in Examples 13 and 14, both have sufficient mechanical strength for practical use, less molecular weight reduction due to melt kneading than the result of relative viscosity, and exhibit more stable quality. A polyamide 66 resin composition was obtained.

  In Comparative Example 9, since the resin temperature was high, an excessive decrease in molecular weight was observed, indicating that the tensile physical properties and friction and wear properties were inferior.

  In Comparative Example 10, since the vent vacuum was low, an excessive decrease in molecular weight was observed, indicating that the tensile properties and friction and wear properties were inferior.

  In Comparative Example 11, since the maximum value of the degree of vent vacuum was large, stable molecular weight pellets could not be obtained continuously, indicating that the tensile properties and frictional wear characteristics were inferior.

Example 15
(A) 79.70% by mass of (a-5) as a polyamide 66 resin, (G) a copper granule containing (C) a copper compound, (D) a halogen compound not containing copper, and (F) another compound ( Except for dry blending g-1) at 0.30% by mass, a polyamide 66 resin composition pellet was obtained and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4.

Example 16
Other conditions were used, except that (a-5) was replaced by 79.70% by weight, and (a-4) was used by 39.85% by weight and (a-6) by 39.85% by weight. In the same manner as in Example 15, pellets of a polyamide 66 resin composition were obtained and evaluated. The evaluation results are shown in Table 4.

[Comparative Example 12]
Except for setting the screw rotation speed to 300 rpm, the other conditions were the same as in Example 15 to obtain a polyamide 66 resin composition pellet, which was evaluated. The evaluation results are shown in Table 4.

[Comparative Example 13]
Except that the degree of vent vacuum was 400 hPa, pellets of a polyamide 66 resin composition were obtained under the same conditions as in Example 15 and evaluated. The evaluation results are shown in Table 4.

[Comparative Example 14]
Except for managing the upper limit of the vent vacuum so as to be 180 to 320 hpa, other conditions were used in the same manner as in Example 15 to obtain polyamide 66 resin composition pellets, which were evaluated. The evaluation results are shown in Table 4.

X concentration: Concentration of halogen component

  As shown in Table 4 above, in Examples 15 and 16, both have practically sufficient mechanical strength, less molecular weight reduction due to melt-kneading than the result of relative viscosity, and exhibit more stable quality. A polyamide 66 resin composition was obtained.

  In Comparative Example 12, since the resin temperature was high, an excessive decrease in molecular weight was observed, indicating that the tensile properties and friction and wear properties were inferior.

  In Comparative Example 13, since the vent vacuum was low, the molecular weight was excessively decreased, indicating that the tensile properties and the friction and wear characteristics were inferior.

  In Comparative Example 14, since the maximum value of the degree of vent vacuum was large, stable molecular weight pellets could not be obtained continuously, indicating that the tensile properties and frictional wear characteristics were inferior.

Example 17
(A) 78.50 mass% of (a-5) as polyamide 66 resin, (H) copper masterbatch containing (C) a copper compound, (D) a halogen compound not containing copper, and (F) other compounds Except for dry blending 1.50% by mass of (h-1), polyamide 66 resin composition pellets were obtained and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.

Example 18
Other conditions were used except that (a-5) was replaced by 78.50% by mass, (a-4) was used by 39.25% by mass, and (a-6) by 39.25% by mass. In the same manner as in Example 17, pellets of a polyamide 66 resin composition were obtained and evaluated. The evaluation results are shown in Table 5.

[Comparative Example 15]
Except for the screw rotation speed being 300 rpm, the other conditions were the same as in Example 17 to obtain a polyamide 66 resin composition pellet, which was evaluated. The evaluation results are shown in Table 5.

[Comparative Example 16]
Except that the degree of vent vacuum was set to 400 hPa, pellets of a polyamide 66 resin composition were obtained in the same manner as in Example 17 and evaluated. The evaluation results are shown in Table 5.

[Comparative Example 17]
Except for managing the upper limit of the vent vacuum so as to be 180 to 325 hpa, pellets of a polyamide 66 resin composition were obtained in the same manner as in Example 17 and evaluated. The evaluation results are shown in Table 5.

  As shown in Table 5 above, in Examples 17 and 18, both have practically sufficient mechanical strength, less decrease in molecular weight due to melt kneading than the result of relative viscosity, and show more stable quality. A polyamide 66 resin composition was obtained.

  In Comparative Example 15, since the resin temperature was high, an excessive decrease in molecular weight was observed, indicating that the tensile physical properties and friction and wear properties were inferior.

  In Comparative Example 16, since the degree of vent vacuum was low, an excessive decrease in molecular weight was observed, indicating that the tensile properties and friction and wear characteristics were inferior.

  In Comparative Example 17, since the maximum value of the degree of vent vacuum was large, stable molecular weight pellets could not be obtained continuously, indicating that the tensile properties and frictional wear characteristics were inferior.

  The method for producing a polyamide 66 resin composition of the present invention has industrial applicability as a production technology for a polyamide 66 resin composition suitable for automobile parts, machine parts, electrical and electronic parts, and the like.

1 Exterior 2 First supply port 3 Second supply port 4 Third supply port 5 Vacuum vent port 6 Screw 7 Resin flow direction L Screw effective length D Screw diameter

Claims (15)

(A) a polyamide 66 resin, (B) glass fiber, and (C) a copper compound are melt-kneaded in an extruder to extrude the polyamide 66 resin composition,
The vent vacuum degree of the extruder in the extrusion step is 30 hPa or more and 350 hPa or less,
In the extrusion step, the fluctuation range of the vent vacuum degree with respect to the initial measured value of 100% of the vent vacuum degree is 75% or more and 125% or less,
The temperature of the polyamide 66 resin composition in the extrusion step is 265 ° C. or higher and 350 ° C. or lower,
A method for producing a polyamide 66 resin composition.   The method for producing a polyamide 66 resin composition according to claim 1, wherein the (A) polyamide 66 resin contains one or more types of polyamide 66 resins (A-1) having a relative viscosity RV of 65 or more and 250 or less.   The manufacturing method of the polyamide 66 resin composition of Claim 1 or 2 in which the said (A) polyamide 66 resin contains 1 or more types of polyamide 66 resin (A-2) whose relative viscosity RV is 25-65. In the extrusion process,
For a total amount of 100 parts by mass of the (A) polyamide 66 resin and the (B) glass fiber,
(A) 50 parts by weight or more and 90 parts by weight or less of the polyamide 66 resin;
The manufacturing method of the polyamide 66 resin composition of any one of Claims 1-3 which melt-kneads said (B) 10 mass parts or more and 50 mass parts or less of glass fiber.   The manufacturing method of the polyamide 66 resin composition of any one of Claims 1-4 whose relative viscosity RV of the obtained polyamide 66 resin composition is 55-240.   The manufacturing method of the polyamide 66 resin composition of any one of Claims 1-5 whose moisture content contained in the obtained polyamide 66 resin composition is 100 ppm or more and less than 1000 ppm.   The manufacturing method of the polyamide 66 resin composition of any one of Claims 1-6 whose density | concentration [Cu] of the copper component contained in the obtained polyamide 66 resin composition is 80 ppm or more and less than 300 ppm.   The manufacturing method of the polyamide 66 resin composition of any one of Claims 1-7 whose density | concentration [X] of the halogen component contained in the obtained polyamide 66 resin composition is 40 ppm or more and 9000 ppm or less.   The ratio ([Cu] / [X]) of the concentration [Cu] of the copper component and the concentration [X] of the halogen component contained in the obtained polyamide 66 resin composition is 0.02 or more and 0.25 or less. The manufacturing method of the polyamide 66 resin composition of any one of Claims 1-8. The (A) polyamide 66 resin and the (C) copper compound are charged from the same supply port of the extruder,
The said (B) glass fiber is injected | thrown-in from the supply port located downstream from the said supply port which injected | thrown-in the said (A) polyamide 66 resin and the said (C) copper compound. A process for producing the polyamide 66 resin composition described in 1.   The said (A) polyamide 66 resin, the said (B) glass fiber, and the said (C) copper compound are thrown in from the same supply port of the said extruder, The any one of Claims 1-9. Of producing a polyamide 66 resin composition. (A) the polyamide 66 resin is charged from the supply port of the extruder,
The (B) glass fiber and the (C) copper compound are charged from the same supply port located downstream from the supply port charged with the (A) polyamide 66 resin. The manufacturing method of the polyamide 66 resin composition of any one. (A) the polyamide 66 resin is charged from the supply port of the extruder,
The (B) glass fiber and the (C) copper compound are charged from different supply ports located downstream from the supply port charged with the (A) polyamide 66 resin. The manufacturing method of the polyamide 66 resin composition of any one.   The method for producing a polyamide 66 resin composition according to any one of claims 1 to 13, wherein the halogen compound not containing (D) copper is further melt-kneaded.   The manufacturing method of the polyamide 66 resin composition of any one of Claims 1-14 which does not contain a higher fatty acid metal salt at the time of melt-kneading.