JP5009336B2 - Polyacetal resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a polyacetal resin composition, a method for producing the same, an injection-molded article, and a gear.

  Since polyacetal resin is excellent in the balance of mechanical strength, chemical resistance and slidability, and its processability is easy, as a typical engineering plastics, mechanical parts such as electrical equipment, gears of electrical equipment, It is widely used mainly for mechanical parts including automobile parts and other precision machines. In particular, polyacetal resin is often used for precision mechanism parts such as electric devices, automobile parts, gears, and cams. In that case, the polyacetal resin is not only slidable but also has long-term durability such as a balance of mechanical properties such as rigidity, strength, and toughness, and that there is no tooth deflection and tooth spill when used in gears. Sex is also required.

  Therefore, conventionally, as a general method, a method in which an inorganic filler such as glass fiber, talc, wollastonite, carbon fiber or the like is blended with polyacetal is used, thereby improving various performances of the polyacetal resin. It has been. However, when glass fiber or inorganic filler is blended with polyacetal resin, it is effective in improving mechanical properties such as rigidity and strength, but the inherent characteristics of polyacetal resin are slidability, creep life and fatigue resistance. Long-term characteristics such as property and toughness may be significantly impaired, and it is not always an effective method. In addition, when a large amount of glass fiber or inorganic filler is blended in the polyacetal resin, the thermal stability of the polyacetal resin may be lowered, which may adversely affect moldability or heat aging resistance.

  By the way, the mechanism parts as described above are generally manufactured by an injection molding method using an injection molding machine, and the obtained molded product is often used as a drive mechanism part of a precision instrument. At that time, a lubricant such as grease is applied to the molded product for the purpose of maintaining the lubricity of the mechanical parts. The term “grease” as used herein refers to silicon-based, soap-based, and olefin-based lubricating oils used for the lubrication of resin gears. In particular, when the molded product is used as a component inside the OA device, the time for exposure to high temperatures becomes longer. Therefore, there is an increasing demand for a molded product that can keep the change in characteristics to a minimum even when exposed to a high temperature environment for a long time in a state where grease is applied.

  In order to meet these demands, a surface treatment is performed on a granular inorganic filler represented by calcium carbonate with a fatty acid and a metal salt thereof, and the inorganic filler after the surface treatment is melt-kneaded into a polyacetal resin. A polyacetal resin composition comprising calcium carbonate having a specific aspect ratio, an organic acid, and a fatty acid ester, the amount ratio of Na to Ca in the composition; A composition (see Patent Document 3) in which the ratio of the amount of Sr is a specific ratio is disclosed.

Japanese Patent Publication No. 8-30137 Japanese Patent No. 3140502 International Publication No. 2005/071011

  However, according to the methods described in Patent Documents 1 to 3, although a polyacetal resin composition having an excellent balance of mechanical properties such as rigidity, toughness (ductility) and creep resistance can be obtained, from the polyacetal resin composition The obtained molded product is not sufficiently strong in gear strength after being exposed to a high temperature environment for a long time in a state where grease is applied, so that it cannot be fully put into practical use.

  Therefore, the present invention has been made in view of the above circumstances, and has an excellent balance of mechanical properties represented by rigidity and toughness, and has been exposed to a high temperature environment for a long time in a state where grease is applied. However, it aims at providing the polyacetal resin composition which can form the molded article which hold | maintained rigidity and the reduction | decrease of the gear characteristic was suppressed, and its manufacturing method.

  The present inventors diligently studied to solve the above problems. As a result, with respect to 100 parts by mass of the polyacetal resin, a predetermined amount of light calcium carbonate having a predetermined particle size and pH, a specific fatty acid, and a specific fatty acid calcium salt are blended. The present inventors have found that a polyacetal resin composition in which the mass ratio of calcium is in a specific range and the mass ratio of the calcium salt of the fatty acid to the fatty acid is in the specific range can solve the above problems, and the present invention has been completed. .

That is, the present invention is as follows.
[1] 100 parts by mass of a polyacetal resin, 5 to 50 parts by mass of light calcium carbonate having an average particle diameter of 50 nm to 500 nm, a pH of 9.2 to 10.0, and not surface-treated, A fatty acid having 12 to 30 carbon atoms and a fatty acid calcium salt, the carbon number X of the fatty acid and the carbon number Y of the fatty acid calcium salt satisfy the condition represented by the following formula (1), and the light The polyacetal resin composition whose mass ratio of the said fatty acid with respect to calcium carbonate is 0.020-0.060, and whose mass ratio of the said fatty acid with respect to the said fatty acid calcium salt is 3-15.
1 ≦ Y−X ≦ 4 (1)
[2] The polyacetal resin composition according to [1], wherein a most probable void radius of the light calcium carbonate is 0.12 μm or more and 0.16 μm or less.
[3] The polyacetal resin composition according to [1] or [2], wherein the polyacetal resin includes a polyacetal copolymer having a melting point of 164 ° C. or higher and 173 ° C. or lower.
[4] The polyacetal resin includes a polyacetal copolymer having a melting point of 167 ° C. or higher and 173 ° C. or lower. Any one of [1] to [3], and [5] 100 parts by mass of the polyacetal resin. The polyacetal resin composition according to any one of [1] to [4], containing 0.01 to 3 parts by mass of a polyamide resin.
[6] A method for producing a polyacetal resin composition according to any one of [1] to [4], wherein the average particle size is from 50 nm to 500 nm, and the pH is from 9.2 to 10.0. And the light calcium carbonate which is not surface-treated, a C12-30 fatty acid, and a fatty acid calcium salt are mixed with a blender in a solid phase to obtain a mixture, the mixture, a polyacetal resin, Are continuously fed from different feeders into the barrel of the extruder and melt-kneaded to obtain a melt-kneaded product, and the melt-kneaded product is continuously extruded from the die of the extruder. The method for producing a polyacetal resin composition, wherein the carbon number X of the fatty acid and the carbon number Y of the fatty acid calcium salt satisfy the condition represented by the following formula (1).
1 ≦ Y−X ≦ 4 (1)
[7] A method for producing the polyacetal resin composition of [5], wherein the average particle size is from 50 nm to 500 nm, the pH is from 9.2 to 10.0, and the surface treatment is not performed. Mixing a light calcium carbonate, a fatty acid having 12 to 30 carbon atoms, a fatty acid calcium salt, and a resin containing a polyamide resin with a blender in a solid phase to obtain a mixture, the mixture, and a polyacetal resin; Are continuously fed from different feeders into the barrel of the extruder and melt-kneaded to obtain a melt-kneaded product, and the melt-kneaded product is continuously extruded from the die of the extruder. The method for producing a polyacetal resin composition, wherein the carbon number X of the fatty acid and the carbon number Y of the fatty acid calcium salt satisfy the condition represented by the following formula (1).
1 ≦ Y−X ≦ 4 (1)
[8] The method for producing a polyacetal resin composition according to [7], wherein the resin containing the polyamide resin is a melt-kneaded product of the polyamide resin and the polyacetal resin.
[9] An injection-molded article comprising the polyacetal resin composition according to any one of [1] to [5].
[10] A gear comprising the polyacetal resin composition according to any one of [1] to [5].

  According to the present invention, it has an excellent balance of mechanical properties represented by rigidity and toughness, retains rigidity even after being exposed to a high temperature environment for a long time with grease applied, and has gear characteristics. It is possible to provide a polyacetal resin composition capable of forming a molded article in which a decrease in the temperature is suppressed and a method for producing the same.

It is a schematic diagram of the twin-screw extruder used in the Example.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.

The polyacetal resin composition of this embodiment has 100 parts by mass of a polyacetal resin, an average particle diameter of 50 nm to 500 nm, a pH by boiling extraction of 9.2 to 10.0, and is surface-treated. 5 to 50 parts by weight of light calcium carbonate, a fatty acid having 12 to 30 carbon atoms, and a fatty acid calcium salt, and the carbon number X of the fatty acid and the carbon number Y of the fatty acid calcium salt are represented by the following formula (1 ), The mass ratio of the fatty acid to the light calcium carbonate is from 0.020 to 0.060, and the mass ratio of the fatty acid to the fatty acid calcium salt is from 3 to 15, It is a thing.
1 ≦ X−Y ≦ 4 (1)
Here, the pH of calcium carbonate is obtained by the following test method (A). That is, 5.0 g of a sample of calcium carbonate is weighed into an Erlenmeyer flask, 100 mL of distilled water is added thereto, stoppered, and shaken for 1 minute. Next, after standing for 30 minutes, the pH of the suspension obtained by further shaking for 10 seconds is measured.

  Examples of the polyacetal resin (I) according to this embodiment include polyacetal homopolymers and polyacetal copolymers. The polyacetal homopolymer is obtained by homopolymerizing a formaldehyde monomer or a cyclic oligomer of formaldehyde such as a trimer (trioxane) or tetramer (tetraoxane). Thus, the polyacetal homopolymer consists essentially of oxymethylene units. The polyacetal copolymer includes formaldehyde monomers or cyclic oligomers of formaldehyde such as trimers (trioxane) and tetramers (tetraoxane), ethylene oxide, propylene oxide, epichlorohydrin, 1,3-dioxolane, 1,4- It is obtained by copolymerizing a glycol such as butanediol formal, a cyclic ether such as a cyclic formal of diglycol, or a cyclic formal. Further, as a polyacetal copolymer, a branched polyacetal copolymer obtained by copolymerizing a monomer of formaldehyde and / or a cyclic oligomer of formaldehyde and a monofunctional glycidyl ether, and a polyfunctional glycidyl ether are copolymerized. The resulting polyacetal copolymer having a crosslinked structure can also be used.

  Furthermore, the polyacetal resin (I) is obtained by polymerizing a formaldehyde monomer or a formaldehyde cyclic oligomer in the presence of a compound having a functional group such as a hydroxyl group at both ends or one end, such as polyalkylene glycol. It may be a polyacetal homopolymer having a block component. Similarly, polyacetal resin (I) is a monomer of formaldehyde or its trimer (trioxane) or tetramer in the presence of a compound having a functional group such as a hydroxyl group at both ends or one end, such as hydrogenated polybutadiene glycol. It may be a polyacetal copolymer having a block component obtained by copolymerizing a cyclic oligomer of formaldehyde such as tetramer and a cyclic ether or cyclic formal. As described above, any of a polyacetal homopolymer and a polyacetal copolymer can be used as the polyacetal resin (I) according to this embodiment. Moreover, polyacetal resin (I) is used individually by 1 type or in combination of 2 or more types. The polyacetal resin (I) preferably contains a polyacetal copolymer.

  When a polyacetal copolymer is obtained using trioxane, the comonomer such as 1,3-dioxolane is generally 0.1 to 60 mol%, preferably 0.1 to 20 mol%, more preferably 100 mol% of trioxane. Is used in an amount of 0.13 to 10 mol%. In this embodiment, the suitable melting point of the polyacetal copolymer is 162 ° C. to 173 ° C., more preferably 167 ° C. to 173 ° C., and further preferably 167 ° C. to 171 ° C. A polyacetal copolymer having a melting point of 167 ° C. to 171 ° C. can be obtained by using about 1.3 to 3.5 mol% of a comonomer with respect to 100 mol% of trioxane.

  As the polymerization catalyst used for the polymerization of the polyacetal copolymer, cationically active catalysts such as Lewis acids, proton acids and esters or anhydrides thereof are preferable. Examples of Lewis acids include boric acid, tin, titanium, phosphorus, arsenic and antimony halides. More specifically, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, Examples thereof include phosphorus pentachloride, antimony pentafluoride, and complex compounds or salts thereof. Specific examples of the protonic acid, its ester or anhydride include perchloric acid, trifluoromethanesulfonic acid, perchloric acid-tertiary butyl ester, acetyl perchlorate, and trimethyloxonium hexafluorophosphate. Among these, boron trifluoride; boron trifluoride hydrate; and a coordination complex compound of an organic compound containing an oxygen atom or a sulfur atom and boron trifluoride are preferable. Specifically, trifluoride is used. Boron diethyl ether and boron trifluoride di-n-butyl ether can be mentioned as suitable examples.

The polyacetal copolymer can be obtained by a conventionally known method, for example, U.S. Pat. Nos. 3,027,352, 3,803,094, German Patents 1,161,421, 1,495,228, 1,720,358, Polymerization can be carried out by the methods described in the specification of US Pat. No. 3,018,898, JP-A-58-98322 and JP-A-7-70267. The polyacetal copolymer obtained by the above polymerization has a thermally unstable terminal portion [— (OCH ₂ ) _n —OH group], so that it is difficult to put it to practical use as it is. Therefore, it is preferable to perform the decomposition and removal treatment of the unstable terminal portion, and specifically, it is preferable to perform the decomposition and removal processing of the specific unstable terminal portion described below. That is, in the decomposition removal treatment of the specific unstable terminal portion, in the presence of at least one quaternary ammonium compound represented by the following general formula (2), at a temperature not lower than the melting point of the polyacetal copolymer and not higher than 260 ° C., A heat treatment is applied to the polyacetal copolymer in a molten state.

[R ¹ R ² R ³ R ⁴ N ⁺ ] _n X ^-n (2)
Here, in formula (2), R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; an aryl group having 6 to 20 carbon atoms; An aralkyl group in which at least one hydrogen atom in a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms; or at least one in an aryl group having 6 to 20 carbon atoms Represents an alkylaryl group in which a hydrogen atom is substituted with a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and the substituted or unsubstituted alkyl group is linear, branched, or cyclic. The substituent in the substituted alkyl group is a halogen atom, a hydroxyl group, an aldehyde group, a carboxyl group, an amino group, or an amide group. In the unsubstituted alkyl group, aryl group, aralkyl group, and alkylaryl group, a hydrogen atom may be substituted with a halogen atom. n shows the integer of 1-3. X represents a hydroxyl group or an acid residue of a carboxylic acid having 1 to 20 carbon atoms, a hydrogen acid other than a hydrogen halide, an oxo acid, an inorganic thioacid, or an organic thioacid having 1 to 20 carbon atoms.

The quaternary ammonium compound is not particularly limited as long as it is represented by the above general formula (2). However, from the viewpoint of more effectively and reliably achieving the above effect according to the present invention, R ¹ in the general formula (2), R ² , R ³ , and R ⁴ are each independently preferably an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms, and further R ¹ , R ² , R ³ , And at least one of R ⁴ is particularly preferably a hydroxyethyl group. Specifically, tetramethylammonium, tetoethylammonium, tetrapropylammonium, tetra-n-butylammonium, cetyltrimethylammonium, tetradecyltrimethylammonium, 1,6-hexamethylenebis (trimethylammonium), decamethylene-bis- ( Trimethylammonium), trimethyl-3-chloro-2-hydroxypropylammonium, trimethyl (2-hydroxyethyl) ammonium, triethyl (2-hydroxyethyl) ammonium, tripropyl (2-hydroxyethyl) ammonium, tri-n-butyl ( 2-hydroxyethyl) ammonium, trimethylbenzylammonium, triethylbenzylammonium, tripropylbenzylammonium, tri-n-butylbenzene Zirammonium, trimethylphenylammonium, triethylphenylammonium, trimethyl-2-oxyethylammonium, monomethyltrihydroxyethylammonium, monoethyltrihydroxyethylammonium, okdadecyltri (2-hydroxyethyl) ammonium, tetrakis (hydroxyethyl) ammonium, etc. Hydroxides of hydrochloric acid, odorous acid, hydrofluoric acid, etc .; sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, chloric acid, iodic acid, silicic acid, perchloric acid, chlorous acid, hypochlorous acid Oxo acid salts such as chlorosulfuric acid, amidosulfuric acid, disulfuric acid, tripolyphosphoric acid; thioic acid salts such as thiosulfuric acid; formic acid, acetic acid, propionic acid, butanoic acid, isobutyric acid, pentanoic acid, caproic acid, caprylic acid, capric acid Carboxylic acid salts such as benzoic acid and oxalic acid That. Among these, hydroxide (OH ⁻ ), sulfuric acid (HSO ₄ ⁻ , SO ₄ ²⁻ ), carbonic acid (HCO ₃ ⁻ , CO ₃ ²⁻ ), boric acid (B (OH) ₄ ⁻ ), and carboxylic acid The salt of is preferred. Of the carboxylic acids, formic acid, acetic acid, and propionic acid are particularly preferred. A quaternary ammonium compound is used individually by 1 type or in combination of 2 or more types. Further, in addition to the quaternary ammonium compound, amines such as ammonia and triethylamine, which are known decomposition accelerators for unstable terminals, may be used in combination.

The amount of the quaternary ammonium compound used is preferably 0.05 in terms of the amount of nitrogen derived from the quaternary ammonium compound represented by the following formula (3) with respect to the total mass of the polyacetal copolymer and the quaternary ammonium compound. It is -50 mass ppm, More preferably, it is 1-30 mass ppm.
P × 14 / Q (3)
Here, in Formula (3), P shows the density | concentration (mass ppm) with respect to the polyacetal copolymer of a quaternary ammonium compound, 14 is the atomic weight of nitrogen, Q shows the molecular weight of a quaternary ammonium compound.

  If the amount of the quaternary ammonium compound used is less than 0.05 ppm by mass, the rate of decomposition and removal of unstable ends tends to decrease, and if it exceeds 50 ppm by mass, the polyacetal copolymer after the decomposition and removal of unstable ends is removed. The color tone tends to deteriorate.

  The unstable end portion of the polyacetal resin (I) according to the present embodiment is decomposed and removed by heat treatment in a state where the polyacetal copolymer is melted at a temperature of the melting point or higher and 260 ° C. or lower. The apparatus used for the decomposition and removal treatment is not particularly limited, but an extruder, a kneader and the like are preferable. Formaldehyde generated by decomposition is usually removed under reduced pressure. There are no particular restrictions on the method of allowing the quaternary ammonium compound to be present in the polyacetal copolymer, and examples thereof include a method of adding it as an aqueous solution in the step of deactivating the polymerization catalyst and a method of spraying the polyacetal copolymer powder produced by the polymerization. Whichever method is used, the quaternary ammonium compound only needs to be present in the copolymer in the step of heat-treating the polyacetal copolymer. For example, a quaternary ammonium compound may be injected into an extruder in which a polyacetal copolymer is melt kneaded and extruded. Alternatively, when the filler or pigment is blended with the polyacetal copolymer using the extruder or the like, the quaternary ammonium compound is first attached to the resin pellet of the polyacetal copolymer, and the unstable end portion is added when the filler or pigment is blended thereafter. A decomposition and removal process may be performed.

  The unstable terminal portion can be decomposed and removed after the polymerization catalyst coexisting with the polyacetal copolymer obtained by polymerization is deactivated, or can be performed without deactivating the polymerization catalyst. Examples of the deactivation treatment of the polymerization catalyst include a method of neutralizing and deactivating the polymerization catalyst in a basic aqueous solution such as amines. When the polymerization catalyst is not deactivated, the copolymer is heated in an inert gas atmosphere at a temperature lower than the melting point of the polyacetal copolymer, and the polymerization catalyst is reduced by volatilization. It is also an effective method to do.

  By the decomposition and removal treatment of the unstable terminal portion as described above, a polyacetal copolymer having very little unstable terminal portion and excellent in thermal stability can be obtained.

  The shape of the particle | grains of the light calcium carbonate (II) which concerns on this embodiment is not specifically limited. Specific examples of the shape include a spherical shape, a cubic shape, a spinning shape, a flake shape, and an indefinite shape. Among these, from the viewpoint of reducing the anisotropy of the injection-molded product and improving the mechanical strength, a cubic shape is preferable, and the aspect ratio (the ratio of the average major axis (L) to the average minor axis (D) of the particles) More preferably, L / D) is 3 or less. The crystal form of light calcium carbonate (II) may be any of the commonly known calcite type, aragonite type and patelite type, and among these, interfacial adhesion with a polyacetal resin, From the viewpoint of improving the balance of mechanical properties of the composition, a calcite type is preferable. Light calcium carbonate (II) is not particularly limited as long as it is artificially synthesized, and preferred is colloidal calcium carbonate, precipitated calcium carbonate, or activated calcium carbonate. Among these, those produced by reacting carbon dioxide with slurry-like calcium hydroxide are particularly preferable. Light calcium carbonate (II) is used singly or in combination of two or more.

  The average particle size of light calcium carbonate (II) is from 50 nm to 500 nm, preferably from 80 nm to 300 nm, more preferably from 80 nm to 200 nm. Even after the molded product obtained from the polyacetal resin composition is exposed to a high temperature environment for a long time in a state where grease is applied, the average particle diameter of light calcium carbonate (II) is 50 nm or more. Its rigidity and toughness can be maintained at a high level. Further, since the average particle diameter of light calcium carbonate (II) is 500 nm or less, the toughness and gear of the molded product can be obtained even after being exposed to a high temperature environment for a long time in a state where grease is applied. Strength can be maintained at a high level. In addition, the average particle diameter, average major axis, and average minor axis of light calcium carbonate (II) are sampled from calcium carbonate particles to be measured by a scanning electron microscope (SEM), and the particles are scaled from 1,000 times to 5 times. Each diameter was measured from a minimum of 100 calcium carbonate particles randomly selected in the obtained image taken at 10,000 times, and obtained as an arithmetic average thereof.

  Moreover, the pH by the said test method (A) of light calcium carbonate (II) is 9.2 or more and 10.0 or less, Preferably it is 9.4 or more and 9.7 or less. It is one requirement for this pH to be 9.2 or more and 10.0 or less to achieve the object of the present invention. The most probable void radius by a mercury intrusion method using a light calcium carbonate (II) mercury porosimeter is preferably 0.12 μm or more and 0.16 μm or less. When the most probable void radius is 0.12 μm or more, there is an effect that a good dispersion is obtained in which an aggregate of calcium carbonate is hardly generated in the composition, and when it is 0.16 μm or less, the composition Even after the molded product is exposed to a high temperature environment for a long time in a state where grease is applied, the rigidity and gear strength can be maintained at a high level.

  The light calcium carbonate (II) according to the present embodiment is not subjected to surface treatment. As used herein, “surface treatment” refers to the addition of at least one known surface treatment agent, adhesive or complexing agent, and anti-aggregation agent for the purpose of preventing particle aggregation in the calcium carbonate production process. As a result, the surface of calcium carbonate is covered with the substance. Here, the surface treatment agent, the adhesive or complexing agent, and the anti-aggregation agent are, for example, 232 to “Elucidation and application technology of dispersion and aggregation, 1992” (supervised by Fumio Kitahara, published by Techno System Co., Ltd.) Examples thereof include anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants as described on page 237. Further, silane coupling agents such as aminosilane and epoxysilane, titanate coupling agents, fatty acids (saturated fatty acids and unsaturated fatty acids), aliphatic carboxylic acids, resin acids and metal soaps are exemplified. The fact that the light calcium carbonate (II) is not subjected to the surface treatment is one requirement that the polyacetal resin composition of the present embodiment achieves the object of the present invention.

  The compounding quantity of the light calcium carbonate (II) in the polyacetal resin composition of this embodiment is 5-50 mass parts with respect to 100 mass parts of polyacetal resin, Preferably it is 10-50 mass parts. The blending amount of 5 to 50 parts by mass is one requirement that the polyacetal resin composition of the present embodiment achieves the object of the present invention.

  The fatty acid (III) having 12 to 30 carbon atoms is a fatty acid having a structure in which a carboxyl group is bonded to a linear or branched aliphatic hydrocarbon group, and the total number of carbon atoms in the molecule is 12 to 30. These fatty acids are used alone or in combination of two or more. Specific examples of the fatty acid (III) include undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, pentadecylic acid, stearic acid, nanodecanoic acid, arachidic acid, behenic acid, lignoceric acid, and serotic acid. , Heptaconic acid, montanic acid, melissic acid, laceric acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, erucic acid, brassic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid.

  The fatty acid (III) may be natural or synthesized, and when the natural one is used, the polyacetal resin composition of the present embodiment is used for the fatty acid (III) and other fatty acids (III). Mixtures with natural ingredients may be included. The fatty acid (III) may be substituted with a functional group such as a hydroxy group. The fatty acid (III) may be a synthetic fatty acid obtained by carboxyl-modifying the end of uniline alcohol, which is a synthetic aliphatic alcohol. Of the above fatty acids, stearic acid and palmitic acid and mixtures of any proportions thereof are particularly preferred.

  In the polyacetal resin composition of the present embodiment, the mass ratio (III) / (II) of the fatty acid (III) having 12 to 30 carbon atoms to the light calcium carbonate (II) is 0.020 to 0.060. , Preferably 0.025 to 0.050. The mass ratio (III) / (II) value of 0.020 to 0.060 is one requirement for the polyacetal resin composition of the present embodiment to achieve the object of the present invention.

  The fatty acid calcium salt (IV) is the number of carbon atoms of the fatty acid (III), that is, the number of carbon atoms of the fatty acid (III), and the number of carbon atoms of the fatty acid calcium salt (IV), that is, the carbon of the fatty acid calcium salt (IV). When the number of atoms is Y, X and Y satisfy the above formula (1). As a combination of fatty acid (III) and fatty acid calcium salt (IV), fatty acid (III) is stearic acid, fatty acid calcium salt (IV) is calcium behenate, and fatty acid (III) is palmitic acid. A combination in which the fatty acid calcium salt (IV) is calcium stearate, a fatty acid (III) is stearic acid, a combination in which the fatty acid calcium salt (IV) is calcium behenate, and the fatty acid (III) is stearic acid, Most preferred is a combination wherein the fatty acid calcium salt (IV) is calcium behenate.

  Further, in the polyacetal resin composition of the present embodiment, the mass ratio (III) / (IV) of the fatty acid (III) to the fatty acid calcium salt (IV) is 3 to 3 from the viewpoint of exhibiting the target performance of the present invention. 15, preferably 5-13.

  The polyacetal resin composition of the present embodiment preferably contains 0.01 to 3 parts by mass of the polyamide resin (V) with respect to 100 parts by mass of the polyacetal resin (I) in order to capture formaldehyde that can be generated from the polyacetal resin. . Examples of the polyamide resin (V) include nylon 4,6, nylon 6, nylon 6,6, nylon 6,10, nylon 6,12, nylon 12, and polymers thereof such as nylon 6 / 6,6. / 6,10, nylon 6 / 6,12.

  If necessary, the polyacetal resin composition of the present embodiment further contains an antioxidant, a polymer or compound containing nitrogen reactive with formaldehyde, a formic acid scavenger, a weathering (light) stabilizer, and a release agent. It may be added in the range of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the polyacetal resin (I) as long as the achievement of the object of the invention is not impaired.

  As the antioxidant, a hindered phenol antioxidant is preferable. Specific examples of the hindered phenol antioxidant include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3 ′ -Methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6 -Hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t- Butyl-4-hydroxyphenyl) -propionate], triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate], Pentaerythritol tetrakis [methylene-3- (3 ', 5'-di -t- butyl-4'-hydroxyphenyl) propionate], and methane. Of these, triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate] and pentaerythritol tetrakis [methylene-3- (3 ′, 5 '-Di-t-butyl-4'-hydroxyphenyl) propionate] methane. These antioxidants are used alone or in combination of two or more.

  Examples of polymers or compounds containing nitrogen reactive with formaldehyde include acrylamide and derivatives thereof, and copolymers of acrylamide and derivatives thereof with other vinyl monomers. More specifically, for example, in addition to the poly-β-alanine copolymer obtained by polymerizing acrylamide and its derivatives and other vinyl monomers in the presence of metal alcoholate, the above polymer or compound Examples include amide compounds, amino-substituted triazine compounds, adducts of amino-substituted triazine compounds and formaldehyde, condensates of amino-substituted triazine compounds and formaldehyde, urea, urea derivatives, hydrazine derivatives, imidazole compounds, and imide compounds.

  Specific examples of the amide compound include polycarboxylic acid amides such as isophthalic acid diamide and anthranilamides. Specific examples of the amino-substituted triazine compound include 2,4-diamino-sym-triazine, 2,4,6-triamino-sym-triazine, N-butylmelamine, N-phenylmelamine, N, N-diphenylmelamine, N , N-diallylmelamine, benzoguanamine (2,4-diamino-6-phenyl-sym-triazine), acetoguanamine (2,4-diamino-6-methyl-sym-triazine), 2,4-diamino-6-butyl -Sym-triazine is mentioned. Specific examples of the adduct of an amino-substituted triazine compound and formaldehyde include N-methylol melamine, N, N′-dimethylol melamine, and N, N ′, N ″ -trimethylol melamine. Specific examples of condensates of aldehyde and formaldehyde include melamine / formaldehyde condensates, and examples of urea derivatives include N-substituted urea, urea condensates, ethylene urea, hydantoin compounds, and ureido compounds. -Specific examples of substituted urea include methylurea substituted with a substituent such as an alkyl group, alkylenebisurea, and aryl-substituted urea, and specific examples of urea condensates include condensates of urea and formaldehyde. Specific examples of hydantoin compounds include hydantoin, 5,5- Specific examples of ureido compounds include allantoin, specific examples of hydrazine derivatives include hydrazide compounds, and specific examples of hydrazide compounds include dicarboxylic acid dihydrazide. More specifically, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, superic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide diisophthalate, Phthalic acid dihydrazide, 2,6-naphthalenedicarbodihydrazide, and specific examples of imide compounds include succinimide, glutarimide, and phthalimide. It is.

  Examples of the formic acid scavenger include the above-mentioned amino-substituted triazine compounds and condensates of amino-substituted triazine compounds with formaldehyde, for example, melamine / formaldehyde condensates. Examples of other formic acid scavengers include alkali metal or alkaline earth metal hydroxides, inorganic acid salts, and alkoxides. More specifically, for example, hydroxides of sodium, potassium, magnesium, calcium or barium, carbonates, phosphates, silicates and borates of the above metals can be mentioned. These formic acid scavengers are used singly or in combination of two or more.

  The weathering (light) stabilizer is preferably at least one selected from benzotriazole-based and oxalic acid anilide-based UV absorbers and hindered amine-based light stabilizers.

  Specific examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butyl- Phenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′, 5′- Bis- (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole. Specific examples of the oxalic acid alinide ultraviolet absorber include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, 2- Ethoxy-3'-dodecyl oxalic acid bisanilide is mentioned. The benzotriazole-based ultraviolet absorber is preferably 2- [2′-hydroxy-3 ′, 5′-bis- (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy- 3 ', 5'-di-tert-butyl-phenyl) benzotriazole. These benzotriazole-based ultraviolet absorbers are used alone or in combination of two or more.

  Specific examples of the hindered amine light stabilizer include N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetra). Methylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N′-bis (2,2 , 6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 Piperidyl) imino}], a condensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, bis (2,2,6,6-tetramethyl-decanoic acid) 1 (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane, the reaction product bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3 5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1,2,3,4-butyl Tetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] a condensate with diethanol The hindered amine light stabilizer is preferably bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate or bis (N-methyl-). 2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, It is a condensate with β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol, one of these hindered amine light stabilizers. Alone or Used in combination with at least species.

  As the mold release agent, alcohol, fatty acid and fatty acid ester thereof, polyoxyalkylene glycol, and an olefin compound having an average polymerization degree of 10 to 500 are preferably used.

  The polyacetal resin composition of the present embodiment may further contain a known additive as required, as long as the object of the present invention is not impaired. Specific examples of such additives include inorganic fillers, crystal nucleating agents, conductive materials, thermoplastic resins, thermoplastic elastomers, and pigments.

  As the inorganic filler, for example, those in the form of fibers, powder particles, plates and hollows are used. Examples of the fibrous filler include glass fiber, carbon fiber, silicone fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium, copper, Examples thereof include inorganic fibers such as metal fibers such as brass. Moreover, you may use whiskers, such as a potassium titanate whisker with short fiber length, and a zinc oxide whisker, as an inorganic filler. In addition, the polyacetal resin composition of this embodiment may contain high melting point organic fibrous materials, such as an aromatic polyamide resin, a fluororesin, and an acrylic resin.

  Examples of the particulate filler include carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, silicates such as wollastonite, iron oxide, and titanium oxide. Metal oxides such as alumina, metal sulfates such as calcium sulfate and barium sulfate, carbonates such as magnesium carbonate and dolomite, silicon carbide, silicon nitride, boron nitride, and various metal powders. Examples of the plate-like filler include mica, glass flakes, and various metal foils. Examples of the hollow filler include glass balloons, silica balloons, shirasu balloons, and metal balloons.

  These fillers are used alone or in combination of two or more. These fillers may be either surface-treated or non-surface-treated, but surface-treated ones may be preferable in terms of the smoothness of the molding surface and mechanical properties. A conventionally well-known thing can be used as a surface treating agent. As the surface treatment agent, for example, various coupling treatment agents such as silane, titanate, aluminum, and zirconium can be used. Specifically, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, isopropyl trisstearoyl titanate, diisopropoxyammonium ethyl acetate, and n-butyl zirconate Can be mentioned.

  Examples of the conductive agent include conductive carbon black, metal powder, and metal fiber.

  Examples of the thermoplastic resin include polyolefin resin, acrylic resin, styrene resin, polycarbonate resin, and uncured epoxy resin. Moreover, you may use the modified material of these resin as a thermoplastic resin. Examples of the thermoplastic elastomer include polyurethane elastomers, polyester elastomers, polystyrene elastomers, and polyamide elastomers.

  Examples of the pigment include inorganic pigments, organic pigments, metallic pigments, and fluorescent pigments. Here, examples of inorganic pigments include those commonly used for coloring resins, such as zinc sulfide, titanium oxide, barium sulfate, titanium yellow, cobalt blue, combustion pigments, carbonates, and phosphoric acid. Examples thereof include salts, acetates, carbon black, acetylene black, and lamp black. Examples of the organic pigment include, for example, condensed zozo, inone, furothocyanin, monoazo, diazo, polyazo, anthraquinone, heterocyclic, pennon, quinacridone, thioindico, berylene, dioxazine. And phthalocyanine pigments. The addition ratio of the pigment to the polyacetal resin composition of the present embodiment is difficult to define clearly because it varies greatly depending on the required color tone, but in general, it is 100 parts by mass of the polyacetal resin (I). On the other hand, it is used in the range of 0.05 to 5 parts by mass.

  Next, the suitable manufacturing method of the polyacetal resin composition of this embodiment is demonstrated. Here, for simplification of description, the polyacetal resin (I), light calcium carbonate (II), fatty acid (III), and fatty acid calcium salt (IV) are simply referred to as component (I) and component (II), respectively. , May be referred to as component (III) and component (IV).

  First, as a device used in the manufacturing method, a kneader generally used in practice can be applied. Examples of the apparatus include a single-screw or multi-screw kneading extruder, a roll, and a Banbury mixer. Among these, a twin screw extruder equipped with a decompression device and a side feeder is particularly preferable. The polyacetal resin composition of the present embodiment can be obtained by melting and kneading the above components using such an apparatus. Melt-kneading methods include a method of melt-kneading all components simultaneously, a method of melt-kneading a premixed mixture, and further supplying each component from the side feeder in the middle of the barrel of the extruder, and melt-kneading. A method is mentioned.

  Specifically, the production method includes: [A] a step of mixing component (I), component (II), component (III) and component (IV) to obtain a mixture, and a step of melt-kneading the mixture. [B] a step of previously mixing component (II), component (III) and component (IV) to obtain a premix, and a step of melt kneading the premix and component (I) And [C] two or three of the above components (I) to (VI) (excluding combinations of component (II), component (III) and component (IV)) .) Is previously mixed or melt-kneaded to obtain a preliminary mixture, and the preliminary mixture and the remaining unmixed components are melt-kneaded. However, the mixing order and melt-kneading order of components (I) to (IV) are not particularly limited. Among these, from the viewpoint of achieving the object of the present invention more effectively and reliably, a mixture of component (II), component (III) and component (IV) is added to the heated melt or solid state component (I). A method of adding and melt-kneading is preferable.

  More specifically, from the viewpoint of obtaining a polyacetal resin composition that can achieve the object of the present invention more effectively and reliably, a preferred production method comprises a component (II), a component (III), and a component (IV) in a solid state. Mixing with a blender to obtain a mixture, continuously feeding the mixture and component (I) from different feeders into the barrel of the extruder, and melt-kneading to obtain a melt-kneaded product, Continuously extruding the melt-kneaded material from the die of the extruder. This production method is a production method in which the component (II) or the like is not subjected to a step of subjecting the component (II) to surface treatment or coating in advance by heating Henschel coating or the like.

  In the case where the polyacetal resin composition contains the polyamide resin (V), a more preferable production method is to combine a component (II), a component (III), a component (IV), and a resin containing the polyamide resin (V) in a solid phase. Mixing with a blender in a state to obtain a mixture, and continuously feeding the mixture and component (I) from different feeders into the barrel of the extruder to obtain a melt-kneaded product by melt-kneading; And a step of continuously extruding the melt-kneaded product from the die of the extruder. In this case, particularly preferably, the resin containing the polyamide resin (V) is a melt-kneaded product of the polyamide resin (V) and the component (I), which is used as a melt masterbatch. Thereby, the dispersibility in the composition of polyamide resin (V) improves.

  Although the pressure reduction degree of an extruder is not specifically limited, 0-0.07 Mpa is preferable. The melt kneading temperature is preferably 1 to 100 ° C. higher than the melting point obtained by differential scanning calorimetry (DSC) measurement of the polyacetal resin (I) used according to JIS K7121. More specifically, the melt kneading temperature is preferably 160 ° C to 240 ° C. The shear rate in the kneader is preferably 100 rpm or more, and the average residence time during kneading is preferably 30 seconds to 1 minute.

  The method for producing a molded product by molding the polyacetal resin composition of the present embodiment is not particularly limited as long as it is the same as the method for molding a conventional polyacetal resin composition. The methods include, for example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, other material molding, gas assist injection molding, firing injection molding, low pressure molding, ultra-thin injection molding (ultra-thin molding) High speed injection molding) and in-mold composite molding (insert molding, outsert molding).

  A molded product obtained from the polyacetal resin composition of the present embodiment by the molding method described above, for example, an injection molded product obtained by injection molding is excellent in mechanical property balance and dimensional accuracy represented by rigidity and toughness. Even after being exposed to a high temperature environment for a long time in a state where grease is applied, the rigidity and gear characteristics can be maintained at a high level. Therefore, the molded product is useful when used as a part having a complicated shape, and can be used as a molded product for various applications. Examples of such molded products include gears, cams, sliders, levers, arms, clutches, felt clutches, idler gears, pulleys, rollers, rollers, key stems, key tops, shutters, reels, shafts, joints, shafts. , Mechanical parts such as bearings and guides, resin parts for outsert molding, resin parts for insert molding, chassis, trays, side plates, parts for office automation equipment such as printers and copiers, VTR (Video Tape Recorder) ), Video movies, digital video cameras, cameras and parts for digital cameras, or parts for video equipment, cassette players, DAT, LD (Laser Disk), MD (Mini Disk), CD (Compact Disk) [CD-ROM (Read Only Memory), CD-R (Recordable), CD-RW (Re writable), DVD (Digital Video Disk) [DVD-ROM, DVD-R, DVD + R, DVD-RW, DVD + RW, DVD-R DL, DVD + R DL, DVD-RAM (Random Access Memory), DVD-Audio Including], Blu-ray Disc, HD-DVD, other optical disk drives, MFD, MO, navigation systems and music, video or information equipment represented by mobile personal computers, communication equipment parts represented by mobile phones and facsimiles , Electrical equipment parts, electronic equipment parts.

  The molded product can also be used as parts for automobiles, for example, fuel-related parts such as gasoline tanks, fuel pump modules, valves, gasoline tank flanges, door locks, door handles. , Door regulators such as window regulators and speaker grills, seat belt slip rings, seat belt peripherals such as press buttons, combination switch parts, switches and clips, and mechanical pencils Pen tip and mechanical pencil core mechanism, wash basin, drain port and drain valve opening / closing mechanism part, vending machine opening / closing part locking mechanism and product discharge mechanism part, clothing cord stopper, adjuster and button, Water spray nozzle and sprinkler hose connection joy As industrial parts represented by building supplies, disposable cameras, toys, fasteners, chains, conveyors, buckles, sports equipment, vending machines, furniture, musical instruments, and housing equipment, which are support tools for floors, stair railings and flooring materials Are also preferably used.

  In particular, the injection-molded article of the present embodiment has excellent gear characteristics, and can maintain the gear characteristics at a high level even after being exposed to a high temperature environment for a long time in a state where grease is applied. It is extremely useful when used as a gear.

  The polyacetal resin composition of the present embodiment includes polyacetal resin (I), light calcium carbonate (II) having a specific pH, fatty acid (III), and fatty acid calcium salt (IV), and fatty acid (III ) And light calcium carbonate (II) and the fatty acid calcium salt (IV) and light calcium carbonate (II) are in a specific range. As a result, the molded product obtained from the composition has an excellent balance of mechanical properties such as rigidity and toughness, and also has rigidity and toughness even after being exposed to a high temperature environment for a long time in a state where grease is applied. Gear characteristics can be maintained at a high level.

  As mentioned above, although the form for implementing this invention was demonstrated, this invention is not limited to the said this embodiment. The present invention can be variously modified without departing from the gist thereof.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited at all by these.

(Measurement and evaluation methods of physical properties and characteristics)
<Measuring method of melting point>
The melting point of the polyacetal resin was measured using a differential calorimeter (trade name “DSC-2C” manufactured by Perkin Elmer Co., Ltd.). At that time, first, the temperature was raised from room temperature to 200 ° C. and held at that temperature for 1 minute to completely melt the polyacetal resin. Thereafter, the polyacetal resin was cooled to 100 ° C. and heated again at a rate of 2.5 ° C./min. The peak temperature of the exothermic spectrum at that time was taken as the melting point.

<Measurement method of tensile properties>
Using an injection molding machine (trade name “IS-100GN”) manufactured by Toshiba Machine Co., Ltd. under injection conditions of cylinder temperature 205 ° C., mold temperature 90 ° C., injection pressure 100 MPa, injection time 35 seconds, and cooling 15 seconds. The polyacetal resin composition was injection-molded to obtain an ISO dumbbell for evaluation as a test piece. About the obtained ISO dumbbell, the tensile elastic modulus and the tensile elongation were measured according to ISO527. Moreover, the same test piece was immersed in the grease (the product name "ISOFLEX TOPAS L32" by Kluber Lubrication) in the container, and the container was sealed in that state. After the sealed container was left in a gear oven at 140 ° C. for 120 hours, a test piece was taken out from the container, and the tensile elastic modulus and tensile elongation of the test piece were measured in the same manner.

<Evaluation method of gear durability>
Using an injection molding machine manufactured by FANUC (trade name “α50i-A injection molding machine”), cylinder temperature 190 ° C., mold temperature 80 ° C., injection pressure 120 MPa, injection time 10 seconds, cooling time 15 seconds. A polyacetal resin composition was injection molded under injection conditions to obtain a spur gear having a module of 0.8, a number of teeth of 50, and a tooth width of 5 mm. The spur gear was installed in a gear durability tester manufactured by Toshiba Machine Co., Ltd. by knitting gears of the same material together. (One gear is on the driving side and the other gear is on the driven side. Next, the driving gear is rotated under the conditions of torque 176 N / m and rotation speed 800 rpm, and the time until the gear breaks is measured. In addition, the same gear was immersed in grease in a container (trade name “ISOFLEX TOPAS L32” manufactured by Kluber Lubrication Co., Ltd.), and the container was sealed in this state. After leaving it to stand, the gear was taken out of the container, the same test was performed, and the time until the gear broke was measured.

(Production of polyacetal resin composition)
A polyacetal resin composition was produced using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., trade name “TEM-48SS extruder”, L / D = 58.4, with vent). A schematic diagram of the extruder 100 is shown in FIG. The extruder 100 includes an independent barrel region 1 to 14 from the upstream side to the downstream side, a die head 15 disposed on the most downstream side, and an extruder for driving a screw (not shown) in the barrel. Machine motor 16, a quantitative feeder 17 connected to the region 1 of the most upstream barrel, a different quantitative feeder 18, a quantitative feeder (side feeder) 19 connected to the downstream barrel region 10, and further downstream And a deaeration vent 20 extending from the barrel region 13. The barrel region 6 is open to the atmosphere to discharge gas from the system. The polyacetal resin composition was manufactured by any of the following manufacturing methods A, B, and C using the extruder 100 shown in FIG.

<Production method A>
Barrel region 1 of extruder 100 is cooled with cooling water, barrel regions 2-4 to 200 ° C, barrel regions 5-9 to 210 ° C, barrel region 10 to 200 ° C, barrel region 11 ˜14 was set to 180 ° C., and the die head 15 was set to 190 ° C. Under this temperature condition, the polyacetal resin (I) is quantitatively determined from the quantitative feeder 17 with a mixture of light calcium carbonate (II), fatty acid (III), fatty acid calcium salt (IV) and polyamide resin (V) in a solid phase. Each was supplied from a feeder 18. At the same time, the mixture is melted and kneaded under the conditions of a screw rotation speed of 300 rpm and an extrusion rate of 200 kg / h while degassing from the degassing vent 20 using a vacuum pump (not shown), and the die head 15 melts and kneads from the die. Was extruded to obtain a polyacetal resin composition.

<Production method B>
Production method A except that a mixture of light calcium carbonate (II), fatty acid (III), fatty acid calcium salt (IV) and polyamide resin (V) in a solid phase is supplied from the quantitative feeder 19 instead of the quantitative feeder 19 In the same manner as above, a polyacetal resin composition was obtained.

<Manufacturing method C>
Instead of the method for supplying the polyacetal resin (I), light calcium carbonate (II), fatty acid (III), fatty acid calcium salt (IV), and polyamide resin (V), all of these solid phases A polyacetal resin composition was obtained in the same manner as in Production Method A except that the mixture in the state was replaced with the method of supplying from the quantitative feeder 17.

The following components were used in Examples and Comparative Examples.
<Polyacetal resin (I)>
(Polyacetal resin (I-i))
A biaxial self-cleaning type polymerization machine (L / D = 8) with a jacket capable of passing a heating medium was adjusted to 80 ° C., 4 kg / hour of trioxane, and 1,3-dioxolane as a comonomer was 42. The melt flow rate at 190 ° C. based on JIS K7210 (hereinafter the same) of the polyacetal resin after polymerization of methylal as a chain transfer agent was 8 g / hour (1.3 mol% relative to 100 mol% trioxane), and 13 g / 10 min. Each amount was added so that Further, boron trifluoride di-n-butyl etherate as a polymerization catalyst was continuously added to the polymerization machine in an amount of 1.5 × 10 ⁻⁵ mol with respect to 1 mol of trioxane, and polymerization was performed. The polyacetal copolymer discharged from the polymerization machine was put into a 0.1% aqueous solution of triethylamine to deactivate the polymerization catalyst. After filtering the deactivated polyacetal copolymer of the polymerization catalyst, 100 parts by mass of the polyacetal copolymer contains choline formate (triethyl-2-hydroxyethylammonium formate) as a quaternary ammonium compound. 1 part by mass of the aqueous solution was added and mixed uniformly, and then dried at 120 ° C. The added amount of choline formate is adjusted by adjusting the concentration of choline formate in the aqueous solution containing the added choline formate, and converted to the amount of nitrogen represented by the above formula (3). To 20 ppm by mass. The dried polyacetal copolymer is supplied to a vented twin screw extruder, and 0.5 parts by mass of water is added to 100 parts by mass of the melted polyacetal copolymer in the extruder, and the extruder set temperature is 200 ° C. The unstable end portion was decomposed and removed under the condition of a residence time of 7 minutes in the extruder. The polyacetal copolymer with the unstable terminal portion decomposed was devolatilized under a condition of a vent vacuum of 20 Torr, extruded as a strand from the die portion of the extruder, and pelletized. Triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate] 0.35 as an antioxidant with respect to 100 parts by mass of the pelletized polyacetal copolymer (polyacetal resin) The mass part was added, and the polyacetal resin pellet was obtained by melt-kneading with a twin screw extruder with a vent. The melting point of the polyacetal resin (Ii) thus obtained was 169.5 ° C.

(Polyacetal resin (I-ii))
The addition amount of 1,3-dioxolane was changed from 42.8 g / hour to 128.3 g / hour (3.9 mol% relative to 100 mol% of trioxane), and the addition amount of methylal was changed to the melt flow of the polyacetal resin after polymerization. The polyacetal resin was pelletized in the same manner as in the polymerization of the polyacetal resin (Ii) except that the rate was changed from 13 g / 10 min to 10 g / 10 min. For 100 parts by mass of the pelletized polyacetal resin, 0.35 parts by mass of triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] is used as an antioxidant. The polyacetal resin pellet was obtained by adding and melt-kneading with a twin screw extruder with a vent. The polyacetal resin (I-ii) thus obtained had a melting point of 164.5 ° C.

(Polyacetal resin (I-iii))
100 parts by mass of dehydrated formaldehyde gas and 0.1 part by mass of dimethyl distearyl ammonium acetate were added as a catalyst to a tank capable of supplying monomers and the like continuously with a stirring blade. Next, acetic anhydride was polymerized at 58 ° C. while continuously supplying the acetic anhydride as a molecular weight regulator in such an amount that the melt flow rate of the polyacetal resin after polymerization was 10 g / 10 min. The obtained crude polyoxymethylene polymer was put into a 1: 1 solvent mixture of hexane and acetic anhydride, and the end groups were chemically treated at 140 ° C. for 2 hours. The obtained polymer was vacuum dried at 120 ° C. for 3 hours under the conditions of 1 mmHg. Next, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] as an antioxidant was added to 100 parts by mass of the dried polyoxymethylene polymer. 35 parts by mass was added and melt-kneaded with a vented twin-screw extruder to obtain polyacetal resin pellets. The polyacetal resin (I-iii) thus obtained had a melting point of 175.0 ° C.

<Calcium carbonate (II)>
(II-i): Shiraishi Kogyo Co., Ltd., average particle size 150 nm, untreated surface, pH = 9.4, most probable void radius 0.13 μm
(II-ii): manufactured by Shiroishi Kogyo Co., Ltd., average particle size 150 nm, untreated surface, pH = 9.7, most probable void radius 0.14 μm
(II-iii): manufactured by Shiroishi Kogyo Co., Ltd., average particle size 150 nm, untreated surface, pH = 9.2, most probable void radius 0.12 μm
(II-iv): Shiraishi Kogyo Co., Ltd., average particle size 150 nm, untreated surface, pH = 10.0, most probable void radius 0.13 μm
(II-v): Shiraishi Kogyo Co., Ltd., average particle size 150 nm, untreated surface, pH = 9.4, most probable void radius 0.10 μm
(II-vi): manufactured by Shiraishi Kogyo Co., Ltd., average particle size 150 nm, untreated surface, pH = 9.4, most probable void radius 0.17 μm
(II-vii): manufactured by Shiroishi Kogyo Co., Ltd., average particle size 150 nm, untreated surface, pH = 9.1, most probable void radius 0.12 μm
(II-viii): manufactured by Shiroishi Kogyo Co., Ltd., average particle size 150 nm, untreated surface, pH = 10.2, most probable void radius 0.14 μm
(II-ix): manufactured by Shiraishi Kogyo Co., Ltd., trade name “Vigot-15” (average particle size 150 nm, surface acid fatty acid treatment, pH = 9.0, most probable void radius 0.12 μm)
(II-x): manufactured by Shiraishi Kogyo Co., Ltd., trade name “Shiraka Hana O” (average particle size 30 nm, surface rosin acid (resin acid) treatment, pH = 8.5, most probable void radius 0.02 μm)
(II-xi): manufactured by Shiraishi Kogyo Co., Ltd., trade name “PC-700” (average particle size 1.2 μm, untreated surface, pH = 9.9)

The calcium carbonates (II-i) to (II-viii) described above are produced by a lime milk / carbon dioxide reaction method that has undergone the following three steps (A), (B), and (C). It is a thing.
(A) Dense limestone was fired in a firing furnace and decomposed into carbon dioxide and quicklime.
(B) Water was added to the obtained quicklime and the mixture was hydrated and refined to obtain slurry-like slaked lime.
(C) Carbon dioxide obtained in (A) was blown into and reacted with the slurry-like slaked lime obtained in (B) to produce calcium carbonate.

<Fatty acid (III)>
(III-i): Stearic acid manufactured by Kawaken Fine Chemical Co., Ltd., trade name “F-3” (melting point: 64 ° C., carbon number: 18)
(III-ii): Palmitic acid (melting point 63 ° C., carbon number 16)

<Fatty acid calcium salt (IV)>
(IV-i): Nitto Kasei Co., Ltd. calcium behenate (carbon number 22)
(IV-ii): Nitto Kasei Co., Ltd. calcium stearate (18 carbon atoms)
(IV-iii): Calcium palmitate (carbon number 16)

<Polyamide resin (V)>
(Vi): Nylon 6,6 (10%)-copolymer acetal A polyacetal copolymer having a melt flow rate of 30 g / 10 min and polyamide 6,6 having a formic acid relative viscosity VR of 22 are mixed at a mass ratio of 9: 1. Then, the mixture was melt-kneaded with a twin-screw extruder set at a cylinder temperature of 260 ° C. The extruded strand was pelletized with a strand cutter, and this was used as a polyamide resin (Vi).

[Examples 1-36]
Each component (I)-(V) was mix | blended in the ratio shown in Table 1, and it melt-kneaded with the manufacturing method shown in Table 1, respectively. The extruded polyacetal resin composition was pelletized with a strand cutter. About the obtained pellet, the tensile elasticity modulus and the tensile elongation were measured by the above-mentioned method, and the gear durability test was done. The results are shown in Table 2.

[Comparative Examples 1 to 30]
Each component (I)-(V) was mix | blended in the ratio shown in Table 3, and it melt-kneaded with the manufacturing method shown in Table 3, respectively. The extruded polyacetal resin composition was pelletized with a strand cutter. About the obtained pellet, the tensile elasticity modulus and the tensile elongation were measured by the above-mentioned method, and the gear durability test was done. The results are shown in Table 4. In addition, about the comparative example 2, 1.5 mass parts of fatty acid (III) is mix | blended with respect to 100 mass parts of polyacetal resin (I), and about the comparative examples 7-9, 23, and 24, fatty acid calcium salt (IV) Was blended in an amount of 0.15 parts by mass with respect to 100 parts by mass of the polyacetal resin (I).

  Since the present invention is excellent in mechanical properties such as rigidity and toughness and dimensional accuracy as described above, it can be suitably used in fields such as automobiles represented by gears, precision parts of electrical and electronic equipment, and other industries. Furthermore, the present invention is excellent in maintaining rigidity and gear characteristics after being exposed to a high temperature environment for a long time in a state where grease is applied. Therefore, in the presence of lubricating oil or grease, such as mechanical parts of OA equipment. It can also be employed for members used in high temperature environments.

  DESCRIPTION OF SYMBOLS 1-15 ... Barrel area | region, 16 ... Extruder motor, 17-19 ... Metering feeder, 20 ... Deaeration vent, 100 ... Twin screw extruder.

Claims (10)

100 parts by mass of a polyacetal resin, 5-50 parts by mass of light calcium carbonate having an average particle size of 50 nm to 500 nm, a pH of 9.2 to 10.0, and no surface treatment, and a carbon number of 12 A fatty acid of ˜30 and a fatty acid calcium salt, the carbon number X of the fatty acid and the carbon number Y of the fatty acid calcium salt satisfy the condition represented by the following formula (1), and the light calcium carbonate The polyacetal resin composition whose mass ratio of the said fatty acid is 0.020-0.060, and whose mass ratio of the said fatty acid with respect to the said fatty acid calcium salt is 3-15.
1 ≦ Y−X ≦ 4 (1)   The polyacetal resin composition according to claim 1, wherein the light calcium carbonate has a most probable void radius of 0.12 μm or more and 0.16 μm or less.   The polyacetal resin composition according to claim 1, wherein the polyacetal resin includes a polyacetal copolymer having a melting point of 164 ° C. or higher and 173 ° C. or lower.   The polyacetal resin composition according to any one of claims 1 to 3, wherein the polyacetal resin includes a polyacetal copolymer having a melting point of 167 ° C or higher and 173 ° C or lower.   The polyacetal resin composition as described in any one of Claims 1-4 which contains 0.01-3 mass parts of polyamide resins with respect to 100 mass parts of said polyacetal resins. A method for producing the polyacetal resin composition according to any one of claims 1 to 4,
A light calcium carbonate having an average particle diameter of 50 nm to 500 nm, a pH of 9.2 to 10.0 and not surface-treated, a fatty acid having 12 to 30 carbon atoms, and a fatty acid calcium salt. Mixing with a blender in a solid phase to obtain a mixture;
A step of continuously supplying the mixture and the polyacetal resin from different feeders into the barrel of the extruder and melt-kneading to obtain a melt-kneaded product;
Continuously extruding the melt-kneaded product from the die of the extruder;
Have
The manufacturing method of the polyacetal resin composition with which carbon number X of the said fatty acid and carbon number Y of the said fatty acid calcium salt satisfy | fill the conditions represented by following formula (1).
1 ≦ Y−X ≦ 4 (1) A method for producing the polyacetal resin composition according to claim 5,
Light calcium carbonate that has an average particle size of 50 nm to 500 nm, a pH of 9.2 to 10.0, and is not surface-treated, a fatty acid having 12 to 30 carbon atoms, a fatty acid calcium salt, and a polyamide Mixing a resin containing resin with a blender in a solid phase to obtain a mixture;
A step of continuously supplying the mixture and the polyacetal resin from different feeders into the barrel of the extruder and melt-kneading to obtain a melt-kneaded product;
Continuously extruding the melt-kneaded product from the die of the extruder;
Have
The manufacturing method of the polyacetal resin composition with which carbon number X of the said fatty acid and carbon number Y of the said fatty acid calcium salt satisfy | fill the conditions represented by following formula (1).
1 ≦ Y−X ≦ 4 (1)   The method for producing a polyacetal resin composition according to claim 7, wherein the resin containing the polyamide resin is a melt-kneaded product of the polyamide resin and the polyacetal resin.   An injection-molded article comprising the polyacetal resin composition according to any one of claims 1 to 5.   The gearwheel containing the polyacetal resin composition as described in any one of Claims 1-5.

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