WO2020013184A1 - Polyacetal resin composition and molded article - Google Patents

Polyacetal resin composition and molded article Download PDF

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Publication number
WO2020013184A1
WO2020013184A1 PCT/JP2019/027159 JP2019027159W WO2020013184A1 WO 2020013184 A1 WO2020013184 A1 WO 2020013184A1 JP 2019027159 W JP2019027159 W JP 2019027159W WO 2020013184 A1 WO2020013184 A1 WO 2020013184A1
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Prior art keywords
polyacetal resin
mass
resin composition
parts
composition according
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PCT/JP2019/027159
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French (fr)
Japanese (ja)
Inventor
石井　崇
磯崎　剛
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三菱エンジニアリングプラスチックス株式会社
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Priority to JP2020530200A priority Critical patent/JP7365338B2/en
Publication of WO2020013184A1 publication Critical patent/WO2020013184A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals

Definitions

  • the present invention relates to a polyacetal resin composition and a molded article.
  • it relates to a molded product used for a fuel pump module.
  • Patent Document 1 contains (A) 100 parts by mass of a polyacetal resin, (B) 0.1 to 2 parts by mass of zinc oxide, and (C) 0.1 to 5 parts by mass of a slidability improving material. Further, there is disclosed a polyacetal resin composition in which the zinc oxide (B) has a number average primary particle diameter of 70 to 500 nm.
  • polyacetal resin for vehicle components, particularly for fuel pump modules, is also being studied. Vehicles are often cleaned with detergents at gas stations and the like. However, it has been found that when a detergent containing fluorine ions is used as the detergent, division may occur in parts inside the vehicle. If such a vehicle interior component is a fuel pump module, the damage can be severe.
  • An object of the present invention is to solve such a problem, and an object of the present invention is to provide a polyacetal resin composition which is less likely to be split even when in contact with a liquid containing fluorine ions, and a molded article thereof.
  • the polyacetal resin by mixing a specific metal hydroxide, a specific nitrogen-containing compound, and a specific divalent metal oxide, The inventors have found that the problem can be solved, and have completed the present invention. Specifically, the above problems have been solved by the following means ⁇ 1>, preferably by ⁇ 2> to ⁇ 10>.
  • a polyacetal resin With respect to 100 parts by mass of a polyacetal resin, 0.1 to 5.0 parts by mass of at least one metal hydroxide composed of magnesium hydroxide and calcium hydroxide, an amine-substituted triazine compound, a carbodiimide compound, and A polyacetal resin composition comprising 0.1 to 3.0 parts by mass of a nitrogen-containing compound selected from the group consisting of hindered amine light stabilizers and 0.1 to 5.0 parts by mass of a divalent metal oxide.
  • a metal hydroxide composed of magnesium hydroxide and calcium hydroxide
  • an amine-substituted triazine compound a carbodiimide compound
  • a polyacetal resin composition comprising 0.1 to 3.0 parts by mass of a nitrogen-containing compound selected from the group consisting of hindered amine light stabilizers and 0.1 to 5.0 parts by mass of a divalent metal oxide.
  • a polyetheresteramide block copolymer based on 100 parts by mass of the polyacetal resin, a polyetheresteramide block copolymer, a poly- ⁇ -olefin, a polyolefin / polyether copolymer, a polyamide copolymer, and a polyamide / polyalkylene glycol block copolymer.
  • a stress relaxing agent selected from the group consisting of polyethylene glycol having a number average molecular weight of 20,000 or more and polyethylene oxide having a number average molecular weight of 20,000 or more.
  • ⁇ 3> ⁇ 1> or ⁇ 2> wherein the ratio of metal hydroxide to divalent metal oxide is 3.0 or less, which is the mass ratio of the metal hydroxide to the divalent metal oxide.
  • 3. The polyacetal resin composition according to item 1. ⁇ 4> The polyacetal resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the divalent metal oxide is zinc oxide. ⁇ 5> the divalent metal oxide is zinc oxide, and the metal hydroxide / zinc oxide, which is a mass ratio of the metal hydroxide and the zinc oxide, is 1.8 or less; ⁇ The polyacetal resin composition according to 1> or ⁇ 2>.
  • ⁇ 6> The polyacetal resin composition according to any one of ⁇ 1> to ⁇ 5>, which has resistance to a liquid containing a fluorine ion.
  • ⁇ 7> The polyacetal resin composition according to any one of ⁇ 1> to ⁇ 6>, which is used for a fuel pump module.
  • ⁇ 8> The polyacetal resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the metal hydroxide is magnesium hydroxide.
  • ⁇ 9> A molded article formed from the polyacetal resin composition according to any one of ⁇ 1> to ⁇ 8>.
  • ⁇ 10> The molded article according to ⁇ 9>, which is used for a fuel pump module.
  • the polyacetal resin composition of the present invention is characterized in that, based on 100 parts by mass of a polyacetal resin, 0.1 to 5.0 parts by mass of a metal hydroxide composed of magnesium hydroxide and calcium hydroxide, and an amine-substituted triazine compound , A carbodiimide compound, a nitrogen-containing compound selected from the group consisting of hindered amine-based light stabilizers in an amount of 0.1 to 3.0 parts by mass, and a divalent metal oxide in an amount of 0.1 to 5.0 parts by mass. It is characterized by the following. Splitting (including cracking, the same applies hereinafter) due to immersion in a solution containing fluorine ions is caused by cracks generated in the molded article and mass reduction.
  • a decrease in mass is suppressed by further mixing a divalent metal oxide. That is, in the present invention, by mixing a metal hydroxide, a divalent metal oxide, and a nitrogen-containing compound in a well-balanced manner, the inventors succeeded in achieving both suppression of crack generation and suppression of mass loss. Succeeded in suppressing the occurrence of division. In particular, even as a thin-walled molded product (for example, a molded product having a portion having a thickness of 0.01 to 3 mm, or even 0.1 to 2 mm), the division can be effectively suppressed.
  • a thin-walled molded product for example, a molded product having a portion having a thickness of 0.01 to 3 mm, or even 0.1 to 2 mm
  • the occurrence of cracks due to residual stress can be effectively suppressed even in a molded product having a complicated shape such as a gate portion by blending a specific polymer compound as a stress relaxation agent.
  • a specific polymer compound as a stress relaxation agent.
  • the (A) polyacetal resin used in the present invention is a polymer having an acetal structure — (— O—CRH—) n — (where R represents a hydrogen atom or an organic group) in a repeating structure, and usually, R is An oxymethylene group (—CH 2 O—) that is a hydrogen atom is used as a main structural unit.
  • the polyacetal resin used in the present invention includes, in addition to the acetal homopolymer having only this repeating structure, a copolymer (including a block copolymer) or a terpolymer containing at least one repeating structural unit other than the oxymethylene group. And may have not only a linear structure but also a branched or crosslinked structure.
  • Examples of the structural unit other than the oxymethylene group include an oxyethylene group (—CH 2 CH 2 O—), an oxypropylene group (—CH 2 CH 2 CH 2 O—), and an oxybutylene group (—CH 2 CH 2 CH).
  • An optionally branched oxyalkylene group having 2 to 10 carbon atoms such as 2 CH 2 O-) is preferable, and an optionally branched oxyalkylene group having 2 to 4 carbon atoms is preferable.
  • an oxyethylene group is preferable.
  • the content of the oxyalkylene structural unit other than the oxymethylene group is preferably from 0.1 mol% to 20 mol%, and more preferably from 0.1 mol% to 15 mol% in the polyacetal resin. Is more preferred.
  • the method for producing the polyacetal resin used in the present invention is arbitrary, and may be produced by any conventionally known method.
  • a method for producing a polyacetal resin having an oxymethylene group and an oxyalkylene group having 2 to 4 carbon atoms as constituent units includes oxymethylene groups such as trimer (trioxane) and tetramer (tetraoxane) of formaldehyde.
  • the polyacetal resin used in the present invention is preferably a copolymer of a cyclic oligomer such as trioxane or tetraoxane and ethylene oxide or 1,3-dioxolan, and particularly a copolymer of trioxane and 1,3-dioxolan. It is preferred that they are united.
  • MI melt index
  • the polyacetal resin composition of the present invention preferably contains the polyacetal resin in a proportion of 80% by mass or more, more preferably 85% by mass or more, and may be 90% by mass or more.
  • the polyacetal resin composition of the present invention may include only one type of polyacetal resin, or may include two or more types of polyacetal resin. When two or more kinds are contained, the total amount is preferably within the above range.
  • the polyacetal resin composition of the present invention contains at least one metal hydroxide composed of magnesium hydroxide and calcium hydroxide, and magnesium hydroxide is preferred. By including the metal hydroxide, the division of the molded article can be effectively suppressed.
  • the type and shape of the metal hydroxide are not particularly limited, but the average particle diameter is preferably 5 ⁇ m or less.
  • the metal hydroxide may be surface-treated. Examples of the surface treatment agent include a silane coupling agent and a fatty acid. The surface treatment is preferred because the dispersibility in the polyacetal resin tends to be further improved.
  • the polyacetal resin composition of the present invention contains 0.1 to 5.0 parts by mass of a metal hydroxide based on 100 parts by mass of the polyacetal resin.
  • the lower limit of the content is preferably 0.2 parts by mass or more.
  • the upper limit of the content is preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less.
  • the polyacetal resin composition of the present invention may contain one or more metal hydroxides, and when two or more metal hydroxides are contained, the total amount is preferably within the above range.
  • the polyacetal resin composition of the present invention contains a nitrogen-containing compound.
  • the nitrogen-containing compound is at least one selected from the group consisting of an amine-substituted compound, a carbodiimide compound, and a hindered amine light stabilizer, and melamine and a derivative thereof and / or a hindered amine light stabilizer are preferable. And derivatives thereof are more preferred.
  • An amine-substituted triazine compound refers to a compound having a triazine skeleton substituted with an amino group, and the amino group may be directly substituted on the triazine ring or may be substituted via a linking group, Is preferably directly substituted.
  • amine-substituted triazine compound examples include, for example, guanamine, melamine, methylolmelamine, N-butylmelamine, N-phenylmelamine, N, N-diphenylmelamine, N, N-diallylmelamine, N, N ′, N ′′ -Triphenylmelamine, N, N ', N "-trimethylolmelamine, benzoguanamine, 2,4-diamino-6-methyl-sym-triazine, 2,4-diamino-6-butyl-sym-triazine, 2,4 -Diamino-6-benzyloxy-sym-triazine, 2,4-diamino-6-butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-sym-triazine, 2,4-diamino-6-chloro- sym-triazine, 2,
  • the carbodiimide compound is not particularly limited as long as it has at least one carbodiimide group in the molecule, and a commercially available one or a compound produced by a known method can be used.
  • Examples of such a carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di- ⁇ -naphthylcarbodiimide, N, In addition to N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, cyclic carbodiimide, carbodilite (registered trademark
  • hindered amine light stabilizer those represented by the formula (5) are preferably used.
  • R 6 is an organic group having a carbon atom bonded to the nitrogen atom
  • X is an organic group bonded to the 4-position of the piperidyl group via an oxygen atom or a nitrogen atom
  • a hydrogen atom Represents
  • R 6 examples include a linear or branched alkyl group having 1 to 10 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a t-butyl group, a hexyl group, an octyl group, and a decyl group. Among them, a methyl group is preferred.
  • preferred hindered amine light stabilizers include, for example, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 1- [2- ⁇ 3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyloxydiethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidyl and tridecyl- 1,2,3,4 butanetetracarboxylate (part of the four ester moieties of butanetetracarboxylate is 1,2,2,6,6-pentamethyl-4-piperidi A mixture of compounds in which the other group is a tridecyl group),
  • the polyacetal resin composition of the present invention contains 0.1 to 3.0 parts by mass of a nitrogen-containing compound based on 100 parts by mass of the polyacetal resin.
  • the lower limit of the content is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and may be 0.4 parts by mass or more.
  • the upper limit of the content is preferably 2.0 parts by mass or less, may be 1.0 part by mass or less, further may be 0.75 parts by mass or less, particularly , 0.6 parts by mass or less.
  • the polyacetal resin composition of the present invention may contain one or more kinds of nitrogen-containing compounds, and when two or more kinds are contained, the total amount is preferably within the above range.
  • the polyacetal resin composition of the present invention contains a divalent metal oxide.
  • a divalent metal oxide By including a divalent metal oxide, mass reduction can be effectively suppressed.
  • the metal constituting the divalent metal oxide include Zn, Mg, Ca, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B, with Zn being preferred.
  • the polyacetal resin composition of the present invention contains 0.1 to 5.0 parts by mass of a divalent metal oxide based on 100 parts by mass of the polyacetal resin.
  • the lower limit of the content is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and may be 0.6 parts by mass or more.
  • the upper limit of the content is preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less.
  • the polyacetal resin composition of the present invention may contain one or more divalent metal oxides, and when it contains two or more, the total amount is preferably in the above range.
  • the metal hydroxide / divalent metal oxide (preferably zinc oxide), which is the mass ratio of the metal hydroxide to the divalent metal oxide (preferably zinc oxide), is 3%. 0.0 or less, more preferably 2.5 or less, and may be 1.8 or less, and further may be 1.5 or less, or 1.2 or less. Further, the lower limit of the mass ratio is preferably 0.1 or more, and may be 0.2 or more and 0.5 or more. By setting it in such a range, the effect of suppressing weight loss and cracking when the detergent containing fluorine ions is touched can be more effectively exhibited.
  • the polyacetal resin composition of the present invention may further contain a stress relaxing agent.
  • the stress relaxing agent include polyetheresteramide block copolymer, poly- ⁇ -olefin, polyolefin / polyether copolymer, polyamide copolymer, polyamide / polyalkylene glycol block copolymer, and a number average molecular weight of 20,000.
  • the polyethylene glycol is preferably at least one selected from the group consisting of polyethylene glycol and polyethylene oxide having a number average molecular weight of 20,000 or more, and more preferably polyethylene oxide having a number average molecular weight of 20,000 or more.
  • the polyetheresteramide block copolymer is preferably selected from those having a melting point lower than 230 ° C, and more preferably from those having a melting point of 150 to 200 ° C.
  • the poly- ⁇ -olefin is preferably selected from an ethylene / propylene copolymer and an ethylene / butene copolymer, and may be modified with an acid anhydride.
  • the polyolefin constituting the polyolefin / polyether copolymer is preferably polyethylene or polypropylene. Further, the polyether is preferably polyethylene glycol.
  • the polyamide copolymer is selected from polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6/66/610 terpolymer, and polyamide 6/66/610/12 quaternary copolymer. It is preferable that the melting point is lower than the maximum processing temperature of the polyacetal resin of 230 ° C.
  • the polyamide constituting the polyamide / polyalkylene glycol block copolymer is preferably a polyamide resin having a melting point lower than 230 ° C, and is preferably polyamide 12 or polyamide 6 having a melting point of 230 ° C or lower. 230 ° C. is equivalent to the maximum processing temperature of the polyacetal resin.
  • the polyalkylene glycol is preferably polyethylene glycol.
  • polyethylene glycol having a number average molecular weight of 20,000 or more those having a number average molecular weight of 20,000 to 100,000 are preferable, and those having a number average molecular weight of 20,000 to 50,000 are more preferable.
  • the polyethylene oxide having a number average molecular weight of 20,000 or more preferably has a number average molecular weight of 20,000 to 500,000, more preferably 80,000 to 30,000, and more preferably 100,000 to 200,000. Is more preferred.
  • catalog values can be adopted for commercial products.
  • the polyacetal resin composition of the present invention preferably contains 0.1 to 5.0 parts by weight of a stress relaxing agent based on 100 parts by weight of the polyacetal resin.
  • the lower limit of the content is more preferably 0.2 parts by mass or more, further preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more, and 1.0 part by mass. And more preferably at least 1.2 parts by mass.
  • the upper limit of the content is more preferably 4.0 parts by mass or less, further preferably 3.0 parts by mass or less, and further preferably 2.0 parts by mass or less.
  • the polyacetal resin composition of the present invention may contain one or more stress relaxation agents, and when two or more stress relaxation agents are contained, the total amount is preferably within the above range.
  • the polyacetal resin composition of the present invention in addition to the above components, a colorant, a nucleating agent, a plasticizer, a fluorescent brightener, a release agent, an antistatic agent, an ultraviolet absorber, an antioxidant, a fluidity modifier, Additives such as antibacterial agents and slidability improvers may be added as necessary.
  • the content of these additives, when contained, is preferably from 0.1 to 10% by mass of the polyacetal resin composition in total.
  • the total of the polyacetal resin, the metal hydroxide, the nitrogen-containing compound, the divalent metal oxide, and the stress relieving agent is 95% by mass, or 98% by mass or more of the composition. Is also preferable.
  • the polyacetal resin composition of the present invention is easily prepared by a known method generally used as a conventional method for preparing a thermoplastic resin composition. For example, (1) a method in which all components constituting the composition are mixed, supplied to an extruder and melt-kneaded to obtain a pellet-shaped composition, (2) a part of the components constituting the composition From the main feed port of the extruder, the remaining components are supplied from the side feed port and melt-kneaded to obtain a pellet-shaped composition. (3) Pellets having a different composition are once prepared by extrusion, etc. A method of adjusting to a predetermined composition by mixing can be adopted.
  • the molded article of the present invention is formed from the polyacetal resin composition of the present invention. Pellets obtained by pelletizing the polyacetal resin composition of the present invention are molded into molded articles by various molding methods. Alternatively, the resin composition melt-kneaded by an extruder can be directly molded into a molded product without passing through a pellet.
  • the shape of the molded article is not particularly limited and can be appropriately selected depending on the use and purpose of the molded article.
  • the molded product of the present invention may be a finished product, a part, or a welded product.
  • the method for molding the molded article is not particularly limited, and a conventionally known molding method can be adopted.
  • a conventionally known molding method can be adopted.
  • the polyacetal resin composition of the present invention and a molded article formed from the polyacetal resin composition are preferably used for applications requiring resistance to liquids containing fluorine ions. Specifically, as described above, it is preferably used for a vehicle-related component, particularly, a fuel pump module.
  • a vehicle-related component particularly, a fuel pump module.
  • each component was blended (the unit of the blending amount of each component in Tables 1 to 3 is parts by mass), and after pre-blend, a 30 mm diameter having one vent port was obtained.
  • Amine-substituted triazine compound melamine, amine-substituted triazine compound from Mitsui Chemicals: benzoguanamine, amine-substituted triazine compound from Nippon Shokubai Co., Ltd .: methylated melamine resin, Cymel 303, Nippon Cytec Carbodiimide compound: Stabacol P, Hindered amine light stabilizer manufactured by Rhein Chemie: Tinuvin 622, divalent metal oxide zinc oxide manufactured by BASF (Zincox Super F1), stress relief agent polyethylene glycol: PEG20000 (Mn20,000) manufactured by Hakusuiteku Co., Ltd., Sanyo Chemical Industries, melting point 68 ° C Polyethylene oxide: PEO-1 (Mn150,000), manufactured by Sumitomo Seika, melting point 71 ° C.
  • Polyetheresteramide block copolymer Perestat 6500, manufactured by Sanyo Chemical Industries, Ltd., melting point 192 ° C
  • Poly- ⁇ -olefin Toughmer DF610, manufactured by Mitsui Chemicals, Inc., melting point 47 ° C.
  • Polyolefin / polyether copolymer Perestat 201, manufactured by Sanyo Chemical Industries, Ltd., melting point: 164 ° C.
  • Polyamide copolymer Amilan CM4000, manufactured by Toray, melting point 148 ° C
  • Polyamide polyalkylene glycol block copolymer Perestat N1200, manufactured by Sanyo Chemical Industries, Ltd., melting point 149 ° C
  • the pellets (polyacetal resin composition) obtained above were injection molded at a mold temperature of 80 ° C. and a cylinder temperature of 190 ° C. into a cap having a diameter of 20 mm and a thickness of 1 mm.
  • the obtained molded product (cap) was evaluated as follows.
  • the melting point of the stress relaxing agent was measured using a differential scanning calorimeter at a nitrogen flow rate of 20 cm 3 / min at a heating rate of 10 ° C./min.
  • a differential scanning calorimeter PYRIS Diamond DSC was used.
  • Mass retention (mass of cap after immersion / mass of cap before immersion) ⁇ 100 (unit:%) The results are shown in Tables 1 to 3.

Abstract

Provided are a polyacetal resin composition and molded article thereof which are unlikely to suffer from splitting even upon contacting a liquid containing fluorine ions. This polyacetal resin composition contains, per 100 parts by mass of a polyacetal resin, 0.1-5.0 parts by mass of at least one type of metal hydroxide from among magnesium hydroxide and calcium hydroxide, 0.1-3.0 parts by mass of a nitrogen-containing compound selected from the group consisting of an amine-substituted triazine compound, a carbodiimide compound, and a hindered amine light stabilizer, and 0.1-5.0 parts by mass of a divalent metal oxide.

Description

ポリアセタール樹脂組成物、および、成形品Polyacetal resin composition and molded article
　本発明は、ポリアセタール樹脂組成物および成形品に関する。特に、燃料ポンプモジュールに用いられる成形品に関する。 The present invention relates to a polyacetal resin composition and a molded article. In particular, it relates to a molded product used for a fuel pump module.
　ポリアセタール樹脂は、機械的強度、耐薬品性、摺動性、耐摩耗性のバランスに優れ、かつ、その加工性が良好であることから、代表的なエンジニアリングプラスチックスとして、電気機器や電子機器の機構部品、自動車部品およびその他の機構部品等、広範囲にわたって用いられている。また、ポリアセタール樹脂は、その利用分野の拡大によって、ますます要求性能が高くなっている。
　例えば、特許文献１には、（Ａ）ポリアセタール樹脂１００質量部と、（Ｂ）酸化亜鉛０．１～２質量部と、（Ｃ）摺動性改良材０．１～５質量部とを含有し、前記（Ｂ）酸化亜鉛の数平均一次粒子径が７０～５００ｎｍである、ポリアセタール樹脂組成物が開示されている。 Polyacetal resin has excellent balance of mechanical strength, chemical resistance, slidability, and abrasion resistance, and its workability is good. It is widely used for mechanical parts, automobile parts and other mechanical parts. In addition, polyacetal resins are required to have higher performance due to the expansion of the application fields.
For example, Patent Document 1 contains (A) 100 parts by mass of a polyacetal resin, (B) 0.1 to 2 parts by mass of zinc oxide, and (C) 0.1 to 5 parts by mass of a slidability improving material. Further, there is disclosed a polyacetal resin composition in which the zinc oxide (B) has a number average primary particle diameter of 70 to 500 nm.
特開２０１５－３４２２１号公報JP 2015-34221 A
　ポリアセタール樹脂は、車両用部材、特に、燃料ポンプモジュールへの利用も検討されている。車両は、ガソリンスタンド等で、洗剤を用いて洗浄されることがしばしばある。しかしながら、洗剤として、フッ素イオンを含む洗剤を用いた場合、車両内部の部品に***が発生する場合があることが分かった。このような車両内部の部品が燃料ポンプモジュールである場合、その被害は深刻なものとなりえる。
　本発明はかかる課題を解決するものであって、フッ素イオンを含む液に接しても***が発生しにくいポリアセタール樹脂組成物およびその成形品を提供することを目的とする。 The use of polyacetal resin for vehicle components, particularly for fuel pump modules, is also being studied. Vehicles are often cleaned with detergents at gas stations and the like. However, it has been found that when a detergent containing fluorine ions is used as the detergent, division may occur in parts inside the vehicle. If such a vehicle interior component is a fuel pump module, the damage can be severe.
An object of the present invention is to solve such a problem, and an object of the present invention is to provide a polyacetal resin composition which is less likely to be split even when in contact with a liquid containing fluorine ions, and a molded article thereof.
　上記課題のもと、本発明者が検討を行った結果、ポリアセタール樹脂に、特定の金属水酸化物と、特定の窒素含有化合物と、特定の二価の金属酸化物を配合することにより、上記課題を解決しうることを見出し、本発明を完成するに至った。具体的には、下記手段＜１＞により、好ましくは＜２＞～＜１０＞により、上記課題は解決された。
＜１＞ポリアセタール樹脂１００質量部に対して、水酸化マグネシウムおよび水酸化カルシウムからなる金属水酸化物の少なくとも１種０．１～５．０質量部と、アミン置換トリアジン化合物、カルボジイミド化合物、ならびに、ヒンダードアミン系光安定剤からなる群から選択される窒素含有化合物０．１～３．０質量部と、二価の金属酸化物０．１～５．０質量部とを含む、ポリアセタール樹脂組成物。
＜２＞さらに、前記ポリアセタール樹脂１００質量部に対し、ポリエーテルエステルアミドブロック共重合体、ポリ－α－オレフィン、ポリオレフィン／ポリエーテル共重合体、ポリアミド共重合体、ポリアミド／ポリアルキレングリコールブロック共重合体、数平均分子量が２０，０００以上のポリエチレングリコール、および、数平均分子量が２０，０００以上のポリエチレンオキシドからなる群から選択される応力緩和剤０．１～５．０質量部を含む、＜１＞に記載のポリアセタール樹脂組成物。
＜３＞前記金属水酸化物と、前記二価の金属酸化物の質量比率である、金属水酸化物／二価の金属酸化物が、３．０以下である、＜１＞または＜２＞に記載のポリアセタール樹脂組成物。
＜４＞前記二価の金属酸化物が、酸化亜鉛である、＜１＞～＜３＞のいずれか１つに記載のポリアセタール樹脂組成物。
＜５＞前記二価の金属酸化物が、酸化亜鉛であり、前記金属水酸化物と、前記酸化亜鉛の質量比率である、金属水酸化物／酸化亜鉛が、１．８以下である、＜１＞または＜２＞に記載のポリアセタール樹脂組成物。
＜６＞フッ素イオンを含む液に対する耐性能を有する、＜１＞～＜５＞のいずれか１つに記載のポリアセタール樹脂組成物。
＜７＞燃料ポンプモジュールに用いられる、＜１＞～＜６＞のいずれか１つに記載のポリアセタール樹脂組成物。
＜８＞前記金属水酸化物が水酸化マグネシウムである、＜１＞～＜７＞のいずれか１つに記載のポリアセタール樹脂組成物。
＜９＞＜１＞～＜８＞のいずれか１つに記載のポリアセタール樹脂組成物から形成される成形品。
＜１０＞燃料ポンプモジュールに用いられる、＜９＞に記載の成形品。 Based on the above problems, as a result of the present inventors' investigation, the polyacetal resin, by mixing a specific metal hydroxide, a specific nitrogen-containing compound, and a specific divalent metal oxide, The inventors have found that the problem can be solved, and have completed the present invention. Specifically, the above problems have been solved by the following means <1>, preferably by <2> to <10>.
<1> With respect to 100 parts by mass of a polyacetal resin, 0.1 to 5.0 parts by mass of at least one metal hydroxide composed of magnesium hydroxide and calcium hydroxide, an amine-substituted triazine compound, a carbodiimide compound, and A polyacetal resin composition comprising 0.1 to 3.0 parts by mass of a nitrogen-containing compound selected from the group consisting of hindered amine light stabilizers and 0.1 to 5.0 parts by mass of a divalent metal oxide.
<2> Further, based on 100 parts by mass of the polyacetal resin, a polyetheresteramide block copolymer, a poly-α-olefin, a polyolefin / polyether copolymer, a polyamide copolymer, and a polyamide / polyalkylene glycol block copolymer. And 0.1 to 5.0 parts by weight of a stress relaxing agent selected from the group consisting of polyethylene glycol having a number average molecular weight of 20,000 or more and polyethylene oxide having a number average molecular weight of 20,000 or more. The polyacetal resin composition according to 1>.
<3><1> or <2>, wherein the ratio of metal hydroxide to divalent metal oxide is 3.0 or less, which is the mass ratio of the metal hydroxide to the divalent metal oxide. 3. The polyacetal resin composition according to item 1.
<4> The polyacetal resin composition according to any one of <1> to <3>, wherein the divalent metal oxide is zinc oxide.
<5> the divalent metal oxide is zinc oxide, and the metal hydroxide / zinc oxide, which is a mass ratio of the metal hydroxide and the zinc oxide, is 1.8 or less; < The polyacetal resin composition according to 1> or <2>.
<6> The polyacetal resin composition according to any one of <1> to <5>, which has resistance to a liquid containing a fluorine ion.
<7> The polyacetal resin composition according to any one of <1> to <6>, which is used for a fuel pump module.
<8> The polyacetal resin composition according to any one of <1> to <7>, wherein the metal hydroxide is magnesium hydroxide.
<9> A molded article formed from the polyacetal resin composition according to any one of <1> to <8>.
<10> The molded article according to <9>, which is used for a fuel pump module.
　本発明により、フッ素イオンを含む液に接しても***が発生しにくいポリアセタール樹脂組成物およびその成形品を提供可能になった。 According to the present invention, it has become possible to provide a polyacetal resin composition that does not easily split even when it comes into contact with a liquid containing fluorine ions, and a molded article thereof.
　以下において、本発明の内容について詳細に説明する。なお、本明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。 内容 Hereinafter, the contents of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.
　本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂１００質量部に対して、水酸化マグネシウムおよび水酸化カルシウムからなる金属水酸化物の少なくとも１種０．１～５．０質量部と、アミン置換トリアジン化合物、カルボジイミド化合物、ならびに、ヒンダードアミン系光安定剤からなる群から選択される窒素含有化合物０．１～３．０質量部と、二価の金属酸化物０．１～５．０質量部とを含むことを特徴とする。
　フッ素イオンを含む液に浸漬したことによる***（割れを含む、以下同じ）は、成形品に発生するクラックと、質量減少によって引き起こされる。特に、燃料ポンプモジュールの溶着部分や凹凸部分について、***が生じやすいことが分かった。また、この原因が、フッ素イオンを含む洗剤にあることが推定された。
　本発明では、ポリアセタール樹脂に所定の窒素含有化合物を配合することによって、フッ素イオン（例えば、ＨＦ成分など）を中和し、***を抑制していると推測される。
　また、本発明では、ポリアセタール樹脂に、特定の金属水酸化物を配合することによって、クラックの発生を抑制できることを見出した。しかしながら、金属水酸化物の含有量が多すぎると、成形品の質量減少を引き起こしてしまうことが分かった。そこで、本発明では、さらに、二価の金属酸化物を配合することによって、質量減少を抑制している。
　すなわち、本発明では、金属水酸化物と、二価の金属酸化物と、窒素含有化合物をバランスよく配合することによって、クラックの発生の抑制および質量減少の抑制の両立を達成することに成功し、***の発生を抑制することに成功した。特に、薄肉成形品（例えば、０．０１～３ｍｍ、さらには、０．１～２ｍｍの厚さの部位を有する成形品）としても、***を効果的に抑制することができる。
　さらに、本発明では、応力緩和剤として特定の高分子化合物を配合することにより、ゲート部など、複雑形状を有する成形品においても、残留応力によるクラックの発生を効果的に抑制できる。
　以下、本発明のポリアセタール樹脂組成物について、詳細に説明する。本発明がこれらに限定されるものではないことは言うまでもない。 The polyacetal resin composition of the present invention is characterized in that, based on 100 parts by mass of a polyacetal resin, 0.1 to 5.0 parts by mass of a metal hydroxide composed of magnesium hydroxide and calcium hydroxide, and an amine-substituted triazine compound , A carbodiimide compound, a nitrogen-containing compound selected from the group consisting of hindered amine-based light stabilizers in an amount of 0.1 to 3.0 parts by mass, and a divalent metal oxide in an amount of 0.1 to 5.0 parts by mass. It is characterized by the following.
Splitting (including cracking, the same applies hereinafter) due to immersion in a solution containing fluorine ions is caused by cracks generated in the molded article and mass reduction. In particular, it was found that splitting easily occurred in the welded portion and the uneven portion of the fuel pump module. It was also presumed that the cause was due to the detergent containing fluorine ions.
In the present invention, it is presumed that the addition of a predetermined nitrogen-containing compound to the polyacetal resin neutralizes fluorine ions (for example, HF components, etc.) and suppresses fragmentation.
Further, in the present invention, it has been found that the occurrence of cracks can be suppressed by blending a specific metal hydroxide with the polyacetal resin. However, it has been found that when the content of the metal hydroxide is too large, the mass of the molded article is reduced. Therefore, in the present invention, a decrease in mass is suppressed by further mixing a divalent metal oxide.
That is, in the present invention, by mixing a metal hydroxide, a divalent metal oxide, and a nitrogen-containing compound in a well-balanced manner, the inventors succeeded in achieving both suppression of crack generation and suppression of mass loss. Succeeded in suppressing the occurrence of division. In particular, even as a thin-walled molded product (for example, a molded product having a portion having a thickness of 0.01 to 3 mm, or even 0.1 to 2 mm), the division can be effectively suppressed.
Furthermore, in the present invention, the occurrence of cracks due to residual stress can be effectively suppressed even in a molded product having a complicated shape such as a gate portion by blending a specific polymer compound as a stress relaxation agent.
Hereinafter, the polyacetal resin composition of the present invention will be described in detail. It goes without saying that the present invention is not limited to these.
＜（Ａ）ポリアセタール樹脂＞
　本発明に用いる（Ａ）ポリアセタール樹脂は、アセタール構造－（－Ｏ－ＣＲＨ－）ｎ－（但しＲは水素原子または有機基を示す。）を繰り返し構造に有する高分子であり、通常はＲが水素原子であるオキシメチレン基（－ＣＨ２Ｏ－）を主たる構成単位とするものである。本発明に用いるポリアセタール樹脂は、この繰り返し構造のみからなるアセタールホモポリマー以外に、前記オキシメチレン基以外の繰り返し構成単位を１種以上含む共重合体（ブロック共重合体を含む）やターポリマー等も含み、さらには線状構造のみならず分岐、架橋構造を有していてもよい。 <(A) polyacetal resin>
The (A) polyacetal resin used in the present invention is a polymer having an acetal structure — (— O—CRH—) n — (where R represents a hydrogen atom or an organic group) in a repeating structure, and usually, R is An oxymethylene group (—CH 2 O—) that is a hydrogen atom is used as a main structural unit. The polyacetal resin used in the present invention includes, in addition to the acetal homopolymer having only this repeating structure, a copolymer (including a block copolymer) or a terpolymer containing at least one repeating structural unit other than the oxymethylene group. And may have not only a linear structure but also a branched or crosslinked structure.
　前記オキシメチレン基以外の構成単位としては例えば、オキシエチレン基（－ＣＨ２ＣＨ２Ｏ－）、オキシプロピレン基（－ＣＨ２ＣＨ２ＣＨ２Ｏ－）、オキシブチレン基（－ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ－）等の炭素数２以上１０以下の、分岐していてもよいオキシアルキレン基が挙げられ、中でも炭素数２以上４以下の、分岐していてもよいオキシアルキレン基が好ましく、特にオキシエチレン基が好ましい。またこの様な、オキシメチレン基以外のオキシアルキレン構成単位の含有量としては、ポリアセタール樹脂中において、０．１ｍｏｌ％以上２０ｍｏｌ％以下であることが好ましく、０．１ｍｏｌ％以上１５ｍｏｌ％以下であることがより好ましい。 Examples of the structural unit other than the oxymethylene group include an oxyethylene group (—CH 2 CH 2 O—), an oxypropylene group (—CH 2 CH 2 CH 2 O—), and an oxybutylene group (—CH 2 CH 2 CH). An optionally branched oxyalkylene group having 2 to 10 carbon atoms such as 2 CH 2 O-) is preferable, and an optionally branched oxyalkylene group having 2 to 4 carbon atoms is preferable. Particularly, an oxyethylene group is preferable. The content of the oxyalkylene structural unit other than the oxymethylene group is preferably from 0.1 mol% to 20 mol%, and more preferably from 0.1 mol% to 15 mol% in the polyacetal resin. Is more preferred.
　本発明に用いるポリアセタール樹脂の製造方法は任意であり、従来公知の任意の方法によって製造すればよい。例えば、オキシメチレン基と、炭素数２以上４以下のオキシアルキレン基を構成単位とするポリアセタール樹脂の製造方法としては、ホルムアルデヒドの３量体（トリオキサン）や４量体（テトラオキサン）等のオキシメチレン基の環状オリゴマーと、エチレンオキサイド、１，３－ジオキソラン、１，３，６－トリオキソカン、１，３－ジオキセパン等の炭素数２以上４以下のオキシアルキレン基を含む環状オリゴマーとを共重合することによって製造することができる。 方法 The method for producing the polyacetal resin used in the present invention is arbitrary, and may be produced by any conventionally known method. For example, a method for producing a polyacetal resin having an oxymethylene group and an oxyalkylene group having 2 to 4 carbon atoms as constituent units includes oxymethylene groups such as trimer (trioxane) and tetramer (tetraoxane) of formaldehyde. And a cyclic oligomer containing an oxyalkylene group having 2 or more and 4 or less carbon atoms, such as ethylene oxide, 1,3-dioxolan, 1,3,6-trioxocan, 1,3-dioxepane and the like. Can be manufactured.
　中でも本発明に用いるポリアセタール樹脂としては、トリオキサンやテトラオキサン等の環状オリゴマーと、エチレンオキサイドまたは１，３－ジオキソランとの共重合体であることが好ましく、特にトリオキサンと１，３－ジオキソランとの共重合体であることが好ましい。その溶融粘度は任意だが、溶融指数（ＭＩ）［ＡＳＴＭ－Ｄ１２３８：１９０℃、２．１６ｋｇ荷重下］で、通常０．０１～１５０ｇ／１０分であり、中でも０．１～１００ｇ／１０分、特に１～７０ｇ／１０分であることが好ましい。 Among them, the polyacetal resin used in the present invention is preferably a copolymer of a cyclic oligomer such as trioxane or tetraoxane and ethylene oxide or 1,3-dioxolan, and particularly a copolymer of trioxane and 1,3-dioxolan. It is preferred that they are united. Although its melt viscosity is arbitrary, its melt index (MI) [ASTM-D1238: 190 ° C., under a load of 2.16 kg] is usually 0.01 to 150 g / 10 min, especially 0.1 to 100 g / 10 min. Particularly, it is preferably 1 to 70 g / 10 minutes.
　本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂を８０質量％以上の割合で含むことが好ましく、８５質量％以上の割合で含むことがより好ましく、９０質量％以上であってもよい。本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、合計量が上記範囲となることが好ましい。 ポ リ The polyacetal resin composition of the present invention preferably contains the polyacetal resin in a proportion of 80% by mass or more, more preferably 85% by mass or more, and may be 90% by mass or more. The polyacetal resin composition of the present invention may include only one type of polyacetal resin, or may include two or more types of polyacetal resin. When two or more kinds are contained, the total amount is preferably within the above range.
＜（Ｂ）金属水酸化物＞
　本発明のポリアセタール樹脂組成物は、水酸化マグネシウムおよび水酸化カルシウムからなる金属水酸化物の少なくとも１種を含み、水酸化マグネシウムが好ましい。金属水酸化物を含むことにより、成形品の***を効果的に抑制できる。
　金属水酸化物は、その種類、形状等特に定めるものではないが、平均粒子径は５μｍ以下であることが好ましい。また、金属水酸化物は、表面処理されていてもよい。表面処理剤としては、シランカップリング剤や脂肪酸が例示される。表面処理を施すことによりポリアセタール樹脂中での分散性がより向上する傾向にあり好ましい。 <(B) Metal hydroxide>
The polyacetal resin composition of the present invention contains at least one metal hydroxide composed of magnesium hydroxide and calcium hydroxide, and magnesium hydroxide is preferred. By including the metal hydroxide, the division of the molded article can be effectively suppressed.
The type and shape of the metal hydroxide are not particularly limited, but the average particle diameter is preferably 5 μm or less. The metal hydroxide may be surface-treated. Examples of the surface treatment agent include a silane coupling agent and a fatty acid. The surface treatment is preferred because the dispersibility in the polyacetal resin tends to be further improved.
　本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂１００質量部に対して、金属水酸化物を０．１～５．０質量部含む。前記含有量の下限は、０．２質量部以上であることが好ましい。また、前記含有量の上限は、４．０質量部以下であることが好ましく、３．０質量部以下であることがより好ましく、２．０質量部以下であることがさらに好ましい。
　本発明のポリアセタール樹脂組成物は、金属水酸化物を１種または２種以上含んでいてもよく、２種以上含む場合は、合計量が上記範囲となることが好ましい。 The polyacetal resin composition of the present invention contains 0.1 to 5.0 parts by mass of a metal hydroxide based on 100 parts by mass of the polyacetal resin. The lower limit of the content is preferably 0.2 parts by mass or more. Further, the upper limit of the content is preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less.
The polyacetal resin composition of the present invention may contain one or more metal hydroxides, and when two or more metal hydroxides are contained, the total amount is preferably within the above range.
＜（Ｃ）窒素含有化合物＞
　本発明のポリアセタール樹脂組成物は、窒素含有化合物を含む。窒素含有化合物を含むことにより、フッ素イオンを含む液を中和し、質量減少を効果的に抑制できる。
　窒素含有化合物は、アミン置換化合物、カルボジイミド化合物、ならびに、ヒンダードアミン系光安定剤からなる群から選択される少なくとも１種であり、メラミンおよびその誘導体、ならびに／あるいは、ヒンダードアミン系光安定剤が好ましく、メラミンおよびその誘導体がより好ましい。
　アミン置換トリアジン化合物とは、アミノ基で置換されたトリアジン骨格を有する化合物をいい、アミノ基は、トリアジン環に直接に置換していても、連結基を介して置換していてもよく、トリアジン環に直接に置換していることが好ましい。
　アミン置換トリアジン化合物の具体例としては、例えば、グアナミン、メラミン、メチロールメラミン、Ｎ－ブチルメラミン、Ｎ－フェニルメラミン、Ｎ，Ｎ－ジフェニルメラミン、Ｎ，Ｎ－ジアリルメラミン、Ｎ，Ｎ’，Ｎ”－トリフェニルメラミン、Ｎ，Ｎ’，Ｎ”－トリメチロールメラミン、ベンゾグアナミン、２，４－ジアミノ－６－メチル－ｓｙｍ－トリアジン、２，４－ジアミノ－６－ブチル－ｓｙｍ－トリアジン、２，４－ジアミノ－６－ベンジルオキシ－ｓｙｍ－トリアジン、２，４－ジアミノ－６－ブトキシ－ｓｙｍ－トリアジン、２，４－ジアミノ－６－シクロヘキシル－ｓｙｍ－トリアジン、２，４－ジアミノ－６－クロロ－ｓｙｍ－トリアジン、２，４－ジアミノ－６－メルカプト－ｓｙｍ－トリアジン、アメリン（Ｎ，Ｎ，Ｎ’，Ｎ’－テトラシアノエチルベンゾグアナミン）、または、それらとホルムアルデヒドとの初期重縮合物等が挙げられる <(C) Nitrogen-containing compound>
The polyacetal resin composition of the present invention contains a nitrogen-containing compound. By containing the nitrogen-containing compound, the solution containing fluorine ions can be neutralized and the decrease in mass can be effectively suppressed.
The nitrogen-containing compound is at least one selected from the group consisting of an amine-substituted compound, a carbodiimide compound, and a hindered amine light stabilizer, and melamine and a derivative thereof and / or a hindered amine light stabilizer are preferable. And derivatives thereof are more preferred.
An amine-substituted triazine compound refers to a compound having a triazine skeleton substituted with an amino group, and the amino group may be directly substituted on the triazine ring or may be substituted via a linking group, Is preferably directly substituted.
Specific examples of the amine-substituted triazine compound include, for example, guanamine, melamine, methylolmelamine, N-butylmelamine, N-phenylmelamine, N, N-diphenylmelamine, N, N-diallylmelamine, N, N ′, N ″ -Triphenylmelamine, N, N ', N "-trimethylolmelamine, benzoguanamine, 2,4-diamino-6-methyl-sym-triazine, 2,4-diamino-6-butyl-sym-triazine, 2,4 -Diamino-6-benzyloxy-sym-triazine, 2,4-diamino-6-butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-sym-triazine, 2,4-diamino-6-chloro- sym-triazine, 2,4-diamino-6-mercapto-sym-triazine, amelin ( , N, N ', N'- tetra-cyanoethyl benzoguanamine), or the initial weight condensate thereof with formaldehyde and the like
　カルボジイミド化合物は、少なくとも分子中に１個以上のカルボジイミド基を有していれば特に限定されるものではなく、市販されているものや、公知の方法で製造されたものを使用することができる。
　このようなカルボジイミド化合物としては、例えば、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、ジメチルカルボジイミド、ジイソブチルカルボジイミド、ジオクチルカルボジイミド、ｔ－ブチルイソプロピルカルボジイミド、ジフェニルカルボジイミド、ジ－ｔ－ブチルカルボジイミド、ジ－β－ナフチルカルボジイミド、Ｎ，Ｎ’－ジ－２，６－ジイソプロピルフェニルカルボジイミド、２，６，２’，６’－テトライソプロピルジフェニルカルボジイミドの他、環状カルボジイミドや、カルボジライト（登録商標：日清紡ケミカル株式会社製）またはスタバクゾール（登録商標：ラインケミー社製）等のポリカルボジイミド等が挙げられる。
　また、特開２０１３－１００３９３号公報の段落００４０～００４４に記載のカルボジイミド化合物も用いることができ、これらの内容は本明細書に組み込まれる。 The carbodiimide compound is not particularly limited as long as it has at least one carbodiimide group in the molecule, and a commercially available one or a compound produced by a known method can be used.
Examples of such a carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, In addition to N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, cyclic carbodiimide, carbodilite (registered trademark: manufactured by Nisshinbo Chemical Co., Ltd.) or stabacol (registered trademark) (Manufactured by Rhein Chemie Co., Ltd.).
In addition, carbodiimide compounds described in paragraphs 0040 to 0044 of JP-A-2013-100393 can also be used, and the contents thereof are incorporated herein.
　ヒンダードアミン系光安定剤は、式（５）で表されるものが好ましく用いられる。
Figure JPOXMLDOC01-appb-C000001
 As the hindered amine light stabilizer, those represented by the formula (5) are preferably used.
Figure JPOXMLDOC01-appb-C000001
　上記式（５）中、Ｒ６は窒素原子との結合部が炭素原子である有機基、Ｘは、酸素原子若しくは窒素原子を介してピペリジル基の４－位と結合する有機基、または水素原子を表す。 In the above formula (5), R 6 is an organic group having a carbon atom bonded to the nitrogen atom, X is an organic group bonded to the 4-position of the piperidyl group via an oxygen atom or a nitrogen atom, or a hydrogen atom Represents
　Ｒ６としては、炭素数１～１０の直鎖状または分岐状のアルキル基等が挙げられる。このようなアルキル基としては、例えばメチル基、エチル基、プロピル基、ｔ－ブチル基、ヘキシル基、オクチル基、デシル基等が挙げられる。中でもメチル基が好ましい。 Examples of R 6 include a linear or branched alkyl group having 1 to 10 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a t-butyl group, a hexyl group, an octyl group, and a decyl group. Among them, a methyl group is preferred.
　好ましいヒンダードアミン系光安定剤の具体例としては、例えばビス（１，２，２，６，６－ペンタメチル－４－ピペリジニル）セバケート、１－［２－｛３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシ｝エチル］－４－［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシ］－２，２，６，６－テトラメチルピペリジン、テトラキス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、１，２，２，６，６－ペンタメチル－４－ピペリジルおよびトリデシル－１，２，３，４ブタンテトラカルボキシレート（ブタンテトラカルボキシレートの４つのエステル部の一部が１，２，２，６，６－ペンタメチル－４－ピペリジル基で他がトリデシル基である化合物の混合物）、１，２，３，４－ブタンテトラカルボン酸と１，２，２，６，６－ペンタメチル－４－ピペリジノールとβ，β，β，β－テトラメチル－３，９（２，４，８，１０－テトラオキサスピロ［５，５］ウデンカン）－ジエタノールとの縮合物、コハク酸ジメチルと４－ヒドロキシ－２，２，６，６－テトラメチル－１－ピペリジンエタノールの縮合物、１，２，２，６，６－ペンタメチル－４－ピペリジルメタクリレート、Ｎ，Ｎ’，Ｎ’’，Ｎ’’’－テトラキス－（４，６－ビス－（ブチル－（Ｎ－メチル－２，２，６，６－テトラメチルピペリジン－４－イル）アミノ）－トリアジン－２－イル）－４，７－ジアザデカン－１，１０－ジアミン、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）［［３，５－ビス（１，１ジメチルエチル）－４－ヒドロキシフェニル］メチル］ブチルマロネートが挙げられる。
　また、特開２０１５－０７４７２４号公報の段落００５６～００６０に記載のヒンダードアミン系光安定剤も用いることができ、これらの内容は本明細書に組み込まれる。 Specific examples of preferred hindered amine light stabilizers include, for example, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 1- [2- {3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyloxydiethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidyl and tridecyl- 1,2,3,4 butanetetracarboxylate (part of the four ester moieties of butanetetracarboxylate is 1,2,2,6,6-pentamethyl-4-piperidi A mixture of compounds in which the other group is a tridecyl group), 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β, β- Condensation product with tetramethyl-3,9 (2,4,8,10-tetraoxaspiro [5,5] udencan) -diethanol, dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl Condensate of -1-piperidineethanol, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- ( Butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, bis (1,2 , 2,6,6-pentamethyl-4-pipe Lysyl) [[3,5-bis (1,1 dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate.
Further, hindered amine light stabilizers described in paragraphs 0056 to 0060 of JP-A-2015-074724 can also be used, and the contents thereof are incorporated in the present specification.
　本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂１００質量部に対して、窒素含有化合物を０．１～３．０質量部含む。前記含有量の下限は、０．２質量部以上であることが好ましく、０．３質量部以上であることがより好ましく、０．４質量部以上であってもよい。また、前記含有量の上限は、２．０質量部以下であることが好ましく、１．０質量部以下であってもよく、さらには、０．７５質量部以下であってもよく、特には、０．６質量部以下であってもよい。
　本発明のポリアセタール樹脂組成物は、窒素含有化合物を１種または２種以上含んでいてもよく、２種以上含む場合は、合計量が上記範囲となることが好ましい。 The polyacetal resin composition of the present invention contains 0.1 to 3.0 parts by mass of a nitrogen-containing compound based on 100 parts by mass of the polyacetal resin. The lower limit of the content is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and may be 0.4 parts by mass or more. Further, the upper limit of the content is preferably 2.0 parts by mass or less, may be 1.0 part by mass or less, further may be 0.75 parts by mass or less, particularly , 0.6 parts by mass or less.
The polyacetal resin composition of the present invention may contain one or more kinds of nitrogen-containing compounds, and when two or more kinds are contained, the total amount is preferably within the above range.
＜（Ｄ）二価の金属酸化物＞
　本発明のポリアセタール樹脂組成物は、二価の金属酸化物を含む。二価の金属酸化物を含むことにより、質量減少を効果的に抑制できる。
　二価の金属酸化物を構成する金属としては、Ｚｎ、Ｍｇ、Ｃａ、Ｓｎ、Ｒｈ、Ｐｔ、Ｐｄ、Ｍｏ、Ｍｎ、Ｐｂ、Ｃｕ、Ｎｉ、Ｃｏ、Ｆｅ、Ｂが例示され、Ｚｎが好ましい。
　本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂１００質量部に対して、二価の金属酸化物を０．１～５．０質量部含む。前記含有量の下限は、０．２質量部以上であることが好ましく、０．３質量部以上であることがより好ましく、０．６質量部以上であってもよい。また、前記含有量の上限は、４．０質量部以下であることが好ましく、３．０質量部以下であることがより好ましく、２．０質量部以下であることがさらに好ましい。
　本発明のポリアセタール樹脂組成物は、二価の金属酸化物を１種または２種以上含んでいてもよく、２種以上含む場合は、合計量が上記範囲となることが好ましい。 <(D) Divalent metal oxide>
The polyacetal resin composition of the present invention contains a divalent metal oxide. By including a divalent metal oxide, mass reduction can be effectively suppressed.
Examples of the metal constituting the divalent metal oxide include Zn, Mg, Ca, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B, with Zn being preferred.
The polyacetal resin composition of the present invention contains 0.1 to 5.0 parts by mass of a divalent metal oxide based on 100 parts by mass of the polyacetal resin. The lower limit of the content is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and may be 0.6 parts by mass or more. Further, the upper limit of the content is preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less.
The polyacetal resin composition of the present invention may contain one or more divalent metal oxides, and when it contains two or more, the total amount is preferably in the above range.
　本発明では、また、金属水酸化物と、二価の金属酸化物（好ましくは酸化亜鉛）の質量比率である、金属水酸化物／二価の金属酸化物（好ましくは酸化亜鉛）が、３．０以下であることが好ましく、２．５以下であることがより好ましく、１．８以下であってもよく、さらには１．５以下、１．２以下であってもよい。また、前記質量比率の下限値は、０．１以上であることが好ましく、０．２以上、０．５以上であってもよい。このような範囲とすることにより、フッ素イオンを含む洗剤に触れた際の重量減少とひび割れを抑制できるという効果がより効果的に発揮される。 In the present invention, the metal hydroxide / divalent metal oxide (preferably zinc oxide), which is the mass ratio of the metal hydroxide to the divalent metal oxide (preferably zinc oxide), is 3%. 0.0 or less, more preferably 2.5 or less, and may be 1.8 or less, and further may be 1.5 or less, or 1.2 or less. Further, the lower limit of the mass ratio is preferably 0.1 or more, and may be 0.2 or more and 0.5 or more. By setting it in such a range, the effect of suppressing weight loss and cracking when the detergent containing fluorine ions is touched can be more effectively exhibited.
＜（Ｅ）応力緩和剤＞
　本発明のポリアセタール樹脂組成物は、さらに、応力緩和剤を含んでいてもよい。
　応力緩和剤は、ポリエーテルエステルアミドブロック共重合体、ポリ－α－オレフィン、ポリオレフィン／ポリエーテル共重合体、ポリアミド共重合体、ポリアミド／ポリアルキレングリコールブロック共重合体、数平均分子量が２０，０００以上のポリエチレングリコール、および、数平均分子量が２０，０００以上のポリエチレンオキシドからなる群から選択される少なくとも１種であることが好ましく、数平均分子量が２０，０００以上のポリエチレンオキシドがより好ましい。このような応力緩和剤を含むことにより、ゲート部など、複雑形状を有する成形品においても、残留応力によるクラックの発生を効果的に抑制できる。 <(E) Stress relaxation agent>
The polyacetal resin composition of the present invention may further contain a stress relaxing agent.
Examples of the stress relaxing agent include polyetheresteramide block copolymer, poly-α-olefin, polyolefin / polyether copolymer, polyamide copolymer, polyamide / polyalkylene glycol block copolymer, and a number average molecular weight of 20,000. The polyethylene glycol is preferably at least one selected from the group consisting of polyethylene glycol and polyethylene oxide having a number average molecular weight of 20,000 or more, and more preferably polyethylene oxide having a number average molecular weight of 20,000 or more. By including such a stress relaxing agent, cracks due to residual stress can be effectively suppressed even in a molded product having a complicated shape such as a gate portion.
　ポリエーテルエステルアミドブロック共重合体は、融点が２３０℃より低いものから選ばれることが好ましく、融点が１５０～２００℃のものから選ばれることがより好ましい。
　ポリ－α－オレフィンは、エチレン／プロピレン共重合体、エチレン／ブテン共重合体から選ばれることが好ましく、酸無水物で変性されてあってもよい。
　ポリオレフィン／ポリエーテル共重合体を構成するポリオレフィンは、ポリエチレンまたはポリプロピレンであることが好ましい。また、ポリエーテルは、ポリエチレングリコールであることが好ましい。
　ポリアミド共重合体は、ポリアミド６／６６共重合体、ポリアミド６／１２共重合体、ポリアミド６／６６／６１０三元共重合体、ポリアミド６／６６／６１０／１２四元共重合体より選択される少なくとも一種で構成され、融点がポリアセタール樹脂の加工最大温度２３０℃より低いことが好ましい。
　ポリアミド／ポリアルキレングリコールブロック共重合体を構成するポリアミドは、融点が２３０℃より低いポリアミド樹脂であることが好ましく、融点が２３０℃以下であるポリアミド１２、ポリアミド６であることが好ましい。２３０℃は、ポリアセタール樹脂の加工最大温度相当である。
また、ポリアルキレングリコールは、ポリエチレングリコールであることが好ましい。
　数平均分子量が２０，０００以上のポリエチレングリコールとしては、数平均分子量２０，０００～１００，０００のものが好ましく、２０，０００～５０，０００のものがより好ましい。
　数平均分子量が２０，０００以上のポリエチレンオキシドは、数平均分子量２０，０００～５００，０００のものが好ましく、８０，０００～３０，０００のものがより好ましく、１００，０００～２００，０００のものがさらに好ましい。
　本発明で用いる応力緩和剤の融点および数平均分子量は、市販品の場合はカタログ値を採用することができる。 The polyetheresteramide block copolymer is preferably selected from those having a melting point lower than 230 ° C, and more preferably from those having a melting point of 150 to 200 ° C.
The poly-α-olefin is preferably selected from an ethylene / propylene copolymer and an ethylene / butene copolymer, and may be modified with an acid anhydride.
The polyolefin constituting the polyolefin / polyether copolymer is preferably polyethylene or polypropylene. Further, the polyether is preferably polyethylene glycol.
The polyamide copolymer is selected from polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6/66/610 terpolymer, and polyamide 6/66/610/12 quaternary copolymer. It is preferable that the melting point is lower than the maximum processing temperature of the polyacetal resin of 230 ° C.
The polyamide constituting the polyamide / polyalkylene glycol block copolymer is preferably a polyamide resin having a melting point lower than 230 ° C, and is preferably polyamide 12 or polyamide 6 having a melting point of 230 ° C or lower. 230 ° C. is equivalent to the maximum processing temperature of the polyacetal resin.
Further, the polyalkylene glycol is preferably polyethylene glycol.
As the polyethylene glycol having a number average molecular weight of 20,000 or more, those having a number average molecular weight of 20,000 to 100,000 are preferable, and those having a number average molecular weight of 20,000 to 50,000 are more preferable.
The polyethylene oxide having a number average molecular weight of 20,000 or more preferably has a number average molecular weight of 20,000 to 500,000, more preferably 80,000 to 30,000, and more preferably 100,000 to 200,000. Is more preferred.
As for the melting point and the number average molecular weight of the stress relaxing agent used in the present invention, catalog values can be adopted for commercial products.
　本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂１００質量部に対して、応力緩和剤を０．１～５．０質量部含むことが好ましい。前記含有量の下限は、０．２質量部以上であることがより好ましく、０．５質量部以上であることがさらに好ましく、０．７質量部以上であることが一層好ましく、１．０質量部以上であることがより一層好ましく、１．２質量部以上であってもよい。また、前記含有量の上限は、４．０質量部以下であることがより好ましく、３．０質量部以下であることがさらに好ましく、２．０質量部以下であることが一層好ましい。
　本発明のポリアセタール樹脂組成物は、応力緩和剤を１種または２種以上含んでいてもよく、２種以上含む場合は、合計量が上記範囲となることが好ましい。 The polyacetal resin composition of the present invention preferably contains 0.1 to 5.0 parts by weight of a stress relaxing agent based on 100 parts by weight of the polyacetal resin. The lower limit of the content is more preferably 0.2 parts by mass or more, further preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more, and 1.0 part by mass. And more preferably at least 1.2 parts by mass. In addition, the upper limit of the content is more preferably 4.0 parts by mass or less, further preferably 3.0 parts by mass or less, and further preferably 2.0 parts by mass or less.
The polyacetal resin composition of the present invention may contain one or more stress relaxation agents, and when two or more stress relaxation agents are contained, the total amount is preferably within the above range.
＜その他の成分＞
　本発明のポリアセタール樹脂組成物は、上記成分の他、着色剤、核剤、可塑剤、蛍光増白剤、離型剤、帯電防止剤、紫外線吸収剤、酸化防止剤、流動性改質剤、抗菌剤、摺動性改良剤等の添加剤を必要に応じて添加してもよい。これらの添加剤の含有量は、含有する場合、合計で、ポリアセタール樹脂組成物の０．１～１０質量％であることが好ましい。
　また、本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂、金属水酸化物、窒素含有化合物、二価の金属酸化物および応力緩和剤の合計が組成物の９５質量％、さらには、９８質量％以上を占める態様も好ましい。 <Other ingredients>
The polyacetal resin composition of the present invention, in addition to the above components, a colorant, a nucleating agent, a plasticizer, a fluorescent brightener, a release agent, an antistatic agent, an ultraviolet absorber, an antioxidant, a fluidity modifier, Additives such as antibacterial agents and slidability improvers may be added as necessary. The content of these additives, when contained, is preferably from 0.1 to 10% by mass of the polyacetal resin composition in total.
Further, in the polyacetal resin composition of the present invention, the total of the polyacetal resin, the metal hydroxide, the nitrogen-containing compound, the divalent metal oxide, and the stress relieving agent is 95% by mass, or 98% by mass or more of the composition. Is also preferable.
＜ポリアセタール樹脂組成物の製造方法＞
　本発明のポリアセタール樹脂組成物は、従来の熱可塑性樹脂組成物の調製法として一般に用いられる公知の方法により容易に調製される。例えば、（１）組成物を構成する全成分を混合し、これを押出機に供給して溶融混練し、ペレット状の組成物を得る方法、（２）組成物を構成する成分の一部を押出機の主フィード口から、残余成分をサイドフィード口から供給して溶融混練し、ペレット状の組成物を得る方法、（３）押出し等により一旦組成の異なるペレットを調製し、それらのペレットを混合して所定の組成に調整する方法等を採用できる。 <Production method of polyacetal resin composition>
The polyacetal resin composition of the present invention is easily prepared by a known method generally used as a conventional method for preparing a thermoplastic resin composition. For example, (1) a method in which all components constituting the composition are mixed, supplied to an extruder and melt-kneaded to obtain a pellet-shaped composition, (2) a part of the components constituting the composition From the main feed port of the extruder, the remaining components are supplied from the side feed port and melt-kneaded to obtain a pellet-shaped composition. (3) Pellets having a different composition are once prepared by extrusion, etc. A method of adjusting to a predetermined composition by mixing can be adopted.
＜成形品＞
　本発明の成形品は、本発明のポリアセタール樹脂組成物から形成される。本発明のポリアセタール樹脂組成物をペレタイズして得られたペレットは、各種の成形法で成形して成形品とされる。またペレットを経由せずに、押出機で溶融混練された樹脂組成物を直接、成形して成形品にすることもできる。
　成形品の形状としては、特に制限はなく、成形品の用途、目的に応じて適宜選択することができ、例えば、板状、プレート状、ロッド状、シート状、フィルム状、円筒状、環状、円形状、楕円形状、歯車状、多角形形状、異形品、中空品、枠状、箱状、パネル状、キャップ状のもの等が挙げられる。本発明の成形品は、完成品であってもよいし、部品であってもよく、それぞれの溶着品でもよい。 <Molded product>
The molded article of the present invention is formed from the polyacetal resin composition of the present invention. Pellets obtained by pelletizing the polyacetal resin composition of the present invention are molded into molded articles by various molding methods. Alternatively, the resin composition melt-kneaded by an extruder can be directly molded into a molded product without passing through a pellet.
The shape of the molded article is not particularly limited and can be appropriately selected depending on the use and purpose of the molded article. For example, a plate, a plate, a rod, a sheet, a film, a cylinder, a ring, Circular, elliptical, gear, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, panel-shaped, cap-shaped, and the like. The molded product of the present invention may be a finished product, a part, or a welded product.
　成形品を成形する方法としては、特に制限されず、従来公知の成形法を採用でき、例えば、射出成形法、射出圧縮成形法、押出成形法、異形押出法、トランスファー成形法、中空成形法、ガスアシスト中空成形法、ブロー成形法、押出ブロー成形、ＩＭＣ（インモールドコーティング成形）成形法、回転成形法、多層成形法、２色成形法、インサート成形法、サンドイッチ成形法、発泡成形法、加圧成形法等が挙げられる。 The method for molding the molded article is not particularly limited, and a conventionally known molding method can be adopted.For example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, molding Pressure molding method and the like.
＜用途＞
　本発明のポリアセタール樹脂組成物およびポリアセタール樹脂組成物から形成される成形品は、フッ素イオンを含む液に対する耐性能を求められる用途に好ましく用いられる。
　具体的には、上述の通り、車両関連部品、特に、燃料ポンプモジュールに好ましく用いられる。
　また、上記以外でも、カム、スライダー、レバー、アーム、クラッチ、フェルトクラッチ、アイドラギアー、プーリー、ローラー、コロ、キーステム、キートップ、シャッター、リール、シャフト、関節、軸、軸受け、およびガイド等に代表される機構部品；アウトサート成形の樹脂部品、インサート成形の樹脂部品、シャーシ、トレー、側板、プリンター、ＨＤＤ内部部品（例えば、ランプ、ラッチ、等）、および複写機に代表されるオフィスオートメーション機器用部品；ＶＴＲ（Video Tape Recorder）、ビデオムービー、デジタルビデオカメラ、カメラ、およびデジタルカメラに代表されるカメラまたはビデオ機器用部品；カセットプレイヤー、ＤＡＴ、ＬＤ（Laser Disk）、ＭＤ（Mini Disk）、ＣＤ（Compact Disk）〔ＣＤ－ＲＯＭ（Read Only Memory）、ＣＤ－Ｒ（Recordable）、ＣＤ－ＲＷ(Rewritable)を含む〕、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を含む〕、Ｂｌｕ－ｒａｙ（登録商標） Ｄｉｓｃ、ＨＤ－ＤＶＤ、その他光デイスクのドライブ；ＭＦＤ、ＭＯ、ナビゲーションシステムおよびモバイルパーソナルコンピュータに代表される音楽、映像または情報機器、携帯電話およびファクシミリに代表される通信機器用部品；電気機器用部品；電子機器用部品等にも用いることができる。 <Application>
The polyacetal resin composition of the present invention and a molded article formed from the polyacetal resin composition are preferably used for applications requiring resistance to liquids containing fluorine ions.
Specifically, as described above, it is preferably used for a vehicle-related component, particularly, a fuel pump module.
Other than the above, represented by cams, sliders, levers, arms, clutches, felt clutches, idler gears, pulleys, rollers, rollers, key stems, key tops, shutters, reels, shafts, joints, shafts, bearings, guides, etc. Outsert molded resin parts, insert molded resin parts, chassis, trays, side plates, printers, HDD internal parts (eg, lamps, latches, etc.), and office automation equipment represented by copiers Parts; VTR (Video Tape Recorder), video movie, digital video camera, camera, and parts for camera or video equipment represented by digital camera; cassette player, DAT, LD (Laser Disk), MD (Mini Disk), CD (Compact Disk) [CD-ROM (Read Only Memory) Includes CD-R (Recordable), CD-RW (Rewritable)], DVD (Digital Video Disk) [DVD-ROM, DVD-R, DVD + R, DVD-RW, DVD + RW, DVD-R DL, DVD + R DL, DVD- RAM (including Random Access Memory) and DVD-Audio], Blu-ray (registered trademark) Disc, HD-DVD, and other optical disk drives; music and video represented by MFD, MO, navigation system, and mobile personal computer Alternatively, it can be used as a part for communication equipment typified by information equipment, a mobile phone and a facsimile; a part for electric equipment; a part for electronic equipment.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below.
実施例１～１６および比較例１～３
　下記表１～表３に示すとおり各成分を配合し（表１～表３における各成分の配合量の単位は質量部である）、プリブレンドした後、１ヶ所のベント口を有する３０ｍｍ径の二軸押出機の主フィード口に投入して溶融混合（押出条件：Ｌ／Ｄ＝３５、押出温度＝１９０℃、スクリュー回転数＝１２０ｒｐｍ）し、ペレット状の組成物を調製した。 Examples 1 to 16 and Comparative Examples 1 to 3
As shown in Tables 1 to 3 below, each component was blended (the unit of the blending amount of each component in Tables 1 to 3 is parts by mass), and after pre-blend, a 30 mm diameter having one vent port was obtained. The mixture was charged into a main feed port of a twin-screw extruder and melt-mixed (extrusion conditions: L / D = 35, extrusion temperature = 190 ° C., screw rotation speed = 120 rpm) to prepare a pellet-shaped composition.
　表１～表３において、各種材料は次のとおりである。
（Ａ）ポリアセタール樹脂：ユピタールＦ２０－０３、三菱エンジニアリングプラスチックス社製
　トリオキサン９６質量％と１，３－ジオキソラン４．０質量％とを共重合させてなるポリアセタール共重合体、メルトフローレート（ＭＦＲ）（１９０℃、荷重２．１６ｋｇで測定）：９ｇ／１０分
（Ｂ）水酸化マグネシウム：Ｓ－６Ｆ、神島化学工業社製、シランカップリング剤で表面処理されている
水酸化カルシウム：ＮＩＣＣ－３０００、井上石灰工業社製
（Ｃ）窒素含有化合物
アミン置換トリアジン化合物：メラミン、三井化学社製
アミン置換トリアジン化合物：ベンゾグアナミン、日本触媒社製
アミン置換トリアジン化合物：メチル化メラミン樹脂、サイメル３０３、日本サイテック社製
カルボジイミド化合物：スタバクゾールＰ、ラインケミー社製
ヒンダードアミン系光安定剤：チヌビン６２２、ＢＡＳＦ社製
（Ｄ）二価の金属酸化物
酸化亜鉛：Ｚｉｎｃｏｘ　Ｓｕｐｅｒ　Ｆ１、ハクスイテック社製
（Ｅ）応力緩和剤
ポリエチレングリコール：ＰＥＧ２００００（Ｍｎ２０，０００）、三洋化成工業社製、融点６８℃
ポリエチレンオキシド：ＰＥＯ－１（Ｍｎ１５０，０００）、住友精化社製、融点７１℃
ポリエーテルエステルアミドブロック共重合体：ペレスタット６５００、三洋化成工業社製、融点１９２℃
ポリ－α－オレフィン：タフマーＤＦ６１０、三井化学社製、融点４７℃
ポリオレフィン／ポリエーテル共重合体：ペレスタット２０１、三洋化成工業社製、融点１６４℃
ポリアミド共重合体：Ａｍｉｌａｎ　ＣＭ４０００、東レ社製、融点１４８℃
ポリアミドポリアルキレングリコールブロック共重合体：ペレスタットＮ１２００、三洋化成工業社製、融点１４９℃ In Tables 1 to 3, various materials are as follows.
(A) Polyacetal resin: Iupital F20-03, a polyacetal copolymer obtained by copolymerizing 96% by mass of trioxane manufactured by Mitsubishi Engineering-Plastics Corporation and 4.0% by mass of 1,3-dioxolane, melt flow rate (MFR) (Measured at 190 ° C. under a load of 2.16 kg): 9 g / 10 minutes (B) Magnesium hydroxide: S-6F, manufactured by Kamishima Chemical Co., Ltd. Calcium hydroxide surface-treated with a silane coupling agent: NICC-3000 (C) Nitrogen-containing compound from Inoue Lime Industry Co., Ltd. Amine-substituted triazine compound: melamine, amine-substituted triazine compound from Mitsui Chemicals: benzoguanamine, amine-substituted triazine compound from Nippon Shokubai Co., Ltd .: methylated melamine resin, Cymel 303, Nippon Cytec Carbodiimide compound: Stabacol P, Hindered amine light stabilizer manufactured by Rhein Chemie: Tinuvin 622, divalent metal oxide zinc oxide manufactured by BASF (Zincox Super F1), stress relief agent polyethylene glycol: PEG20000 (Mn20,000) manufactured by Hakusuiteku Co., Ltd., Sanyo Chemical Industries, melting point 68 ° C
Polyethylene oxide: PEO-1 (Mn150,000), manufactured by Sumitomo Seika, melting point 71 ° C.
Polyetheresteramide block copolymer: Perestat 6500, manufactured by Sanyo Chemical Industries, Ltd., melting point 192 ° C
Poly-α-olefin: Toughmer DF610, manufactured by Mitsui Chemicals, Inc., melting point 47 ° C.
Polyolefin / polyether copolymer: Perestat 201, manufactured by Sanyo Chemical Industries, Ltd., melting point: 164 ° C.
Polyamide copolymer: Amilan CM4000, manufactured by Toray, melting point 148 ° C
Polyamide polyalkylene glycol block copolymer: Perestat N1200, manufactured by Sanyo Chemical Industries, Ltd., melting point 149 ° C
　上記で得られたペレット（ポリアセタール樹脂組成物）を、金型温度８０℃、シリンダー温度１９０℃で、直径２０ｍｍで、１ｍｍ厚のキャップ状に射出成形した。
　得られた成形品（キャップ）について、以下の通り評価した。 The pellets (polyacetal resin composition) obtained above were injection molded at a mold temperature of 80 ° C. and a cylinder temperature of 190 ° C. into a cap having a diameter of 20 mm and a thickness of 1 mm.
The obtained molded product (cap) was evaluated as follows.
＜融点の測定＞
　応力緩和剤の融点は、示差走査熱量計を用い、窒素流量２０ｃｍ３／分で１０℃／分の昇温速度で測定した。
　示差走査熱量計は、ＰＹＲＩＳ　Ｄｉａｍｏｎｄ　ＤＳＣを用いた。 <Measurement of melting point>
The melting point of the stress relaxing agent was measured using a differential scanning calorimeter at a nitrogen flow rate of 20 cm 3 / min at a heating rate of 10 ° C./min.
As a differential scanning calorimeter, PYRIS Diamond DSC was used.
＜***＞
　上記で得られたキャップを２３℃、相対湿度（ＲＨ）５０％下で４８時間静置した後、ブラジル製、カーホイール洗剤ＬＩＭＰ　ＢＥＭ（フッ素イオンを含む洗剤）に浸漬し、６０℃に加温した。３６時間後取り出し、キャップ***しているか否かを確認し、以下の通り評価した。
Ａ：***しなかった。
Ｂ：***はなかったが、多少のクラックが認められた。
Ｃ：***してしまった。
　結果を表１～表３に示した。 <Division>
After leaving the cap obtained above at 23 ° C. and a relative humidity (RH) of 50% for 48 hours, it is immersed in a car wheel detergent LIMP BEM (a detergent containing fluorine ions) made in Brazil and heated to 60 ° C. did. It was taken out after 36 hours, and it was confirmed whether or not the cap was split, and evaluated as follows.
A: It did not split.
B: There was no division, but some cracks were observed.
C: It has split.
The results are shown in Tables 1 to 3.
＜質量保持率＞
　上記で得られたキャップを２３℃、相対湿度（ＲＨ）５０％下で４８時間静置した後、ブラジル製、カーホイール洗剤ＬＩＭＰ　ＢＥＭ（フッ素イオンを含む洗剤）に浸漬し、６０℃に加温した。３６時間後取り出し、質量保持率を以下の通り算出した。
質量保持率＝（浸漬後のキャップの質量／浸漬前のキャップの質量）×１００（単位：％）
　結果を表１～表３に示した。
  <Mass retention>
After leaving the cap obtained above at 23 ° C. and a relative humidity (RH) of 50% for 48 hours, it is immersed in a car wheel detergent LIMP BEM (a detergent containing fluorine ions) made in Brazil and heated to 60 ° C. did. It was taken out after 36 hours, and the mass retention was calculated as follows.
Mass retention = (mass of cap after immersion / mass of cap before immersion) × 100 (unit:%)
The results are shown in Tables 1 to 3.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上記結果から明らかなとおり、本発明のポリアセタール樹脂組成物から形成された成形品は、クラックの発生が抑制され、質量保持率も高かった。結果として、薄肉部を有するキャップでも***が生じなかった（実施例１～１６）。特に、金属水酸化物／二価の金属酸化物を、１．８以下としたとき、顕著な効果が認められた。
　これに対し、金属水酸化物を含まない場合（比較例１）、成形品の***が起きてしまった。また、窒素含有化合物を含まない場合（比較例２）、質量保持率が低かった。さらに、二価の金属酸化物を含まない場合（比較例３）、質量保持率が低かった。 As is clear from the above results, in the molded article formed from the polyacetal resin composition of the present invention, generation of cracks was suppressed and the mass retention was high. As a result, no splitting occurred even in the cap having the thin portion (Examples 1 to 16). In particular, when the ratio of metal hydroxide / divalent metal oxide was 1.8 or less, a remarkable effect was observed.
On the other hand, when no metal hydroxide was contained (Comparative Example 1), splitting of the molded product occurred. When no nitrogen-containing compound was contained (Comparative Example 2), the mass retention was low. Further, when no divalent metal oxide was contained (Comparative Example 3), the mass retention was low.

Claims (10)

  1. ポリアセタール樹脂１００質量部に対して、
    水酸化マグネシウムおよび水酸化カルシウムからなる金属水酸化物の少なくとも１種０．１～５．０質量部と、
    アミン置換トリアジン化合物、カルボジイミド化合物、ならびに、ヒンダードアミン系光安定剤からなる群から選択される窒素含有化合物０．１～３．０質量部と、
    二価の金属酸化物０．１～５．０質量部と
    を含む、ポリアセタール樹脂組成物。     For 100 parts by mass of polyacetal resin,
    0.1 to 5.0 parts by mass of at least one kind of metal hydroxide composed of magnesium hydroxide and calcium hydroxide;
    0.1 to 3.0 parts by mass of a nitrogen-containing compound selected from the group consisting of an amine-substituted triazine compound, a carbodiimide compound, and a hindered amine light stabilizer;
    A polyacetal resin composition comprising 0.1 to 5.0 parts by mass of a divalent metal oxide.
  2. さらに、前記ポリアセタール樹脂１００質量部に対し、ポリエーテルエステルアミドブロック共重合体、ポリ－α－オレフィン、ポリオレフィン／ポリエーテル共重合体、ポリアミド共重合体、ポリアミド／ポリアルキレングリコールブロック共重合体、数平均分子量が２０，０００以上のポリエチレングリコール、および、数平均分子量が２０，０００以上のポリエチレンオキシドからなる群から選択される応力緩和剤０．１～５．０質量部を含む、請求項１に記載のポリアセタール樹脂組成物。 Further, based on 100 parts by mass of the polyacetal resin, a polyether ester amide block copolymer, a poly-α-olefin, a polyolefin / polyether copolymer, a polyamide copolymer, a polyamide / polyalkylene glycol block copolymer, The composition according to claim 1, further comprising 0.1 to 5.0 parts by mass of a stress relaxation agent selected from the group consisting of polyethylene glycol having an average molecular weight of 20,000 or more and polyethylene oxide having a number average molecular weight of 20,000 or more. The polyacetal resin composition according to the above.
  3. 前記金属水酸化物と、前記二価の金属酸化物の質量比率である、金属水酸化物／二価の金属酸化物が、３．０以下である、請求項１または２に記載のポリアセタール樹脂組成物。 3. The polyacetal resin according to claim 1, wherein the ratio of metal hydroxide / divalent metal oxide, which is a mass ratio of the metal hydroxide and the divalent metal oxide, is 3.0 or less. 4. Composition.
  4. 前記二価の金属酸化物が、酸化亜鉛である、請求項１～３のいずれか１項に記載のポリアセタール樹脂組成物。 4. The polyacetal resin composition according to claim 1, wherein the divalent metal oxide is zinc oxide.
  5. 前記二価の金属酸化物が、酸化亜鉛であり、前記金属水酸化物と、前記酸化亜鉛の質量比率である、金属水酸化物／酸化亜鉛が、１．８以下である、請求項１または２に記載のポリアセタール樹脂組成物。 The said divalent metal oxide is a zinc oxide, The metal hydroxide / zinc oxide which is the mass ratio of the said metal hydroxide and the said zinc oxide is 1.8 or less. 3. The polyacetal resin composition according to 2.
  6. フッ素イオンを含む液に対する耐性能を有する、請求項１～５のいずれか１項に記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to any one of claims 1 to 5, which has resistance to a liquid containing fluorine ions.
  7. 燃料ポンプモジュールに用いられる、請求項１～６のいずれか１項に記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to any one of claims 1 to 6, which is used for a fuel pump module.
  8. 前記金属水酸化物が水酸化マグネシウムである、請求項１～７のいずれか１項に記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to any one of claims 1 to 7, wherein the metal hydroxide is magnesium hydroxide.
  9. 請求項１～８のいずれか１項に記載のポリアセタール樹脂組成物から形成される成形品。 A molded article formed from the polyacetal resin composition according to any one of claims 1 to 8.
  10. 燃料ポンプモジュールに用いられる、請求項９に記載の成形品。 The molded article according to claim 9, which is used for a fuel pump module.
PCT/JP2019/027159 2018-07-11 2019-07-09 Polyacetal resin composition and molded article WO2020013184A1 (en)

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