JP7492334B2 - Polyacetal resin composition, molded article and automobile part using said polyacetal resin composition, and method for improving acidic liquid resistance - Google Patents
Polyacetal resin composition, molded article and automobile part using said polyacetal resin composition, and method for improving acidic liquid resistance Download PDFInfo
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- JP7492334B2 JP7492334B2 JP2019235132A JP2019235132A JP7492334B2 JP 7492334 B2 JP7492334 B2 JP 7492334B2 JP 2019235132 A JP2019235132 A JP 2019235132A JP 2019235132 A JP2019235132 A JP 2019235132A JP 7492334 B2 JP7492334 B2 JP 7492334B2
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- 229930182556 Polyacetal Natural products 0.000 title claims description 72
- 229920006324 polyoxymethylene Polymers 0.000 title claims description 72
- 239000011342 resin composition Substances 0.000 title claims description 43
- 239000007788 liquid Substances 0.000 title claims description 26
- 230000002378 acidificating effect Effects 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 11
- 229920000642 polymer Polymers 0.000 claims description 16
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 15
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 12
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- -1 alkali metal acetate Chemical class 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- 239000000463 material Substances 0.000 claims 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003599 detergent Substances 0.000 description 8
- 150000001242 acetic acid derivatives Chemical class 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- TUYBEVLJKZQJPO-UHFFFAOYSA-N 19-(3,5-ditert-butyl-4-hydroxyphenyl)heptatriacontan-19-ylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCC(CCCCCCCCCCCCCCCCCC)(P(O)(O)=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 TUYBEVLJKZQJPO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920004943 Delrin® Polymers 0.000 description 1
- 229920005177 Duracon® POM Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、酸成分に対して高い耐性を有するポリアセタール樹脂組成物、そのポリアセタール樹脂組成物を用いた成形品および自動車部品、ならびに酸性液体耐性を向上させる方法に関する。 The present invention relates to a polyacetal resin composition having high resistance to acid components, a molded article and an automobile part using the polyacetal resin composition, and a method for improving resistance to acidic liquids.
ポリアセタール樹脂は耐薬品性に優れることから、ポリアセタール樹脂を原料とする成形体は自動車部品として広く使用されている。例えば、燃料油と直接接触する燃料ポンプモジュール等燃料接触体に代表される燃料搬送ユニット等の大型部品として用いられる。 Since polyacetal resin has excellent chemical resistance, molded articles made from polyacetal resin are widely used as automobile parts. For example, they are used as large parts such as fuel delivery units, which are representative of fuel contact bodies such as fuel pump modules that come into direct contact with fuel oil.
近年、各国の環境規制に対応するため、燃料の低硫黄化が進められている。しかしながら、脱硫設備には多大な費用がかかることから、一部の国では未だ高硫黄燃料が流通している。これらの高硫黄燃料は、低硫黄燃料に比べてポリアセタール樹脂を劣化させやすい傾向がある。 In recent years, efforts are being made to reduce the sulfur content of fuels in order to comply with environmental regulations in each country. However, because desulfurization equipment is very expensive, high-sulfur fuels are still in circulation in some countries. These high-sulfur fuels tend to deteriorate polyacetal resin more easily than low-sulfur fuels.
これらの課題に対して、本願出願人は、ポリアセタール樹脂にアルカリ土類金属酸化物、ポリアルキレングリコール、特定のエステル化合物を含有させることにより、大幅に改善できることを報告している（特許文献１）。特に高硫黄燃料に接触する燃料搬送ユニット等の部品に対しては、大きな改善策が得られた、 The applicant of the present application has reported that these problems can be significantly improved by incorporating alkaline earth metal oxides, polyalkylene glycols, and specific ester compounds into polyacetal resin (Patent Document 1). This has resulted in significant improvements, particularly for parts such as fuel delivery units that come into contact with high-sulfur fuels.
燃料搬送ユニット等の自動車部品は、ボンネット等の筐体によって覆われているものの、洗車時に洗浄剤の飛沫が付着することがある。特に、ホイールに付着したブレーキダスト等を除去する際には、高硫黄燃料を上回る強酸性の洗浄剤を用いることがあり、この洗浄剤によるポリアセタール樹脂からなる自動車部品の劣化も大きな課題としてある。 Although automotive parts such as fuel delivery units are covered by a hood or other housing, splashes of detergent may adhere to them when washing the car. In particular, when removing brake dust and other particles that have adhered to the wheels, detergents with higher acidity than those used in high-sulfur fuels may be used, and the deterioration of automotive parts made of polyacetal resin due to these detergents is also a major issue.
本発明は、成形品にした際、酸性液体に接触したときの劣化を抑えることの可能なポリアセタール樹脂組成物、そのポリアセタール樹脂組成物を用いた成形品および自動車部品、ならびに酸成分に対する耐性を向上させる方法を提供することを目的とする。 The present invention aims to provide a polyacetal resin composition that, when molded into a molded article, is capable of suppressing deterioration when it comes into contact with an acidic liquid, a molded article and an automobile part that use the polyacetal resin composition, and a method for improving resistance to acid components.
本発明者らは、上記課題を解決するため鋭意検討を重ねた結果、ポリアセタール樹脂組成物の組成を特定の組成にすることで、成形品にした際、酸性液体に接触したときの劣化を最小限に抑えられることを見出した。 As a result of extensive research into solving the above problems, the inventors discovered that by making the polyacetal resin composition into a specific composition, it is possible to minimize the deterioration that occurs when a molded product comes into contact with an acidic liquid.
従来、アルカリ土類金属酸化物の配合量が過剰の場合は、ポリアセタール樹脂中の不安定末端の分解を促進し、機械特性・成形性等に好ましくない影響が見られた（特許文献１）。本発明者らは、特定のアルカリ金属塩を含む組成にすることで上記の好ましくない影響を実用上問題ない範囲に抑制し、かつ酸性液体が接触したときの耐性（以下、酸性液体耐性ともいう）を著しく向上できることを発見し、本発明を完成するに至った。 Conventionally, when the amount of alkaline earth metal oxide blended is excessive, the decomposition of unstable terminals in the polyacetal resin is accelerated, and undesirable effects have been observed in mechanical properties, moldability, etc. (Patent Document 1). The present inventors have discovered that by using a composition containing a specific alkali metal salt, it is possible to suppress the above undesirable effects to a practically acceptable range and to significantly improve resistance when contacted with acidic liquids (hereinafter also referred to as acidic liquid resistance), and have thus completed the present invention.
すなわち本発明の目的は、下記によって達成された。
１． 少なくとも、（Ａ）ポリアセタール重合体１００質量部に対し、
（Ｂ）ヒンダードフェノール系酸化防止剤０．１～２．０質量部、
（Ｃ）アルカリ金属の炭酸塩および酢酸塩から選ばれる少なくとも一種３．０～１０質量部、
とを含有するポリアセタール樹脂組成物。
２． 前記（Ａ）ポリアセタール重合体がポリアセタールコポリマーである前記１に記載のポリアセタール樹脂組成物。
３． 前記（Ｃ）のアルカリ金属が、ナトリウム又はカリウムである前記１又は２記載のポリアセタール樹脂組成物。
４． さらに、（Ｄ）ポリアルキレングリコール０．５～３．０質量部、を含有する前記１～３いずれかに記載のポリアセタール樹脂組成物。
５． 前記、（Ｄ）ポリアルキレングリコールが、ポリエチレングリコール又はポリプロピレングリコールである前記1～４いずれかに記載のポリアセタール樹脂組成物。
６． 前記１～５いずれかに記載のポリアセタール樹脂組成物を用いて得られる酸性液体と接触する成形品。
７． 前記１～５いずれかに記載のポリアセタール樹脂組成物を用いて得られる酸性液体と接触する自動車部品。
８． 前記１～５いずれかに記載のポリアセタール樹脂組成物からなる成形品を用いて、酸性液体耐性を向上させる方法。
That is, the object of the present invention has been achieved as follows.
1. At least, relative to 100 parts by mass of the polyacetal polymer (A),
(B) 0.1 to 2.0 parts by mass of a hindered phenol-based antioxidant,
(C) 3.0 to 10 parts by mass of at least one selected from the group consisting of alkali metal carbonates and acetates,
A polyacetal resin composition comprising:
2. The polyacetal resin composition according to 1 above, wherein the polyacetal polymer (A) is a polyacetal copolymer.
3. The polyacetal resin composition according to 1 or 2 above, wherein the alkali metal (C) is sodium or potassium.
4. The polyacetal resin composition according to any one of 1 to 3 above, further comprising: (D) 0.5 to 3.0 parts by mass of a polyalkylene glycol.
5. The polyacetal resin composition according to any one of 1 to 4 above, wherein the polyalkylene glycol (D) is polyethylene glycol or polypropylene glycol.
6. A molded article which is obtained by using the polyacetal resin composition according to any one of 1 to 5 above and which is to come into contact with an acidic liquid.
7. An automobile part which is obtained by using the polyacetal resin composition according to any one of 1 to 5 above and which comes into contact with an acidic liquid.
8. A method for improving acidic liquid resistance by using a molded article made of the polyacetal resin composition according to any one of 1 to 5 above.
本発明によれば、成形品にした際、酸性液体に接触したときの劣化を最小限に抑えることの可能なポリアセタール樹脂組成物を提供することができる。
なお、本発明において、「酸性液体」とは、ｐＨが６以下、場合によりｐＨが２以下の液体を言い、例えば、車用洗剤（カーシャンプー，ホイールクリーナー），住宅用洗剤（トイレクリーナー，風呂場用洗剤，キッチン用洗剤）等が挙げられる。
According to the present invention, it is possible to provide a polyacetal resin composition which, when molded into a molded article, can minimize deterioration when the article comes into contact with an acidic liquid.
In the present invention, the term "acidic liquid" refers to a liquid having a pH of 6 or less, and in some cases a pH of 2 or less, and examples thereof include car detergents (car shampoos, wheel cleaners), household detergents (toilet cleaners, bathroom detergents, kitchen detergents), etc.
以下、本発明の具体的な実施形態について、詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Specific embodiments of the present invention are described in detail below, but the present invention is not limited to the following embodiments and can be modified as appropriate within the scope of the invention.
＜ポリアセタール樹脂組成物＞
本発明のポリアセタール樹脂組成物は、少なくとも、（Ａ）ポリアセタール重合体１００質量部に対し、（Ｂ）ヒンダードフェノール系酸化防止剤０．１～２．０質量部、（Ｃ）アルカリ金属の炭酸塩および酢酸塩から選ばれる少なくとも一種３．０～１０質量部を含有する組成物であるポリアセタール樹脂組成物であることを特徴とする。
<Polyacetal resin composition>
The polyacetal resin composition of the present invention is characterized in that it is a polyacetal resin composition which contains at least (A) 0.1 to 2.0 parts by mass of a hindered phenol-based antioxidant and (C) 3.0 to 10 parts by mass of at least one type selected from alkali metal carbonates and acetates, relative to 100 parts by mass of a polyacetal polymer.
以下、本発明のポリアセタール樹脂組成物の構成について詳細に説明する。
≪（Ａ）ポリアセタール重合体≫
本発明に使用される（Ａ）ポリアセタール重合体は、オキシメチレン基（－ＯＣＨ２－）を構成単位とするホモポリマー（例えば米国ＤｕＰｏｎｔ社製、商品名「デルリン」等）でもよいし、オキシメチレン単位以外に他のコモノマー単位を有するコポリマー（例えば、ポリプラスチックス（株）製、商品名「ジュラコン」等）であってもよい。熱安定性などの点からコポリマー（以下、ポリアセタール共重合体ともいう）であることが好ましい。
The configuration of the polyacetal resin composition of the present invention will be described in detail below.
<(A) Polyacetal polymer>
The polyacetal polymer (A) used in the present invention may be a homopolymer having an oxymethylene group (-OCH 2 -) as a constituent unit (for example, "Delrin", a product name, manufactured by DuPont, USA), or a copolymer having other comonomer units in addition to the oxymethylene unit (for example, "Duracon", a product name, manufactured by Polyplastics Co., Ltd.). From the viewpoint of thermal stability, etc., a copolymer (hereinafter also referred to as a polyacetal copolymer) is preferable.
一般的にはホルムアルデヒド又はホルムアルデヒドの環状化合物を主モノマーとし、環状エーテルや環状ホルマールから選ばれた化合物をコモノマーとして共重合させることによって製造され、通常、熱分解、（アルカリ）加水分解等によって末端の不安定部分を除去して安定化される。 They are generally produced by copolymerizing formaldehyde or a cyclic compound of formaldehyde as the main monomer with a compound selected from cyclic ethers and cyclic formals as the comonomer, and are usually stabilized by removing unstable terminal portions through thermal decomposition or (alkali) hydrolysis.
特に、主モノマーとしてはホルムアルデヒドの環状三量体であるトリオキサンを用いるのが一般的である。トリオキサンは、一般的には酸性触媒の存在下でホルムアルデヒド水溶液を反応させることにより得られ、これを蒸留などの方法で精製して使用される。重合に用いるトリオキサンは、水、メタノール、蟻酸などの不純物の含有量が極力少ないものが好ましい。 In particular, trioxane, a cyclic trimer of formaldehyde, is commonly used as the main monomer. Trioxane is generally obtained by reacting an aqueous solution of formaldehyde in the presence of an acid catalyst, and is purified by methods such as distillation before use. It is preferable that the trioxane used in the polymerization contains as little impurities as possible, such as water, methanol, and formic acid.
コモノマーとしては、一般的な環状エーテル及び環状ホルマール、また分岐構造や架橋構造を形成可能なグリシジルエーテル化合物などを単独で又は二種以上組み合わせて使用できる。 As comonomers, general cyclic ethers and cyclic formals, as well as glycidyl ether compounds capable of forming branched or crosslinked structures, can be used alone or in combination of two or more.
上記の如きポリアセタール共重合体は、一般には適量の分子量調整剤を添加し、カチオン重合触媒を用いてカチオン重合することにより得ることができる。使用される分子量調整剤、カチオン重合触媒、重合方法、重合装置、重合後の触媒の失活化処理、重合によって得られた粗ポリアセタール共重合体の末端安定化処理法などは多くの文献によって公知であり、基本的にはそれらが何れも利用できる。 The polyacetal copolymers described above can generally be obtained by adding an appropriate amount of a molecular weight regulator and carrying out cationic polymerization using a cationic polymerization catalyst. The molecular weight regulators, cationic polymerization catalysts, polymerization methods, polymerization apparatuses, catalyst deactivation treatments after polymerization, and terminal stabilization treatment methods for crude polyacetal copolymers obtained by polymerization are all well known in many literature, and basically any of them can be used.
本発明で使用するポリアセタール共重合体の分子量は特に限定されないが、１，１，１，３，３，３－ヘキサフルオロイソプロパノールを溶離液とするＳＥＣ（サイズ排除クロマトグラフィー）法にて決定したポリメタクリル酸メチル相当の重量平均分子量が１０，０００～４００，０００のものが好ましい。また、樹脂の流動性の指標となるメルトインデックス（ＩＳＯ１１３３に準じ、１９０℃、荷重２.１６ｋｇで測定）が０．１～１００ｇ／１０分であるものが好ましく、さらに好ましくは０．５～８０ｇ／１０分である。 The molecular weight of the polyacetal copolymer used in the present invention is not particularly limited, but it is preferable that the weight average molecular weight equivalent to polymethyl methacrylate determined by SEC (size exclusion chromatography) using 1,1,1,3,3,3-hexafluoroisopropanol as an eluent is 10,000 to 400,000. In addition, it is preferable that the melt index (measured in accordance with ISO1133 at 190°C and a load of 2.16 kg), which is an index of the fluidity of the resin, is 0.1 to 100 g/10 min, and more preferably 0.5 to 80 g/10 min.
本発明において使用する（Ａ）ポリアセタール重合体は、特定の末端特性を有していることが特に好ましい。具体的には、ヘミホルマール末端基量が１．０ｍｍｏｌ／ｋｇ以下、ホルミル末端基量が０．５ｍｍｏｌ／ｋｇ以下、不安定末端量が０．５質量％以下である。ここでヘミホルマール末端基は－ＯＣＨ２ＯＨで示されるものであり、ヒドロキシメトキシ基あるいはヘミアセタール末端基とも称される。 It is particularly preferred that the polyacetal polymer (A) used in the present invention has specific terminal characteristics. Specifically, the amount of hemiformal terminal groups is 1.0 mmol/kg or less, the amount of formyl terminal groups is 0.5 mmol/kg or less, and the amount of unstable terminals is 0.5 mass % or less. Here, the hemiformal terminal group is represented by --OCH 2 OH, and is also called a hydroxymethoxy group or a hemiacetal terminal group.
また、ホルミル末端基は－ＯＣＨＯで示される。このようなヘミホルマール末端基およびホルミル末端基の量は１Ｈ－ＮＭＲ測定により求めることができ、その具体的な測定方法は、特開２００１－１１１４３号公報に記載された方法を参照できる。 The amount of the hemiformal end group and the formyl end group can be determined by 1 H-NMR measurement, and the specific measurement method can be found in the method described in JP-A-2001-11143.
また、不安定末端量とは、ポリアセタール重合体の末端部分に存在し、熱や塩基に対して不安定で分解し易い部分の量を示す。かかる不安定末端量は、ポリアセタール共重合体１ｇを、０．５％（体積％）の水酸化アンモニウムを含む５０％（体積％）メタノール水溶液１００ｍｌとともに耐圧密閉容器に入れ、１８０℃で４５分間加熱処理した後、冷却し、開封して得られる溶液中に分解溶出したホルムアルデヒド量を定量し、ポリアセタール共重合体に対する質量％で表したものである。 The amount of unstable terminals refers to the amount of parts present at the terminals of the polyacetal polymer that are unstable to heat or bases and easily decompose. The amount of unstable terminals is determined by placing 1 g of polyacetal copolymer in a pressure-resistant sealed container together with 100 ml of a 50% (volume%) aqueous methanol solution containing 0.5% (volume%) ammonium hydroxide, heating the container at 180°C for 45 minutes, cooling the container, and opening the container to quantify the amount of formaldehyde that has decomposed and dissolved in the resulting solution, and expressing the amount as a mass % relative to the polyacetal copolymer.
≪（Ｂ）ヒンダードフェノール系酸化防止剤≫
本発明において使用される（Ｂ）ヒンダードフェノール系酸化防止剤としては、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、ヘキサメチレングリコール－ビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシヒドロシンナメート）、ペンタエリトリトール－テトラキス－３－（３、５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、トリエチレングリコール－ビス－３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ベンジル）ベンゼン、ｎ－オクタデシル－３－（４’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェノール）プロピオネート、４，４’－メチレンビス（２，６－ジ－ｔ－ブチルフェノール）、４，４’－ブチリデン－ビス（６－ｔ－ブチル－３－メチル－フェノール）、ジ－ステアリル－３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジルホスホネート、２－ｔ－ブチル－６－（３－ｔ－ブチル－５－メチル－２－ヒドロキシベンジル）－４－メチルフェニルアクリレート、３，９－ビス｛２－〔３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ〕－１，１－ジメチルエチル｝－２，４，８，１０－テトラオキサスピロ〔５，５〕ウンデカン等が例示される。
<(B) Hindered phenol-based antioxidant>
Examples of the hindered phenol-based antioxidant (B) used in the present invention include 2,2'-methylenebis(4-methyl-6-t-butylphenol), hexamethylene glycol-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamate), pentaerythritol-tetrakis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy-benzyl)benzene, n-octadecyl-3-(4'-hydrocinnamate), ... Examples include 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-3-methyl-phenol), di-stearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenyl acrylate, 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, and the like.
本発明においては、これらの酸化防止剤から選ばれた少なくとも一種又は二種以上を使用することができる。 In the present invention, at least one or more of these antioxidants may be used.
本発明における（Ｂ）ヒンダードフェノール系酸化防止剤の含有量は、（Ａ）ポリアセタール重合体１００質量部に対し、０．１～２．０質量部であり、０．２～１．５質量部であることがより好ましい。 The content of the (B) hindered phenol-based antioxidant in the present invention is 0.1 to 2.0 parts by mass, and more preferably 0.2 to 1.5 parts by mass, per 100 parts by mass of the (A) polyacetal polymer.
（Ｂ）酸化防止剤の配合量が少ないと、本来の目的である酸化防止特性が不十分になるだけでなく、本発明の目的である耐洗浄剤性も劣るものとなる。（Ｂ）酸化防止剤の配合量が過剰の場合は、樹脂組成物の機械的性質や成形性等に好ましくない影響が生じる。 If the amount of (B) antioxidant is too small, not only will the antioxidant properties, which are the original objective, be insufficient, but the detergent resistance, which is the objective of this invention, will also be poor. If the amount of (B) antioxidant is too large, this will have an undesirable effect on the mechanical properties, moldability, etc. of the resin composition.
≪（Ｃ）アルカリ金属の炭酸塩および酢酸塩から選ばれる少なくとも一種≫
本発明で使用される（Ｃ）アルカリ金属の炭酸塩および酢酸塩から選ばれる少なくとも一種は、酸性液体耐性性能が優れており好ましい。アルカリ金属の中でもナトリウムとカリウムが好ましく、炭酸ナトリウム、炭酸カリウム、酢酸ナトリウムおよび酢酸カリウムが好ましい。これらは、一種又は二種以上を混合して使用してもよい。
<<(C) At least one selected from alkali metal carbonates and acetates>>
At least one of the alkali metal carbonates and acetates (C) used in the present invention is preferable because it has excellent acidic liquid resistance. Among the alkali metals, sodium and potassium are preferable, and sodium carbonate, potassium carbonate, sodium acetate and potassium acetate are preferable. These may be used alone or in combination of two or more.
本発明における（Ｃ）アルカリ金属の炭酸塩および酢酸塩から選ばれる少なくとも一種の含有量は、（Ａ）ポリアセタール重合体１００質量部に対して３．０～１０質量部であることが好ましい。（Ｃ）アルカリ金属の炭酸塩および酢酸塩の少なくとも何れか一つの含有量が少ないと酸性液体と接触する際の劣化抑止が不十分となり、（Ｃ）アルカリ金属の炭酸塩および酢酸塩から選ばれる少なくとも一種の含有量が過剰の場合は、樹脂組成物の機械的性質や成形性等に好ましくない影響が生じる。 In the present invention, the content of at least one selected from (C) alkali metal carbonates and acetates is preferably 3.0 to 10 parts by mass per 100 parts by mass of (A) polyacetal polymer. If the content of at least one of (C) alkali metal carbonates and acetates is low, the inhibition of deterioration upon contact with acidic liquids becomes insufficient, and if the content of (C) at least one selected from alkali metal carbonates and acetates is excessive, undesirable effects are caused on the mechanical properties, moldability, etc. of the resin composition.
≪（Ｄ）ポリアルキレングリコール]≫
本発明においては、場合により（Ｄ）ポリアルキレングリコールを含有させることも好ましい。これらの種類は特に限定されないが、ポリアセタール重合体との親和性の観点から、ポリエチレングリコール又はポリプロピレングリコールを含有するものが好ましく、ポリエチレングリコールを含有するものがより好ましい。
<(D) Polyalkylene glycol>>
In the present invention, it is also preferable to contain (D) a polyalkylene glycol in some cases. The type of polyalkylene glycol is not particularly limited, but from the viewpoint of affinity with the polyacetal polymer, those containing polyethylene glycol or polypropylene glycol are preferred, and those containing polyethylene glycol are more preferred.
ポリアルキレングリコールの数平均分子量は特に限定されないが、ポリアセタール樹脂組成物中での分散性の観点から、１,０００～５０,０００であることが好ましく、５,０００～３０,０００であることがより好ましい。なお、本発明において、ポリアルキレングリコールの数平均分子量は、テトラヒドロフランを溶離液とするＳＥＣ法によって求めたポリスチレン換算の分子量であるものとする。 The number average molecular weight of the polyalkylene glycol is not particularly limited, but from the viewpoint of dispersibility in the polyacetal resin composition, it is preferably 1,000 to 50,000, and more preferably 5,000 to 30,000. In the present invention, the number average molecular weight of the polyalkylene glycol is the polystyrene-equivalent molecular weight determined by the SEC method using tetrahydrofuran as an eluent.
本発明における（Ｄ）ポリアルキレングリコールの含有量は、（Ａ）ポリアセタール重合体１００質量部に対し、０．５～３．０質量部であり、１．０～２．０質量部であることがより好ましい。（Ｄ）ポリアルキレングリコールを含有させなくとも十分な酸性液体耐性が得られる場合は、含有させる必要はない。添加量の上限は、成形体の機械的性質とのバランスで選択される。これらは２種以上を混合して使用しても良い。 The content of (D) polyalkylene glycol in the present invention is 0.5 to 3.0 parts by mass, and more preferably 1.0 to 2.0 parts by mass, per 100 parts by mass of (A) polyacetal polymer. If sufficient acidic liquid resistance can be obtained without adding (D) polyalkylene glycol, it is not necessary to add it. The upper limit of the amount added is selected based on the balance with the mechanical properties of the molded body. Two or more of these may be mixed and used.
≪その他の成分≫
本発明のポリアセタール樹脂組成物には、本発明を阻害しない限り、必要に応じて、さらに、耐侯（光）安定剤、耐衝撃性改良剤、光沢性制御剤、摺動性改良剤、充填剤、着色剤、核剤、帯電防止剤、界面活性剤、相溶化剤、などを一種又は二種以上配合することができる。
Other Ingredients
The polyacetal resin composition of the present invention may further contain, as necessary, one or more of the following additives, so long as they do not impair the present invention: weather (light) stabilizers, impact resistance improvers, gloss control agents, sliding property improvers, fillers, colorants, nucleating agents, antistatic agents, surfactants, compatibilizers, etc.
≪ポリアセタール樹脂組成物の成形品≫
本発明のポリアセタール樹脂組成物からなる成形品は、上記ポリアセタール樹脂組成物を用いて、慣用の成形方法、例えば、射出成形、押出成形、圧縮成形、ブロー成形、真空成形、発泡成形、回転成形等の方法で成形することにより得ることができる。
<Molded article of polyacetal resin composition>
A molded article made of the polyacetal resin composition of the present invention can be obtained by molding the polyacetal resin composition by a conventional molding method, such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, and rotational molding.
本発明の成形品は、例えばｐＨ２以下の強酸性の液体に接触したとしても、劣化が抑制され、良好な成形品表面外観を保持できる。本発明の成形品の用途は特に限定されないが、例えば、自動車のホイール等車体洗浄の際に酸性洗浄剤に触れる可能性のある自動車部品の全てに特に好適に使用することができる。 The molded article of the present invention is inhibited from deteriorating and can maintain a good surface appearance even when it comes into contact with a strongly acidic liquid, for example, pH 2 or less. The uses of the molded article of the present invention are not particularly limited, but it can be particularly suitable for use in all automobile parts that may come into contact with acidic cleaning agents when washing the vehicle, such as automobile wheels.
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるもので
はない。
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these.
表１における各種成分は次のとおりである。表中の単位は質量部である。
（Ａ）ポリアセタール重合体
（Ａ－１）トリオキサン９６．７質量％と１，３－ジオキソラン３．３質量％とを共重合させてなるポリアセタールコポリマー（メルトインデックス（ＩＳＯ１１３３に準拠し、１９０℃，荷重２．１６ｋｇで測定）：９ｇ／１０ｍｉｎ）
（Ｂ）ヒンダードフェノール系酸化防止剤
（Ｂ－１）ペンタエリトリトール－テトラキス－３－（３、５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート（製品名：Ｉｒｇａｎｏｘ１０１０、ＢＡＳＦ社製）
The various components in Table 1 are as follows. The units in the table are parts by mass.
(A) Polyacetal Polymer (A-1) Polyacetal copolymer obtained by copolymerizing 96.7% by mass of trioxane and 3.3% by mass of 1,3-dioxolane (Melt index (measured in accordance with ISO1133 at 190°C and a load of 2.16 kg): 9 g/10 min)
(B) Hindered phenol-based antioxidant (B-1) Pentaerythritol-tetrakis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (product name: Irganox 1010, manufactured by BASF)
（Ｃ）アルカリ金属塩－全て富士フイルム和光純薬（株）製試薬を使用
（Ｃ－１）炭酸ナトリウム
（Ｃ－２）酢酸ナトリウム
（Ｃ－３）炭酸カリウム
（Ｃ－４）ステアリン酸ナトリウム
（Ｃ－５）塩化ナトリウム
（Ｄ）ポリアルキレングリコール
（Ｄ－１）製品名：ＰＥＧ６０００Ｓ（三洋化成工業（株）製）
（Ｄ－２）製品名：ＰＥＧ２００００Ｐ（三洋化成工業（株）製）
(C) Alkali metal salts - all reagents manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (C-1) Sodium carbonate (C-2) Sodium acetate (C-3) Potassium carbonate (C-4) Sodium stearate (C-5) Sodium chloride (D) Polyalkylene glycol (D-1) Product name: PEG6000S (manufactured by Sanyo Chemical Industries, Ltd.)
(D-2) Product name: PEG20000P (manufactured by Sanyo Chemical Industries, Ltd.)
＜実施例及び比較例＞
表１に示す各種成分を表１に示す割合で添加混合し、二軸の押出機で溶融混練してペレット状の組成物を調製した。
<Examples and Comparative Examples>
The various components shown in Table 1 were mixed in the ratios shown in Table 1, and melt-kneaded in a twin-screw extruder to prepare a pellet-shaped composition.
＜評価＞
（１）酸性液体耐性の評価
実施例及び比較例で調製したポリアセタール樹脂組成物を用い、射出成形により厚さ４ｍｍｔのＩＳＯｔｙｐｅ１－Ａ引張試験片を作製した。なお比較例９では、成形性が著しく悪化したため、成形品を作製することができなかった。
<Evaluation>
(1) Evaluation of Acidic Liquid Resistance Using the polyacetal resin compositions prepared in the Examples and Comparative Examples, ISO type 1-A tensile test pieces having a thickness of 4 mm were prepared by injection molding. In Comparative Example 9, moldability was significantly deteriorated, so that a molded product could not be prepared.
［評価方法］
ポリアセタール樹脂組成物の酸性液体耐性を評価するため、上記引張試験片の両端を固定し、曲げ歪み１．５％となる様に湾曲させた。２３℃５０％±１０％ＲＨの条件下にて、引張試験片の湾曲の頂点（試験片の長さ方向の中央付近）の表面に下記酸性液体を１０μＬ滴下し、酸性液体滴下部にクラックが発生するまで静置した。
酸性液体組成：リン酸１０質量％水溶液
[Evaluation method]
In order to evaluate the acidic liquid resistance of the polyacetal resin composition, both ends of the tensile test piece were fixed and curved to a bending strain of 1.5%. Under conditions of 23°C and 50%±10% RH, 10 μL of the following acidic liquid was dropped onto the surface of the apex of the curve of the tensile test piece (near the center in the longitudinal direction of the test piece), and the test piece was left to stand until cracks were generated at the part where the acidic liquid was dropped.
Acid liquid composition: 10% by weight aqueous solution of phosphoric acid
［評価基準］
酸性液体滴下から試験片にクラックが確認されるまでの時間で以下の様に×～◎に区分した。結果を表１および２に示す。
◎：１０時間以上
○：７時間以上１０時間未満
△：４時間以上７時間未満
×：４時間未満
[Evaluation criteria]
The time from when the acidic liquid was dropped until cracks were confirmed on the test piece was classified as follows: × to ⊚. The results are shown in Tables 1 and 2.
◎: 10 hours or more ○: 7 hours or more but less than 10 hours △: 4 hours or more but less than 7 hours ×: Less than 4 hours
（２）機械的性質評価
（１）にて成形した引張試験片を用いて、ＩＳＯ５２７－１、５２７－２に準拠し引張破断呼び歪測定を行った。測定室は、２３℃５０％ＲＨの雰囲気を保持した。引張破断呼び歪の値によって以下のように区分した。結果を表１および２に示す。
○：２５％以上
△：１５％以上２５％未満
×：１５％未満
(2) Mechanical property evaluation Using the tensile test pieces molded in (1), nominal tensile breaking strain measurements were performed in accordance with ISO 527-1 and 527-2. The atmosphere in the measurement room was maintained at 23°C and 50% RH. The nominal tensile breaking strain values were classified as follows. The results are shown in Tables 1 and 2.
○: 25% or more △: 15% or more but less than 25% ×: Less than 15%
実施例１～１１及び比較例４、６および８のポリアセタール樹脂組成物からなる試験片では、４時間以上でも試験片にクラックが生じることはなかったが、比較例１～３、５、７、９および１０のポリアセタール樹脂組成物からなる試験片では、４時間までの間に、試験片にクラックが生じた。 In the test pieces made of the polyacetal resin compositions of Examples 1 to 11 and Comparative Examples 4, 6, and 8, no cracks were generated in the test pieces even after 4 hours or more, but in the test pieces made of the polyacetal resin compositions of Comparative Examples 1 to 3, 5, 7, 9, and 10, cracks were generated in the test pieces within 4 hours.
実施例１～１１及び比較例１～３、５、７および１０のポリアセタール樹脂組成物からなる試験片では、引張破断呼び歪が１５％以上であったが、比較例４、６、および８のポリアセタール樹脂組成物からなる試験片では、１５％より低い値となった。 The test pieces made of the polyacetal resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3, 5, 7, and 10 had nominal tensile break strains of 15% or more, whereas the test pieces made of the polyacetal resin compositions of Comparative Examples 4, 6, and 8 had values lower than 15%.
実施例、比較例より、本発明品は、酸性液体耐性および機械的性質においてともに優れていることが確認された。
From the Examples and Comparative Examples, it was confirmed that the product of the present invention is excellent in both acidic liquid resistance and mechanical properties.
Claims (10)
（Ａ）ポリアセタール重合体１００質量部に対し、
（Ｂ）ヒンダードフェノール系酸化防止剤を０．１～２．０質量部、
（Ｃ）アルカリ金属の炭酸塩または酢酸塩を６～９質量部、含有し、
前記アルカリ金属の炭酸塩および酢酸塩は被覆材で被覆されていない、
ポリアセタール樹脂組成物。 at least,
(A) per 100 parts by mass of polyacetal polymer,
(B) 0.1 to 2.0 parts by mass of a hindered phenol-based antioxidant,
(C) 6 to 9 parts by mass of an alkali metal carbonate or acetate,
The alkali metal carbonate and acetate are not coated with a coating material.
Polyacetal resin composition.
（Ｂ）ヒンダードフェノール系酸化防止剤の含有量が０．１～２．０質量部であり、
（Ｃ）アルカリ金属の炭酸塩および酢酸塩の合計の含有量が６質量部、であるポリアセタール樹脂組成物。 (A) per 100 parts by mass of polyacetal polymer,
(B) the content of the hindered phenol-based antioxidant is 0.1 to 2.0 parts by mass,
(C) A polyacetal resin composition having a total content of an alkali metal carbonate and an alkali metal acetate of 6 parts by mass .
（Ｂ）ヒンダードフェノール系酸化防止剤を０．１～２．０質量部、
（Ｃ）アルカリ金属の炭酸塩を３．０～５．０質量部、
（Ｄ）ポリアルキレングリコールを１．０～３．０質量部、含有し、
前記ポリアルキレングリコールが、ポリエチレングリコール又はポリプロピレングリコールであり、
前記アルカリ金属の炭酸塩は被覆材で被覆されていない、
ポリアセタール樹脂組成物。 (A) per 100 parts by mass of polyacetal polymer,
(B) 0.1 to 2.0 parts by mass of a hindered phenol-based antioxidant,
(C) 3.0 to 5.0 parts by mass of an alkali metal carbonate ,
(D) 1.0 to 3.0 parts by mass of polyalkylene glycol,
the polyalkylene glycol is polyethylene glycol or polypropylene glycol,
The alkali metal carbonate is not coated with a coating material.
Polyacetal resin composition.
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| JPH0517547A (en) * | 1991-07-12 | 1993-01-26 | Toray Ind Inc | Production of oxymethylene copolymer |
| DE4235958A1 (en) * | 1992-10-24 | 1994-04-28 | Degussa | Polyoxymethylene with improved stability against acids, process for its preparation and use |
| JPH11302497A (en) * | 1998-04-24 | 1999-11-02 | Toyota Motor Corp | Acid-resistant polyacetal-based resin material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001139977A (en) | 1999-11-11 | 2001-05-22 | Oiles Ind Co Ltd | Resin composition for sliding member and sliding bearing |
| JP2003268195A (en) | 2002-03-15 | 2003-09-25 | Toray Ind Inc | Manufacturing method of polyoxymethylene resin composition |
| JP2009132768A (en) | 2007-11-29 | 2009-06-18 | Polyplastics Co | Polyacetal resin molded article excellent in acid resistance |
| JP5814419B1 (en) | 2014-04-25 | 2015-11-17 | ポリプラスチックス株式会社 | Polyacetal resin composition and sulfur fuel contact body provided with molded article of polyacetal resin composition |
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