JPH07109403A - Polyoxymethylene composition - Google Patents
Polyoxymethylene compositionInfo
- Publication number
- JPH07109403A JPH07109403A JP27737693A JP27737693A JPH07109403A JP H07109403 A JPH07109403 A JP H07109403A JP 27737693 A JP27737693 A JP 27737693A JP 27737693 A JP27737693 A JP 27737693A JP H07109403 A JPH07109403 A JP H07109403A
- Authority
- JP
- Japan
- Prior art keywords
- polyoxymethylene
- weight
- group
- parts
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Polyoxymethylene Polymers 0.000 title claims abstract description 71
- 229930040373 Paraformaldehyde Natural products 0.000 title claims abstract description 36
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001336 alkenes Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 241001082241 Lythrum hyssopifolia Species 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000000314 lubricant Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920009382 Polyoxymethylene Homopolymer Polymers 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- CXURGFRDGROIKG-UHFFFAOYSA-N 3,3-bis(chloromethyl)oxetane Chemical group ClCC1(CCl)COC1 CXURGFRDGROIKG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical group CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリオキシメチレン成形
品同志が互いにコスレ合う時に発するキシミ音が無く、
且つ成形品の外観（ゲート部フローマーク）にすぐれた
ポリオキシメチレン組成物に関するものである。BACKGROUND OF THE INVENTION The present invention eliminates the squeaking noises generated when polyoxymethylene molded products come into contact with each other.
The present invention also relates to a polyoxymethylene composition having an excellent appearance (flow mark of the gate portion) of a molded product.
【０００２】[0002]
【従来の技術】ポリオキシメチレンは、機械的強度、耐
疲労性、電気特性、自己潤滑性にすぐれていることか
ら、歯車、軸受け、及びその他の機械や電気等の機構部
品を中心に多岐に渡って使用されている。しかしなが
ら、スターター部品のような部品にポリオキシメチレン
成形品同志を組み合わせて使用した場合、コスレ合う音
が激しく、そのキシミ音の改良が切に望まれている。2. Description of the Related Art Polyoxymethylene is excellent in mechanical strength, fatigue resistance, electrical characteristics and self-lubricating property. Therefore, it is widely used in gears, bearings and other mechanical parts such as machinery and electricity. Used across. However, when a polyoxymethylene molded product is used in combination with a part such as a starter part, a sharp sound is produced, and improvement in the squeaking noise is eagerly desired.
【０００３】従来、ポリオキシメチレンの摺動性を改良
する方法として、例えば（１）二硫化モリブデン等の固
体潤滑剤を添加する方法、（２）ポリエチレン、ポリ四
フッ化エチレン等の粉末や繊維を添加する方法、（３）
石油系潤滑油、合成潤滑油等の液体、もしくは固体潤滑
剤を添加する方法等がよく知られている。中でもポリエ
チレン、流動パラフィン等のオレフィン系潤滑剤を添加
することは、ポリオキシメチレンの摺動性を向上させる
点で非常に有用な方法である。しかしながら、これらの
オレフィン系潤滑剤は、本質的にポリオキシメチレンに
対する相溶性が低く、そのため成形品の外観を損うとい
う欠点を有している。Conventionally, as a method for improving the slidability of polyoxymethylene, for example, (1) a method of adding a solid lubricant such as molybdenum disulfide, (2) a powder or fiber of polyethylene, polytetrafluoroethylene, etc. Method of adding (3)
A method of adding a liquid such as a petroleum-based lubricating oil or a synthetic lubricating oil, or a solid lubricant is well known. Above all, the addition of an olefinic lubricant such as polyethylene or liquid paraffin is a very useful method from the viewpoint of improving the slidability of polyoxymethylene. However, these olefinic lubricants inherently have low compatibility with polyoxymethylene, and therefore have the drawback of impairing the appearance of molded articles.
【０００４】即ち、本組成物から得られた成形品を摺動
部品として用いた場合、成形品表面にブリードアウトし
た潤滑剤が摺動界面に存在し、成形品同志のコスレ音
（キシミ音）は無くなるが、潤滑剤のポリオキシメチレ
ンに対する相溶性が低いことから、成形品の外観が悪
く、両者を満足するものは得られていない。一方、ポリ
オキシメチレンにオレフィン系化合物とノニオン系界面
活性剤を添加し、ポリオキシメチレンの摺動性を改良す
る方法（特開平５−６５３９０号公報）が提案されてい
る。しかしこの方法でも、成形品のキシミ音が激しく、
又、成形品の外観も悪いのであって、やはり両者を満足
するものは得られていない。That is, when a molded product obtained from the composition is used as a sliding part, the lubricant bleeding out on the surface of the molded product is present at the sliding interface, and the creaking noise (creeping sound) of the molded products is generated. However, since the compatibility of the lubricant with polyoxymethylene is low, the appearance of the molded product is poor, and no one satisfying both requirements has been obtained. On the other hand, a method has been proposed in which an olefin compound and a nonionic surfactant are added to polyoxymethylene to improve the slidability of polyoxymethylene (JP-A-5-65390). However, even with this method, the creaking noise of the molded product is severe,
Moreover, the appearance of the molded product is also poor, and no one satisfying both of them has been obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、ポリ
オキシメチレン成形品同志が互いにコスレ合う時に発す
るキシミ音が無く、且つ成形品外観にすぐれたポリオキ
シメチレン組成物を提供することにある。更に詳しく言
えば、本発明の目的は本発明の組成物から得られる成形
品をスターター部品に用いた場合、成形品同志がコスレ
合う時に発する音が無く、且つ成形品の外観良好である
材料を提供することである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyoxymethylene composition which is free of creaking noises generated when polyoxymethylene molded articles are co-existing with each other and has an excellent molded article appearance. . More specifically, when the molded article obtained from the composition of the present invention is used as a starter part, the object of the present invention is to produce a material that does not emit a sound when the molded articles are co-existing and has a good appearance of the molded article. Is to provide.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討した結果、ポリオキシメチレン
にある特定のオレフィン化合物、ポリオキシアルキレン
グリコールを添加して得られる組成物を用いた成形品が
キシミ音と成形品外観にすぐれていることを見出した。
即ち、本発明は、（Ａ）ポリオキシメチレン１００重量
部と、（Ｂ）一般式Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have used a composition obtained by adding a specific olefin compound in polyoxymethylene and polyoxyalkylene glycol. It was found that the molded product had excellent creaking noise and appearance.
That is, the present invention comprises (A) 100 parts by weight of polyoxymethylene and (B) a general formula.
【０００７】[0007]
【化３】 （Ｒ1 ，Ｒ2 は水素、アルキル基、置換アルキル基、ア
リール基、置換アリール基、エーテル基より選ばれ、各
々同一であってもよく異ってもよい。ｎ＝３０〜２０
０）で表わされる少なくとも１種のオレフィン単位から
構成されるオレフィン化合物０．０５〜２重量部と、
（Ｃ）一般式[Chemical 3] (R 1 and R 2 are selected from hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an ether group, and may be the same or different. N = 30 to 20
0) an olefin compound composed of at least one olefin unit represented by 0.05 to 2 parts by weight;
(C) General formula
【０００８】[0008]
【化４】 （Ｒ3 は水素、アルキル基、置換アルキル基、アリール
基より選ばれ、各々同一であっても異ってもよい。Ｘ＝
２〜６、Ｙ＝１０００〜２００００）で表わされるポリ
アルキレングリコール０．０５〜５重量部からなること
を特徴とするポリオキシメチレン組成物である。[Chemical 4] (R 3 is selected from hydrogen, an alkyl group, a substituted alkyl group and an aryl group and may be the same or different. X =
2 to 6, Y = 1000 to 20000), and a polyoxymethylene composition characterized by comprising 0.05 to 5 parts by weight of a polyalkylene glycol.
【０００９】以下、本発明のポリオキシメチレン組成物
について具体的に説明する。本発明で言うポリオキシメ
チレンとは、オキシメチレン単位The polyoxymethylene composition of the present invention will be specifically described below. The polyoxymethylene referred to in the present invention is an oxymethylene unit.
【００１０】[0010]
【化５】 の繰り返しよりなる単独重合体（ポリオキシメチレンホ
モポリマー）、及び、オキシメチレン単位の繰り返しよ
りなる単独重合体に、エチレンオキシド、プロピレンオ
キシド、１，３ジオキソラン等のコモノマーを挿入した
共重合体（ポリオキシメチレンコポリマー）、及び３次
元架橋構造を有する共重合体等を公知の方法で安定化し
たものを言う。又、オキシメチレン単位と異なる繰り返
し単位を有する公知のポリオキシメチレンブロックコポ
リマーも本発明で言うポリオキシメチレンに含まれる。[Chemical 5] A homopolymer of polyoxymethylene (polyoxymethylene homopolymer), and a homopolymer of polyoxymethylene units each having a comonomer such as ethylene oxide, propylene oxide or 1,3 dioxolane (polyoxymethylene homopolymer). (Methylene copolymer), a copolymer having a three-dimensional crosslinked structure, and the like stabilized by a known method. Known polyoxymethylene block copolymers having repeating units different from oxymethylene units are also included in the polyoxymethylene referred to in the present invention.
【００１１】次に潤滑剤として用いるオレフィン化合物
について詳細に説明する。本発明に用いることのできる
オレフィン化合物は、一般式Next, the olefin compound used as the lubricant will be described in detail. The olefin compound that can be used in the present invention has a general formula
【００１２】[0012]
【化６】 （Ｒ1 ，Ｒ2 ，ｎは前述の通り）で表わされる少なくと
も１種のオレフィン単位から構成されるオレフィン化合
物である。[Chemical 6] (R 1 , R 2 , and n are as described above), which is an olefin compound composed of at least one olefin unit.
【００１３】アルキル基としては、例えばエチル基、プ
ロピル基、ブチル基、ヘキシル基、オクチル基、デシル
基、ラウリル基、セチル基、ステアリル基等があり、ア
リール基としては、例えばフェニル基、Ｐ−ブチルフェ
ニル基、Ｐ−オクチルフェニル基、Ｐ−ノニルフェニル
基、ベンジル基、Ｐ−ブチルベンジル基、トリル基、キ
シリル基等がある。又、エーテル基としては、例えばエ
チルエーテル基、プロピルエーテル基、ブチルエーテル
基等がある。好ましいオレフィン単位としては、成形品
同志が互いにコスレ合う時に発するキシミ音改良の観点
より、下記のものが挙げられる。The alkyl group includes, for example, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, lauryl group, cetyl group, stearyl group and the like, and the aryl group includes, for example, phenyl group, P- group. There are butylphenyl group, P-octylphenyl group, P-nonylphenyl group, benzyl group, P-butylbenzyl group, tolyl group, xylyl group and the like. Examples of the ether group include ethyl ether group, propyl ether group, butyl ether group and the like. The preferable olefin units include the following units from the viewpoint of improving the squeaking noise generated when the molded products are mutually elastic.
【００１４】[0014]
【化７】 [Chemical 7]
【００１５】[0015]
【化８】 [Chemical 8]
【００１６】[0016]
【化９】 [Chemical 9]
【００１７】本発明に用いるオレフィン化合物は、１種
のオレフィン単位から構成される化合物、又は２種以上
の異なるオレフィン単位から構成される化合物のいずれ
であってもかまわない。即ち、例えばポリエチレン単位
とプロピレン単位とから構成されるブロック構造、又
は、グラフト構造を有するオレフィン化合物も本発明の
オレフィン化合物に含まれる。The olefin compound used in the present invention may be a compound composed of one olefin unit or a compound composed of two or more different olefin units. That is, for example, an olefin compound having a block structure composed of a polyethylene unit and a propylene unit or having a graft structure is also included in the olefin compound of the present invention.
【００１８】本発明の成形品同志が互いにコスレ合う音
（キシミ音）改良の観点から、オレフィン化合物の構造
はグラフト構造に比べて線状構造である方が好ましい。
オレフィン化合物を構成するモノマーとしては、例えば
エチレン、プロピレン、１−ブテン、２−ブテン、イソ
ブテン、３−メチル−１−ブテン、２−メチル−２−ブ
テン、１−ヘキサン、２，３−ジメチル−２−ブテン、
１−ヘプテン、１−オクテン、１−ノネン、１−デセン
等で表わされるオレフィン系モノマー、又はアレン、
１，２−ブタジエン、１，３−ブタジエン、１，３−ペ
ンタジエン、１，４−ペンタジエン、１，５−ヘキサジ
エン、シクロペンタジエン等で表わされるジオレフィン
系モノマーがある。From the viewpoint of improving the sound (creeping sound) in which the molded articles according to the present invention are mutually elastic, it is preferable that the structure of the olefin compound is linear rather than the graft structure.
Examples of the monomer constituting the olefin compound include ethylene, propylene, 1-butene, 2-butene, isobutene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexane and 2,3-dimethyl-. 2-butene,
An olefinic monomer represented by 1-heptene, 1-octene, 1-nonene, 1-decene, or allene;
There are diolefin-based monomers represented by 1,2-butadiene, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, cyclopentadiene and the like.
【００１９】本発明に用いるオレフィン化合物は、これ
らのオレフィン系モノマー、ジオレフィン系モノマーの
２種以上を共重合して得られる化合物であってもかまわ
ない。オレフィン化合物がジオレフィン系モノマーを重
合して得られる化合物である場合は、本ポリオキシメチ
レン組成物の熱安定性の向上の観点より、慣用の水素添
加法を用いて炭素−炭素不飽和結合を極力少なくしたオ
レフィン化合物を用いる方が好ましい。The olefin compound used in the present invention may be a compound obtained by copolymerizing two or more of these olefin monomers and diolefin monomers. When the olefin compound is a compound obtained by polymerizing a diolefin-based monomer, from the viewpoint of improving the thermal stability of the polyoxymethylene composition, a carbon-carbon unsaturated bond is formed by using a conventional hydrogenation method. It is preferable to use an olefin compound which has been reduced as much as possible.
【００２０】オレフィン化合物を構成するオレフィン単
位の平均重合度ｎは３０〜２００の間にある必要があ
る。平均重合度ｎが３０より小さい場合は、本ポリオキ
シメチレン組成物のキシミ音がまったく改良されない。
ｎが２００より大きい場合は、ポリオキシメチレンとの
相溶性が悪いことから成形品のゲート部ではく離を起こ
し、成形品の外観を著しく低下させる。オレフィン単位
の平均重合度ｎは７０〜２００の間にあることが好まし
い。The average degree of polymerization n of the olefin units constituting the olefin compound must be between 30 and 200. When the average degree of polymerization n is less than 30, the squeaking noise of the polyoxymethylene composition is not improved at all.
When n is greater than 200, the compatibility with polyoxymethylene is poor and peeling occurs at the gate of the molded product, resulting in a marked deterioration in the appearance of the molded product. The average degree of polymerization n of the olefin unit is preferably between 70 and 200.
【００２１】オレフィン化合物のポリオキシメチレンに
対する添加量は、ポリオキシメチレン１００重量部に対
して０．０５〜２重量部の範囲にある方が好ましい。添
加量が０．０５重量部より少ない場合は、本組成物の成
形品キシミ音を改良することがまったくできず、２重量
部より多いと成形品の外観を著しく低下させる。オレフ
ィン化合物の添加量は、更には０．１〜１．０重量部が
好ましい。これらのオレフィン化合物は、２種類以上を
併用して用いてもかまわない。The addition amount of the olefin compound to polyoxymethylene is preferably in the range of 0.05 to 2 parts by weight with respect to 100 parts by weight of polyoxymethylene. If the amount added is less than 0.05 parts by weight, the creaking noise of the molded product of the present composition cannot be improved at all, and if it is more than 2 parts by weight, the appearance of the molded product is significantly deteriorated. The addition amount of the olefin compound is more preferably 0.1 to 1.0 part by weight. These olefin compounds may be used in combination of two or more kinds.
【００２２】次に、相溶化剤として用いるポリアルキレ
ングリコールについて詳細に説明する。本発明に用いる
ことのできるポリアルキレンオキシドは、一般式Next, the polyalkylene glycol used as the compatibilizer will be described in detail. The polyalkylene oxide that can be used in the present invention has the general formula
【００２３】[0023]
【化１０】 （Ｒ3 ，Ｘ，Ｙは前述の通り）で表わされるポリアルキ
レンオキシドである。[Chemical 10] (R 3 , X and Y are as described above).
【００２４】具体的なポリアルキレンオキシドとして
は、例えばエチレンオキシド、プロピレンオキシド、ブ
チレンオキシド、エピクロルヒドリン、スチレンオキシ
ド、オキセタン、３，３−ビス（クロロメチル）オキセ
タン、テトラヒドロフラン、２−メチルテトラヒドロフ
ラン、オキセパン等がある。これらのアルキレンオキシ
ドの中でもポリオキシメチレンとの親和性よりエチレン
オキシド及びプロピレンオキシドが特に好ましい。Specific examples of the polyalkylene oxide include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, oxetane, 3,3-bis (chloromethyl) oxetane, tetrahydrofuran, 2-methyltetrahydrofuran and oxepane. . Among these alkylene oxides, ethylene oxide and propylene oxide are particularly preferable because of their affinity with polyoxymethylene.
【００２５】アルキレンオキシドの重付加モル数は、
１，０００〜２０，０００の範囲にあることが必要であ
る。重付加モル数が１，０００未満の場合、成形品外観
を著しく低下させ、２０，０００を超える場合、成形品
キシミ音は改良されない。より好ましくはポリアルキレ
ンオキシドの重付加モル数は、３，０００〜１０，００
０の範囲である。The number of moles of polyaddition of alkylene oxide is
It should be in the range of 1,000 to 20,000. When the number of polyadditions is less than 1,000, the appearance of the molded product is significantly deteriorated, and when it exceeds 20,000, the squeaking noise of the molded product is not improved. More preferably, the polyalkylene oxide has a polyaddition mole number of 3,000 to 10,000.
The range is 0.
【００２６】ポリオキシアルキレンオキシドのポリオキ
シメチレンに対する添加量は、ポリオキシメチレン１０
０重量部に対して０．０５〜５重量部の範囲にある方が
好ましい。添加量が０．０５重量部より少ない場合は、
成形品外観は悪く、５重量部よりも多い場合も又、成形
品外観を著しく悪くする。ポリアルキレンオキシドの添
加量は、更には０．１〜３重量部が好ましい。これらの
ポリアルキレンオキシドは、２種類以上を併用して用い
てもかまわない。The amount of polyoxyalkylene oxide added to polyoxymethylene is 10% by weight of polyoxymethylene.
It is preferably in the range of 0.05 to 5 parts by weight with respect to 0 parts by weight. If the addition amount is less than 0.05 parts by weight,
The appearance of the molded product is poor, and when it is more than 5 parts by weight, the external appearance of the molded product is remarkably degraded. The addition amount of polyalkylene oxide is more preferably 0.1 to 3 parts by weight. These polyalkylene oxides may be used in combination of two or more kinds.
【００２７】本発明組成物には、その用途や目的に応じ
て必要な特性を付与するために、公知の添加剤、例えば
熱安定剤、酸化防止剤、核剤、離型剤、無機充てん剤、
帯電防止剤、滑剤等を本発明の目的を損わない範囲で添
加することができる。 本発明組成物において、その
製造方法は特に制限は無く、溶融したポリオキシメチレ
ンに前記各成分を混練する方法が一般的に用いられる。To the composition of the present invention, known additives such as a heat stabilizer, an antioxidant, a nucleating agent, a releasing agent, and an inorganic filler are added in order to impart necessary properties depending on its use and purpose. ,
Antistatic agents, lubricants and the like can be added within a range that does not impair the object of the present invention. The method for producing the composition of the present invention is not particularly limited, and a method of kneading the above-mentioned components with molten polyoxymethylene is generally used.
【００２８】[0028]
【実施例】次に、実施例により本発明を説明する。尚、
実施例及び比較例における組成物の各特性は次のように
して求めた。EXAMPLES Next, the present invention will be described with reference to examples. still,
The properties of the compositions in the examples and comparative examples were determined as follows.
【００２９】成形品キシミ音 予め８０℃×３時間乾燥させたペレットを射出成形機
で、１７６×２０×３mmの試験片を成形し、６時間放置
した。その後、試験片３本を束ね、上下に折り曲げなが
らその時に発する成形品キシミ音を以下に示した方法で
測定した。 装置 ＲＩＯＮ社（製）騒音計 条件 ファンクションスイッチ Ａ メータースピード ＳＬＯＷMolded product squeak noise A pellet of 176 × 20 × 3 mm was molded with an injection molding machine from pellets that had been dried in advance at 80 ° C. for 3 hours and left for 6 hours. After that, three test pieces were bundled and bent up and down, and the creaking noise of the molded product generated at that time was measured by the method shown below. Equipment RION (manufactured) Sound level meter Conditions Function switch A Meter speed SLOW
【００３０】成形品の外観（ゲート部のフローマー
ク） 成形機 東芝ＩＳ−８０Ａ 条件 シリンダー温度 ２００℃ 金型温度 ７０℃ 射出圧 ７０kg／cm2 Ｇ 射出スピード ダイヤル設定 Ｂ−５ 判定基準 ０；ゲート部のフローマーク無し １；フローマークわずかに目立つ ２；フローマークはっきりしている ３；ゲート部がはく離しているAppearance of molded product (flow mark on gate part) Molding machine Toshiba IS-80A Conditions Cylinder temperature 200 ° C Mold temperature 70 ° C Injection pressure 70kg / cm 2 G Injection speed dial setting B-5 Judgment standard 0; Gate part No flow mark 1; Flow mark is slightly noticeable 2; Flow mark is clear 3; Gate part is separated
【００３１】物性 ＡＳＴＭ Ｄ６３８に準じて行った。 （イ）オレフィン化合物Physical Properties The measurement was carried out according to ASTM D638. (A) Olefin compound
【００３２】[0032]
【化１１】 [Chemical 11]
【００３３】[0033]
【化１２】 [Chemical 12]
【００３４】[0034]
【化１３】 [Chemical 13]
【００３５】（ロ）ポリアルキレンオキサイド Ｃ−１：平均分子量約１，０００のポリエチレングリコ
ール Ｃ−２：平均分子量約３，０００のポリエチレングリコ
ール Ｃ−３：平均分子量約６，０００のポリエチレングリコ
ール Ｃ−４：平均分子量約１０，０００のポリエチレングリ
コール Ｃ−５：平均分子量約２０，０００のポリエチレングリ
コール Ｃ−６：平均分子量約１０，０００のポリプロピレング
リコール Ｃ−７：平均分子量約７００のポリエチレングリコール Ｃ−８：平均分子量約２５，０００のポリエチレングリ
コール(B) Polyalkylene oxide C-1: Polyethylene glycol having an average molecular weight of about 1,000 C-2: Polyethylene glycol having an average molecular weight of about 3,000 C-3: Polyethylene glycol having an average molecular weight of about 6,000 C- 4: Polyethylene glycol having an average molecular weight of about 10,000 C-5: Polyethylene glycol having an average molecular weight of about 20,000 C-6: Polypropylene glycol having an average molecular weight of about 10,000 C-7: Polyethylene glycol having an average molecular weight of about 700 8: Polyethylene glycol having an average molecular weight of about 25,000
【００３６】実施例１〜２２及び比較例１〜１０ ポリオキシメチレンホモポリマー（メルトインデックス
１５ｇ／１０分）１００重量部に対して、熱安定剤とし
てポリ−β−アラニン０．２重量部と酸化防止剤トリエ
チレングリコール−ビス〔３−（３−ｔ−ブチル−５−
メチル−４−ヒドロキシフェニル）プロピオネート〕
０．１５重量部を予め溶融混練し、押出されたストラン
ドに、第１表〜に示す添加剤をヘンシェルミキサー
で均一混合し、３０φ押出し機で押出しペレットにし
た。ただちに８０℃×３時間乾燥した。乾燥後、各評価
に用いた。結果を第１表〜に示す。Examples 1 to 22 and Comparative Examples 1 to 10 To 100 parts by weight of polyoxymethylene homopolymer (melt index 15 g / 10 minutes), 0.2 part by weight of poly-β-alanine as a heat stabilizer and oxidation Inhibitor triethylene glycol-bis [3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate]
0.15 parts by weight was melt-kneaded in advance, and the extruded strands were uniformly mixed with the additives shown in Table 1 by a Henschel mixer, and extruded into pellets by a 30φ extruder. Immediately, it was dried at 80 ° C. for 3 hours. After drying, it was used for each evaluation. The results are shown in Table 1-.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【表２】 [Table 2]
【００３９】[0039]
【表３】 [Table 3]
【００４０】[0040]
【表４】 [Table 4]
【００４１】[0041]
【表５】 [Table 5]
【００４２】[0042]
【表６】 [Table 6]
【００４３】実施例２３ トリオキサンと３ mol％のエチレンオキシドとを共重合
して得られたポリオキシメチレンコポリマー（メルトイ
ンデックス１５ｇ／１０分）１００重量部に対して、ポ
リカプロラクタム／ポリヘキサメチレンアジパミド／ポ
リヘキサメチレンヘバカミドのターポリマー０．０５重
量部、トリエチレングリコール−ビス〔３−（３−ｔ−
ブチル−５−メチル−４−ヒドロキシフェニル）プロピ
オネート〕０．３重量部を予め溶融混練し押出されたス
トランドに添加剤としてオレフィン系化合物Ｂ−３を
０．２重量部及びポリアルキレングリコールＣ−３を
１．０重量部ヘンシェルミキサーで均一混合し、３０φ
押出し機で押出しペレットにした。ただちに８０℃×３
時間乾燥した。乾燥後、各評価に用いた。結果は成形品
キシミ音３９〜４０dBで、成形品外観（ゲート部フロー
マーク）は０であった。Example 23 100 parts by weight of a polyoxymethylene copolymer (melt index 15 g / 10 min) obtained by copolymerizing trioxane and 3 mol% of ethylene oxide was added to polycaprolactam / polyhexamethylene adipamide. /0.05 parts by weight of terpolymer of polyhexamethylene hevacamide, triethylene glycol-bis [3- (3-t-
Butyl-5-methyl-4-hydroxyphenyl) propionate] 0.3 part by weight was melt-kneaded in advance and 0.2 part by weight of an olefinic compound B-3 as an additive and polyalkylene glycol C-3 as an additive to the extruded strand. 1.0 part by weight of Henschel mixer
Extruded into pellets with an extruder. Immediately 80 ℃ × 3
Dried for hours. After drying, it was used for each evaluation. As a result, the creaking noise of the molded product was 39 to 40 dB, and the appearance of the molded product (flow mark at the gate portion) was 0.
【００４４】[0044]
【発明の効果】本発明のポリオキシメチレン組成物は、
成形品同志が互いにコスレ合う時に発生するキシミ音が
無く、従来のポリオキシメチレンには無いすぐれた摺動
性を有するものであり、又、成形品の外観も良好である
ので、スターター部品等の摺動部材として好適に用いる
ことができる。The polyoxymethylene composition of the present invention is
There is no squeaking noise generated when the molded products come to touch each other, and it has excellent slidability that conventional polyoxymethylene does not have, and because the molded product has a good appearance, it can be used for starter parts, etc. It can be suitably used as a sliding member.
Claims (1)
と、 （Ｂ）一般式 【化１】 （Ｒ1 ，Ｒ2 は水素、アルキル基、置換アルキル基、ア
リール基、置換アリール基、エーテル基より選ばれ、各
々同一であってもよく異ってもよい。ｎ＝３０〜２０
０）で表わされる少なくとも１種のオレフィン単位から
構成されるオレフィン化合物０．０５〜２重量部と、 （Ｃ）一般式 【化２】 （Ｒ3 は水素、アルキル基、置換アルキル基、アリール
基より選ばれ、各々同一であっても異ってもよい。Ｘ＝
２〜６、Ｙ＝１０００〜２００００）で表わされるポリ
アルキレングリコール０．０５〜５重量部からなること
を特徴とするポリオキシメチレン組成物。1. (A) 100 parts by weight of polyoxymethylene, and (B) a general formula: (R 1 and R 2 are selected from hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an ether group, and may be the same or different. N = 30 to 20
0) 0.05 to 2 parts by weight of an olefin compound composed of at least one olefin unit, and (C) the general formula: (R 3 is selected from hydrogen, an alkyl group, a substituted alkyl group and an aryl group and may be the same or different. X =
2 to 6, Y = 1000 to 20000), and a polyoxymethylene composition comprising 0.05 to 5 parts by weight of a polyalkylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05277376A JP3114463B2 (en) | 1993-10-12 | 1993-10-12 | Polyoxymethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05277376A JP3114463B2 (en) | 1993-10-12 | 1993-10-12 | Polyoxymethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07109403A true JPH07109403A (en) | 1995-04-25 |
| JP3114463B2 JP3114463B2 (en) | 2000-12-04 |
Family
ID=17582668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05277376A Expired - Lifetime JP3114463B2 (en) | 1993-10-12 | 1993-10-12 | Polyoxymethylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3114463B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6194515B1 (en) | 1997-10-10 | 2001-02-27 | E. I. Du Pont De Nemours And Company | Polyacetal composition with improved toughness |
| JP2020026448A (en) * | 2018-08-09 | 2020-02-20 | 旭化成株式会社 | Polyoxymethylene resin composition and molded article |
-
1993
- 1993-10-12 JP JP05277376A patent/JP3114463B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6194515B1 (en) | 1997-10-10 | 2001-02-27 | E. I. Du Pont De Nemours And Company | Polyacetal composition with improved toughness |
| JP2020026448A (en) * | 2018-08-09 | 2020-02-20 | 旭化成株式会社 | Polyoxymethylene resin composition and molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3114463B2 (en) | 2000-12-04 |
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