JPH0548781B2 - - Google Patents
Info
- Publication number
- JPH0548781B2 JPH0548781B2 JP2986889A JP2986889A JPH0548781B2 JP H0548781 B2 JPH0548781 B2 JP H0548781B2 JP 2986889 A JP2986889 A JP 2986889A JP 2986889 A JP2986889 A JP 2986889A JP H0548781 B2 JPH0548781 B2 JP H0548781B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyacetal resin
- aliphatic hydrocarbon
- heat resistance
- butyl
- 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.)
- Expired - Lifetime
Links
- 229930182556 Polyacetal Natural products 0.000 claims description 25
- 229920006324 polyoxymethylene Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 5
- -1 Fatty acid calcium salt Chemical class 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 230000007774 longterm Effects 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-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
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- OMCYEZUIYGPHDJ-UHFFFAOYSA-N 2-hydroxy-N-[(2-hydroxyphenyl)methylideneamino]benzamide Chemical compound OC1=CC=CC=C1C=NNC(=O)C1=CC=CC=C1O OMCYEZUIYGPHDJ-UHFFFAOYSA-N 0.000 description 1
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 1
- RNIOOCGWPGSASJ-UHFFFAOYSA-N 4-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]butyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 RNIOOCGWPGSASJ-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- HRBZRZSCMANEHQ-UHFFFAOYSA-L calcium;hexadecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O HRBZRZSCMANEHQ-UHFFFAOYSA-L 0.000 description 1
- LSFBQOPXRBJSSI-UHFFFAOYSA-L calcium;tetradecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O LSFBQOPXRBJSSI-UHFFFAOYSA-L 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- TXSUIVPRHHQNTM-UHFFFAOYSA-N n'-(3-methylanilino)-n-phenyliminobenzenecarboximidamide Chemical compound CC1=CC=CC(NN=C(N=NC=2C=CC=CC=2)C=2C=CC=CC=2)=C1 TXSUIVPRHHQNTM-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- RDDGGSBCDBLPDO-UHFFFAOYSA-N octadecyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C)=C(O)C(C(C)(C)C)=C1 RDDGGSBCDBLPDO-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- GUWLXCFSEPHWCL-UHFFFAOYSA-N tetradecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GUWLXCFSEPHWCL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は、酸素の存在下での短期耐熱特性及び
熱風環境下での長期耐熱特性に優れたポリアセタ
ール樹脂組成物に関するものである。
〔従来の技術〕
ポリアセタール樹脂は、機械強度と剛性、クリ
ープ特性、耐溶剤性に優れており、その用途は主
として、自動車、電気製品、機械などの機械部品
や外装部品に多く使用されている。しかし、とく
に耐熱性を要求される用途においては、ポリアセ
タール樹脂の構造上の問題から使用されていない
のが現実である。
ポリアセタール樹脂の耐熱性を改良する方法と
して、従来より熱安定剤、酸化防止剤、抗酸剤な
どの添加剤を配合し安定化する方法が知られてい
る。
例えば、特公昭62−58387号公報では、アミン
置換トリアジン類、立体障害性フエノール類とカ
ルボン酸塩類の三元系の組合せが提案されてい
る。
〔発明が解決しようとする課題〕
しかし、これら添加剤の組合せでは、ポリアセ
タール樹脂組成物の酸素の存在下での短期耐熱特
性及び熱風環境下での長期耐熱特性は不十分であ
る。よつて、さらに改良すべき点を見出した。
即ち、従来のポリアセタール樹脂組成物は、酸
素の存在下で溶融し滞留させた時に、短時間でポ
リアセタール樹脂を分解し、多くのホルムアルデ
ヒドガスを発生する。また、ポリアセタール樹脂
組成物の成型品を熱風環境下に置き、ポリアセタ
ール樹脂の物性を見ると、著しく速く物性低下を
する。このように従来のポリアセタール樹脂は、
酸素の存在下での短期耐熱特性及び熱風環境下で
の長期耐熱特性において不十分である。
〔問題を解決するための手段〕
本発明者は、これらの問題点を解決すべく鋭意
検討を重ねた結果、非常に優れたポリアセタール
樹脂組成物を見出した。
即ち、本発明は；
ポリアセタール樹脂100重量部に対して、
(a) 一般式〔Ａ〕：
（式中、R1、R2は、水素原子または炭素数
１〜６個の脂肪族炭化水素であり、R3は、脂
肪族炭化水素またはエーテル結合を持つた脂肪
族炭化水素である。ｎは、R3の価数と一致す
る。）
で示される化合物0.01〜３重量部と、
(b) 一般式〔Ｂ〕
（式中、R4、R5は、水素原子または炭素数
１〜６個の脂肪族炭化水素であり、R6は、脂
肪族炭化水素またはエーテル結合を持つた脂肪
族炭化水素である。ｎは、R6の価数に一致す
る。）
で示される化合物0.01〜３重量部と、
(c) 鉄と錯体を形成しうる立体障害性フエノール
類〔Ｃ〕0.01〜１重量部及び、
(d) 炭素数12〜35個の脂肪酸カルシウム塩〔Ｄ〕
0.01〜1.0重量部、
を添加してなるポリアセタール樹脂組成物であ
る。
このように、本発明は、従来より用いられてい
る酸化防止剤、抗酸剤の組合せに加え、金属、特
に鉄と錯体を形成しうる立体障害性フエノール類
を添加することを特長としている。即ち、短期及
び長期耐熱特性低下の原因は、押出し、成形時に
混入する金属、特に鉄によつて起こるポリアセタ
ール樹脂の分解であり、このような短期及び長期
耐熱特性を向上させるためには、鉄と錯体を形成
しうる立体障害性フエノール類の添加が必要不可
欠である。
このように四元系の化合物を配合して得られた
ポリアセタール樹脂組成物は、従来の組成物と異
なり、酸素の存在下240℃の高温でポリアセター
ル樹脂を溶融させた時に、５％のホルムアルデヒ
ドガスが発生するのに要する時間が、約２倍にも
向上した。
この事実は、シリンダー内に長時間滞留させて
もポリアセタール樹脂の分解によつて、発生する
ホルムアルデヒドガス量が激減することを意味す
るものであり、これによつて、成型時の作業環境
が著しく改善される。
さらに加えて、140℃熱風環境下での長期試験
においても、引張強度、伸度の保持率は、従来品
では、1000時間経過後に、劣化見られるのに対
し、本発明の組成物から得られた成型品は、劣化
傾向を全く示さない。
上記説明から明らかなように、本発明のポリア
セタール樹脂組成物は、従来の組成物よりも優れ
た耐熱特性を提供するものである。
本発明に用いる化合物のうち、化合物〔Ａ〕と
しては、ｎ−オクタデシル−３−（3′，5′−ジ−
ｔ−ブチル−4′−ヒドロキシフエニル）−プロピ
オネート、ｎ−オクタデシル−３−（3′−メチル
−5′−ｔ−ブチル−4′−ヒドロキシフエニル）−
プロピオネート、ｎ−テトラデシル−３−（3′，
5′−ジ−ｔ−ブチル−4′−ヒドロキシフエニル）
−プロピオネート、１，６−ヘキサンジオール−
ビス−〔３−（３，５−ジ−ｔ−ブチル−４−ヒド
ロキシフエニル）−プロピオネート〕、１，４−ブ
タンジオール−ビス−〔３−（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシフエニル）−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−５−メチル−４−ヒドロキシフエ
ニル）−プロピオネート〕、テトラキス−〔メチレ
ン−３−（3′，5′−ジ−ｔ−ブチル−4′−ヒドロキ
シフエニル）プロピオネート〕メタン、３，９−
ビス〔２−（３−（３−ｔ−ブチル−４−ヒドロキ
シ−５−メチルフエニル）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〕ウンデカン等を挙
げることができ、なかでも、トリエチレングリコ
ール−ビス−〔３−（３−ｔ−ブチル−５−メチル
−４−ヒドロキシフエニル）プロピオネート〕、
３，９−ビス〔２−（３−（３−ｔ−ブチル−４−
ヒドロキシ−５−メチルフエニル）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
ンが特に効果的である。
化合物〔Ｂ〕としては、Ｎ，N′−ビス−３−
（3′，5′−ジ−ｔ−ブチル−４−ヒドロキシフエ
ニル）プロピオニルヘキサメチレンジアミン、
Ｎ，N′−テトラメチレンビス−３−（3′−メチル
−5′−ｔ−ブチル−４−ヒドロキシフエニル）プ
ロピオニルジアミンが挙げられる。中でも、Ｎ，
N′−ビス−３−（3′，5′−ジ−ｔ−ブチル−４−
ヒドロキシフエニル）プロピオニルヘキサメチレ
ンジアミンが効果的である。
化合物〔Ｃ〕としては、Ｎ，N′−ビス−〔３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフエ
ニル）プロピオニル〕ヒドラジン、Ｎ−サリチロ
イル−N′−サリチリデンヒドラジン、３−（Ｎ−
サリチロイル）アミノ−１，２，４−トリアゾー
ル、Ｎ，N′−ビス〔２−（３−（３，５−ジ−ｔ
−ブチル−４−ヒドロキシフエニル）プロピオニ
ルオキシ）エチル〕オキシアミド等が挙げられ
る。そのなかでも、特にＮ，N′−ビス−〔３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフエ
ニル）プロピオニル〕ヒドラジンが効果的であ
る。
これら化合物〔Ｃ〕は、押出し成形時に混入す
る鉄と錯体を形成するフエノール類であつて、他
の金属と錯体を形成していてもよい。
化合物〔Ｄ〕としては、ステアリン酸カルシウ
ム、パルミチン酸カルシウム、ミリスチン酸カル
シウム、リシノール酸カルシウムなどがあり、そ
のなかでも、ステアリン酸カルシウムが効果的で
ある。
これら添加剤の配合量は、その種類により異な
り、通常にはポリアセタール樹脂100重量部に対
して、化合物〔Ａ〕、〔Ｂ〕は0.01〜３重量部で、
好ましくは0.05〜１重量部の範囲、さらに好まし
くは0.1〜0.7重量部である。また、化合物〔Ｃ〕
は、0.01〜１重量部で、好ましくは0.02〜0.2重量
部の範囲、そして化合物〔Ｄ〕は、0.01〜１重量
部で、好ましくは0.05〜0.8重量部の範囲で適宜
選ばれる。
これら添加剤の配合量は、限定範囲を外れた場
合には、それぞれ短期及び長期耐熱特性を著しく
阻害し好ましくない。
また、夫々の添加順序は限定されず、添加剤の
添加の形態は、粉体であつも溶融状態であつても
構わない。添加剤の添加方法は、一般に押出機で
ポリアセタール樹脂と添加剤とを一緒に配合し、
練り込むことによつて行われる。この時の押出機
は、一軸あるいは二軸であつてもよく、又重合工
程で添加されても構わない。
なお、押出機の温度は、180℃〜240℃であり、
好ましくは180℃〜220℃の範囲で選ばれる。
本発明組成物に用いるポリアセタールとして
は、ホモポリマー、コポリマーいずれであつても
よい。ホモポリマーとしては、ポリマーの末端を
アセチル化処理して安定化したホルムアルデヒド
重合体が好ましく、コポリマーとしては、トリオ
キサンとエチレンオキサイドもしくはジオキソラ
ン等の共重合体であつて、オキシメチレン主鎖中
に炭素数２個以上のオキシアルキレン単位を0.4
〜30モル％、特に好ましくは、0.4〜10モル％含
有し、ポリマーの末端を熱処理等により安定化し
た共重合体が好ましい。これら重合体、共重合体
の平均分子量は、10000〜100000が好ましく、特
に好ましくは25000〜70000である。
また、本発明組成物には、通常用いられるガラ
ス繊維、フツ素樹脂粉末、炭素繊維、その他顔料
など、従来公知の添加剤を添加し得る。
以下に実施例を示すが、これらは本発明の範囲
を制限するものでない。
式中、％及び重量部はすべて重量基準である。
なお、樹脂組成物の耐熱特性は、次に示す方法に
従つて評価した。
（短期耐熱特性）
理学電機(株)製熱天秤を用い、電気炉にサンプ
ル50mgと空気5Nl／hrをフイードし、40℃から
20℃／分の割合で昇温させる。
240℃になつてからの５％サンプル重量減少
に要する時間で評価した。
（長期耐熱特性）
140℃の環境下にしたギヤーオーブン内に、
下記成形条件で成形したサンプルを置き、物性
低下及び劣化状態を見た。
成形条件
成形機：東芝(株)製IS−80A
シリンダー温度：200℃
射出圧力：60Kg／cm2Ｇ
射出時間：15秒
冷却時間：10秒
金型温度：70℃
実施例１〜７および比較例１〜18
トリオキサンとエチレンオキサイド（2.0％）
の共重合体〔M.I（190℃）〜〜10ｇ／10分〕の不
安定末端を処理したポリアセタール樹脂コポリマ
ー100部に、第１表に示す添加剤を添加し、200℃
で押出して造粒、製品化した。これを、80℃で14
時間乾燥したのち、短期及び長期耐熱性試験を行
つた。
その結果を第１〜２表に示す。
実施例 ８
ホルムアルデヒドの単独重合体〔M.I（190℃）
〜10ｇ／10分〕の末端をアセテート置換したポリ
アセタール樹脂ホモポリマー100重量部に第２表
に示す添加剤を添加し、200℃で押出し造粒し、
製品化した。これを、80℃で14時間乾燥したの
ち、耐熱性試験（長期熱風環境試験）を行つた。
その結果を第２表に示す。
[Industrial Field of Application] The present invention relates to a polyacetal resin composition that has excellent short-term heat resistance in the presence of oxygen and long-term heat resistance in a hot air environment. [Prior Art] Polyacetal resin has excellent mechanical strength and rigidity, creep properties, and solvent resistance, and is mainly used for mechanical parts and exterior parts of automobiles, electrical products, machines, etc. However, the reality is that polyacetal resins are not used in applications that require particular heat resistance due to structural problems. As a method of improving the heat resistance of polyacetal resin, a method of stabilizing it by adding additives such as a heat stabilizer, an antioxidant, and an anti-acid agent is conventionally known. For example, Japanese Patent Publication No. 62-58387 proposes a ternary combination of amine-substituted triazines, sterically hindered phenols, and carboxylic acid salts. [Problems to be Solved by the Invention] However, with the combination of these additives, the short-term heat resistance properties of the polyacetal resin composition in the presence of oxygen and the long-term heat resistance properties in a hot air environment are insufficient. As a result, we found points that need further improvement. That is, when conventional polyacetal resin compositions are melted and retained in the presence of oxygen, the polyacetal resin decomposes in a short time and generates a large amount of formaldehyde gas. Moreover, when a molded article of a polyacetal resin composition is placed in a hot air environment and the physical properties of the polyacetal resin are examined, the physical properties deteriorate rapidly. In this way, conventional polyacetal resin
Insufficient short-term heat resistance in the presence of oxygen and long-term heat resistance in a hot air environment. [Means for Solving the Problems] As a result of intensive studies to solve these problems, the present inventors have discovered an extremely excellent polyacetal resin composition. That is, the present invention: (a) General formula [A]: (In the formula, R 1 and R 2 are a hydrogen atom or an aliphatic hydrocarbon having 1 to 6 carbon atoms, and R 3 is an aliphatic hydrocarbon or an aliphatic hydrocarbon having an ether bond.n corresponds to the valence of R3 .) 0.01 to 3 parts by weight of the compound represented by (b) General formula [B] (In the formula, R 4 and R 5 are a hydrogen atom or an aliphatic hydrocarbon having 1 to 6 carbon atoms, and R 6 is an aliphatic hydrocarbon or an aliphatic hydrocarbon having an ether bond.n corresponds to the valence of R 6 ); (c) 0.01 to 1 part by weight of a sterically hindered phenol [C] capable of forming a complex with iron; and (d ) Fatty acid calcium salt with 12 to 35 carbon atoms [D]
0.01 to 1.0 parts by weight of a polyacetal resin composition. As described above, the present invention is characterized by the addition of sterically hindered phenols that can form complexes with metals, particularly iron, in addition to the conventionally used combination of antioxidants and antiacidants. In other words, the cause of the decline in short-term and long-term heat resistance properties is the decomposition of polyacetal resin caused by metals mixed in during extrusion and molding, especially iron.In order to improve such short-term and long-term heat resistance properties, it is necessary to The addition of sterically hindered phenols capable of forming complexes is essential. The polyacetal resin composition obtained by blending quaternary compounds in this way differs from conventional compositions in that when the polyacetal resin is melted at a high temperature of 240°C in the presence of oxygen, it contains 5% formaldehyde gas. The time required for this to occur was approximately doubled. This fact means that the amount of formaldehyde gas generated due to the decomposition of the polyacetal resin is drastically reduced even if it remains in the cylinder for a long time, which significantly improves the working environment during molding. be done. In addition, even in a long-term test in a hot air environment of 140°C, the retention of tensile strength and elongation was found to deteriorate after 1,000 hours with conventional products, whereas the retention of tensile strength and elongation was observed with the composition of the present invention. The molded product shows no tendency to deteriorate. As is clear from the above description, the polyacetal resin composition of the present invention provides better heat resistance than conventional compositions. Among the compounds used in the present invention, compound [A] is n-octadecyl-3-(3',5'-di-
t-Butyl-4'-hydroxyphenyl)-propionate, n-octadecyl-3-(3'-methyl-5'-t-butyl-4'-hydroxyphenyl)-
Propionate, n-tetradecyl-3-(3',
5'-di-t-butyl-4'-hydroxyphenyl)
-Propionate, 1,6-hexanediol-
Bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate], 1,4-butanediol-bis-[3-(3,5-di-t-butyl-4 -hydroxyphenyl)-propionate], triethylene glycol-bis-[3-(3
-t-butyl-5-methyl-4-hydroxyphenyl)-propionate], tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, 3,9-
Bis[2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)
-1,1-dimethylethyl]-2,4,8,10-
Tetraoxaspiro[5,5]undecane, among others, triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
3,9-bis[2-(3-(3-t-butyl-4-
Hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,
8,10-tetraoxaspiro[5,5]undecane is particularly effective. Compound [B] is N,N'-bis-3-
(3',5'-di-t-butyl-4-hydroxyphenyl)propionylhexamethylene diamine,
N,N'-tetramethylenebis-3-(3'-methyl-5'-t-butyl-4-hydroxyphenyl)propionyldiamine is mentioned. Among them, N,
N'-bis-3-(3',5'-di-t-butyl-4-
Hydroxyphenyl)propionylhexamethylene diamine is effective. As the compound [C], N,N'-bis-[3-
(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3-(N-
salicyloyl)amino-1,2,4-triazole, N,N'-bis[2-(3-(3,5-di-t
-butyl-4-hydroxyphenyl)propionyloxy)ethyl]oxyamide, and the like. Among them, N,N′-bis-[3-
(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine is effective. These compounds [C] are phenols that form a complex with iron mixed during extrusion molding, and may form a complex with other metals. Examples of the compound [D] include calcium stearate, calcium palmitate, calcium myristate, and calcium ricinoleate, among which calcium stearate is effective. The amount of these additives varies depending on their type, and usually compounds [A] and [B] are 0.01 to 3 parts by weight per 100 parts by weight of the polyacetal resin.
It is preferably in the range of 0.05 to 1 part by weight, more preferably 0.1 to 0.7 part by weight. Also, compound [C]
is 0.01 to 1 part by weight, preferably 0.02 to 0.2 part by weight, and compound [D] is appropriately selected in a range of 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight. If the blending amount of these additives is out of the limited range, it is not preferable because it will significantly impede the short-term and long-term heat resistance properties, respectively. Further, the order of addition is not limited, and the additives may be added in the form of a powder or a molten state. Generally, additives are added by blending polyacetal resin and additives together in an extruder.
It is done by practicing. The extruder at this time may be a single-screw or twin-screw extruder, or it may be added during the polymerization process. In addition, the temperature of the extruder is 180°C to 240°C,
Preferably, the temperature is selected within the range of 180°C to 220°C. The polyacetal used in the composition of the present invention may be either a homopolymer or a copolymer. As a homopolymer, a formaldehyde polymer stabilized by acetylation treatment at the polymer end is preferable, and as a copolymer, a copolymer of trioxane and ethylene oxide or dioxolane, etc., having a number of carbon atoms in the oxymethylene main chain is preferable. 0.4 or more oxyalkylene units
A copolymer containing up to 30 mol %, particularly preferably 0.4 to 10 mol %, with the terminal end of the polymer stabilized by heat treatment or the like is preferred. The average molecular weight of these polymers and copolymers is preferably 10,000 to 100,000, particularly preferably 25,000 to 70,000. Furthermore, conventionally known additives such as commonly used glass fibers, fluororesin powders, carbon fibers, and other pigments may be added to the composition of the present invention. Examples are shown below, but these are not intended to limit the scope of the present invention. In the formula, all percentages and parts by weight are by weight.
Note that the heat resistance properties of the resin composition were evaluated according to the method shown below. (Short-term heat resistance characteristics) Using a thermobalance manufactured by Rigaku Denki Co., Ltd., feed 50 mg of sample and 5 Nl/hr of air into an electric furnace, and heat the sample from 40℃.
Raise the temperature at a rate of 20°C/min. The evaluation was based on the time required for the sample weight to decrease by 5% after the temperature reached 240°C. (Long-term heat resistance characteristics) In a gear oven under an environment of 140℃,
Samples molded under the following molding conditions were placed and observed for physical property deterioration and deterioration. Molding conditions Molding machine: Toshiba Corporation IS-80A Cylinder temperature: 200℃ Injection pressure: 60Kg/ cm2G Injection time: 15 seconds Cooling time: 10 seconds Mold temperature: 70℃ Examples 1 to 7 and comparative examples 1-18 Trioxane and ethylene oxide (2.0%)
The additives shown in Table 1 were added to 100 parts of the unstable end-treated polyacetal resin copolymer [MI (190°C) ~ 10g/10 min], and the mixture was heated at 200°C.
It was extruded, granulated, and manufactured into a product. This was heated at 80℃ for 14
After drying for several hours, short-term and long-term heat resistance tests were conducted. The results are shown in Tables 1 and 2. Example 8 Formaldehyde homopolymer [MI (190°C)
The additives shown in Table 2 were added to 100 parts by weight of a polyacetal resin homopolymer whose ends were substituted with acetate (~10 g/10 min), and the mixture was extruded and granulated at 200°C.
Commercialized. After drying this at 80°C for 14 hours, a heat resistance test (long-term hot air environment test) was conducted. The results are shown in Table 2.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
以上のとおり、本発明においては、特定の四元
系の化合物の組合せを適用することにより、酸素
の存在下での短期耐熱特性および熱風環境下での
長期耐熱特性が、従来のものに比してはるかに優
れたポリアセタール樹脂組成物を提供することが
できる。
As described above, in the present invention, by applying a combination of specific quaternary compounds, short-term heat resistance in the presence of oxygen and long-term heat resistance in a hot air environment are improved compared to conventional ones. This makes it possible to provide a much superior polyacetal resin composition.
Claims (1)
１〜６個の脂肪族炭化水素であり、R3は、脂
肪族炭化水素またはエーテル結合を持つた脂肪
族炭化水素である。ｎは、R3の価数と一致す
る。） で示される化合物0.01〜３重量部と、 (b) 一般式〔Ｂ〕： （式中、R4、R5は、水素原子または炭素数
１〜６個の脂肪族炭化水素であり、R6は、脂
肪族炭化水素またはエーテル結合を持つた脂肪
族炭化水素である。ｎは、R6の価数に一致す
る。） で示される化合物0.01〜３重量部と、 (c) 鉄と錯体を形成しうる立体障害性フエノール
類〔Ｃ〕0.01〜１重量部及び、 (d) 炭素数12〜35個の脂肪酸カルシウム塩〔Ｄ〕
0.01〜1.0重量部、 を添加してなるポリアセタール樹脂組成物。[Claims] 1. For 100 parts by weight of polyacetal resin, (a) General formula [A]: (In the formula, R 1 and R 2 are a hydrogen atom or an aliphatic hydrocarbon having 1 to 6 carbon atoms, and R 3 is an aliphatic hydrocarbon or an aliphatic hydrocarbon having an ether bond.n corresponds to the valence of R3 .) 0.01 to 3 parts by weight of the compound represented by (b) General formula [B]: (In the formula, R 4 and R 5 are a hydrogen atom or an aliphatic hydrocarbon having 1 to 6 carbon atoms, and R 6 is an aliphatic hydrocarbon or an aliphatic hydrocarbon having an ether bond.n corresponds to the valence of R 6 ); (c) 0.01 to 1 part by weight of a sterically hindered phenol [C] capable of forming a complex with iron; and (d ) Fatty acid calcium salt with 12 to 35 carbon atoms [D]
0.01 to 1.0 parts by weight of a polyacetal resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2986889A JPH02209944A (en) | 1989-02-10 | 1989-02-10 | Polyacetal resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2986889A JPH02209944A (en) | 1989-02-10 | 1989-02-10 | Polyacetal resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02209944A JPH02209944A (en) | 1990-08-21 |
| JPH0548781B2 true JPH0548781B2 (en) | 1993-07-22 |
Family
ID=12287950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2986889A Granted JPH02209944A (en) | 1989-02-10 | 1989-02-10 | Polyacetal resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02209944A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3578540B2 (en) | 1996-02-19 | 2004-10-20 | 旭化成ケミカルズ株式会社 | Polyacetal resin composition with excellent aging properties |
| SG68701A1 (en) * | 1997-12-05 | 1999-11-16 | Ciba Sc Holding Ag | Stabilisation of polyamide polyester and polyacetal |
| US6156834A (en) * | 1998-03-20 | 2000-12-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyacetal resin composition |
| JP6978906B2 (en) * | 2017-11-16 | 2021-12-08 | 旭化成株式会社 | Polyacetal resin composition |
-
1989
- 1989-02-10 JP JP2986889A patent/JPH02209944A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02209944A (en) | 1990-08-21 |
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