JPS6411214B2 - - Google Patents
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- Publication number
- JPS6411214B2 JPS6411214B2 JP20131884A JP20131884A JPS6411214B2 JP S6411214 B2 JPS6411214 B2 JP S6411214B2 JP 20131884 A JP20131884 A JP 20131884A JP 20131884 A JP20131884 A JP 20131884A JP S6411214 B2 JPS6411214 B2 JP S6411214B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- fatty acid
- weight
- total amount
- properties
- 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
Links
- 238000000034 method Methods 0.000 claims description 29
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 24
- 229930195729 fatty acid Natural products 0.000 claims description 24
- 239000000194 fatty acid Substances 0.000 claims description 24
- 229920005672 polyolefin resin Polymers 0.000 claims description 21
- -1 glycerin fatty acid ester Chemical class 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 230000000694 effects Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TVIMZSOUQXNWHO-UHFFFAOYSA-N 2-tetradecanoylglycerol Chemical compound CCCCCCCCCCCCCC(=O)OC(CO)CO TVIMZSOUQXNWHO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CGBXSWXZXBQCMR-UHFFFAOYSA-N Glycerol 1-hexadecanoate Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCC(O)=O CGBXSWXZXBQCMR-UHFFFAOYSA-N 0.000 description 1
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- BYNVYIUJKRRNNC-UHFFFAOYSA-N docosanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCCCCCC(O)=O BYNVYIUJKRRNNC-UHFFFAOYSA-N 0.000 description 1
- UWLPCYBIJSLGQO-UHFFFAOYSA-N dodecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCC(O)=O UWLPCYBIJSLGQO-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229940031957 lauric acid diethanolamide Drugs 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002075 main ingredient 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
- 239000000178 monomer Substances 0.000 description 1
- UWDGKUMOFQTNHC-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)N(CCO)CCO UWDGKUMOFQTNHC-UHFFFAOYSA-N 0.000 description 1
- VJESJEJNMGVQLZ-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)N(CCO)CCO VJESJEJNMGVQLZ-UHFFFAOYSA-N 0.000 description 1
- XGZOMURMPLSSKQ-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)N(CCO)CCO XGZOMURMPLSSKQ-UHFFFAOYSA-N 0.000 description 1
- SKDZEPBJPGSFHS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)N(CCO)CCO SKDZEPBJPGSFHS-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
＜産業上の利用分野＞
本発明はポリオレフイン樹脂へ帯電防止性及び
防曇性を付与する方法に関する。
一般に合成高分子材料は、疎水性が強く、その
結果としての帯電性等のために、該材料を用いた
成形品の製造工程やその成形品の使用段階におい
て、種々の加工上のトラブル、静電シヨツク、塵
埃付着、更には水滴凝集等、多くの問題を招き易
い。ポリオレフイン樹脂についても同様であり、
例えば、その成形品であるフイルムやシートを包
装用や農業用等に使用する場合、前述したような
その帯電性による問題や多湿雰囲気における成形
品表面への微少水滴の凝集等が大きな障害とな
る。
そこで、ポリオレフイン樹脂へ帯電防止性及び
防曇性を付与することが要請されるが、該要請に
応える工業上最も有利な手段として、ポリオレフ
イン樹脂へ帯電防止剤をはじめとする親水性化合
物を添加混合する方法がある。
本発明はかかる方法に関し、特定の組み合わせ
た添加剤をポリオレフイン樹脂へ混合することに
より、該ポリオレフイン樹脂本来の外観等その他
の諸物性を損なうことなく、該ポリオレフイン樹
脂へ経時安定性の優れた帯電防止性及び防曇性を
付与する方法に関するものである。
＜従来の技術とその問題点＞
従来、種々の添加剤を加えることによつてポリ
オレフイン樹脂へ帯電防止性や防曇性を付与する
方法として、次のような多くの提案がある。例え
ば、Ｎ，Ｎ―ビスヒドロキシエチルアルキルアミ
ンを主剤としポリマーを併用する方法（特公昭48
−17746）、主剤に多価アルコール脂肪酸エステル
を併用する方法（特公昭44−925）、主剤に脂肪族
アルコールを併用する方法（特公昭46−1253）、
主剤にグリセリンモノ脂肪酸エステルと有機ホス
フアイトとを併用する方法（特開昭58−79042）、
主剤にＮ，Ｎ―ビスヒドロキシエチルアルキルア
ミン脂肪酸エステルを併用する方法（特公昭55−
12060）、主剤にアルカノールアミドを併用する方
法（特開昭56−2333）、Ｎ，Ｎ―ビスヒドロキシ
エチルアルキルアミン脂肪酸エステルを用いる方
法（特開昭58−191729）或いはこれにグリセリン
モノ脂肪酸エステルを併用する方法（特開昭54−
48866）、ベタイン型両性界面活性剤を用いる方法
（特公昭49−5746）、炭素数が18より大きい脂肪酸
ジエタノールアミドを用いる方法（特開昭54−
14452）、脂肪酸ジエタノールアミドとソルビタン
脂肪酸エステルとを併用する方法（特開昭53−
69247号）等がある。
ところが、これら従来の提案中に多く見られ
る、Ｎ，Ｎ―ビスヒドロキシエチルアミン或いは
このエステル化誘導体を使用する方法によると、
それらが成形品表面へ経時的にブリードする性質
が強いため、初期に所望の効果を与えるだけの量
を使用した場合には経時後にブリード過多となつ
て成形品であるフイルムやシート等では表面汚れ
やブロツキング等の問題を起し易く、逆に経時後
に好ましい効果を与える程度の量を使用したので
は初期に所望の効果が得られず、他の成分を併用
しても、実用上経時的に安定した効果を得難い。
また、ベタイン型両性界面活性剤を使用する方法
によると、これが成形品表面へ移行する性質が弱
いため、添加後に加熱やコロナ処理等の何らかの
工程を必要とする一般には採用し難い煩わしさが
ある。脂肪族のアルカノールアミド類を使用する
方法もほぼ同様である。更に、アンチブロツキン
グ性やストリツプ性等を補なうために種々の成分
を併用する他の従来提案によつても、実際には所
望通りの効果が得られなかつたり、効果の経時的
劣化を促したり、或いは成形品表面を白化したり
する等、多くの問題があるのが実情である。
＜発明が解決しようとする問題点＞
本発明は、ポリオレフイン樹脂へ充分な帯電防
止性及び防曇性を付与することを前提として、叙
上の如き従来提案の問題点すなわち、
付与した帯電防止性及び防曇性が経時的に劣
化する等、不安定であるという問題点、
白化、着色、表面ベタツキ等、外観その他の
諸物性に悪影響を及ぼすという問題点、
加熱、コロナ処理等、煩わしい工程が必要で
あるという問題点、
以上の問題点を解決するものである。
＜問題点を解決するための手段＞
しかして本発明者らは、前述の問題点を解決す
るべく鋭意研究した結果、所定のグリセリン脂肪
酸エステルとジエタノールアミドとの混合物にお
いて、双方の重量比及び該混合物中の炭素数の分
布状態を特定した添加剤を適用すると、双方の単
体からは予測できない所期効果の得られることを
見出し、本発明を完成するに到つた。
すなわち本発明は、次のＡに該当するグリセリ
ン脂肪酸エステルとＢに該当するジエタノールア
ミドとから成り、双方の重量比がＡ／Ｂ＝８／２
〜２／８であつて、双方が次の(1)又は(2)を充足す
る添加剤を、ポリオレフイン樹脂に対し0.05〜
2.0重量％となるように添加することを特徴とす
るポリオレフイン樹脂への帯電防止性及び防曇性
付与方法に係る。
Ａ：炭素数12〜22の脂肪酸を使用して誘導され
る、モノエステルの含有率が90重量％以上であ
るグリセリン脂肪酸エステル。
Ｂ：炭素数12〜22の脂肪酸を使用して誘導される
ジエタノールアミド。
(1) 使用する脂肪酸の炭素数の差が４以内のとも
に同じ炭素数範囲にあるＡに該当する各成分と
Ｂに該当する各成分との合計量がＡ及びＢの全
体量の80重量％以上であり、且つ上記各成分の
合計量中において双方の重量比がＡに該当する
各成分の合計量／Ｂに該当する各成分の合計量
８／２〜２／８であること。
(2) 使用する脂肪酸の炭素数が同じであるＡに該
当する成分とＢに該当する成分とが対を形成し
て１対以上存在し、これらの各対において双方
の重量比がＡに該当する成分／Ｂに該当する成
分＝８／２〜２／８であり、且つ上記対を形成
する双方の各成分の合計量がＡ及びＢの全体量
の70重量％以上であること。
本発明で使用する前記Ａのグリセリン脂肪酸エ
ステルの具体例としては、グリセリンモノラウレ
ート、グリセリンモノミリステート、グリセリン
モノパルミテート、グリセリンモノステアレー
ト、グリセリンモノベヘネート等が挙げられる。
通常グリセリン脂肪酸エステルは、エステル化或
いはエステル交換反応によりモノ、ジ及びトリエ
ステルの混合物として得られるので、この場合に
本発明では、該混合物を精製し、モノエステルの
含有率が90重量％以上としたものを使用する必要
がある。これより低純度のものでは本発明の目的
性能が得られない。
また、本発明で使用する前記Ｂのジエタノール
アミドの具体例としては、ラウリン酸ジエタノー
ルアミド、ミリスチン酸ジエタノールアミド、パ
ルミチン酸ジエタノールアミド、ステアリン酸ジ
エタノールアミド、ベヘニン酸ジエタノールアミ
ド等が挙げられる。これらは通常、等モルのジエ
タノールアミドと脂肪酸或いは脂肪酸エステルと
からアミド化やアミノリシスによつて得られる。
本発明において、前記ＡとＢとを用いる際の重
量比はＡ／Ｂ＝８／２〜２／８であることが必要
である。この重量比範囲を外れると、ＡとＢとの
好ましい相互作用が失なわれる。例えば、Ａが多
すぎると、目的性能それ自体の減少或いは該性能
の経時的減少や成形品表面の白化等が生じ、逆に
Ｂが多すぎると成形品表面にベタツキが生じるよ
うになる。
また本発明において、前記ＡとＢとの前述した
ような混合物中におけるアシル基の炭素数（Ａや
Ｂを誘導する際に使用する脂肪酸の炭素数）の分
布も双方の好ましい相互作用を発揮させるために
は重要である。該炭素数はいずれも12〜22の範囲
にあることが必要であつて、この範囲内において
双方の該炭素数が近いほどその効果をより良く発
揮し、かかる意味で該炭素数の分布状態に関して
は前述した(1)又は(2)の条件を充足することが必要
なのであり、したがつて(1)及び(2)の条件を同時に
充足する場合に本発明の効果は最も優れたものと
なるのである。前記アシル基の炭素数が12〜22の
範囲を外れたり、或いは該炭素数の分布状態に関
して前述した(1)又は(2)の条件を充足しない場合に
は、本発明の所期効果は得られない。
以上説明したＡとＢとから成る添加剤はポリオ
レフイン樹脂に対して0.05〜2.0重量％使用する
ことが必要である。多すぎても、逆に少なすぎて
も本発明の所期効果は得られない。
＜作用等＞
本発明における添加剤の使用方法は特に限定さ
れるものではない。ポリオレフイン樹脂に対し、
(1)及び／又は(2)の条件を充足するようにして、Ａ
及びＢを別々に加えても、又は予め双方を混合し
た後に加えてもよく、更には樹脂に直接加えて
も、又は一旦高濃度のマスターバツチとした後に
加えてもよい。
本発明の適用できる樹脂はポリオレフイン樹脂
全般であり、ポリエチレン、ポリプロピレン、ポ
リブタジエンの他に、これらに酢酸ビニル、エチ
ルアクリレート、アクリル酸等の他のモノマーを
共重合した樹脂等である。そして本発明の効果
は、インフレーシヨン、キヤステイング、押出成
形、射出成形等の成形加工法や、フイルム、シー
ト、繊維等の成形品形態による制約を受けない。
尚、本発明の効果を損なわない範囲で、他の目
的のために滑剤、安定剤、アンチブロツキング剤
等を本発明の実施に際して併用しても差し支えな
い。
＜発明の効果＞
以上説明した通り本発明には、加熱やコロナ処
理等の煩わしい余分な工程を必要とせず、そして
ポリオレフイン樹脂本来の外観その他の諸物性に
悪影響を及ぼすことなく、ポリオレフイン樹脂へ
経時的に安定で且つ充分な帯電防止性及び防曇性
を付与することができる効果がある。
＜実施例＞
以下、実施例及び比較例を挙げて本発明の構成
及び効果をより具体的にするが、本発明はここに
挙げる実施例に限定されるものではない。
実施例１〜５、比較例１〜９
低密度ポリエチレン樹脂（住友化学社製、スミ
カセンＦ―208―１）へ、第１表記載の各添加剤
をそれぞれ４重量％又は0.8重量％（比較例５）
となるように、ロール混練機を用いて温度150℃
で混練後、シートカツターにより３mm角ペレツト
状のマスターバツチを作成した。
次いで、各マスターバツチ５重量部と前記低密
度ポリエチレン樹脂95重量部とを混合後、シリン
ダー温度180〜210℃、ブローアツプ比2.0の条件
にてインフレーシヨン成形を行ない、厚さ30μの
フイルムを作成し、これを試料とした。
実施例６〜８、比較例10〜11
低密度ポリエチレン樹脂に代えて直鎖低密度ポ
リエチレン樹脂（三井石油化学社製、ウルトゼツ
クス3021F）を、また第１表記載の各添加剤に代
えて第２表記載の各添加剤を使用し、マスターバ
ツチの各添加剤濃度を８重量％にしたこと以外、
実施例１〜５の場合と同様にした。
実施例９〜12、比較例12〜17
ポリプロピレン樹脂（住友化学社製、ノーブレ
ンＦ―6411）へ、第３表記載の各添加剤をそれぞ
れ0.6重量％又は2.2重量％（比較例13）となるよ
うに、ラボプラストミル（東洋精機社製）を用い
て温度200℃で５分間混練後、温度200℃、圧力
350Kg/cm2の条件にて１分間プレスを行ない、厚さ
約100μのシートを作成しこれを試料とした。
そして、以上の各試料を用い、次のように測定
乃至評価した。結果を第４表〜第６表に示した。
●表面状態（外観）
各試料を20℃×60％RHの恒温恒湿室に放置
し、３日後及び２か月後において、それぞれ表面
の白化の度合を次の基準で肉眼評価した。
◎：全く白化していない
〇：部分的に薄く白化している
△：全体が薄く白化している
×：全体が濃く白化している
●帯電防止性
各試料を20℃×60％RHの恒温恒湿室に放置
し、３日後及び２か月後において、放置条件と同
じ条件下で表面抵抗を測定した。
●防曇性
100ml容のビーカーに20℃の水30mlを入れ、こ
れを20℃×60％RHの恒温恒湿室に３日又は２か
月放置した各試料で密閉し、５℃の冷蔵庫中に１
時間放置後、各試料の内面への水滴付着状態を次
の基準で肉眼評価した。
５：水滴の付着がほとんどなく、透明である。
４：大きな水滴がわずかに付着しているが、透
明である。
３：部分的に水滴の付着が認められるが、透明
感はある。
２：多くの水滴が付着し、透明性が低下してい
る。
１：微小水滴が全面に付着し、透明性が不良で
ある。
<Industrial Application Field> The present invention relates to a method for imparting antistatic properties and antifogging properties to polyolefin resins. In general, synthetic polymer materials have strong hydrophobicity and, as a result, have electrostatic properties, which can cause various processing problems and static electricity during the manufacturing process of molded products using the material and the use stage of the molded products. This can easily lead to many problems such as electric shock, dust adhesion, and even water droplet aggregation. The same applies to polyolefin resin.
For example, when the molded products such as films and sheets are used for packaging, agriculture, etc., problems such as the above-mentioned electrostatic properties and the agglomeration of minute water droplets on the molded product surface in a humid atmosphere pose major obstacles. . Therefore, it is required to impart antistatic properties and antifogging properties to polyolefin resins, and the most advantageous industrial means to meet these demands is to add and mix hydrophilic compounds such as antistatic agents to polyolefin resins. There is a way to do it. The present invention relates to such a method, and by mixing a specific combination of additives into the polyolefin resin, the polyolefin resin is provided with antistatic properties that have excellent stability over time without impairing the original appearance and other physical properties of the polyolefin resin. The present invention relates to a method for imparting antifogging properties and antifogging properties. <Prior art and its problems> Conventionally, there have been many proposals as follows as methods for imparting antistatic properties and antifogging properties to polyolefin resins by adding various additives. For example, a method using N,N-bishydroxyethylalkylamine as the main ingredient and a polymer in combination (Japanese Patent Publication No. 48
-17746), method of using polyhydric alcohol fatty acid ester in combination with the main agent (Japanese Patent Publication No. 44-925), method using aliphatic alcohol together with the main agent (Japanese Patent Publication No. 46-1253),
A method of using glycerin monofatty acid ester and organic phosphite together as the main agent (Japanese Patent Application Laid-open No. 58-79042),
Method of using N,N-bishydroxyethylalkylamine fatty acid ester in combination with the main agent
12060), a method of using alkanolamide in combination as the main agent (Japanese Patent Application Laid-open No. 56-2333), a method of using N,N-bishydroxyethylalkylamine fatty acid ester (Japanese Patent Application Publication No. 58-191729), or a method of using glycerin monofatty acid ester in combination with this method. Method of combined use (Unexamined Japanese Patent Publication No. 54-
48866), a method using a betaine type amphoteric surfactant (Japanese Patent Publication No. 1973-5746), a method using a fatty acid diethanolamide having a carbon number of more than 18 (Japanese Patent Publication No. 1983-1999).
14452), a method of using fatty acid diethanolamide and sorbitan fatty acid ester in combination (JP-A-1988-1445-
69247) etc. However, according to the method using N,N-bishydroxyethylamine or its esterified derivative, which is often seen in these conventional proposals,
They have a strong tendency to bleed onto the surface of molded products over time, so if they are used in an initial amount that is sufficient to give the desired effect, they will bleed excessively over time and cause surface stains on molded products such as films and sheets. On the other hand, if a sufficient amount is used to give a desired effect after a period of time, the desired effect may not be obtained initially, and even if other ingredients are used in combination, problems such as Difficult to obtain stable effects.
Additionally, the method of using a betaine type amphoteric surfactant has a weak tendency to transfer to the surface of the molded product, so it requires some kind of process such as heating or corona treatment after addition, which is cumbersome and difficult to adopt in general. . The method using aliphatic alkanolamides is almost the same. Furthermore, even with other conventional proposals that use various ingredients in combination to compensate for anti-blocking properties, stripping properties, etc., the desired effects may not actually be obtained, or the effects may deteriorate over time. The reality is that there are many problems, such as promoting whitening or whitening the surface of the molded product. <Problems to be Solved by the Invention> The present invention is based on the premise of imparting sufficient antistatic properties and antifogging properties to a polyolefin resin, and solves the problems of conventional proposals as described above, namely, the imparted antistatic properties. problems such as instability, such as deterioration of anti-fogging properties over time; problems with negative effects on appearance and other physical properties such as whitening, coloring, and surface stickiness; and troublesome processes such as heating and corona treatment. This solves the problem of necessity and the above problems. <Means for Solving the Problems> However, as a result of intensive research in order to solve the above-mentioned problems, the present inventors found that in a given mixture of glycerin fatty acid ester and diethanolamide, the weight ratio of both and the The present inventors have discovered that by applying an additive with a specified distribution of carbon numbers in a mixture, a desired effect that cannot be predicted from either of them alone can be obtained, and the present invention has been completed. That is, the present invention consists of glycerin fatty acid ester corresponding to the following A and diethanolamide corresponding to B, and the weight ratio of both is A/B = 8/2.
~2/8 of the additive that both satisfy the following (1) or (2) is added to the polyolefin resin at a rate of 0.05~2/8.
It relates to a method of imparting antistatic properties and antifogging properties to a polyolefin resin, characterized in that the amount of the antistatic property and antifogging property is added to a polyolefin resin in an amount of 2.0% by weight. A: Glycerin fatty acid ester with a monoester content of 90% by weight or more, which is derived using a fatty acid having 12 to 22 carbon atoms. B: Diethanolamide derived using a fatty acid having 12 to 22 carbon atoms. (1) The total amount of each component that falls under A and each component that falls under B, where the difference in carbon number of the fatty acids used is within 4 and is in the same carbon number range, is 80% by weight of the total amount of A and B. above, and in the total amount of each component, the weight ratio of both components is 8/2 to 2/8 of the total amount of each component corresponding to A/total amount of each component corresponding to B. (2) There is one or more pairs of a component that falls under A and a component that falls under B where the number of carbon atoms in the fatty acids used are the same, and the weight ratio of both of these pairs falls under A. component corresponding to component B/component corresponding to B = 8/2 to 2/8, and the total amount of both components forming the above pair is 70% by weight or more of the total amount of A and B. Specific examples of the glycerin fatty acid ester A used in the present invention include glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, and the like.
Generally, glycerin fatty acid esters are obtained as a mixture of mono-, di-, and triesters through esterification or transesterification. You need to use what you have. If the purity is lower than this, the desired performance of the present invention cannot be obtained. Specific examples of the diethanolamide B used in the present invention include lauric acid diethanolamide, myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, and behenic acid diethanolamide. These are usually obtained from equimolar amounts of diethanolamide and fatty acid or fatty acid ester by amidation or aminolysis. In the present invention, it is necessary that the weight ratio of A and B is A/B=8/2 to 2/8. Outside this weight ratio range, the favorable interaction between A and B is lost. For example, if there is too much A, the desired performance itself may decrease, or the performance may decrease over time, or the surface of the molded product may become white, whereas if B is too large, the surface of the molded product may become sticky. In addition, in the present invention, the distribution of the number of carbon atoms in the acyl group (the number of carbon atoms in the fatty acid used to derive A and B) in the mixture of A and B as described above also exerts a favorable interaction between the two. It is important for It is necessary that the number of carbon atoms is in the range of 12 to 22, and within this range, the closer the carbon numbers are to each other, the better the effect will be exhibited, and in this sense, regarding the distribution state of the carbon numbers. It is necessary to satisfy the above-mentioned conditions (1) or (2). Therefore, the effects of the present invention are most excellent when conditions (1) and (2) are simultaneously satisfied. It is. If the number of carbon atoms in the acyl group is outside the range of 12 to 22, or if the above-mentioned conditions (1) or (2) regarding the distribution of the carbon numbers are not satisfied, the intended effects of the present invention may not be obtained. I can't. It is necessary to use the additives consisting of A and B described above in an amount of 0.05 to 2.0% by weight based on the polyolefin resin. If it is too large or too small, the desired effect of the present invention cannot be obtained. <Effects, etc.> The method of using the additive in the present invention is not particularly limited. For polyolefin resin,
A by satisfying the conditions (1) and/or (2).
and B may be added separately, or may be added after premixing both, or may be added directly to the resin, or may be added once a highly concentrated masterbatch is formed. Resins to which the present invention can be applied include polyolefin resins in general, including polyethylene, polypropylene, polybutadiene, and resins obtained by copolymerizing these with other monomers such as vinyl acetate, ethyl acrylate, and acrylic acid. The effects of the present invention are not limited by molding methods such as inflation, casting, extrusion molding, and injection molding, or by the form of molded products such as films, sheets, and fibers. It should be noted that lubricants, stabilizers, anti-blocking agents, etc. may be used in conjunction with the present invention for other purposes as long as the effects of the present invention are not impaired. <Effects of the Invention> As explained above, the present invention does not require troublesome extra steps such as heating or corona treatment, and does not adversely affect the appearance or other physical properties of the polyolefin resin, and can be applied to polyolefin resins over time. It has the effect of being economically stable and imparting sufficient antistatic and antifogging properties. <Examples> Hereinafter, the structure and effects of the present invention will be made more concrete by giving Examples and Comparative Examples, but the present invention is not limited to the Examples listed here. Examples 1 to 5, Comparative Examples 1 to 9 Each additive listed in Table 1 was added to a low density polyethylene resin (Sumitomo Chemical Co., Ltd., Sumikasen F-208-1) at 4% by weight or 0.8% by weight (Comparative Example). 5)
Using a roll kneader, the temperature is 150℃ so that
After kneading, a masterbatch in the form of 3 mm square pellets was prepared using a sheet cutter. Next, 5 parts by weight of each masterbatch and 95 parts by weight of the low-density polyethylene resin were mixed, and then inflation molding was performed at a cylinder temperature of 180 to 210°C and a blow-up ratio of 2.0 to create a 30μ thick film. This was used as a sample. Examples 6 to 8, Comparative Examples 10 to 11 In place of the low density polyethylene resin, linear low density polyethylene resin (manufactured by Mitsui Petrochemical Co., Ltd., Ultzex 3021F) was used, and in place of each of the additives listed in Table 1, Except that each additive listed in the table was used and the concentration of each additive in the master batch was 8% by weight.
The same procedure as in Examples 1 to 5 was carried out. Examples 9 to 12, Comparative Examples 12 to 17 Each additive listed in Table 3 was added to polypropylene resin (Sumitomo Chemical Co., Ltd., Noblen F-6411) at a concentration of 0.6% by weight or 2.2% by weight (Comparative Example 13). After kneading for 5 minutes at a temperature of 200℃ using Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.),
Pressing was performed for 1 minute at 350 kg/cm 2 to produce a sheet with a thickness of about 100 μm, which was used as a sample. Using each of the above samples, measurements and evaluations were made as follows. The results are shown in Tables 4 to 6. ●Surface condition (appearance) Each sample was left in a constant temperature and humidity room at 20°C x 60% RH, and after 3 days and 2 months, the degree of whitening on the surface was visually evaluated using the following criteria. ◎: Not whitened at all 〇: Partially slightly whitened △: Lightly whitened all over ×: Deeply whitened all over ●Antistatic properties Each sample was kept at a constant temperature of 20℃ x 60%RH. The sample was left in a constant humidity room, and after 3 days and 2 months, the surface resistance was measured under the same conditions as the leaving condition. ●Anti-fogging property Put 30ml of 20℃ water into a 100ml beaker, leave it in a constant temperature and humidity room at 20℃ x 60% RH for 3 days or 2 months, seal it with each sample, and place it in a refrigerator at 5℃. to 1
After standing for a period of time, the state of adhesion of water droplets on the inner surface of each sample was visually evaluated using the following criteria. 5: Transparent with almost no water droplets attached. 4: There are a few large water droplets attached, but it is transparent. 3: Adhesion of water droplets is observed partially, but there is a sense of transparency. 2: Many water droplets adhered, reducing transparency. 1: Microscopic water droplets adhere to the entire surface and transparency is poor.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
じ。
[Table] Ji.
【表】
合も同じ。
[Table] Same goes for case.
【表】【table】
【表】
第４表〜第６表における、各比較例に対する各
実施例の結果からも、本発明の効果は明白であ
る。[Table] The effects of the present invention are clear from the results of each Example relative to each Comparative Example in Tables 4 to 6.
Claims (1)
とＢに該当するジエタノールアミドとから成り、
双方の重量比がＡ／Ｂ＝８／２〜２／８であつ
て、双方が次の(1)又は(2)を充足する添加剤を、ポ
リオレフイン樹脂に対し0.05〜2.0重量％となる
ように添加することを特徴とするポリオレフイン
樹脂への帯電防止性及び防曇性付与方法。 Ａ：炭素数12〜22の脂肪酸を使用して誘導され
る、モノエステルの含有率が90重量％以上であ
るグリセリン脂肪酸エステル。 Ｂ：炭素数12〜22の脂肪酸を使用して誘導される
ジエタノールアミド。 (1) 使用する脂肪酸の炭素数の差が４以内のとも
に同じ炭素数範囲にあるＡに該当する各成分と
Ｂに該当する各成分との合計量がＡ及びＢの全
体量の80重量％以上であり、且つ上記各成分の
合計量中において双方の重量比がＡに該当する
各成分の合計量／Ｂに該当する各成分の合計量
＝８／２〜２／８であること。 (2) 使用する脂肪酸の炭素数が同じであるＡに該
当する成分とＢに該当する成分とが対を形成し
て１対以上存在し、これらの各対において双方
の重量比がＡに該当する成分／Ｂに該当する成
分＝８／２〜２／８であり、且つ上記対を形成
する双方の各成分の合計量がＡ及びＢの全体量
の70重量％以上であること。 ２ 特許請求の範囲第１項の記載において、(1)及
び(2)を同時に充足するポリオレフイン樹脂への帯
電防止性及び防曇性付与方法。[Claims] 1. Consisting of glycerin fatty acid ester corresponding to A and diethanolamide corresponding to B,
The weight ratio of both A/B is 8/2 to 2/8, and the amount of additives that both satisfy the following (1) or (2) is 0.05 to 2.0% by weight based on the polyolefin resin. A method for imparting antistatic properties and antifogging properties to a polyolefin resin, the method comprising: adding antistatic properties and antifogging properties to a polyolefin resin. A: Glycerin fatty acid ester with a monoester content of 90% by weight or more, which is derived using a fatty acid having 12 to 22 carbon atoms. B: Diethanolamide derived using a fatty acid having 12 to 22 carbon atoms. (1) The total amount of each component that falls under A and each component that falls under B, where the difference in carbon number of the fatty acids used is within 4 and is in the same carbon number range, is 80% by weight of the total amount of A and B. The above is true, and in the total amount of each component, the weight ratio of both components is 8/2 to 2/8. (2) There is one or more pairs of a component that falls under A and a component that falls under B where the number of carbon atoms in the fatty acids used are the same, and the weight ratio of both of these pairs falls under A. component corresponding to component B/component corresponding to B = 8/2 to 2/8, and the total amount of both components forming the above pair is 70% by weight or more of the total amount of A and B. 2. A method for imparting antistatic properties and antifogging properties to a polyolefin resin, which satisfies (1) and (2) at the same time as set forth in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59201318A JPS6178854A (en) | 1984-09-25 | 1984-09-25 | Method for imparting antistatic and anti-fogging properties to polyolefin resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59201318A JPS6178854A (en) | 1984-09-25 | 1984-09-25 | Method for imparting antistatic and anti-fogging properties to polyolefin resin |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013227A Division JPH0621198B2 (en) | 1990-01-22 | 1990-01-22 | Method for imparting antistatic property and antifogging property to polyolefin resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6178854A JPS6178854A (en) | 1986-04-22 |
| JPS6411214B2 true JPS6411214B2 (en) | 1989-02-23 |
Family
ID=16439017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59201318A Granted JPS6178854A (en) | 1984-09-25 | 1984-09-25 | Method for imparting antistatic and anti-fogging properties to polyolefin resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6178854A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6262836A (en) * | 1985-09-13 | 1987-03-19 | Kao Corp | Master pellet for antistatic resin |
| JPH0742364B2 (en) * | 1987-02-27 | 1995-05-10 | 花王株式会社 | Method for imparting antistatic property to polyolefin resin injection molded products |
| JP2601509B2 (en) * | 1988-04-08 | 1997-04-16 | 旭化成工業株式会社 | Polyethylene resin composition for antifogging film |
| CN105026471B (en) * | 2013-03-14 | 2019-05-10 | 三井化学东赛璐株式会社 | Preservative film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04143618A (en) * | 1990-10-05 | 1992-05-18 | Matsushita Electric Ind Co Ltd | Position detector |
| JPH04307329A (en) * | 1991-04-03 | 1992-10-29 | Copal Co Ltd | Optical displacement detecting apparatus |
| JPH04351918A (en) * | 1991-05-30 | 1992-12-07 | Nippondenso Co Ltd | Encoder |
| JPH0540046A (en) * | 1991-08-07 | 1993-02-19 | Nikon Corp | Lighting device for absolute encoder |
| US7566863B2 (en) * | 2006-10-16 | 2009-07-28 | Chang Christopher C | Optical encoder with diffractive encoder member |
| JP5562076B2 (en) * | 2010-03-10 | 2014-07-30 | キヤノン株式会社 | Optical encoder and displacement measuring device |
| US8723103B2 (en) * | 2011-11-08 | 2014-05-13 | Mitutoyo Corporation | Optical encoder readhead configured to block stray light with dummy vias |
-
1984
- 1984-09-25 JP JP59201318A patent/JPS6178854A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6178854A (en) | 1986-04-22 |
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| LAPS | Cancellation because of no payment of annual fees |