JPWO2023021103A5

JPWO2023021103A5 -

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Publication number: JPWO2023021103A5
Application number: JP2024509336A
Authority: JP
Publication date: 2025-08-25

Description

試験結果：
本発明のポリマーＰ．１及びＰ．２のみが、２８日後のＯＥＣＤ３０１Ｆ試験で有意な生分解特性（＞１０％）を示す。したがって、本発明の材料（ポリマーＰ．１及びＰ．２）のみが、洗浄性能（すなわち、配合物の可視的な改善）と生分解性との良好な組み合わせを示す。
ｏ＝＜１０％
＋＝１０～２０％
＋＋＝２０～５０％
＋＋＋＝＞５０％

本発明は例えば以下の実施形態を含む。
［項１]
修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミンであって、下記の工程ａ）～ｂ）：
ａ）ｉ）重量平均分子量（Ｍｗ）が４００ｇ／モル未満の少なくとも１つのオリゴアルキレンイミン又は重量平均分子量（Ｍｗ）が４００ｇ／モル未満の少なくとも１つのオリゴアミンと、ｉｉ）少なくとも１つのアルキレンオキシド（ＡＯ）との反応であって、１モルのオリゴアルキレンイミン又はオリゴアミンのＮＨ官能基あたり少なくとも１０モルのアルキレンオキシド（ＡＯ）が用いられて、中間体（Ｉ）を得る、反応と、
ｂ）前記中間体（Ｉ）と、少なくとも１つのラクトン（ＬＡ）及び／又は少なくとも１つのハイドロックス炭酸（ＨＡ）との反応であって、（（工程ａ）で用いられた））１モルのオリゴアルキレンイミン又はオリゴアミンのＮＨ官能基あたり、少なくとも１．０モルのラクトン（ＬＡ）及び／又はヒドロキシ炭酸（ＨＡ）が用いられて、修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミンを得る、反応と、
を含むプロセスによって得ることが可能な、修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項２］
工程ａ）で用いられた、前記重量平均分子量（Ｍｗ）が４００ｇ／モル未満の少なくとも１つのオリゴアルキレンイミン又は前記重量平均分子量（Ｍｗ）が４００ｇ／モル未満の少なくとも１つのオリゴアミンが、一般式（Ｉ）に従って定義され、
式中、前記変数はそれぞれ下記の通り定義され、
Ｒは、同一か又は異なる
ｉ）直鎖若しくは分枝鎖のＣ_２～Ｃ_１２アルキレンラジカル、又は
ｉｉ）以下の式（ＩＩＩ）のエーテルアルキル単位であって：
式中、前記変数はそれぞれ下記の通り定義され、
Ｒ^１０、Ｒ^１１、Ｒ^１２は、同一か若しくは異なる、直鎖若しくは分枝鎖のＣ_２～Ｃ_６アルキレンラジカルを表し、
ｄは、０～６の範囲の値を有する整数である、
エーテルアルキル単位であるか、又は
ｉｉｉ）任意選択的に少なくとも１つのＣ_１～Ｃ_３アルキルで置換されたＣ_５～Ｃ_１０シクロアルキレンラジカルを表し、
ｙは０～８の範囲の値を有する整数であり、
Ｅ^１は、同一か又は異なる
ｉ）水素、又は、
ｉｉ）水素及び／若しくはＣ_１～Ｃ_１８－アルキルを表し、
Ｂは、分枝によるオリゴアルキレンイミンの延長を表し、
ｚは０～８の範囲の値を有する整数であり、
ｙ＋ｚの和は、０～８の範囲、好ましくは０～７の範囲の値を有する整数であり、
好ましくは、Ｒは同一か又は異なる
ｉ）直鎖若しくは分枝鎖のＣ_２～Ｃ_１２アルキレンラジカルであって、より好ましくはＲがエチレン、プロピレン、若しくはヘキサメチレンである、アルキレンラジカル、又はｉｉ）任意選択的に少なくとも１つのＣ_１～Ｃ_３アルキルで置換されたＣ_５～Ｃ_１０シクロアルキレンラジカルであって、より好ましくは、Ｒが、少なくとも１つのメチル若しくはエチルで置換された少なくとも１つのＣ_６～Ｃ_７シクロアルキレンラジカルである、シクロアルキレンラジカルを表し、
好ましくは、Ｅ^１がＨ及び／又はメチルを表し、
より好ましくは、Ｅ^１がＨを表す、
項１に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項３］
一般式（ＩＩａ）の少なくとも１つの残基を含有し、
式中、前記変数はそれぞれ下記の通り定義され、
Ｒ^２は、水素であるか、又は非置換若しくは少なくとも一置換のＣ_１～Ｃ_２２－アルキル、Ｃ_７～Ｃ_２２－アラルキル、－（ＣＯ）－Ｃ_１～Ｃ_２２－アルキル、－（ＣＯ）－Ｃ_２～Ｃ_３０－アルケニル、及び／若しくは－（ＣＯ）－Ｃ_７～Ｃ_２２－アラルキルの群から選択され、前記置換基は－ＣＯＯＨ若しくはその塩から選択され、
Ｒ^３は、直鎖又は分枝鎖のＣ_１～Ｃ_２２アルキレンラジカルを表し、
Ｒ^４はＣ_２～Ｃ_２２－（１，２－アルキレン）ラジカルを表し、
ｍは、少なくとも１～２０の値を有する整数であり、
ｐは、少なくとも１０～１００の値を有する整数であり、
好ましくは、一般式（ＩＩａ）内の前記変数は以下の通りに定義され、
Ｒ^２は、水素、Ｃ_１～Ｃ_４－アルキル、－（ＣＯ）－Ｃ_１～Ｃ_４－アルキルを表し、より好ましくは水素、メチル、エチル若しくは－（ＣＯ）－Ｃ_１～Ｃ_２－アルキルを表し、最も好ましくは水素を表し、並びに／又は、
Ｒ^３は、直鎖若しくは分枝鎖のＣ_２～Ｃ_１０アルキレンラジカルを表し、より好ましくは直鎖若しくは分枝鎖のＣ_２～Ｃ_５アルキレンラジカルを表し、並びに／又は
Ｒ^４は、１，２－エチレン及び／若しくは１，２－プロピレン、より好ましくは１，２－エチレンを表し、並びに／又は
ｍは、１～１５、より好ましくは１～１０、最も好ましくは２～１０の範囲の値を有する整数であり、並びに／又は
ｐは、１０～５０、より好ましくは１５～４０、最も好ましくは２０～３５の範囲の値を有する整数である、
項１又は２に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項４］
一般式（ＩＩｂ）の少なくとも１つの残基を含有し、
式中、前記変数は下記の通り定義され、
Ｒ^２は、水素であるか、又は非置換若しくは少なくとも一置換のＣ_１～Ｃ_２２－アルキル、Ｃ_７～Ｃ_２２－アラルキル、－（ＣＯ）－Ｃ_１～Ｃ_２２－アルキル、－（ＣＯ）－Ｃ_２～Ｃ_３０－アルケニル、及び／若しくは－（ＣＯ）－Ｃ_７～Ｃ_２２－アラルキルの群から選択され、置換基は－ＣＯＯＨ若しくはその塩から選択され、
Ｒ^４はＣ_２～Ｃ_２２－（１，２－アルキレン）ラジカルを表し、
ｐは、少なくとも１０～１００の値を有する整数であり、
好ましくは、一般式（ＩＩｂ）内の前記変数は以下の通りに定義され、
Ｒ^２は、水素、Ｃ_１～Ｃ_４－アルキル、－（ＣＯ）－Ｃ_１～Ｃ_４－アルキルを表し、好ましくは水素、メチル、エチル若しくは－（ＣＯ）－Ｃ_１～Ｃ_２－アルキルを表し、最も好ましくは水素を表し、並びに／又は、
Ｒ^４は、１，２－エチレン及び／若しくは１，２－プロピレン、より好ましくは１，２－エチレンを表し、並びに／又は
ｐは、１０～５０、より好ましくは１５～４０、最も好ましくは２０～３５の範囲の値を有する整数である、
項１～３のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項５］
ｉ）工程ａ）は水の不在下、及び／若しくは触媒の存在下で実施され、並びに／或いはｉｉ）工程ａ）は２工程反応として実施されて、第１の工程は水の存在下で実施され、第２の工程は、水なしであるが、触媒の存在下で実施され、並びに／或いは
ｉｉｉ）工程ａ）で用いられる前記アルキレンオキシド（ＡＯ）の５０重量％超がエチレンオキシドをベースとし、並びに／或いは
ｉｖ）工程ａ）で用いられるオリゴアルキレンイミン又はオリゴアミンの重量平均分子量（Ｍｗ）が６０～３９０ｇ／モルの範囲内、好ましくは６０～３６０ｇ／モルの範囲内にあるか、或いは
ｖ）工程ａ）で用いられるオリゴアルキレンイミン又はオリゴアミンの重量平均分子量（Ｍｗ）が１００～２００ｇ／モルの範囲内にあるか、或いは
ｖｉ）工程ａ）で用いられるオリゴアルキレンイミン又はオリゴアミンの重量平均分子量（Ｍｗ）が２５０～３５０ｇ／モルの範囲内にある、
項１～４のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項６］
前記変数はそれぞれ下記の通り定義され、
Ｒはエチレン及び／又はプロピレン、好ましくはエチレンであり、
ｙ＋ｚの和は、１～８の範囲、好ましくは１～７の範囲の値を有する整数である、
項２～５のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン。
［項７］
ｙは、０～８の範囲、好ましくは０～７の範囲の値を有する整数であり、
ｚは０であり、
Ｅ^１はＨ及び／又はメチルを表し、
Ｒは、同一か又は異なる、式（ＩＩＩ）の直鎖又は分枝鎖のＣ_２～Ｃ_１２アルキレンラジカル又はエーテルアルキル単位を表し、式中、
ｄは０～６であり、
Ｒ^１０、Ｒ^１１、Ｒ^１２は、独立して、直鎖又は分枝鎖のＣ_３～Ｃ_４アルキレンラジカルから選択され、
好ましくは、Ｒは、同一か又は異なる、直鎖Ｃ_２及び／又はＣ_３アルキレンラジカルを表す、
項２～５のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項８］
前記修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン中に存在する窒素原子の最大１００％が更に四級化され、好ましくは、前記修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン中に存在する前記窒素原子の四級化の程度は、１０％～９５％の範囲内にある、項１～７のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項９］
ｉ）工程ａ）において、前記アルキレンオキシド（ＡＯ）は、少なくとも１つのＣ_２～Ｃ_２２エポキシド、好ましくはエチレンオキシド及び／若しくはプロピレンオキシド、より好ましくはエチレンオキシドであり、
ｉｉ）工程ｂ）において、前記ラクトン（ＬＡ）はカプロラクトン若しくはラクチドであり、並びに／又は
ｉｉｉ）工程ｂ）において、前記ヒドロキシ炭酸（ＨＡ）は乳酸若しくはグリコール酸である、
項１～８のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項１０］
ｉ）工程ａ）において、１モルのオリゴアルキレンイミン又はオリゴアミンのＮＨ官能基あたり１０～１００モル、好ましくは１０～５０モル、より好ましくは１５～４０モル、最も好ましくは２０～３５モルのアルキレンオキシド（ＡＯ）が用いられ、並びに／又は
ｉｉ）工程ｂ）において、１モルのオリゴアルキレンイミン又はオリゴアミンのＮＨ官能基（工程ａ）で用いられた）あたり１．０～１０モル、好ましくは１．０～６．０モル、より好ましくは２．０～４．０モルのラクトン（ＬＡ）、及び／若しくは１．０～２０モル、好ましくは２．０～１５モル、より好ましくは３．０～１０モルのヒドロキシ炭酸（ＨＡ）が用いられる、
項１～９のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項１１］
ｉ）工程ａ）において、前記アルキレンオキシド（ＡＯ）はエチレンオキシドであり、ｉｉ）工程ａ）において、１モルのオリゴアルキレンイミン又はオリゴアミンのＮＨ官能基あたり１０～１００モル、好ましくは１０～５０モル、より好ましくは１５～４０モル、最も好ましくは２０～３５モルのアルキレンオキシド（ＡＯ）が用いられ、並びに／又は
ｉｉｉ）工程ｂ）において、前記ラクトンはカプロラクトンであり、１モルのオリゴアルキレンイミン又はオリゴアミンのＮＨ官能基（工程ａ）で用いられた）あたり１．０～１０モル、好ましくは１．０～６．０モル、より好ましくは２．０～４．０モルのカプロラクトンが用いられる、
項１～１０のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミン。
［項１２］
洗浄組成物中の、布地ケア及びホームケア生成物中の、化粧品配合物中の、原油エマルジョン破壊剤としての、インクジェットインク用顔料分散体中の、電気めっき用配合物中の、セメント系組成物中の、及び／又は農薬配合物用分散剤としての、項１～１１のいずれか一項に記載の修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミンの使用。
［項１３］
ｉ）油性／脂肪性染みの除去の改善、並びに／又は
ｉｉ）粘土の除去、並びに／又は
ｉｉｉ）粒子状の染みの汚れの除去、並びに／又は
ｉｖ）汚れの分散及び／若しくは乳化、並びに／又は
ｖ）後の再汚染の際の除去を改善するための処理表面の修飾、並びに／又は
ｖｉ）白色度の改善、並びに／又は
ｖｉｉ）リパーゼ、ヒドロラーゼ、アミラーゼ、プロテアーゼ、セルラーゼ、ヘミセルラーゼ、ホスホリパーゼ、エステラーゼ、ＤＮａｓｅ、マンナナーゼ、キシラナーゼ、ディスパーシン、オキシドレダクターゼ、クチナーゼ、ペクチン酸リアーゼ、ペクチナーゼ、ラクターゼ、及びペルオキシダーゼ、並びに上記の種類のうち少なくとも２つの組み合わせからなるリストから選択される、好ましくは、１つ以上のリパーゼ、ヒドロラーゼ、アミラーゼ、プロテアーゼ、セルラーゼ、及び上記の種類のうち少なくとも２つの組み合わせから選択される少なくとも１つの酵素、より好ましくは、リパーゼから選択される少なくとも１つの酵素が存在する場合、追加的に、油性／脂肪性染み、食品の染みの除去、及び／若しくは複合染みの除去の改善
のための、洗浄組成物、並びに／又は布地ケア及びホームケア生成物における、好ましくは洗浄組成物における、
最も好ましくは、
ｉ）油性／脂肪性染みの除去の改善のための洗浄組成物
における、項１２に記載の使用であって、
上記の選択肢ｉ）～ｖｉｉ）のそれぞれが、好ましくは洗濯洗剤配合物及び／又は手動食器洗い用洗剤配合物で、より好ましくは液体洗濯洗剤配合物及び／又は液体手動食器用洗剤配合物で使用するためのものである、使用。
［項１４］
項１～１１のいずれか一項に記載の少なくとも１つの修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミンを含む、洗浄組成物、布地ケア及びホームケア生成物、業務用洗浄生成物、化粧品配合物、原油エマルジョン破壊剤、インクジェットインク用顔料分散体、電気めっき用配合物、セメント系組成物、及び／又は農薬配合物用分散剤、
好ましくは、項１～１１のいずれか一項に記載の少なくとも１つの修飾アルコキシル化オリゴアルキレンイミン又は修飾アルコキシル化オリゴアミンを含む、洗浄組成物、及び／又は布地ケア及びホームケア生成物、及び／又は業務用洗浄生成物。
［項１５］
ｉ）油性／脂肪性染みの除去の改善、並びに／又は
ｉｉ）粘土の除去、並びに／又は
ｉｉｉ）粒子状の染みの汚れの除去、並びに／又は
ｉｖ）汚れの分散及び／若しくは乳化、並びに／又は
ｖ）後の再汚染の際の除去を改善するための処理表面の修飾、並びに／又は
ｖｉ）白色度の改善、並びに／又は
ｖｉｉ）リパーゼ、ヒドロラーゼ、アミラーゼ、プロテアーゼ、セルラーゼ、ヘミセルラーゼ、ホスホリパーゼ、エステラーゼ、ＤＮａｓｅ、マンナナーゼ、キシラナーゼ、ディスパーシン、オキシドレダクターゼ、クチナーゼ、ペクチン酸リアーゼ、ペクチナーゼ、ラクターゼ、及びペルオキシダーゼ、並びに上記の種類のうち少なくとも２つの組み合わせからなるリストから選択される、好ましくは、１つ以上のリパーゼ、ヒドロラーゼ、アミラーゼ、プロテアーゼ、セルラーゼ、及び上記の種類のうち少なくとも２つの組み合わせから選択される少なくとも１つの酵素、より好ましくは、リパーゼから選択される少なくとも１つの酵素が存在する場合、追加的に、油性／脂肪性染み、食品の染みの除去、及び／若しくは複合染みの除去の改善のための、
最も好ましくは、
ｉ）油性／脂肪性染みの除去の改善
のための洗浄組成物における、
項１４に記載の洗浄組成物であって、
上記の選択肢ｉ）～ｖｉｉ）のそれぞれが、好ましくは、洗濯洗剤配合物及び／又は手動食器洗い用洗剤配合物で、より好ましくは、液体洗濯洗剤配合物、及び／又は液体手動食器用洗剤配合物、及び／又は固体若しくは液体自動食器洗い用配合物で使用するためのものである、洗浄組成物。 Test results:
Only the polymers P.1 and P.2 of the present invention show significant biodegradation properties (>10%) in the OECD 301F test after 28 days. Thus, only the materials of the present invention (polymers P.1 and P.2) show a good combination of cleaning performance (i.e., visible improvement of the formulation) and biodegradability.
o = < 10%
+=10-20%
++=20-50%
+++=>50%

The present invention includes, for example, the following embodiments.
[Section 1]
A modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine, comprising the steps of:
a) reacting i) at least one oligoalkyleneimine having a weight average molecular weight (Mw) of less than 400 g/mol or at least one oligoamine having a weight average molecular weight (Mw) of less than 400 g/mol with ii) at least one alkylene oxide (AO), wherein at least 10 moles of alkylene oxide (AO) are used per mole of NH functional group of the oligoalkyleneimine or oligoamine to obtain intermediate (I);
b) reacting said intermediate (I) with at least one lactone (LA) and/or at least one hydroxycarbonate (HA), wherein at least 1.0 mole of lactone (LA) and/or hydroxycarbonate (HA) is used per mole of NH functional group of the oligoalkyleneimine or oligoamine (used in step a)) to obtain a modified alkoxylated oligoalkyleneimine or modified alkoxylated oligoamine;
1. A modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine obtainable by a process comprising:
[Section 2]
The at least one oligoalkyleneimine having a weight average molecular weight (Mw) of less than 400 g/mol or the at least one oligoamine having a weight average molecular weight (Mw) of less than 400 g/mol used in step a) is defined according to general formula (I),
wherein the variables are defined as follows:
R is the same or different: i) a linear or branched C ₂ -C ₁₂ alkylene radical, or ii) an ether alkyl unit of formula (III):
wherein the variables are defined as follows:
R ¹⁰ , R ¹¹ , R ¹² are the same or different and represent linear or branched C ₂ -C ₆ alkylene radicals;
d is an integer having a value ranging from 0 to 6;
ether alkyl unit, or iii) represents a _C5 - _C10 cycloalkylene radical optionally substituted with at least one _C1 - _C3 alkyl;
y is an integer having a value ranging from 0 to 8;
E ¹ is the same or different: i) hydrogen, or
ii) represents hydrogen and/or C ₁ -C ₁₈ -alkyl,
B represents the extension of the oligoalkyleneimine by branching,
z is an integer having a value ranging from 0 to 8;
the sum y+z is an integer having a value in the range of 0 to 8, preferably in the range of 0 to 7;
Preferably, R are identical or different and represent i) a linear or branched C ₂ -C ₁₂ alkylene radical, more preferably R is ethylene, propylene, or hexamethylene, or ii) a C ₅ -C ₁₀ cycloalkylene radical optionally substituted with at least one C ₁ -C ₃ alkyl, more preferably R is at least one C ₆ -C ₇ cycloalkylene radical substituted with at least one methyl or ethyl;
Preferably, ^E1 represents H and/or methyl,
More preferably, ^E1 represents H.
Item 2. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to Item 1.
[Section 3]
containing at least one residue of general formula (IIa)
wherein the variables are defined as follows:
R ² is hydrogen or is selected from the group of unsubstituted or at least monosubstituted C ₁ -C ₂₂ -alkyl, C ₇ -C ₂₂ -aralkyl, —(CO)—C ₁ -C ₂₂ -alkyl, —(CO)—C ₂ -C ₃₀ -alkenyl and/or —(CO)—C ₇ -C ₂₂ -aralkyl, wherein said substituents are selected from —COOH or salts thereof,
^R3 represents a linear or branched _C1 - _C22 alkylene radical;
^R4 represents a _C2 - _C22- (1,2-alkylene) radical;
m is an integer having a value of at least 1 to 20;
p is an integer having a value of at least 10 to 100;
Preferably, the variables in general formula (IIa) are defined as follows:
R ² represents hydrogen, C ₁ -C ₄ -alkyl, —(CO)—C ₁ -C ₄ -alkyl, more preferably hydrogen, methyl, ethyl or —(CO)—C ₁ -C ₂ -alkyl, most preferably hydrogen, and/or
R ³ represents a linear or branched C ₂ -C ₁₀ alkylene radical, more preferably a linear or branched C ₂ -C ₅ alkylene radical, and/or R ⁴ represents 1,2-ethylene and/or 1,2-propylene, more preferably 1,2-ethylene, and/or m is an integer having a value in the range from 1 to 15, more preferably from 1 to 10, most preferably from 2 to 10, and/or p is an integer having a value in the range from 10 to 50, more preferably from 15 to 40, most preferably from 20 to 35,
Item 3. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to Item 1 or 2.
[Section 4]
containing at least one residue of general formula (IIb)
wherein the variables are defined as follows:
R ² is hydrogen or is selected from the group of unsubstituted or at least monosubstituted C ₁ -C ₂₂ -alkyl, C ₇ -C ₂₂ -aralkyl, —(CO)—C ₁ -C ₂₂ -alkyl, —(CO)—C ₂ -C ₃₀ -alkenyl and/or —(CO)—C ₇ -C ₂₂ -aralkyl, wherein the substituents are selected from —COOH or salts thereof,
^R4 represents a _C2 - _C22- (1,2-alkylene) radical;
p is an integer having a value of at least 10 to 100;
Preferably, the variables in general formula (IIb) are defined as follows:
R ² represents hydrogen, C ₁ -C ₄ -alkyl, —(CO)—C ₁ -C ₄ -alkyl, preferably hydrogen, methyl, ethyl or —(CO)—C ₁ -C ₂ -alkyl, most preferably hydrogen, and/or
^R4 represents 1,2-ethylene and/or 1,2-propylene, more preferably 1,2-ethylene, and/or p is an integer having a value ranging from 10 to 50, more preferably from 15 to 40, most preferably from 20 to 35;
Item 4. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of Items 1 to 3.
[Section 5]
i) step a) is carried out in the absence of water and/or in the presence of a catalyst, and/or ii) step a) is carried out as a two-step reaction, the first step being carried out in the presence of water and the second step being carried out without water but in the presence of a catalyst, and/or iii) more than 50% by weight of the alkylene oxide (AO) used in step a) is based on ethylene oxide, and/or iv) the weight average molecular weight (Mw) of the oligoalkyleneimine or oligoamine used in step a) is in the range of 60 to 390 g/mol, preferably in the range of 60 to 360 g/mol, or v) the weight average molecular weight (Mw) of the oligoalkyleneimine or oligoamine used in step a) is in the range of 100 to 200 g/mol, or vi) the weight average molecular weight (Mw) of the oligoalkyleneimine or oligoamine used in step a) is in the range of 250 to 350 g/mol.
Item 5. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of Items 1 to 4.
[Section 6]
The variables are defined as follows:
R is ethylene and/or propylene, preferably ethylene;
the sum y+z is an integer having a value in the range of 1 to 8, preferably in the range of 1 to 7;
Item 6. The modified alkoxylated oligoalkyleneimine according to any one of Items 2 to 5.
[Section 7]
y is an integer having a value ranging from 0 to 8, preferably from 0 to 7;
z is 0,
^E1 represents H and/or methyl;
R represents the same or different linear or branched C ₂ -C ₁₂ alkylene radicals or ether alkyl units of formula (III), wherein:
d is 0 to 6;
R ¹⁰ , R ¹¹ , R ¹² are independently selected from linear or branched C ₃ -C ₄ alkylene radicals;
Preferably, R represents identical or different linear _C2 and/or _C3 alkylene radicals,
Item 6. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of Items 2 to 5.
[Section 8]
8. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of paragraphs 1 to 7, wherein up to 100% of the nitrogen atoms present in the modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine are further quaternized, preferably the degree of quaternization of the nitrogen atoms present in the modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine is in the range of 10% to 95%.
[Section 9]
i) in step a), said alkylene oxide (AO) is at least one C ₂ -C ₂₂ epoxide, preferably ethylene oxide and/or propylene oxide, more preferably ethylene oxide;
ii) in step b), the lactone (LA) is caprolactone or lactide, and/or iii) in step b), the hydroxycarbonic acid (HA) is lactic acid or glycolic acid;
Item 9. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of items 1 to 8.
[Section 10]
i) in step a) 10 to 100 moles, preferably 10 to 50 moles, more preferably 15 to 40 moles, most preferably 20 to 35 moles of alkylene oxide (AO) are used per mole of NH functional group of the oligoalkyleneimine or oligoamine, and/or ii) in step b) 1.0 to 10 moles, preferably 1.0 to 6.0 moles, more preferably 2.0 to 4.0 moles of lactone (LA) and/or 1.0 to 20 moles, preferably 2.0 to 15 moles, more preferably 3.0 to 10 moles of hydroxycarbonic acid (HA) are used per mole of NH functional group of the oligoalkyleneimine or oligoamine (used in step a)),
Item 10. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of items 1 to 9.
[Section 11]
i) in step a), the alkylene oxide (AO) is ethylene oxide, ii) in step a), 10 to 100 moles, preferably 10 to 50 moles, more preferably 15 to 40 moles, most preferably 20 to 35 moles of alkylene oxide (AO) are used per mole of NH functional group of the oligoalkyleneimine or oligoamine, and/or iii) in step b), the lactone is caprolactone, and 1.0 to 10 moles, preferably 1.0 to 6.0 moles, more preferably 2.0 to 4.0 moles of caprolactone are used per mole of NH functional group of the oligoalkyleneimine or oligoamine (used in step a),
Item 11. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of Items 1 to 10.
[Section 12]
12. Use of the modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of paragraphs 1 to 11 in cleaning compositions, in fabric care and home care products, in cosmetic formulations, as a crude oil emulsion breaker, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions, and/or as a dispersant for pesticide formulations.
[Section 13]
i) improved removal of oily/greasy stains, and/or ii) clay removal, and/or iii) particulate stain soil removal, and/or iv) soil dispersion and/or emulsification, and/or v) modification of treated surfaces to improve removal upon subsequent re-soiling, and/or vi) improved whiteness, and/or vii) at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the above classes, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the above classes, more preferably lipases, when present, additionally in cleaning compositions and/or fabric care and home care products, preferably in cleaning compositions, for improved removal of oily/greasy stains, food stains and/or combination stains,
Most preferably,
i) Use according to item 12 in a cleaning composition for improved removal of oily/greasy stains,
Use wherein each of options i) to vii) above is preferably for use in a laundry detergent formulation and/or a manual dishwashing detergent formulation, more preferably in a liquid laundry detergent formulation and/or a liquid manual dishwashing detergent formulation.
[Section 14]
12. A cleaning composition, a fabric care and home care product, an institutional cleaning product, a cosmetic formulation, a crude oil emulsion breaker, a pigment dispersion for ink-jet inks, an electroplating formulation, a cementitious composition, and/or a dispersant for agrochemical formulations, comprising at least one modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of claims 1 to 11.
Preferably, a cleaning composition, and/or a fabric care and home care product, and/or an institutional cleaning product, comprising at least one modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to any one of paragraphs 1 to 11.
[Section 15]
i) improved removal of oily/greasy stains, and/or ii) clay removal, and/or iii) particulate stain soil removal, and/or iv) soil dispersion and/or emulsification, and/or v) modification of treated surfaces to improve removal upon subsequent re-soiling, and/or vi) improved whiteness, and/or vii) at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, and peroxidases, and combinations of at least two of the above classes, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the above classes, more preferably lipases, when at least one enzyme selected from lipases is present, additionally for improved removal of oily/greasy stains, food stains, and/or combination stains,
Most preferably,
i) in cleaning compositions for improved removal of oily/greasy stains,
Item 15. The cleaning composition according to item 14,
A cleaning composition wherein each of options i) to vii) above is preferably for use in a laundry detergent formulation and/or a manual dishwashing detergent formulation, more preferably a liquid laundry detergent formulation, and/or a liquid manual dishwashing detergent formulation, and/or a solid or liquid automatic dishwashing formulation.

Claims

A modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine, comprising the steps of:
a) reacting i) at least one oligoalkyleneimine having a weight average molecular weight (Mw) of less than 400 g/mol or at least one oligoamine having a weight average molecular weight (Mw) of less than 400 g/mol with ii) at least one alkylene oxide (AO), wherein at least 10 moles of alkylene oxide (AO) are used per mole of NH functional group of the oligoalkyleneimine or oligoamine to obtain intermediate (I);
b) reacting said intermediate (I) with at least one lactone (LA) and/or at least one hydroxycarbonate (HA), wherein at least 1.0 mole of lactone (LA) and/or hydroxycarbonate (HA) is used per mole of NH functional group of the oligoalkyleneimine or oligoamine (used in step a)) to obtain a modified alkoxylated oligoalkyleneimine or modified alkoxylated oligoamine;
1. A modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine obtainable by a process comprising:

The at least one oligoalkyleneimine having a weight average molecular weight (Mw) of less than 400 g/mol or the at least one oligoamine having a weight average molecular weight (Mw) of less than 400 g/mol used in step a) is defined according to general formula (I),
wherein the variables are defined as follows:
R is the same or different: i) a linear or branched C ₂ -C ₁₂ alkylene radical, or ii) an ether alkyl unit of formula (III):
wherein the variables are defined as follows:
R ¹⁰ , R ¹¹ , R ¹² are the same or different and represent linear or branched C ₂ -C ₆ alkylene radicals;
d is an integer having a value ranging from 0 to 6;
ether alkyl unit, or iii) represents a _C5 - _C10 cycloalkylene radical optionally substituted with at least one _C1 - _C3 alkyl;
y is an integer having a value ranging from 0 to 8;
E ¹ is the same or different: i) hydrogen, or
ii) represents hydrogen and/or C ₁ -C ₁₈ -alkyl,
B represents the extension of the oligoalkyleneimine by branching,
z is an integer having a value ranging from 0 to 8;
the sum y+z is an integer having a value in the range of 0 to 8, preferably in the range of 0 to 7;
Preferably, R are identical or different and represent i) a linear or branched C ₂ -C ₁₂ alkylene radical, more preferably R is ethylene, propylene, or hexamethylene, or ii) a C ₅ -C ₁₀ cycloalkylene radical optionally substituted with at least one C ₁ -C ₃ alkyl, more preferably R is at least one C ₆ -C ₇ cycloalkylene radical substituted with at least one methyl or ethyl;
Preferably, ^E1 represents H and/or methyl,
More preferably, ^E1 represents H.
The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1.

containing at least one residue of general formula (IIa),
wherein the variables are defined as follows:
R ² is hydrogen or is selected from the group of unsubstituted or at least monosubstituted C ₁ -C ₂₂ -alkyl, C ₇ -C ₂₂ -aralkyl, —(CO)—C ₁ -C ₂₂ -alkyl, —(CO)—C ₂ -C ₃₀ -alkenyl and/or —(CO)—C ₇ -C ₂₂ -aralkyl, wherein said substituents are selected from —COOH or salts thereof,
^R3 represents a linear or branched _C1 - _C22 alkylene radical;
^R4 represents a _C2 - _C22- (1,2-alkylene) radical;
m is an integer having a value of at least 1 to 20;
p is an integer having a value of at least 10 to 100;
Preferably, the variables in general formula (IIa) are defined as follows:
R ² represents hydrogen, C ₁ -C ₄ -alkyl, —(CO)—C ₁ -C ₄ -alkyl, more preferably hydrogen, methyl, ethyl or —(CO)—C ₁ -C ₂ -alkyl, most preferably hydrogen, and/or
R ³ represents a linear or branched C ₂ -C ₁₀ alkylene radical, more preferably a linear or branched C ₂ -C ₅ alkylene radical, and/or R ⁴ represents 1,2-ethylene and/or 1,2-propylene, more preferably 1,2-ethylene, and/or m is an integer having a value in the range from 1 to 15, more preferably from 1 to 10, most preferably from 2 to 10, and/or p is an integer having a value in the range from 10 to 50, more preferably from 15 to 40, most preferably from 20 to 35,
The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1 .

containing at least one residue of general formula (IIb)
wherein the variables are defined as follows:
R ² is hydrogen or is selected from the group of unsubstituted or at least monosubstituted C ₁ -C ₂₂ -alkyl, C ₇ -C ₂₂ -aralkyl, —(CO)—C ₁ -C ₂₂ -alkyl, —(CO)—C ₂ -C ₃₀ -alkenyl and/or —(CO)—C ₇ -C ₂₂ -aralkyl, wherein the substituents are selected from —COOH or salts thereof,
^R4 represents a _C2 - _C22- (1,2-alkylene) radical;
p is an integer having a value of at least 10 to 100;
Preferably, the variables in general formula (IIb) are defined as follows:
R ² represents hydrogen, C ₁ -C ₄ -alkyl, —(CO)—C ₁ -C ₄ -alkyl, preferably hydrogen, methyl, ethyl or —(CO)—C ₁ -C ₂ -alkyl, most preferably hydrogen, and/or
^R4 represents 1,2-ethylene and/or 1,2-propylene, more preferably 1,2-ethylene, and/or p is an integer having a value ranging from 10 to 50, more preferably from 15 to 40, most preferably from 20 to 35;
The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1 .

i) step a) is carried out in the absence of water and/or in the presence of a catalyst, and/or ii) step a) is carried out as a two-step reaction, the first step being carried out in the presence of water and the second step being carried out without water but in the presence of a catalyst, and/or iii) more than 50% by weight of the alkylene oxide (AO) used in step a) is based on ethylene oxide, and/or iv) the weight average molecular weight (Mw) of the oligoalkyleneimine or oligoamine used in step a) is in the range of 60 to 390 g/mol, preferably in the range of 60 to 360 g/mol, or v) the weight average molecular weight (Mw) of the oligoalkyleneimine or oligoamine used in step a) is in the range of 100 to 200 g/mol, or vi) the weight average molecular weight (Mw) of the oligoalkyleneimine or oligoamine used in step a) is in the range of 250 to 350 g/mol.
The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1 .

The variables are defined as follows:
R is ethylene and/or propylene, preferably ethylene;
the sum y+z is an integer having a value in the range of 1 to 8, preferably in the range of 1 to 7;
The modified alkoxylated oligoalkyleneimine of claim 2 .

y is an integer having a value ranging from 0 to 8, preferably from 0 to 7;
z is 0,
^E1 represents H and/or methyl;
R represents the same or different linear or branched C ₂ -C ₁₂ alkylene radicals or ether alkyl units of formula (III), wherein:
d is 0 to 6;
R ¹⁰ , R ¹¹ , R ¹² are independently selected from linear or branched C ₃ -C ₄ alkylene radicals;
Preferably, R represents identical or different linear _C2 and/or _C3 alkylene radicals,
The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 2 .

2. The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1, wherein up to 100% of the nitrogen atoms present in the modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine are further quaternized, and preferably the degree of quaternization of the nitrogen atoms present in the modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine is in the range of 10 % to 95%.

i) in step a), said alkylene oxide (AO) is at least one C ₂ -C ₂₂ epoxide, preferably ethylene oxide and/or propylene oxide, more preferably ethylene oxide;
ii) in step b), the lactone (LA) is caprolactone or lactide, and/or iii) in step b), the hydroxycarbonic acid (HA) is lactic acid or glycolic acid;
The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1 .

i) in step a) 10 to 100 moles, preferably 10 to 50 moles, more preferably 15 to 40 moles, most preferably 20 to 35 moles of alkylene oxide (AO) are used per mole of NH functional group of the oligoalkyleneimine or oligoamine, and/or ii) in step b) 1.0 to 10 moles, preferably 1.0 to 6.0 moles, more preferably 2.0 to 4.0 moles of lactone (LA) and/or 1.0 to 20 moles, preferably 2.0 to 15 moles, more preferably 3.0 to 10 moles of hydroxycarbonic acid (HA) are used per mole of NH functional group of the oligoalkyleneimine or oligoamine (used in step a)),
The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1 .

i) in step a), the alkylene oxide (AO) is ethylene oxide, ii) in step a), 10 to 100 moles, preferably 10 to 50 moles, more preferably 15 to 40 moles, most preferably 20 to 35 moles of alkylene oxide (AO) are used per mole of NH functional group of the oligoalkyleneimine or oligoamine, and/or iii) in step b), the lactone is caprolactone, and 1.0 to 10 moles, preferably 1.0 to 6.0 moles, more preferably 2.0 to 4.0 moles of caprolactone are used per mole of NH functional group of the oligoalkyleneimine or oligoamine (used in step a),
The modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1 .

10. Use of the modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1 in cleaning compositions, in fabric care and home care products, in cosmetic formulations, as a crude oil emulsion breaker, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions, and/or as a dispersant for pesticide formulations.

i) improved removal of oily/greasy stains, and/or ii) clay removal, and/or iii) particulate stain soil removal, and/or iv) soil dispersion and/or emulsification, and/or v) modification of treated surfaces to improve removal upon subsequent re-soiling, and/or vi) improved whiteness, and/or vii) at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the above classes, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the above classes, more preferably lipases, when present, additionally in cleaning compositions and/or fabric care and home care products, preferably in cleaning compositions, for improved removal of oily/greasy stains, food stains and/or combination stains,
Most preferably,
i) Use according to claim 12 in a cleaning composition for improved removal of oily/greasy stains,
Use wherein each of options i) to vii) above is preferably for use in a laundry detergent formulation and/or a manual dishwashing detergent formulation, more preferably in a liquid laundry detergent formulation and/or a liquid manual dishwashing detergent formulation.

10. A cleaning composition, fabric care and home care product, institutional cleaning product, cosmetic formulation, crude oil emulsion breaker, pigment dispersion for inkjet ink, electroplating formulation, cementitious composition, and/or dispersant for pesticide formulation, comprising at least one modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine of claim 1;
Preferably, cleaning compositions, and/or fabric care and home care products, and/or institutional cleaning products, comprising at least one modified alkoxylated oligoalkylenimine or modified alkoxylated oligoamine according to claim 1 .

i) improved removal of oily/greasy stains, and/or ii) clay removal, and/or iii) particulate stain soil removal, and/or iv) soil dispersion and/or emulsification, and/or v) modification of treated surfaces to improve removal upon subsequent re-soiling, and/or vi) improved whiteness, and/or vii) at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, and peroxidases, and combinations of at least two of the above classes, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the above classes, more preferably lipases, when at least one enzyme selected from lipases is present, additionally for improved removal of oily/greasy stains, food stains, and/or combination stains,
Most preferably,
i) in cleaning compositions for improved removal of oily/greasy stains,
15. The cleaning composition of claim 14,
A cleaning composition wherein each of options i) to vii) above is preferably for use in a laundry detergent formulation and/or a manual dishwashing detergent formulation, more preferably a liquid laundry detergent formulation, and/or a liquid manual dishwashing detergent formulation, and/or a solid or liquid automatic dishwashing formulation.