WO2017167599A1 - Concentrés, procédés de fabrication et utilisations - Google Patents

Concentrés, procédés de fabrication et utilisations Download PDF

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Publication number
WO2017167599A1
WO2017167599A1 PCT/EP2017/056534 EP2017056534W WO2017167599A1 WO 2017167599 A1 WO2017167599 A1 WO 2017167599A1 EP 2017056534 W EP2017056534 W EP 2017056534W WO 2017167599 A1 WO2017167599 A1 WO 2017167599A1
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Prior art keywords
range
branched
chain
straight
alkyl
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PCT/EP2017/056534
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English (en)
Inventor
Frederic Bauer
Roland Ettl
Jean-Marc Ricca
Inga Vockenroth
Luca Bellomi
Silke Menke
Original Assignee
Basf Se
Henkel Ag & Co. Kgaa
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Publication of WO2017167599A1 publication Critical patent/WO2017167599A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions

Definitions

  • the present invention is directed towards concentrates comprising (A) in the range of from 70 to 99.5 % by weight of at least one non-ionic surfactant with at least one secondary hydroxyl group or at least one ester group per molecule,
  • Dishwashing compositions and especially automatic dishwashing (ADW) compositions have to satisfy many requirements. Thus, they have to fundamentally clean the dishes, they should have no harmful or potentially harmful substances in the waste water, they should permit the run-off and drying of the water from the dishes, and they should not lead to problems during operation of the dishwasher. Finally, they should not lead to esthetically undesired consequences on the ware to be cleaned. In this connection, mention is to be made particularly of glass corrosion.
  • Glass corrosion arises not only as the result of mechanical effects, for example by glasses rubbing together or mechanical contact of the glasses with parts of the dishwasher, but is primarily caused by chemical effects.
  • certain ions can be removed from the glass through repeated machine washing, which changes the optical and thus the esthetic properties in an adverse manner.
  • concentrates refers to formulations that are solid or preferably liquid at ambient temperature and that contain non-ionic surfactant (A) and polyalkylenimine (B) as defined below at a minimum of 50% by weight of the entire concentrate.
  • Inventive concentrates may contain active ingredients for ADW, such as one or more non- ionic surfactants other than non-ionic surfactant (A) or organic (co)polymers other than polyalkylenimine (B).
  • active ingredients for ADW such as one or more non- ionic surfactants other than non-ionic surfactant (A) or organic (co)polymers other than polyalkylenimine (B).
  • Other - optional - ingredients of inventive concentrates are amphoteric surfac- tants, anionic surfactants, cationic surfactants, preservatives, and dyestuffs,
  • inventive concentrates do not have a sharp melting point but a softening point.
  • the softening point sometimes also being referred to as softening temperature, is defined as the very temperature at which amorphous or partially crystalline inventive concentrate goes over from the vitreous, hard-elastic state into a soft state.
  • the Vicat softening temperature of non-curable plastics (DIN EN ISO 306: 2004- 10) is selected.
  • inventive concentrates have a melting or softening point in the range from -30 to 45°C.
  • the melting point is preferably determined by differential scanning calorimetry ("DSC"), with a heat rate of 1 °C/min.
  • Inventive concentrates comprise (A) in the range of from 70 to 99.5 % by weight of at least one non-ionic surfactant with at least one secondary hydroxyl group or at least one ester group per molecule, said non- ionic surfactant hereinafter also being referred to as surfactant (A),
  • polyalkylenimine (B) in the range of from 0.5 to 30% by weight of at least one polyalkylenimine that may be alkoxylated or substituted with CH2COOH groups as free acid or partially or fully neutralized with alkali, said polyalkylenimine hereinafter also being referred to as polyalkylenimine (B), percentages being based on the total solids content of said concentrate.
  • inventive concentrates contain total in the range of from 65 to 95 % by weight surfactant (A) and polyalkylenimine (B), the balance being, for example, water, an organic solvent, a surfactant other than surfactant (A), an organic (co)polymer other than polyalkylenimine (B), or a combination of the foregoing.
  • inventive concentrates may contain an organic solvent that is miscible with water at ambient temperature, for example 1 ,2-propandiol or ethylene glycol.
  • inventive concentrates may contain water.
  • inventive concentrates Prefera- bly, inventive concentrates contain 0.05 to 10% by weight of water, preferably 0.05 to 5% by weight, the percentage referring to the total inventive concentrate.
  • the sole solids of an inventive concentrate are surfactant(s) (A) and polyalkylen- imine(s) (B).
  • Surfactants (A) bear at least one secondary hydroxyl group or at least one ester group per molecule. Secondary hydroxyl groups preferably constitute part of a— CH2-CH(OH)-CH2- unit. Surfactants (A) that bear an ester group preferably bear an ester group that caps a polyalkylene oxide chain.
  • surfactants (A) that bear a secondary hydroxyl group are selected from compounds according to general formulae (I a)
  • R 1 are same or - if applicable - different and selected from C4-C3o-alkyl, straight-chain or branched, and from C4-C3o-alkylene, straight-chain or branched, with at least one C-C double bond, preferred is C4-C3o-alkyl, straight-chain or branched, more preferred is straight-chain C4-C3o-alkyl and even more preferred is n-C6-Ci6-alkyl, for example n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n- hexadecyl.
  • both R 1 are the same.
  • x and y take the same value.
  • AO is selected from identical or different alkylene oxides selected from CH2-CH2-O,
  • AO CH 2 -CH 2 -0
  • EO EO
  • (AO) x is selected from (EO) x i , x1 being selected from one to 50.
  • (AO) x is selected from -(EO) X 2-(CH2CH(CH3)-0) X 3 and -(EO) X 2-(CH(CH3)CH2-0) X 3, x2 and x3 being identical or different and selected from 1 to 30.
  • x or x1 or x2 and x3 or x4 are to be understood as aver- age values, the number average being preferred. Therefore, each x or x1 or x2 or x3 or x4 - if applicable - can refer to a fraction although a specific molecule can only carry a whole number of alkylene oxide units.
  • R 2 is selected from selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C30- alkylene, straight-chain or branched, with at least one C-C double bond, preferred is Ce- Ci4-alkyl, for example n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, 2-n-propylheptyl, n-undecyl, iso-undecyl, n-dodecyl, isodo- decyl, n-tetradecyl, and combinations of isomers of any of the forgoing, more preferred is Cs-Cn-alkyl.
  • Ce- Ci4-alkyl for example n-hexyl,
  • a 1 is selected from C2-Cio-alkylene, straight chain or branched, for example -CH2-CH2-, -CH 2 -CH(CH 3 )-, -CH 2 -CH(CH 2 CH 3 )-, -CH 2 -CH(n-C 3 H 7 )-, -CH 2 -CH(n-C 4 H 9 )-,
  • Preferred residues A 1 are -CH2-CH2-, CH 2 -CH(CH 3 )-, -CH 2 -CH(CH 2 CH 3 )-, -CH 2 -CH(n-C 3 H 7 )-, -CH 2 -CH(n-C 4 H 9 )-, -CH 2 -CH(n-C 6 Hi 3 )-, and -(CH 2 ) 4 -.
  • compound according to general formula (I a) is preferred.
  • compound according to general formula (I a) has at least one branching per molecule.
  • R 2 in compounds according to general formula (I a) is selected from branched C6-Ci4-alkyl and all AO are EO.
  • Such branched C6-C14- alkyl may have one or more branches, for example iso-hexyl, iso-heptyl, 2-ethylhexyl ("2-EH”), isooctyl, isodecyl, 2-n-propylheptyl ("2-PH”), 2-isopropyl-5-methylhexyl, isotrideyl, especially tetramethylnonyl.
  • branches for example iso-hexyl, iso-heptyl, 2-ethylhexyl (“2-EH”), isooctyl, isodecyl, 2-n-propylheptyl (“2-PH”), 2-isopropyl-5-methylhexyl, isotrideyl, especially tetramethylnonyl.
  • R 2 in compound according to general formula (I a) is selected from linear C6-Ci4-alkyl and an average of at least 0.5 AO per molecule is a propylene oxide group, the other AO groups preferably being EO groups.
  • R 2 in compound according to general formula (I a) is selected from linear C6-Ci4-alkyl and an average of at least 0.5 AO per molecule is a propylene oxide group, the other AO groups preferably being EO groups.
  • an average of 0.5 to 1 AO groups per molecule is a propylene oxide group, and the other AO groups are EO groups.
  • surfactants (A) according to general formula (I iso-Cn H23-0-(EO)4o-CH2-CH(OH)-n-C 8 Hi7
  • inventive concentrate contains two different compounds according to general formula (I a) or two different compounds according to general formula (I b).
  • R 1 is selected from C4-C3o-alkyl, straight-chain or branched, and from C4-C3o-alkylene, straight-chain or branched, with at least one C-C double bond, preferred is C4-C3o-alkyl, straight-chain or branched, more preferred is straight-chain C4-C3o-alkyl and even more preferred is n-C6-Ci6-alkyl, for example n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n-hexadecyl.
  • R 2 is selected from selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C30- alkylene, straight-chain or branched, with at least one C-C double bond, preferred is C6- Ci4-alkyl, for example n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, 2-n-propylheptyl, n-undecyl, iso-undecyl, n-dodecyl, isodo- decyl, n-tetradecyl, and combinations of isomers of any of the forgoing, more preferred is Cs-Cn-alkyl, for example n-hexyl, iso-hexyl,
  • compound according to general formula (II) is selected from those with
  • R 1 being selected from C6-Ci6-alkyl, straight-chain or branched, preferably n-hexyl, n-heptyl, n- octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, or n-hexadecyl,
  • (AO)x being selected from (PO) X 5(EO) X 6(PO) X 7, with PO being propylene oxide, x5 and x7 each being in the range of from 1 to 5, same or different, and x6 being in the range from 12 to 35, and R 2 being a straight-chain Cs-Ci7-alkyl.
  • Polyalkylenimine (B) as used herein refers to polymers of one or more polyalkylenimines that are usually made by ring-opening polymerization of the respective alkylenimine or by polycon- densation reactions of alkylendiamines or of hydroxyalkylamines such as, but not limited to eth- anolamine.
  • Polyalkylenimine (B) may bear substituents at primary or secondary N-atoms of the backbone polyalkylenimine.
  • polyalkylenimines (B) are non-substituted.
  • Suitable substituents are polyalkylenoxide chains such as, but not limited to polyethylenoxide chains and polypropylen-oxide chains and mixed polyalkylenoxide chains. Further examples of substituents are CH2COOH groups, as free acids or partially or fully neutralized with alkali.
  • Polyalkylenimines bearing one or more of the foregoing substituents are hereinafter also referred to as substituted polyalkylenimines (B).
  • polyaylkylenimines (B) are polyethylenimine and polypropylenimine, hereinafter also referred to as polyethylenimine (B) and polypropylenimine (B), respectively.
  • Preferred examples of substituted polyaylkylenimines (B) are substituted polyethylenimine and substituted polypropylenimine, hereinafter also referred to as substituted polyethylenimine (B) and as substituted polypropylenimine (B), respectively.
  • polyaylkylen- imines (B) are referred to that are neither polyalkoxylated nor substituted with CH2COOH groups such polyaylkylenimines (B) may also be referred to as non-substituted polyaylkylenimines (B).
  • the average molecular weights M w of polyalkylen- imine (B) and especially of polyethylenimine (B) that are non-substituted are in the range of from 400 to 50,000 g/mol, preferably 500 to 25,000 g/mol and more preferably from 750 up to 15,000 g/mol.
  • the average molecular weight M w of non-substituted polyalkylenimines (B) may be determined by gel permeation chromatography (GPC), with 1.5 % by weight aqueous formic acid as eluent and cross-linked poly-hydroxyethylmethacrylate as stationary phase.
  • the average molecular weight M w of substituted polyalkylenimine (B) is in the range of from 800 to 500,000 g/mol, preferably up to 100,000 g/mol.
  • the average molecular weight M w of substituted polyalkylenimines (B) may be determined by gel permeation chromatography (GPC), with 1.5 % by weight aqueous formic acid as eluent and cross-linked poly-hydroxyethylmethacrylate as stationary phase.
  • GPC gel permeation chromatography
  • the molecular weight refers to the respective free acid.
  • substituted polyethylenimine (B) is selected from those with alkylene oxide units and N atoms in a molar ratio in the range of from 1 : 1 to 100 : 1 , preferably in the range of from 2:1 to 50:1 , the N atoms stemming from alkylenimine units.
  • the alkylenimine units are ethylenimine units in their majority, for example at least 60 mol-%, referring to the total of alkylenimine units, preferably at least 70 mol-%.
  • inventive alkoxylated polyethylenimine (B) is selected from those with alkylene oxide units and N atoms in a molar ratio in the range of from 1 : 1 to 100 : 1 , preferably in the range of from 2:1 to 50:1 , the N atoms resulting from ethylenimine units, and no alkylenimine units other than ethylenimine units being present.
  • substituted polyethylenimine (B) is selected from those with 40 to 85 % of all N atoms being substituted with CH2COOH groups, the N atoms stemming from NH- and Nhb-units and the CH2COOH groups being free acid or partially or fully neutralized with alkali.
  • Alkoxylated polyalkylenimines (B) can be conveniently made by alkoxylation of non-substituted polyalkylenimines (B).
  • Non-substituted polyalkylenimines (B) will be described in more detail below.
  • Preferred non-substituted polyalkylenimines (B) are selected from non-substituted polypropyl- enimines (B) and even more preferred are non-substituted polyethylenimines ((B).
  • polyethylenimines in the context of the present invention does not only refer to poly- ethylenimine homopolymers but also to polyalkylenimines containing NH-CH2-CH2-NH structural elements together with other alkylene diamine structural elements, for example NH-CH2-CH2- CH2-NH structural elements, NH-CH 2 -CH(CH 3 )-NH structural elements, NH-(CH 2 ) 4 -NH structural elements, NH-(CH2)6-NH structural elements or (NH-(CH2)8-NH structural elements but the NH- CH2-CH2- NH structural elements being in the majority with respect to the molar share.
  • Preferred polyethylenimines contain NH-CH2-CH2-NH structural elements being in the majority with respect to the molar share, for example amounting to 60 mol-% or more, more preferably amounting to at least 70 mol-%, referring to all alkylenimine structural elements.
  • the term polyethylenimine refers to those polyalkylenimines that bear only one or zero alkylenimine structural element per molecule that is different from NH-CH2-CH2-NH.
  • Branches may be alkylenamino groups such as, but not limited to -CH2-CH2-NH2 groups or (CH2)3-NH2-groups. Longer branches may be, for examples, -(CH2)3-N(CH2CH2CH2NH2)2 or -(CH2)2-N(CH2CH2NH2)2 groups.
  • Highly branched polyethylenimines are, e.g., polyethylenimine dendrimers or related molecules with a degree of branching in the range from 0.25 to 0.95, preferably in the range from 0.30 to 0.80 and particularly preferably at least 0.5.
  • the degree of branching can be determined for example by 13 C-NMR or 15 N-NMR spectroscopy, preferably in D2O, and is defined as follows:
  • DB D+T/D+T+L with D (dendritic) corresponding to the fraction of tertiary amino groups, L (linear) corresponding to the fraction of secondary amino groups and T (terminal) corresponding to the fraction of pri- mary amino groups.
  • preferred non-substituted polyethylenimines (B) are non-substituted polyethylenimines (B) with DB in the range from 0.25 to 0.95, particularly preferably in the range from 0.30 to 0.90% and very particularly preferably at least 0.5.
  • CH3-groups are not being considered as branches in polyalkylenimines (B).
  • surfactant (A) is selected from compounds accord- ing to general formula (I a) or (I b) and polyalkylenimine (B) is selected from non-substituted polyethylenimines with an average molecular weight in the range of from 400 to 25,000 g/mol.
  • inventive concentrates comprise
  • inventive concentrates comprise
  • surfactant (A) being selected from compounds according to general formula (I a), and
  • polyalkylenimine (B) being selected from non-substituted polyethyl- enimines with an average molecular weight M w in the range of from 400 to 25,000 g/mol.
  • inventive concentrates comprise in the range of from 1 ppm to 0.8 % by weight of water, preferably 0.05 to 0.5 % by weight.
  • the water content may be determined, e.g., by Karl-Fischer titration.
  • inventive concentrates display a very low turbidity.
  • the turbidity may be in the range of from 0.3 to 30, preferably from 0.5 up to 10 nephelometric turbidity units ("NTU”), determined at 23°C.
  • inventive concentrates may comprise a surfactant other than surfactant (A), an organic (co)polymer other than polyalkylenimine (B), or a combination of the foregoing.
  • surfactants other than surfactant (A) are especially non-ionic surfactants.
  • Preferred non-ionic surfactants are alkoxylated alcohols, di- and multiblock copolymers of eth- ylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APG), hydroxyalkyl mixed ethers and amine oxides.
  • APG alkyl polyglycosides
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III)
  • R 3 is selected from Cs-C22-alkyl, branched or linear, for example n-CsH , n-doHb-i , n-Ci2H25, ⁇ - ⁇ 4 ⁇ 29, n-Ci6H33 or n-CieH37
  • R 4 is selected from Ci-Cio-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or
  • compounds of the general formula (III) may be block copolymers or random copolymers, preference being given to block copolymers.
  • alkoxylated alcohols are, for example, compounds of the general formula (IV)
  • R 5 is identical or different and selected from hydrogen and linear Ci-Co-alkyl, preferably identical in each case and ethyl and particularly preferably hydrogen or methyl
  • R 6 is selected from C6-C2o-alkyl, branched or linear, in particular n-CsH , n-doHb-i , n-Ci2H25, n-Ci3H27, n-Ci5H3i , n-Ci 4 H29, n-Ci6H33, n-CieH37,
  • a is a number in the range from zero to 10, preferably from 1 to 6
  • b is a number in the range from 1 to 80, preferably from 4 to 20
  • d is a number in the range from zero to 50, preferably 4 to 25.
  • the sum a + b + d is preferably in the range of from 5 to 100, even more preferably in the range of from 9 to 50.
  • n and n are in the range from zero to 300, where the sum of n and m is at least one, preferably in the range of from 5 to 50.
  • m is in the range from 1 to 100 and n is in the range from 0 to 30.
  • Compounds of the general formula (IV) and (V) may be block copolymers or random copolymers, preference being given to block copolymers.
  • nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-Ci6-alkyl polyglucosides and branched Cs-C-u-alkyl polyglycosides such as compounds of general average formula (VI) are likewise suitable.
  • R 7 is Ci-C4-alkyl, in particular ethyl, n-propyl or isopropyl,
  • R 8 is -(CH 2 ) 2 -R 7 ,
  • G 1 is selected from monosaccharides with 4 to 6 carbon atoms, especially from glucose and xylose, s in the range of from 1.1 to 4, s being an average number,
  • non-ionic surfactants are compounds of general formula (VII) and (VIII)
  • R 6 and AO are defined as above,
  • R 9 selected from Cs-Cis-alkyl, branched or linear, and R 5 is defined as above.
  • a 3 0 is selected from propylene oxide and butylene oxide,
  • w is a number in the range of from 15 to 70, preferably 30 to 50,
  • w1 and w3 are numbers in the range of from 1 to 5, and
  • w2 is a number in the range of from 13 to 35.
  • Mixtures of two or more different nonionic surfactants selected from the foregoing may also be present.
  • Inventive concentrates are an excellent intermediate for making hard surface cleaners, for ex- ample for tile cleaning, glass cleaning, oven cleaners, degreasers, floor cleaners, all purpose cleaners, toilet cleaners, and especially for making automatic dishwashing formulations.
  • Such automatic dishwashing formulations may be in liquid form, in solid form, or gel-type.
  • Particularly preferred embodiments of automatic dishwashing formulations are tablets.
  • An aspect of the present invention is thus the use of inventive concentrates for the manufacture of hard surface cleaners.
  • a preferred aspect of the present invention is the use of inventive concentrates for the manufacture of automatic dishwashing formulations, liquid or solid or gel-type.
  • inventive process comprises the step of mixing surfactant(s) (A) and polyalkylenimine (B) in liquid phase. Mixing may be supported by stirring, shaking, static mixers, and circulation.
  • the inventive manufacturing process is carried out at a temperature in the range of from 15 to 90°C, preferably 25 to 85°C; even more preferably 35 to 80°C.
  • the inventive process may be carried out under air.
  • the inventive process is carried out under an atmosphere of inert gas, for example a noble gas such as argon, or under nitrogen.
  • a mixture is made by combining surfactant(s) (A) and polyalkylenimine (B), and in a second step further amounts of surfactant (A) or a further surfactant is added.
  • Further surfactant (A) and mixture of surfactant(s) (A) and polyalkylenimine (B) may be combined at a mass ratio in the range of from 1 :10 to 10:1.
  • a further aspect of the present invention relates to hard surface cleaners and especially to automatic dishwashing formulations that contain (A) one non-ionic surfactant with at least one secondary hydroxyl group or at least one ester group per molecule, (B) in the range of from 1.5 to 30% by weight of at least one polyalkylenimine that may be alkoxylated or substituted with CH2COOH groups as free acid or partially or fully neutralized with alkali, in the weight ratio in the range of from 7 : 3 to 65.7 : 1.
  • inventive hard surface cleaners and especially inventive automatic dishwashing formulations comprise
  • inventive hard surface cleaners and especially inventive automatic dishwashing formulations comprise
  • surfactant (A) being selected from compounds according to general formula (I a), and polyalkylenimine (B) being selected from non-substituted polyethylenimines with an average molecular weight in the range of from 400 to 25,000 g/mol. in a weight ratio in the range of from 9 : 1 to 7 : 3.
  • inventive hard surface cleaners and especially inventive automatic dishwashing formulations comprise 0.5 to 10% by weight of inventive concentrate, preferably 0.5 to 8.5% by weight, even more preferably 0.75 to 8% by weight.
  • Such automatic dishwashing formulations may comprise ingredients other than surfactant (A) and polyalkylenimine (B).
  • inventive automatic dishwashing formulations may comprise on or more surfactants other than surfactant (A), an organic (co)polymer other than polyalkylenimine (B), or a combination of the foregoing.
  • non-ionic surfactants other than surfactant (A) any of the foregoing may be used, or a combination of at least two of them.
  • Inventive automatic dishwashing formulations may comprise one or more anionic or zwitterionic surfactants.
  • amphoteric surfactants are those that bear a positive and a negative charge in the same molecule under use conditions.
  • Preferred examples of amphoteric surfactants are so- called betaine-surfactants.
  • Many examples of betaine-surfactants bear one quaternized nitrogen atom and one carboxylic acid group per molecule.
  • a particularly preferred example of amphoter- ic surfactants is cocamidopropyl betaine (lauramidopropyl betaine).
  • amine oxide surfactants are compounds of the general formula (IX)
  • R 9 is selected from C8-C20- alkyl or C2-C 4 -alkylene Cio-C2o-alkylamido and R 10 and R 11 are both methyl.
  • a particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide.
  • a further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide.
  • Suitable anionic surfactants are alkali metal and ammonium salts of Cs-C-is-alkyl sulfates, of Cs-Cis-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C 4 - Ci2-alkylphenols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, furthermore of Ci2-Ci8-alkylsulfonic acids and of Cio-Ci8-alkylarylsulfonic acids.
  • Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.
  • Suitable anionic surfactants are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates, and alkylether phosphates.
  • inventive solid detergent compositions for cleaners may contain 0.1 to 60 % by weight of at least one surfactant, selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.
  • inventive automatic dishwashing formulations do not contain any anionic surfactant.
  • Inventive solid detergent compositions for hard surface cleaning and inventive solid laundry detergent compositions may contain at least one bleaching agent, also referred to as bleach.
  • Bleaching agents may be selected from chlorine bleach and peroxide bleach, and peroxide bleach may be selected from inorganic peroxide bleach and organic peroxide bleach.
  • Preferred are inorganic peroxide bleaches, selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
  • Examples of organic peroxide bleaches are organic percarboxylic acids, especially organic per- carboxylic acids.
  • alkali metal percarbonates especially sodium percarbonates
  • Such coatings may be of organic or inorganic nature. Examples are glycerol, sodium sulfate, silicate, sodium carbonate, and combinations of at least two of the foregoing, for example combinations of sodium carbonate and sodium sulfate.
  • Suitable chlorine-containing bleaches are, for example, 1 ,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
  • Inventive solid detergent compositions for hard surface cleaning and inventive solid laundry detergent compositions may comprise, for example, in the range from 3 to 10% by weight of chlorine-containing bleach.
  • Inventive solid detergent compositions for hard surface cleaning and inventive solid laundry de- tergent compositions may comprise one or more bleach catalysts.
  • Bleach catalysts can be selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and rutheni- um-amine complexes can also be used as bleach catalysts.
  • Inventive solid detergent compositions for hard surface cleaning and inventive solid laundry detergent compositions may comprise one or more bleach activators, for example N- methylmorpholinium-acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N- acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro- 1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N- methylmorpholinium-acetonitrile salts
  • DADHT dioxohexahydro- 1 ,3,5-triazine
  • nitrile quats trimethylammonium acetonitrile salts
  • TAED tetraacetylethylenediamine
  • TAED tetraacetylhexylenediamine
  • inventive solid detergent compositions for hard surface cleaning and inventive solid laundry detergent compositions may comprise one or more corrosion inhibitors.
  • corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, ami- notriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
  • inventive solid detergent compositions for hard surface cleaning and inventive solid laundry detergent compositions comprise in total in the range from 0.1 to 1.5% by weight of corrosion inhibitor.
  • Inventive automatic dishwashing formulations may comprise one or more builders, selected from organic and inorganic builders.
  • suitable inorganic builders are sodium sulfate or sodium carbonate or silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, in particular those of the formula a-Na2Si20s, 3-Na2Si20s, and 5-Na2Si20s, also fatty acid sulfonates, ohydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid.
  • organic builders are especially polymers and copolymers.
  • organic builders are selected from polycarboxylates, for example alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.
  • Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
  • a suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40 000 g/mol, preferably 2000 to 10 000 g/mol, in particular 3000 to 8000 g/mol.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid, and in the same range of molecular weight.
  • Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with 10 or more carbon atoms or mixtures thereof, such as, for example, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1 - docosene, 1-tetracosene and 1 -hexacosene, C22-a-olefin, a mixture of C2o-C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.
  • Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups, and also nonionic monomers with hydroxyl function or alkylene oxide groups.
  • Polyalkylene glycols here may comprise 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
  • Particularly preferred sulfonic-acid-group-containing monomers here are 1-acrylamido- 1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-
  • Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.
  • a further example of builders is carboxymethyl inulin.
  • amphoteric polymers can also be used as builders.
  • Such polymeric builders may be comprised in inventive concentrate or may be added separately-
  • Inventive automatic dishwashing formulations may comprise, for example, in the range from in total 10 to 70% by weight, preferably up to 50% by weight, of builder.
  • MGDA is not counted as builder.
  • inventive automatic dishwashing formulations may comprise one or more cobuilders.
  • Inventive automatic dishwashing formulations may comprise one or more antifoams, selected for example from silicone oils and paraffin oils.
  • inventive automatic dishwashing formulations comprise in total in the range from 0.05 to 0.5% by weight of antifoam.
  • Inventive automatic dishwashing formulations may comprise one or more enzymes.
  • enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
  • Particularly advantageous inventive automatic dishwashing formulations may contain one or more complexing agent (in the context of the present invention also referred to as sequestrant).
  • sequestrants other than a salt according to the present invention are IDS (iminodisuccinate), citrate, phosphonic acid derivatives, for example the disodium salt of hydroxyethane-1 ,1 -diphosphonic acid (“HEDP”), and aminocarboxylic acids and their respective alkali metal salts, for example methylglycine diacetic acid (“MGDA”), glutamic acid diacetic acid (“GLDA”), iminodiacetic acid (“IDA”), and iminodisuccinic acid (“IDS”).
  • IDS aminodisuccinate
  • citrate citrate
  • phosphonic acid derivatives for example the disodium salt of hydroxyethane-1 ,1 -diphosphonic acid
  • HEDP hydroxyethane-1 ,1 -diphosphonic acid
  • sequestrants are trisodium citrate and phosphates such as STPP (sodium tripoly- phosphate). Due to the fact that phosphates raise environmental concerns it is preferred that advantageous detergent compositions for cleaners and advantageous laundry detergent compositions are free from phosphate. "Free from phosphate” should be understood in the context of the present invention, as meaning that the content of phosphate and polyphosphate is in sum in the range from 10 ppm to 0.2% by weight, determined by gravimetric analysis.
  • MGDA and GLDA are comprised in the form of alkali metal salts, for example in the form of potassium salts or sodium salts or as mixed sodi- um-potassium salts.
  • Preferred sequestrants are compounds according to the general formula (X)
  • M 1 is selected from alkali metal cations, same or different, preferably potassium and especially sodium, and
  • R 1 is selected from Ci-C4-alkyl, especially methyl, wherein r is in the range of from zero to 0.5, and of formula (XI)
  • r is an average number.
  • inventive automatic dishwashing formulations may comprise, for example, up to 5% by weight of enzyme, preference being given to 0.1 to 3% by weight.
  • Said enzyme may be stabilized, for example with the sodium salt of at least one C1-C3- carboxylic acid or C4-Cio-dicarboxylic acid. Preferred are formates, acetates, adipates, and suc- cinates.
  • inventive automatic dishwashing formulations comprise at least one zinc salt.
  • Zinc salts may be selected from water-soluble and water- insoluble zinc salts.
  • water- insoluble is used to refer to those zinc salts which, in distilled water at 25°C, have a solubility of 0.1 g/l or less.
  • Zinc salts which have a higher solubility in water are accordingly referred to within the context of the present invention as water-soluble zinc salts.
  • zinc salt is selected from zinc benzoate, zinc glu- conate, zinc lactate, zinc formate, ZnC , ZnS0 4 , zinc acetate, zinc citrate, Zn(NOs)2,
  • Zn(CH3S03)2 and zinc gallate preferably ZnC , ZnS0 4 , zinc acetate, zinc citrate, Zn(NOs)2, Zn(CH3S03)2 and zinc gallate.
  • zinc salt is selected from ZnO, ZnOaq, Zn(OH)2 and ZnC03. Preference is given to ZnOaq.
  • zinc salt is selected from zinc oxides with an average particle diameter (weight-average) in the range from 10 nm to 100 ⁇ .
  • the cation in zinc salt can be present in complexed form, for example complexed with ammonia ligands or water ligands, and in particular be present in hydrated form.
  • ligands are generally omitted if they are water ligands.
  • zinc salt can change.
  • Zinc salt may be present in those inventive automatic dishwashing formulations which are solid at room temperature are preferably present in the form of particles which have for example an average diameter (number-average) in the range from 10 nm to 100 ⁇ , preferably 100 nm to 5 ⁇ , determined for example by X-ray scattering. Zinc salt may be present in those detergent compositions for home care applications that are liquid at room temperature in dissolved or in solid or in colloidal form.
  • inventive automatic dishwashing formulations comprise in total in the range from 0.05 to 0.4% by weight of zinc salt, based in each case on the solids content of the composition in question.
  • the fraction of zinc salt is given as zinc or zinc ions. From this, it is possible to calculate the counterion fraction.
  • inventive automatic dishwashing formulations are free from heavy metals apart from zinc compounds.
  • inventive automatic dishwashing formulations are free from those heavy metal compounds which do not act as bleach catalysts, in particular of compounds of iron and of bismuth.
  • "free from” in connection with heavy metal compounds is to be understood as meaning that the content of heavy metal compounds that do not act as bleach catalysts is in sum in the range from 0 to 100 ppm, determined by the leach method and based on the solids content.
  • automatic dishwashing formulations according to the invention has, apart from zinc, a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question.
  • heavy metals are defined to be any metal with a specific density of at least 6 g/cm 3 with the exception of zinc.
  • the heavy metals are metals such as bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
  • inventive automatic dishwashing formulations comprise no measurable fractions of bismuth compounds, i.e. for example less than 1 ppm.
  • inventive automatic dishwashing formulations comprise one or more further ingredient such as fragrances, dyestuffs, organic solvents, buffers, disintegrants for tabs, and/or acids such as methylsulfonic acid.
  • Preferred example automatic dishwashing formulations may be selected according to table 1.
  • turbidity - nephelometric turbidity units In each run, a HACH RATIO/XR TURBIDIMETER (serial number: 890501402; model: 43900) was charged with 30 ml of the respective concentrate and sealed under an atmosphere of dry nitrogen. After 2 hours the bubbles had gone. Then, the turbidity was determined. Each sample was measured 10 times. All measurements were performed at 23°C. The experimental error was less than 2%.
  • the turbidity in Table 2 is the [NTU] - nephelometric turbidity unit
  • inventive concentrates excellent phosphate-free dishwash compositions can be made. Especially the breakage of tablets was low.
  • CONC.2, CONC.3 and CONC.4 with any of ADW.1 to ADW.3 from Table 3 are advantageous in preventing glass corrosion and providing excellent rinse efficiency.
  • the dynamic viscosity ⁇ was determined at 23°C with a Brookfield viscosimeter, spindle 1 .

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Abstract

L'invention concerne des concentrés comprenant (A) dans la plage allant de 70 à 99,5 % en poids d'au moins un tensioactif non ionique présentant au moins un groupe hydroxyle secondaire ou au moins un groupe ester par molécule, (B) dans la plage allant de 0,5 à 30 % en poids d'au moins une polyalkylèneimine pouvant être alcoxylé ou substitué par des groupes CH2COOH en tant qu'acide libre ou partiellement ou totalement neutralisée par un alcali, les pourcentages étant basés sur la teneur totale en solides dudit concentré.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11098269B2 (en) 2016-11-08 2021-08-24 Basf Se Composition suitable as surfactant
CN115772070A (zh) * 2022-11-29 2023-03-10 亚培烯科技（杭州）有限公司 多醚化合物及其制备方法和基于其制备的空气压缩机油

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0851023A2 (fr) 1996-12-23 1998-07-01 Unilever N.V. Tablettes pour machine à laver la vaisselle contenant un peracide
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
WO2006032371A1 (fr) * 2004-09-17 2006-03-30 Henkel Kommanditgesellschaft Auf Aktien Constituants de produits nettoyants
WO2010020765A1 (fr) * 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition
WO2013056965A1 (fr) 2011-10-19 2013-04-25 Basf Se Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation
DE102014212728A1 (de) * 2014-07-01 2016-01-07 Henkel Ag & Co. Kgaa Geschirrspülmittel
WO2016024093A1 (fr) 2014-08-11 2016-02-18 Reckitt Benckiser (Brands) Limited Détergent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0851023A2 (fr) 1996-12-23 1998-07-01 Unilever N.V. Tablettes pour machine à laver la vaisselle contenant un peracide
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
WO2006032371A1 (fr) * 2004-09-17 2006-03-30 Henkel Kommanditgesellschaft Auf Aktien Constituants de produits nettoyants
WO2010020765A1 (fr) * 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition
WO2013056965A1 (fr) 2011-10-19 2013-04-25 Basf Se Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation
DE102014212728A1 (de) * 2014-07-01 2016-01-07 Henkel Ag & Co. Kgaa Geschirrspülmittel
WO2016024093A1 (fr) 2014-08-11 2016-02-18 Reckitt Benckiser (Brands) Limited Détergent

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11098269B2 (en) 2016-11-08 2021-08-24 Basf Se Composition suitable as surfactant
CN115772070A (zh) * 2022-11-29 2023-03-10 亚培烯科技（杭州）有限公司 多醚化合物及其制备方法和基于其制备的空气压缩机油
CN115772070B (zh) * 2022-11-29 2024-01-02 亚培烯科技（杭州）有限公司 多醚化合物及其制备方法和基于其制备的空气压缩机油

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