WO2017167599A1

WO2017167599A1 - Concentrates, methods of manufacture, and uses

Info

Publication number: WO2017167599A1
Application number: PCT/EP2017/056534
Authority: WO
Inventors: Frederic Bauer; Roland Ettl; Jean-Marc Ricca; Inga Vockenroth; Luca Bellomi; Silke Menke
Original assignee: Henkel AG and Co KGaA; BASF SE
Current assignee: Henkel AG and Co KGaA; BASF SE
Priority date: 2016-03-30
Filing date: 2017-03-20
Publication date: 2017-10-05
Anticipated expiration: 2018-09-30

Abstract

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, (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, percentages being based on the total solids content of said concentrate.

Description

Concentrates, methods of manufacture, and uses

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,

(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 neutral- ized with alkali, percentages being based on the total solids content of said concentrate.

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. For example, 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.

In the event of glass corrosion, several effects are observed. Firstly, the formation of microscopically fine cracks can be observed, which become noticeable in the form of lines. Secondly, in many cases, a general hazing can be observed, for example a roughening, which makes the glass in question appear unattractive. Effects of this type are overall also subdivided into iridescent discoloration, formation of ridges, and also sheet-like and ring-like hazing.

In WO 2013/056965, certain automatic dishwashing reagents are disclosed that comprise an aminocarboxylic acid-based complexing agent, a bleaching agent, the sodium salt of citric acid and a homopolymer of ethylenimine. Although the effects on glass are good in some cases problems may be observed when trying to evenly formulate the above components into tablets. Such tablets are observed to break prematurely. In WO 2016/024093, so-called self-standing automatic dishwashing gels are disclosed that contain at least 50 wt. % non-ionic liquid surfactant and a water-soluble C14-C22 fatty acid. It was therefore an objective of the present invention to provide an ingredient for automatic dishwashing agents that allows for protecting glassware from glass corrosion but that also allows for easy formulating into tablets. Accordingly, the concentrates as defined at the outset have been found, hereinafter also referred to as inventive concentrates or concentrates according to the present invention. Inventive concentrates will be defined in more detail below.

The term "concentrates" as used in context of the present invention 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). Other - optional - ingredients of inventive concentrates are amphoteric surfac- tants, anionic surfactants, cationic surfactants, preservatives, and dyestuffs,

In many embodiment of the present invention, 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. In a preferred variant, the Vicat softening temperature of non-curable plastics (DIN EN ISO 306: 2004- 10) is selected.

In one embodiment of the present invention 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),

(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.

In a preferred embodiment of the present invention, 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. 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.

Preferably, 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.

In a preferred embodiment of the present invention, surfactants (A) that bear a secondary hydroxyl group are selected from compounds according to general formulae (I a)

R -CH(OH)-CH₂-0-(AO)x-R² (I a), or to general formula (I b)

R -CH(OH)-CH₂-0-(AO)x-A -0-(AO)y-CH₂-CH(OH)-R¹ (I b) wherein

R¹ 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. In compounds according to general formula (I b) it is preferred that both R¹ are the same. x, y same or - applicable - different and selected from 6 to 50, preferably 12 to 25. In compounds according to general formula (I b), it is preferred that x and y take the same value.

AO is selected from identical or different alkylene oxides selected from CH2-CH2-O,

-(CH₂)₃-0, -(CH₂)4-0, -CH₂CH(CH₃)-0, -CH(CH₃)-CH₂-0- and CH₂CH(n-C₃H₇)-0. Preferred example of AO is CH₂-CH₂-0 ("EO"). In the context of the present invention, the expressions EO and EO groups may be used interchangeably.

In one embodiment of the present invention, (AO)_x is selected from (EO)_xi , x1 being selected from one to 50.

In one embodiment of the present invention, (AO)_x is selected from -(EO)_X2-(CH2CH(CH3)-0)_X3 and -(EO)_X2-(CH(CH3)CH2-0)_X3, x2 and x3 being identical or different and selected from 1 to 30. In one embodiment of the present invention, (AO)_x is selected from -(EO)_x4, x4 = being in the range of from 10 to 50, AO being EO, and R¹ and R² each being independently selected from Cs-C-u-alkyl.

In the context of the present invention, 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.

In compounds according to general formula (I b), the same applies to (AO)_y mutatis mutandis.

In compounds according to general formula (I a),

R² 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. In compounds according to general formula (I b),

A¹ is selected from C2-Cio-alkylene, straight chain or branched, for example -CH2-CH2-, -CH₂-CH(CH₃)-, -CH₂-CH(CH₂CH₃)-, -CH₂-CH(n-C₃H₇)-, -CH₂-CH(n-C₄H₉)-,

-CH₂-CH(n-C₅Hi i)-, -CH₂-CH(n-C₆Hi₃)-, -CH₂-CH(n-C₈Hi₇)-, -CH(CH₃)-CH(CH₃)-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅-, -(CH₂)₆-, -(CH₂)₈-, -(CH₂)io-, -C(CH₃)₂-, -CH2-C(CH₃)2-CH₂-, and

-CH2-[C(CH₃)2]2-CH₂-.

Preferred residues A¹ are -CH2-CH2-, CH₂-CH(CH₃)-, -CH₂-CH(CH₂CH₃)-, -CH₂-CH(n-C₃H₇)-, -CH₂-CH(n-C₄H₉)-, -CH₂-CH(n-C₆Hi₃)-, and -(CH₂)₄-.

Among compounds according to general formula (I a) and compounds according to general formula (I b), compounds according to general formula (I a) are preferred. In a preferred embodiment of the present invention, compound according to general formula (I a) has at least one branching per molecule. In one class of examples of said preferred embodiment, R² 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.

In another preferred embodiment of the present invention, R² 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. For example, in such a compound an average of 0.5 to 1 AO groups per molecule is a propylene oxide group, and the other AO groups are EO groups.

Examples of particularly suitable surfactants (A) according to general formula (I iso-Cn H23-0-(EO)4o-CH2-CH(OH)-n-C₈Hi7

iso-tridecyl-0-(EO)4o-CH₂-CH(OH)-n-C₈Hi7

n-CioH₂i-0-CH2-CH(CH3)-(EO)22-0-CH2-CH(OH)-n-C₈Hi7

iso-Cii H23-0-(EO)4o-CH₂-CH(OH)-n-CioH2i

iso-tridecyl-0-(EO)4o-CH₂-CH(OH)-n-CioH₂i

n-CioH₂i-0-CH2-CH(CH₃)-0-(EO)22-CH2-CH(OH)-n-CioH2i n-CioH₂i-0-CH2-CH(CH3)-0-(EO)22-CH₂CH(OH)-n-C8Hi7

n-C₈Hi7-0-CH2-CH(CH3)-0-(EO)22-CH2CH(OH)-n-C₈Hi7

n-CioH₂i-0-CH2-CH(CH3)-0-(EO)4o-CH₂CH(OH)-n-C₈Hi7

n-C₈Hi7-O-CH2-CH(CH3)-O-(EO)40-CH₂CH(OH)-n-C₈Hi7

n-CioH₂i-0-CH2-CH(CH3)-0-(EO)22-CH₂CH(OH)-n-CioH2i

n-C₈Hi7-0-CH2-CH(CH3)-0-(EO)22-CH₂CH(OH)-n-CioH2i

n-CioH₂i-0-CH2-CH(CH3)-0-(EO)4o-CH₂CH(OH)-n-CioH2i

n-C₈Hi7-0-CH2-CH(CH3)-0-(EO)4o-CH₂CH(OH)-n-CioH2i Examples of particularly suitable surfactants (A) according to general formula (I b) are

with both R¹ in formula (I b.1 ) and (I b.2) and (b.3) being the same and selected from n-CsH

In one embodiment of the present invention inventive concentrate contains two different compounds according to general formula (I a) or two different compounds according to general formula (I b).

In one embodiment of the present invention, in

R -CH₂-CH₂-0-(AO)x-C(0)-R² (II)

R¹ 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. In compounds according to general formula (I b) it is preferred that both R¹ are the same. R² 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. x is selected from 10 to 50, preferably 12 to 25.

In a preferred embodiment of the present invention, compound according to general formula (II) is selected from those with

R¹ 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)_X5(EO)_X6(PO)_X7, 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 R² 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. In other embodiments, 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). Preferred examples of 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. In embodiments wherein 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). In one embodiment of the present invention, 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.

In one embodiment of the present invention, 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. In case of

ChbCOOH-substituents, the molecular weight refers to the respective free acid.

Polyalkylenimines (B) including non-substituted polyethylenimines (B) and substituted polyalkylenimines (B) may display a polydispersity Q = M_w/M_n in the range of from 1 .1 to 20, preferably in the range of from 1.5 to 10 and more preferably up to 5.5. In one embodiment of the present invention, 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. Preferably, 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-%.

In a special embodiment of the present invention, 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.

In one embodiment of the present invention, 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). The term "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-CH₂-CH(CH₃)-NH structural elements, NH-(CH₂)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. In a special embodiment, 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 ¹³C-NMR or ¹⁵N-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.

Within the context of the present invention, 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.

In the context of the present invention, CH3-groups are not being considered as branches in polyalkylenimines (B).

In one embodiment of the present invention, 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.

In a preferred embodiment, inventive concentrates comprise

90 to 99.5 % by weight of surfactant (A) being selected from compounds according to general formula (I b), more preferably up to 99 % by weight and even more preferably up to 97.5% by weight, and 0.5 to 10 % by weight of 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, preferably at least 1.0 % by weight and even more preferably at least 2.5% by weight. In another preferred embodiment, inventive concentrates comprise

70 to 90 % by weight of surfactant (A) being selected from compounds according to general formula (I a), and

10 to 30 % by weight of 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.

In a preferred embodiment, 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. In a preferred embodiment, 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.

As mentioned before, inventive concentrates may comprise a surfactant other than surfactant (A), an organic (co)polymer other than polyalkylenimine (B), or a combination of the foregoing.

Examples of such 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.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III)

in which the variables are defined as follows:

R³ is selected from Cs-C22-alkyl, branched or linear, for example n-CsH , n-doHb-i , n-Ci2H25, η-Οι₄Η29, n-Ci6H33 or n-CieH37, R⁴ 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 isodecyl, R⁵ is identical or different and selected from hydrogen and linear Ci-Cio-alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl, m 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 3 to 50. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

In one embodiment, compounds of the general formula (III) may be block copolymers or random copolymers, preference being given to block copolymers. Other preferred examples of alkoxylated alcohols are, for example, compounds of the general formula (IV)

in which the variables are defined as follows:

R⁵ 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, R⁶ is selected from C6-C2o-alkyl, branched or linear, in particular n-CsH , n-doHb-i , n-Ci2H25, n-Ci3H27, n-Ci5H3i , n-Ci₄H29, 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.

The variables m 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. Preferably, 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.

Further suitable 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.

wherein:

R⁷ is Ci-C4-alkyl, in particular ethyl, n-propyl or isopropyl,

R⁸ is -(CH₂)₂-R⁷,

G¹ 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,

Further examples of non-ionic surfactants are compounds of general formula (VII) and (VIII)

R⁶ and AO are defined as above,

R⁹ selected from Cs-Cis-alkyl, branched or linear, and R⁵ is defined as above. A³0 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.

An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE- A 198 19 187.

Mixtures of two or more different nonionic surfactants selected from the foregoing may also be present.

Examples of (co)polymers that may be comprised are described further down below.

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.

Another aspect of the present invention is related to a process for making inventive concentrates, said process also being referred to as inventive manufacturing process. The 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.

In one embodiment of the present invention, 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. In a preferred embodiment of the present invention, the inventive process is carried out under an atmosphere of inert gas, for example a noble gas such as argon, or under nitrogen.

In one embodiment of the inventive manufacturing process, in a first step 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.

In a preferred embodiment, inventive hard surface cleaners and especially inventive automatic dishwashing formulations comprise

surfactant (A) being selected from compounds according to general formula (I b) 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 65.7 : 1 , preferably up to 49 : 1 and even more preferably up to 48.5 : 1 . In another preferred embodiment, 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.

In a preferred embodiment, 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). For example, 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.

As 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. Examples of 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).

Examples of amine oxide surfactants are compounds of the general formula (IX)

_R9Rio_Ri i _N→0 (IX) wherein R⁹, R¹⁰, and R¹¹ are selected independently from each other from aliphatic, cycloali- phatic or C2-C4-alkylene Cio-C2o-alkylamido moieties. Preferably, R⁹ is selected from C8-C20- alkyl or C2-C₄-alkylene Cio-C2o-alkylamido and R¹⁰ and R¹¹ 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.

Examples of 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 C₄- 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.

Further examples for suitable anionic surfactants are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates, and alkylether phosphates.

In one embodiment of the present invention, 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.

In a preferred embodiment, 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.

In inventive solid detergent compositions for hard surface cleaning and in inventive solid laundry detergent compositions, alkali metal percarbonates, especially sodium percarbonates, are preferably used in coated form. 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).

Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

Inventive solid detergent compositions for hard surface cleaning and inventive solid laundry detergent compositions may comprise one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds that inhibit the corrosion of metal. Examples of suitable 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. In one embodiment of the present invention, 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. Examples of 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.

Examples of organic builders are especially polymers and copolymers. In one embodiment of the present invention, 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. Also of suitability are 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. It is also possible to use copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-Cio-mono- or C4-Cio-dicarboxylic acids or anhydrides thereof, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilic or hydrophobic monomer as listed below. 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. By way of example, mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, meth- oxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxy- poly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol

(meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol

(meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. 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-

2- methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid,

3- methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, al- lyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy- 3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1 -sulfonic acid, styrenesulfonic ac- id, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacry- late, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of said acids, such as sodium, potassium or ammonium salts thereof.

Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.

A further example of builders is carboxymethyl inulin.

Moreover, 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. In the context of the present invention, MGDA is not counted as builder.

In one embodiment of the present invention, 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.

In one embodiment of the present invention, 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. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

Particularly advantageous inventive automatic dishwashing formulations, especially for home care, may contain one or more complexing agent (in the context of the present invention also referred to as sequestrant). Examples for 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"). Further examples of 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.

In inventive automatic dishwashing formulations, 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)

[R -CH(COO)-N(CH₂-COO)₂]M 3-rH_r (X) wherein

M¹ is selected from alkali metal cations, same or different, preferably potassium and especially sodium, and

R¹ is selected from Ci-C4-alkyl, especially methyl, wherein r is in the range of from zero to 0.5, and of formula (XI)

[OOC-CH₂CH2-CH(COO)-N(CH₂-COO)2]M 4_-rH_r (XI) Wherein r is in the range of from zero to 1.5.

It is to be understood that r is an average number.

Compounds according to general formula (X) and (XI) may be comprised as racemic mixture or as pure enantiomers, especially as L-enantiomers, or as non-racemic mixtures of enantiomers, for example with an enantiomeric excess in the range of from 20 to 85%, the respective L- enantiomer being the predominant enantiomer. In one embodiment of the present invention, 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.

In one embodiment of the present invention, inventive automatic dishwashing formulations comprise at least one zinc salt. Zinc salts may be selected from water-soluble and water- insoluble zinc salts. In this connection, within the context of the present invention, 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.

In one embodiment of the present invention, zinc salt is selected from zinc benzoate, zinc glu- conate, zinc lactate, zinc formate, ZnC , ZnS0₄, zinc acetate, zinc citrate, Zn(NOs)2,

Zn(CH3S03)2 and zinc gallate, preferably ZnC , ZnS0₄, zinc acetate, zinc citrate, Zn(NOs)2, Zn(CH3S03)2 and zinc gallate.

In another embodiment of the present invention, zinc salt is selected from ZnO, ZnOaq, Zn(OH)2 and ZnC03. Preference is given to ZnOaq.

In one embodiment of the present invention, zinc salt is selected from zinc oxides with an average particle diameter (weight-average) in the range from 10 nm to 100 μηη. 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. To simplify the notation, within the context of the present invention, ligands are generally omitted if they are water ligands. Depending on how the pH of mixture according to the invention is adjusted, zinc salt can change. Thus, it is for example possible to use zinc acetate or ZnC for preparing formulation according to the invention, but this converts at a pH of 8 or 9 in an aqueous environment to ZnO, Zn(OH)2 or ZnOaq, which can be present in non-complexed or in complexed form. 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 μηη, preferably 100 nm to 5 μηη, 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. In one embodiment of the present invention, 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. Here, the fraction of zinc salt is given as zinc or zinc ions. From this, it is possible to calculate the counterion fraction.

In one embodiment of the present invention, inventive automatic dishwashing formulations are free from heavy metals apart from zinc compounds. Within the context of the present, this may be understood as meaning that 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. Within the context of the present invention, "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. Preferably, 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. The fraction of zinc is thus not included. Within the context of the present invention, "heavy metals" are defined to be any metal with a specific density of at least 6 g/cm³ with the exception of zinc. In particular, the heavy metals are metals such as bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.

Preferably, inventive automatic dishwashing formulations comprise no measurable fractions of bismuth compounds, i.e. for example less than 1 ppm.

In one embodiment of the present invention, 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.

Table 1 : Example detergent compositions for automatic dishwashing

Inventive automatic dishwashing formulations are excellent in preventing glass corrosion. The invention is further explained by the following working examples.

General remarks: Melting points were determined by DSC with a heat rate of 1 °C/min in an open aluminum crucible, peak at second cycle, air flow 3 l/h. In the context of the present invention and unless expressly specified otherwise, percentages and ppm refer to % by weight and weight ppm.

The following substances were used:

Surfactant (A.1 ):

Polymer (B.1 ): polyethylenimine homopolymer, density: 1 .03 g/cm³, M_w: 800 g/mol, M_n: 600 g/mol Manufacture of concentrates CONC.1 to CONC.4:

Under a blanket of dry nitrogen, a 2-I beaker was charged with surfactant (A.1 ) according to Table 2. With a pipette (Eppendorf), polymer (B.1 ) was added. The mixture was stirred at 600 rounds per minute ("rpm") under a blanket of dry nitrogen for 2 hours. Concentrates according to the invention were obtained.

Determination of 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%.

Table 2: concentrates according to the invention

The turbidity in Table 2 is the [NTU] - nephelometric turbidity unit,

n.d.: not determined

With inventive concentrates, excellent phosphate-free dishwash compositions can be made. Especially the breakage of tablets was low. In particular, formulations of each CONC.1.

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.

Determination of dynamic viscosity:

The dynamic viscosity η was determined at 23°C with a Brookfield viscosimeter, spindle 1 .

Claims

Claims:

Concentrate 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,

(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, percentages being based on the total solids content of said concentrate.

Concentrate according to claim 1 , wherein non-ionic surfactant (A) is selected from compounds according to general formula (I a)

R -CH(OH)-CH₂-0-(AO)x-R² (I a) or to general formula (I b)

R -CH(OH)-CH₂-0-(AO)x-A -0-(AO)y-CH₂-CH(OH)-R¹ (I b) wherein

R¹ are same or 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,

R² is selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C3o-alkylene, straight-chain or branched, with at least one C-C double bond,

A¹ is selected from C2-Cio-alkylene, straight chain or branched, x, y same or different and selected from 6 to 50,

AO is selected from identical or different alkylene oxides, selected from CH2-CH2-O, (CH₂)₃-0, (CH₂)₄-0, CH₂CH(CH₃)-0, CH(CH₃)-CH₂-0- and CH₂CH(n-C₃H₇)-0.

Concentrate according to claim 1 wherein non-ionic surfactant (A) is selected from compounds according to general formula (I I)

R -CH₂-CH₂-0-(AO)x-C(0)-R² (II) wherein

R¹ are 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,

R² are selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C3o-alkylene, straight-chain or branched, with at least one C-C double bond, x selected from 6 to 50, and

AO is selected from identical or different alkylene oxides, selected from CH2-CH2-O, (CH₂)₃-0, (CH₂)4-0, CH₂CH(CH₃)-0, CH(CH₃)-CH₂-0- and CH₂CH(n-C₃H₇)-0.

4. Concentrate according to any of the preceding claims wherein in compound according to general formula (I a) or (I b) R¹ is selected from n-C6-Ci6-alkyl.

5. Concentrate according to any of the preceding claims wherein in compound according to general formula (I a) R² is selected from branched C6-Ci4-alkyl and all AO are

CH₂-CH₂-0 groups.

6. Concentrate according to any of the preceding claims wherein x is selected from 10 to 25.

7. Concentrate according to any of the preceding claims containing in the range of from 1 ppm to 0.8 % by weight of water.

8. Concentrates according to any of the preceding claims having a turbidity in the range of from 0.3 to 30 nephelometric turbidity units.

9. Concentrate according to any of the preceding claims wherein (B) is selected from poly- ethylenimines.

10. Concentrate according to any of the preceding claims containing in total in the range of from 65 to 95 % by weight surfactant (A) and polyalkylenimine (B). 1 1 . Concentrate according to any of the preceding claims having a melting or softening point from -30 to +45°C.

12. Process for making a concentrate according to any of the preceding claims comprising the step of mixing surfactant(s) (A) and polyalkylenimine (B) in liquid phase under inert gas.

13. Use of concentrates according to any of claims 1 to 1 1 for the manufacture of hard surface cleaners. Use according to claim 13 wherein such hard surface cleaners are automatic dishwashing formulations, liquid or solid or gel-type.

Automatic dishwashing formulation containing

(A) one non-ionic surfactant with at least one secondary hydroxyl group or at least one ester group per molecule,

(B) 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.