Rinse aid compositions containing structural polypeptides

Abstract

The present invention relates to dishwasher rinse aid compositions comprising structural polypeptides, methods of machine washing dishware using said rinse aid compositions, the use of structural polypeptides in machine dishwasher rinse aid compositions, and the use of said compositions in processes for washing soiled dishware.

Description

[Technical Field]

[0001] The present invention relates to dishwasher rinse aid compositions comprising structural polypeptides, methods of machine washing dishware using said rinse aid compositions, the use of structural polypeptides in machine dishwasher rinse aid compositions, and the use of said compositions in processes for washing soiled dishware. [Background technology]

[0002] The use of rinse aids is common in domestic dishwashers and commercial and institutional dishwashers (i.e., in the industrial and institutional (I&I) washing sector). In a typical machine dishwashing process (also called automatic dishwashing, or ADW for short), wash items, such as dishes or utensils soiled with food or other substances, undergo multiple treatments in a series of zones and / or cycles. The actual washing process is completed by a rinse cycle, in which the dishes undergo a final rinse that serves to remove pre-final rinse water and the associated detergent and soil residues. Rinse aids can be released into the liquid used to treat dishes by the dishwasher's dosing device, or can be part of an automatic dishwashing composition with corresponding release characteristics. Rinse aid formulations are often liquid solutions, but additional forms, such as granules, lozenges, or granular solids, are also known.

[0003] A practical rinse aid must meet a complex application profile, including good, clear rinsing properties, low sudsing, and fast drying. To achieve this, rinse aids contain surfactants that reduce surface tension and improve rinse water wetting, so that the rinse water drains from the surface of the dishware in a thin sheet rather than forming droplets, leaving no streaks, films, or spots. Spot formation is prevented by avoiding the formation of droplets of rinse water, which may still contain dissolved solids and soils from the wash cycle, causing residue upon evaporation. Low sudsing prevents the formation of foam traces on rinsed substrates. A further desirable property of modern rinse aids is that they allow the surface of the dishware to dry quickly after the rinse aid is applied.

[0004] An established criterion for selecting a suitable surfactant for a rinse aid is the so-called cloud point. The cloud point is defined as the temperature at which a 1% by weight aqueous solution of the surfactant becomes cloudy when heated. At temperatures above the cloud point, it is believed that the surfactant in the rinse aid is absorbed onto the surface of the dishware, thereby reducing the solid-liquid interfacial energy and contact angle. This results in the formation of a continuous sheet that drains evenly from the surface and minimizes spot formation. Generally, high-foaming surfactants have cloud points above the temperature of the rinse water or do not exhibit a cloud point at all, and therefore do not promote sheet formation, which results in spot formation.

[0005] WO 2005 / 047440 describes a rinse aid composition containing at least one alcohol ethoxylate compound having an alkyl group with up to 12 carbon atoms as a sheeting agent and an effective amount of an antifoaming component. The antifoaming component is selected from nonionic ethylene oxide surfactants that are water-soluble and have a cloud point lower than the intended use temperature of the rinse aid composition. The alcohol ethoxylates used are advantageously biodegradable, environmentally friendly, and generally non-toxic.

[0006] The use of rinse aids based on nonionic surfactants with low cloud points does not always result in very good rinsing results, especially if the rinse liquid still contains a certain amount of soil particles that can redeposit on the dishes and / or if the water hardness is too high. In those cases, the use of additional builders is recommended to prevent the formation of crystals, especially on glass surfaces, and can be advantageous to improve the suspension of soil particles in the liquid. It is known that spotting, filming and / or streaking can be further reduced by adding polymer builders, such as low molecular weight (partially) neutralized polyacrylic acid, to the rinse water.

[0007] International Publication No. 2021 / 046285 states: (1)(i) at least one polymer P1) comprising polymerized units of at least one monomer selected from α,β-ethylenically unsaturated carboxylic acids, their salts, anhydrides, and mixtures thereof; (ii) at least one nonionic surfactant; a solid copolymer surfactant comprising (2) at least one additional surfactant and / or polymer A solid surfactant system for use as a rinse aid is described, comprising:

[0008] The systems described are used for their high efficacy in terms of defoaming, surface sheeting, wetting and drying time.

[0009] There is a continuing need for rinse aid compositions that have high clear rinsing effectiveness at the lowest possible application rate, while at the same time having excellent rinsing properties. In particular, new rinse aids should have at least one, and preferably several, of the following: improved spotting and filling performance, even when using high-hardness water; a high gloss level, especially on glasses and cutlery; and good drying properties. Rinse aid compositions should also meet consumer demands for sustainable and safe products, and should be non-toxic, not harmful to the environment, and safe for humans and animals.

[0010] Surprisingly, it has been found that structural polypeptides such as silk polypeptides are suitable for formulating rinse aid compositions with improved application properties.Silk polypeptides are polymers that exhibit excellent application properties, and can provide rinse aid formulations with various benefits, including improved spot-forming and film-forming performance and good drying properties.Structural polypeptides such as silk polypeptides are biocompatible, non-toxic, and environmentally friendly, and are suitable for use in any type of rinse aid formulation, such as the components of liquid and multi-compartment formulations. Summary of the Invention

[0011] The first object of the present invention is to a) a structural polypeptide, and b) at least one nonionic surfactant A rinse aid composition comprising:

[0012] In a particular embodiment, the rinse aid composition is a liquid, in particular an aqueous formulation comprising water as component c).

[0013] In certain embodiments, the rinse aid composition comprises at least one functional additive (component d) selected from surfactants different from component b), builders, hydrotropes, antifoaming agents, pH adjusters, additional additives, and mixtures thereof.

[0014] In further particular embodiments, the rinse aid composition comprises at least one additional additive selected from bleaches, enzymes, optical brighteners, anti-redeposition agents, antimicrobial agents, antioxidants, rheology modifiers, solubility modifiers, stabilizers, corrosion inhibitors, dyes, fragrances, fillers, tableting aids, disintegrants, humectants, electrolytes, water conditioners, and mixtures thereof.

[0015] A further object of the present invention is a method for the machine washing of dishes, in which the dishes to be washed are contacted with a rinse aid composition as defined above and below.

[0016] A further object of the present invention is the use of structural polypeptides, in particular silk polypeptides, in rinse aid compositions.

[0017] A further object of the present invention is to provide a method for treating soiled dishware in an automatic dishwashing machine, comprising: - provide good sheeting and wetting properties, - reducing spotting and filming on tableware, especially glassware and cutlery; - To give a good luster to tableware, - Prevent recontamination of tableware, - to provide surface protection to tableware, in particular to prevent corrosive changes to the surface of glassware; - to formulate low-foaming products; -Reducing the surface tension of tableware -Improved drying of dishes, The present invention relates to the use of a rinse aid composition as defined above and below for:

[0018] This summary does not necessarily describe all features of the present invention, and other embodiments will become apparent upon consideration of the following detailed description. DETAILED DESCRIPTION OF THE INVENTION

[0019] Before describing the present invention in detail below, it is to be understood that this invention is not limited to the particular methodology, protocols, and reagents described herein, as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention, which is limited only by the appended claims. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

[0020] Preferably, the terms used herein are defined as set forth in "A multilingual glossary of biotechnological terms: (IUPAC Recommendations)", Leuenberger, H.G.W., Nagel, B. and Kolbl, H. eds. (1995), Helvetica Chimica Acta, CH-4010 Basel, Switzerland.

[0021] Several documents are cited throughout the text of this specification. Each of the documents cited herein (including all patents, patent applications, scientific publications, manufacturer's specifications, instructions, GenBank accession number sequence deposits, etc.), whether supra or infra, is incorporated herein by reference in its entirety. Nothing in this specification should be construed as granting the present invention no right to antedate such disclosure by virtue of prior art.

[0022] The components of the present invention are described below. These components are listed with specific embodiments. However, it should be understood that they may be combined in any manner and in any number to create further embodiments. The various described examples and preferred embodiments should not be construed as limiting the invention to only the explicitly described embodiments. The description should be understood to support and encompass embodiments combining the explicitly described embodiments with any number of the disclosed and / or preferred components. Furthermore, any permutation and combination of all elements described in this application is permitted where the context requires. Unless otherwise indicated, all such disclosures should be considered to be disclosed by the description of this application.

[0023] As used herein, the term "rinse aid" (specifically "dishwasher rinse aid") refers to an agent / composition used to prevent the formation of droplets so that water drains from a surface in a thin sheet rather than forming droplets. In particular, rinse aids prevent "spotting" on dishware such as glassware (caused by water droplets drying and leaving behind a trail of dissolved limescale minerals) and can also improve drying performance because less water remains to be dried. A thinner water sheet also has a much larger surface area than a droplet of the same volume, which increases the likelihood that the water molecules will evaporate.

[0024] More specifically, rinse aid reduces the surface tension of water, thus ensuring that the water film on dishes and cutlery flows better when the dishes are washed in a dishwasher. It prevents limescale and limescale deposits from forming and makes the dishes and cutlery shine. The rinse aid reservoir is usually located inside the dishwasher door.

[0025] Structural polypeptides such as silk polypeptides are particularly advantageous for use in rinse aid compositions that must meet a complex property profile. The rinse aids of the present invention have at least one, and preferably two, three or more of the following advantages: The compositions of the present invention are generally suitable for use in washing and rinsing dishes and cutlery, requiring a composition that provides good sheeting, wetting and drying properties. The compositions of the present invention effectively reduce spotting and film formation. This reduces surface tension and improves the wetting action of the rinse water, so that the rinse water is discharged from the surface of the dish in a thin sheet rather than forming droplets. After the washing process, the dishware, especially glassware and cutlery, has a good shine and shows significantly fewer water marks, stains and / or spots compared to conventional products of the prior art. Structural polypeptides, especially silk polypeptides, are particularly suitable for formulating low-foaming products. They are characterized by good compatibility with nonionic low-foaming surfactants, providing cleaning and rinsing benefits without introducing excessive foaming into the formulation. The use of antifoaming agents can be omitted or their application amounts can be reduced. The low foaming properties prevent foam traces on rinsed substrates. The rinse aid of the present invention allows for quick drying of the surface of the dish. The compositions of the present invention are suitable for imparting reduced surface tension to dishware: the contact angle of deionized water on dishes, especially glasses, treated in a dishwasher with the rinse aid compositions of the present invention is significantly reduced compared to conventional products from the prior art. The composition of the invention is suitable for providing surface protection to tableware, in particular it does not corrosively alter the surface of glassware, even with repeated use, and in particular does not cause clouding, staining or scratches, or iridescence of the glass surface. The compositions are effective even at very low application doses. In many cases, the use of structural polypeptides, such as silk polypeptides, allows for a reduction in the amount of surfactants in the formulation. The structural polypeptides, particularly silk proteins, contained in the rinse aid compositions according to the invention are biocompatible, non-toxic, not harmful to the environment, and safe for humans and animals.

[0026] Without being bound by any theory, it is believed that the structural polypeptides used, particularly silk polypeptides, are suitable for surface modification of dishware to impart improved properties to the dishware. The structural polypeptides form a coating on the surface that allows for efficient drainage of wash and / or rinse water. This helps prevent the formation of water droplets that, when dried, can deposit residue on the dish surface and form visible spots or streaks. The structural polypeptides impart good "sheeting properties" to dishware, cutlery, and similar hard surfaces. That is, they result in the formation of a continuous sheet that drains evenly from the surface and minimizes spot formation. Structural polypeptides can be advantageously used in combination with surfactants, particularly nonionic surfactants with low cloud points. It can be assumed that rinse aids are absorbed onto the surface of ware at temperatures above the surfactant's cloud point, thereby reducing the solid-liquid interfacial energy and contact angle. Thus, the use of structural polypeptides in rinse aid compositions allows for good drainage during the rinsing process, leaving protection against surface damage and recontamination. Generally, a low contact angle is associated with improved sheeting. That is, compositions with lower contact angles form droplets with a larger surface area on the substrate than compositions with higher contact angles. The increased surface area results in faster drying times and fewer spots forming on the substrate.

[0027] In the sense of the present application, the term dishware encompasses all kinds of soiled objects that can be subjected to an automatic cleaning process in a dishwasher. The term dishware therefore encompasses dishes (tableware), cookware, cutlery, kitchen utensils and other items for practical and decorative purposes.

[0028] The rinse aids of the present invention can be in any form suitable for consumer and I&I products, including for use in automatic dosing machines. In a preferred embodiment, the rinse aid composition is in liquid form.

[0029] The term (meth)acrylate as used in this application includes both methacrylate and acrylate derivatives.

[0030] Component a) (Structural Polypeptide) In the context of the present invention, the terms "polypeptide" and "protein" are used interchangeably and refer to a long chain of amino acids with peptide bonds, for example at least 30 amino acids in length.

[0031] The term "structural polypeptide" as used herein refers to any polypeptide comprising repeating units (repeating building blocks) of amino acids. The structural polypeptide preferably has the ability to undergo polypeptide assembly. In particular, the structural polypeptide can form protein complexes (aggregates) in formulations, e.g., hydrogels in aqueous formulations. The structural polypeptide may be selected from the group consisting of silk polypeptides (including fibroin), keratin, fibroin, collagen, and elastin, or variants or combinations thereof. The structural polypeptide is, in particular, a recombinant or synthetic structural polypeptide. The structural polypeptide is preferably a (recombinant or synthetic) silk polypeptide, such as a (recombinant or synthetic) spider silk polypeptide. Exemplary processes for producing silk polypeptides are described in WO 2006 / 008163 and WO 2011 / 120690.

[0032] The term "silk polypeptide" as used herein refers to a polypeptide that exhibits a highly unusual amino acid composition compared to other polypeptides. In particular, silk polypeptides have a large amount of hydrophobic amino acids such as glycine or alanine. In addition, silk polypeptides contain highly repetitive amino acid sequences or repeating units (repeat units, modules), especially in their large core domains. Based on DNA analysis, it has been shown that all silk polypeptides are chains of repeating units that further contain a limited set of distinct shorter peptide motifs. The terms "peptide motif" and "consensus sequence" can be used interchangeably herein. In general, silk consensus sequences can be classified into four major categories: GPGXX, GGX, Ax or (GA)n, and spacer. These categories of peptide motifs in silk polypeptides include the following structures: Structural roles have been assigned to these motifs. For example, the GPGXX motif has been suggested to be involved in a beta-turn spiral, likely providing elasticity. The GGX motif is known to be involved in a glycine-rich 31-helix. Both the GPGXX and GGX motifs are thought to be involved in the formation of an amorphous matrix connecting crystalline regions, thereby providing elasticity to the fibers. The alanine-rich motif typically contains 6 to 9 residues and has been found to form crystalline beta-sheets. The spacer, typically containing a charged group, separates the repeating peptide motifs into clusters. Silk polypeptides are capable of polypeptide assembly.

[0033] Fibroin is, in the sense of the present invention, a structural polypeptide and a silk polypeptide.

[0034] The silk polypeptide is in particular a recombinant or synthetic silk polypeptide.

[0035] Preferably, the (recombinant or synthetic) silk polypeptide is a (recombinant or synthetic) spider silk polypeptide.

[0036] The term "polypeptide assembly" as used herein refers to the process by which a pre-existing disordered system of polypeptides forms an organized structure or pattern without external guidance or triggering as a result of specific local interactions between the polypeptides themselves (e.g., van der Waals forces, hydrophobic interactions, hydrogen bonds, and / or salt bridges, etc.), although external factors may affect the rate and nature of polypeptide assembly. This specifically means that when two or more disordered and / or unfolded polypeptides are brought into contact, they interact with each other, resulting in the formation of a three-dimensional structure. The change from a disordered system to an organized structure or pattern during self-polypeptide assembly is characterized by a transition from a fluid state to a gel-like and / or solid state and a corresponding increase in viscosity. The transition from a fluid state to a gel-like state can be monitored, for example, by optical or rheological measurements. These techniques are known to those skilled in the art. The transition from a fluid state to a solid state can be monitored, for example, using optical methods.

[0037] Preferably, the structural polypeptides comprising the polypeptide assembly are silk polypeptides (recombinant or synthetic), such as spider silk polypeptides (recombinant or synthetic).

[0038] The term "polypeptide aggregate" (or polypeptide complex) as used herein refers to a polypeptide structure formed as a result of polypeptide self-assembly. In the process of polypeptide self-assembly, multiple copies / units of a polypeptide self-assemble into a body or mass without external guidance or triggering, although external factors may affect the rate and nature of the self-polypeptide assembly. In a polypeptide aggregate, different polypeptides are connected or bonded to each other through covalent bonds (e.g., disulfide bridges) and / or non-covalent interactions (e.g., van der Waals forces, hydrophobic interactions, hydrogen bonds, and / or salt bridges). It should be clear that a polypeptide aggregate comprises at least two polypeptides. In the context of the present invention, the self-assembly of (recombinant or synthetic) silk polypeptides is described. During the process of silk polypeptide self-assembly, a silk polypeptide aggregate (silk polypeptide complex) is formed.

[0039] As used herein, the term "hydrogel" refers to a structure formed when the concentration of structural polypeptides is high enough to create a continuous network in which a liquid component is immobilized. The network is preferably formed by polypeptide assembly of the structural polypeptides, which provide the basis for the hydrogel. In particular, a hydrogel is a hydrophilic polymer network of structural polypeptides. The network is formed by the chemical interactions between the structural polypeptides. The network is stabilized by chemical and / or physical interactions. The network is dispersed throughout the immobilized aqueous phase. The hydrophilicity and stability of the hydrogel allows it to penetrate and absorb water (swell) without dissolving, thus maintaining its three-dimensional (3D) structure and function.

[0040] A preferred embodiment of the hydrogel is a flowable hydrogel. As used herein, the term "flowable hydrogel" refers to a hydrogel that can flow, especially when exposed to gravity. A flowable hydrogel is in a liquid state (meaning that it is not yet self-supporting, i.e., it retains an assigned shape without a shape-stabilizing container). The compliance of a hydrogel can be easily determined by those skilled in the art, for example, by rheological or viscosity measurements. Compliance measurements are preferably carried out under standard conditions (20°C). Methods for determining the viscosity of a gel are described in detail below.

[0041] Alternatively, the hydrogel is a non-flowable hydrogel, which can be converted into a flowable hydrogel by shear thinning, as well as structural polypeptides within the meaning of the present invention that are in solid form.

[0042] Preferably, the structural polypeptide used in accordance with the present invention is in the form of a hydrogel. More preferably, the structural polypeptide in the form of a hydrogel is a silk polypeptide. In particular, the structural polypeptide in the form of a hydrogel is a recombinant or synthetic silk polypeptide.

[0043] Preferably, the structural polypeptide used in accordance with the present invention is in the form of a fluid hydrogel. More preferably, the structural polypeptide in the form of a fluid hydrogel is a silk polypeptide. In particular, the structural polypeptide in the form of a fluid hydrogel is a recombinant or synthetic silk polypeptide.

[0044] The hydrogel is hereinafter also referred to as silk protein gel or silk gel. The production of the hydrogel is described, for example, in WO2020035361, WO2022258500 or WO2022258499.

[0045] In a preferred embodiment, a rinse aid composition according to the present invention comprises structural polypeptides capable of forming polypeptide aggregates, in particular, said polypeptides having the potential to assemble into fibrous structures (i.e., fibrous aggregates (complexes) of structural polypeptides).

[0046] Preferably, the structural polypeptide is selected from silk polypeptides, keratin, collagen, elastin, and combinations thereof. In one embodiment, the silk polypeptide is fibroin. In particular, the structural polypeptide is a recombinant polypeptide, such as a recombinant silk polypeptide, keratin, collagen, or elastin.

[0047] More preferably, the structural polypeptide is a silk polypeptide, especially a recombinant silk polypeptide.

[0048] In a preferred embodiment, the (recombinant) silk polypeptide is a spider silk polypeptide. Suitable spider silk polypeptides are major ampullate silk polypeptides, such as dragline silk polypeptides of orb-web spiders, minor ampullate silk polypeptides, or whip silk polypeptides. Specifically, the silk polypeptide is a spider silk polypeptide, more specifically a recombinant spider silk polypeptide.

[0049] In a preferred embodiment, the silk polypeptide comprises or consists of 25 to 4000 amino acids. Even more preferably, the silk polypeptide comprises or consists of 30 to 1500 amino acids, particularly 35 to 1200 amino acids. In a particular embodiment, the silk polypeptide comprises or consists of 60 to 600 amino acids.

[0050] In a preferred embodiment, the silk polypeptide consists of a single unit of amino acids. This embodiment is defined in that the protein chain does not have several (at least two) units with the same or similar sequence motifs. In this embodiment, the silk polypeptide preferably consists of 25 to 250 amino acids, particularly 30 to 150 amino acids.

[0051] In an alternative preferred embodiment, the silk polypeptide is a polypeptide having an amino acid sequence comprising or consisting of at least 50% copies of a repeating unit. The amino acid sequence may consist of up to 100% copies of a repeating unit. More preferably, the silk polypeptide is a polypeptide having an amino acid sequence comprising or consisting of at least 50%, particularly at least 60%, particularly at least 65%, particularly at least 70%, particularly at least 75%, particularly particularly at least 80%, particularly at least 85%, particularly at least 90%, particularly at least 95%, or particularly at least 99% copies of a repeating unit, or even 100% copies of a repeating unit. The repeating units may be identical or different.

[0052] When the amino acid sequence of the silk polypeptide is a polypeptide comprising or consisting of multiple copies of a repeating unit, each repeating unit preferably comprises or consists of 25 to 250 amino acids, in particular 30 to 150 amino acids.

[0053] If the amino acid sequence of the silk polypeptide is a polypeptide comprising or consisting of multiple copies of a repeat unit, the total number of amino acids in all repeat units is preferably in the range of 25 to 3000 amino acids, more preferably 30 to 1500 amino acids, particularly 35 to 1200 amino acids, and especially 60 to 600 amino acids.

[0054] In a preferred embodiment, the silk polypeptide comprises or consists of at least two identical repeating units, for example, the silk polypeptide comprises 2 to 96 repeating units, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 11 8, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95 or 96 repeating units.

[0055] In particular, the repeat units may independently be: - module C having the amino acid sequence set forth in SEQ ID NO: 1 (GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP) or a variant thereof, - module C having the amino acid sequence set forth in SEQ ID NO: 2 (GSSAAAAAAAASGPGGYGPENQGPCGPGGYGPGGP) Cys or a variant thereof, - module C having the amino acid sequence set forth in SEQ ID NO: 3 (GSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP) Lys or a variant thereof, is selected from the group consisting of:

[0056] Module C Cys (SEQ ID NO: 2) is a variant of module C (SEQ ID NO: 1). In this module, the amino acid serine (Ser) at position 25 is replaced by the amino acid cysteine ​​(Cys). Module C Lys (SEQ ID NO: 3) is also a variant of module C (SEQ ID NO: 1), in which the amino acid glutamic acid (Glu) at position 20 is replaced by the amino acid lysine (Lys).

[0057] A module C variant differs from the reference module C from which it is derived by up to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 amino acid changes in amino acid sequence (i.e., substitutions, additions, insertions, deletions, N-terminal truncations, and / or C-terminal truncations). Such a module variant may alternatively or additionally be characterized by a degree of sequence identity to the reference module from which it is derived. Thus, module C variants have at least 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99% or even 99.9% sequence identity to the respective reference module C. Preferably, the sequence identity is over a contiguous stretch of at least 5, 10, 15, 18, 20, 24, 27, 28, 30, 34 or more amino acids, and preferably over the entire length of the respective reference module C.

[0058] The sequence identity may be at least 80% over the entire length of each reference module C, may be at least 85% over the entire length, may be at least 90% over the entire length, may be at least 95% over the entire length, may be at least 98% over the entire length, or may be at least 99% over the entire length. Alternatively, the sequence identity may be at least 80% over a contiguous stretch of at least 5, 10, 15, 18, 20, 24, 28, or 30 amino acids of the respective reference module C, at least 85% over a contiguous stretch of at least 5, 10, 15, 18, 20, 24, 28, or 30 amino acids, at least 90% over a contiguous stretch of at least 5, 10, 15, 18, 20, 24, 28, or 30 amino acids, at least 95% over a contiguous stretch of at least 5, 10, 15, 18, 20, 24, 28, or 30 amino acids, at least 98% over a contiguous stretch of at least 5, 10, 15, 18, 20, 24, 28, or 30 amino acids, or at least 99% over a contiguous stretch of at least 5, 10, 15, 18, 20, 24, 28, or 30 amino acids.

[0059] A fragment (or deletion) variant of module C preferably has a deletion of up to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 amino acids at its N-terminus and / or its C-terminus. The deletion may also be internal.

[0060] Furthermore, a module C variant or fragment is considered a module C variant or fragment within the context of the present invention only if the modifications to the amino acid sequence of the variant or fragment do not adversely affect the ability of the silk polypeptide to process dishes in a dishwasher. Those skilled in the art can easily assess whether a silk polypeptide comprising a module C variant or fragment can still process dishes. In this regard, see the Examples included in the experimental section of this patent application.

[0061] C Cys or CLys Variants are also encompassed by the present invention. Cys or C Lys With respect to the variants, the same explanations / definitions as given with respect to the module C variants (see above) apply.

[0062] Silk polypeptides are (C) m , (C) m C Cys 、 (C) m C Lys , C Cys ( C) m , C Lys (C) m , (C Cys ) m and (C Lys ) m (wherein m is an integer from 1 to 96).

[0063] Silk polypeptides are C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , C 25 , C 26 , C 27 , C 28 , C 29 , C 30 , C 31 , C 32 , C 33 , C 34 , C 35 , C 36 , C 37 , C 38 , C 32 , C 39 , C 40 , C41 、C 42 、C 43 、C 44 、C 45 、C 46 、C 47 、C 48 、 (C)1C Cys 、(C)2C Cys 、(C)3C Cys 、(C)4C Cys 、(C)5C Cys 、(C)6C Cys 、(C)7C Cys 、(C)8C Cys 、(C)9C Cys 、(C) 10 C Cys 、(C) 11 C Cys 、(C) 12 C Cys 、(C) 13 C Cys 、(C) 14 C Cys 、(C) 15 C Cys 、(C) 16 C Cys 、(C) 17 C Cys 、(C) 18 C Cys 、(C) 19 C Cys 、(C) 20 C Cys 、(C) 21 C Cys 、(C) 22 C Cys 、(C) 23 C Cys 、(C) 24 C Cys 、(C) 25 C Cys 、(C) 26 C Cys 、(C) 27 C Cys 、(C) 28 C Cys 、(C) 29 C Cys 、(C) 30 C Cys 、(C) 31 C Cys 、(C) 32 CCys 、(C) 33 C Cys 、(C) 34 C Cys 、(C) 35 C Cys 、(C) 36 C Cys 、(C) 37 C Cys 、(C) 38 C Cys 、(C) 32 C Cys 、(C) 39 C Cys 、(C) 40 C Cys 、(C) 41 C Cys 、(C) 42 C Cys 、(C) 43 C Cys 、(C) 44 C Cys 、(C) 45 C Cys 、(C) 46 C Cys 、(C) 47 C Cys 、(C) 48 C Cys 、 (C)1C Lys 、(C)2C Lys 、(C)3C Lys 、(C)4C Lys 、(C)5C Lys 、(C)6C Lys 、(C)7C Lys 、(C)8C Lys 、(C)9C Lys 、(C) 10 C Lys 、(C) 11 C Lys 、(C) 12 C Lys 、(C) 13 C Lys 、(C) 14 C Lys 、(C) 15 C Lys 、(C) 16 C Lys 、(C) 17 C Lys 、(C) 18 C Lys、(C) 19 C Lys 、(C) 20 C Lys 、(C) 21 C Lys 、(C) 22 C Lys 、(C) 23 C Lys 、(C) 24 C Lys 、(C) 25 C Lys 、(C) 26 C Lys 、(C) 27 C Lys 、(C) 28 C Lys 、(C) 29 C Lys 、(C) 30 C Lys 、(C) 31 C Lys 、(C) 32 C Lys 、(C) 33 C Lys 、(C) 34 C Lys 、(C) 35 C Lys 、(C) 36 C Lys 、(C) 37 C Lys 、(C) 38 C Lys 、(C) 32 C Lys 、(C) 39 C Lys 、(C) 40 C Lys 、(C) 41 C Lys 、(C) 42 C Lys 、(C) 43 C Lys 、(C) 44 C Lys 、(C) 45 C Lys 、(C) 46 C Lys 、(C) 47 C Lys 、(C) 48 C Lys 、 C Cys (C)1、CCys (C)2、C Cys (C)3、C Cys (C)4、C Cys (C)5、C Cys (C)6、C Cys (C)7、C Cys (C)8、C Cys (C)9、C Cys (C) 10 、C Cys (C) 11 、C Cys (C) 12 、C Cys (C) 13 、C Cys (C) 14 、C Cys (C) 15 、C Cys (C) 16 、C Cys (C) 17 、C Cys (C) 18 、C Cys (C) 19 、C Cys (C) 20 、C Cys (C) 21 、C Cys (C) 22 、C Cys (C) 23 、C Cys (C) 24 、C Cys (C) 25 、C Cys (C) 26 、C Cys (C) 27 、C Cys (C) 28 、C Cys (C) 29 、C Cys (C) 30 、C Cys (C) 31 、C Cys (C) 32 、C Cys (C) 33 、C Cys (C) 34 、C Cys (C) 35 、C Cys (C) 36 、C Cys(C) 37 、C Cys (C) 38 、C Cys (C) 39 、C Cys (C) 40 、C Cys (C) 41 、C Cys (C) 42 、C Cys (C) 43 、C Cys (C) 44 、C Cys (C) 45 、C Cys (C) 46 、C Cys (C) 47 、C Cys (C) 48 、 C Lys (C)1、C Lys (C)2、C Lys (C)3、C Lys (C)4、C Lys (C)5、C Lys (C)6、C Lys (C)7、C Lys (C)8、C Lys (C)9、C Lys (C) 10 、C Lys (C) 11 、C Lys (C) 12 、C Lys (C)1 3、C Lys (C) 14 、C Lys (C) 15 、C Lys (C) 16 、C Lys (C) 17 、C Lys (C) 18 、C Lys (C) 19 、C Lys (C) 20 、C Lys (C) 21 、C Lys (C) 22 、C Lys (C) 23 、C Lys (C)24 , C Lys (C) 25 , C Lys (C) 26 , C Lys (C) 27 , C Lys (C) 28 , C Lys (C) 29 , C Lys (C) 30 , C Lys (C) 31 , C Lys (C) 32 , C Lys (C) 33 , C Lys (C) 34 , C Lys (C) 35 , C Lys (C) 36 , C Lys (C) 37 , C Lys (C) 38 , C Lys (C) 39 , C Lys (C) 40 , C Lys (C) 41 , C Lys (C) 42 , C Lys (C) 43 , C Lys (C) 44 , C Lys (C) 45 , C Lys (C) 46 , C Lys (C) 47 and C Lys (C) 48 It is most preferably selected from the group consisting of:

[0064] In one embodiment, the silk polypeptide comprises an amino-terminal TAG, e.g., consisting of the amino acid sequence MASMTGGQQMG (SEQ ID NO: 4). In another embodiment, the silk polypeptide comprises an amino-terminal TAG and a linker, e.g., consisting of the amino acid sequence RGSM (SEQ ID NO: 5).

[0065] In one example, the silk polypeptide is 16 times larger than module C (=C 16 ) and has an amino acid sequence according to SEQ ID NO: 6 (containing the TAG shown in SEQ ID NO: 4 and the linker shown in SEQ ID NO: 5 at the N-terminus).

[0066] In another example, silk polypeptides have 16 C Lys Module (C Lys 16 ) (SEQ ID NO: 7).

[0067] In another example, the silk polypeptide comprises 17 modules, the first module (N-terminus) or the last module (C-terminus) being C Cys The other 16 modules are C modules (SEQ ID NO: 1). 16 C Cys (SEQ ID NO: 8).

[0068] In another example, the silk polypeptide comprises 17 modules, the first module (N-terminus) or the last module (C-terminus) being C Lys The first module is SEQ ID NO:3, and the other 16 modules are C modules (SEQ ID NO:1).

[0069] An exemplary larger silk polypeptide based on the C module is silk polypeptide C having the amino acid sequence set forth in SEQ ID NO:9. 32 (32-fold module C) and silk polypeptide C having the amino acid sequence set forth in SEQ ID NO: 10 48 (48x Module C).

[0070] In particular, the silk polypeptide consists only of repeat units. In other words, the silk polypeptide does not particularly comprise / are free of non-repeated units. The only component that may additionally be present as part of the silk polypeptide is a tag or moiety that allows, for example, easy transcription of the silk polypeptide in an expression system and / or easy isolation of the silk polypeptide from an expression system. The tag may be a his tag or a flag tag.

[0071] The rinse aid composition according to the invention preferably contains from 0.0005 to 2.5% by weight, more preferably from 0.001 to 2.0% by weight, especially from 0.05 to 1.5% by weight, based on the total weight of the composition, for example 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4 , 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5% by weight of at least one structural polypeptide (component a)).

[0072] For the formulation of rinse aid compositions, structural polypeptide a) can be used in solid form, for example, in the form of a powder. Structural polypeptide a) can also be used in the form of a solution. Preferred solvents are water, at least partially water-miscible organic solvents, and mixtures thereof. Structural polypeptide a) can also be used in the form of a gel. Gel forms preferably contain the structural polypeptide in an amount of 0.5 to 30% by weight, more preferably 1 to 20% by weight, e.g., 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30% by weight, based on the total weight of the gel.

[0073] Component b) (nonionic surfactant) Suitable as nonionic surfactants b) are generally nonionic surfactants which have at least one nonpolar group and at least one polar group and which contain a polyether group. In principle, the structural polypeptides a), and in particular the silk polypeptides, are compatible with a wide variety of non-ionic surfactants useful for cleaning purposes.

[0074] Suitable nonionic surfactants can be obtained by modifying hydrophobic compounds with hydrophilic alkylene oxide moieties. Generally, any hydrophobic compound having a hydroxyl group, carboxyl group, amino group, or amide group with a reactive hydrogen atom can be condensed with alkylene oxide or its polyhydration products to form a nonionic surfactant. The alkylene oxide is preferably selected from ethylene oxide (EO), 1,2-propylene oxide (PO), 1,2-butylene oxide (BO), 1,2-pentylene oxide, and mixtures thereof. Here, the ether component can be derived from random copolymers and block copolymers. In a preferred embodiment, the alkylene oxide is preferably selected from ethylene oxide and mixtures of ethylene oxide with propylene oxide and / or butylene oxide. The length of the hydrophilic polyoxyalkylene chain condensed with the hydrophobic compound can be easily adjusted to produce a water-soluble or water-dispersible compound with the desired balance between hydrophilicity and hydrophobicity.

[0075] In one embodiment, the nonionic surfactant b) is selected from compounds having a hydrophilic-lipophilic balance (HLB) value ranging from 2 to 17.

[0076] Examples of classes of compounds useful as nonionic surfactants b) are: (i) Ethoxylated Alcohols In one embodiment, the nonionic surfactant b) is selected from the condensation products of one mole of saturated or unsaturated, linear or branched alcohol having 1 to 30 carbon atoms, preferably 4 to 24 carbon atoms, and especially 6 to 18 carbon atoms, with 2 to 100 moles, preferably 3 to 50 moles, of ethylene oxide. The alcohol moiety can be derived from a specific alcohol having a specific number of carbon atoms within the above-mentioned range of carbon atoms, or from a mixture of alcohols within the above-mentioned range.

[0077] Particularly preferred are the condensation products of alcohols having alkyl groups containing from 8 to 20 carbon atoms with from about 2 to about 25 moles of ethylene oxide per mole of alcohol.

[0078] In one embodiment, the nonionic surfactant b) has the formula RO-(EO) n1 (Wherein, R is , linear or branched C4-C 24 - alkyl group, preferably C6-C 18 -Alkyl groups, especially C6-C 12 represents an alkyl group.

[0079] Examples of commercially available compounds of this type include certain Genapol® surfactants sold by Clariant, such as Genapol® X089, an ethoxylated C 13 Further examples include C-rich iso-C11-C14 alcohols available commercially under the Lutensol® AT brand from BASF SE. 16 C 18 A further example is C ethoxylate, available from BASF under the Lutensol® AO brand. 13 C 15 An additional example is the C oxo alcohol ethoxylate available from BASF under the Lutensol® M brand. 10 C 18Further examples include C ethoxylates available from BASF under the Lutensol® TO brand. 13 Further examples are Guerbet alcohol alkoxylates available from BASF under the Lutensol® XP and XL brands.

[0080] (ii) Block copolymers of fatty alcohols with EO and PO and / or BO In another embodiment, the nonionic surfactant b) is selected from the condensation products of one mole of saturated or unsaturated, linear or branched alcohols having from 6 to 30 carbon atoms, preferably from 8 to 24 carbon atoms, with at least one further alkylene oxide selected from ethylene oxide and propylene oxide, butylene oxide and mixtures thereof, preferably ethoxylated and propoxylated and / or butoxylated C6-C 18 It is a fatty alcohol. The degree of ethoxylation is preferably from 2 to 50, more preferably from 3 to 30. The degree of propoxylation is preferably from 1 to 10, more preferably from 1 to 5, in particular 1, 2 or 3. The degree of butoxylation, if present, is preferably 1 or 2, in particular 1.

[0081] In another embodiment, the nonionic surfactant b) has the formula RO-(EO) n1 (PO) m1 (Wherein R is a linear or branched C4-C 24 - alkyl group, preferably C6-C 18 -Alkyl groups, especially C6-C 12 -represents an alkyl group.

[0082] In another embodiment, the nonionic surfactant b) has the formula RO-(EO) n1 (BO) m1 (Wherein R is a linear or branched C4-C 24 - alkyl group, preferably C6-C 18 -Alkyl groups, especially C6-C 12- represents an alkyl group. Preferably, n1 is 2 to 6, more preferably 3, 4 or 5, and m1 is 1 or 2, preferably 1.

[0083] Examples of commercially available compounds of this type include certain Genapol® surfactants sold by Clariant, such as Genapol® EP2454, a lauryl alcohol EO / PO adduct, or Genapol® EP2464, C 12 / C 15 Included are oxo alcohol EO / PO adducts. Further examples are the EP / PO, EO / PO / EO and PO / EO / PO block copolymers available commercially from BASF under the Pluronic® PE and RPE brands.

[0084] (iii) EO / PO block copolymers from polyvalent initiators In another embodiment, the nonionic surfactant b) is preferably an EO / PO block copolymer based on at least one polyhydric initiator selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, ethylenediamine and mixtures thereof. The polymers are selected from polymers. One embodiment is a difunctional compound derived from an initiator having two reactive hydrogens. In a particular embodiment, the EO / PO block copolymer is formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to two hydroxyl groups of propylene glycol. The hydrophobic portion has a number average molecular weight of about 1000 to about 4000. Ethylene oxide is then added to sandwich the core portion between the hydrophilic groups. Preferably, the number average molecular weight of the (hydrophobic) core portion ranges from 10 to 90% by weight of the final molecule. Preferably, the number average molecular weight of the (hydrophilic) end groups ranges from 10 to 90% by weight of the final molecule. Commercially available examples of this type of compound include certain Pluronic® surfactants sold by BASF and Genapol® surfactants sold by Clariant. Another class of suitable nonionic surfactants b) are tetrafunctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The number average molecular weight of the propylene oxide units ranges from about 500 to about 7000, and the number average molecular weight of the hydrophilic ethylene oxide units ranges from about 10% to about 80% by weight of the molecule. Examples of commercially available compounds of this class include the Tetronic® compounds sold by BASF.

[0085] (iv) Ethoxylated Carboxylic Acids (Polyethylene Glycol Esters) In another embodiment, the nonionic surfactant b) is selected from the condensation products of one mole of a saturated or unsaturated, linear or branched carboxylic acid having 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, with 2 to 100 moles, preferably 3 to 50 moles, of ethylene oxide. The acid moiety can be composed of a specific acid having a specific number of carbon atoms within the range of carbon atoms mentioned above, or a mixture of acids within the range mentioned above. Particularly preferred are the condensation products of acids having an alkyl group containing 8 to 20 carbon atoms with about 2 to about 25 moles of ethylene oxide per mole of alcohol.

[0086] (v) polyhydroxy fatty acid amides In another embodiment, the nonionic surfactant b) is selected from polyhydroxy fatty acid amides. 2 CONR 1 Z (in the formula, R 1 is selected from H, a C1-C4 alkyl group, a 2-hydroxyethyl group, and a 2-hydroxypropyl group; R 2 is a straight or branched chain, saturated or unsaturated C4-C 30 wherein Z represents an alcohol-containing moiety having two or more (e.g., 3, 4, 5, 6 or more) hydroxy groups, or an alkoxylated derivative thereof (preferably an ethoxylated and / or propoxylated derivative).

[0087] Preferably, R 1 is selected from C1-C4 alkyl groups, in particular methyl groups.

[0088] Preferably, R 2 is a straight chain C5-C 19 Alkyl groups and C5-C 19 Alkenyl groups, more preferably straight chain C9-C 17 Alkyl groups and C9-C 17 alkenyl groups, as well as mixtures thereof.

[0089] Preferably, Z is derived from units of glycerol and at least one reducing sugar such as glucose, fructose, maltose, lactose, galactose, mannose, etc. In a particular embodiment, Z is a glycityl moiety.

[0090] (vi) alkyl polysaccharides In another embodiment, the nonionic surfactant b) is an alkyl polysaccharide having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and The sugar units are selected from polysaccharides, e.g., polyglycosides, having hydrophilic groups containing 1.3 to about 10, preferably about 1.3 to about 3, and most preferably about 1.3 to about 2.7 sugar units. Any reducing sugar containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose, and galactosyl moieties can be substituted for glucosyl moieties. Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc. position, thus providing glucose or galactose, as opposed to glucoside or galactoside. The intersugar bond can be, for example, between one position of the additional sugar unit and the 2-, 3-, 4-, and / or 6-position on the preceding sugar unit.

[0091] (vii) fatty acid amide alkoxylates In another embodiment, the nonionic surfactant b) is selected from fatty acid amide alkoxylates. Suitable fatty acid amide surfactants are those of the formula R 6 CON(R 7 )2(wherein, R 6 represents an alkyl group containing 7 to 21, preferably 9 to 17, carbon atoms; R 7 are respectively a hydrogen atom, a C1-C4 alkyl group, a C1-C4 hydroxyalkyl group, and -(C2H4O) x H, where x is in the range of 1 to 3. The ether component can be derived from ethylene oxide units, propylene oxide units, 1,2-butylene oxide units, 1,4-butylene oxide units, and random and block copolymers thereof.

[0092] (viii) Rhamnolipid In another embodiment, the nonionic surfactant b) is selected from rhamnolipids. Rhamnolipids are a type of glycolipid that have a rhamnose moiety as a glycosyl head group and a 3-(hydroxyalkanoyloxy)alkanoic acid (HAA) fatty acid tail, such as 3-hydroxydecanoic acid. They are produced by bacteria such as Pseudomonas aeruginosa and are also called bacterial surfactants. Specifically, there are two major classes of rhamnolipids, mono-rhamnolipids and di-rhamnolipids, each composed of one or two rhamnose groups.

[0093] (ix) Sophorolipid In another embodiment, the non-ionic surfactants b) are selected from sophorolipids. Sophorolipids are glycolipids consisting of a hydrophobic fatty acid tail of 16 or 18 carbon atoms and sophorose (a glucose-derived disaccharide with a β-1,2 bond that can be acetylated at the 6' and / or 6" positions) as a hydrophilic carbohydrate head. One terminal or subterminal hydroxylated fatty acid is β-glycosidically linked to the sophorose module. The carboxyl terminus of this fatty acid is either free (acidic or open-ring form) or internally esterified at the 4" or 6' or 6" positions (lactone form).

[0094] In a preferred embodiment, component b) comprises or consists of at least one low-foaming surfactant.

[0095] Methods for determining the foaming properties of low-foaming nonionic surfactants and nonionic surfactants are known in principle to those skilled in the art. The foaming and defoaming power of surfactants can be determined by the turbine agitation method according to DIN EN 13996:2003-01. Another suitable method for measuring the foaming ability of surfactants and the stability of the foam produced based on height measurements is the Ross-Miles method or the method according to ASTM D 1173 based on the Ross-Miles method. For example, to simulate industrial conditions such as dishwashers, a Glewwe foam meter can be used, which provides a dynamic foam test rather than a static test (as in the Ross-Miles foam test). The apparatus and general procedure for the Glewwe foam test are described in U.S. Pat. No. 3,899,387. at column 12, line 45 et seq. Further details regarding the Grubeform test are provided in U.S. Patent No. 5,447,648, both of which are incorporated herein by reference in their entireties.

[0096] Nonionic surfactant solutions tend to become cloudy as the temperature increases. The water molecules attached to the ether oxygens of the polyoxyalkylene groups separate (dehydrate) as the temperature increases, and their solubility in water decreases, causing liquid-liquid separation that makes the liquid cloudy. The cloud point is the temperature at which the nonionic surfactant separates from the solution. Below the cloud point, the surfactant exhibits higher foaming, and above the cloud point, foaming decreases significantly.

[0097] Preferably, component b) comprises or consists of at least one low-foaming nonionic surfactant, in particular component b) comprises or consists of at least one nonionic surfactant having a cloud point of 60°C or less, preferably 50°C or less, in particular 40°C or less.

[0098] Nonionic surfactants from classes (i) and (ii) above are generally suitable as low foaming nonionic surfactants.

[0099] The rinse aid composition according to the invention preferably comprises from 0.5 to 89.9995% by weight, more preferably from 1.0 to 74.9995% by weight, in particular from 2.0 to 59.9995% by weight, especially from 2.5 to 25% by weight, more especially from 2.5 to 20% by weight of at least one nonionic surfactant (component b)), relative to the total weight of the composition.

[0100] Water (component c) In a preferred embodiment, the rinse aid composition is a liquid (aqueous) formulation that contains water as a solvent.

[0101] A rinse aid according to any of the preceding claims preferably comprises 10 to 95% by weight, more preferably 25 to 90% by weight, especially 40 to 85% by weight of water (component c)), based on the total weight of the composition.

[0102] Additional ingredients : The rinse aid composition of the present invention may comprise at least one additional component selected from a functional additive (component d)), an organic solvent, and mixtures thereof. The term functional additive is broadly understood to include any component that imparts desired properties to the composition, such as its direct use as a rinse aid, the way it is formulated, as well as aesthetic aspects. Within the meaning of this application, solvents, whether organic solvents or water, are not considered functional additives d). Some specific examples of functional additives are described in more detail below, although the specific components discussed are given by way of example only, and a wide variety of other functional additives d) may be used.

[0103] In one embodiment, the rinse aid composition consists solely of the structural polypeptide a) and the non-ionic surfactant b).

[0104] In another embodiment, the rinse aid consists solely of a structural polypeptide a), a non-ionic surfactant b), and water c).

[0105] In another embodiment, the structural polypeptide a), the nonionic surfactant b), and, if present, the water c), comprise the majority of the rinse aid composition, preferably at least 50%, more preferably at least 75%, and especially at least 90% by weight, based on the total weight of the rinse aid composition. In another embodiment, at least some of the structural polypeptide a), the nonionic surfactant b), and, if present, the water c), comprise at least 50%, more preferably at least 75%, and especially at least 90% by weight, based on the total weight of the rinse aid composition. At least one additional ingredient may be included in the rinse aid composition.

[0106] In a preferred embodiment, the rinse aid composition according to the present invention comprises at least one additional component selected from functional additives (component d)), organic solvents and mixtures thereof.

[0107] Functional additives (ingredient d) Preferably, the at least one functional additive is selected from surfactants different from component b), builders, hydrotropes, antifoaming agents, pH adjusters, further additives and mixtures thereof.

[0108] In one embodiment, the rinse aid composition does not contain any further additives other than additional surfactants (other than component b)), builders, hydrotropes, antifoaming agents, pH adjusters, and mixtures thereof. In another embodiment, the rinse aid composition comprises at least one further additive. The further additive is preferably selected from bleaches, enzymes, optical brighteners, anti-redeposition agents, antimicrobial agents, antioxidants, rheology modifiers, solubility modifiers, stabilizers, corrosion inhibitors, dyes, fragrances, fillers, tableting aids, disintegrants, humectants, electrolytes, water conditioners, and mixtures thereof.

[0109] In one embodiment, the rinse aid comprises a total amount of functional additives of 0 to 50 wt. %, particularly 0 to 25 wt. %, more particularly 1 to 10 wt. %, based on the total weight of the composition. When the rinse aid comprises at least one functional additive, the total amount of functional additives is at least 0.1 wt. %, more preferably at least 0.5 wt. %, and especially at least 1.0 wt. %, based on the total weight of the composition. In some embodiments, the rinse composition comprises 0.1 to 50 wt. %, particularly 0.1 to 25 wt. %, more particularly 0.5 to 10 wt. %, based in each case on the total weight of the composition.

[0110] In a preferred embodiment, the rinse aid composition does not contain any added (extraneous) organic solvents. In a further preferred embodiment, the rinse aid composition comprises 0.1 to 25% by weight, preferably 0.1 to 10% by weight, in particular 0.2 to 5% by weight, of at least one organic solvent, based on the total weight of the composition.

[0111] Preferred organic solvents are partially or completely water-miscible organic solvents. Suitable organic solvents are selected from mono- or polyhydric alcohols, alkanolamines, glycol ethers and mixtures thereof. The organic solvent is preferably selected from ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, tert-butanol, isobutanol, glycol, propanediol, butanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether or dipropylene glycol monoethyl ether, diisopropylene glycol monomethyl ether, diisopropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tert-butyl ether and mixtures of these solvents.

[0112] Additional surfactants The rinse aid composition may contain at least one surfactant different from component b). Suitable surfactants d) are generally anionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof.

[0113] It has been found that the combination of at least one structural polypeptide a) and at least one nonionic surfactant b) allows for the formulation of rinse aids with excellent application properties. Compositions of the present invention based solely on nonionic surfactants are generally suitable for use in rinse aid compositions that provide good sheeting, wetting, and drying properties. In certain embodiments, the rinse aid compositions of the present invention comprise only nonionic surfactants.

[0114] In order to provide the composition with additional cleaning properties and functionality, at least one surfactant different from component b) can be used.Suitable anionic surfactants are soap, alkyl sulfonate, alkyl benzene sulfonate, olefin sulfonate, methyl ester sulfonate, sulfofatty acid, alkyl sulfate, mono- and dialkyl sulfosuccinate, mono- and dialkyl sulfosuccinamate, sulfotriglyceride, amide soap, ether carboxylic acid and its salt, fatty acid isethionate, fatty acid sarcosinate, fatty acid tauride, N-acylamino acid such as acyl lactylate, acyl tartrate, acyl glutamate and acyl aspartate, alkyl oligoglucoside sulfate, alkyl glucose carboxylate, protein fatty acid condensate and alkyl (ether) phosphate.

[0115] Suitable anionic surfactants are also surfactants containing polyether groups, preferably selected from alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfonates, alkylaryl polyether sulfonates, alkyl polyether phosphates, aryl polyether phosphates, alkylaryl polyether phosphates, glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether) sulfates, fatty acid amide ether sulfates and mixtures thereof.

[0116] Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or alkylamphopropionates, alkylamphodiacetates or alkylamphodipropionates. For example, it is possible to use cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine, sodium cocoamphopropionate or tetradecyldimethylamine oxide.

[0117] Suitable cationic surfactants include, for example, quaternized ammonium compounds, especially alkyltrimethylammonium and dialkyldimethylammonium halides and alkyl sulfates, as well as pyridine and imidazoline derivatives, especially alkylpyridinium halides. For example, behenyl- or cetyltrimethylammonium chloride can be used.

[0118] builder The rinse aid composition according to the invention may comprise at least one builder as functional additive d).

[0119] In the terms of the present invention, the term builder also includes co-builders. Builders are, inter alia, sequestrants, sequestering agents, Also called builder materials, complexing agents, chelators, softening agents, or crystal growth inhibitors, these compounds bind with alkaline earth metal and other water-soluble metal salts and prevent the precipitation of solid crystals on washed items and on dishwasher surfaces. When used in rinse aids, they are particularly useful for dispersing soil components not removed during the wash cycle and preventing their redeposit on washed dishes.

[0120] Rinse aid compositions according to the invention preferably comprise up to 50%, more preferably up to 25%, and especially up to 10% by weight of at least one builder, based on the total weight of the composition. In certain embodiments, the rinse aid composition comprises 0.1 to 50%, more preferably 0.5 to 25%, and especially 1 to 10% by weight of at least one builder.

[0121] Suitable builders are in principle all kinds of organic builders.Examples of suitable types of builders are polycarboxylic acids and their salts, hydroxycarboxylic acids and their salts, phosphonic acids and their salts, such as hydroxyalkylphosphonic acids and their salts, aminopolycarboxylic acids and their salts, polymeric compounds containing carboxylic acid groups and their salts, polymeric compounds containing sulfonic acid groups and their salts, phosphates and polyphosphates, and their mixtures.

[0122] Suitable builders are, for example, C4-C 30 -di-, -tri- and -tetracarboxylic acids, such as succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and C-C 20 Alkyl- and alkenyl succinic acids containing -alkyl or -alkenyl groups.

[0123] Suitable builders are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C4-C 20 -hydroxycarboxylic acids, such as malic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid, and sucrose mono-, di-, and tricarboxylic acids. Preferred is citric acid and its salts. A preferred salt is sodium citrate.

[0124] Suitable builders are further phosphonic acids, such as hydroxyalkylphosphonic acids, aminophosphonic acids, and their salts.These include, for example, phosphonobutanetricarboxylic acid, aminotris(methylene-phosphonic acid) (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), hexamethylenediaminetetramethylenephosphonic acid (HDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), morpholinomethanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and mixtures thereof.1-hydroxyethane-1,1-diphosphonic acid and its salts are preferred.

[0125] Suitable builders are further aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, β-alanine diacetic acid (β-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid, N-(hydroxyalkyl)ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cyclohexylene-1,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediaminedisuccinic acid, serine diacetic acid, isoserine diacetic acid, L-asparagine diacetic acid, L-glutamine diacetic acid (GLDA), methylglycine diacetic acid (MGDA), and salts of said aminopolycarboxylic acids, and mixtures thereof. Preferred are ethylenediaminetetraacetic acid (EDTA) and its salts, L-glutamine diacetic acid (GLDA) and its salts, methylglycine diacetic acid (MGDA) and its salts, and mixtures thereof.

[0126] Suitable builders are further polymeric compounds containing carboxylic acid groups. Examples include acrylic acid homopolymers and copolymers and their salts. The acrylic acid homopolymers preferably have a number-average molecular weight ranging from 800 to 70,000 g / mol, more preferably from 900 to 50,000 g / mol, particularly from 1,000 to 20,000 g / mol, and especially from 1,000 to 10,000 g / mol. The term "acrylic acid homopolymer" also includes polymers in which some or all of the carboxylic acid groups are neutralized. These include acrylic acid homopolymers in which some or all of the carboxylic acid groups are in the form of alkali metal salts or ammonium salts. Acrylic acid homopolymers in which the carboxylic acid groups are protonated or in which some or all of the carboxylic acid groups are in the form of sodium salts are preferred.

[0127] Suitable builders are further oligomaleic acids and their salts.

[0128] Suitable builders are further terpolymers of unsaturated C4-C8 dicarboxylic acids, where the polymerized comonomers may comprise monoethylenically unsaturated monomers from group (i) specified below in an amount of up to 95% by weight, from group (ii) in an amount of up to 60% by weight, and from group (iii) in an amount of up to 20% by weight. Suitable unsaturated C4-C8 dicarboxylic acids in this context are, for example, maleic acid, fumaric acid, itaconic acid, and citraconic acid. Group (i) includes monoethylenically unsaturated C3-C8 monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and vinylacetic acid. From group (i), it is preferred to use acrylic acid and methacrylic acid. Group (ii) includes monoethylenically unsaturated C2-C 22These include C-olefins, vinyl alkyl ethers with C1-C8 alkyl groups, styrene, vinyl esters of C1-C8 carboxylic acids, (meth)acrylamides, and vinylpyrrolidone. From group (ii), C2-C6 olefins, vinyl alkyl ethers with C1-C4 alkyl groups, vinyl acetate, and vinyl propionate are preferably used. When polymers of group (ii) contain vinyl esters in polymerized form, these vinyl esters may be present partially or completely hydrolyzed to vinyl alcohol structural units. Group (iii) includes (meth)acrylic esters of C1-C6 alcohols, (meth)acrylonitrile, (meth)acrylamides of C1-C8 amines, N-vinylformamide, and N-vinylimidazole.

[0129] Suitable builders are furthermore, for example, homopolymers of monoethylenically unsaturated C3-C8-monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, in particular acrylic acid and methacrylic acid; copolymers of dicarboxylic acids, for example copolymers of maleic acid and acrylic acid having a molar mass of 1,000 to 150,000, in a weight ratio of 10:90 to 95:5, more preferably 30:70 to 90:10; copolymers of itaconic acid and acrylic acid in a weight ratio of 10:90 to 95:5; copolymers of maleic acid and acrylic acid in a weight ratio of 10:70 to 90:10; Terpolymers of maleic acid, acrylic acid and vinyl esters of C1-C3-carboxylic acids in a weight ratio of from 90 (acrylic acid + vinyl ester) to 95 (maleic acid):10 (acrylic acid + vinyl ester), where the weight ratio of acrylic acid to vinyl ester can vary within the range of from 30:70 to 70:30; copolymers of maleic acid and C2-C8-olefins in a molar ratio of from 40:60 to 80:20, particularly preferably copolymers of maleic acid and ethylene, propylene or isobutene in a molar ratio of 50:50.

[0130] Suitable builders are further sulfonated copolymers comprising, in copolymerized form, at least one monoethylenically unsaturated monomer having a sulfonic acid group and / or its salt and at least one ethylenically unsaturated comonomer. The ethylenically unsaturated comonomer is preferably selected from monoethylenically unsaturated monocarboxylic acids and their salts, monoethylenically unsaturated dicarboxylic acids and their anhydrides and their salts, and further ethylenically unsaturated monomers copolymerizable therewith. Suitable salts of the aforementioned acid monomers are, for example, sodium salts, potassium salts, The salts are ammonium salts.

[0131] Suitable monoethylenically unsaturated monomers having a sulfonic acid group are 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), 2-methacrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallyl sulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and salts of these acids.

[0132] Suitable monoethylenically unsaturated monocarboxylic acids are C3-C6 monocarboxylic acids such as acrylic acid, methacrylic acid, ethylacrylic acid, crotonic acid, vinylacetic acid, allylacetic acid, their sodium, potassium or ammonium salts and mixtures thereof. Acrylic acid, methacrylic acid and their salts and mixtures are preferred.

[0133] Suitable monoethylenically unsaturated dicarboxylic acids and their anhydrides and salts are maleic acid, maleic anhydride, maleates, itaconic acid, itaconic anhydride, itaconates, fumaric acid, fumarate and mixtures thereof, as well as the corresponding sodium, potassium or ammonium salts of maleic acid or itaconic acid. Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and salts of maleic acid and itaconic acid are preferred.

[0134] Further suitable ethylenically unsaturated monomers are C1-C8-alkyl esters of (meth)acrylic acid, C1-C4-hydroxyalkyl esters of (meth)acrylic acid, (meth)acrylamide, N,N-di(C1-C4-alkyl)-substituted (meth)acrylamides, vinylphosphonic acid, vinyl acetate, vinyl propionate, allyl alcohol, sulfonated allyl alcohol, vinyl aromatic monomers, (meth)acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylimidazole or N-vinylpyridine, and mixtures thereof. Preferably, the C1-C8-alkyl esters of (meth)acrylic acid are selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and mixtures thereof. The C1-C4-hydroxyalkyl ester of (meth)acrylic acid is preferably selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and mixtures thereof. The vinyl aromatic monomer is preferably selected from styrene, α-methylstyrene, p-tert-butylstyrene, o- or p-vinyltoluene, and mixtures thereof.

[0135] In one embodiment, the builder, in copolymerized form, is - 2% to 50% by weight of at least one monoethylenically unsaturated monomer having a sulfonic acid group and / or a salt thereof, 50% to 98% by weight of at least one monoethylenically unsaturated monocarboxylic acid and / or salt thereof, 0 to 30% by weight (for example 1 to 30% by weight) of at least one ethylenically unsaturated C4-C8-dicarboxylic acid and / or anhydride or salt thereof, - 0 to 30% by weight (for example 1 to 30% by weight) of at least one further monomer copolymerizable with the aforementioned monomers, Includes.

[0136] The further monomers are preferably selected from C1-C4-alkyl esters of (meth)acrylic acid, C1-C4-hydroxyalkyl esters of (meth)acrylic acid, acrylamide, N-alkyl-substituted acrylamides, N,N-dialkyl-substituted acrylamides, vinylphosphonic acid, vinyl acetate, allyl alcohol, sulfonated allyl alcohol, styrene and other vinyl aromatics, acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole or N-vinylpyridine. The weight-average molecular weight of these copolymers is in the range of 3,000 to 50,000 daltons.

[0137] In another embodiment, the builder is in copolymerized form - 5 to 15% by weight of at least one monoethylenically unsaturated monomer having a sulfonic acid group and / or a salt thereof, from 30 to 60% by weight of at least one monoethylenically unsaturated monocarboxylic acid and / or salt thereof, from 30 to 60% by weight of at least one ethylenically unsaturated C4-C8-dicarboxylic acid and / or anhydride or salt thereof, - 0 to 30% by weight (for example 1 to 30% by weight) of at least one further monomer copolymerizable with the aforementioned monomers, Includes.

[0138] Preferably, the copolymer has a weight average molecular weight of about 1,000 to about 50,000.

[0139] In another embodiment, the builder is selected from the sulfonated polymers described in WO 2010 / 067054 A1.

[0140] A preferred embodiment is a copolymer of at least one ethylenically unsaturated C3-C6-monocarboxylic acid and at least one ethylenically unsaturated sulfonic acid, in particular a copolymer of acrylic acid and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), commercially available from The Dow Chemical Company under the trade name ACUSOL 588. A particularly suitable copolymer is a copolymer of about 77% by weight of at least one ethylenically unsaturated C3-C6-monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid.

[0141] Further suitable organic builders are graft polymers of unsaturated carboxylic acids onto low molecular weight carbohydrates or hydrogenated carbohydrates. In this case, suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid, and vinylacetic acid, as well as mixtures of acrylic acid and maleic acid, which are grafted in an amount of 40 to 95% by weight based on the component to be grafted. Up to 30% by weight of other monoethylenically unsaturated monomers based on the component to be grafted can be used. Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii). Suitable graft bases are degraded polysaccharides, such as acid- or enzymatically degraded starch, inulin or cellulose, protein hydrolysates and reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides, such as mannitol, sorbitol, aminosorbitol and N-alkylglucamines, as well as polyalkylene glycols with molar masses up to Mw=5000, such as polyethylene glycol, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyvalent C-C alkylenes.22 It's alcohol.

[0142] Suitable organic builders are further polyglyoxylic acids.

[0143] Suitable organic builders are further polyamidocarboxylic acids and modified polyamidocarboxylic acids.

[0144] Suitable organic builders are further polyaspartic acids or aspartic acid and further amino acids, C4 to C 25 Mono- or dicarboxylic acids and / or C4 to C 25 A particular embodiment is a co-condensation product of a mono- or diamine prepared in phosphoric acid and containing C6 to C 22 Mono- or dicarboxylic acids or C6 to C 22 It is a polyaspartic acid modified with mono- or diamines.

[0145] A preferred class of builders are polymeric compounds containing carboxylic acid groups. Particularly preferred as builders are polyacrylic acid homo- and copolymers, which may be in partially or fully neutralized form.

[0146] Suitable organic builders are furthermore iminodisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, alkylpolyaminocarboxylates, aminopolyalkylenephosphonates, polyglutamates, hydrophobically modified citric acids, e.g. agaricic acid, poly-α-hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylenediamine triacetate, and alkylamides of ethylenediaminetetraacetic acid, such as EDTA tallowamide.

[0147] In certain embodiments, the rinse aid composition comprises a builder b) selected from methylglycine diacetic acid (MGDA) and its salts, glutamic acid-N,N-diacetic acid (GLDA) and its salts, iminodisuccinic acid and its salts, ethylenediaminetetraacetic acid (EDTA) and its salts, diethylenetriaminepentaacetic acid (DTPA) and its salts, hydroxyethylethylenediaminetriacetic acid (HEDTA) and its salts, carboxymethyl inulin and its salts, and mixtures of the aforementioned builders.

[0148] In a particular embodiment, a mixture of different builders is used. The mixture of different builders preferably comprises at least two of the following components: at least one polymeric compound containing carboxylic acid groups or their partially or fully neutralized forms (preferably polyacrylic acid or its partially or fully neutralized forms), at least one (poly)hydroxycarboxylic acid or a salt thereof (preferably citric acid or a citrate, in particular sodium citrate), at least one aminopolycarboxylic acid or a salt thereof, preferably chosen from methylglycine diacetic acid (MGDA) and its salts, ethylenediaminetetraacetic acid (EDTA) and its salts, and L-glutamine diacetic acid (GLDA) and its salts, at least one hydroxyalkylphosphonic acid or aminophosphonic acid, preferably 1-hydroxyethane-1-(1,1-diphosphonic acid) (HEDP), at least one sulfonated copolymer and / or salt thereof;

[0149] In one preferred embodiment, the rinse aid composition comprises at least one polymer builder, preferably selected from sulfonated copolymers and salts thereof, preferably AMPS copolymers.

[0150] In another preferred embodiment, the rinse aid composition comprises at least one builder selected from hydroxycarboxylic acids, salts of hydroxycarboxylic acids, polyhydroxycarboxylic acids (sugar acids), salts of polyhydroxycarboxylic acids, and mixtures thereof. Preferred is citric acid and its salts. A preferred salt is sodium citrate. These ingredients are useful as builders. It may function as a desiccant and pH adjusting component.

[0151] Hydrotrope Hydrotropes are ingredients that function as viscosity modifiers, gel inhibitors, stabilizers, and / or dispersing aids. Commonly used hydrotropes include alcohols and alcohol derivatives, including glycols and alkoxylated alcohols. Suitable hydrotropes for use herein also include anionic hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium, and ammonium toluene sulfonate, sodium, potassium, and ammonium cumene sulfonate, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and mixtures thereof. Dialkyl sulfosuccinates and alkyl naphthalene sulfonates have been previously described as anionic surfactants. In particular, the hydrotrope may be selected from sodium cumene sulfonate, sodium xylene sulfonate, sodium toluene sulfonate, dihexyl sodium sulfosuccinate, dioctyl sodium sulfosuccinate, alkyl naphthalene sulfonates, and mixtures thereof.

[0152] The rinse aids of the present invention preferably contain from 0 to 15%, more preferably from 0 to 12%, and especially from 0 to 10%, by weight of at least one hydrotrope, based on the total weight of the composition. If the rinse aid contains at least one hydrotrope, the amount is at least 0.1%, more preferably at least 0.5%, and especially at least 1.0%, by weight, based on the total weight of the composition.

[0153] Antifoaming agent / antifoaming agent / foam suppressant It has been found that the combination of at least one structural polypeptide a) and at least one nonionic surfactant b) allows for the formulation of rinse aids with low foaming properties without the use of additional anti-foaming components. In particular, when the nonionic surfactant b) comprises or consists of one of the aforementioned low-foaming nonionic surfactants, the use of an additional anti-foaming agent can usually be omitted.

[0154] In certain embodiments, the rinse aid composition according to the present invention does not contain any additional anti-foaming agent other than the nonionic surfactant b).

[0155] In another embodiment, the rinse aid composition comprises at most 10% by weight, more preferably at most 5% by weight, particularly at most 1% by weight, and especially at most 0.1% by weight of at least one antifoaming agent. Preferably, when an antifoaming agent is desired, the rinse aid may contain at least one nonionic EO-containing surfactant b) that is hydrophilic and water-soluble at relatively low temperatures, particularly at temperatures below the temperature at which the rinse aid is used.

[0156] Suitable defoaming agents include phosphate ester defoamers, especially alkyl phosphate esters containing 16 to 20 carbon atoms. Such phosphate ester defoamers may be monostearate or monooleate phosphate or salts thereof, preferably alkali metal salts. Silicone defoamers are also suitable.

[0157] pH adjuster The rinse aid composition may contain at least one pH adjuster to adjust the pH value of the composition and / or the pH value of the resulting rinse solution under the conditions of use of the composition. In one embodiment, the rinse aid composition comprises at least one pH adjuster selected from acids, bases, and pH buffer systems. The rinse aid composition can be formulated so that during use, for example, in an aqueous liquid in a dishwashing process, the rinse solution has a desired pH value. For example, the rinse aid composition may be formulated so that during use (e.g., in the rinse cycle of a dishwasher), the rinse solution has a desired pH value. The solution may be formulated to have a pH in the range of 11.0 or less, more preferably 10.0 or less, particularly 9.0 or less, and especially 8.5 or less. In another embodiment, the pH value of the rinse solution ranges from 3 to 9, more preferably 5 to 8.5. Techniques for controlling pH values ​​at recommended usage levels, including the use of acids, bases, buffers, etc., are well known to those skilled in the art.

[0158] In one embodiment, aqueous rinse aid compositions according to the present invention, particularly for I&I applications, have a pH value ranging from about 2 to about 4. In another embodiment, particularly for consumer applications, aqueous rinse aid compositions have a pH value ranging from 4 to 9.

[0159] Suitable bases (also referred to as alkali source or alkali reserve) are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, ammonium carbonate, alkali metal bicarbonates, alkaline earth metal bicarbonates, ammonium bicarbonate, alkali metal silicates and mixtures thereof.

[0160] Suitable acids are carboxylic acids, hydroxycarboxylic acids and phosphoric acids. Preferably, the acid is selected from citric acid, gluconic acid, tartaric acid, glucoheptonic acid, mucic acid, galactonic acid, saccharinic acid, fumaric acid, succinic acid, glutaric acid, adipic acid and phosphoric acid. Particularly preferred is citric acid.

[0161] bleach The rinse aid composition according to the invention may comprise at least one bleaching agent as functional additive d).

[0162] In the sense of the present application, the term bleaching agent also means a bleaching system, optionally also comprising bleach activators, bleach catalysts and / or bleach stabilizers.

[0163] The rinse aid composition according to the invention preferably comprises 0 to 30% by weight, more preferably 0 to 25% by weight, of at least one bleaching agent (component d)), based on the total weight of the composition. When the rinse aid composition comprises at least one bleaching agent, the amount is at least 0.5% by weight, more preferably at least 1% by weight, based on the total weight of the composition. When the bleaching agent comprises two or more components, the aforementioned amount refers to the sum of all components of the bleaching system.

[0164] Suitable bleaching agents are, for example, percarboxylic acids (e.g., diperoxododecanedicarboxylic acid, phthalimidopercaproic acid, monoperoxophthalic acid or monoperoxoterephthalic acid), salts of percarboxylic acids (e.g., sodium percarbonate), adducts of hydrogen peroxide with inorganic salts (e.g., sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrogenate or sodium phosphate perhydrogenate), adducts of hydrogen peroxide with organic compounds (e.g., urea perhydrogenate), or inorganic peroxo salts (e.g., alkali metal persulfates or peroxodisulfates).

[0165] Suitable bleach activators are, for example, polyacylated sugars (e.g. pentaacetylglucose), acyloxybenzenesulfonic acids and their alkali metal and alkaline earth metal salts (e.g. sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate), N,N-diacylated and N,N,N',Ni-tetraacylated amines (e.g. N,N,N',N'-tetraacetylmethylenediamine and ethylenediamine (TAED), N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylated hydantoins, (e.g. 1,3-diacetyl-5,5-dimethylhydantoin)), N-alkyl-N-sulfonylcarbonamides (e.g. N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide), N-acylated cyclic hydrazides, acylated triazoles or urazoles (e.g. monoacetamides, thylmaleic hydrazide), O,N,N-trisubstituted hydroxylamines (e.g., O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinylhydroxylamine, or O,N,N-triacetylhydroxylamine), N,N'-diacylsulfurylamides (e.g., N,N'-dimethyl-N,N'-diacetylsulfurylamide or N,N'-diethyl-N,N'-dipropionylsulfurylamide), acylated lactams (e.g., acetylcaprolactam, octanoic acid benzoylcaprolactam or carbonylbiscaprolactam), anthranil derivatives (e.g., 2-methylanthranil or 2-phenylanthranil), triacyl cyanurates (e.g., triacetyl cyanurate or tribenzoyl cyanurate), oxime esters and bisoxime esters (e.g., O-acetylacetone oxime or bisisopropyliminocarbonate), carboxylic acid anhydrides (e.g., acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or benzoic anhydride), acetoxyimidazoline), enol esters (e.g., isopropenyl acetate), 1,3-diacyl-4,5-diacyloxyimidazoline (e.g., 1,3-diacetyl-4,5-diacetoxyimidazoline), tetraacetyl glycoluril and tetrapropionyl glycoluril, diacylated 2,5-diketopiperazines (e.g., 1,4-diacetyl-2,5-diketopiperazine), ammonium-substituted nitriles (e.g., N-methylmorpholinium acetonitrile methyl sulfate), propylene diurea and 2,2 -dimethylpropylenediurea acylation products (e.g., tetraacetylpropylenediurea), α-acyloxypolyacylmalonamides (e.g., α-acetoxy-N,N'-diacetylmalonamide), diacyldioxohexahydro-1,3,5-triazines (e.g., 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine), and benz-(4H)-1,3-oxazin-4-ones having an alkyl group (e.g., a methyl group) or an aromatic group (e.g., a phenyl group) at the 2-position.

[0166] The bleaching system consisting of a bleaching agent and a bleaching activator may optionally contain a bleaching catalyst. Suitable bleaching catalysts are, for example, quaternized imines and sulfonimines, as described, for example, in U.S. Patent No. 5,360,569 and European Patent Application Publication No. 453003. Particularly effective bleaching catalysts are, for example, manganese complexes, as described, for example, in WO 94 / 21777. In addition to the bleaching systems described above consisting of a bleaching agent, a bleaching activator, and optionally a bleaching catalyst, systems with enzymatic peroxide release may also be used.

[0167] enzyme Rinse aid compositions according to the present invention may comprise at least one enzyme.

[0168] The rinse aid composition according to the invention preferably comprises at least one enzyme in an amount of 0 to 10% by weight, more preferably 0 to 8% by weight, especially 0 to 5% by weight of enzyme protein, based on the total weight of the composition.

[0169] If the rinse aid composition comprises at least one enzyme, the amount of enzyme protein is preferably at least 0.001 wt. %, more preferably at least 0.01 wt. %, especially at least 0.05 wt. %, based on the total weight of the composition.

[0170] Enzymes are often used in dishwashing formulations not in the form of pure active enzyme protein, but in combination with a carrier and / or in encapsulated form, and optionally with further additives, and the aforementioned amounts refer to the active enzyme protein without any further ingredients.

[0171] The enzyme is preferably an aminopeptidase, an amylase, an arabinase, a carbohydrase, a carboxypeptidase, a catalase, a cellulase, a chitinase, a cutinase, a cyclodextrin glycosyltransferase, a deoxyribonuclease, an esterase, a galactanase, an α-galactosidase, a β-galactosidase, or a glucanase. , glucoamylase, α-glucosidase, beta-glucosidase, haloperoxidase, hydrolases, invertase, isomerase, keratinase, laccase, lipase, mannanase, mannosidase, oxidase, pectolytic enzyme, peptidoglutaminase, peroxidase, peroxygenase, phytase, polyphenol oxidase, proteolytic enzyme, ribonuclease, transglutaminase, transferase, xylanase and mixtures thereof.

[0172] In particular, the rinse aid composition comprises one or more enzymes selected from amylase, arabinase, carbohydrase, cellulase (e.g., endoglucanase), cutinase, deoxyribonuclease, galactanase, haloperoxygenase, lipase, mannanase, oxidase (e.g., laccase and / or peroxidase), pectinase, pectin lyase, protease, xylanase, xanthanase, xyloglucanase, oxidoreductase, and mixtures thereof. Preferably, the rinse aid composition comprises at least one enzyme selected from amylase, arabinase, carbohydrase, cellulase, galactanase, lipase, mannanase, pectinase, pectin lyase, protease, and mixtures thereof.

[0173] In certain embodiments, the rinse aid composition comprises at least one amylase. When the composition comprises at least one amylase and at least one additional enzyme, the additional enzyme is preferably a protease and / or a lipase.

[0174] Anti-reattachment agent In one embodiment, the rinse aid composition can include at least one anti-redeposition agent that can promote sustained suspension of soils in the rinse solution and prevent removed soils from redepositing on the substrate being rinsed. Examples of suitable anti-redeposition agents include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, styrene maleic anhydride copolymers, and cellulose derivatives (e.g., hydroxyethyl cellulose, hydroxypropyl cellulose).

[0175] The rinse aid composition according to the invention preferably comprises at least one anti-redeposition agent in an amount of 0 to 10% by weight, more preferably 0 to 8% by weight, in particular 0 to 5% by weight, based on the total weight of the composition.

[0176] antimicrobial agents In one embodiment, the rinse aid composition can include at least one antimicrobial (disinfecting) agent. The combination of at least one structural polypeptide a) and at least one nonionic surfactant b) is suitable for providing a two-in-one disinfecting rinse composition with antimicrobial efficacy against a wide range of microorganisms. Suitable antimicrobial agents are, in particular, quaternary ammonium compounds. Quaternary ammonium compounds and their use in rinse aid formulations are described in U.S. Patent Application Publication No. 2022386598. Preferably, the antimicrobial quaternary ammonium compound is C 12 -C 16The quaternary ammonium compound is selected from alkyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, octyldecyldimethylammonium chloride, or combinations thereof. Further examples of quaternary ammonium compounds are benzethonium chloride, ethylbenzylalkonium chloride, myristyltrimethylammonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetrimonium bromide (CTAB), carnitine, dophanium chloride, tetraethylammonium bromide (TEAB), domiphen bromide, benzododecinium bromide, benzoxonium chloride, choline, cocamidopropyl betaine (CAPB), denatonium, and mixtures thereof. The antimicrobial agents are effective against a wide range of different types of microorganisms (aerobic and non-aerobic), including bacteria, yeasts, molds, fungi, algae, and other problematic microorganisms. The quaternary ammonium compounds provide broad-spectrum activity against both anaerobic microorganisms, including gram-positive and gram-negative microorganisms. The amount of quaternary ammonium compound in the use solution preferably ranges from 1 ppm to 10,000 ppm by weight, more preferably from 1 ppm to 1,000 ppm by weight, and especially from 5 ppm to 400 ppm by weight. Concentrate compositions generally contain at least one antimicrobial agent in an amount of 0.1 to 75% by weight, preferably 1 to 70% by weight.

[0177] moisturizer In one embodiment, the rinse aid composition can comprise at least one moisturizing agent. A moisturizing agent is a substance that has an affinity for water. The use of a moisturizing agent can be advantageous to help reduce the visibility of the film on the substrate surface of the article. This can be particularly concerning when the rinse water contains a certain amount of dissolved solids. Generally, the combination of at least one structural polypeptide a) and at least one nonionic surfactant b) provides excellent rinsing properties, so that the use of a moisturizing agent can be omitted in typical rinse aid applications, such as household and industrial dishwashers.

[0178] In some embodiments, the rinse aid composition may include dyes, odorants including perfumes, and other aesthetic enhancers.

[0179] In certain embodiments, rinse aid compositions according to the present invention comprise: a) at least one structural polypeptide b) at least one nonionic surfactant c) water d1) at least one builder, preferably -Citric acid and citrates sulfonated copolymers and their salts, and -A mixture of them Selected from d2) optionally at least one hydrotrope It comprises or consists of:

[0180] In all aspects / embodiments described above, the structural polypeptide, in particular the silk polypeptide, is preferably present in the rinse aid composition in gel form, in particular in hydrogel form.

[0181] Various modifications and variations of the present invention will be apparent to those skilled in the art without departing from the scope of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention that are obvious to those skilled in the relevant fields are intended to be covered by the present invention.

[0182] Preferred Embodiments of the Invention 1.a) a structural polypeptide, and b) at least one nonionic surfactant 1. A rinse aid composition comprising: 2. The rinse aid composition of embodiment 1, wherein the structural polypeptide a) is a silk polypeptide. 3. The rinse aid composition of embodiment 2, wherein the silk polypeptide is a recombinant or synthetic silk polypeptide, preferably a spider silk polypeptide. 4. Silk polypeptides are -comprises or consists of a protein chain that does not have at least two units (single units of amino acids) of the same sequence motif, or - comprising or consisting of at least two identical repeating units, 4. The rinse aid composition of embodiment 2 or 3. 5. The rinse aid composition of any one of embodiments 2 to 4, wherein the silk polypeptide does not contain non-repeating units. 6. The single unit or repeating unit may, independently: - Module C having the amino acid sequence set forth in SEQ ID NO: 1 or a variant thereof - module C having the amino acid sequence set forth in SEQ ID NO: 2 Cys or its variants - module C having the amino acid sequence set forth in SEQ ID NO: 3 Lys or its variants 6. The rinse aid composition of embodiment 4 or 5, selected from the group consisting of: 7. Silk polypeptides are (C)m and (C)mC Cys , (C)mC Lys , C Cys (C)m, C Lys (C)m, (C Cys )m and (C Lys 7. The rinse aid composition of any of embodiments 2-6, wherein the compound is selected from the group consisting of: 8. Silk polypeptides are C1, C2, C3, C4, C5, C6, C7, C8, C16, C32, C48, (C)1C Cys , (C)2C Cys , (C)3C Cys , (C)4C Cys , (C)5C Cys , (C)6C Cys , (C)7C Cys , (C)8C Cys , (C) 16 C Cys , (C) 32 C Cys , (C) 48 CCys 、 (C)1C Lys 、(C)2C Lys 、(C)3C Lys 、(C)4C Lys 、(C)5C Lys 、(C)6C Lys 、(C)7C Lys 、(C)8C Lys 、(C) 16 C Lys 、(C) 32 C Lys 、(C) 48 C Lys 、C Cys (C)1、C Cys (C)2、C Cys (C)3、C Cys (C)4、C Cys (C)5、C Lys (C)6、C Cys (C)7、C Cys (C)8、C Cys (C) 16 、C Cys (C) 32 、C Cys (C) 48 、 C Lys (C)1、C Lys (C)2、C Lys (C)3、C Lys (C)4、C Lys (C)5、C Lys (C)6、C Lys (C)7、C Lys (C)8、C Lys (C) 16 、C Lys (C) 32 、C Lys (C) 48 、 C Cys 1、C Cys 2、C Cys 3、C Cys 4、C Cys 5、C Cys 6、C Cys 7、C Cys 8、C Cys 16 、C Cys 32 、C Cys 48 、 C Lys 1. C Lys 2. C Lys 3. C Lys 4. C Lys 5. C Lys 6. C Lys 7. C Lys 8. C Lys 16 , C Lys 32 , C Lys 48 , 8. The rinse aid composition of embodiment 7, selected from the group consisting of: 9. A rinse aid composition according to any of the previous embodiments, comprising 0.0005 to 2.5% by weight, preferably 0.001 to 2.0% by weight, in particular 0.005 to 1.5% by weight of at least one structural polypeptide (component a)), based on the total weight of the composition. 10. A rinse aid composition according to any of the previous embodiments, comprising 0.5 to 89.9995% by weight, preferably 1.0 to 74.9995% by weight, in particular 2.0 to 59.9995% by weight, and especially 2.5 to 25% by weight of at least one nonionic surfactant (component b)), based on the total weight of the composition. 11. A rinse aid composition according to any of the previous embodiments, wherein component b) comprises or consists of at least one low-foaming nonionic surfactant, in particular wherein component b) comprises or consists of at least one nonionic surfactant having a cloud point of 60°C or less, preferably 50°C or less, in particular 40°C or less. 12. A rinse aid composition according to any of the previous embodiments, comprising 10 to 95% by weight, preferably 25 to 90% by weight, in particular 40 to 85% by weight, of water (component c)), based on the total weight of the composition. 13. The rinse aid composition of any of the previous embodiments, comprising at least one additional component selected from a functional additive (component d)), an organic solvent, and mixtures thereof. 14. At least one functional additive d) selected from surfactants, builders, hydrotropes, antifoaming agents, pH adjusters, further additives and mixtures thereof, different from component b). 14. The rinse aid composition of embodiment 13, comprising: 15. The rinse aid composition of embodiment 14, comprising at least one further additive selected from bleaches, enzymes, optical brighteners, anti-redeposition agents, antimicrobial agents, antioxidants, rheology modifiers, solubility modifiers, stabilizers, corrosion inhibitors, dyes, fragrances, humectants, electrolytes, water conditioners, and mixtures thereof. 16. The rinse aid composition of any one of embodiments 13 to 15, comprising a total amount of functional additives of 0 to 50 wt. %, particularly 0 to 25 wt. %, more particularly 0 to 10 wt. %, based on the total weight of the composition (e.g., 0.1 to 25 wt. % or 0.5 to 10 wt. % of the functional additives). 17. The rinse-aid composition according to any one of embodiments 13 to 16, comprising 0 to 25% by weight, preferably 0.1 to 10% by weight, in particular 0.2 to 5% by weight, of at least one organic solvent, based on the total weight of the composition. 18. A rinse aid composition according to any of the previous embodiments, comprising at least one polymer builder, preferably selected from sulfonated copolymers and salts thereof. 19. A rinse aid composition according to any of the previous embodiments, comprising at least one builder selected from hydroxycarboxylic acids, salts of hydroxycarboxylic acids, polyhydroxycarboxylic acids, salts of polyhydroxycarboxylic acids and mixtures thereof, in particular citric acid and / or citrate salts. 20. a) at least one structural polypeptide b) at least one nonionic surfactant c) water d1) Preferably -Citric acid and citrates sulfonated copolymers and their salts, and -A mixture of them at least one builder selected from d2) optionally at least one hydrotrope; 3. The rinse aid composition of any of the previous embodiments, comprising: 21. The rinse aid composition of any of the preceding embodiments, wherein the rinse aid composition is present in the form of a gel, particularly a hydrogel. 22. A method for machine washing dishware, comprising contacting the dishware to be washed with the rinse aid composition of any one of embodiments 1-21. 23. Use of a structural polypeptide, in particular a silk polypeptide, in a rinse aid composition. 24. The use according to embodiment 23, wherein the structural polypeptide is as defined in any of embodiments 2 to 21. twenty five. - provide good sheeting and wetting properties, - reducing spotting and filming on tableware, especially glassware and cutlery; - To give a good luster to tableware, - Prevent recontamination of tableware, - to provide surface protection to tableware, in particular to prevent corrosive changes to the surface of glassware; - to formulate low-foaming products; -Reducing the surface tension of tableware -Improved drying of dishes, 25. The use according to embodiment 23 or 24 for [Brief explanation of the drawings]

[0183] The following drawings are merely illustrative of the present invention and should not be construed in any way as limiting the scope of the invention as set forth by the appended claims. [Figure 1] Figure 1 shows the results of the different evaluated rinse aids on glasses: (1) Comparison with the commercial market leader (Formulation 3, no silk gel (hydrogel)): The three glasses on the left show obvious streaks and spots and are more matte than the glasses on the right; (2) Formulation 4 according to the invention (with silk gel (hydrogel)): The three glasses on the right are very clear, spotless and show a good gloss. [Figure 2]Figure 2 shows digital scans of three wash cycles (A, B, C) of glass treated with IEC-D + IEC-C according to the Fresenius Standard Method 03_2016 Comparative Rinse Aid Test for Automatic Dishwashing Detergents and the test procedure and conditions described above. The results of the digital image analysis were classified as follows: 5 = very large spots, 4 = large spots, 3 = medium-sized spots, 2 = small spots, and 1 = very small spots. After three consecutive wash cycles, medium-sized spots were detected on the glass surface. The spot formation rating was classified as 3 for the treated glass samples. [Figure 3] Figure 3 shows digital scans of three wash cycles (A, B, C) of glass treated with IEC-D + IEC-C + Silk Gel according to the Fresenius Standard Method 03_2016 automatic dishwashing detergent comparative rinse aid test and the test procedure and conditions described above. The results of the digital image analysis were classified as follows: 5 = very large spots, 4 = large spots, 3 = medium-sized spots, 2 = small spots, and 1 = very small spots. After three consecutive wash cycles, small spots were detected on the glass surface. The spot formation rating was classified as 2 for the treated glass sample, thus indicating an improvement compared to glass washed with detergent and rinse aid only. [Example]

[0184] Example The following examples are illustrative of the automatic dishwashing compositions of the present invention and are not intended to limit the invention as described above in any way.

[0185] Example 1: I) Rinse-aid formulations I.1) Liquid Formulations The following liquid formulations 1 to 4 were prepared: Comparative Examples 1 to 3 do not contain the structural protein (silk protein) according to the present invention; and Formulation 4 contains the structural protein (silk protein) according to the present invention.

[0186] [Table 1] a) That is, 0.09% total content of silk protein in the composition

[0187] II) Application examples Rinse Aid Performance The rinse aid performance method is based on EN50242 / EN60436 - "Domestic electric dishwashers - Methods for measuring performance". Tests were carried out on glass and knife

[0188] [Table 2]

[0189] Rating scale: Step 1 (spot counting): The rating depends on the number of spots (glass and knife). The highest number of spots on the dish is 60 or more (≧60). The higher the number of spots on the glass and knife, the less effective the rinse aid. The best rating (7) is achieved with the lowest number of spots (0-8).

[0190] [Table 3]

[0191] Process 2 (evaluation of gloss level) The rating depends on the gloss level. The knife surface is too small to be evaluated, so only the glass was evaluated. The higher the score, the better the effect.

[0192] [Table 4]

[0193] [Table 5]

[0194] [Table 6]

[0195] The examples show that even with small amounts of structural protein, rinse aids according to the invention are superior when used in the rinse cycle of a dishwasher. The difference between the formulations of the invention and the prior art formulations is even more evident in the avoidance of spot formation.

[0196] Figure 1 shows the results of the different evaluated rinse aids on glass.

[0197] 1: Comparative Example Using a Commercial Market Leader (Formulation 3): The three glasses on the left show clear signs of streaks and spots and are more matte than the glasses on the right.

[0198] 2: Formulation 4 according to the present invention: The three glasses on the right are very clear, spotless and have a good luster.

[0199] The examples demonstrate that rinse aid formulations according to the invention, which contain silk protein as a structural protein, have excellent spotting / filming performance.

[0200] Example 2: Test Method: Comparative rinse aid testing of automatic dishwashing detergents according to Fresenius Standard Method 03_2016.

[0201] Test conditions: The washing machine used was a Miele GSL 2. The program was set to 50°C for 8 minutes with a 65°C rinse cycle. The water hardness was 9±1°dH. Dosage: 20 ppm in cleaning solution No rinse aid was used. The cumulative number of cycles was 3.

[0202] Ballast contamination: 50 g of ballast soil was used per cycle with the ingredients (ketchup, milk, starch, fat, egg yolk, benzoic acid and water).

[0203] machine inputs; The machine was loaded with three glass plates (black (Alcolock)), three porcelain plates (black (Schoenwald)), four long drink glasses (Schott Paris 79), and four juice glasses (Schott Paris 12).

[0204] Usage sample: IEC60436-TypD (detergent, batch number CFT-GSM D~020 rev.2020 CFT), hereinafter referred to as IEC-D, was used as the detergent. IEC60436-TypC (rinse aid, batch number KSC.241-788 11.04.2022 wfk) is referred to below as IEC-C and was used as rinse aid.

[0205] Test procedure: Glasses, plates and knives were placed in the dishwasher and treated with Neodisher and citric acid, followed by two cycles with the test detergent.

[0206] The dishwasher was modified so that the commercial ion exchanger was shut off, and the machine was supplied with regular water via an external tank.

[0207] The rinse aid dispenser was empty and test use of the rinse aid was done by hand using a pipette.

[0208] At the start of the wash cycle, 50g of ballast soil was added. After the program finished, the front door was left closed for a further 10 minutes. The door was then fully opened and the dishwasher rack was fully extended from the machine.

[0209] Evaluation began after 20 minutes. After the dishes had completely dried, rinse aid effectiveness was evaluated visually in a "black box" under defined lighting conditions. Dried drops, streaks, deposits or dull films on dishes and cutlery were evaluated. Each product was tested in three replicates (cumulative) and the arithmetic mean was calculated.

[0210] result: 1. Visual assessment of water and salt spots Glass Alcoloc plates and porcelain Schonwald plates were treated according to the test conditions and procedures described above. Briefly, plates were placed in the dishwasher with ballast soil and either (i) detergent (IEC-D) and rinse aid (IEC-C) or (ii) detergent (IEC-D) and rinse aid combined with silk gel (IEC-C) was added. Three repeats (cumulative) of the wash cycle were performed on each product, followed by visual grading for salt and water spots. In addition, the arithmetic mean was calculated.

[0211] Visual grading of the spots was performed by an independent laboratory (Fresenius Institute) according to an 8-point scale for water and salt spots. 8 = No spots or stripes. 7 = Very slight stripes and / or a few very small spots. 6 = slight stripes and / or a few small spots. 5 = slight or moderate stripes and / or a few moderate spots. 4 = medium stripes and / or few medium-sized spots. 3 = Moderate stripes and / or a few large spots. 2 = few large stripes and / or large spots, and 1 = large stripes and / or many large spots, and 0 = very large stripes and / or very many large spots.

[0212] The arithmetic mean for glass Alcoloc plates washed with IEC-D + IEC-C was calculated to be 7.0, whereas the arithmetic mean after the addition of IEC-D + IEC-C + silk gel was 7.2. The arithmetic mean for porcelain Schönwald plates washed with IEC-D + IEC-C was calculated to be 7.0, whereas the arithmetic mean after the addition of IEC-D + IEC-C + silk gel was 7.3.

[0213] In summary, when glass Alcoloc plates and porcelain Schönwald plates were cleaned with IEC-D + IEC-C + Silk Gel, the number of spots was reduced compared to when the plates were cleaned with IEC-D + IEC-C alone (Table 1).

[0214] [Table 7] Table 1: Table 1 shows the results of comparative rinse aid testing of automatic dishwashing detergents according to Fresenius Standard Method 03_2016. Detergent IEC 60436-Type D (referred to herein as IEC-D) and rinse aid IEC 60436-Type C (referred to herein as IEC-C) were tested with and without Silkgel. Combinations are compared for reduction in spot formation on plates after three wash cycles in a washing machine according to Fresenius Standard Method 03_2016 SOP M 2422 Version 2.

[0215] 2. Digital Image Analysis The tested drinking glasses were visually evaluated and subsequently measured by digital image analysis. For this purpose, each glass was fixed in a rack and illuminated with a special light source. During the digital measurement, the glass was rotated 360°. As a result, a flat image was obtained. Special software was used to analyze the glass. , the number, size and intensity of the spots could be calculated. The bottom and top of the glass were ignored.

[0216] The results were classified using the following grading: 5=Very large spot. 4=Big spot. 3 = medium size spot. 2 = small spots, and 1 = very small spot.

[0217] When glassware was treated with detergent and rinse aid (IEC-D+IEC-C)-silk gel, medium-sized spots were detected on the glass surface after three consecutive washing rounds.

[0218] For glassware washed with detergent and rinse aid (IEC-D+IEC-C)+silk gel, only small sized spots were detected on the glass surface after three consecutive washing rounds.

[0219] The spot formation rating was 3 for the glass samples treated with detergent and rinse aid (IEC-D + IEC-C) - silk gel and 2 for the glass samples treated with detergent and rinse aid (IEC-D + IEC-C) + silk gel.

[0220] Thus, the addition of silk gel to rinse aids and detergents results in reduced spot formation on glassware and provides optical improvements (see Figures 2 and 3).

[0221] In the above experiments, spider silk polypeptide C 16 The use of is preferred.

[0222] Sequence Listing AA sequence in the sequence table C X -Model SEQ ID NO: 1 (Module C): GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP Sequence number 2 (module C Cys ): GSSAAAAAAAASGPGGYGPENQGPCGPGGYGPGGP Sequence number 3 (Module C Lys ): GSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP

[0223] Tags and Linkers SEQ ID NO: 4 (T7-tag) MASMTGGQQMG SEQ ID NO: 5 (linker) RGSM

[0224] C x 16-Protein SEQ ID NO: 6(C 16 ): MASMTGGQQMGRGSMGSSAAAAAAAASGPGGYGPENQGPPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSSAAAAAAAASGPGGYGPENQGPSGGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGGGYGPGGPGSSAA AAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSS AAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPG

[0225] sequence number7(C Lys 16 ): MASMTGGQQMGRGSMGSSAAAAAAAASGPGGYGPGPGPS GYGPGGPGSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPGGYGPGPGGSSAAAAAAAASGPGGYGPKNQGPS

[0226] sequence number8(C) 16 C Cys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

[0227] Larger C-protein SEQ ID NO: 9 C32 MASMTGGQQMGRGSMGSSAAAAAAAASGPGGYGPENQGPS

[0228] SEQ ID NO: 10 C48 MASMTGGQQMGRGSMGSSAAAAAAAASGPGGYGPENQGPPSGPGGYGPGGPGSSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPPSGPGGYGPGGPGSSSAAAAAAA ASGPGGYGPENQGPSGPGGYGPGGPGSSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGPGGSSAAAAAAAASGPGGYGPENQGPS GPGGYGPGGPGSSSAAAAAAAASGPGGYGPENQGPSGGGYGPGPGGSSAAAAAAAASGPGGYGPENQGPSGGGYGPGGPGSSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPENQGPSGGGYGPGGPGSSAAAAAAAASGPG GYGPENQGPSGPGGYGPGGPGSSAAAAAAAASGPGGYGPGGYGPGPGGYGPGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPGGYGPGGYGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPGGYGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPGGYGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPGGYGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPGGYGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPGGYGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPGGYGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPGGYGPGGSSAAAAAAAASGPGGYGPGGYGPGGYGPG AAASGPGGYGPGPGPSAAAAAAAS

Claims

1. a) a structural polypeptide, and b) at least one nonionic surfactant 1. A rinse aid composition comprising:

2. 2. A rinse aid composition according to claim 1, wherein the structural polypeptide a) is a silk polypeptide, preferably a recombinant or synthetic silk polypeptide, in particular a spider silk polypeptide.

3. The silk polypeptide - comprises or consists of a protein chain that does not have at least two units of the same sequence motif (single unit of amino acid), or - comprising or consisting of at least two identical repeating units, 3. The rinse aid composition of claim 2.

4. 4. The rinse aid composition of claim 2 or claim 3, wherein the silk polypeptide does not contain non-repeating units.

5. The single unit or the repeating unit is - module C having the amino acid sequence set forth in SEQ ID NO: 1 or a variant thereof, - module C having the amino acid sequence set forth in SEQ ID NO: 2 Ｃｙｓ or a variant thereof, - module C having the amino acid sequence set forth in SEQ ID NO: 3 Ｌｙｓ or a variant thereof, 5. The rinse aid composition of claim 3 or claim 4, independently selected from the group consisting of:

6. The silk polypeptide is (C) ｍ , (C) ｍ C Ｃｙｓ , (C) ｍ C Ｌｙｓ , C Ｃｙｓ (C) ｍ , C Ｌｙｓ (C) ｍ , (C Ｃｙｓ ) ｍ and (C Ｌｙｓ ) ｍ 6. The rinse aid composition of any one of claims 2 to 5, wherein m is selected from the group consisting of: wherein m is an integer from 1 to 96.

7. The silk polypeptide C １ 、C ２ 、C ３ 、C ４ 、C ５ 、C ６ 、C ７ 、C ８ 、C １６ 、C ３２ 、C ４８ 、 (C) １ C Ｃｙｓ 、(C) ２ C Ｃｙｓ 、(C) ３ C Ｃｙｓ 、(C) ４ C Ｃｙｓ 、(C) ５ C Ｃｙｓ 、(C) ６ C Ｃｙｓ 、(C) ７ C Ｃｙｓ 、(C) ８ C Ｃｙｓ 、(C) １６ C Ｌｙｓ 、(C) ３２ C Ｌｙｓ 、(C) ４８ C Ｌｙｓ 、 (C) １ C Ｌｙｓ 、(C) ２ C Ｌｙｓ 、(C) ３ C Ｌｙｓ 、(C) ４ C Ｌｙｓ 、(C) ５ C Ｌｙｓ 、(C) ６ C Ｌｙｓ 、(C) ７ C Ｌｙｓ 、(C) ８ C Ｌｙｓ 、(C) １６ C Ｌｙｓ 、(C) ３２ C Ｌｙｓ 、(C) ４８ C Ｌｙｓ 、 C Ｃｙｓ (C) １ 、C Ｃｙｓ (C) ２ 、C Ｃｙｓ (C) ３ 、C Ｃｙｓ (C) ４ 、C Ｃｙｓ (C) ５ 、C Ｃｙｓ (C) ６ 、C Ｃｙｓ (C) ７ 、C Ｃｙｓ (C) ８ 、C Ｃｙｓ (C) １６ 、C Ｃｙｓ (C) ３２ 、C Ｃｙｓ (C) ４８ 、 C Ｌｙｓ (C) １ 、C Ｌｙｓ (C) ２ 、C Ｌｙｓ (C) ３ 、C Ｌｙｓ (C) ４ 、C Ｌｙｓ (C) ５ 、C Ｌｙｓ (C) ６ 、C Ｌｙｓ (C) ７ 、C Ｌｙｓ (C) ８ 、C Ｌｙｓ (C) １６ 、C Ｌｙｓ (C) ３２ 、C Ｌｙｓ (C) ４８ 、 C Ｃｙｓ １ 、C Ｃｙｓ ２ 、C Ｃｙｓ ３ 、C Ｃｙｓ ４ 、C Ｃｙｓ ５ 、C Ｃｙｓ ６ 、C Ｃｙｓ ７ 、C Ｃｙｓ ８ 、C Ｃｙｓ １６ 、C Ｃｙｓ ３２ 、C Ｃｙｓ ４８ 、 C Ｌｙｓ １ 、C Ｌｙｓ ２ 、C Ｌｙｓ ３ 、C Ｌｙｓ ４ 、C Ｌｙｓ ５ 、C Ｌｙｓ ６ 、C Ｌｙｓ ７ 、C Ｌｙｓ ８ 、C Ｌｙｓ １６ 、C Ｌｙｓ ３２ 、and C Ｌｙｓ ４８ 、 7. The rinse aid composition of claim 6, selected from the group consisting of:

8. 8. A rinse-aid composition according to any one of claims 1 to 7, comprising 0.0005 to 2.5% by weight, preferably 0.001 to 2.0% by weight, in particular 0.005 to 1.5% by weight of at least one structural polypeptide (component a)), based on the total weight of the composition.

9. 9. A rinse aid composition according to any one of claims 1 to 8, comprising 0.5 to 89.9995% by weight, preferably 1.0 to 74.9995% by weight, in particular 2.0 to 59.9995% by weight, and especially 2.5 to 25% by weight of at least one nonionic surfactant (component b)), based on the total weight of the composition.

10. 10. A rinse aid composition according to any one of claims 1 to 9, comprising 10 to 95% by weight, preferably 25 to 90% by weight, in particular 40 to 85% by weight of water (component c)), based on the total weight of the composition.

11. 11. The rinse aid composition according to any one of claims 1 to 10, comprising at least one additional component selected from functional additives (component d)), organic solvents and mixtures thereof, wherein the at least one functional additive d) is preferably selected from surfactants different from component b), builders, hydrotropes, defoamers, pH adjusters, further additives and mixtures thereof.

12. 12. The rinse aid composition of claim 11, comprising at least one further additive selected from bleaches, enzymes, optical brighteners, anti-redeposition agents, antimicrobial agents, antioxidants, rheology modifiers, solubility modifiers, stabilizers, corrosion inhibitors, dyes, fragrances, humectants, electrolytes, water conditioners, and mixtures thereof.

13. a) at least one structural polypeptide; b) at least one nonionic surfactant; c) water; d1) preferably - Citric acid and citrates sulfonated copolymers and their salts, and - their mixtures at least one builder selected from d2) optionally at least one hydrotrope 13. The rinse aid composition of any one of claims 1 to 12, comprising:

14. 14. A rinse-aid composition according to any one of the preceding claims, wherein the rinse-aid composition is in the form of a gel, in particular a hydrogel.

15. A method for machine washing dishware, comprising contacting the dishware to be washed with a rinse aid composition according to any one of claims 1 to 14.

16. - provide good sheeting and wetting properties, - reducing spotting and filming on tableware, especially glassware and cutlery; - imparting a good luster to tableware; - prevent recontamination of tableware, - to provide surface protection to tableware, in particular to prevent corrosive changes to the surface of glassware; - to formulate low-foaming products; - Reduce the surface tension of tableware - Improve the drying of dishes, 15. Use of a rinse aid composition according to any one of claims 1 to 14 in treating soiled dishware in an automatic dishwashing machine, for example.

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