Automatic dishwashing compositions containing structural polypeptides

Abstract

The present invention relates to automatic dishwashing compositions containing structural polypeptides, methods for machine washing dishes, the use of structural polypeptides in automatic dishwashing compositions, and the use of automatic dishwashing compositions for treating soiled dishes.

Description

[Technical Field]

[0001] The present invention relates to automatic dishwashing compositions comprising structural polypeptides, methods for machine cleaning of dishes, the use of structural polypeptides in automatic dishwashing compositions, and the use of automatic dishwashing compositions for treating soiled dishes. [Background technology]

[0002] In a typical mechanical dishwashing process (automated dishwashing, abbreviated ADW) for home and commercial use, including I&I (industrial and institutional) applications, the objects to be washed, such as food-soiled dishes or utensils, undergo numerous treatments in a series of zones and / or cycles. The washing process generally consists of several consecutive steps, including the actual washing operation. In the washing zone, the soiled dishes are typically sprayed with a liquid detergent at a pressure sufficient to loosen the soil present on the dishes. The washing zone may be preceded by at least one pretreatment zone, e.g., to mechanically remove loosely attached food residues, in which case the dishes are also contacted with water or another liquid cleaning medium. The actual washing process is typically followed by at least one rinsing step and a drying step for the washed dishes. These operations are performed in a more or less automated fashion, with the central device being the dishwasher, which performs at least the washing step, typically followed by a rinsing step and / or a drying step.

[0003] In a domestic dishwasher, soiled dishes are typically washed in a single chamber, with the aforementioned treatment steps progressing sequentially according to a controlled program. Fresh water passes through a water softener unit into a pump well and is sprayed onto the dishes by a moving spray arm. Rinse-water-insoluble materials are filtered within the pump well. During the first wash cycle, a cleaning composition, typically alkaline, is added to the liquid wash medium, heated to a set temperature, and sprayed onto the dishes. During the rinse cycle, a rinse builder is added to the treatment solution to reduce surface tension, allowing the treatment solution to flow more easily from the dishes. After the final rinse cycle, the dishes are dried. The ingredients used in the ADW process, such as water treatment agents, cleaning actives, and rinse builders, can be used either in the form of individual components or in multi-compartment formulations.

[0004] Commercial dishwashers are basically comprised of fixed bath tanks, each of which sprays or sprays a primarily aqueous cleaning solution onto dishes, e.g., dishes on a conveyor belt pass through these tanks, and the used cleaning solution returns to the bath tanks. Water enters the last bath tank, flows stepwise through overflows to all other tanks, and is discharged from the machine by overflow from the first tank. The application of the cleaning solution, which is typically highly alkaline, is carried out, for example, by dedicated nozzles or a dedicated spray system, usually located in the center of the machine.

[0005] Current automatic dishwashing compositions are complex formulations containing many different ingredients, such as sequestrants / dispersants, nonionic surfactants, enzymes, bleaching agents, corrosion inhibitors, thickeners, etc. These can be dispensed into the dishwasher individually or in the form of a mixture of two or more components. Many different forms of ADW detergent compositions are known in the art. Possible forms include powders, granules, gels, pastes, liquids, tablets (tablets), capsules (capsules), water-soluble pouches (liquid tablets), water-soluble containers, etc. Water-soluble film-forming polymers, especially those with specific release characteristics, can be used as sheaths or coatings that contain the entire dishwashing composition or at least some of its ingredients. The capsules or containers can be single-compartment or multi-compartment. The ADW composition may also be a system. Thus, ingredients that have stability issues, for example, because they are hygroscopic or incompatible with other ingredients, can be used in complex dishwashing compositions. Thus, the ADW composition may also include a mixture of two or more forms, for example, a gel component and a powder component.

[0006] In the home, so-called "single-use" products, which contain a quantity of dishwashing composition sufficient for one dishwashing operation, are common. Gel formulations are also very attractive to consumers because they are easier to dispense than low-viscosity products and are aesthetically pleasing, especially in the form of clear or translucent gels.

[0007] ADW compositions must meet complex requirements, including cleaning soiled dishes well, leaving them shiny and streak-free, not damaging them even after repeated washing, providing special surface protection, being versatile for different types of surfaces and soils, and allowing for good drying of washed items. Staining and filming on dishes, especially glassware and cutlery, are essential criteria for judging the performance of dishwashing formulations. Staining refers to scattered residues on glassware that form when water droplets evaporate, leaving behind dissolved solids. Filming refers to widespread, uniform deposition on the glass surface. ADW formulations should be able to inhibit both inorganic and organic filming. Inorganic filming is primarily caused by calcium and magnesium salts in water and the builders used in standard dishwashing compositions. Organic filming is particularly caused by soil components from the rinse liquor, such as protein, starch, and fat deposits. There is also growing interest in using environmentally friendly and / or bio-based ingredients in ADW compositions.

[0008] There continues to be a need for automatic dishwashing compositions that have at least one, and preferably several, of the following properties: good surface protection, improved stain and film formation even with hard water, and good drying. The application of additional properties of the ADW composition should not adversely affect cleaning effectiveness, among other things. The ingredients contained in the ADW composition should be non-toxic, non-hazardous to the environment, and safe for humans and animals. It should be possible to provide the product in the form of a gel.

[0009] Surprisingly, it has been found that structural polypeptides such as silk polypeptides are suitable for the formulation of ADW compositions with improved properties.Silk polypeptides are polymers that exhibit excellent properties, and can provide ADW formulations with various advantages, including good surface protection, improved stain and film formation, and good drying properties.Structural polypeptides such as silk polypeptides are biocompatible, non-toxic, and environmentally friendly, and are suitable for the formulation of machine dishwashing compositions in all forms, such as gels and other forms. Summary of the Invention

[0010] The present invention is a dishwashing composition comprising: a) a structural polypeptide, in particular a silk polypeptide, and b) Contains at least one builder. The cleaning composition is in particular a manual dishwashing composition or an automatic dishwashing composition. Therefore, a first object of the present invention is to provide a method for cleaning a dishwashing composition comprising: a) a structural polypeptide, in particular a silk polypeptide, and b) An automatic dishwashing composition comprising at least one builder. As a preferred embodiment, a) structural polypeptides, in particular silk polypeptides; b) at least one builder (also called a sequestering agent, builder material, complexing agent, chelating agent, chelating compound, water softener, or crystal growth inhibitor); c) optionally at least one enzyme; d) optionally at least one bleaching component; e) optionally at least one rheology modifier (also called thickener); f) optionally at least one further additive different from components a) to e), preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antimicrobial components, antioxidants and mixtures thereof, and g) Optionally, water 1. An automatic dishwashing composition comprising:

[0011] The present invention is a method for washing dishes, in which the dishes to be washed are contacted with a dishwashing composition as defined above and below. The method is in particular a method for manual washing of dishes or a method for machine washing of dishes. A further object of the present invention is therefore a method for machine washing of dishes, in which the dishes to be washed are contacted with an automatic dishwashing composition as defined above and below.

[0012] The present invention relates to the use of structural polypeptides, particularly silk polypeptides, in dishwashing compositions.The dishwashing compositions are particularly manual dishwashing compositions or automatic dishwashing compositions.Therefore, a further object of the present invention is the use of structural polypeptides, particularly silk polypeptides, in automatic dishwashing compositions.

[0013] The present invention reduces staining and filming on tableware, especially glassware and cutlery; Gives tableware a good shine, Improves the ability to remove stains from dishes, Prevents recontamination of dishes, Provides surface protection to tableware, especially glassware, preventing corrosive changes to the surface; Reduces the surface tension of tableware, Reduces or eliminates the need for separate rinse aid products The use of a dishwashing composition as defined above and below in the treatment of soiled dishes to improve the drying of the dishes. In particular, the dishwashing composition is a manual dishwashing composition or an automatic dishwashing composition. Reduces staining and filming on tableware, especially glassware and cutlery; Gives tableware a good shine, Improves the ability to remove stains from dishes, Prevents recontamination of tableware, provides surface protection to tableware, and prevents corrosion of the surface of glassware in particular; Reduces the surface tension of tableware, Reduces or eliminates the need for separate rinse aid products Use of an automatic dishwashing composition as defined above and below in treating soiled dishes in an automatic dishwashing machine to improve the drying of the dishes.

[0014] This summary of the invention does not necessarily describe all features of the invention. Other embodiments will become apparent by consideration of the following detailed description.

[0015] Before describing the present invention in detail below, it is to be understood that this invention is not limited to the particular methodology, procedures, 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 are commonly understood by those of ordinary skill in the art. has the same meaning as that given in the preceding sentence.

[0016] Preferably, the terms used herein are defined as set forth in "A multilingual glossary of biotechnological terms: (IUPAC Recommendations)," Leuenberger, HGW, Nagel, B. and Koelbl, H. eds. (1995), Helvetica Chimica Acta, CH-4010 Basel, Switzerland.

[0017] Several documents are cited throughout the text of this specification. Each document cited herein (including all patents, patent applications, scientific publications, manufacturer's specifications, instructions, sequence entries with GenBank accession numbers, etc.), whether supra or infra, is incorporated herein by reference in its entirety. Nothing stated herein should be construed as an admission that the present invention is not entitled to antedate such disclosure by virtue of prior invention.

[0018] The components of the present invention are described below. These elements are listed with specific embodiments. However, it should be understood that they can be combined in any manner and in any number to create additional embodiments. The various described examples and preferred embodiments should not be interpreted as limiting the invention to only the explicitly described embodiments. The description should be understood to support and encompass embodiments that combine the explicitly described embodiments with any number of the disclosed and / or preferred elements. Furthermore, any permutation and combination of all elements described in this application should be considered disclosed by the description of this application unless the context indicates otherwise.

[0019] The term "dishwashing composition," as used herein, refers to a composition adapted for washing dishes with water. The term "dishwashing composition" encompasses manual dishwashing compositions or automatic dishwashing compositions.

[0020] Structural polypeptides, such as silk polypeptides, are particularly advantageous for use in automatic dishwashing compositions that must meet a complex property profile. The automatic dishwashing compositions of the present invention have at least one, and preferably two, three, or more, of the following advantages: structural polypeptides, particularly silk polypeptides, are polymers that exhibit excellent application properties and can provide various benefits to ADW formulations. The compositions of the present invention can effectively reduce staining and film formation. After the washing process, tableware, particularly glassware and cutlery, have a good luster and exhibit significantly fewer water marks, soils, and / or stains compared to conventional products using the prior art. The compositions exhibit good cleaning even in hard water and heavily soiled dishes. They are suitable for improving stain removal and / or preventing re-soiling of dishes. The compositions of the present invention are suitable for providing surface protection to dishes. In particular, they do not corrode the surface of glassware, even with repeated use, and in particular do not cause clouding, stains, scratches, or iridescence of the glass surface. The compositions of the present invention are suitable for imparting low surface tension to dishes. When dishes, particularly glass dishes, are washed in a dishwasher using the automatic dishwashing composition of the present invention, the contact angle of deionized water on the washed items is significantly reduced compared to conventional products from the prior art. Dishes treated with the compositions of the present invention exhibit improved drying properties. This composition effectively works even with very low application rates. The structural proteins, particularly silk proteins, contained in the ADW compositions of the present invention are biocompatible, non-toxic, non-harmful to the environment, and safe for humans and animals. Silk proteins, in particular, are made exclusively from renewable resources, are 100% biodegradable, and do not contain microplastics. In terms of regulatory and environmental issues, this may be more advantageous than compositions based on conventional ingredients. Structural proteins, particularly silk proteins, are suitable for use in phosphate-free formulations.Structural proteins, particularly silk proteins, are suitable for use in a wide variety of different forms, such as gels, aqueous solutions, and organic solvents.This composition is particularly suitable for single-dose products.

[0021] Without wishing to be bound by any theory, it is believed that the structural polypeptides used, particularly silk polypeptides, are suitable for surface modification of dishware, imparting improved properties to the dishware. The structural polypeptides adhere to the surface, thus allowing for efficient cleaning and drainage of the wash solution and / or rinse water. This helps prevent the formation of water droplets, which can lead to the buildup of residue on the dishware surface and the formation of visible stains or streaks during drying. Surprisingly, this surface modification can be affected by delivering the structural polypeptides into the main wash solution along with the remaining cleaning composition, allowing them to remain on the surface of the dishware during and even after the rinse cycle. Thus, the use of structural polypeptides in the ADW composition allows for good drainage during the rinse phase, maintaining protection against surface damage and recontamination. This reduces or eliminates the need for a separate rinse aid product.

[0022] For the purposes of this application, the term dishware encompasses any type of soiled item that is subject to the automatic cleaning process in a dishwasher. Thus, the term dishware encompasses dishware (tableware), cookware, cutlery, kitchen utensils, and other items for practical and decorative purposes.

[0023] The automatic dishwashing compositions of the present invention may be in any form, such as powder, granules, gel, paste, liquid, tablet, capsule, water-soluble pouch, water-soluble container, etc. In particular, a water-soluble film-forming polymer having special cleaning properties may be used as a sheath or coating for the entire dishwashing composition or at least one of its components. The capsule or container may be a single compartment or a multi-compartment system.

[0024] In a preferred embodiment, the automatic dishwashing composition is in the form of a gel formulation. In particular, the automatic dishwashing composition may be in the form of a gel, or the automatic dishwashing composition may be a multi-compartment formulation containing the structural polypeptide in the form of a gel or in solution. Preferred solvents are water, at least partially water-miscible organic solvents, and mixtures thereof. In a particular embodiment, the automatic dishwashing composition is a multi-compartment formulation containing the structural polypeptide in the form of a hydrogel.

[0025] In a preferred embodiment, the automatic dishwashing composition is in the form of a single dose product (ie, containing the correct amount of dishwashing composition sufficient for one dishwashing operation).

[0026] In a more preferred embodiment, the automatic dishwashing composition is in the form of a unit dose. Unit dose products include tablets, capsules, sachets, pouches, containers, etc. The automatic dishwashing composition of the present invention is preferably in the form of a multi-compartment formulation. A multi-compartment formulation (including a multi-chamber or multi-functional formulation / system) is a water-soluble multi-compartment pack made of a water-soluble polymer, for example, in the form of a film or molded body, having one, two, three, four, five, six, or more than six individual sections. Preferred for use in the present invention are tablets (including tablets, capsules, sachets, and pouches) coated or packaged with a water-soluble polymer film, and containers made of water-soluble polymers. Each section of the multi-compartment formulation may be independently filled with powder, granules, gel, paste, liquid, or a combination thereof.

[0027] In a possible embodiment, the structural polypeptide a) can be distributed in separate compartments of a multi-compartment formulation.

[0028] The automatic dishwashing composition of the present invention is preferably free of phosphoric acid. "Free of phosphoric acid" is understood herein to mean that the composition contains less than 1% by weight of phosphoric acid, preferably less than 0.1% by weight, and in particular less than 0.05% by weight of phosphoric acid, based on the total weight of the composition. "Free of phosphoric acid" means that the automatic dishwashing composition does not contain alkali metal orthophosphates and alkali metal polyphosphates, in particular pentasodium triphosphate (sodium tripolyphosphate, STPP).

[0029] Component a) (Structural Polypeptide) In the present invention, the terms "polypeptide" and "protein" are used interchangeably and refer to a long chain of peptide-linked amino acids, e.g., at least 30 amino acids in length.

[0030] In the present invention, the term "structural polypeptide" refers to any polypeptide comprising repeating units (repeated components) of amino acids. The structural polypeptide preferably has the ability to undergo polypeptide assembly. In particular, the structural polypeptide is capable of forming protein complexes (aggregates) in a formulation, e.g., a hydrogel in an aqueous formulation. The structural polypeptide may be selected from the group consisting of silk polypeptides (including fibroin), keratin, collagen, and elastin, or variants or combinations thereof. The structural polypeptide is particularly a recombinant or synthetic structural polypeptide. The structural polypeptide is preferably a silk polypeptide (recombinant or synthetic), such as a spider silk polypeptide (recombinant or synthetic). Exemplary methods for producing silk polypeptides are described in WO2006 / 008163 and WO2011 / 120690.

[0031] In the present invention, the term "silk polypeptide" refers to a polypeptide that exhibits a highly unusual amino acid composition compared to other polypeptides. In particular, silk polypeptides are highly enriched in hydrophobic amino acids such as glycine or alanine. Furthermore, silk polypeptides contain highly repetitive amino acid sequences or repeating units (repeat units, modules), particularly in their large core domains. DNA analysis has shown that all silk polypeptides are chains of repeating units that further contain a limited set of distinct, significantly shorter peptide motifs. The terms "peptide motif" and "consensus sequence" can be used interchangeably in the present invention. In general, silk consensus sequences can be classified into four major categories: GPGXX, GGX, Ax or (GA)n, and spacers. These peptide motif categories in silk polypeptides have been assigned structural roles. For example, the GPGXX motif has been suggested to be involved in a β-turn helix, likely providing elasticity. The GGX motif is known to be involved in a glycine-rich 31-helix. Both GPGXX and GGX motifs are thought to be involved in the formation of an amorphous matrix that connects crystalline regions and thereby provides the fiber's elasticity. The alanine-rich motifs, typically containing 6-9 residues, have been found to form crystalline beta sheets. The spacers, typically containing charged groups, separate the repeating peptide motifs into clusters. Silk polypeptides are capable of polypeptide assembly.

[0032] Fibroin is a structural polypeptide and a silk polypeptide in the present invention.

[0033] The silk polypeptide is in particular a recombinant or synthetic silk polypeptide.

[0034] Preferably, the (recombinant or synthetic) silk polypeptide is a (recombinant or synthetic) spider silk polypeptide. It is a silk polypeptide derived from silkworms.

[0035] The term "polypeptide assembly," as used herein, refers to the process by which a pre-existing disordered state of polypeptides forms an organized structure or pattern 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.) without any external action or trigger, 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 come into contact, they interact with each other, resulting in the formation of a three-dimensional structure. The change from a disordered state 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 concomitant increase in viscosity. The transition from a fluid state to a gel-like state can be monitored, for example, by optical or rheological measurements.

[0036] Preferably, the structural polypeptides that assemble the polypeptides are (recombinant or synthetic) silk polypeptides, such as (recombinant or synthetic) spider-derived silk polypeptides.

[0037] The term "polypeptide aggregate" (or polypeptide complex), as used herein, refers to a polypeptide structure formed as a result of polypeptide self-assembly. During polypeptide self-assembly, multiple copies / units of a polypeptide self-assemble into bodies or clumps without any external action or trigger, although external factors may affect the rate and nature of self-polypeptide assembly. In polypeptide aggregates, different polypeptides are linked 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 is clear that a polypeptide aggregate encompasses at least two polypeptides. In the present invention, the self-assembly of (recombinant or / synthetic) silk polypeptides is described. During the self-assembly of silk polypeptides, silk polypeptide aggregates (silk polypeptide complexes) are formed.

[0038] The term "hydrogel," as used herein, refers to a structure formed when the concentration of structural polypeptides is high enough to immobilize the liquid components and establish a continuous network. The network is preferably formed by a polypeptide assembly of the structural polypeptides, which provides the basis for the hydrogel. In particular, a hydrogel is a hydrophilic polymer network of structural polypeptides. The network is stabilized by chemical and / or physical interactions between the structural polypeptides. The network is dispersed throughout an immobilized liquid phase. The hydrogel's hydrophilicity and stability allow it to penetrate and absorb water (swell) without dissolving, thus maintaining its three-dimensional (3D) structure and function.

[0039] 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 subjected to gravity. A flowable hydrogel is in a liquid state (i.e., it is not yet self-supporting, in the sense that it cannot maintain an assigned shape without a shape-stabilizing coating). The compliance of a hydrogel can be easily determined by one skilled in the art, for example, by rheological or viscosity measurements. Compliance measurements are preferably performed under standard conditions (20°C). A method for determining the viscosity of a gel is described in detail below.

[0040] In other words, the hydrogel is a non-flowable hydrogel. This hydrogel can be converted into a flowable hydrogel by shear-thinning. The same applies to solid forms. This also applies to the structural polypeptide of the present invention, which is

[0041] 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.

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

[0043] 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.

[0044] In a preferred embodiment, the automatic dishwashing compositions according to the present invention comprise structural polypeptides capable of forming polypeptide aggregates, in particular, said polypeptides having the potential to assemble into fibrillar structures (i.e., fibrillar aggregates (complexes) of structural polypeptides).

[0045] Preferably, the structural polypeptide is selected from silk polypeptides, keratin, collagen, elastin, and combinations thereof. In some embodiments, the silk polypeptide is fibroin. In particular, the structural polypeptide is a recombinant polypeptide, such as a recombinant silk polypeptide, keratin, collagen, or elastin.

[0046] More preferably, the structural polypeptide is a silk polypeptide, especially a recombinant silk polypeptide.

[0047] In a preferred embodiment, the (recombinant) silk polypeptide is a spider-derived silk polypeptide. Suitable spider-derived silk polypeptides are major ampullate silk polypeptides, such as dragline silk polypeptides, minor ampullate silk polypeptides, or flagelliform silk polypeptides of orb-web spiders. In particular, the silk polypeptide is a spider-derived silk polypeptide, more preferably a recombinant spider-derived silk polypeptide.

[0048] In a preferred embodiment, the silk polypeptide comprises or consists of 25 to 4000 amino acids, more preferably 30 to 1500 amino acids, particularly 35 to 1200 amino acids, and in a particular embodiment, the silk polypeptide comprises or consists of 60 to 600 amino acids.

[0049] In a preferred embodiment, the silk polypeptide consists of a single unit of amino acids. In this embodiment, the protein chain is defined as having no units (at least two) of the same or similar sequence motif. In this embodiment, the silk polypeptide preferably consists of 25 to 250 amino acids, particularly 30 to 150 amino acids.

[0050] In another preferred embodiment, the silk polypeptide comprises at least two repeating units. A silk polypeptide is a polypeptide having an amino acid sequence that comprises or consists of 50% of multiple copies of repeat units. The amino acid sequence may be composed of 100% of multiple repeat units. More preferably, the silk polypeptide is a polypeptide having an amino acid sequence that comprises or consists of at least 50%, particularly at least 60%, particularly at least 65%, particularly at least 70%, particularly at least 75%, particularly at least 80%, particularly at least 85%, particularly at least 90%, particularly at least 95%, or particularly at least 99% of multiple copies of repeat units. The repeat units may be identical or different.

[0051] When the amino acid sequence of the silk polypeptide is a polypeptide comprising or consisting of multiple copies of a repeat unit, each repeat unit preferably comprises or consists of 25 to 250 amino acids, in particular 30 to 150 amino acids.

[0052] When 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.

[0053] 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 or 96 repeating units.

[0054] In particular, the repeat unit is a group consisting of module C having the amino acid sequence of SEQ ID NO: 1 (GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP) or a variant thereof, module C having the amino acid sequence of SEQ ID NO: 2 (GSSAAAAAAAASGPGGYGPENQGPCGPGGYGPGGP) or a variant thereof Cys , module C having the amino acid sequence of SEQ ID NO: 3 (GSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP) or a variant thereof Lys are independently selected from the group consisting of:

[0055] Module C Cys (SEQ ID NO: 2) is a variant of module C (SEQ ID NO: 1). In this module, the 25th amino acid, Ser, is replaced by the amino acid Cys. Module C Lys (SEQ ID NO: 3) is also a variant of module C (SEQ ID NO: 1), in which the 20th amino acid, Glu, is replaced by the amino acid Lys.

[0056] 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 module variants may alternatively or additionally be characterized by a degree of sequence identity to the reference module from which it is derived. Thus, a module C variant may 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, 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, or 115 amino acid changes in amino acid sequence (i.e., substitutions, additions, insertions, deletions, N-terminal truncations, and / or C-terminal truncations). , 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. 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, preferably over the entire length of the respective reference module C.

[0057] The sequence identity may be at least 80% over the entire length of each reference module C, at least 85% over the entire length, at least 90% over the entire length, at least 95% over the entire length, at least 98% over the entire length, or 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.

[0058] A fragment (or deletion) variant of module C preferably has a deletion of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or up to 15 amino acids at its N-terminus and / or its C-terminus. Deletions can also be made internally.

[0059] Furthermore, a module C variant or fragment is considered a module C variant or fragment in the present invention only if the modifications to the amino acid sequence on which the variant or fragment is based do not adversely affect the efficacy of the silk polypeptide in processing dishes in a dishwasher. Those skilled in the art can easily assess whether a silk polypeptide containing a module C variant or fragment can still process dishes. In this regard, the examples of the present application are provided.

[0060] C Cys or C Lys Variants are also encompassed by the present invention. Cys or C Lys Regarding variants, the same explanations / definitions apply as for Module C variants (see above).

[0061] It is even more preferred that the silk polypeptide is selected from the group consisting of: m , (C) m C Cys (C) m C Lys , C Cys (C) m , C Lys (C) m , (C Cys ) m and (C Lys ) m , Here, m is an integer from 1 to 96.

[0062] It is even more preferred that the silk polypeptide is selected from the group consisting of: 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 , C32 、C 39 、C 40 、C 41 、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 CCys 、(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) 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、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)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) 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) 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 .

[0063] In one embodiment, the silk polypeptide comprises a tag (TAG) at the amino terminus, for example, consisting of the amino acid sequence MASMTGGQQMG (SEQ ID NO: 4). In another embodiment, the silk polypeptide comprises an amino terminus tag (TAG) and a linker, for example, consisting of the amino acid sequence RGSM (SEQ ID NO: 5).

[0064] As an example, silk polypeptides consist of 16 modules C (=C 16 ) and has the amino acid sequence of SEQ ID NO: 6 (TAG of SEQ ID NO: 4 and linker of SEQ ID NO: 5 at the N-terminus).

[0065] In another example, the silk polypeptide has 16 C Lys Module (C Lys 16 ) (SEQ ID NO: 7).

[0066] In another example, the silk polypeptide comprises 17 modules, where the first module (N-terminus) or the last module (C-terminus) is C Cys The other 16 modules are C modules (SEQ ID NO: 1). A specific example is (C) 16 C Cys (SEQ ID NO: 8).

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

[0068] Exemplary, a larger silk polypeptide based on the C module is silk polypeptide C having an amino acid sequence according to SEQ ID NO: 9. 32 (32 times that of module C) and silk polypeptide C having an amino acid sequence according to SEQ ID NO: 10 48 (48 times that of module C).

[0069] In particular, the silk polypeptide consists only of repeat units. In other words, the silk polypeptide does not particularly contain / have non-repeated units. A component that can be added as part of the silk polypeptide is a tag or group, for example, which allows the silk polypeptide to be easily transferred in an expression system and / or easily isolated from the expression system. The tag can be a his tag or a flag tag.

[0070] The automatic dishwashing composition according to the invention preferably contains from 0.0005 to 2.5 wt. %, more preferably from 0.001 to 2.0 wt. %, especially from 0.05 to 1.5 wt. %, based on the total weight of the composition, of hydroxybenzoates, e.g., 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. 0.09, 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 wt% of at least one structural polypeptide (component a).

[0071] For the formulation of automatic dishwashing compositions, the structural polypeptide a) can be used in solid form, for example, in the form of a powder. The 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. The structural polypeptide a) can also be used in the form of a gel. The gel form preferably contains 0.5 to 30% by weight, more preferably 1 to 20% by weight, based on the total weight of the gel, for example, 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, 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 22, 23, 24, 25, 26, 27, 28, 29 or 30% by weight of the structural polypeptide.

[0072] Component b) (builder) The automatic dishwashing composition according to the invention comprises at least one builder (=component b)).

[0073] In the present invention, the term "builder" also encompasses co-builders. Builders, also known as sequestering agents, sequestrants, builder materials, complexing agents, chelating agents, chelating compounds, softeners, or crystal growth inhibitors, bind with alkaline earth metal and other water-soluble metal salts to prevent the precipitation of solid crystals on the surfaces of washed items and dishwasher appliances. They help break down soils, disperse soil components, and exfoliate soils, and in some cases even exhibit cleaning effects themselves. Furthermore, when used in powder formulations, they are solids, allowing the powder to remain free-flowing.

[0074] The automatic dishwashing composition of the present invention preferably comprises from 1 to 90 wt. %, more preferably from 2 to 80 wt. %, especially from 10 to 50 wt. % of at least one builder (component b), based on the total weight of the composition.

[0075] Suitable builders can be organic or inorganic 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 having carboxylic acid groups and their salts, aluminosilicates, inorganic carbonates, phosphoric and polyphosphoric acids, and mixtures thereof.

[0076] Suitable organic builders include, for example, C4-C 30 -di-, -tri- and -tetracarboxylic acids, such as succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and C2-C6 20 Alkyl succinic acids and alkenyl succinic acids having -alkyl or -alkenyl groups.

[0077] Suitable organic 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. Citric acid and its salts are preferred. A preferred salt is sodium citrate.

[0078] Suitable organic builders are additional phosphonic acids, such as hydroxyalkylphosphonic acid, aminophosphonic acid and their salts.These include, for example, phosphonobutanetricarboxylic acid, aminotris(methylenephosphonic acid) (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), hexamethylenediaminetetramethylenephosphonic acid (HDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), morpholinomethanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and their mixtures.Preferably, 1-hydroxyethane-1,1-diphosphonic acid and its salts.

[0079] Suitable organic builders are further aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic acid 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, ethylenediaminetriacetic acid, ethylenediaminetetra ... The aminopolycarboxylic acids include ethylenediamine disuccinic acid, serine diacetic acid, isoserine diacetic acid, L-asparagine diacetic acid, L-glutamine diacetic acid (GLDA), methylglycine diacetic acid (MGDA), and salts of the above 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.

[0080] Suitable organic builders are polymeric compounds further 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 in the range of 800 to 70,000 g / mol, more preferably 900 to 50,000 g / mol, particularly 1,000 to 20,000 g / mol, and especially 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 in neutralized form. 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.

[0081] Suitable organic builders are further oligomaleic acids and their salts. Suitable organic builders are terpolymers of unsaturated C4-C8 dicarboxylic acids, which may contain copolymerized monomers from group (i) containing up to 95% by weight of monoethylenically unsaturated monomers, group (ii) containing up to 60% by weight of monoethylenically unsaturated monomers, and group (iii) containing up to 20% by weight of monoethylenically unsaturated monomers. Suitable unsaturated C4-C8 dicarboxylic acids in the present invention 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 monocarboxylic acids.22 Group (ii) includes C2-C6 olefins, vinyl alkyl ethers with C1-C8 alkyl groups, styrene, vinyl esters of C1-C8 carboxylic acids, (meth)acrylamides, and vinylpyrrolidone. From group (ii), it is preferred to use C2-C6 olefins, vinyl alkyl ethers with C1-C4 alkyl groups, vinyl acetate, and vinyl propionate. When polymers of group (ii) contain vinyl esters in polymerized form, they may be partially or completely hydrolyzed to form 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.

[0082] Further organic builders applicable to the present invention include homopolymers of monoethylenically unsaturated C3-C8 monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, and vinylacetic acid. Homopolymers of acrylic acid and methacrylic acid are particularly preferred. Copolymers of dicarboxylic acids are also preferred, such as copolymers of maleic acid and acrylic acid obtained in a weight ratio of 10:90 to 95:5, with those having a weight ratio of 30:70 to 90:10 and a molecular weight of 1,000 to 150,000 being particularly preferred. Copolymers of itaconic acid and acrylic acid in a weight ratio of 10:90 to 95:5 are also suitable. Terpolymers composed of maleic acid, acrylic acid, and vinyl esters of C1-C3 carboxylic acids, with a weight ratio of (maleic acid):(acrylic acid + vinyl ester) = 10:90 to 95:10, are also preferred. In this case, the weight ratio of acrylic acid to vinyl ester may be in the range of 30:70 to 70:30. Also useful are copolymers of maleic acid and C2-C8 olefin in a molar ratio of 40:60 to 80:20, and particularly preferred are copolymers of maleic acid and ethylene, propylene, or isobutene in a molar ratio of 50:50.

[0083] Further suitable organic builders include copolymers of 50 to 98% by weight of an ethylenically unsaturated weakly acidic carboxylic acid and 2 to 50% by weight of an ethylenically unsaturated sulfonic acid. Ethylenically unsaturated carboxylic acids suitable for the present invention are particularly preferred C3 to C6 monocarboxylic acids, such as acrylic acid and methacrylic acid. Suitable ethylenically unsaturated sulfonic acids include 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 thereof. These copolymers may further contain 0 to 30% by weight of an ethylenically unsaturated C4-C8 dicarboxylic acid (e.g., maleic acid) and / or 0 to 30% by weight of at least one monomer copolymerizable with the aforementioned monomers. Examples of the latter include C1-C4 alkyl esters of (meth)acrylic acid, C1-C4 hydroxyalkyl esters of (meth)acrylic acid, acrylamide, alkyl-substituted acrylamides, N,N-dialkyl-substituted acrylamides, vinylphosphonic acid, vinyl acetate, allyl alcohol, sulfonated allyl alcohol, styrene and other vinyl aromatic compounds, acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, and N-vinylpyridine. The weight-average molecular weight of these copolymers ranges from 3,000 to 50,000 daltons. Particularly preferred embodiments include copolymers of an ethylenically unsaturated C3-C6 monocarboxylic acid and at least one ethylenically unsaturated sulfonic acid, and a copolymer of acrylic acid and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) is particularly preferred. (This type of polymer is commercially available under the trademark ACUSOL 588 of Dow Chemical Company.)) A particularly suitable copolymer is one that consists 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.

[0084] Suitable organic builders include graft polymers in which unsaturated carboxylic acids are grafted onto low-molecular-weight carbohydrates or reduced carbohydrates. Suitable unsaturated carboxylic acids in this context include, 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, grafted in an amount of 40 to 95% by weight relative to the grafted component. Furthermore, up to 30% by weight of further monoethylenically unsaturated monomers, based on the grafted component, can also be used. Suitable modifying monomers are those of groups (ii) and (iii) above. 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, polyalkylene glycols with a molar mass 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 C1-C 22 It's alcohol.

[0085] Further suitable organic builders are polyglyoxylic acids.

[0086] Suitable organic builders are furthermore polyamidocarboxylic acids and modified polyamidocarboxylic acids.

[0087] Suitable organic builders are also polyaspartic acid or aspartic acid and amino acids. , C4~C 25Mono- or dicarboxylic acids and / or C4-C 25 In a particular embodiment, it is prepared with phosphoric acid and is a co-condensation product of C6-C 22 Mono- or dicarboxylic acids or C6-C 22 It is a polyaspartic acid modified with mono- or diamines.

[0088] A preferred class of builders are polymeric compounds containing carboxylic acid groups. Particularly preferred as builders are polyacrylic acid homopolymers and copolymers, which may be in partially or fully neutralized form.

[0089] Suitable organic builders are furthermore iminodisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, alkylpolyaminocarboxylates, aminopolyalkylenephosphonates, polyglutamic acid, hydrophobically modified citric acids, for example agaric acid, poly-α-hydroxyacrylic acid, N-acylethylenediamine triacetates, for example lauroylethylenediamine triacetate, and alkylamides of ethylenediaminetetraacetic acid, for example EDTA tallowamide.

[0090] In certain embodiments, the automatic dishwashing 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, carboxymethylinulin and its salts, and mixtures of the above builders.

[0091] Suitable inorganic builders b) are, for example, crystalline or amorphous aluminosilicates with ion exchange properties, such as zeolites. Various types of zeolites are suitable, especially zeolites A and X. BPMAP and HS are their sodium salts or salts in which Na is partially exchanged with other cations, such as Li, K, Ca, Mg, or ammonium. Crystalline silicates suitable as builders are, for example, disilicates or layered silicates, such as 5-Na2Si2O5 or B-Na2Si2O5 (SKS 6 or SKS 7). Silicates can be used in the form of their alkali metal, alkaline earth metal, or ammonium salts, preferably sodium, lithium, and magnesium silicates. Amorphous silicates, such as sodium silicate with a polymeric structure, or amorphous disilicate (Britesil® H 20, manufacturer: Akzo) can also be used.

[0092] Suitable organic builders are further carbonates and bicarbonates.These can be used in the form of alkali metal, alkaline earth metal or ammonium salts.Preferably sodium carbonate, lithium and magnesium carbonate or sodium, lithium and magnesium bicarbonate, especially sodium carbonate and / or sodium bicarbonate, are used.

[0093] In a particular embodiment, a mixture of different builders is used as component b), which preferably comprises at least two of the following components: at least one polymeric compound containing carboxylic acid groups or carboxylic acid groups in partially or fully neutralized form (preferably polyacrylic acid or partially or fully neutralized form), at least one (poly)hydroxycarboxylic acid or its salts (preferably citric acid or citrates, in particular sodium citrate), at least one aminopolycarboxylic acid or its salts, preferably selected 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. Preferred are those selected from acids or aminophosphonic acids, preferably 1-hydroxyethane-1-(1,1-diphosphonic acid) (HEDP), at least one inorganic builder, carbonates, silicates and mixtures thereof.

[0094] Component c) (enzyme) The automatic dishwashing composition according to the invention may also comprise at least one enzyme (=component c)).

[0095] Suitable enzymes are those typically used as industrial enzymes, and these include, in particular, enzymes with optimal activity in the neutral to alkaline pH range.

[0096] When the automatic dishwashing 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.

[0097] The automatic dishwashing machine composition of the present invention preferably contains at least one enzyme in an amount of enzyme protein of 0.001 to 10 wt %, more preferably 0.005 to 8 wt %, and particularly 0.01 to 5 wt %, relative to the total weight of the composition.

[0098] 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 in combination with further additives, and the amounts mentioned above refer to the active enzyme protein, free of carriers, etc.

[0099] The enzyme is preferably selected from aminopeptidases, amylases, arabinases, carbohydrases, carboxypeptidases, catalases, cellulases, chitinases, cutinases, cyclodextrin glycosyltransferases, deoxyribonucleases, esterases, galactanases, alpha-galactosidases, beta-galactosidases, glucanases, glucoamylases, alpha-glucosidases, beta-glucosidases, haloperoxidases, hydrolases, invertases, isomerases, keratinases, laccases, lipases, mannanases, mannosidases, oxidases, pectinolytic enzymes, peptidoglutaminases, peroxidases, peroxygenases, phytases, polyphenol oxidases, proteolytic enzymes, ribonucleases, transglutaminases, transferases, xylanases and mixtures thereof.

[0100] In particular, the automatic dishwashing composition comprises one or more enzymes selected from amylases, arabinases, carbohydrases, cellulases (e.g., endoglucanases), cutinases, deoxyribonucleases, galactanases, haloperidol oxygenases, lipases, mannanases, oxidases (e.g., laccases and / or peroxidases), pectinases, pectin lyases, proteases, xylanases, xanthanases, xyloglucanases, oxidoreductases, and mixtures thereof. Preferably, the automatic dishwashing composition comprises at least one enzyme selected from amylases, arabinases, carbohydrases, cellulases, galactanases, lipases, mannanases, pectinases, pectin lyases, proteases, and mixtures thereof.

[0101] In particular embodiments, the automatic dishwashing composition comprises at least one amylase. When the composition comprises at least one amylase and at least one other enzyme, the other enzyme is preferably a protease and / or a lipase.

[0102] Proteases The composition may include one or more proteases, including those of bacterial, fungal, plant, viral, or animal origin. Proteases of microbial origin are preferred. The protease may be an alkaline protease, such as a serine protease or a metalloprotease. The serine protease may be, for example, from the SI family, such as trypsin, or the S8 family, such as subtilisin. The metalloprotease may be, for example, thermolysin, which belongs to family M4, or other metalloproteases belonging to families M5, M7, or M8.

[0103] An example of a metalloprotease is the neutral metalloprotease derived from Bacillus amyloliquefaciens and described in WO2007 / 044993 (Genencor Int.).

[0104] Suitable commercially available protease enzymes include those under the following brands: Alcalase®, Duralase®, Durazym®, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Blaze®, Blaze Evity® 100T, Blaze Evity® 125T, Blaze Evity® 150T, Neutrase®, Everlase®, Esperase®, Progress® Uno, and Progress® Excel (Novozymes). A / S), including those sold under the trade names Maxatase®, Maxacai®, Maxapem®, Purafect®, Purafect® Ox, Purafect® OxP, Purafect Prime®, Puramax®, FN2®, FN3®, FN4®, Excellase®, Excellenz P1000®, Excellenz P1250®, Eraser®, Preferenz® P100, Preferenz® P110, Effectenz P1000®, Effectenz P1050®, and Effectenz P2000®, Purafast®, Properase®, Opticlean® and Optimase® (Danisco / DuPont), Axapem® (Gist-Brocases NV)), BLAP (sequence shown in Figure 29 of U.S. Pat. No. 5,352,604) and variants thereof (Henkel AG) and KAP (Bacillus alkalophilus subtilisin), available commercially from Kao.

[0105] Lipase and cutinase Suitable lipases and cutinases include those of bacterial or fungal origin, including chemically modified or protein-engineered mutant enzymes. Examples include lipases from Thermomyces, such as T. lanuginosus (formerly known as Humicola lanuginosa), as described in EP 258068 and EP 305216, cutinases from Humicola, such as H. insolens (WO 96 / 13580), Pseudomonas alcaligenes or P. pseudoalcaligenes (EP 218272), Pseudomonas cepacia, and the like. Lipases from Pseudomonas strains (some of which have now been renamed Burkholderia), such as P. cepacia (EP331376), P. sp. strain SD705 (WO95 / 06720 and WO96 / 27002), and P. wisconsinensis (WO96 / 12012), GDSL-type Streptomyces lipase (WO2010 / 065455), cutinase from Magnaporthe grisea (WO2010 / 107560), and Pseudomonas mendocina (WO2010 / 107561). mendocina cutinase (US 5,389,536), Thermobifida fusca lipase (WO2011 / 084412), Geobacillus stearothermophilus lipase (WO2011 / 084417), Bacillus subtilis lipase (WO2011 / 084599), as well as Streptomyces griseus (WO2011 / 150157) and Streptomyces pristinaespiralis (S. Examples of lipases include those derived from Lactobacillus pristinaespiralis (WO2012 / 137147).

[0106] Preferred commercially available lipase products include Lipolase™, Lipex®, Lipolex® and Lipoclean® (Novozymes A / S), Lumafast (from Genencor) and Lipomax (from Gist-Brocades).

[0107] Also suitable are lipases called acyltransferases or perhydrolases, such as acyltransferases homologous to Candida antarctica lipase A (WO 2010 / 111143), acyltransferases from Mycobacterium smegmatis (WO 2005 / 056782), perhydrolases from the CE7 family (WO 2009 / 067279), as well as variants of Mycobacterium smegmatis perhydrolase, in particular the S54V variant used in the commercial product Gentle Power Bleach from Huntsman Textile Effects Pte Ltd (WO 2010 / 100028).

[0108] amylase Suitable amylases that can be used with proteases include alpha-amylases or glucoamylases and can be of bacterial or fungal origin, including chemically modified or protein-engineered variants. Examples of amylases include alpha-amylases obtained from special strains of bacillus, such as Bacillus licheniformis, which are described in detail in GB 1,296,839.

[0109] Suitable amylases include those having SEQ ID NO: 2 of WO95 / 10603 or variants having 90% sequence identity to SEQ ID NO: 3. Variants having substitutions at one or more of positions 15, 23, 105, 106, 124, 128, 133, 154, 156, 178, 179, 181, 188, 190, 197, 201, 202, 207, 208, 209, 211, 243, 264, 304, 305, 391, 408 and 444 are preferred and are set out in SEQ ID NO: 4 of WO94 / 02597, WO94 / 18314, WO97 / 43424 and WO99 / 19467.

[0110] More suitable amylases include the amylase having SEQ ID NO: 6 of WO02 / 10355, or a variant thereof having 90% sequence identity with SEQ ID NO: 6. A preferred post-valine sequence of SEQ ID NO: 6 has deletions at positions 181 and 182 and a substitution at position 193.

[0111] A further suitable amylase is a hybrid α-amylase comprising residues 1-33 of the α-amylase from B. amyloliquefaciens as set forth in SEQ ID NO: 6 of WO 2006 / 066594 and residues 36-483 of the B. licheniformis α-amylase as set forth in SEQ ID NO: 4 of WO 2006 / 066594 or a variant with 90% sequence identity. This hybrid α-amylase variant preferably has at least one substitution, deletion or insertion at the following positions: G48, T49, G107, H156, A181, N190, M197, I201, A209 and Q264. In the most suitable variant of the hybrid α-amylase comprising residues 1-33 of the α-amylase from Bacillus amyloliquefaciens shown in SEQ ID NO: 6 of WO2006 / 066594 and residues 36-483 of SEQ ID NO: 4, the following substitutions are made: M197T; Hl56Y+A181T+Nl90F+A209V+Q264S; or G48A+T49I+G107A+H156Y+A181T+N190F+I201F+A209V+Q264S.

[0112] Further suitable amylases are those having the sequence of SEQ ID NO: 6 of WO99 / 19467, or variants having 90% sequence identity to SEQ ID NO: 6. Preferred variants of SEQ ID NO: 6 are those having substitutions, deletions or insertions at one or more of the following positions: R181, G182, H183, G184, N195, I206, E212, E216 and K269. Particularly preferred amylases are those having deletions at positions R181 and G182, or at positions H183 and G184.

[0113] Further suitable amylases that may be used are those having SEQ ID NO:1, SEQ ID NO:3, SEQ ID NO:2 or SEQ ID NO:7 of WO96 / 23873, or variants thereof having 90% sequence identity to SEQ ID NO:1, SEQ ID NO:2, SEQ ID NO:3 or SEQ ID NO:7. Preferred variants of SEQ ID NO:1, SEQ ID NO:2, SEQ ID NO:3 or SEQ ID NO:7 are those having substitutions, deletions or insertions at one or more of positions 140, 181, 182, 183, 184, 195, 206, 212, 243, 260, 269, 304 and 476, numbering using SEQ ID NO:2 of WO96 / 23873. More preferred variants are those having deletions at two positions selected from 181, 182, 183 and 184 (e.g., 181 and 182, 182 and 183, or positions 183 and 184). The most preferred amylase variants of SEQ ID NO:1, SEQ ID NO:2 or SEQ ID NO:7 have a deletion at positions 183 and 184 and one or more substitutions at positions 140, 195, 206, 243, 260, 304 and 476.

[0114] Further suitable amylases that can be used are amylases having SEQ ID NO: 2 of WO2008 / 153815, SEQ ID NO: 10 of WO01 / 66712, or variants thereof having 90% sequence identity with SEQ ID NO: 2 of WO2008 / 153815 or 90% sequence identity with SEQ ID NO: 10 of WO01 / 66712. Preferred variants of SEQ ID NO: 10 in WO01 / 66712 are those which have substitutions, deletions or insertions at one or more of the following positions: 176, 177, 178, 179, 190, 201, 207, 211 and 264.

[0115] Further suitable amylases are those having SEQ ID NO: 2 of WO2009 / 061380 or variants thereof having 90% sequence identity to SEQ ID NO: 2. Preferred variants of SEQ ID NO: 2 have C-terminal truncations and / or substitutions, deletions or insertions at one or more of the following positions: Q87, Q98, S125, N128, T131, T165, K178, R180, S181, T182, G183, M201, F202, N225, S243, N272, N282, Y305, R309, D319, Q320, Q359, K444 and G475. More preferred variants of SEQ ID NO:2 are those having substitutions at one or more of the following positions: Q87E, R, Q98R, S125A, N128C, T131I, T165I, K178L, T182G, M201L, F202Y, N225E, R, N272E, R, S243Q, A, E, D, Y305R, R309A, Q320R, Q359E, K444E and G475K, and / or deletions at positions R180 and / or S181, or T182 and / or G183. The most preferred amylase variants of SEQ ID NO:2 are those having substitutions: N128C+K178L+T182G+Y305R+G475K; N128C+K178L+T182G+F202Y+Y305R+D319T+G475K; S125A+N128C+K178L+T182G+Y305R+G475K; or S125A+N128C+T131I+T165I+K178L+T182G+Y305R+G475K wherein the variant is C-terminally truncated and optionally further comprises a substitution at position 243 and / or a deletion at positions 180 and / or 181.

[0116] A further suitable amylase is the amylase having SEQ ID NO: 1 of WO2013 / 184577 or a variant thereof having 90% sequence identity to SEQ ID NO: 1. Preferably, the variant of SEQ ID NO: 1 has substitutions, deletions or insertions at one or more of the following positions: K176, R178, G179, T180, G181, E187, N192, M199, 1203, S241, R458, T459, D460, G476 and G477. More preferably, the variant of SEQ ID NO: 1 has a substitution at one or more of the following positions: K176L, E187P, N192FYH, M199L, I203YF, S241QADN, R458N, T459S, D460T, G476K and G477K, and / or a deletion at positions R178 and / or S179, or T180 and / or G181. Most preferably, the variant of SEQ ID NO: 1 has the following substitutions: E187P+I203Y+G476K E187P+I203Y+R458N+T459S+D460T+G476K, optionally further comprising a substitution at position 241 and / or a deletion at positions 178 and / or 179.

[0117] Further suitable amylases are those having SEQ ID NO: 1 of WO2010 / 104675 or variants thereof having 90% sequence identity to SEQ ID NO: 1. Preferably, the SEQ ID NO: 1 variant has one or more substitutions, deletions or insertions at the following positions: N21, D97, V128 K177, R179, S180, I181, G182, M200, L204, E242, G477 and G478.

[0118] Further suitable amylases are α-amylases having SEQ ID NO: 12 of WO01 / 66712, or variants having at least 90% sequence identity to SEQ ID NO: 12. Preferably, the amylase variants have substitutions, deletions or insertions at one or more of the following positions of SEQ ID NO: 12 of WO01 / 66712: R28, R118, N174; R181, G182, D183, G184, G186, W189, N195, M202, Y298, N299, K302, S303, N306, R310, N314; R320, H324, E345, Y396, R400, W439, R444, N445, K446, Q449, R458, N471, N484. Particularly preferred amylases include variants having a deletion of D183 and G184 and substitutions of R118K, N195F, R320K and R458K, as well as variants with further substitutions at one or more positions selected from M9, G149, G182, G186, M202, T257, Y295, N299, M323, E345 and A339, most preferably variants with further substitutions at all of these positions.

[0119] Suitable commercially available amylases include Duramyl®, Termamyl®, Fungamil®, Stainzyme®, Stainzyme Plus®, Natalase®, Liquozyme X, BAN®, Amplify® and Amplify® Prime (from Novozymes A / S), as well as Rapidase®, Purastar® / Effectenz®, Powerase, Preferenz SI000, Preferenz SI00 and Preferenz SI 10 (from Genencor International Inc. / DuPont).

[0120] Deoxyribonucleases (DNases) Suitable deoxyribonucleases (DNases) are any enzymes that catalyze the hydrolytic cleavage of phosphodiester bonds in the DNA backbone, degrading DNA. DNases obtained from bacteria are preferred, particularly those obtained from Bacillus species, and particularly those obtained from Bacillus subtilis or Bacillus licheniformis. Examples of such DNases are described in WO2011 / 098579 and WO2014 / 087011.

[0121] oxidoreductase In one embodiment, the composition may comprise an oxidoreductase, which is an enzyme that catalyzes an oxidation-reduction reaction. A preferred oxidoreductase is superoxide dismutase.

[0122] The enzymes can be a separate component of the automatic dishwashing composition, for example, they can be contained in a separate compartment of a multi-compartment formulation, or they can be used in the form of an enzyme-containing film.

[0123] Automatic dishwashing compositions preferably contain at least one protease and / or amylase.

[0124] In certain embodiments, there is at least one enzyme mixture, for example, an enzyme mixture comprising or consisting of the following enzymes is preferred: proteases and amylases, proteases and lipases (or lipolytic enzymes), proteases and cellulases, amylase, cellulase and lipase (or lipolytic enzymes), proteases, amylases and lipases (or lipolytic enzymes), Proteases, lipases (or fat-degrading enzymes) and cellulases.

[0125] The enzymes may be adsorbed onto a carrier material to protect them from premature decomposition. If desired, the automatic dishwashing composition may also include an enzyme stabilizer, such as propyl phosphate. Examples of suitable boronic acids include calcium formate, sodium formate, boric acid, boronic acids and their salts such as 4-formylphenylboronic acid, peptides and peptide derivatives such as peptide aldehydes, polyols such as propane-1,2-diol, and mixtures thereof.

[0126] Component d) (bleaching agent) In this application, the term "bleach" also refers to a bleach system, optionally including a bleach activator, a bleach catalyst, and / or a bleach stabilizer.

[0127] The automatic dishwashing compositions of the present invention preferably contain 0 to 30 wt. %, more preferably 0 to 25 wt. % of at least one bleaching agent (component d), based on the total weight of the composition. When the automatic dishwashing composition contains at least one bleaching agent, the amount is at least 0.5 wt. %, more preferably at least 1 wt. %, based on the total weight of the composition. When the bleaching agent contains two or more components, the above amounts refer to the sum of all components of the bleach system.

[0128] Suitable bleaching agents are, for example, percarboxylic acids, such as diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or -terephthalic acid, salts of percarboxylic acids, such as sodium percarbonate, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide with organic compounds, such as urea perhydrate, or inorganic peroxo salts, such as alkali metal persulfates or peroxodisulfates.

[0129] Suitable bleach activators are, for example, polyacylated sugars, such as pentaacetylglucose; acyloxybenzenesulfonic acids and their alkali metal and alkaline earth metal salts, such as sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; N,N-diacylated and N,N,N',Ni-tetraacylated amines, such as N,N,N',N'-tetraacetylmethylenediamine and ethylenediamine (TAED); N,N-diacetylaniline, N,N-diacetyl-p- Toluidine or 1,3-diacidylhydantoin, for example 1,3-diacetyl-5,5-dimethylhydantoin; N-alkyl-N-sulfonylcarbonamides, for example N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide; N-acylated cyclic hydrazides, acylated triazoles or urazoles, for example monoacetylmaleic hydrazide; O,N,N-trisubstituted hydroxylamines, for example O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinylhydroxylamine. or O,N,N-triacetylhydroxylamine; N,N'-diacylsulfurylamides, such as N,N'-dimethyl-N,N'-diacetylsulfurylamide or N,N'-diethyl-N,N'-dipropionylsulfurylamide; acylated lactams, such as acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam; anthranil derivatives, such as 2-methylanthranil or 2-phenylanthranil; triacylcyanurates, such as triacetylcyanurates. oxime esters and bisoxime esters, for example, O-acetylacetone oxime or bisisopropyliminocarbonate; carboxylic acid anhydrides, for example, acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; enol esters, for example, isopropenyl acetate; 1,3-diacyl-4,5-diacyloxyimidazolines, for example, 1,3-diacetyl-4,5-diacetoxyimidazoline; tetraacetylglycoluril and tetrapropionylglycoluril;Diacyl 2,5-diketopiperazines, such as 1,4-diacetyl-2,5-diketopiperazine; ammonium-substituted nitriles, such as N-methylmorpholinioacetonenitrile methyl sulfate; acylation products of propylene diurea and 2,2-dimethylpropylene diurea, such as tetraacetylpropylene; diurea; α-acyloxypolyacylmalonamides, such as α-acetoxy-N,N'-diacetylmalonamide; diacyldioxohexahydro-1,3,5-triazines, such as 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine; benz-(4H)-1,3-oxazin-4-ones bearing an alkyl radical, such as methyl, or an aromatic radical, such as phenyl, in the 2-position.

[0130] The bleaching system, consisting of a bleaching agent and a bleach activator, may optionally contain a bleaching catalyst. Suitable bleaching catalysts are, for example, the quaternized imines and sulfonimines described in U.S. Pat. No. 5,360,569 and EP-A-453003. Particularly effective bleaching catalysts are, for example, the manganese complexes described in WO 94 / 21777. In addition to the bleaching systems described above, consisting of a bleaching agent, a bleach activator, and optionally a bleaching catalyst, it is also possible to use systems involving enzymatic peroxide washing.

[0131] Component e) (Rheology Modifier) In order to impart the desired viscosity to liquids, in particular to water-containing automatic dishwashing compositions, it is possible to use at least one rheology modifier (= component e)). In the context of this application, the terms "rheology modifier" and "thickener" are used synonymously.

[0132] The automatic dishwashing compositions of the present invention preferably comprise 0 to 10 wt. %, more preferably 0 to 8 wt. %, especially 0 to 6 wt. % of at least one rheology modifier (component e), based on the total weight of the composition. If the automatic dishwashing composition comprises at least one bleaching agent, the amount thereof is at least 0.1 wt. %, more preferably at least 0.3 wt. %, based on the total weight of the composition.

[0133] In principle, any known rheology modifier (thickener) is suitable, provided that it does not adversely affect the operation of the dishwashing composition.

[0134] Suitable thickening agents may be naturally occurring or synthetic.

[0135] Examples of naturally occurring thickeners are xanthan gum, carob seed flour, guar gum, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrin, pectin, and cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, etc.

[0136] Naturally occurring thickeners are also inorganic thickeners, such as polysilicic acids and clay minerals, such as sheet silicates, and the silicates specified for builder b).

[0137] Examples of synthetic thickeners are polyacrylic and polymethacrylic acid compounds, for example (partially) crosslinked homopolymers of acrylic acid crosslinked with allyl ethers of sucrose or pentaerythritol, or homopolymers of acrylic acid crosslinked with propylene (Carbomer), for example the Carbopol® products from Lubrizol or the Polygel® products from 3V Sigma; copolymers of ethylenically unsaturated mono- or dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl or ethyl acrylate and (meth)acrylates derived from long-chain ethoxylated alcohols, for example the Acusol® products from Dow; copolymers of two or more monomers selected from acrylic acid, methacrylic acid and their C1-C4-alkyl esters, for example methacrylic acid, butyl acrylate and methyl methacrylate or butyl acrylate and methyl methacrylate. copolymers, such as the Aculyn® and Acusol® products from Dow, or crosslinked high molecular weight acrylic acid copolymers, such as copolymers crosslinked with allyl ethers of sucrose or pentaerythritol, C 10 ~C 30 -copolymers of alkyl acrylates with one or more comonomers selected from acrylic acid, methacrylic acid and their C1-C4-alkyl esters.

[0138] Suitable synthetic thickeners are also reaction products of maleic acid polymers with ethoxylated long chain alcohols, polyethylene glycols, polyamides, polyimines and polycarboxylic acids.

[0139] Mixtures of two or more of the above thickeners are also suitable.

[0140] Preferred thickening agents are xanthan and the polyacrylic and polymethacrylic acid compounds described above.

[0141] Further additives (component f) The automatic dishwashing composition may comprise at least one further additive as additive f), which is preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting builders, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antimicrobial components, antioxidants, and mixtures thereof.

[0142] Suitable for the automatic dishwashing compositions of the present invention are in principle typical additives known to those skilled in the art. In the following, suitable and preferred embodiments of some additives are defined in detail.

[0143] The automatic dishwashing composition of the present invention preferably comprises 0 to 90 wt. %, more preferably 0 to 80 wt. %, of at least one additive different from components a) to e) (component e)), based on the total weight of the composition. This amount refers to the total weight of all additives. In the following, the individual amounts for the single additives are defined.

[0144] When the automatic dishwashing composition comprises at least one further additive, the amount is at least 0.01 wt. %, more preferably at least 0.1 wt. %, based on the total weight of the composition.

[0145] surfactants Suitable surfactants f) are nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof.

[0146] In certain embodiments, the automatic dishwashing composition comprises at least one nonionic surfactant. In even more certain embodiments, the automatic dishwashing composition comprises only nonionic surfactants.

[0147] In general, nonionic and ionic surfactants having at least one nonpolar group and at least one polar group, and including a polyether group, are suitable.

[0148] Suitable nonionic surfactants are surfactants containing polyether groups, preferably alkyl polyoxyalkylene ethers, aryl polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers, alkoxylated animal and / or vegetable fats and / or oils, fatty amine alkoxylates, fatty acid amide alkoxylates. esters, fatty acid diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid esters and mixtures thereof.

[0149] Suitable nonionic surfactants g) are, for example, surfactants containing a polyether group PE, for example low molecular weight C3-C6 alcohols or C7-C 30 Alkyl polyoxyalkylene ethers derived from fatty alcohols, where the ether component may 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.

[0150] Suitable nonionic surfactants g) are furthermore fatty alcohol alkoxylates and oxoalcohol alkoxylates of isotridecyl alcohol polyoxyethylene ethers and oleyl alcohol polyoxyethylene ethers.

[0151] Hydroxyl-containing polyoxyalkylene ethers and polyoxyalkylene esters are also suitable, including, for example, polyoxyethylene lauryl alcohol acetate.

[0152] Also suitable are alkylaryl alcohol polyoxyethylene ethers, such as octylphenol polyoxyethylene ethers, alkoxylated animal and / or vegetable fats and / or oils, such as corn oil ethoxylate, castor oil ethoxylate, tallow ethoxylate, alkylphenol alkoxylates, such as ethoxylated isooctyl-, octyl- or nonylphenol, tributylphenol polyoxyethylene ether, fatty amine alkoxylates, fatty acid amide and fatty acid diethanolamide alkoxylates, in particular their ethoxylates, and polyoxyalkylene sorbitan fatty acid esters.

[0153] Further suitable as surfactants g) are alkyl polyether sulfates, such as sodium dodecylpoly(oxyethylene) sulfate (sodium lauryl ether sulfate, SLES).

[0154] Suitable nonionic surfactants g) are further glyceryl esters, such as glyceryl monostearate, sugar surfactants, sorbitol esters, such as sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkyl gluconamides, alkyl methyl sulfoxides, alkyl dimethyl phosphine oxides, such as tetradecyl dimethyl phosphine oxide.

[0155] Suitable anionic surfactants g) are soaps, alkylsulfonates, alkylbenzenesulfonates, olefinsulfonates, methyl ester sulfonates, sulfofatty acids, alkyl sulfates, mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, alkyl glucose carboxylates, protein fatty acid condensates and alkyl (ether) phosphates.

[0156] Suitable anionic surfactants g) are also surfactants containing polyether groups, preferably alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfates, alkyl ... The alkyl aryl polyether phosphate may be selected from alkyl polyether sulfonates, alkyl aryl polyether sulfonates, alkyl polyether phosphates, aryl polyether phosphates, alkyl aryl polyether phosphates, glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether) sulfates, fatty acid amide ether sulfates, and mixtures thereof.

[0157] Suitable amphoteric surfactants g) are, for example, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or alkyl amphopropionates, alkyl amphodiacetates or alkyl amphodipropionates, such as cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine, sodium cocoamphopropionate, tetradecyldimethylamine oxide, etc.

[0158] Suitable cationic surfactants g) include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkyl sulfates, as well as pyridine and imidazoline derivatives, in particular alkylpyridinium halides. For example, behenyl chloride or cetyltrimethylammonium chloride can be used.

[0159] solvent Suitable organic solvents g) are selected from monohydric or polyhydric alcohols, alkanolamines and glycol ethers.Solvent g) is preferably selected from ethanol, n- or isopropanol, butanol, 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 t-butyl ether and mixtures of these solvents.

[0160] Antifoaming agents / foam inhibitors / foam suppressors Useful suds inhibitors (also referred to as antifoam agents or suds suppressors) f) include, for example, soap, paraffin or silicone oil, alkyl phosphate esters or combinations thereof.

[0161] The automatic dishwashing composition of the present invention preferably comprises 0 to 10 wt.-%, more preferably 0 to 5 wt.-%, and in particular 0 to 1.5 wt.-% of at least one antifoaming agent g), based on the total weight of the composition. If the automatic dishwashing composition comprises at least one antifoaming agent, the amount thereof is at least 0.0001 wt.-%, more preferably at least 0.001 wt.-%, and in particular at least 0.01 wt.-%, based on the total weight of the composition.

[0162] The compositions of the present invention preferably contain a suds suppressor, especially when the compositions contain anionic surfactants. Preferred silicone suds suppressors are polydimethylsiloxanes capped with trimethylsilyl or other end groups. These are suitable for use with silica and They may also be incorporated as non-silicone surfactants. Suitable silicone suds suppressors include solid silica, silicone fluids, or silicone resins. Silicone suds suppressors may be in the form of granules or liquids, for example. Other silicone-based suds suppressors include dimethylpolysiloxane, hydrophilic polysiloxane compounds with polyethyleneoxy-propyleneoxy groups in the side chains, and finely divided silica.

[0163] Suitable phosphate ester suds suppressors are alkyl phosphate esters containing 16 to 20 carbon atoms. Such phosphate ester suds suppressors may be monostearate or monooleate phosphate or salts thereof, preferably alkali metal salts.

[0164] base Suitable bases (also referred to as alkalinity sources or alkalinity reserves) 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 hydrogen carbonate, alkali metal silicates and mixtures thereof. The pH value of the wash liquor of the automatic dishwashing composition according to the invention is typically in the alkaline range, preferably in the range of 7.5 to 12, more preferably 8.0 to 10.0.

[0165] Furthermore, the automatic dishwashing compositions according to the invention may contain further additives g) which further improve their performance and / or aesthetic properties. To improve the aesthetic impression of the dishwashing compositions according to the invention, they can be colored, for example, with suitable dyes. Preferred dyes, the selection of which does not present any difficulty to those skilled in the art, have high storage stability and insensitivity to the other components of the composition and to light.

[0166] Hydrotrope Current dishwashing compositions often contain anionic surfactants, which can gel unless prevented by various solvents or hydrotropes. Hydrotropes act as viscosity control agents, gel inhibitors, stabilizers, and dispersibility builders. Commonly used hydrotropes include alcohols and alcohol derivatives, including glycols and alkoxylated alcohols. Hydrotropes suitable for use herein include anionic-type hydrotropes, particularly sodium xylene sulfonate, potassium and ammonium xylene sulfonate, sodium toluene sulfonate, potassium and ammonium toluene sulfonate, sodium cumene sulfonate, potassium and ammonium cumene sulfonate, and mixtures thereof, as well as related compounds. The automatic dishwashing compositions of the present invention preferably contain 0 to 15 wt. %, more preferably 0.1 to 10 wt. %, and especially 1 to 8 wt. % of the hydrotrope, based on the total weight of the composition.

[0167] water (ingredient g)) The automatic dishwashing composition may comprise water. Preferably, the automatic dishwashing composition according to the present invention comprises water in an amount of 0 to 90 wt. %, more preferably 0 to 80 wt. %, based on the total weight of the composition.

[0168] When the automatic dishwashing composition includes water, the amount is at least 0.1 wt. %, more preferably at least 1.0 wt. %, based on the total weight of the composition. Water-containing ADW compositions can be in liquid or gel form, and multi-compartment formulations can include one or more components, including water.

[0169] The automatic dishwashing composition preferably comprises: a) at least one structural polypeptide; b) at least one builder (also called a sequestering agent, builder material, complexing agent, chelating agent, chelating compound, softener or crystal growth inhibitor); c) optionally at least one enzyme; d) optionally at least one bleaching agent; e) optionally water; f) optionally at least one rheology modifier, and g) optionally comprising at least one further additive different from components a) to f), preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antibacterial components, antioxidants.

[0170] The automatic dishwashing composition preferably comprises, based on the total weight of the composition: a) 0.0005 to 2.5% by weight, based on the total weight of the composition, of at least one structural polypeptide; b) 1 to 90 wt. % of at least one builder, based on the total weight of the composition; c) 0 to 10% by weight (preferably 0.001 to 10% by weight, more preferably 0.005 to 8% by weight, in particular 0.01 to 5% by weight) of at least one enzyme, based on the proportion of enzyme protein in the total weight of the composition; d) 0 to 30 wt. % (preferably at least 0.5 wt. %, more preferably at least 1 wt. %) of at least one bleaching agent component, based on the total weight of the composition; e) 0 to 10 wt. % (preferably at least 0.1 wt. %, more preferably at least 0.3 wt. %) of at least one rheology modifier, based on the total weight of the composition; f) 0 to 90% by weight (preferably at least 0.01% by weight, more preferably at least 0.1% by weight) of at least one additive different from components a) to e), based on the total weight of the composition, preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antimicrobial components, antioxidants, and mixtures thereof; and g) 0 to 90 wt. % (preferably at least 0.1 wt. %, more preferably at least 1.0 wt. %) water, based on the total weight of the composition, provided that the weights of components a) through g) add up to 100 wt. %.

[0171] The automatic dishwashing composition more preferably comprises, based on the total weight of the composition: a) 0.001 to 2.0% by weight, based on the total weight of the composition, of at least one structural polypeptide; b) 2 to 80 wt. % of at least one builder, based on the total weight of the composition; c) 0 to 8% by weight (preferably 0.001 to 10% by weight, more preferably 0.005 to 8% by weight, in particular 0.01 to 5% by weight) of at least one enzyme, based on the proportion of enzyme protein in the total weight of the composition; d) 0 to 20% by weight (preferably at least 0.5% by weight, more preferably at least 1% by weight) of at least one bleaching agent, based on the total weight of the composition; e) 0 to 8 wt. % (preferably at least 0.1 wt. %, more preferably at least 0.3 wt. %) of at least one rheology modifier, based on the total weight of the composition; f) 0 to 80% by weight (preferably at least 0.01% by weight, more preferably at least 0.1% by weight) of at least one additive different from components a) to e), based on the total weight of the composition, preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antimicrobial components, antioxidants, and mixtures thereof; and g) 0 to 90 wt. % (preferably at least 0.1 wt. %, more preferably at least 1.0 wt. %) water, based on the total weight of the composition, provided that the weights of components a) through g) add up to 100 wt. %.

[0172] A particular embodiment of the present invention is an automatic dishwashing composition in gel form. In the present invention, this means that the composition is in the form of a gel under standard conditions (20°C). A gel-like consistency has a higher viscosity than a liquid and is particularly self-sustaining, meaning that it can retain a desired shape without a shape-sustaining container. However, in contrast to a solid form, a gel form is easily deformed or poured upon heating and / or shear forces. The viscosity of an automatic dishwashing composition in gel form at 20°C is preferably in the range of 600 to 10,000,000 mPa·s, more preferably 1,000 to 1,000,000 mPa·s, and especially 2,000 to 500,000 mPa·s. Measurements can be performed at 20°C using a Brookfield viscometer. Depending on the viscosity, the spindle and rotation speed must be adapted.

[0173] All embodiments described above with respect to automatic dishwashing compositions can also be applied to manual dishwashing compositions, unless technically stated to the contrary. The same applies to all methods and uses described above.

[0174] In all the above aspects / embodiments, the structural polypeptide, in particular the silk polypeptide, is preferably present in the (automatic / manual) dishwashing composition in the form of a gel, in particular a hydrogel.

[0175] Various modifications and variations of this 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. [Brief explanation of the drawings]

[0176] [Figure 1] FIG. 11 is a digital image analysis of a drinking glass surface from a comparative rinse aid test of automatic dishwashing detergents according to Fresenius Standard Method 03 2016. DETAILED DESCRIPTION OF THE INVENTION

[0177] 1.a) a structural polypeptide; b) (automatic / manual) dishwashing compositions comprising at least one builder.

[0178] 2. The (automatic / manual) dishwashing composition of embodiment 1, wherein the structural polypeptide in a) is a silk polypeptide.

[0179] 3. The (automatic / manual) dishwashing composition according to embodiment 2, wherein said silk polypeptide is a recombinant or synthetic silk polypeptide, preferably a silk polypeptide from spiders.

[0180] 4. The silk polypeptide is comprising or consisting of protein chains that do not have at least two identical sequence motifs (single units of amino acids), or, comprising or consisting of at least two identical repeat units, 4. The (automatic / manual) dishwashing composition according to embodiment 2 or 3.

[0181] 5. Any of embodiments 2-4, wherein the silk polypeptide does not contain any non-repeated units. The (automatic / manual) dishwashing composition according to claim 1.

[0182] 6. The single or repeating units of the amino acids are: Module C having the amino acid sequence of SEQ ID NO: 1 or a variant thereof; Module C having the amino acid sequence of SEQ ID NO: 2 or a variant thereof Cys , Module C having the amino acid sequence of SEQ ID NO: 3 or a variant thereof Lys , 6. The (automatic / manual) dishwashing composition according to embodiment 4 or 5, independently selected from the group consisting of:

[0183] 7. The silk polypeptide is (C)m, (C)mC Cys , (C)mC Lys , C Cys (C)m, C Lys (C)m, (C Cys )m and (C Lys 7. The (automatic / manual) dishwashing composition according to any one of embodiments 2 to 6, wherein m is selected from the group consisting of:

[0184] 8. The silk polypeptide is C1, C2, C3, C4, C5, C6, C7, C8, C 16 , C 32 , 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) 16 C Cys , (C) 32 C Cys , (C) 48 C Cys , (C)1C Lys , (C)2C Lys , (C)3CLys 、(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 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、CLys 7. C Lys 8. C Lys 16 , C Lys 32 and C Lys 48 8. The (automatic / manual) utensil cleaning composition according to embodiment 7, selected from the group consisting of:

[0185] 9. A composition for (automatic / manual) utensil cleaning according to any one of embodiments 1 to 8, comprising 0.0005 to 2.5 wt. %, preferably 0.001 to 2.0 wt. %, in particular 0.005 to 1.5 wt. % of at least one structural polypeptide (component a), based on the total weight of the composition.

[0186] 10. The (automatic / manual) dishwashing composition according to any one of the preceding embodiments, comprising 1 to 90% by weight, preferably 2 to 80% by weight, in particular 10 to 50% by weight, of at least one builder (component b), based on the total weight of the composition.

[0187] 11. The (automatic / manual) dishwashing composition according to any of embodiments 1 to 10, comprising at least one enzyme (component c).

[0188] 12. The (automatic / manual) dishwashing composition according to any of the preceding embodiments, comprising at least 0.001 wt.-%, preferably at least 0.01 wt.-%, in particular at least 0.05 wt.-%, of at least one enzyme (component c), based on the total weight of the composition.

[0189] 13. The (automatic / manual) dishwashing composition of any of embodiments 1 to 12, comprising at least one bleaching agent (component d).

[0190] 14. The (automatic / manual) dishwashing composition according to any one of embodiments 1 to 13, comprising 0.5 to 30 wt.-%, preferably 1 to 25 wt.-%, of at least one bleaching agent (component d), based on the total weight of the composition.

[0191] 15. The (automatic / manual) dishwashing composition of any of embodiments 1 to 14, comprising at least one rheology modifier (component e).

[0192] 16. The (automatic / manual) dishwashing composition according to any one of the preceding embodiments, comprising 0.1 to 10 wt.-%, preferably 0.3 to 6 wt.-%, of at least one rheology modifier (component e), based on the total weight of the composition.

[0193] 17. The (automatic / manual) dishwashing composition according to any one of the preceding embodiments, further comprising at least one additive different from components a) to e) (=component f)), preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antimicrobial components, antioxidants and mixtures thereof.

[0194] 18. The (automatic / manual) dishwashing composition of any one of embodiments 1 to 17, comprising water (component g).

[0195] 19. a) at least one structural polypeptide; b) at least one builder; c) optionally at least one enzyme; d) optionally at least one bleaching component; e) optionally at least one thickening agent; f) optionally at least one further additive different from components a) to e), preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antimicrobial components, antioxidants and mixtures thereof; and g) optionally containing water; 19. The (automatic / manual) dishwashing composition according to any one of embodiments 1 to 18.

[0196] 20. a) 0.0005 to 2.5% by weight, based on the total weight of the composition, of at least one structural polypeptide; b) 1 to 90 wt. % of at least one builder, based on the total weight of the composition; and c) 0 to 10% by weight (preferably 0.001 to 10% by weight, more preferably 0.005 to 8% by weight, particularly 0.01 to 5% by weight) of at least one enzyme based on the proportion of enzyme protein in the total weight of the composition; d) 0 to 30 wt. % (preferably at least 0.5 wt. %, more preferably at least 1 wt. %) of at least one bleaching agent component, based on the total weight of the composition; e) 0 to 10 wt. % (preferably at least 0.1 wt. %, more preferably at least 0.3 wt. %) of at least one rheology modifier, based on the total weight of the composition; f) 0 to 90% by weight (preferably at least 0.01% by weight, more preferably at least 0.1% by weight) of at least one additive different from components a) to e), based on the total weight of the composition, preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antibacterial components, antioxidants, and mixtures thereof; g) 0 to 90% by weight (at least 0.1% by weight, more preferably at least 1.0% by weight) of water, based on the total weight of the composition, provided that the total weight of components a) to g) does not exceed 1. 20. The (automatic / manual) dishwashing composition of any one of embodiments 1 to 19, provided that the total weight of the composition is 00%.

[0197] 21. a) 0.001 to 2.0% by weight of at least one structural polypeptide, based on the total weight of the composition; b) 2 to 80 wt. % of at least one builder, based on the total weight of the composition; and c) 0 to 8% by weight (preferably 0.001 to 10% by weight, more preferably 0.005 to 8% by weight, particularly 0.01 to 5% by weight) of at least one enzyme, based on the proportion of enzyme protein in the total weight of the composition; d) 0 to 20% by weight (preferably at least 0.5% by weight, more preferably at least 1% by weight) of at least one bleaching agent, based on the total weight of the composition; e) 0 to 8 wt. % (preferably 0.001 to 10 wt. %, more preferably 0.005 to 8 wt. %, especially 0.01 to 5 wt. %) of at least one rheology modifier, based on the total weight of the composition; f) 0 to 80% by weight (preferably at least 0.01% by weight, more preferably at least 0.1% by weight) of at least one additive different from components a) to e), based on the total weight of the composition, preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antimicrobial components, antioxidants, and mixtures thereof; g) 0 to 90 wt. % (at least 0.1 wt. %, more preferably at least 1.0 wt. %) of water, based on the total weight of the composition, with the proviso that the weights of components a) to g) add up to 100 wt. %.

[0198] 22. The (automatic / manual) dishwashing composition of any of the preceding embodiments, wherein the automatic dishwashing composition is in gel form or the automatic dishwashing composition is a multi-compartment formulation containing a structural polypeptide in gel form.

[0199] 23. The composition for automatic / manual dishwashing according to any one of embodiments 22, wherein the structural polypeptide a) is in the form of a gel, preferably a hydrogel.

[0200] 24. A method of machine washing by contacting dishes to be washed with a (automatic / manual) dishwashing composition as defined in any of embodiments 1 to 23.

[0201] 25. Use of structural polypeptides, in particular silk polypeptides, in the above (automatic / manual) dishwashing compositions.

[0202] 26. The use according to embodiment 25, wherein the structural polypeptide a) is defined in any of embodiments 2 to 8, 22 or 23.

[0203] 27. Reduces staining and filming on tableware, especially glassware and cutlery; Gives tableware a good shine, Improves the ability to remove stains from dishes, Prevents recontamination of dishes, Provides surface protection to tableware, especially glassware, preventing corrosive changes to the surface; Reduces the surface tension of dishes, Reduces or eliminates the need for separate rinse aid products 27. Use according to embodiment 25 or 26 for improving the drying of tableware.

[0204] 28. Reduces staining and filming on tableware, especially glassware and cutlery; Gives tableware a good shine, Improves the ability to remove stains from dishes, Prevents recontamination of dishes, Provides surface protection to tableware, especially glass tableware, preventing corrosion and changes to the surface. Reduces the surface tension of dishes, Reduces or eliminates the need for separate rinse aid products Use of the (automatic / manual) dishwashing composition as defined in any of embodiments 1-23 in the treatment of soiled dishes (in an automatic dishwasher / manual) to improve drying of the dishes. [Example]

[0205] 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.

[0206] Example 1: I) Dishwashing detergent I.1) Gel formulation The following gel formulations 1 to 3 were prepared. In each case, component a) is a comparative example that does not contain the structural protein (silk protein) of the present invention. Formulation b) contains the structural protein (silk protein) of the present invention. Combination Agent 1 a) No structural protein (comparison example) b) comprising a structural protein gel containing 3% by weight of silk protein (according to the invention) Ingredients Weight% Silk Protein Gel (ingredient b) 3.0 (3% active ingredient = silk protein) 0.09% of the total content Sodium Citrate 30.0 (50% active ingredient) Builder Polyacrylic-Itaconic Acid Copolymer 9.0 Builder / Chelating Agent Polyacrylic Crosslinked Polymer 1.5 Rheology Modifier C 12 ~C 14 EO / PO Alkoxylate 2.2% (90% active ingredient) NI surfactant Glycerol 2.0 Solvent Protease 1.0 Enzyme Amylase 0.2 enzyme Benzisothiazolinone (BIT) 0.05 Preservative Sodium hydroxide (appropriate amount) to adjust the pH to 8.5 Deionized water (appropriate amount) Adjust to 100% Viscosity [mPas]: 4000 (Brookfield, 20 rpm, 24 °C) pH value: 8.5 Combination Agent 2 a) No structural protein (comparative example) b) comprising a structural protein gel containing 3% by weight of silk protein (according to the invention) Ingredients Weight% Silk Protein Gel (ingredient b) 3.0 (3% active ingredient = silk protein) 0.09% of the total content Sodium Polyacrylate 6.0 (40% active ingredient) (Mw=4000~6000) Builder / anti-redeposition agent Polyacrylic-Maleic Acid Copolymer 9.0 Builder / Chelating Agent EDTA 4.0 (40% active ingredient) Builders / Chelating Agents Sodium Citrate 0.5 (100% active ingredient) Xanthan Gum 1.0 Rheology Modifier C 12 ~C 14 EO / PO Alkoxylate 5.0% (100% active ingredient) NI surfactant Glycerol 2.0 Solvent Protease (Subtilisin) 4.0 (40% active ingredient) Enzyme Amylase 1.0 (40% active ingredient) Enzyme Benzisothiazolinone (BIT) 0.05 Preservative Sodium hydroxide (appropriate amount) to adjust the pH to 8.5 Deionized water (appropriate amount) Adjust to 100% pH value: 8.5 Combination Agent 3 a) No structural protein (comparative example) b) comprising a structural protein gel containing 3% by weight of silk protein (according to the invention) Ingredients Weight% Silk Protein Gel (ingredient b) 3.0 (3% active ingredient = silk protein) Total content 0.09%) GLDA 30.0 (active ingredient 47%) Sulfonated Builder / Chelating Agent Acrylic Copolymer 8.0 (Active Ingredients 40%) Builder / anti-redeposition agent Sodium Citrate 0.5 (100% active ingredient) Builder Xanthan Gum 1.0 Rheology Modifier C 12 ~C 14 EO / PO alkoxylate 4.0% (active ingredient 100%) NI surfactant Glycerol 10.0 Solvent Protease (Subtilisin) 4.0 (Active Ingredient 40%) Enzyme Amylase 1.0 (40% active ingredient) Enzyme Benzisothiazolinone (BIT) 0.05 Preservative Sodium hydroxide (appropriate amount) to adjust the pH to 8.5 Deionized water (appropriate amount) Adjust to 100% Viscosity [mPas]: 1250 mPas (Brookfield, 20 rpm, 24 ° C) pH value: 8.5 I.2) Multicompartment formulations Combination Agent 4 (ADW tub with three compartments: two for powder and one for liquid.) [Table 0] a) The total content of silk proteins in the composition is 0.09%

[0207] II) Application examples II.1) Cleaning Effect of Automatic Dishwasher Gel Detergency measurements were performed based on the IKW method "Recommendations for the Quality Assessment of Detergency Performance of Dishwasher Detergents (Part B, Update 2015)." According to the IKW method, there are eight types of soils, divided into four classes. Corresponding to the bleach, alkali, and enzyme dishwashing detergent formulations, at least one soil type from each of the four soil classes (bleachable, persistent / alkali-sensitive, starch-containing / amylase-sensitive, and protein-containing / protease-sensitive) was used for testing. Eight soil types were selected, with at least one soil type selected from each class (see Table 1 below). After each wash cycle, a visual evaluation was performed using a score from 0 to 10, depending on the degree of cleaning and the type of soil. A higher score indicates better cleaning effectiveness. IKW test conditions Dishwasher: Bosch Program: Eco 50° Cycle Water hardness: 21°GH (general hardness) Dosage: 25g of gel formulation in the main cycle The test results are shown in Table 1. [Table 1] The IKW test demonstrates the high level of cleaning performance of the tested dishwashing detergents. The presence of structural proteins does not have a negative effect on cleaning performance. II.2 Gloss test The dishes were evaluated and scored for staining and filming levels as follows: 5 - Strongest staining / filming 4 - Very strong staining / filming 3-Severe staining / filming 2- Slight staining / filming 1 stain / no film formation Stain / film formation test conditions Dishwasher: Bosch Program: Eco 50° Cycle Water hardness: 21°GH The results are shown in Table 2 below. [Table 2] Stain = staining, film formation = film formation These tests demonstrate that automatic dishwashing formulations according to the present invention containing silk protein as a structural protein have superior stain / filming performance.

[0208] Example 2: Test Method: Comparative rinse aid testing of automatic dishwashing detergents according to Fresenius Standard Method 03 2016. 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 builder was used. The cumulative number of cycles was 3. Ballast soil: 50 g of ballast soil was used per cycle with the ingredients ketchup, milk, starch, fat, egg yolk, benzoic acid and water. Loading the dishwasher: The dishwasher was loaded with six blue plastic melamine dishes, three black glass dishes (Alcolock), four long drink glasses (Shot Paris 79), and four juice glasses (Shot Paris 12). Samples used: IEC 60436-Typ D (detergent, batch number CFT-GSM D~020 rev.2020 CFT), hereafter abbreviated as IEC-D, was used as the detergent. Test procedure: Glasses and plates were placed in a dishwasher and treated with Neo-Disher and citric acid, followed by two cycles with the test detergent. The dishwasher was modified to prevent commercial ion exchangers from operating. The machine was supplied with a fixed amount of water via an external tank. The rinse builder dispenser was emptied. If rinse builder was used in the test, it was added manually with a pipette. 50g of ballast soil was added at the start of the wash cycle. After the program finished, the full door was left closed for an additional 10 minutes. The door was then fully opened and the dishwasher rack was completely removed from the machine. Evaluation began after 20 minutes. After the dishes were completely dried, the rinse aid effectiveness was visually evaluated in a "black box" under defined lighting conditions. Dried water droplets, streaks, residue or cloudy film on dishes and cutlery were evaluated. Three replicates (cumulative) were tested for each product and the arithmetic mean was calculated. result: 1. Visual assessment of water and salt stains Blue melamine dishes and Alcolock glass dishes were treated under the test conditions and procedures described above. Briefly, the plates were placed in a dishwasher with ballast soil and either (i) cleaning agent (IEC-D) or (ii) cleaning agent combined with silk gel (IEC-D) was added. After three (cumulative) wash cycles for each product, visual grading was performed for salt and water stains. Arithmetic means were calculated. Visual grading of stains was performed by an independent laboratory (Fresenius Institute) on an 8-point scale for water and salt stains, as shown below: 8=No stains or streaks, 7 = Very slight streaks and / or very minor stains; 6 = slight streaks and / or small stains; 5 = slight or moderate streaks and / or medium-sized stains; 4 = Some medium streaks and / or medium-sized stains; 3 = moderate streaks and / or several large stains; 2 = several large streaks and / or large stains; 1 = large streaks and / or numerous large stains; 0 = Very large streaks and / or numerous large stains. The arithmetic mean of blue melamine dishes washed with IEC-D was calculated to be 3.8, while that of IEC-D + spider silk was 5.6. The arithmetic mean of the Alcoloc glass dish washed with IEC-D was calculated to be 5.6, while the arithmetic mean of the dish washed with IEC-D plus spider silk was 6.0. In summary, a reduction in the number of stains was observed when blue melamine dishes and Alcolock glass dishes were washed with IEC-D + silk gel compared to washing with IEC-D alone (Table 3). [Table 3] Table 3: Comparative results of cleaning detergent testing of detergents for automatic dishwashers according to Fresenius Standard Method 03 2016. Detergent IEC 60436-Typ D (abbreviated here as IEC-D) was tested with and without silk gel. The combinations were compared in terms of the reduction of stain formation on plates after three repeated wash cycles (cycle 1=A, cycle 2=B, cycle 3=C) in a washing machine according to Fresenius Standard Method 03 2016 SOP M 2422 Version 2. 2. Digital Image Analysis The tested drinking glasses were visually evaluated and then measured by digital image analysis. For this, each glass was fixed in a rack and illuminated with a specific light source. During the digital measurement, the glass was rotated 360 degrees. The result was a flat image. Special software made it possible to calculate the number, size and intensity of stains. The bottom and top of the glass were excluded. The classification of the results was carried out using the following grading: 5 = very large stain, 4=large stain, 3 = medium size stain; 2 = small stains, and 1 = very small stain. When glassware was treated with detergent IEC-D-Silk Gel, medium-sized stains were detected on the glass surface after three consecutive washing cycles. For glassware washed with detergent IEC-D+Silk Gel, only small-sized stains were detected on the glass surface after three consecutive washing cycles. The stain formation rating was 3 for the glass samples treated with the detergent IEC-D-Silk Gel and 2 for the glass samples treated with the detergent and rinse builder IEC-D+Silk Gel. Therefore, adding silk gel to detergent IEC-D results in reduced stain formation on glassware and improved visibility (see Figure 1). In the above experiment, spider-derived silk polypeptide C 16 The use of is preferred.

Claims

1. a) a structural polypeptide; and b) An automatic dishwashing composition comprising at least one builder.

2. 10. The automatic dishwashing composition of claim 1, wherein said a) structural polypeptide is a silk polypeptide.

3. 3. The automatic dishwashing composition of claim 2, wherein the silk polypeptide is a recombinant or synthetic silk polypeptide, preferably a silk polypeptide from spiders.

4. The silk polypeptide Proteins that do not have at least two identical sequence motifs (single units of amino acids) comprising or consisting of polymer chains, or, comprising or consisting of at least two identical repeat units, 4. The automatic dishwashing composition of claim 2 or 3.

5. 5. The automatic dishwashing composition of claim 2, wherein the silk polypeptide does not contain any non-repeating units.

6. The single unit or the repeating unit may be Module C having the amino acid sequence of SEQ ID NO: 1 or a variant thereof; Module C having the amino acid sequence of SEQ ID NO: 2 or a variant thereof Ｃｙｓ , Module C having the amino acid sequence of SEQ ID NO: 3 or a variant thereof Ｌｙｓ , 6. The automatic dishwashing composition of claim 4 or 5, independently selected from the group consisting of:

7. 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 wherein m is an integer from 1 to 96; 7. The automatic dishwashing composition of claim 2.

8. The silk polypeptide is 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 Ｃｙｓ 、(C) ３２ C Ｃｙｓ 、(C) ４８ C Ｃｙｓ 、(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 8. The automatic dishwashing composition of claim 7 selected from the group consisting of:

9. 0.0005-2.5% by weight, preferably 0.001% by weight, based on the total weight of the composition An automatic dishwashing composition according to any one of claims 1 to 8, comprising -2.0% by weight, in particular 0.005-1.5% by weight, of at least one structural polypeptide (component a).

10. a) at least one structural polypeptide; b) at least one builder; c) optionally at least one enzyme; d) optionally at least one bleaching component; e) optionally at least one thickening agent; f) optionally at least one further additive different from components a) to e), preferably selected from surfactants, bases, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, tableting aids, disintegrants, solubilizers, organic solvents, electrolytes, optical brighteners, hydrotropes, anti-redeposition agents, antimicrobial components, antioxidants and mixtures thereof, g) optionally water, 10. The automatic dishwashing composition of claim 1, comprising:

11. 11. The automatic dishwashing composition of claim 1, wherein the automatic dishwashing composition is in the form of a gel or a multi-compartment formulation comprising a structural polypeptide in the form of a gel.

12. 12. A method of automatically cleaning dishware by contacting the dishwashing composition of any one of claims 1 to 11.

13. 12. Use of a structural polypeptide, particularly a silk polypeptide, according to any one of claims 2 to 8 or 11 in an automatic dishwashing composition.

14. reducing staining and filming on tableware, especially glassware and cutlery; Gives tableware a good shine, Improved stain removal from dishes, Preventing recontamination of tableware, Providing surface protection for tableware, especially preventing corrosive changes to the surface of glassware; Reduces the surface tension of tableware, Reduces or eliminates the need for separate rinse aid products; 14. Use according to claim 13 for improving the drying of tableware.

15. When processing dirty dishes in an automatic dishwasher, reducing staining and filming on tableware, especially glassware and cutlery; Gives tableware a good shine, Improved stain removal from dishes, Preventing recontamination of tableware, Providing surface protection for tableware, especially preventing corrosive changes to the surface of glassware; Reduces the surface tension of tableware, Reduces or eliminates the need for separate rinse aid products; To improve the drying of dishes, Use of the composition according to any one of claims 1 to 11 for automatic dishwashing.

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