Process for the preparation of isosorbide ester sulfates and compositions thereof

Abstract

This invention relates to an improved method for preparing isosorbide sulfate and compositions comprising isosorbide sulfate and fatty alcohol sulfate, and the use of such compositions, particularly in cleaning compositions such as laundry detergents or compositions for hand tableware, or in emulsion polymerization as emulsifiers.

Description

[0001] This invention relates to an improved method for preparing isosorbide sulfate and compositions comprising isosorbide sulfate and fatty alcohol sulfate, and the use of such compositions, particularly in cleaning compositions such as laundry detergents, compositions for hand tableware, or in emulsion polymerization, as emulsifiers.

[0002] Detergent and household care product formulators are constantly faced with the task of developing improved products to remove a broad spectrum of dirt and stains from fabrics and hard surfaces. Chemically and physicochemically, the spectrum of dirt and stains ranges from polar dirt such as proteins, clays, and inorganic dirt to non-polar dirt such as cooking fumes, carbon black, and byproducts of incomplete combustion of hydrocarbons, as well as organic dirt like sebum and starch-based stains. Given the emerging trend of improving the “footprint” of any cleaning product, these challenging needs become even more demanding, whether in terms of its source (e.g., from natural or renewable resources), production efficiency compared to previous products (and thus reduced energy consumption), usage efficiency (e.g., reduced amount of performance at the same level or improved performance at the same dosage), persistence in the natural environment after use, and especially biodegradability, as recycling is technically very challenging and therefore not economically attractive.

[0003] Because of these trends, there is a strong need for improved and more sustainable surfactant production methods. One step in this direction is to reduce the energy used in surfactant preparation processes. A major factor contributing to energy efficiency during surfactant production is the temperature applied during the various synthetic steps.

[0004] Regarding surfactants, BASF examined the suitability of various isosorbide derivatives for use in detergents, cleaning agents, and cosmetics using a broad screening methodology between 2008 and 2011. As a result, isosorbide esters have proven to be of particular interest for detergent applications and cosmetic products. Alkoxylated derivatives performed well in cleaning plastic surfaces, while sulfated esters showed good foaming properties.

[0005] Isosorbide sulfate is synthesized from isosorbide and carboxylic acid by reacting these two substrates in a condensation reaction to form isosorbide monoester. This intermediate compound is then sulfated. Due to the relatively high melting point of isosorbide monoester (above 60°C), two alternative methods for sulfation have been developed. One method involves a batch process using chlorosulfonic acid and tetrahydrofuran (THF) as solvents at room temperature. However, this batch process is inefficient, and chlorosulfonic acid and THF are considered hazardous (GH SO7), health hazards (GH SO8), and corrosive, and therefore their use should be avoided. Alternatively, sulfation can be carried out using a falling film reactor at temperatures between 90°C and 100°C using sulfur trioxide, fuming sulfuric acid, or pyrosulfonic acid. These temperatures are required because of the high viscosity of isosorbide ester at lower temperatures and the arrangement of pipes in the falling film reactor. However, this method is energy inefficient due to its high temperature.

[0006] The following provides an overview of the current knowledge and most relevant disclosures in the field of this invention, and the synthesis of isosorbide sulfate.

[0007] EP 2270017 B1 discloses the synthesis of isosorbide ether sulfate in Example 2. The synthetic scheme involves sulfation using chlorosulfonic acid and tetrahydrofuran (THF) as solvents at a temperature not exceeding 25°C. As mentioned above, these compounds are hazardous (GH S07), health hazardous (GH S08), and corrosive.

[0008] Therefore, there is a need in the art for a method for preparing isosorbide sulfate that is free of organic solvents, does not involve compounds that are harmful, have health hazards or are corrosive, is energy efficient and does not depend on high-temperature steps, and is also suitable for falling film reactor technology to provide efficient synthesis.

[0009] Surprisingly, the inventors of this invention discovered that isosorbide monoesters can be combined with fatty alcohols to achieve i) a significantly lower melting point of the mixture compared to that of isosorbide monoesters alone, and ii) simultaneously, a significantly lower viscosity compared to that of isosorbide monoesters at similar temperatures. Therefore, the mixture of isosorbide monoesters and fatty alcohols can be sulfated in a reaction free of organic solvents and that can be carried out in a falling film reactor. Furthermore, the temperature of the sulfation step can be reduced to below 98°C, making the method energy efficient. The resulting composition containing isosorbide ester sulfate and fatty alcohol sulfate can be used, for example, as a laundry or handwashing detergent composition.

[0010] In addition, it was unexpectedly discovered that compositions containing isosorbide sulfate and fatty alcohol sulfate can be used as emulsifiers for emulsion polymerization.

[0011] Therefore, the object of the present invention is to provide a novel method for preparing isosorbide sulfate, the method comprising the following steps a) to c):

[0012] a) React i) isosorbide and ii) a carboxylic acid containing at least 10 carbon atoms to obtain the first intermediate (I1);

[0013] b) Mixing i) the first intermediate (I1) with ii) a fatty alcohol comprising at least 10 carbon atoms to obtain a second intermediate mixture (I2), wherein the second intermediate mixture (I2) comprises 35% to 90% by weight of the fatty alcohol; and

[0014] c) React i) the second intermediate mixture (I2) with ii) at least one of sulfur trioxide, fuming sulfuric acid or pyrosulfuric acid in a falling film reactor to obtain the isosorbide sulfate.

[0015] As used herein, the term "isosorbide sulfate" refers to a group of compounds prepared according to the method of the present invention. In a preferred embodiment, isosorbide sulfate is a compound according to formula (I):

[0016] (I),

[0017] Where R is a straight-chain C9-C 33 Alkyl, preferably straight-chain C 10 -C 24 Alkyl, more preferably C 11 -C 17 Alkyl groups, and even more preferably C4 groups. 11 -C 13 Alkyl group. In other preferred embodiments, R is a straight-chain C. 11 C 13 C 15 Or C 17 Alkyl groups or mixtures thereof. Preferred mixtures contain R being a straight-chain C. 11 and C 13 Alkyl or R is a straight-chain C 15 and C 17 Alkyl isosorbide sulfate. In other preferred embodiments, the straight-chain alkyl group is saturated.

[0018] As used herein, the term "isosorbide" refers to a compound having the structure of formula (II). Isosorbide is also known as D-isosorbide, 1,4:3,6-didehydro-D-sorbitol, 1,4-didehydrosorbitol, and (3R,3aR,6S,6aR)-hexahydrofurano[3,2-b]furan-3,6-diol.

[0019] (II)

[0020] As used herein, the term “carboxylic acid containing at least 10 carbon atoms” refers to a straight-chain carboxylic acid according to formula (III), its deprotonated (anionic) form, or a salt thereof.

[0021] (III),

[0022] Wherein R is defined as described above. For clarity, R is a straight-chain C9-C33 alkyl, preferably a straight-chain C10-C24 alkyl, more preferably a C11-C17 alkyl, and even more preferably a C11-C13 alkyl. In other preferred embodiments, R is a straight-chain C11, C13, C15, or C17 alkyl, or a mixture thereof. Preferred mixtures comprise carboxylic acids wherein R is a straight-chain C11 and C13 alkyl or R is a straight-chain C15 and C17 alkyl. In other preferred embodiments, the straight-chain alkyl is saturated.

[0023] As used herein, the term "first intermediate (I1)" refers to isosorbide monoester. In a preferred embodiment, the first intermediate (I1) is a compound according to formula (IV):

[0024] (IV),

[0025] Wherein R is a straight-chain C9-C33 alkyl, preferably a straight-chain C10-C24 alkyl, more preferably a C11-C17 alkyl, and even more preferably a C11-C13 alkyl. In other preferred embodiments, R is a straight-chain C11, C13, C15, or C17 alkyl, or a mixture thereof. Preferred mixtures comprise isosorbide sulfates wherein R is a straight-chain C11 and C13 alkyl or R is a straight-chain C15 and C17 alkyl. In other preferred embodiments, the straight-chain alkyl group is saturated.

[0026] The reaction for obtaining the first intermediate (I1) is a condensation reaction comprising isosorbide and the aforementioned carboxylic acid containing at least 10 carbon atoms. Specifically, the reaction conditions include applying several different temperatures, including temperatures up to 225°C. Furthermore, in one embodiment, a catalyst may be used for the reaction. The catalyst may be tin (II) oxalate. Alternatively, those skilled in the art know of similar catalysts that can be used to obtain the first intermediate (I1). In other embodiments, the yield of the reaction is at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, or at least 85% of the theoretical yield.

[0027] As used herein, the term "fatty alcohol comprising at least 10 carbon atoms" refers to a primary alcohol. In a preferred embodiment, the fatty alcohol is a monovalent and saturated primary fatty alcohol. Alternatively, the fatty alcohol is a compound according to formula (V):

[0028] H3C-(CH2) n -CH2-OH (V),

[0029] Wherein n is at least 8, at least 9, or at least 10. In a preferred embodiment, n is an integer ranging from 8 to 31, more preferably from 9 to 22, even more preferably from 10 to 16, and most preferably from 10 to 12. In other preferred embodiments, n is 10, 12, 14, or 16, or a mixture thereof. A preferred mixture comprises a fatty alcohol wherein n is 10 and 12 or n is 14 and 16.

[0030] As used herein, the term "second intermediate mixture (I2)" refers to (i) the first intermediate (I1) / isosorbitol monoester described above and (ii) the fatty alcohol described above comprising at least 10 carbon atoms. It should be noted that the first intermediate (I1) and the fatty alcohol itself can be a mixture. This means that each of the first intermediate (I1) and the fatty alcohol can comprise a group of heterogeneous compounds as described above. Thus, for example, the second intermediate mixture (I2) can comprise an isosorbitol monoester having formula (IV) (where R is a straight-chain C11 and C13 alkyl group) and a fatty alcohol having formula (V) (where n is 10 and 12). In other preferred embodiments, the melting point of the second intermediate mixture (I2) is below 70°C, below 65°C, below 60°C, below 55°C, below 50°C, below 45°C, below 40°C, or below 37°C.

[0031] The second intermediate mixture (I2) comprises 35% to 90% fatty alcohol by weight. In a preferred embodiment, the second intermediate mixture (I2) comprises 40% to 90%, 45% to 85%, 50% to 80%, 55% to 75%, or 60% to 70% fatty alcohol by weight.

[0032] As used herein, the term "sulfur trioxide" refers to a compound having the formula SO3 or its salt. Synonyms include sulfonylidene oxidane, sulfuric anhydride, and sulfur oxide (VI).

[0033] As used herein, the term "pyrosulfuric acid" refers to a compound having formula (VI), its deprotonated form, or a salt thereof:

[0034] (VI).

[0035] As used herein, the term "fuming sulfuric acid" refers to a solution of sulfur trioxide of various compositions in sulfuric acid (H2SO4), or more specifically, to disulfuric acid (also known as pyrosulfuric acid and shown in formula (VI)). Fuming sulfuric acid is identified by CAS number 8014-95-7.

[0036] The final reaction used to obtain isosorbide sulfate is a sulfation reaction, which involves the reaction of the above-mentioned second intermediate mixture (I2) with sulfur trioxide, fuming sulfuric acid, or pyrosulfuric acid in a falling film reactor. The reaction temperature may not exceed 98°C, 90°C, 80°C, 75°C, 70°C, 65°C, 60°C, 55°C, 50°C, 45°C, 40°C, or 37°C.

[0037] Sulphation can be carried out continuously, especially in reactors operating according to the falling film principle. The reaction is preferably carried out in the absence of a solvent. Specifically, the reaction conditions involve the reaction with gaseous sulfur trioxide in the form of a mixture with an inert gas. The sulfur trioxide is diluted with air or nitrogen, and preferably used in the form of a gaseous mixture containing approximately 1% to 7%, particularly 3% to 5%, of sulfur trioxide. The reaction can be carried out at a molar ratio of isosorbide ester / fatty alcohol mixture to sulfur trioxide of 1:0.9 to 1:1.3. Sulphation can be carried out at temperatures ranging from 50°C to 98°C. To ensure sufficiently low viscosity of the feedstock while avoiding excessive thermal stress during the reaction, sulfation is recommended to be carried out between 50°C and 80°C.

[0038] The acidic sulfation product resulting from the reaction of isosorbide / fatty alcohol mixtures with sulfur trioxide can then be neutralized by combining the sulfide product with an alkaline aqueous solution and maintaining a pH of 6.0 to 7.5 by adding a suitable buffer solution (e.g., KH₂PO₄, NaH₂PO₄). Alkali metal hydroxides (such as sodium hydroxide and potassium hydroxide) can be considered as the base for neutralization.

[0039] Step c) is carried out in a falling film reactor. Such falling film reactors and their use for sulfation (sulfonation) are well known in the art and include falling film reactors from Stepan (e.g., as described in US 3169142A) and annular film reactors from Chemithon (e.g., as described in US 3427342 A).

[0040] In another embodiment, the carboxylic acid contains at least 10 carbon atoms.

[0041] - It's a linear chain;

[0042] - Possesses a carboxyl group as its sole functional group; and / or

[0043] - It is a C12 or C14 carboxylic acid or a mixture thereof.

[0044] "Straight-chain" carboxylic acids mean that, apart from the carbon atom of the carboxyl group, the compound contains only one terminal primary carbon atom, and the remaining carbon atoms are secondary carbon atoms attached to two other carbon atoms.

[0045] As used in this article, the term "the only functional group is a carboxyl group" describes a compound in which the only functional group is a carboxyl group, and no other groups such as other carboxyl groups, alcohol groups, carbonyl groups, heteroatomic groups, etc. are present.

[0046] In another embodiment, the fatty alcohol contains at least 10 carbon atoms.

[0047] - It's a linear chain;

[0048] - Possesses a primary alcohol group as its sole functional group; and / or

[0049] - It is a C12, C14, C16 or C18 fatty alcohol or a mixture thereof, preferably a mixture of C12 and C14 fatty alcohols or a mixture of C16 and C18 fatty alcohols.

[0050] The term "straight chain" is as defined for carboxylic acids. As used herein, the term "the only functional group is a primary alcohol group" describes a compound in which the only functional group is a primary alcohol group, and no other groups such as other alcohol groups, carboxylic acid groups, carbonyl groups, heteroatomic groups, etc. are present.

[0051] In another embodiment, the second intermediate mixture (I2) comprises 40% to 85%, preferably 50% to 80%, more preferably 60% to 75% by weight of fatty alcohols or mixtures thereof.

[0052] In another embodiment, in step c) of the method of the present invention, the second intermediate mixture (I2) is reacted with sulfur trioxide.

[0053] In another embodiment, the temperature in step c) of the method of the present invention is not higher than 98°C, not higher than 90°C, not higher than 80°C, not higher than 75°C, not higher than 70°C, not higher than 65°C, preferably not higher than 60°C, or more preferably not higher than 55°C.

[0054] In another embodiment, in step a) of the method of the present invention, the molar ratio of isosorbide to carboxylic acid is at least 1.5:1, preferably at least 4:1, or more preferably at least 6:1. Furthermore, in step a) of the method of the present invention, the molar ratio of isosorbide to carboxylic acid is not higher than 20:1, preferably not higher than 15:1, or more preferably not higher than 10:1.

[0055] In another embodiment, the first intermediate (I1) is purified by distillation. Following this purification, the first intermediate (I1) has a purity level of at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or at least 99.5% based on a mole fraction (i.e., the amount of the first intermediate (I1) in moles divided by the total amount of all components in the mixture, also in moles). Specifically, the purification step is performed to separate the first intermediate (I1) from the unreacted substrate isosorbide and carboxylic acid, as well as from isosorbide diester (i.e., isosorbide, in which each of the two alcohol groups reacts with the carboxylic acid).

[0056] In addition, isosorbide sulfate can be further subjected to the following method steps.

[0057] a) Purification using standard methods such as steam distillation, hot distillation, vacuum evaporation (including removal of all solvents), dialysis, and / or

[0058] b) Drying is performed using standard drying methods such as spray drying, drum drying, paddle drying, and vacuum drying. These drying methods include agglomeration methods such as fluidized bed drying.

[0059] To obtain purified isosorbide sulfate solution, purified isosorbide sulfate liquid, solid (e.g., granulated or co-granulated) isosorbide sulfate or purified solid isosorbide sulfate, respectively.

[0060] If, after the reaction that produces isosorbide sulfate, the residual substrate is present to an undesirable degree, the resulting mixture containing isosorbide sulfate can be further purified by standard methods to reduce the content of residual substrate, and also to reduce the amount of possible byproducts, reduce the amount of one or more solvents used (i.e., concentration), or replace one or more solvents with other solvents. Such methods are known to those skilled in the art.

[0061] Preferably, the unwanted amount of residual substrate is removed by a distillation method, more preferably by a thermal distillation method, which may additionally include applying reduced pressure to improve the rate and / or efficiency of removal.

[0062] In a preferred embodiment, only this additional method step a) is used.

[0063] In another embodiment, at least one of isosorbide, carboxylic acid, and fatty alcohol is a renewable compound, preferably isolated from organisms such as bacteria, fungi, or plants. In a preferred embodiment, all three substrates mentioned above are renewable compounds. Therefore, isosorbide can be produced from sorbitol. Sorbitol is produced from (corn) starch as a raw material, using enzymatic liquefaction and saccharification methods to produce glucose, which is then concentrated and hydrogenated to produce sorbitol. Naturally derived and renewable isosorbide is commercially available from Roquette Frères, Lestrem, France, and is available as POLYSORB. ® Sale.

[0064] Long-chain carboxylic acids are well-known metabolites of bacteria, fungi, or plants. Therefore, these compounds are naturally occurring and renewable. Several different schemes have been developed for their isolation, and thus such carboxylic acids are generally commercially available. Furthermore, these carboxylic acids can also be produced indirectly by (a) direct hydrogenation to fatty alcohols, or (b) by forming methyl esters followed by hydrogenation to fatty alcohols. Therefore, those skilled in the art also know how naturally occurring and renewable fatty alcohols can be synthesized.

[0065] In a second aspect, the present invention relates to the use of a fatty alcohol comprising at least 10 carbon atoms during the sulfation of isosorbide esters, preferably for reducing the melt temperature and / or viscosity of the isosorbide esters, wherein the isosorbide esters comprise alkyl groups having at least 10 carbon atoms, wherein the sulfation is preferably carried out in a falling film reactor.

[0066] All terms in the second aspect that have been defined and explained in detail in the description of the first aspect (i.e., the method for preparing isosorbide sulfate) shall of course apply to the second aspect.

[0067] In a preferred embodiment, the use of fatty alcohols comprising at least 10 carbon atoms during the sulfation of isosorbide esters is carried out using a falling film reactor. Such falling film reactors and their use for sulfation (sulfonation) are well known in the art and include falling film reactors from Stepan Corporation (e.g., as described in US 3169142 A) and annular film reactors from Chemithon Corporation (e.g., as described in US 3427342 A).

[0068] In a third aspect, the present invention relates to a composition comprising isosorbide sulfate and fatty alcohol sulfate, wherein the isosorbide sulfate and the fatty alcohol sulfate each comprise an alkyl group having at least 10 carbon atoms, and at least 40% by combined weight of the isosorbide sulfate and the fatty alcohol sulfate is based on the fatty alcohol sulfate.

[0069] All terms and definitions in the third aspect that have been defined and explained in detail in the preceding descriptions of the first and second aspects (i.e., the method for preparing isosorbide sulfate and the use of fatty alcohols during the sulfation of isosorbide ester) shall of course apply to the third aspect.

[0070] As used herein, the term “fatty alcohol sulfate” refers to a compound according to formula (VII), its deprotonated (anionic) form, or a salt thereof.

[0071] (VII),

[0072] Wherein n is at least 8, at least 9, or at least 10. In a preferred embodiment, n is an integer ranging from 8 to 31, more preferably from 9 to 22, even more preferably from 10 to 16, and most preferably from 10 to 12. In other preferred embodiments, n is 10, 12, 14, or 16, or a mixture thereof. A preferred mixture comprises a fatty alcohol sulfate wherein n is 10 and 12 or n is 14 and 16.

[0073] As used herein, the term "alkyl group of isosorbide sulfate" refers to the group represented by R in formula (I). As used herein, the term "alkyl group of fatty alcohol sulfate" refers to the group represented by R in formula (VII). The groups are indicated by dashed lines, where the dashed lines indicate bonds with sulfated groups.

[0074] In another embodiment, the alkyl group of isosorbide sulfate...

[0075] - It is a linear chain; and / or

[0076] - It is a C12 or C14 alkyl group, or the composition contains a mixture of C12 and C14 isosorbide sulfate.

[0077] In another embodiment, fatty alcohol sulfates

[0078] - It is a linear chain; and / or

[0079] - It is a C12, C14, C16 or C18 fatty alcohol sulfate or a mixture thereof, preferably a mixture of C12 and C14 fatty alcohol sulfate or a mixture of C16 and C18 fatty alcohol sulfate.

[0080] In another embodiment, at least 45%, preferably at least 50%, and more preferably at least 60% of the combined weight of isosorbide sulfate and fatty alcohol sulfate is based on fatty alcohol sulfate or a mixture thereof. In other embodiments, no more than 90%, preferably no more than 80%, and more preferably no more than 70% of the combined weight of isosorbide sulfate and fatty alcohol sulfate is based on fatty alcohol sulfate or a mixture thereof.

[0081] In alternative embodiments, the molar ratio between isosorbide sulfate and fatty alcohol sulfate in the compositions of the present invention ranges from 1:0.5 to 1:10, preferably 1:1 to 1:7, more preferably 1:1.5 to 1:5, and even more preferably 1:2 to 1:3.

[0082] In another embodiment, the compositions of the present invention are selected from the group consisting of: cleaning compositions, fabric and household care products, industrial and institutional cleaning products, cosmetic formulations, emulsifiers for emulsion polymerization, crude oil demulsifiers, pigment dispersions for inkjet inks, formulations for electroplating, adhesive compositions, dispersants for agricultural chemical formulations, preferably cleaning compositions and / or fabric and household care products and / or industrial and institutional cleaning products.

[0083] The compositions of this invention can be added to cosmetic formulations, as crude oil demulsifiers, as emulsifiers in emulsion polymerization, in pigment dispersions for inkjet inks, in formulations for electroplating, and in adhesive compositions. However, the compositions of this invention can also be added to washing or cleaning compositions.

[0084] Therefore, another subject of the present invention is a cleaning composition, fabric and household care product, industrial and institutional cleaning product, cosmetic formulation, crude oil demulsifier, pigment dispersion for inkjet ink, formulation for electroplating, adhesive composition and / or dispersant for agricultural chemical formulation, comprising at least one isosorbide sulfate and at least one fatty alcohol sulfate, each as defined above.

[0085] Preferably, it is a cleaning composition and / or a fabric and household care product (which contains the composition of the invention as defined above, preferably for improved clay removal or oil and grease stain removal), more preferably a laundry detergent formulation and / or a detergent formulation for hand dishwashing, more preferably a liquid laundry detergent formulation and / or a liquid detergent formulation for hand dishwashing.

[0086] In another preferred embodiment of the invention, the cleaning composition can be used for the removal of particulate stains and / or oily and greasy stains, and additionally for whiteness maintenance, preferably in garment care.

[0087] In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that can be used to clean various surfaces such as hardwood, tile, ceramic, plastic, leather, metal, and glass.

[0088] In another embodiment, the cleaning composition of the present invention is a liquid or solid detergent composition for automatic tableware washing, preferably a solid detergent composition for automatic tableware washing, which can be used to clean tableware, such as glassware, wherein the composition of the present invention improves the removal of stubborn dirt.

[0089] In another embodiment, the cleaning composition is designed for use in personal care and pet care compositions such as shampoo compositions, shower gel formulations, liquid or solid soaps.

[0090] In this invention, the preferred application areas for using the compositions of this invention are the fields of fabric and home care products and cleaning compositions, preferably cleaning compositions for industrial and institutional use, as well as for consumer use in their homes.

[0091] Furthermore, the composition of the present invention further comprises

[0092] a) at least one element from the group consisting of: nonionic surfactants, amphoteric surfactants, builders, chelating agents, co-builders, alcohols, thickeners, water-soluble polymers, clay stain removers / anti-redeposition agents, polymer detergents, bleaching agents, bleach activators, brighteners, odor control agents, pigments, dyes, opacifiers, toners, dye transfer inhibitors, defoamers, corrosion inhibitors, softeners, and fragrances;

[0093] b) An antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether; and / or

[0094] c) At least one enzyme selected from the list of lipases, hydrolases, amylases, deoxyribonucleases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersases, oxidoreductases, keratinases, pectinases, pectinases, lactases, and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably selected from proteases.

[0095] In a fourth aspect, the present invention relates to the use of the compositions of the present invention, the compositions

[0096] A) Preferably, cleaning compositions and / or fabric and household care products are used for

[0097] i) Improved removal of oily / greasy stains, and / or

[0098] ii) Clay removal, and / or

[0099] iii) Removal of particulate stains, and / or

[0100] iv) Dispersion and / or emulsification of dirt, and / or

[0101] v) Modification of the treated surface to improve re-contamination removal, and / or

[0102] vi) Whiteness improvement and / or

[0103] Most preferably used in cleaning compositions

[0104] i) Removal of oily / greasy stains, and / or ii) Clay removal,

[0105] Each of the preceding options i) to vi) is preferably used in laundry detergent formulations and / or handwashing detergent formulations and / or formulations suitable for (pre)treating textiles and / or soap, more preferably in liquid laundry detergent formulations and / or liquid handwashing detergent formulations; or

[0106] B) Preferably used as an emulsifier in the polymerization reaction.

[0107] In another aspect, the composition claimed herein is used in a method of emulsion polymerization, the method comprising the following steps:

[0108] 1. The reaction mixture is charged into the reactor, the reaction mixture comprising:

[0109] a. At least one monomer having an olefinic unsaturated double bond,

[0110] b. The composition of the present invention, and

[0111] c. at least one polymerization initiator; and

[0112] 2. The reaction mixture of step (1) is kept in a reactor at a temperature in the range of ≥ 20°C to ≤ 105°C for a period of time in the range of ≥ 30 minutes to ≤ 12 hours.

[0113] Emulsion polymerization can be a batch process, a semi-continuous process, or a fully continuous process, such as a feed process.

[0114] Suitable reactors include, but are not limited to, continuous stirred tank reactors (CSTRs), tubular reactors, circulating reactors, extruder reactors, or any reactor suitable for continuous operation.

[0115] A CSTR is a batch reactor equipped with cooling coils and / or cooling jackets. The cooling coils and / or cooling jackets must be sufficient to remove any heat absorbed by the polymerization not due to the temperature rise of the continuously charged monomer composition, in order to maintain the pre-selected temperature for polymerization in the reactor. Such a CSTR may be equipped with at least one, and typically more, stirrers to provide a well-mixed reaction zone. Such a CSTR can operate at a variable fill level from 20% to 100% full (liquid-fill reactor, LFR). In one embodiment, the reactor is more than 50% full but less than 100% full. In another embodiment, the reactor is 100% liquid-fill.

[0116] In a preferred embodiment, the temperature in step (2) is in the range of ≥ 40°C to ≤ 105°C or ≥ 40°C to ≤ 100°C or ≥ 40°C to ≤ 95°C or ≥ 40°C to ≤ 85°C, more preferably in the range of ≥ 50°C to ≤ 105°C or ≥ 50°C to ≤ 100°C or ≥ 50°C to ≤ 95°C or ≥ 50°C to ≤ 85°C, and even more preferably in the range of ≥ 60°C to ≤ 105°C or ≥ 60°C to ≤ 100°C or ≥ 60°C to ≤ 95°C or ≥ 60°C to ≤ 90°C.

[0117] The most favorable temperature selected depends on the decomposition characteristics of one or more initiators used.

[0118] Pressure conditions are usually not critical, and for example, pressures in the range of atmospheric pressure to 10 bar are suitable.

[0119] In a preferred embodiment, the emulsion polymerization time period is in the range of ≥ 1 hour to ≤ 10 hours, ≥ 1 hour to ≤ 9 hours, ≥ 1 hour to ≤ 8 hours, ≥ 1 hour to ≤ 7 hours, or ≥ 1 hour to ≤ 6 hours, more preferably in the range of ≥ 2 hours to ≤ 10 hours, ≥ 2 hours to ≤ 9 hours, ≥ 2 hours to ≤ 8 hours, ≥ 2 hours to ≤ 7 hours, ≥ 2 hours to ≤ 6 hours, or ≥ 2 hours to ≤ 5 hours.

[0120] Steps (1) and (2) can preferably be carried out in the presence of an inert gas such as nitrogen or argon.

[0121] In the embodiments, the reaction mixture of the method of the invention claimed herein contains at least one solvent.

[0122] The at least one monomer having an olefinic unsaturated double bond is selected from the group consisting of:

[0123] - Acrylic monomers;

[0124] - Vinyl aromatic hydrocarbons; and

[0125] - Saturated aliphatic C2-C 24 Vinyl esters, allyl esters, and methyl allyl esters of monocarboxylic acids.

[0126] In a preferred embodiment of the invention claimed herein, the at least one monomer having an olefinic unsaturated double bond is an acrylic monomer.

[0127] In another preferred embodiment of the invention claimed herein, the acrylic monomer is a (meth)acrylic monomer.

[0128] As used herein, “(meth)acrylate monomer” means acrylic acid or methacrylic acid, esters of acrylic acid or methacrylic acid, salts, amides and other suitable derivatives of acrylic acid or methacrylic acid, and mixtures thereof. Examples of suitable acrylic monomers include, but are not limited to, the following methacrylates: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, isoamyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, trifluoroethyl methacrylate, glycidyl methacrylate, benzyl methacrylate, allyl methacrylate, 2-butoxyethyl methacrylate, 2-chloroethyl methacrylate, etc. sec-butyl acrylate, tert-butyl acrylate, 2-ethylbutyl acrylate, cinnamon acrylate, crotonyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, 2-ethoxyethyl acrylate, furfuryl acrylate, hexafluoroisopropyl acrylate, allyl acrylate, 3-methoxybutyl acrylate, 2-methoxybutyl acrylate, 2-nitro-2-methylpropyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-phenoxyethyl acrylate, 2-phenylethyl acrylate, phenyl acrylate, propargyl acrylate, tetrahydrofurfuryl acrylate, and tetrahydropyranyl acrylate. Examples of suitable acrylates include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and n-decyl acrylate.

[0129] Examples of other suitable acrylic monomers include, but are not limited to, methacrylic acid derivatives such as: methacrylic acid and its salts, methacrylonitrile, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N,N-diethylmethacrylamide, N,N-dimethylmethacrylamide, N-phenylmethacrylamide, and methacrolein. Examples of acrylic acid derivatives include, but are not limited to, acrylic acid and its salts, acrylonitrile, acrylamide, methyl α-chloroacrylate, methyl 2-cyanoacrylate, N-ethylacrylamide, N,N-diethylacrylamide, and acrolein.

[0130] Preferably, the at least one acrylic monomer is selected from the group consisting of: ethyl acrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, and acrylic acid.

[0131] More preferably, the (meth)acrylic monomer is selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, n-butyl acrylate and acrylic acid.

[0132] In a preferred embodiment of the invention claimed herein, the vinyl aromatic hydrocarbon is selected from the group consisting of styrene, vinyltoluene, tert-butylstyrene, and α-methylstyrene. More preferably, the vinyl aromatic hydrocarbon is styrene.

[0133] In a preferred embodiment, the at least one monomer having an olefinic unsaturated double bond is selected from saturated aliphatic C2-C. 24 The group consisting of vinyl esters, allyl esters and methyl allyl esters of monocarboxylic acids.

[0134] In a preferred embodiment, the at least one monomer having an olefinic unsaturated double bond is a saturated aliphatic C2-C. 24 Vinyl esters of monocarboxylic acids.

[0135] In another preferred embodiment, saturated aliphatic C2-C 24 Vinyl esters of monocarboxylic acids are selected from the group consisting of: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl laurate, and vinyl stearate.

[0136] In a preferred embodiment, the amount of the at least one monomer having an olefinic unsaturated double bond is in the range of 35% to 80% by weight based on the total weight of the reaction mixture.

[0137] Polymerization initiator

[0138] Emulsion polymerization is achieved using at least one initiator. This at least one polymerization initiator, suitable for carrying out the method of the invention claimed herein, can thermally decompose into free radicals in a first-order reaction.

[0139] In a preferred embodiment, the at least one initiator is an inorganic free radical initiator.

[0140] In a preferred embodiment, the inorganic free radical initiator is selected from the group consisting of: ammonium persulfate, potassium persulfate, sodium persulfate, potassium peroxydicarbonate, potassium peroxydiphosphate, and mixtures thereof.

[0141] The at least one initiator can be selected from the group consisting of: peroxides or systems containing at least one peroxide, such as redox initiators containing at least one peroxide. Examples of suitable peroxides are alkali metal peroxydisulfates such as sodium peroxydisulfate or ammonium peroxydisulfate, hydrogen peroxide, and organic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, dipentyl peroxide, dioctyl peroxide, didecyl peroxide, dilauryl peroxide, dibenzoyl peroxide, bis(o-toluyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permaleate, tert-butyl perisobutyrate, tert-butyl perpentanoate, tert-butyl peroctanoate, tert-butyl perdecanoate, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, tert-butyl peroxy-2-ethylhexanoate, and diisopropyl peroxydicarbamate. Azo compounds, such as azobisisobutyronitrile, azobis(2-amidopropane) dihydrochloride, and 2,2'-azobis(2-methylbutyronitrile), are also suitable. Redox initiators are similarly suitable, for example, those comprising peroxides or oxidizable sulfur compounds. Examples include combinations of at least one Fe(II) compound such as FeSO4 and at least one peroxide such as H2O2, combinations of sodium persulfate and sodium metabisulfite, combinations of organic hydroperoxides and sodium metabisulfite, and combinations of tertiary amines and dibenzoyl peroxides.

[0142] The amount of polymerization initiator depends on the reaction conditions and can be adjusted accordingly.

[0143] In a preferred embodiment, the at least one polymerization initiator is present in an amount of ≥ 0.1% to ≤ 5% by weight, preferably ≥ 0.1% to ≤ 4.5% or ≥ 0.1% to ≤ 4%, more preferably ≥ 0.1% to ≤ 5% or ≥ 0.1% to ≤ 4.5% or ≥ 0.1% to ≤ 4.0%, and most preferably ≥ 0.2% to ≤ 4.5% or ≥ 0.2% to ≤ 4.0% or ≥ 0.2% to ≤ 3.5% or ≥ 0.2% to ≤ 3.0%, based on the total weight of the reaction mixture in each case.

[0144] In a preferred embodiment, step (C) is performed using a terminating compound selected from the group consisting of sodium bisulfite and sodium metabisulfite.

[0145] solvent

[0146] In a preferred embodiment, the reaction mixture of the method of the invention claimed herein contains at least one solvent.

[0147] The at least one solvent can be fed into the reactor together with the at least one monomer having an olefinic unsaturated double bond, that is, the at least one solvent and the at least one monomer having an olefinic unsaturated double bond are fed in a single feed, or the at least one solvent can be fed into the reactor alone, that is, the at least one solvent and the at least one monomer having an unsaturated double bond are fed in a dual feed.

[0148] In a preferred embodiment, the at least one solvent is selected from the group consisting of: water, xylene, toluene, ethylbenzene, light naphtha, heavy naphtha, acetone, methyl ethyl ketone, methyl pentyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, isopropanol, propylene glycol monomethyl ether acetate, acetic acid, propyl acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, ethyl 3-ethoxypropionate, and isoparaffins.

[0149] In a preferred embodiment, the at least one solvent is water.

[0150] The at least one solvent, by weight, is ≥ 15% to ≤ 60%, or ≥ 15% to ≤ 59%, or ≥ 15% to ≤ 58%, or ≥ 15% to ≤ 57%, or ≥ 15% to ≤ 56%, or ≥ 15% to ≤ 55%, or ≥ 15% to ≤ 54%, or ≥ 15% to ≤ 53%, or ≥ 15% to ≤ 52%, or ≥ 15% to ≤ 51%, or ≥ 15% to ≤ 50%, or ≥ 15% to ≤ 49%, or ≥ 15% to ≤ 48%, or ≥ 15% to ≤ 47%, or ≥ 15% to ≤ 46%, or ≥ 15% to ≤ 45%, or ≥ 15% to ≤ 44%, or ≥ 15% to ≤ 43%, or ≥ 15% to ≤ 42%, or ≥ 15% to ≤ More preferably, within the range of 41% or ≥ 15% to ≤ 40% or ≥ 15% to ≤ 39% or ≥ 15% to ≤ 38% or ≥ 15% to ≤ 37% or ≥ 15% to ≤ 36% or ≥ 15% to ≤ 35%, and more preferably within the range of ≥ 20% to ≤ 60% or ≥ 20% to ≤ 59% or ≥ 20% to ≤ 58% or ≥ 20% to ≤ 57% or ≥ 20% to ≤ 56% or ≥ 20% to ≤ 55% or ≥ 20% to ≤ 54% or ≥ 20% to ≤ 53% or ≥ 20% to ≤ 52% or ≥ 20% to ≤ 51% or ≥ 20% to ≤ 50% or ≥ 20% to ≤ 49% or ≥ 20% to ≤ 48% or ≥ 20% to ≤ The amount present is within the range of 47% or ≥ 20% to ≤ 46% or ≥ 20% to ≤ 45% or ≥ 20% to ≤ 44% or ≥ 20% to ≤ 43% or ≥ 20% to ≤ 42% or ≥ 20% to ≤ 41% or ≥ 20% to ≤ 40% or ≥ 20% to ≤ 39% or ≥ 20% to ≤ 38% or ≥ 20% to ≤ 37% or ≥ 20% to ≤ 36% or ≥ 20% to ≤ 35%, in each case based on the total weight of the reaction mixture.

[0151] In another aspect, the invention claimed herein relates to a mixture comprising

[0152] 1. At least one monomer having an olefinic unsaturated double bond, selected from acrylic monomers, vinyl aromatic hydrocarbons, and saturated aliphatic C2-C... 24 The group consisting of vinyl esters, allyl esters, and methyl allyl esters of monocarboxylic acids.

[0153] 2. The composition of the present invention as described above, and

[0154] 3. Water.

[0155] In the embodiments, the at least one monomer is selected from the group consisting of: acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, n-butyl acrylate, styrene, vinyltoluene, tert-butylstyrene and α-methylstyrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, 2-ethylhexanoate, vinyl lauryl ester and vinyl stearate.

[0156] In another aspect, the invention claimed herein relates to a mixture comprising

[0157] 1. The composition of the present invention as described above,

[0158] 2. A polymer P, wherein polymer P comprises at least one monomer in polymerizable form selected from the group consisting of: acrylic monomers, vinyl aromatic hydrocarbons, and saturated aliphatic C2-C... 24 Vinyl esters, allyl esters, and methyl allyl esters of monocarboxylic acids, and

[0159] 3. Water.

[0160] In the embodiments, the at least one monomer is selected from the group consisting of: acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, n-butyl acrylate, styrene, vinyltoluene, tert-butylstyrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, 2-ethylhexanoate, vinyl lauryl ester, and vinyl stearate.

[0161] All terms in the fourth aspect that have been defined and explained in detail in the descriptions of the first, second, and third aspects shall of course apply to the fourth aspect.

[0162] In other embodiments, the compositions of the present invention are used or provided for low-temperature washing processes and / or low-water-consumption processes. In this regard, as used herein, the term "low-temperature washing" means that the temperature of the washing liquid is preferably between 20°C and 45°C, more preferably between 30°C and 40°C, and particularly between 32°C and 35°C at a given time t1, and preferably between 30°C and 55°C, more preferably between 35°C and 50°C, and particularly between 40°C and 45°C at another given time t2. In a particularly preferred embodiment of the washing process, the temperature of the washing liquid at time t2 is higher than the temperature of the rinsing liquid at time t1. t1 refers to an optional pre-rinse. The corresponding temperature profile where the temperature of the washing liquid at time t2 is higher than the temperature of the rinsing liquid at time t1 has been shown to be excellent in terms of cleaning and final rinsing performance.

[0163] As used herein, the term "low water consumption" refers to the total water consumption of a cleaning process, wherein the water volume used in the process does not exceed 80%, 70%, 60%, 50%, 40%, or even 30% of the volume of a standard process as defined by the manufacturer of the cleaning equipment (i.e., a washing machine or automatic dishwashing machine) or the manufacturer of the cleaning agent. Modern cleaning equipment often includes washing programs labeled "eco," "green," or "sustainable." For the sense of this application, such a program qualifies as "low water consumption."

[0164] The compositions of this invention comprise at least one isosorbide sulfate and at least one fatty alcohol sulfate as described herein. The compositions of this invention may be part of another composition, preferably a cleaning composition. The compositions of this invention should be present in an effective amount. The terms “effective amount,” “effective concentration,” or “effective dosage” are defined herein as the amount, concentration, or dosage at which the compositions of this invention achieve a significant effect in removing oily / greasy stains and / or clay removal and / or whitening clothing. In a preferred embodiment, the cleaning composition comprises 0.001% to 10% by weight of the compositions of this invention.

[0165] Cleaning compositions can be solid, semi-solid, or gel-like, liquid (including sprays), or aerosol. They can be formulated in all types commonly used for the respective applications, such as blocks, powders, granules, agglomerates, pastes, gels, solutions, emulsions, suspensions, etc. They can also be formulated as liquid compositions absorbed in wipes or pads.

[0166] Cleaning compositions typically contain a carrier. In liquid, semi-solid, or gel compositions, the carrier is or contains a solvent, primarily water, (and / or) an alkanol (typically C2-C3-alkanols, i.e., ethanol, n-propanol, and / or isopropanol; these also typically act as wetting agents to allow the composition to better wet or penetrate the treated substrate; this latter effect is particularly useful if the composition does not contain a surfactant), a different organic solvent (details of such additional solvents are given below in the context of preferred embodiments of the composition), or mixtures thereof. In solid, semi-solid, or gel compositions, the carrier is or contains a solid carrier. In solid soaps, the soap component (e.g., a solid salt of a long-chain fatty acid) is also typically a carrier.

[0167] Depending on the intended use, cleaning compositions often contain additional components. Examples include pH adjusters, multivalent chelating agents, thickeners, antifreeze agents, defoamers, colorants, or fragrances. Further details of such additional components are given below in the context of preferred embodiments of the cleaning compositions.

[0168] In a preferred embodiment, the (liquid) cleaning composition comprises

[0169] (a) at least one preservative at a weight of 0% to 2% (= 2 to 90 < 100 ppm) relative to the total weight of the composition;

[0170] (b) 0.01%-10% by weight of the composition of the present invention relative to the total weight of the composition;

[0171] (c) One or more (anionic and / or nonionic) surfactants, in amounts of 0% to 10% by weight relative to the total weight of the composition;

[0172] (d) at least one C2-C3-alkanol in 0% to 90% by weight relative to the total weight of the composition;

[0173] (e) at least one organic solvent, in amounts of 0 to 10% by weight relative to the total weight of the composition;

[0174] (f) at least one multivalent chelating agent in an amount of 0% to 10% by weight relative to the total weight of the composition;

[0175] (g) 0% to 10% by weight of additional additives relative to the total weight of the composition;

[0176] (h) at least one enzyme, comprising 0% to 5% by weight relative to the total weight of the composition; and / or

[0177] (i) water, which is 100% by weight but at least 30% by weight relative to the total weight of the composition.

[0178] Preferably, at least one of components (c) to (h) is present. More preferably, at least component (c) is present.

[0179] Additional surfactants (or surfactant compounds) (referred to as component (c) in the examples above and below) may be anionic, cationic, nonionic, or amphoteric. Anionic, cationic, nonionic, and amphoteric surfactants are widely known in the art.

[0180] Anionic surfactants are, for example, of the sulfate, sulfonate, or carboxylate type, or mixtures thereof. Examples are...

[0181] - Alkyl sulfates (typically having the formula RO-SO3) - M + R is a long-chain alkyl group, such as C8-C 24 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 +(mono-, di-, or triethanolamine); for example, sodium lauryl sulfate;

[0182] - Alkyl ether sulfates (typically having the formula R-(CH2CH2-O)) x -O-SO3 - M + R is a long-chain alkyl group, such as C8-C 24 -alkyl, x is 1-10, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, sodium lauryl ether sulfate (SLES).

[0183] - Alkylbenzene sulfonates (typically having the formula R-(C6H4)-SO3) - M + R is a long-chain alkyl group, such as C8-C 24 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, sodium dodecylbenzenesulfonate;

[0184] - Olefin sulfonates (typically having the formula R-SO3) - M + Where R is a long-chain monoolefin group, such as C 12 -C 24 -Alkenyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, C 14 / C 16 -a-olefin sulfonate sodium;

[0185] - Alkane sulfonates (typically having the formula R-SO3) - M + R is a long-chain alkyl group, such as C8-C 24 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, C 13 -C 17 Alkane sulfonates, alkali metal salts, or ammonium salts;

[0186] - Sulfated monoglycerides (typically having the formula R-COO-CH2-CH(OH)-CH2-O-SO3) - M + R is a long-chain alkyl group, such as C8-C 24 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, sodium cocoyl monoglyceride sulfate;

[0187] - Alkyl sulfosuccinates, such as disodium N-octadecyl sulfosuccinate, diammonium lauryl sulfosuccinate, tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate; dipentyl ester, dihexyl ester or dioctyl ester of sodium sulfosuccinate.

[0188] - Acyl taurine salts, such as N-alkyl taurine, prepared by reacting dodecylamine with sodium hydroxyethyl sulfonate, or N-acyl taurine, obtained by reacting N-methyl taurine with fatty acids;

[0189] - Acylhydroxyethyl sulfonate (usually having the formula R-COO-CH2CH2-SO3) - M + R is a long-chain alkyl group, such as C 10 -C 30 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolammonium); for example, cocoyl hydroxyethyl sulfonate ammonium, cocoyl hydroxyethyl sulfonate sodium, or lauroyl hydroxyethyl sulfonate sodium;

[0190] - Alkyl glycerol ether sulfonates (typically having the formula RO-CH2-CH(OH)-CH2-SO3) - M + R is a long-chain alkyl group, such as C8-C 24 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, coconut oil glyceryl ether sulfonate;

[0191] - Sulfonated fatty acids and sulfonated fatty acid methyl esters (usually having the formula R-CH(SO3M) + )-COOH and R-CH(SO3 M +)-COOCH3, where R is a long-chain alkyl group, such as C8-C 24 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, α-sulfonated coconut fatty acids or lauryl methyl ester;

[0192] - Acylglutamate (usually having the formula R-CO-N(COOH)-CH2CH2-COO) - M + R is a long-chain alkyl group, such as C8-C 24 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, sodium lauroyl glutamate or sodium cocoyl glutamate;

[0193] - Acylsarcosine salts (typically having the formula R-CO-N(CH3)-CH2-COO) - M + R is a long-chain alkyl group, such as C8-C 24 -alkyl, and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, or ammonium lauroyl sarcosinate;

[0194] - Alkyl sulfonate salt,

[0195] - Fatty acid salts, which are typically derived from the saponification of oils or fats, such as palm oil or tallow, and have 8 to 24 carbon atoms in the alkyl / alkenyl moiety (thus including, in particular, oleates, linoleates, palmitates, myristates, stearates, etc.), wherein the counter cation is typically Na. + K + NH4 + Mono-, di-, or triethanolammonium;

[0196] - Alkyl and alkenyl ether carboxylates (typically having the formula R-(OCH2CH2)) x -OCH2-COO - M + R is a long-chain alkyl or alkenyl group, such as C8-C 24 -alkyl or -alkenyl, x is 1 to 10 and M +It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, sodium lauryl ether carboxylate;

[0197] - Acyl peptide,

[0198] - Acyl lactates (typically having the formula R-CO-[OCH(CH3)-CO)) x -COO - M + R is a long-chain alkyl or alkenyl group, such as C8-C 24 -alkyl or -alkenyl, x is 3 and M + It is a cation equivalent, usually Na + K + NH4 + (mono-, di-, or triethanolamine); for example, sodium cocoyl lactylate.

[0199] Another suitable additional class of anionic surfactants are polyalkoxylated polycarboxylated surfactants, such as those described in US 5,376,298, EP-A-0129328, WO 03 / 018733, and US 5,120,326. Polyalkoxylated polycarboxylated surfactants can be derived from the formula RO-(C2H4O). x -[CH(L)CH(L)] y -[CH2CH(CH3)O) z Q description,

[0200] Wherein R is a hydrophobic hydrocarbon group containing 6 to 16, preferably 8 to 14 carbon atoms, preferably an alkyl group; x is a number from 0 to 60, preferably 4 to 50, more preferably 6 to 50; L is a C1-C3 alkyl group or has the formula -CH(COO) - )-CH2(COO - The group is a -CH(COO) group, wherein at least one L group in each molecule is a -CH(COO) group. - )-CH2(COO - ); y is a number from 1 to 12, preferably 2 to 10, more preferably 3 to 8; z is a number from 0 to 20, preferably 0 to 15, more preferably 0 to 10; and Q is selected from the group consisting of H and sulfonate groups, the compound being electrically neutral by the presence of cationic groups, which are preferably selected from the group consisting of sodium, potassium, and substituted ammonium (e.g., monoethanolammonium) cations. Such polyalkoxylated polycarboxylate surfactants are commercially available under the BASF Plurafac® brand, for example Plurafac® CS-10.

[0201] Cationic surfactants are, for example, ammonium salts, such as C8-C.16 - Dialkyl dimethyl ammonium halide, dialkoxy dimethyl ammonium halide, or imidazoline onion salts having long-chain alkyl groups.

[0202] Nonionic surfactants are typically condensation products of one or more alkyl oxidases (primarily ethylene oxide) with various reactive hydrogen-containing compounds having hydrophobic chains (e.g., having 8-24 carbon atoms), such as condensation products of polyethylene oxide with fatty alcohols, long-chain branched alkyl alcohols, fatty acids, fatty amines, polyols, or polypropylene oxide.

[0203] Suitable alkoxylated alcohols are listed below. Of course, they are only suitable as component (c) if they differ from the alkoxylated alkanols of component (b), i.e., if they are not C6-C alkoxylated on average with 3 to 5 ethylene oxide units. 14 -Alkyl alcohols, for example, if they contain an average of more than 5 or less than 3 ethylene oxide units, or if they are not alkoxylated C6-C with an average total of 3 to 5 ethylene oxide and propylene oxide units. 14 -Alkanols; if they have less than 6 or more than 14 carbon atoms in the alcohol moiety, if the alcohol moiety is not derived from an alkanol and / or if they are alternatively or additionally alkoxylated with another alkylene oxide (e.g., propylene oxide only, PO) or alkylene glycol (e.g., 1,2-propanediol or 1,3-propanediol only).

[0204] Suitable alkoxylated, favorably ethoxylated alcohols, especially alkoxylated, favorably ethoxylated primary alcohols, preferably having 8 to 18 carbon atoms and an average of 1 to 20, preferably 1 to 12 mol of ethylene oxide (EO) per mole of alcohol, wherein the alcohol group can be straight-chain or branched, particularly 2-methyl-branched, or can contain a mixture of straight-chain and methyl-branched groups, as typically present in oxo-alcohol groups. Also suitable are alkyl alcohols synthesized by the Guerbet method, such as 2-ethylhexanol, 2-n-propylheptanol, 2-isopropylheptanol, 2-n-butyloctanol, and 2-n-pentylnonanol, with 2-ethylhexanol, 2-n-propylheptanol, and 2-isopropylheptanol being preferred. 2-n-propylheptanol is more preferred. Nonionic surfactants synthesized from the latter alcohol are marketed by BASF under the brand names Lutensol® XP and Lutensol® XL.

[0205] Other preferred ethoxylated alkyl alcohols have a high degree of branching, especially those ethoxylated alkyl alcohols available under the BASF brand names Lutensol® TO, Lutensol® ON, and Lutensol® TDA.

[0206] Suitable alternatives include alcohol ethoxylates having straight-chain groups and an average of 2 to 12 EOs per mole of alcohol, these straight-chain groups being formed from naturally sourced alcohols having 12 to 18 carbon atoms (e.g., coconut alcohol, palm alcohol, tallow alcohol, or oleyl alcohol). Preferred ethoxylated alcohols include, for example, C esters having 7 or 10 EOs. 12 -C 14 - Alcohols, C9-C having 7 or 10 EO atoms 11 - Alcohols, C with 7, 8, or 10 EO atoms 13 -C 15 - Alcohols, C with 7 or 10 EO atoms 12 -C 18 - Alcohols and mixtures thereof. The degree of ethoxylation is a statistical average and may be an integer or a fraction for a specific product. Alcohol ethoxylates with a narrow homologue distribution (narrow-range ethoxylates, NREs) are also suitable. In addition to these alkoxylated alcohols, fatty alcohols with more than 12 EOs can also be used. Examples include tallow fatty alcohols with 14, 25, or 30 EOs. Alcohols containing both EO and PO groups in the molecule can also be used. In this case, block copolymers with EO-PO block units or PO-EO block units can be used, but EO-PO-EO copolymers or PO-EO-PO copolymers can also be used. It will be understood that mixed alkoxylated nonionic surfactants in which the EO and PO units are not block but randomly distributed can also be used. Such products can be obtained by simultaneously acting ethylene oxide and propylene oxide on the fatty alcohol.

[0207] Suitable alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters preferably have 1 to 4 carbon atoms in the alkyl chain, and especially fatty acid methyl esters.

[0208] Non-ethoxylated nonionic surfactants are, for example, sugar surfactants, glycerol monoethers, polyhydroxyamides (glucosamides), or amine oxides.

[0209] Sugar surfactants are, for example, alkyl and / or alkenyl polysaccharides, sugar or alkyl sugar fatty acid esters and fatty sugar amides.

[0210] Alkyl and / or alkenyl polyglycosides are nonionic surfactants having a carbohydrate as the hydrophilic portion and a fatty alcohol or fatty acid as the hydrophobic component. Examples are compounds having the following formula.

[0211] ROG p ,

[0212] Where R is a long-chain alkyl or alkenyl group, mainly a long-chain alkyl or alkenyl group with 4-22 carbon atoms, G is an aldose or ketose moiety, mainly a glucose moiety, and p is 1 to 10.

[0213] Component G is preferably derived from an aldose or ketose having 5 or 6 carbon atoms. In one embodiment, component G is selected from the group consisting of pentoses, preferably from the group consisting of allose, arbutin, glucose, mannose, gulose, idole, galactose, tarose, allulose, fructose, sorbose, and tagatose, and more preferably glucose. In another embodiment, component G is selected from the group consisting of pentoses, preferably from the group consisting of ribulose, xylulose, ribose, arabinose, xylose, and lysolose, and more preferably from the group consisting of xylose and arabinose.

[0214] The exponent p in the above formula gives the degree of aggregation (DP) and is a number between 1 and 10. In one embodiment, p is between 1.1 and 3.0.

[0215] R can be straight-chain or branched. For example, group R is derived from straight-chain primary alcohols, such as fatty alcohols, or from branched primary alcohols, particularly so-called oxo alcohols. Examples of R derived from straight-chain primary alcohols are n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-heptadecyl, or n-octadecyl. Examples of R derived from branched primary alcohols are isopentyl, isohexyl, isoheptyl, 2-ethylhexyl, and 2-propylheptyl.

[0216] Mixtures of different alkyl and / or alkenyl polysaccharides can also be used. Therefore, all possible combinations of various aldoses or ketoses with all possible alkyl and / or alkenyl groups can be used.

[0217] Commercially available alkyl and / or alkenyl polysaccharides are, for example, products sold by Henkel under the brands PLANATAREN® and PLANTACARE®, such as PLANTAREN 1200, PLANTAREN 1300, PLANTAREN 2000, PLANTACARE 2000, PLANTACARE 818, and PLANTACARE 1200; products sold by Seppic under the brand TRITON® CG, such as TRITON CG 110 (or ORAMIX CG 110) and TRITON CG 312 (or ORAMIX NS 10); products sold by BASF under the brand LUTENSOL® GD 70; and products sold by BASF under the brand Glucopon®, such as Glucopon 100 DK, Glucopon 215 UP, Glucopon 225 DK, Glucopon 425 N / HH, and Glucopon GD. 70, Glucopon 50 G, Glucopon 600 CSUP or Glucopon 650 EC; and Plantatex® LLE from BASF.

[0218] Sugar or alkyl sugar fatty acid esters are sugars or alkyl sugars C4-C 22 Fatty acid esters, among which the following deserve special mention:

[0219] (C1-C4) alkyl glucoside esters, such as methyl glucoside monostearate, for example, the product sold by Grillowerke under the name GRILLOCOSE® IS; methyl glucoside sesquistearate, for example, the product sold by Amerchol under the name GLUCATE SS; 6-ethyl glucoside decanoate, for example, the product sold by Novo under the name BIOSURF 10; mixtures of mono- and dicocoate (82 / 7) of 6-ethyl glucoside, for example, the product sold by Novo under the name BIOSURF® COCO; mixtures of mono- and dilaurate (84 / 8) of 6-ethyl glucoside, for example, the product sold by Novo under the name BIOSURF® 12; butyl glucoside C 12 -C 18 Fatty acid monoesters, such as butyl glucoside monocolate, for example, products sold under the names REWOPOL® V3101 or REWOSAN® V3101, and polyoxyethylene butyl glucoside monocolate containing 3 moles of ethylene oxide, for example, products sold by Rewo under the name REWOPOL® V3122;

[0220] Glucose esters, such as 6-O-hexadecyl-[α]-D-glucose, 6-O-octyl-D-glucose, 6-O-oleyl-D-glucose, and 6-O-linoleyl-D-glucose, can be prepared, for example, from the corresponding acyl chloride and D-glucose; sucrose monoesters, such as sucrose monolaurate, for example, products sold by the Grillo Group under the name GRILLOTEN® LES 65 and sucrose monococarboxylate under the name GRILLOTEN® LES 65K.

[0221] Fatty glycoamides are compounds comprising at least one amide functional group and at least one sugar or sugar derivative moiety and at least one fatty chain; such compounds can be produced, for example, by the action of a fatty acid or fatty acid derivative on the amine functional group of an amino sugar, or by the action of a fatty amine on a sugar comprising a carboxylic acid functional group (free or in lactone form) or a carboxylic acid-derived functional group or alternatively a carbonyl functional group, and optionally in the presence of a suitable co-agent. Examples are N-substituted aldose amides, polyhydroxylated fatty acid amides, or mixtures thereof.

[0222] N-substituted aldosamides include, for example, N-substituted lactosamide, N-substituted maltoseamide, N-substituted cellobioseamide, N-substituted melibiamide, and N-substituted gentiobioseamide, such as:

[0223] N-alkyl lactosamide, N-alkyl maltamide, N-alkyl cellulose disaccharide, N-alkyl melbisulfonamide, or N-alkyl gentiobisulfonamide, which are mono- or disubstituted with the following groups: saturated or unsaturated, straight-chain or branched aliphatic hydrocarbon groups, which may contain heteroatoms, preferably having up to 36 carbon atoms, more preferably up to 24 carbon atoms, and even more particularly 8 to 18 carbon atoms (e.g., methyl, ethyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl; allyl, undecenyl, oleyl, linoleyl, propenyl, heptenyl), aromatic hydrocarbon groups (e.g., benzyl, aniline, substituted benzyl, phenethyl, phenoxyethyl, vinylbenzyl), or alicyclic groups (e.g., cyclopentyl, cyclohexyl).

[0224] N-lactoyl amino acid esters, wherein the amino acids may specifically represent: alanine, valine, glycine, lysine, leucine, arginine, aspartic acid, glutamic acid, threonine, serine, cysteine, histidine, tyrosine, methionine, or may be selected from, for example, [β]-alanine, sarcosine, γ-aminobutyric acid, ornithine, citrulline, or equivalents thereof; said N-lactoyl amino acid ester having the formula -(CH2) nMonosubstituted groups of -C(=O)-OR, where R is an aliphatic hydrocarbon group that can contain up to 36 carbon atoms and n is an integer greater than 1, and the corresponding N-maltodextrin amino acid esters, N-mercaptodextrin amino acid esters, N-celluloseobiose acyl amino acid esters and N-gentiobiose acyl amino acid esters.

[0225] N-(alkoxy)alkyl lactosamide, with a -(CH2) group n -OR' is mono- or disubstituted, where R' is an aliphatic, aromatic, or alicyclic hydrocarbon group;

[0226] N-(polyalkoxy)alkyl lactose amide,

[0227] N-(polyalkoxy)alkylmaltamide,

[0228] N-(polyalkoxy)alkyl cellulose disaccharide amide,

[0229] N-(polyalkoxy)alkyl melbisulfonamide or

[0230] N-(polyalkoxy)alkyl gentiobisulfonamide, with the -R'-(OR') group n R'R'' is mono- or disubstituted, where R' is an alkylene group, such as ethylene, propyleneene, or a mixture thereof, n is an integer greater than 1, and R'' is a lactosamide, maltamide, cellobioseamide, melibiamide, or gentiobioseamide group.

[0231] Examples of polyhydroxylated fatty amides are compounds having the following formula

[0232] TC(=O)-N(V)-W

[0233] Where T represents C5-C 31 Hydrocarbon group, preferably C7-C 15 A straight-chain alkyl or alkenyl chain; V represents hydrogen, a C1-C4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C1-C4 alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl and more particularly methyl; and W represents a group containing a polyhydroxy hydrocarbon having a straight-chain hydrocarbon chain (having at least 3 hydroxyl groups directly attached to the chain), or an alkoxylated derivative of said group (preferably ethoxylated or propoxylated).

[0234] W is preferably a reducing sugar derivative obtained through a reductive amination reaction, and more preferably a sugar alcohol group. Among reducing sugars, glucose, maltose, lactose, galactose, mannose, and xylose may be mentioned. Preferably, W is selected from groups having the following formula: -(CH2)-(CHOH) n -CH2OH;-CH-(CH2OH)-(CHOH) n-1-CH2OH; and -CH2-(CHOH)2(CHOR')-(CHOH)-CH2OH, wherein n is an integer ranging from 3 to 5, and R' is one of hydrogen, cyclic or aliphatic monosaccharides or their alkoxylated derivatives. Preferably, n is a 4-sugar alcohol group, and in particular the group -(CH2)-(CHOH)4-CH2OH.

[0235] The group TC(=O)-N- can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, decamide, palmitamide, or shea butteramide.

[0236] Amine oxide type nonionic surfactants typically have the formula R a R b R c N + -O - , where R a It is a long-chain alkyl group, such as C 10 -C 18 -alkyl, preferably C 12 -C 16 -alkyl, and R b and R c These are short-chain alkyl or hydroxyalkyl groups, such as methyl, ethyl, or 2-hydroxyethyl. A specific example is lauryl dimethylamine oxide. Alternatively, long-chain alkyl groups can be derived from natural sources (oils or fats) to produce mixtures of such amine oxides, such as N-cocoalkyl-N,N-dimethylamine oxide and N-tartrate-N,N-dihydroxyethylamine oxide.

[0237] Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, such as C6-C. 18 -alkyl betaine (e.g., cocamidopropyl betaine; disodium cocoamphodiacetate (DSCADA)) or C6-C 18 - Alkyl sulfobetaine, or amine oxides such as alkyl dimethylamine oxide.

[0238] C2-C3 alkanols [component (d)] are ethanol, n-propanol, and isopropanol. Mixtures of them are also suitable.

[0239] Organic solvents, unlike those in component (d) [component (e)], are typically used to provide stable cleaning compositions, especially if the cleaning composition is a concentrate containing a large amount of organic matter.

[0240] Therefore, suitable solvents are polar protic or polar aprotic solvents. Examples of suitable solvents (e) are alkanols other than C2-C3-alkanols, such as n-butanol or tert-butanol; C2-C8-alkyldiols; C1-C8-alkyl monoethers of C2-C8-alkyldiols; diethylene glycol, C1-C8-alkyl monoethers of diethylene glycol, polyether polyols; C1-C8-alkyl monoethers of polyether polyols; amino alcohols, such as ethanolamine, diethanolamine, and triethanolamine; and monophenyl ethers of C2-C3-alkyldiols, such as 2-phenoxyethanol or phenoxypropanol.

[0241] Among the solvents mentioned above, preferred are C1-C8-alkyl monoethers of C2-C8-alkyldiols and C1-C8-alkyl monoethers of diethylene glycol. More preferred are C2-C4-alkyldiols (especially ethylene glycol and propylene glycol), C1-C4-alkyl monoethers of C2-C3-alkyldiols, such as C1-C4-alkyl monoethers of ethylene glycol or propylene glycol, specific examples being ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether (also known as butyl glycol), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether; as well as C1-C4-alkyl monoethers of diethylene glycol (e.g., butyl diethylene glycol) and n-hexanol and mixtures thereof ethoxylated by 1-3 EO.

[0242] Multivalent chelating agents [component(f)], also known as builders, structural substances, framework substances, complexing agents, chelates, chelating agents, or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitation. They help break down dirt, disperse dirt components, facilitate dirt separation, and in some cases, they themselves have a detergent effect. Many of the multivalent chelating agents listed below are multifunctional, meaning that these substances have additional functions, such as dispersing activity.

[0243] Suitable multivalent chelating agents can be organic or inorganic in nature. Examples include aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylic acids, hydroxycarboxylic acids, phosphonates such as hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and their salts, as well as polymer compounds containing carboxylic acid groups and their salts.

[0244] Suitable inorganic multivalent chelating agents include crystalline or amorphous aluminosilicates with ion-exchange properties, such as zeolites. Suitable crystalline silicates as multivalent chelating agents include disilicates or phyllosilicates, such as d-Na₂Si₂O₅ or b-Na₂Si₂O₅ (SKS 6 or SKS 7). Suitable carbonate-based inorganic multivalent chelating agents are carbonates and bicarbonates. These can be used in the form of their alkali metal salts, alkaline earth metal salts, or ammonium salts. Commonly used phosphates as inorganic multivalent chelating agents are alkali metal orthophosphates and / or polyphosphates, such as pentasodium triphosphate.

[0245] Suitable organic multivalent chelating agents are, for example, C4-C. 30 -Di-, tri-, and -tetracarboxylic acids, such as succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and those with C2-C... 20 Alkyl or alkenyl alkyl- and alkenyl succinic acids. Suitable organic multivalent chelating agents are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (glycolic acids). These include C4-C... 20 -Hydroxycarboxylic acids, such as malic acid, tartaric acid, gluconic acid, mucoic acid, lactic acid, glutaric acid, citric acid, malonic acid, glucohepanoic acid, lactobionic acid, and sucrose mono-, di-, and tricarboxylic acids. Among these, citric acid and its salts are preferred. Another class is carboxylated fructans. Fructans are polymers of fructose molecules. They are composed of fructose residues, typically with sucrose units (i.e., glucose-fructobiose) at positions that would otherwise be reducing ends. The bonding of fructose residues usually occurs at one of the two primary hydroxyl groups (OH-1 or OH-6). In inulin, the fructose residues are linked by β-2,1-bonds. In fructans and phlein, the fructose residues are linked by β-2,6-bonds. Gramineae fructans contain both β-2,1-bonds and β-2,6-bonds. Preferably, carboxylated fructans are derived from inulin. Specific examples are carboxymethyl inulin and carboxyethyl inulin. Suitable carboxylated fructans are described in EP 3561032 A1 and WO 2010 / 106077.

[0246] Suitable organic multivalent chelating agents are phosphonic acids, such as hydroxyalkylphosphonic acids or aminophosphonic acids and their salts. These include, for example, phosphonobutanetricarboxylic acid (2-phosphonobutane-1,2,4-tricarboxylic acid; PBTC), aminotrimethylenephosphonic acid (N[CH2PO(OH)2]3), sodium aminotris(methylenephosphonic acid) (ATMP; N[CH2PO(ONa)2]3), ethylenediaminetetra(methylenephosphonic acid) (EDTMPA), hexamethylenediamine (tetramethylenephosphonic acid), potassium hexamethylenediamine (tetramethylenephosphonic acid) (C 10 H (28-x) N2K x O 12 P4 (x=6)), bis(hexamethylene)triamine (pentamethylenephosphonic acid) ((HO2)POCH2N[(CH2)2N[CH2PO(OH)2]2]2), diethylenetriamine-pentamethylenephosphonic acid (DTPMP; (HO)2POCH2N[CH2CH2N[CH2PO(OH)2]2]2), sodium diethylenetriamine-pentamethylenephosphonic acid (C9H) (28-x) N3Na x O 15P5 (x=7)); Tetramethylene-triamine-pentaphosphonic acid, hydroxyethylamine diphosphonic acid, 2-hydroxyethyliminobis(methylenephosphonic acid) (HOCH2CH2N[CH2PO(OH)2]2), morpholinomethane diphosphonic acid, 1-hydroxy-C1-to-C 10-alkyl-1,1-diphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP; CH2C(OH)[PO(OH)2]2). Furthermore, suitable organic multivalent chelating agents are polyaspartic acid. Polyaspartic acid comprises salts of polyaspartic acid. The salt-forming cation can be monovalent or polyvalent, examples being ammonium salts of sodium, potassium, magnesium, calcium, ammonium, and mono-, di-, and triethanolamines. Such polymers can be copolymers, particularly copolymers of: (a) L- or D-aspartic acid (preferably L-aspartic acid), (b) carboxylic acid, and (c) diamine or amino alcohol. Such copolymers typically contain 70-95 mol% of (a), 5-30 mol% of (b), and 2-20 mol% of (c). The molar ratio of the carboxyl-containing compound (b) to the diamine or amino alcohol (c) is preferably between 5:1 and 1:1.5 or between 3:1 and 1:1.2, and more preferably between 3:1 and 1:1 or between 2:1 and 1:1. Suitable organic polyvalent chelating agents are also amino polycarboxylic acids, such as nitrotriacetic acid (NTA), nitromonoacetic acid dipropionic acid, nitrotriacetic acid, β-alanine diacetic acid (β-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 1,3-propanediaminetetraacetic acid, 1,2-propanediaminetetraacetic acid, N-(alkyl)ethylenediaminetetraacetic acid, N-(hydroxyalkyl)ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid, cyclohexyl-1,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediaminedisuccinic acid, serine diacetic acid, isoserine diacetic acid, L-asparagine diacetic acid, L-glutamine diacetic acid, methylglycine diacetic acid (MGDA), and salts of the above amino polycarboxylic acids. Suitable organic polyvalent chelating agents are also polymer compounds containing carboxylic acid groups, such as acrylic acid homopolymers. The term "acrylic acid homopolymer" also includes polymers in which some or all of the carboxylic acid groups are in a neutralized form. Suitable polymer compounds containing carboxylic acid groups are oligomeric maleic acid. Suitable polymer compounds containing carboxylic acid groups are also terpolymers of unsaturated C4-C8-dicarboxylic acids. In this case, suitable unsaturated C4-C8-dicarboxylic acids are, for example, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesoconic acid, methylene malonic acid, and citraconic acid. Suitable polymer compounds containing carboxylic acid groups are also homopolymers of monoolefinically unsaturated C3-C8-monocarboxylic acids (e.g., acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, 2-phenylacrylic acid, cinnamic acid, vinylacetic acid, and sorbic acid); copolymers of dicarboxylic acids (e.g., maleic acid and acrylic acid); terpolymers of maleic acid, acrylic acid, and vinyl esters of C1-C3-carboxylic acids; and copolymers of maleic acid with C2-C8-olefins.

[0247] Other additives [component (g)] are, for example, pH adjusters, thickeners, antifreeze agents, defoamers, colorants and flavorings [i.e., different from components (a) and (b)].

[0248] Depending on the desired pH of the cleaning composition, the pH adjuster (pH modifier) ​​is either an acid or a base. pH can also be adjusted using a buffer system.

[0249] Acids can be inorganic or organic. Suitable inorganic acids are, for example, sulfuric acid, hydrochloric acid, and phosphoric acid, with sulfuric acid generally preferred. Suitable organic acids are, for example, aliphatic, saturated, unsubstituted C1-C6 mono-, di-, and tri-carboxylic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, glutaric acid, and adipic acid; aliphatic, saturated C1-C6 mono-, di-, and tri-carboxylic acids with one or more OH groups, such as glycolic acid, lactic acid, tartaric acid, and citric acid; aliphatic, unsaturated C1-C6 mono-, di-, and tri-carboxylic acids, such as sorbic acid; aromatic carboxylic acids, such as benzoic acid, salicylic acid, and mandelic acid; and sulfonic acids, such as methanesulfonic acid or toluenesulfonic acid. Organic acids are primarily used to adjust the pH of cleaning compositions, but some of them (such as di- and tricarboxylic acids) can also be used as multivalent chelating agents.

[0250] Suitable bases, especially inorganic bases, include carbonates mentioned in the context of polyvalent chelating agents, such as sodium carbonate or potassium carbonate; other options include ammonium carbonate, alkali metal and alkaline earth metal bicarbonates, such as sodium bicarbonate or potassium bicarbonate, alkali metal and alkaline earth metal hydroxides, such as NaOH or KOH, or ammonium hydroxide. Organic bases may also be used; examples are alkanolamines, such as monoethanolamine, triethanolamine, or aminomethylpropanol, or guanidine derivatives, such as 1,1,3,3-tetramethylguanidine or triazabicyclodecene.

[0251] Suitable buffers are typical systems such as hydrogen phosphate / dihydrogen phosphate buffer, carbonate / bicarbonate buffer, acetate / acetate buffer, or Tris buffer. In addition, most of the weak acids mentioned above whose anions are not strong salts also have buffering capacity.

[0252] Thickeners are used to impart the desired viscosity to the cleaning compositions of the present invention.

[0253] Any known thickener (rheology modifier) ​​is suitable in principle, provided that it does not adversely affect the effectiveness of the cleaning composition. Suitable thickeners can be of natural origin or synthetic nature.

[0254] Most naturally derived thickeners are derived from polysaccharides. Examples include xanthan gum, gellan gum, carob powder, guar powder or guar gum, carrageenan, agar, tragacanth gum, gum arabic, alginate, modified starches such as hydroxyethyl starch, starch phosphate or starch acetate, dextrin, pectin, and cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, etc. Naturally derived thickeners are also inorganic, such as polysilicic acid and clay minerals, such as pisilicates, and silicates mentioned in relation to detergent builders.

[0255] Examples of synthetic thickeners are polyacrylic and polymethacrylic acid compounds, such as (partially) crosslinked homopolymers of acrylic acid, for example, allyl ethers of sucrose or pentaerythritol or propylene crosslinked acrylic homopolymers (carbomer), such as Carbopol® from BF Goodrich (e.g., Carbopol® 676, 940, 941, 934, etc.) or Polygel® from 3V Sigma (e.g., Polygel® DA); copolymers of olefinically unsaturated monocarboxylic or dicarboxylic acids, such as terpolymers of acrylic acid, methacrylic acid, or maleic acid with methyl acrylate or ethyl acrylate and (meth)acrylates derived from long-chain ethoxylated alcohols, such as Acusol® from Rohm & Haas (e.g., Acusol® 820 or 1206A); copolymers of two or more monomers selected from acrylic acid, methacrylic acid and their C1-C4-alkyl esters, such as copolymers of methacrylic acid, butyl acrylate and methyl methacrylate, or copolymers of butyl acrylate and methyl methacrylate, such as Aculyn® and Acusol® brands from Rohm and Haas (e.g., Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830); or crosslinked high molecular weight acrylic copolymers, such as acrylic acid C 10 -C 30 - A copolymer of an alkyl ester with one or more comonomers selected from acrylic acid, methacrylic acid, and their C1-C4-alkyl esters, said copolymer having been crosslinked with an allyl ether of sucrose or pentaerythritol (e.g., Carbopol® ETD 2623, Carbopol® 1382, or Carbopol® AQUA30 from Rohm and Haas). Another preferred group of materials is the Rheovis® brand from BASF, such as Rheovis® AT 120.

[0256] Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea, and glycerin.

[0257] Examples of suitable defoamers are silicones, long-chain alcohols, and salts of fatty acids.

[0258] Suitable colorants (e.g., red, blue, or green) are low-water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, ferric hexacyanate ferrite) and organic colorants (e.g., alizarin, azo, and phthalocyanine colorants).

[0259] Flavors can be of natural or synthetic origin; their properties are usually not critical.

[0260] Furthermore, the cleaning composition may contain an enzyme [component (h)]. Preferably, the at least one enzyme is a detergent enzyme.

[0261] In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), transferase (EC 2), hydrolase (EC 3), lyase (EC 4), isomerase (EC 5), or ligase (EC 6). The EC numbers are based on the enzyme nomenclature recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (1992), including its supplements published between 1993 and 1999. Preferably, the enzyme is a hydrolase (EC 3).

[0262] In a preferred embodiment, the enzyme is selected from the group consisting of:

[0263] Protease, amylase, lipase, cellulase, mannanase, hemicellulase, phospholipase, esterase, pectinase, lactase, peroxidase, xylanase, keratinase, pectic acid lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, amylopectinase, tanninase, pentosanase, malicase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, nuclease, deoxyribonucleic acid The enzyme comprises phosphodiesterase, phytase, carbohydrate enzyme, galactanase, xanthan gumase, xyloglucanase, oxidoreductase, hydrolase, aminopeptidase, asparaginase, carbohydrate enzyme, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, α-galactosidase, β-galactosidase, glucosylamylase, α-glucosidase, β-glucosidase, invertase, ribonuclease, transglutaminase, and dispersase, as well as combinations of at least two of the aforementioned types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersases, pectinases, oxidoreductases, and keratinases, as well as combinations of at least two of the aforementioned types. Most preferably, the enzyme is a protease, preferably a serine protease, and more preferably a subtilisin.

[0264] Preferably, the protease is a protease having at least 90% sequence identity with SEQ ID NO: 22 of EP 1921147 B1 and having an amino acid substitution R101E (according to the BPN number). Preferably, the amylase is an amylase having at least 90% sequence identity with SEQ ID NO: 54 of WO 2021032881A1.

[0265] The compositions of the present invention may contain one type of enzyme or more than one different type of enzyme, such as amylase and protease, or more than one enzyme of the same type, such as two or more different proteases, or a mixture thereof, such as amylase and two different proteases.

[0266] The enzyme may be incorporated into the composition in an effective amount sufficient to provide for achieving beneficial effects, preferably for primary and / or secondary washing effects, such as anti-ashing or anti-pilling effects (e.g., in the case of cellulase). Preferably, the enzyme is present in the composition at a level of about 0.00001% to about 5% by weight of the composition, preferably about 0.00001% to about 2%, more preferably about 0.0001% to about 1%, or even more preferably about 0.001% to about 0.5% of enzyme protein.

[0267] Preferably, the enzyme-containing composition further comprises an enzyme stabilizing system.

[0268] Preferably, the enzyme-containing composition described herein comprises about 0.001% to about 10%, about 0.005% to about 8%, or about 0.01% to about 6% by weight of the composition of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system compatible with the enzyme.

[0269] Preferably, the enzyme stabilizing system comprises at least one compound selected from the group consisting of: polyols (preferably 1,3-propanediol, ethylene glycol, glycerol, 1,2-propanediol, or sorbitol), inorganic salts (preferably CaCl2, MgCl2, or NaCl), short-chain (preferably C1-C3) carboxylic acids or their salts (preferably formic acid, formate (preferably sodium formate), acetic acid, acetate, or lactate), borates, boric acid, boronic acids (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes (preferably Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde bisulfite adducts. Preferably, the enzyme stabilizing system comprises a combination of at least two compounds selected from the group consisting of salts, polyols, and short-chain carboxylic acids, and preferably one or more compounds selected from the group consisting of borates, boric acids, boric acid compounds (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde bisulfite adducts. In particular, if a protease is present in the composition, a protease inhibitor may be added, preferably selected from borates, boric acids, boric acid compounds (preferably 4-FPBA), peptide aldehydes (preferably peptide aldehydes such as Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde bisulfite adducts.

[0270] As used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular form "a / an" also includes the corresponding plural. In the context of this invention, the terms "about" and "approximately" indicate a range of precision that, as will be understood by those skilled in the art, still ensures the technical effect of the features discussed. This term typically indicates a deviation from the indicated numerical value of ±20%, preferably ±15%, more preferably ±10%, and even more preferably ±5%.

[0271] Furthermore, the terms “first,” “second,” “third,” or “(a),” “(b),” “(c),” “(d),” etc., used in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequential or chronological order. It should be understood that such terms are interchangeable where appropriate, and the embodiments of the invention described herein can operate in orders other than those described or shown herein. Where the terms “first,” “second,” “third,” or “(a),” “(b),” “(c),” “(d),” “i,” “ii,” etc., relate to steps of a method, use, or experiment, there is no temporal or time interval coherence between these steps; that is, these steps may be performed simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months, or even years between such steps, unless otherwise indicated in this application as stated above or below.

[0272] Throughout this application, various publications have been cited. The disclosures of all such publications, and of the references cited therein, are hereby incorporated in their entirety into this application in order to provide a more comprehensive description of the prior art to which this invention pertains.

[0273] It should be understood that the term "comprising" is not limiting. For the purposes of this invention, the term "consisting of" is considered a preferred embodiment of the term "comprising / including". If a group is defined below as including at least a certain number of members, this means that groups consisting solely of those members are also covered.

[0274] The invention is further illustrated by the following examples, sequences, and accompanying drawings, from which other features, embodiments, aspects, and advantages of the invention can be obtained. Furthermore, unless otherwise indicated, these materials, methods, and examples are illustrative only and are not intended to be limiting. Attached Figure Description

[0275] Figure (1) shows a comparison of the temperature-dependent viscosity of pure C12 / C14-isosorbitol monoester (black figure) with the temperature-dependent viscosity of mixtures of C12 / C14-isosorbitol monoester with C12 / C14-fatty alcohol in 50:50 (gray) and 30:70 (light gray) ratios. The dotted lines indicate heating from 30°C / 40°C to 100°C, and the diamond lines indicate cooling from 100°C to 25°C / 30°C. Example

[0276] A) Synthesis of isosorbide sulfate

[0277] i) Synthesis of isosorbide monoester

[0278] Example 1

[0279] In a 2 L flask equipped with a 2-blade stirrer, heating mantle, and condenser, add 8 mol of isosorbide (1169.6 g; 146.2 g / mol), 1 mol of myristic acid (230.0 g; 228.4 g / mol; C14), and 1 mol of lauric acid (202.0 g; 200.3 g / mol; C12).

[0280] These substances were heated to 100°C under light nitrogen purging. At 110°C (the substances were completely liquid, two phases), a stirrer was started (250 rpm) and the temperature was increased to 160°C. At this temperature, a catalyst (tin(II) oxalate 0.5 g) was added, and the temperature was increased to 225°C at a rate of 25° / h.

[0281] The condensation began at 185°C. The reaction temperature was maintained for 4 h until the condensation was complete. The temperature was then maintained at 225°C for another 1.5 h. The mixture was then cooled to 130°C, at which point 10 g of water was added to deactivate the catalyst. The temperature was maintained at 130°C for another 30 min. The excess isosorbide was then stripped by distillation at 225°C / 10 mbar, and the remaining crude product was cooled to 100°C.

[0282] The reaction was controlled by gas chromatography. The process produced 535.5 g of dark brown waxy product, representing 85% of the theoretical yield (686.4 g).

[0283] ii) Sulphation

[0284] Example 2

[0285] In a continuously operating falling film reactor with jacketed cooling and overhead SO3 fumigation, 600 g of a mixture of 30% C12 / 14 isosorbide esters and 70% C12 / 14 fatty alcohols (Lorol® series, such as those commercially available from BASF) was reacted with 259.7 g of SO3. The SO3 was vented from 399.8 g of 65% fuming sulfuric acid by heating, diluted with nitrogen to 5% by volume, and brought into contact with the isosorbide-fatty alcohol mixture film via a nozzle. The crude sulfation product was neutralized in water containing 1% sodium dihydrogen phosphate x 1 H2O, and the pH was continuously adjusted to 6.5–7.5 with a 50% sodium hydroxide solution while cooling to < 40°C and mixing with ultra-turrax.

[0286] Example 3

[0287] In a continuously operating falling film reactor with jacketed cooling and overhead SO3 fumigation, 600 g of a mixture of 50% C12 / 14 isosorbide esters and 50% C12 / 14 fatty alcohols (Lorol® series, such as those commercially available from BASF) was reacted with 234.8 g of SO3. The SO3 was vented from 361.5 g of 65% fuming sulfuric acid by heating, diluted with nitrogen to 5% by volume, and brought into contact with the isosorbide-fatty alcohol mixture film via a nozzle. The crude sulfation product was neutralized in water containing 1% sodium dihydrogen phosphate x 1 H2O, and the pH was continuously adjusted to 6.5–7.5 with a 50% sodium hydroxide solution while cooling to < 40°C and mixing with ultra-turrax.

[0288] B) Measurement and application of isosorbide monoester (sulfate) / fatty alcohol (sulfate) mixtures

[0289] Example 4: Clear Melting Point Measurement

[0290] The clear melting points of isosorbide monoesters, fatty alcohols, and mixtures thereof were measured using a Reichert-Jung 302101 microscope, a Reichert Jung 651501 heating system and a V40W80 R6416 heating plate, and a testoterm 7000pT 100 temperature sensor, all under polarized light. For optical magnification to visually inspect the clear melting points, a Bausch & Lomb WF10x / 18 binocular and a 60 / - objective lens were used in the microscope. Prior to measurement, the samples were heated to 15°C above the estimated melting point, and a droplet of the sample was placed on a coverslip (VWR 18x18 mm, No. 1, ECN 631-1567), covered with a plastic cap, and stored at 23°C for 24 h. The plastic cap was removed, and the coverslip was then placed on the heating plate. The heating system was started at the lowest heat transfer rate. Observe the sample, and once the test sample changes from an opaque solid to a clear liquid, record the clear melting point displayed on the testoterm temperature sensor. The standard deviation of the clear melting point is ±0.5°C.

[0291] Table 1 shows clear melting point measurements for isosorbide monoesters, fatty alcohols, and mixtures thereof.

[0292] Table 1:

[0293]

[0294] Example 5: Viscosity

[0295] Oscillatory temperature sweep experiments were conducted using an HR 20 Discovery hybrid rheometer (TA Instruments, Germany) at a constant strain amplitude (10%) and frequency (1 Hz) using a plate-to-plate geometry (diameter = 40 mm, gap = 1000 µm). The material was first subjected to temperature ramps in the ranges of 30°C–100°C or 40°C–100°C, with a ramp rate of 1°C / min. The thermal reversibility of the material was then investigated by decreasing the temperature from 100°C to the initial temperature set for the ramp at the same rate (1°C / min).

[0296] i) C12 / C14 isosorbide monoester, ii) a 50:50 mixture of C12 / C14 isosorbide monoester / C12 / C14 fatty alcohol, and iii) a 30:70 mixture of C12 / C14 isosorbide monoester / C12 / C14 fatty alcohol, with temperature-dependent viscosity at [missing information]. Figure 1 As shown in the image.

[0297] C) Example 6: Emulsion polymerization of styrene / acrylic resins using a mixture of C12 / C14 isosorbide monoester sulfate / C12 / C14 fatty alcohol sulfate

[0298] equipment:

[0299] A 1.7-liter reaction vessel equipped with an anchor stirrer (stirring speed 100 rpm) immersed in a water bath for temperature control and a feed container attached to a weighing module for precise feed control (stirred container for monomer premixes, unstirred container for initiator feed).

[0300] Preparation of comonomer premixes:

[0301] Styrene, n-butyl acrylate, methacrylic acid, demineralized water, and a mixture of C12 / C14 isosorbide monoester sulfate / C12 / C14 fatty alcohol sulfate are mixed to produce a comonomer premix, which is then filled into a stirred feed container.

[0302] Preparation of initiator solution:

[0303] Sodium metabisulfite was dissolved in demineralized water to obtain an initiator solution, which was then filled into a non-stirred feed container.

[0304] Reaction procedure:

[0305] A solution of potassium persulfate in demineralized water was pre-filled into the reaction vessel. Then, 225 g of the comonomer premix was added and the temperature was raised to 60°C. At 60°C, 8 g of initiator solution was added to the reaction vessel. After 5 min, the comonomer premix and initiator solution were fed simultaneously. The comonomer premix was fed over a 150-minute period, and the initiator solution over a 160-minute period. After the initiator solution had been completely fed, the temperature was raised to 65°C and the mixture was stirred for another hour. The resulting dispersion was cooled to room temperature. The pH was adjusted to 7-8 using an ammonia solution (25% by weight).

[0306] Post-processing and analysis:

[0307] The dispersion was filtered through a 125 μm filter. The filter residue was rinsed with water, dried, and weighed to obtain the condensate content.

[0308] The amounts of the reactants mentioned above are given in Table 2.

[0309] Table 2:

[0310]

[0311] The styrene / acrylic dispersions prepared in Examples 6A and 6B were analyzed. The analytical data are detailed in Table 3.

[0312] Analytical methods for polymer dispersions:

[0313] Solids content: determined by drying approximately 5 g of polymer dispersion at 150°C for 20 minutes using a Mettler Toledo HR 83 moisture analyzer.

[0314] Viscosity: Measured at room temperature using a Büchner viscometer DV-II+ (RV rotor assembly) at 20 rpm.

[0315] Conversion rate: Calculated by dividing the measured solids content by the theoretical solids content.

[0316] Cocoate: Reported as dry coagulant as the sum of coagulant obtained by filtering the polymer dispersion using a 125-micron filter and coagulant collected from the agitator and reactor walls. Wet coagulant was dried at 130°C in a Mettler Toledo HR 83 moisture analyzer until constant weight was achieved.

[0317] Particle size: Reported as d50 measured using a Beckman Coulter LS 13320 laser diffraction particle size analyzer.

[0318] Visual evaluation: The polymer dispersion was cast onto a glass plate using a 100-micron doctor blade coater. After drying at room temperature for 24 hours, the polymer film was visually evaluated and graded on a scale of 1 to 6, with 1 being the best and 6 being the worst.

[0319] Water absorption: The polymer membrane (approximately 75 mm x 35 mm x 2 mm) was cast by drying the polymer dispersion in a Teflon mold at 50°C for 48 hours. The dried membrane was weighed and then immersed in deionized water at room temperature for 24 hours. The membrane was then weighed again after removing excess water. The weight increase due to water absorption was reported as a percentage.

[0320] Electrolyte stability: The following six electrolyte solutions were prepared and tested in this order: 1% NaCl, 10% NaCl, 1% CaCl2, 10% CaCl2, 1% Al2(SO4)3, and 10% Al2(SO4)3. To check electrolyte stability, 10 ml of polymer dispersion was mixed with 10 ml of electrolyte solution. The polymer dispersion was visually observed for coagulation after shaking the mixture. The concentrations of electrolytes at which the polymer dispersion remained stable (without coagulation) were reported.

[0321] Shear stability: 50 g of polymer emulsion was filled into a glass cylinder and placed under shear stress using a high-speed stirrer (LatexMST, MK2 model for synthetic rubber) at 14,000 rpm. Shear stress was applied for 30 minutes. If the emulsion coagulated before 30 minutes, the time of coagulation was recorded. If the emulsion remained stable for 30 minutes, it was filtered, and the filtration residue was measured.

[0322] Table 3:

[0323]

[0324] As shown in Table 3, stable styrene / acrylic polymers can be prepared using the anionic surfactant mixture of the present invention as an emulsifier. The conversion rate and water absorption rate are improved compared to the comparative examples.

Claims

1. A method for preparing isosorbide sulfate, the method comprising the following steps a) to c): a) React i) isosorbide and ii) a carboxylic acid containing at least 10 carbon atoms to obtain the first intermediate (I1); b) Mixing i) the first intermediate (I1) with ii) a fatty alcohol comprising at least 10 carbon atoms to obtain a second intermediate mixture (I2), wherein the second intermediate mixture (I2) comprises 35% to 90% by weight of the fatty alcohol; and c) Reacting i) the second intermediate mixture (I2) with ii) at least one of sulfur trioxide, fuming sulfuric acid, or pyrosulfuric acid in a falling film reactor. In order to obtain the isosorbide sulfate.

2. The method according to claim 1, wherein, This carboxylic acid contains at least 10 carbon atoms. - It's a linear chain; - Possesses a carboxyl group as its sole functional group; and / or - It is a C12 or C14 carboxylic acid or a mixture thereof.

3. The method according to claim 1 or 2, wherein, This fatty alcohol contains at least 10 carbon atoms. - It's a linear chain; - Possesses a primary alcohol group as its sole functional group; and / or - It is a C12, C14, C16 or C18 fatty alcohol or a mixture thereof, preferably a mixture of C12 and C14 fatty alcohols or a mixture of C16 and C18 fatty alcohols.

4. The method according to any one of claims 1 to 3, wherein, The second intermediate mixture (I2) contains 40% to 85%, preferably 50% to 80%, more preferably 60% to 75% by weight of the fatty alcohol or a mixture thereof.

5. The method according to any one of claims 1 to 4, wherein, In step c), the second intermediate mixture (I2) is reacted with sulfur trioxide.

6. The method according to any one of claims 1 to 5, wherein, The temperature in step c) is not higher than 98°C, not higher than 90°C, not higher than 80°C, not higher than 75°C, not higher than 70°C, not higher than 65°C, preferably not higher than 60°C, not higher than 55°C, or more preferably not higher than 50°C.

7. The method according to any one of claims 1 to 6, wherein, In step a), the molar ratio of isosorbide to carboxylic acid is at least 1.5:1, preferably at least 4:1 or more preferably at least 6:

1.

8. The method according to any one of claims 1 to 7, wherein, The first intermediate (I1) was purified by distillation.

9. Use of a fatty alcohol containing at least 10 carbon atoms during the sulfation of isosorbide esters, preferably for reducing the melt temperature and / or viscosity of the isosorbide esters, wherein the isosorbide esters contain an alkyl group having at least 10 carbon atoms and the sulfation is carried out in a falling film reactor.

10. A composition comprising isosorbide sulfate and fatty alcohol sulfate, wherein the isosorbide sulfate and the fatty alcohol sulfate each comprise an alkyl group having at least 10 carbon atoms, and at least 40% by combined weight of the isosorbide sulfate and the fatty alcohol sulfate is based on the fatty alcohol sulfate.

11. The composition according to claim 10, wherein, The alkyl group of the isosorbide sulfate - It is a linear chain; and / or - It is a C12 or C14 alkyl group, or the composition contains a mixture of C12 and C14 isosorbide sulfate.

12. The composition according to claim 10 or 11, wherein, The fatty alcohol sulfate - It is a linear chain; and / or - It is a C12, C14, C16 or C18 fatty alcohol sulfate or a mixture thereof, preferably a mixture of C12 and C14 fatty alcohol sulfate or a mixture of C16 and C18 fatty alcohol sulfate.

13. The composition according to any one of claims 10 to 12, wherein, At least 45%, preferably at least 50%, and more preferably at least 60% of the combined weight of the isosorbide sulfate and the fatty alcohol sulfate are based on the fatty alcohol sulfate or a mixture thereof.

14. The composition according to any one of claims 10 to 13, wherein, The composition is selected from the group consisting of: cleaning compositions, fabric and household care products, industrial and institutional cleaning products, cosmetic formulations, emulsifiers for emulsion polymerization, crude oil demulsifiers, pigment dispersions for inkjet inks, formulations for electroplating, adhesive compositions, dispersants for agricultural chemical formulations, preferably cleaning compositions and / or fabric and household care products and / or industrial and institutional cleaning products.

15. The composition according to any one of claims 10 to 14, further comprising: a) at least one element from the group consisting of: nonionic surfactants, amphoteric surfactants, builders, chelating agents, co-builders, alcohols, thickeners, water-soluble polymers, clay stain removers / anti-redeposition agents, polymer detergents, bleaching agents, bleach activators, brighteners, odor control agents, pigments, dyes, opacifiers, toners, dye transfer inhibitors, defoamers, corrosion inhibitors, softeners, and fragrances; b) An antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether; and / or c) At least one enzyme selected from the list of lipases, hydrolases, amylases, deoxyribonucleases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersases, oxidoreductases, keratinases, pectinases, pectinases, lactases, and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably selected from proteases.

16. Use of the composition according to any one of claims 10 to 15, wherein the composition A) Preferably, cleaning compositions and / or fabric and household care products are used for i) Improved removal of oily / greasy stains, and / or ii) Clay removal, and / or iii) Removal of particulate stains, and / or iv) Dispersion and / or emulsification of dirt, and / or v) Modification of the treated surface to improve re-contamination removal, and / or vi) Whiteness improvement and / or Most preferably used in cleaning compositions i) Removal of oily / greasy stains, and / or ii) Clay removal, Each of the preceding options i) to vi) is preferably used in laundry detergent formulations and / or handwashing detergent formulations and / or formulations suitable for (pre)treating textiles and / or soap, more preferably in liquid laundry detergent formulations and / or liquid handwashing detergent formulations; or B) Preferably used as an emulsifier in the polymerization reaction.

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