Non-caustic cleaning methods and their applications

Abstract

Detergent compositions and methods for cleaning articles and / or films using the surfactants described herein are disclosed. Compounds, compositions, and methods for using these compounds and compositions in detergents or cleaning compositions are also provided. These compounds, compositions, and methods particularly relate to cleaning compositions and methods that exhibit advantageous cleaning properties at a pH of 7 or lower. In particular, the compounds, compositions, and methods described herein can also be used as general surfactants in detergent compositions or in methods for cleaning articles or films.

Description

[0001] Cross-reference to related applications

[0002] This international patent application claims the benefit of U.S. Provisional Patent Application No. 63 / 033,998, filed June 3, 2020, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] Detergent compositions comprising the compounds described herein are provided, which may be used, for example, in methods of cleaning articles and / or membranes. Background Technology

[0004] Ethoxylated alkylphenols, particularly those containing a nonylphenol moiety as one of their structural units, have been used in industry as surfactants in cleaning solutions and detergents. However, nonylphenol and its ethoxylated derivatives are known to be toxic, particularly as endocrine hormone disruptors. Therefore, there is a need for more environmentally friendly, nonylphenol-free alternatives to these chemicals, and for the preparation of effective cleaning compositions that do not require the use of caustic agents (e.g., pH 7 or lower).

[0005] Due to the toxicity of nonylphenol and its ethoxylated derivatives, industrial applications have largely shifted towards linear / branched alcohol ethoxylates (LAEs). However, LAEs are generally less effective than nonylphenol ethoxylates. Therefore, there is a need for novel surfactants that are effective in several non-caustic (e.g., pH 7 or lower) industries or used as surfactants in cleaning applications. Summary of the Invention

[0006] This document discloses methods for using compounds and compositions that can be used as detergent / cleaning compositions to aid in cleaning films or articles. For example, this document discloses a method for cleaning articles, the method comprising contacting the articles with a cleaning composition comprising a compound having the following structure:

[0007]

[0008] Where A is optionally substituted phenyl, naphthalene, indole, purine, pyridine, quinoline, isoquinoline, pyrimidine, pyrrole, furan, thiophene, imidazole, or thiazole; and Z has a structure that partially comprises A or partially comprises B:

[0009]

[0010] Where X is -O-, -N(R) 10 -, -OC(O)-, -C(O)O-, -N(R) 10 )C(O)-、-C(O)N(R 10-, -OC(O)O-, -OC(O)N(R) 10 )-、-N(R 10 )C(O)O-, or -N(R 10 )C(O)N(R 10 -; n is an integer from 0 to 10; R6 and R9 are independently hydrogen, alkyl, or aryl; R7 is alkyl, aryl, or -(CH2)zOR 11 R8 is independently hydrogen, alkyl, or aryl; R 10 It is hydrogen, alkyl, or Z; R 11 It is hydrogen or alkyl; m is independently an integer from 3 to 20; and z is an integer from 1 to 10; and the pH of the cleaning composition is 7 or lower.

[0011] The methods described herein can be used to create cleaning compositions with a pH of about 1 to 7.

[0012] The portion B may have a structure of portion B1 or portion B2:

[0013]

[0014] Wherein R9 is independently hydrogen, alkyl, or aryl; and R 12 Independently for C3 to C 22 Alkyl or alkenyl groups.

[0015] The method described herein may have A with optional substituted phenyl, naphthyl, pyridyl, quinolinyl or isoquinolinyl groups.

[0016] The method according to claim 4, wherein A is an optionally substituted phenyl or naphthyl group.

[0017] This disclosure also relates to a method for using a cleaning article, the method comprising contacting the article with a cleaning composition comprising a compound having the following structure:

[0018]

[0019] R1, R2, R3, R4, and R5 are independently hydrogen, Z, alkyl, alkoxy, or two adjacent R groups combined to form a fused ring; Z has a structure that is partially A or partially B.

[0020]

[0021] Where X is -O-, -N(R) 10 -, -OC(O)-, -C(O)O-, -N(R) 10 )C(O)-、-C(O)N(R 10 -, -OC(O)O-, -OC(O)N(R) 10)-、-N(R 10 )C(O)O-, or -N(R 10 )C(O)N(R 10 -; n is an integer from 0 to 10; R6 and R9 are independently hydrogen, alkyl, or aryl; R7 is alkyl, aryl, or -(CH2)zOR 11 R8 is independently hydrogen, alkyl, or aryl; R 10 It is hydrogen, alkyl, or Z; R 11 It is hydrogen or alkyl; m is an integer from 3 to 20; and z is an integer from 1 to 10; and the pH of the cleaning composition is 7 or lower.

[0022] The methods described herein have cleaning compositions with a pH of about 1 to 7, 2 to 7, 3 to 7, 4 to 7, or 5 to 7.

[0023] The B structure has a partial B1 or partial B2 structure:

[0024]

[0025] Wherein R9 is independently hydrogen, alkyl, or aryl; and R 12 Independently for C3 to C 22 Alkyl or alkenyl groups.

[0026] The method described herein, wherein for the structure of Equation 2, at least one of R1, R2, R3, R4, and R5 is Z.

[0027] The compound may have the structure of Formula 3:

[0028]

[0029] Wherein R1, R2, R4, and R5 are independently hydrogen, alkyl, alkoxy, or Z; and

[0030] Z1, Z2, and Z independently possess a structure that is part of A or part of B:

[0031]

[0032] Where X is -O- or -N(R) 10 -; n is an integer from 0 to 5; R6 and R9 are independently hydrogen or alkyl; R7 is an alkyl group, or -(CH2)zOR 11 R8 is independently hydrogen, alkyl, or aryl; R 10 It is hydrogen, alkyl, or Z; R 11 It is hydrogen or alkyl; m is an integer from 3 to 20; z is an integer from 1 to 10.

[0033] The methods described herein, wherein for formulas 1 to 3, R1, R2, R3, R4 and R5 may be independently hydrogen or C1 to C4 alkyl.

[0034] For compounds of formulas 1 to 3, R1, R2, R3, R4 and R5 can be hydrogen.

[0035] In the method described herein, for compounds of formulas 1 to 3, R6 and R9 may be hydrogen.

[0036] For compounds of formulas 1 to 3, R8 can be hydrogen or methyl.

[0037] Compounds of formulas 1 to 3 may have the form -(CH2). z -OR 11 R7.

[0038] The methods described herein may have compounds of formulas 1 to 3, wherein the z of the compounds is 1 to 3.

[0039] Compounds of formulas 1 to 3 may have a C4 to C3 configuration. 22 alkyl R 11 .

[0040] The method disclosed herein can have compounds of formula 1 to formula 3, wherein X of the compound is -O- or -N(R10)-.

[0041] Compounds of Formulas 1 to 3 may have an X that is -O-.

[0042] Compounds of formulas 1 to 3 may have -N(R) 10 )-of X.

[0043] Compounds of formulas 1 to 3 may also have R as hydrogen. 10 .

[0044] The methods described herein may include compounds of Formula 1 or Formula 2, which have structures corresponding to the following

[0045]

[0046] Where m is an integer from 6 to 12.

[0047] Compounds of Formula 1 or Formula 2 may have m as an integer of 9 or 10.

[0048] The methods described herein may include articles, which are metal surfaces, glass surfaces, fabrics, utensils, polycarbonate surfaces, polysulfone surfaces, melamine surfaces, ceramic surfaces, porcelain surfaces, films, or combinations thereof.

[0049] The cleaning composition further comprises a cleaning aid.

[0050] The detergent additive may be an enzyme, an oxidizing agent, a condensed phosphate, an alkali metal silicate, an alkali metal metasilicate, a phosphonate, an aminocarboxylic acid, a carboxylic acid polymer, or a combination thereof.

[0051] Preferably, the article is a fabric, a vessel, or a film.

[0052] The membrane may be a membrane used in dairy processing.

[0053] The membrane may be a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, or a combination thereof.

[0054] The product may be contaminated with protein or oily soil.

[0055] The cleaning compositions used in the methods described herein may have a pH of about 2 to 7, about 3 to 7, about 4 to 7, or about 5 to 7.

[0056] Other purposes and features will be partly obvious and partly noted below. Attached Figure Description

[0057] Figure 1 The percentage of creamy dirt removal is shown by weight of the test pieces cleaned at pH 7, 9, and 11 using compounds A-9EO, NPE 9.5, and EH9 as described in Example 4, compared to the percentage of dried, soiled test pieces.

[0058] Figure 2 The percentage of milk fat removal, calculated by weight, is shown for cleaned specimens of compounds A-9EO, A-10EO, NPE 9.5, Barlox 12, and EH9 as described in Example 4, compared to dried, soiled specimens, with no pH adjustment or with the pH adjusted to 11.

[0059] Figure 3A The percentage of dirt removed by a tergotometer as described in Example 5 is shown for 500 ppm Aquanomic 2.0 low-temperature detergent and 600 ppm builder (1x), 1000 ppm Aquanomic 2.0 low-temperature detergent and 1200 ppm builder (2x), 500 ppm compound A-10EO, 500 ppm compound A-10EO plus 600 ppm builder, 500 ppm compound A-9EO, and 500 ppm compound A-9EO plus 600 ppm builder (natural beige dirt from L'Oreal TrueMatch Foundation).

[0060] Figure 3BThe percentage of dirt removed by an oscillating scrubber as described in Example 5 is shown for 500 ppm Aquanomic 2.0 low-temperature detergent (1x), 500 ppm Aquanomic 2.0 low-temperature detergent and 600 ppm Aquanomic 2.0 low-temperature builder (1x + builder), 500 ppm compound A-9EO, and 500 ppm compound A-9EO plus 600 ppm Aquanomic 2.0 low-temperature builder, 500 ppm compound A-10EO, 500 ppm compound A-10EO plus 600 ppm builder, 500 ppm NPE, and 500 ppm NPE plus 600 ppm builder (natural beige dirt from Neutrogena Healthy Skin Foundation).

[0061] In all the accompanying drawings, the corresponding reference numerals indicate the corresponding parts. Detailed Implementation

[0062] Compounds, compositions, and methods for using these compounds and compositions in detergent or cleaning compositions are provided. These compounds, compositions, and methods particularly relate to cleaning compositions and methods that exhibit favorable cleaning properties at a pH of 7 or lower. In particular, the compounds, compositions, and methods described herein can also be used as general surfactants in detergent compositions or in methods for cleaning articles or films.

[0063] This document discloses methods for using compounds and compositions that can be used as detergent / cleaning compositions to aid in cleaning films or articles. For example, this document discloses a method for cleaning articles, the method comprising contacting the articles with a cleaning composition comprising a compound having the following structure:

[0064]

[0065] Where A is optionally substituted phenyl, naphthalene, indole, purine, pyridine, quinoline, isoquinoline, pyrimidine, pyrrole, furan, thiophene, imidazole, or thiazole; and Z has a structure that partially comprises A or partially comprises B:

[0066]

[0067] Where X is -O-, -N(R) 10 -, -OC(O)-, -C(O)O-, -N(R) 10 )C(O)-、-C(O)N(R 10 -, -OC(O)O-, -OC(O)N(R) 10 )-、-N(R 10 )C(O)O-, or -N(R10 )C(O)N(R 10 -; n is an integer from 0 to 10; R6 and R9 are independently hydrogen, alkyl, or aryl; R7 is alkyl, aryl, or -(CH2)zOR 11 R8 is independently hydrogen, alkyl, or aryl; R 10 It is hydrogen, alkyl, or Z; R 11 It is hydrogen or alkyl; m is independently an integer from 3 to 20; and z is an integer from 1 to 10; and the pH of the cleaning composition is 7 or lower.

[0068] The methods described herein may include a cleaning composition having a pH of about 1 to 7, about 2 to 7, about 3 to 7, about 4 to 7, or about 5 to 7.

[0069] Part B may have the structure of part B1 or part B2:

[0070]

[0071] Wherein R9 is independently hydrogen, alkyl, or aryl; and R 12 Independently for C3 to C 22 Alkyl or alkenyl groups.

[0072] The method described herein may have A with optional substituted phenyl, naphthyl, pyridyl, quinolinyl or isoquinolinyl groups.

[0073] The methods described herein may also have A with optional substituted phenyl or naphthyl groups.

[0074] This disclosure also relates to a method for using a cleaning article, the method comprising contacting the article with a cleaning composition comprising a compound having the following structure:

[0075]

[0076] R1, R2, R3, R4, and R5 are independently hydrogen, Z, alkyl, alkoxy, or two adjacent R groups combined to form a fused ring; Z has a structure that is partially A or partially B.

[0077]

[0078] Where X is -O-, -N(R) 10 -, -OC(O)-, -C(O)O-, -N(R) 10 )C(O)-、-C(O)N(R 10 -, -OC(O)O-, -OC(O)N(R) 10 )-、-N(R 10 )C(O)O-, or -N(R10 )C(O)N(R 10 -; n is an integer from 0 to 10; R6 and R9 are independently hydrogen, alkyl, or aryl; R7 is alkyl, aryl, or -(CH2)zOR 11 R8 is independently hydrogen, alkyl, or aryl; R 10 It is hydrogen, alkyl, or Z; R 11 It is hydrogen or alkyl; m is an integer from 3 to 20; and z is an integer from 1 to 10; and the pH of the cleaning composition is 7 or lower.

[0079] The methods described herein have cleaning compositions with a pH of about 1 to 7, 2 to 7, 3 to 7, 4 to 7, or 5 to 7.

[0080] The B structure has a partial B1 or partial B2 structure:

[0081]

[0082] Wherein R9 is independently hydrogen, alkyl, or aryl; and R 12 Independently for C3 to C 22 Alkyl or alkenyl groups.

[0083] The method described herein, wherein for the structure of Equation 2, at least one of R1, R2, R3, R4, and R5 is Z.

[0084] The compound may have the structure of Formula 3:

[0085]

[0086] Wherein R1, R2, R4, and R5 are independently hydrogen, alkyl, alkoxy, or Z; and

[0087] Z1, Z2, and Z independently possess a structure that is part of A or part of B:

[0088]

[0089] Where X is -O- or -N(R) 10 -; n is an integer from 0 to 5; R6 and R9 are independently hydrogen or alkyl; R7 is an alkyl group, or -(CH2)zOR 11 R8 is independently hydrogen, alkyl, or aryl; R 10 It is hydrogen, alkyl, or Z; R 11 It is hydrogen or alkyl; m is an integer from 3 to 20; z is an integer from 1 to 10.

[0090] The methods described herein, wherein for formulas 1 to 3, R1, R2, R3, R4 and R5 may be independently hydrogen or C1 to C4 alkyl.

[0091] For compounds of formulas 1 to 3, R1, R2, R3, R4 and R5 can be hydrogen.

[0092] In the method described herein, for compounds of formulas 1 to 3, R6 and R9 may be hydrogen.

[0093] For compounds of formulas 1 to 3, R8 can be hydrogen or methyl.

[0094] Compounds of formulas 1 to 3 may have the form -(CH2). z -OR 11 R7.

[0095] The methods described herein may have compounds of formulas 1 to 3, wherein the z of the compounds is 1 to 3.

[0096] Compounds of formulas 1 to 3 may have a C4 to C3 configuration. 22 alkyl R 11 .

[0097] The method disclosed herein can have compounds of formula 1 to formula 3, wherein X of the compound is -O- or -N(R10)-.

[0098] Compounds of Formulas 1 to 3 may have an X that is -O-.

[0099] Compounds of formulas 1 to 3 may have -N(R) 10 )-of X.

[0100] Compounds of formulas 1 to 3 may also have R as hydrogen. 10 .

[0101] The methods described herein may include compounds of Formula 1 or Formula 2, which have structures corresponding to the following

[0102]

[0103] Where m is an integer from 6 to 12.

[0104] Compounds of Formula 1 or Formula 2 may have m as an integer of 9 or 10.

[0105] The methods described herein may include articles, which are metal surfaces, glass surfaces, fabrics, utensils, polycarbonate surfaces, polysulfone surfaces, melamine surfaces, ceramic surfaces, porcelain surfaces, films, or combinations thereof.

[0106] The cleaning composition further comprises a cleaning aid.

[0107] The detergent additive may be an enzyme, an oxidizing agent, a condensed phosphate, an alkali metal silicate, an alkali metal metasilicate, a phosphonate, an aminocarboxylic acid, a carboxylic acid polymer, or a combination thereof.

[0108] Preferably, the article is a fabric, a vessel, or a film.

[0109] The membrane may be a membrane used in dairy processing.

[0110] The membrane may be a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, or a combination thereof.

[0111] The product may be contaminated with protein or oily soil.

[0112] A method for preparing the compounds described herein is also disclosed, the method comprising reacting compound (A) with compound (B) to form compound (C); and further reacting compound (C) with compound (D) to form compound (E).

[0113]

[0114] A, X, R6, R7, R8, R9, n, and m are as defined above for compounds.

[0115] Another method for preparing the compounds described herein includes reacting compound (F) with R-XH and an acid catalyst to form compound (G); and further reacting compound (G) with compound (D) to form compound (H); or

[0116]

[0117] Compound (F) is reacted with R-XH and a base catalyst to form compound (J); and compound (J) is further reacted with compound (D) to form compound (K);

[0118]

[0119] Wherein A, X, R6, R7, R8, R9, n and m are as defined with respect to the compounds herein; and R is independently hydrogen or alkyl.

[0120] The compounds having the structure of Formula 1, Formula 2, or Formula 3 can be prepared by the following synthetic schemes:

[0121]

[0122] A, X, R6, R7, R8, m, and n are defined as above.

[0123]

[0124] Where A, X, m, and n are as defined above, and R is independently hydrogen or alkyl.

[0125] Composition

[0126] The compounds described herein can also be used as general surfactants, for example, in detergents or cleaning solutions.

[0127] Exemplary cleaning or detergent compositions include, but are not limited to, dishwashing detergents, rinsing aids, floor cleaners, pre-soaks, hand cleaners, degreasers, hard surface cleaners, laundry detergents, disinfectants, food and beverage equipment cleaners, and dairy cleaners. Cleaning compositions and detergent compositions comprising compounds of formula 1, 2, or 3 as described herein are provided. These compositions can be used in a variety of cleaning applications as described above, but are particularly suitable as detergents or membrane cleaners.

[0128] The cleaning and / or detergent compositions described herein may comprise compounds of formula 1, 2 or 3 as described herein, as well as at least one of a builder, chelating agent, scale inhibitor, surfactant or any combination thereof.

[0129] Based on the total weight of the detergent and / or cleaning composition as described herein, the detergent and / or cleaning composition may contain from about 0.001% by weight to about 99% by weight of a compound of formula 1, formula 2 or formula 3.

[0130] builder

[0131] Therefore, cleaning compositions or detergent compositions are provided that comprise a cleaning aid and a compound of formula 1, 2 or 3 as described herein.

[0132] Based on the total weight of the detergent composition or cleaning composition, the detergent composition or cleaning composition may contain about 0.1% by weight to about 90% by weight of a detergent builder.

[0133] Examples of suitable detergent builders include, but are not limited to, alkali metal carbonates, alkali metal hydroxides, and alkali metal silicates. Exemplary alkali metal carbonates that may be used include, but are not limited to, sodium or potassium carbonates, bicarbonates, sesquicarbonates, and mixtures thereof. Exemplary alkali metal hydroxides that may be used include, but are not limited to, sodium hydroxide or potassium hydroxide. Alkali metal hydroxides may be added to the composition in any form known in the art, including as solid beads, dissolved in an aqueous solution, or combinations thereof. Examples of alkali metal silicates include, but are not limited to, sodium or potassium silicate or polysilicates, sodium metasilicate or potassium metasilicate, and hydrated sodium metasilicate or potassium metasilicate, or combinations thereof.

[0134] Builders may include alkaline detergent builders. For example, builders may include enzymes, oxidants, condensed phosphates, alkali metal carbonates, alkali metal silicates, alkali metal metasilicates, phosphonates, aminocarboxylic acids, carboxylic acid polymers, or combinations thereof. The detergent composition or cleaning composition may further comprise chelating agents, surfactants, enzymes, or other components as described below.

[0135] Chelating agents

[0136] The cleaning or detergent compositions disclosed herein may also contain chelating agents. Chelating agents include, but are not limited to, chelating agents, sequestering agents, and sequestrants. Examples of chelating agents include, but are not limited to, phosphonates, phosphates, aminocarboxylates and their derivatives, pyrophosphates, polyphosphates, ethylenediamine and ethylenetriamine derivatives, hydroxy acids, and monocarboxylates, dicarboxylates, and tricarboxylates and their corresponding acids. Other exemplary chelating agents include aluminosilicates, nitroacetates and their derivatives, and mixtures thereof.

[0137] Suitable aminocarboxylic acids according to this disclosure include, but are not limited to, methylglycine diacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA) (including tetrasodium ethylenediaminetetraacetic acid), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminesuccinic acid (EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid (IDS), 3-hydroxy-2-2′-iminodisuccinic acid (HIDS), and other similar acids or salts thereof having an amino group with a carboxylic acid substituent. Further descriptions of suitable aminocarboxylate salts suitable for use as chelating agents and / or multivalent chelating agents are presented in Volume 5, pp. 339-366 and Volume 23, pp. 319-320 of the third edition of the Encyclopedia of Chemical Technology, the disclosures of which are incorporated herein by reference.

[0138] The chelating agent may be water-soluble and / or biodegradable. Other exemplary chelating agents include TKPP (tetrapotassium pyrophosphate), PAA (polyacrylic acid) and its salts, phosphonobutane carboxylic acid, alanine, N,N-bis(carboxymethyl)-,trisodium salt, and sodium gluconate.

[0139] The chelating agent may be phosphorus-free. The chelating agent may also be used as a curing agent to help form a solid composition (e.g., a sodium salt of citric acid).

[0140] Preferably, the chelating agent is a sodium salt of an aminocarboxylic acid. More preferably, the chelating agent is methylglycine diacetic acid (MGDA).

[0141] Alternatively, the cleaning or detergent compositions disclosed herein may be free of chelating agents, detergent builders, or both. Alternatively, the cleaning or detergent compositions disclosed herein may be free of phosphorus-containing chelating agents, phosphorus-containing detergent builders, or both.

[0142] scale inhibitor

[0143] The cleaning or detergent composition may further comprise one or more scale inhibitors. Suitable scale inhibitors include, but are not limited to, phosphates, phosphate esters, phosphoric acid, phosphonates, phosphonic acids, polyacrylamide, salts of acrylamide methyl propane sulfonate / acrylic acid copolymer (AMPS / AA), phosphomaleic acid copolymer (PHOS / MA), monophosphosuccinic acid (PSO) derivatives, diphosphosuccinic acid derivatives and oligophosphosuccinic acid derivatives, polycarboxylic acids, hydrophobically modified polycarboxylic acids, and salts of polymaleic acid / acrylic acid / acrylamide methyl propane sulfonate terpolymer (PMA / AA / AMPS). Suitable polycarboxylic acid polymers may comprise one or more monomers selected from the group consisting of: acrylic acid, methacrylic acid, ethylacrylic acid, maleic acid, maleic anhydride, and itaconic acid.

[0144] Alternatively, the cleaning or detergent compositions disclosed herein may be free of scale inhibitors.

[0145] enzymes

[0146] The cleaning or detergent compositions disclosed herein may contain enzymes. The enzymes in the cleaning or detergent compositions enhance dirt removal, prevent redeposition, and / or reduce foaming during application of the cleaning composition or its solution. The function of the enzymes is to break down adhered dirt, such as starchy or proteinaceous substances, which are typically present on soiled surfaces and are removed by the cleaning or detergent composition entering the wash water source.

[0147] Exemplary types of enzymes that may be incorporated into the cleaning or detergent compositions disclosed herein include, but are not limited to, amylases, proteases, lipases, cellulases, keratins, glucosidases, peroxidases, and / or mixtures thereof. The cleaning compositions disclosed herein may employ more than one enzyme from any suitable source (e.g., plant, animal, bacterial, fungal, or yeast sources). The enzyme may be a protease. As used herein, the term "protease" refers to an enzyme that catalyzes the hydrolysis of peptide bonds.

[0148] As those skilled in the art will understand, enzymes are designed to work against specific types of dirt. For example, proteases can be used in dishwashing applications because they are effective at the high temperatures of dishwashing equipment and in reducing protein-based dirt. Proteases are particularly effective at cleaning protein-containing dirt such as blood, skin flakes, mucus, grass, food (e.g., eggs, milk, spinach, meat scraps, tomato sauce), etc. Proteases are able to cleave the large protein chains of amino acid residues and break down the substrate into smaller fragments that are easily dissolved or dispersed in aqueous solutions. Due to their ability to break down dirt through a chemical reaction called hydrolysis, proteases are often referred to as cleaning enzymes. Proteases can be obtained, for example, from Bacillus subtilis, Bacillus licheniformis, and Streptomyces griseus. Proteases are also commercially available in the form of serine endopeptides.

[0149] Examples of commercially available proteases can be obtained under the following product names: PrimeL, Prosperase, and BLAP.

[0150] The enzyme to be included in the cleaning composition can be a standalone entity and / or can be formulated in combination with the cleaning composition. For example, the enzyme can be formulated into a cleaning composition in liquid or solid form. Additionally, the enzyme composition can be formulated into various delayed-release or controlled-release formulations. For instance, a solid molding cleaning composition can be prepared without heating. Enzymes can denature due to heat, so using enzymes in a cleaning composition may require a method for forming the cleaning composition that does not rely on heat as a step in the forming process (e.g., curing).

[0151] Enzyme compositions are commercially available in solid (i.e., ice ball, powder, etc.) or liquid formulations. Commercially available enzymes are typically combined with stabilizers, buffers, cofactors, and inert carriers. As understood in the art, the actual active enzyme content depends on the manufacturing method.

[0152] Alternatively, the enzyme composition may be provided separately from the cleaning composition or detergent composition and, for example, added directly to the use solution or washing liquid of the cleaning composition or detergent composition, or to the washing water of an application (e.g., a dishwasher).

[0153] surfactants

[0154] The cleaning composition or detergent composition may also contain a surfactant. The surfactant may be anionic, cationic, nonionic, amphoteric, zwitterionic, and / or twinned surfactants.

[0155] Anionic surfactants

[0156] Cleaning compositions or detergent compositions may contain anionic surfactants. Anionic surfactants are surfactants with a negative charge on their hydrophobic components; or surfactants (e.g., carboxylic acids) whose hydrophobic portions of the molecule are uncharged unless the pH is raised to neutral or higher. Carboxylates, sulfonates, sulfates, and phosphates are polar (hydrophilic) solubilizing groups present in anionic surfactants. Among the cations (counterions) associated with these polar groups, sodium, lithium, and potassium impart water solubility; ammonium and substituted ammonium ions provide both water and oil solubility; and calcium, barium, and magnesium promote oil solubility. As those skilled in the art will understand, anionic surfactants are excellent detergent surfactants and are therefore advantageously added to heavy-duty cleaning compositions.

[0157] Suitable anionic sulfate surfactants for use in this composition include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oil-based glycerol sulfates, alkylphenol ethylene oxide ether sulfates, and C5-C... 17 Acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) reduced glucosamine sulfates and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides. Also includes alkyl sulfates, alkyl poly(ethyloxy) ether sulfates, and aromatic poly(ethyloxy) sulfates, such as sulfates or condensation products of ethylene oxide and nonylphenol (typically having 1 to 6 vinyl oxide groups per molecule).

[0158] The anionic sulfonate surfactants suitable for use in the compositions of the present invention also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

[0159] Anionic carboxylate surfactants suitable for use in the compositions of the present invention include carboxylic acids (and carboxylates), such as alkyl acids (and alkylates), carboxylic acid esters (e.g., alkyl succinate esters), carboxylic acid ethers, sulfonated fatty acids, such as sulfonated oleic acid, etc. Such carboxylates include alkyl ethoxycarboxylates, alkyl aryl ethoxycarboxylates, alkyl polyethoxy polycarboxylates surfactants, and soaps (e.g., alkyl carboxyl groups). Secondary carboxylates that can be used in the compositions of the present invention include those containing a carboxyl unit linked to a secondary carbon. The secondary carbon may be cyclic, such as in the form of p-octylbenzoic acid or in the form of an alkyl-substituted cyclohexylcarboxylate. Secondary carboxylate surfactants typically do not contain ether bonds, ester bonds, or hydroxyl groups. Furthermore, they generally do not have a nitrogen atom in the head group (amphiphilic moiety). Suitable secondary soap surfactants typically contain 11 to 13 total carbon atoms, but more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acyl amino acids (and salts), such as acylglutamate, acyl peptides, sarcosine salts (e.g., N-acylsarcosine), tartrates (e.g., fatty acid amides of N-acyl tartrate and methylaminoethanesulfonate), etc.

[0160] Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula:

[0161] R–O–(CH2CH2O) n (CH2) m –CO2X (3)

[0162] Where R is C8 to C 22 alkyl groups or Where R 1 It is C4-C 16 Alkyl group; n is an integer from 1 to 20; m is an integer from 1 to 3; and X is a counterion, such as hydrogen, sodium, potassium, lithium, ammonium, or an amine salt, such as monoethanolamine, diethanolamine, or triethanolamine. In some embodiments, n is an integer from 4 to 10 and m is 1. In some embodiments, R is C8-C. 16 Alkyl group. In some embodiments, R is C 12 -C 14 Alkyl groups, n is 4, and m is 1.

[0163] In other embodiments, R is... And R 1 For C6-C 12 Alkyl group. In yet other embodiments, R 1 It is a C9 alkyl group, n is 10 and m is 1.

[0164] These alkyl and alkylaryl ethoxycarboxylates are commercially available. These ethoxycarboxylates are typically obtained in acidic form that can be readily converted to anionic or salt forms. Commercially available carboxylates include: NEODOX 23-4 (a C... 12 -C 13 Alkyl polyethoxy(4)carboxylic acid (Shell Chemical) and EMCOL CNP-110 (a C9 alkyl aryl polyethoxy(10)carboxylic acid (Witco Chemical)). Carboxylates are also available from Clariant, for example, the product SANDOPAN DTC, a C... 13 Alkyl polyethoxy(7)carboxylic acid.

[0165] In some embodiments, the cleaning or detergent compositions disclosed herein do not contain anionic surfactants.

[0166] Nonionic surfactants

[0167] Cleaning compositions or detergent compositions may contain nonionic surfactants.

[0168] Suitable nonionic surfactants are typically characterized by the presence of both organic hydrophobic and organic hydrophilic groups, and are generally produced by the condensation of an organic aliphatic, alkyl aromatic, or polyoxyethylene hydrophobic compound with a hydrophilic basic oxide moiety, typically ethylene oxide or its polyhydrated form, polyethylene glycol. In fact, any hydrophobic compound having hydroxyl, carboxyl, amino, or amide groups with reactive hydrogen atoms can be condensed with ethylene oxide, its polyhydrated adduct, or a mixture thereof with an ethylene oxide such as propylene oxide to form a nonionic surfactant. The length of the hydrophilic polyoxyethylene moiety condensed with any particular hydrophobic compound can be readily adjusted to produce a water-dispersible or water-soluble compound with a desired balance between hydrophilic and hydrophobic properties. Useful nonionic surfactants include block polyoxypropylene-polyoxyethylene polymers based on reactive hydrogen compounds initiated by propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine. Examples of polymeric compounds prepared by sequential propoxylation and ethoxylation of an initiator are commercially available from BASF Corp. One class of compounds is a bifunctional (two reactive hydrogens) compound formed by the condensation of ethylene oxide with a hydrophobic matrix, the hydrophobic matrix being formed by adding propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule weighs from about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobic component between hydrophilic groups, the length of which is controlled to constitute from about 10% to about 80% by weight of the final molecule. Another class of compounds is a tetrafunctional block copolymer derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the hydrotype propylene oxide is in the range of about 500 to about 7,000; and the hydrophilic ethylene oxide is added to constitute from about 10% to about 80% by weight of the molecule.

[0169] Suitable nonionic surfactants also include condensation products of one mole of alkylphenol and about 3 to about 50 moles of ethylene oxide, wherein the alkylphenol contains about 8 to about 18 carbon atoms in a straight-chain or branched alkyl chain, or a monoalkyl or dialkyl component. The alkyl group can be represented by, for example, diisobutylene, dipentyl, polypropylene, isooctyl, nonyl, and dinonyl. These surfactants can be polyoxyethylene, polyoxypropylene, and polyoxybutylene condensates of alkylphenols. Examples of commercially available compounds with this chemical property are available under trade names. (Made by Rhone-Poulenc) and (Originally manufactured by Union Carbide)

[0170] Nonionic surfactants can also be the condensation product of one mole of a saturated or unsaturated, straight-chain or branched alcohol having about 6 to about 24 carbon atoms and about 3 to about 50 moles of ethylene oxide. The alcohol moiety can consist of a mixture of alcohols within the carbon range described above, or it can consist of alcohols having a specific number of carbon atoms within this range. An example of a similar commercial surfactant is LUTENSOL, manufactured by BASF. TM DEHYDOL TM NEODOL manufactured by Shell Chemical Co. TM and ALFONIC manufactured by Vista Chemical Company TM get.

[0171] The nonionic surfactant also includes one mole of a condensation product of a saturated or unsaturated, straight-chain or branched carboxylic acid having about 8 to about 18 carbon atoms and about 6 to about 50 moles of ethylene oxide. The acid moiety may consist of a mixture of acids within the carbon atom range defined above, or may consist of acids having a specific number of carbon atoms within the said range. Examples of commercially available compounds of this chemical substance are manufactured by BASF under the trade names Disponil or Agnique and by Lipo Chemicals, Inc. under the trade name LIPOPEG. TM get.

[0172] In addition to ethoxylated carboxylic acids commonly referred to as polyethylene glycol esters, other alkyl esters formed by reacting with glycerol esters, glycerol, and polyhydroxy (saccharides or dehydrated sorbitol / sorbitol) alcohols also have applications in certain embodiments of this disclosure, particularly in indirect food additive applications. All these ester moieties have one or more reactive hydrogen sites on their molecules, which can be further acylated or added to ethylene oxide (alkoxide) to control the hydrophilicity of these substances. When these fatty esters or acylated carbohydrates are added to compositions containing amylases and / or lipases, special care must be taken due to potential incompatibilities.

[0173] Examples of nonionic low-foaming surfactants include substantially opposite compounds modified by adding ethylene oxide to ethylene glycol to provide hydrophilicity at a specified molecular weight; and then adding propylene oxide to obtain a hydrophobic block at the molecule's exterior (end). The molecular weight of the hydrophobic portion of the molecule is from about 1,000 to about 3,100, with the intermediate hydrophilic portion accounting for 10% to about 80% by weight of the final molecule. These inverse Pluronics are manufactured by BASF under the trademark PLURONIC. TM R surfactant. Similarly, TETRONIC TMThe R surfactant is produced by BASF by sequentially adding ethylene oxide and propylene oxide to ethylenediamine. The hydrophobic portion of the molecule has a molecular weight of about 2,100 to about 6,700, while the intermediate hydrophilic portion accounts for 10% to 80% by weight of the final molecule.

[0174] Compounds modified in the following ways reduce foaming by "end-capping" or "terminal blocking" one or more terminal hydroxyl groups (of the multifunctional moiety) through reaction with hydrophobic small molecules such as propylene oxide, butane oxide, and benzyl chloride; and short-chain fatty acids, alcohols, or alkyl halides containing one to five carbon atoms; and mixtures thereof. Reactants that convert terminal hydroxyl groups to chlorine groups, such as thionyl chloride, are also included. This modification of the terminal hydroxyl group can produce fully block, intercalated, intercalated, or fully mixed nonionic surfactants.

[0175] Additional examples of effective low-foaming nonionic surfactants include, but are not limited to:

[0176] (a) Alkylphenoxy polyethoxyalkyl alcohols of U.S. Patent No. 2,903,486 to Brown et al., issued on September 8, 1959, and represented by the following formula:

[0177]

[0178] Where R is an alkyl group with 8 to 9 carbon atoms, A is an alkylene chain with 3 to 4 carbon atoms, n is an integer from 7 to 16, and m is an integer from 1 to 10.

[0179] (b) A polyalkylene glycol condensate of U.S. Patent No. 3,048,548 to Martin et al., issued on August 7, 1962, having alternating hydrophilic ethylene oxide chains and hydrophobic propylene oxide chains, wherein the weight of the terminal hydrophobic chain, the weight of the intermediate hydrophobic unit, and the weight of the connecting hydrophilic unit each constitute about one-third of the condensate.

[0180] (c) The defoaming nonionic surfactant disclosed in U.S. Patent No. 3,382,178 to Lissant et al., issued on May 7, 1968, having the general formula Z[(OR)] n [OH]z, where Z is an alkoxylated substance, R is a free radical derived from an oxidized alkene, which may be ethylene or propyleneene, and n is, for example, an integer from 10 to 2,000 or greater, and z is an integer determined by the number of reactive alkoxylated groups.

[0181] (d) The conjugated polyoxyethylene compound described in U.S. Patent No. 2,677,700 to Jackson et al., issued on May 4, 1954, which corresponds to the formula Y(C3H6O). n (C2H4O) mH, where Y is a residue of an organic compound having about 1 to 6 carbon atoms and one reactive hydrogen atom, as determined by the number of hydroxyl groups, n has an average value of at least about 6.4, and m has a value such that the oxyethylene moiety constitutes about 10% to about 90% by weight of the molecule.

[0182] (e) The conjugated polyoxyalkylene compound described in U.S. Patent No. 2,674,619 to Lundsted et al., issued on April 6, 1954, having the formula Y[(C3H6O)] n (C2H4O) m H] x Wherein Y is a residue of an organic compound having about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, wherein the value of x is at least about 2, the value of n is such that the molecular weight of the hydrophobic polyoxypropylene matrix is ​​at least about 900, and the value of m is such that the ethylene oxide content of the molecule is from about 10% by weight to about 90% by weight. Compounds falling within the definition of Y include, for example, propylene glycol, glycerol, pentaerythritol, trimethylolpropane, ethylenediamine, etc. The propylene oxide chain optionally but advantageously contains a small amount of ethylene oxide, and the ethylene oxide chain also optionally but advantageously contains a small amount of propylene oxide.

[0183] Advantageously, the additional conjugated polyoxyethylene surfactant used in the compositions of this disclosure corresponds to the formula: P[(C3H6O)] n (C2H4O) m H] x , wherein P is a residue of an organic compound having about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, wherein the value of x is 1 or 2, n has a value such that the molecular weight of the polyoxyethylene moiety is at least about 44, and m has a value such that the propylene oxide content of the molecule is 10% to 90% by weight. In either case, the propylene oxide chain may optionally but advantageously contain a small amount of ethylene oxide, and the ethylene oxide chain may also optionally but advantageously contain a small amount of propylene oxide.

[0184] Suitable polyhydroxy fatty acid amide surfactants for use in the compositions of the present invention include those having the structural formula R2CONR. 1 Z is a polyhydroxy fatty acid amide surfactant, wherein: R 1 It is H, C1-C4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or a mixture thereof; R2 is C5-C 31 The hydrocarbon group can be straight-chain; and Z is a polyhydroxy hydrocarbon group or its alkoxylated derivative (preferably ethoxylated or propoxylated) having a straight-chain hydrocarbon chain with at least three hydroxyl groups directly linked to the chain. Z can be derived from reducing sugars in reductive amination reactions, such as the glycidyl moiety.

[0185] Alkyl ethoxylation condensation products of fatty alcohols with about 0 to about 25 moles of ethylene oxide are suitable for use in the compositions of the present invention. The alkyl chain of the fatty alcohol may be straight or branched, primary or secondary, and typically contains 6 to 22 carbon atoms.

[0186] Ethoxylated C6-C 18 fatty alcohols and C6-C 18 Mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the compositions disclosed herein, particularly in water-soluble compositions. Suitable ethoxylated fatty alcohols comprise C6-C atoms with an ethoxylation degree of 3 to 50. 18 Ethoxylated fatty alcohols.

[0187] Suitable nonionic alkyl polysaccharide surfactants particularly suitable for use in the compositions disclosed herein include those disclosed in U.S. Patent 4,565,647 to Llenado, issued January 21, 1986. These surfactants comprise a hydrophobic group containing about 6 to about 30 carbon atoms; and a hydrophilic group of a polysaccharide, such as a polysaccharide glycoside containing about 1.3 to about 10 sugar units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example, glucose, galactose, and galactosyl moieties can be used to replace the glucosyl moieties. (Optionally, the hydrophobic group is attached to 2-, 3-, 4-, etc., positions, thus yielding glucose or galactose as opposed to glucosides or galactosides). The interglycosylation can, for example, be located between a position of another sugar unit and the aforementioned 2-, 3-, 4-, and / or 6-positions on the sugar unit.

[0188] The fatty acid amide surfactant suitable for this composition comprises having the formula: R 6 CON(R 7 Those of )2, among which R 6 An alkyl group containing 7 to 21 carbon atoms and each R 7 Independently hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, or --(C2H4O) X H, where x is in the range of 1 to 3.

[0189] The applicable categories of nonionic surfactants include those defined as alkoxylated amines or, most specifically, alcohol alkoxylated / amined / alkoxylated surfactants. These nonionic surfactants can be represented, at least in part, by the following general formula: R 20 --(PO) S N--(EO) t H, R 20 --(PO) S N--(EO) t H(EO) t H and R 20 --N(EO) tH; where R 20 The alkyl, alkenyl, or other aliphatic or alkyl-aryl groups having 8 to 20, preferably 12 to 14 carbon atoms, EO being ethylene oxide, PO being propylene oxide, s being 1 to 20, preferably 2-5, and t being 1-10, preferably 2-5. Other variations in the range of these compounds can be expressed by the following alternative formulas: R 20 --(PO) V --N[(EO) w H][(EO) z H], where R 20 As defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and z are independently 1-10, preferably 2-5. These compounds are commercially represented by a range of products sold by Huntsman Chemicals as nonionic surfactants. Preferred chemicals in this category include SURFONIC. TM PEA 25 amine alkoxylate. Preferred nonionic surfactants used in the compositions disclosed herein include alcohol alkoxylates, EO / PO block copolymers, alkylphenol alkoxylates, etc.

[0190] The paper "Nonionic Surfactants," edited by Schick, MJ, Volume 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983, is an excellent reference for the wide variety of nonionic compounds commonly used in the practice of this invention. A typical list of nonionic classes and species of these surfactants is given in U.S. Patent No. 3,929,678, published by Laughlin and Heuring on December 30, 1975. Further examples are given in "Surfactants and Detergents" (Volumes I and II, by Schwartz, Perry, and Berch).

[0191] Suitable nonionic surfactants for use with the compositions disclosed herein include alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, fully or partially capped EO / PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixtures thereof, etc. Suitable alkoxylated surfactants for use as solvents include EO / PO block copolymers such as Pluronic and reverse Pluronic surfactants; alcohol alkoxylates such as Dehypon LS-54 (R-(EO)5(PO)4) and Dehypon LS-36 (R-(EO)3(PO)6); and capped alcohol alkoxylates such as Plurafac LF221 and Tegoten EC11; mixtures thereof, etc.

[0192] When the composition is not a cleaning composition, the composition may be free of nonionic surfactants.

[0193] Semi-polar nonionic surfactants

[0194] Cleaning compositions or detergent compositions may contain semi-polar nonionic surfactants.

[0195] Semi-polar nonionic surfactants are another class of nonionic surfactants that can be used in the compositions disclosed herein. Typically, semi-polar nonionic surfactants are high-foaming agents and foam stabilizers, which limits their application in CIP systems. However, in some embodiments designed for high-foaming or cleaning compositions, semi-polar nonionic surfactants will have direct utility. Semi-polar nonionic surfactants include, but are not limited to, amine oxides, phosphine oxides, sulfoxides, and their alkoxylated derivatives.

[0196] Amine oxides are tertiary amine oxides corresponding to the following general formula:

[0197]

[0198] The arrows typically represent semi-polar bonds; and R 1 R 2 and R 3 It can be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. Typically, for detergent-related amine oxides, R... 1 It is an alkyl radical having approximately 8 to approximately 24 carbon atoms; R 2 and R 3 It is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, or a mixture thereof; R 2 and R 3 A ring structure can be formed, for example, by oxygen or nitrogen atoms attaching to each other; R 4It is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms; and n is in the range of 0 to about 20.

[0199] Suitable water-soluble amine oxide surfactants are selected from coconut or animal fat alkyl di-(low carbon number alkyl) amine oxides, specific examples of which are dodecyl dimethyl amine oxide, tridecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, pentadecyl dimethyl amine oxide, hexadecyl dimethyl amine oxide, heptadecanyl dimethyl amine oxide, octadecyl dimethyl amine oxide, dodecyl dipropyl amine oxide, tetradecyl dipropyl amine oxide, hexadecyl dipropyl amine oxide, tetradecyl dibutyl amine oxide, octadecyl dibutyl amine oxide, bis(2-hydroxyethyl) dodecyl amine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropyl amine oxide, dimethyl-(2-hydroxydodecyl) amine oxide, 3,6,9-trioctadecyl dimethyl amine oxide, and 3-dodecoxy-2-hydroxypropyl di-(2-hydroxyethyl) amine oxide.

[0200] Suitable semi-polar nonionic surfactants also include water-soluble phosphine oxides having the following structure:

[0201]

[0202] The arrows represent the conventional representation of semi-polar bonds; R1 is an alkyl, alkenyl, or hydroxyalkyl moiety with a chain length ranging from 10 to about 24 carbon atoms; and R2 and R3 are each alkyl moiety selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

[0203] Examples of suitable phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, and bis(hydroxymethyl)tetradecylphosphine oxide.

[0204] The semi-polar nonionic surfactants applicable to this article also include water-soluble sulfoxide compounds having the following structures:

[0205]

[0206] The arrows represent the conventional representation of semi-polar bonds; and R1 is an alkyl or hydroxyalkyl moiety having about 8 to about 28 carbon atoms, 0 to about 5 ether bonds and 0 to about 2 hydroxyl substituents; and R2 is an alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.

[0207] Available examples of these sulfoxides include dodecylmethyl sulfoxide, 3-hydroxytridecylmethyl sulfoxide, 3-methoxytridecylmethyl sulfoxide, and 3-hydroxy-4-dodecoxybutylmethyl sulfoxide.

[0208] Semi-polar nonionic surfactants used in the composition include dimethyl amine oxides, such as lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, and combinations thereof. Available water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coconut, or animal fat alkyl di-(low carbon number alkyl) amine oxides, with specific examples including octyl dimethyl amine oxide, nonyl dimethyl amine oxide, decyl dimethyl amine oxide, undecyl dimethyl amine oxide, dodecyl dimethyl amine oxide, isododecyl dimethyl amine oxide, tridecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, pentadecyl dimethyl amine oxide, hexadecyl dimethyl amine oxide, and heptadecanyl dimethyl amine oxide. Aminohydride, octadecyl dimethylamine oxide, dodecyl dipropylamine oxide, tetradecyl dipropylamine oxide, hexadecyl dipropylamine oxide, tetradecyl dibutylamine oxide, octadecyl dibutylamine oxide, bis(2-hydroxyethyl) dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-tris(octadecyl)dimethylamine oxide and 3-dodecoxy-2-hydroxypropyl di-(2-hydroxyethyl)amine oxide.

[0209] Alternatively, the cleaning or detergent compositions disclosed herein may be free of semi-polar nonionic surfactants.

[0210] cationic surfactants

[0211] Cleaning compositions or detergent compositions may contain cationic surfactants.

[0212] If the co-water solvent portion of the molecule has a positive charge, then the surfactant is classified as cationic. This group also includes surfactants in which the co-water solvent is uncharged unless the pH is lowered to near neutral or lower, but which are then cationic (e.g., alkylamines). Theoretically, cationic surfactants can be made from surfactants containing an ononium structure R... n The synthesis can be any combination of X+Y elements and can include non-nitrogen (ammonium) compounds such as phosphorus (phosphonium) and sulfur (sulfonium). In fact, nitrogen-containing compounds dominate the field of cationic surfactants, possibly because the synthetic routes of nitrogen-containing cationic surfactants are simple and direct, and the yields of the products are high, which can make them less expensive.

[0213] Cationic surfactants preferably comprise, and more preferably, compounds containing at least one long-chain hydrophobic group and at least one positively charged nitrogen atom. The long-chain group can be directly attached to the nitrogen atom via simple substitution; or more preferably indirectly attached to the nitrogen atom via one or more bridging functional groups in so-called cleaved alkylamines and amide amines. Such functional groups can make the molecule more hydrophilic and / or more water-dispersible, more readily soluble in water via co-surfactant mixtures, and / or soluble in water. To improve water solubility, additional primary, secondary, or tertiary amines can be introduced, or the amino nitrogen can be quaternized using low-molecular-weight alkyl groups. Further, the nitrogen can be part of a branched or straight-chain portion of varying degrees of unsaturation, or part of a saturated or unsaturated heterocycle. Additionally, cationic surfactants can contain complex bonds having more than one cationic nitrogen atom.

[0214] Surfactant compounds classified as amine oxides, amphoteric surfactants, and zwitterionic surfactants are typically cationic in near-neutral to acidic pH solutions and may overlap with surfactant classifications. Polyoxyethylated cationic surfactants generally behave similarly to nonionic surfactants in alkaline solutions and similarly to cationic surfactants in acidic solutions.

[0215] The simplest cationic amines, amine salts, and quaternary ammonium compounds can be schematically described as follows:

[0216]

[0217] Wherein, R represents an alkyl chain, R', R”, and R”’ can be alkyl chains, aryl groups, or hydrogen, and X represents an anion. For practical use, amine salts and quaternary ammonium compounds are preferred because of their high water solubility.

[0218] Most commercially available cationic surfactants can be subdivided into four main categories and additional subgroups, as known to those skilled in the art and described in the Surfactant Encyclopedia, Cosmetics & Toiletries, Vol. 104(2) 86-96 (1989). The first category includes alkylamines and their salts. The second category includes alkylimidazolines. The third category includes ethoxylated amines. The fourth category includes quaternary ammonium salts, such as alkylbenzyl dimethyl ammonium salts, alkylbenzene salts, heterocyclic ammonium salts, tetraalkyl ammonium salts, etc. Cationic surfactants are known to possess a variety of properties that can be beneficial in the compositions of the present invention. These desirable properties can include detergency, antimicrobial efficacy, thickening or gelling properties in compositions at or below neutral pH, etc.

[0219] The cationic surfactants suitable for use in the compositions disclosed herein comprise having the formula R 1 m R 2 x Y L Those of Z, where each of R 1 It is an organic group containing a straight-chain or branched alkyl or alkenyl group, which is optionally substituted with up to three phenyl or hydroxyl groups and optionally with up to four of the following structures:

[0220]

[0221] These structures may be interrupted by isomers or mixtures, and they contain approximately 8 to 22 carbon atoms. R 1 The group may additionally contain up to 12 ethoxy groups, and m is a number from 1 to 3. Preferably, when m is 2, no more than one R1 group in the molecule has 16 or more carbon atoms, or when m is 3, it has more than 12 carbon atoms. Each R2 is an alkyl, hydroxyalkyl, or benzyl group containing 1 to 4 carbon atoms, wherein no more than one R1 group in the molecule has 12 carbon atoms. 2 It is benzyl, and x is 0 to 11, preferably 0 to 6. The remaining portion of any carbon atom position on the Y group is filled with hydrogen.

[0222] Y may include, but is not limited to, the following groups:

[0223]

[0224] p = approximately 1 to approximately 12

[0225] p = approximately 1 to approximately 12

[0226]

[0227] Or a mixture thereof. Preferably, L is 1 or 2, wherein when L is 2, the Y group is composed of R groups having 1 to about 22 carbon atoms and two free carbon single bonds. 1 and R 2 The analogues (preferably alkylene or alkenylene) are separated. Z is a water-soluble anion, such as a halide, sulfate, methyl sulfate, hydroxide, or nitrate anion, particularly preferably a chloride, bromide, iodide, sulfate, or methyl sulfate anion, in an amount that makes the cationic component electrically neutral.

[0228] Alternatively, the cleaning or detergent compositions disclosed herein may be free of cationic surfactants.

[0229] Amphoteric surfactants

[0230] Cleaning compositions or detergent compositions may contain amphoteric surfactants.

[0231] Amphoteric surfactants contain both basic and acidic hydrophilic groups, as well as organic hydrophobic groups. These ionic entities can be any of the anionic or cationic groups described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups used as basic and acidic hydrophilic groups. In several surfactants, sulfonate, sulfate, phosphonate, or phosphate groups provide a negative charge.

[0232] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, wherein the aliphatic group can be linear or branched and wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms and one contains an anionic water-co-solubilizing group, such as a carboxyl, sulfonic acid, sulfate, phosphate, or phosphonoyl group. Amphoteric surfactants are subdivided into two main categories, as known to those skilled in the art and described in the Surfactant Encyclopedia, Cosmetics & Toiletries, Vol. 104(2)69-71 (1989), which is incorporated herein by reference in its entirety. The first category comprises acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second category comprises N-alkyl amino acids and their salts. Some amphoteric surfactants may be considered to fall into either of these categories.

[0233] Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkylhydroxyethyl imidazoline can be synthesized by condensation and ring-closure of a long-chain carboxylic acid (or derivative) with a dialkylethylenediamine. Commercially available amphoteric surfactants are derivatized by alkylation, for example, using chloroacetic acid or ethyl acetate, which sequentially hydrolyzes and ring-opens the imidazoline ring. During alkylation, one or both carboxyl groups react to form a tertiary amine and an ether bond, wherein different alkylating agents produce different tertiary amines.

[0234] The long-chain imidazole derivatives used in this disclosure generally have the general formula:

[0235]

[0236] neutral pH zwitterions

[0237] Amphoteric sulfonates

[0238]

[0239] Wherein R is a noncyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation used to neutralize the charge of the anion, typically sodium. Commercially known imidazoline-derived amphoteric surfactants that can be used in the compositions of this invention include, for example: cocoa amphoteric propionate, cocoa amphoteric carboxypropionate, cocoa amphoteric glycinate, cocoa amphoteric carboxyglycinate, cocoa amphoteric propylsulfonate, and cocoa amphoteric carboxypropionic acid. The amphoteric carboxylic acid can be generated from aliphatic imidazolines, wherein the dicarboxylic acid functional group of the amphoteric dicarboxylic acid is diacetic acid and / or dipropionic acid.

[0240] The carboxymethylated compounds (glycine salts) described above in this article are often referred to as betaine. Betaine is a special class of amphoteric surfactants that will be discussed below in the section on zwitterionic surfactants.

[0241] Long-chain N-alkyl amino acids can be readily prepared by reacting RNH2 fatty amines with halocarboxylic acids, where R = C8-C. 18 Straight-chain or branched alkyl groups. Alkylation of the primary amino group of an amino acid yields secondary and tertiary amines. Alkyl substituents may have additional amino groups providing more than one reactive nitrogen center. Most commercially available N-alkylamino acids are alkyl derivatives of β-alanine or β-N(2-carboxyethyl)alanine. Examples of commercially available N-alkyl amino acid amphoteric electrolytes with applications include alkyl β-aminodipropionates, RN(C2H4COOM)2, and RNHC2H4COOM. In embodiments, R may be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation used to neutralize the charge of the anion.

[0242] Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. Other suitable coconut-derived surfactants include an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety (e.g., glycine), or a combination thereof as part of their structure; and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants can also be considered alkyl amphoteric dicarboxylic acids. These amphoteric surfactants can include chemical structures represented as follows: C 12 -alkyl-C(O)-NH-CH2-CH2-N+(CH2-CH2-CO2Na)2-CH2-CH2-OH or C 12 -alkyl-C(O)-N(H)-CH2-CH2-N+(CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoate is a suitable amphoteric surfactant and is available from Rhodia Inc., Cranbury, NJ under the trademark MIRANOL. TMPurchased from FBS. Another suitable coconut-derived chemical name is disodium cocoate diacetate, an amphoteric surfactant also produced by Rhodia Corporation in Clembury, New Jersey, under the brand name MIRATAINE. TM JCHA is available in the market.

[0243] A typical list of the amphoteric classes and types of these surfactants is given in U.S. Patent No. 3,929,678, published by Laughlin and Heuring on December 30, 1975. Further examples are given in *Surface Active Agents and Detergents* (Volumes I and II, by Schwartz, Perry, and Berch). These references are each incorporated herein by reference in their entirety.

[0244] Alternatively, the cleaning or detergent compositions disclosed herein may be free of amphoteric surfactants.

[0245] zwitterionic surfactants

[0246] Cleaning compositions or detergent compositions may contain facultative zwitterionic surfactants.

[0247] Facultative zwitterions can be considered a subgroup of amphoteric surfactants and may include anionic charges. Broadly, facultative zwitterions can be described as derivatives of secondary or tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, facultative zwitterions include positively charged quaternary ammonium ions, or in some cases, sulfonium or phosphonium ions; negatively charged carboxyl groups; and alkyl groups. Facultative zwitterions generally contain cationic and anionic groups that are ionized to nearly equal degree in the isoelectric region of the molecule and can generate a strong “internal salt” attraction between the positive and negative charge centers. Examples of such synthetic facultative zwitterions include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, wherein the aliphatic groups can be straight-chain or branched, and wherein one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains anionic water-co-solubilizing groups, such as carboxyl, sulfonate, sulfate, phosphate, or phosphonate groups.

[0248] Betaine surfactants and sulfobetaine surfactants are exemplary zwitterionic surfactants used herein. The general formula for these compounds is:

[0249]

[0250] R1 contains an alkyl, alkenyl, or hydroxyalkyl group having 8 to 18 carbon atoms having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moieties; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R 2 It is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom; R 3 It is an alkylene or hydroxyalkylene or hydroxyalkylene group with 1 to 4 carbon atoms, and Z is a group selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate.

[0251] Examples of zwitterionic surfactants having the structures listed above include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonium]-butane-1-carboxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonium]-3-hydroxypentane-1-sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetracosylphosphine]-2-hydroxypropane-1-phosphate; 3-[N,N-dipropyl-N-3-dodecyloxy-2-hydroxypropyl-ammonium]-propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulfonate; 3-(N,N-dimethyl- N-hexadecylammonium)-2-hydroxy-propane-1-sulfonate; 4-[N,N-bis(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonium]-butane-1-carboxylate; 3-[S-ethyl-S-(3-dodecyloxy-2-hydroxypropyl)sulfonium]-propane-1-phosphate; 3-[P,P-dimethyl-P-dodecylphosphino]-propane-1-phosphonate; and S[N,N-bis(3-hydroxypropyl)-N-hexadecylammonium]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in the surfactant of the cleaning composition may be straight-chain or branched and may be saturated or unsaturated.

[0252] The zwitterionic surfactants suitable for use in this composition comprise betaine having the following general formula:

[0253]

[0254] Where R', R” and R”' are straight-chain or branched alkyl or alkyl ether groups.

[0255] These surfactants, such as betaine, typically do not exhibit strong cationic or anionic properties at extreme pH values, nor do they show a decrease in water solubility over their isoelectric range. Unlike "external" quaternary ammonium salts, betaine is compatible with anionic surfactants. Examples of suitable betaines include cocoylamidopropyl dimethyl betaine; hexadecyl dimethyl betaine; C 12-14 Acylamidopropyl betaine; C 8-14Acylamidohexyldiethylbetaine; 4-C 14-16 Acylmethylamidodiethylammonium-1-carboxybutane; C 16-18 Acylamidodimethylbetaine; C 12-16 Acylamidopentanediethyl betaine; and C 12-16 Acylmethylamidodimethylbetaine.

[0256] The sulfobetaines that can be used in this disclosure include those having the formula (R(R)). 1 )2N+R 2 Compounds of SO3-, where R is C6-C 18 Hydrocarbon group, each R 1 Typically, it is independently a C1-C3 alkyl group, such as methyl, and R 2 It is a C1-C6 hydrocarbon group, such as a C1-C3 alkylene group or a hydroxyalkylene group.

[0257] A typical list of zwitterionic classes and types of these surfactants is given in U.S. Patent No. 3,929,678, published by Laughlin and Heuring on December 30, 1975. Further examples are given in *Surface Active Agents and Detergents* (Volumes I and II, by Schwartz, Perry, and Berch). These references are each incorporated herein in full.

[0258] Alternatively, the detergent or cleaning compositions disclosed herein may be free of zwitterionic surfactants.

[0259] Twin surfactants

[0260] Cleaning compositions or detergent compositions may contain twinned surfactants.

[0261] While conventional surfactants typically have one hydrophilic group and one hydrophobic group, twinned surfactants have at least two hydrophobic groups and at least two hydrophilic groups. These surfactants have the general formula A1-G-A2 and are named for comprising two surfactant moieties (A1, A2) connected by a spacer group (G), each surfactant moiety (A1, A2) having both a hydrophilic and a hydrophobic group. Typically, the two surfactant moieties (A1, A2) are identical, but they can be different.

[0262] Twin surfactants can be anionic, nonionic, cationic, or amphoteric. The hydrophilic and hydrophobic groups of each surfactant moiety (A1, A2) can be any groups known for use in conventional surfactants having one hydrophilic group and one hydrophobic group. For example, a typical nonionic twin surfactant (e.g., a dipolyoxyethylene alkyl ether) would contain two polyoxyethylene alkyl ether moieties.

[0263] Each part will contain hydrophilic groups (e.g., polyethylene oxide) and hydrophobic groups (e.g., alkyl chains).

[0264] Anionic and nonionic twinned surfactants include those with the following formula:

[0265]

[0266] Where R 30 Independently, it is C1 to C 22 Alkyl, R 34 --C(O)--or R 34 --B—R 35 --, where R 34 It's from C1 to C 22 Alkyl, R 35 It's from C1 to C 12 Alkyl group, and B is an amide group, --C(O)N(R) 36 )--、Amino--N(R 36 --, Carboxyl group --C(O)--O--, Carbonyl group or polyether group --(EO) a (PO) b --, where EO represents ethyleneoxy, PO represents propyleneoxy, a and b are numbers from 0 to 100, a is preferably from about 0 to about 30, and b is preferably from about 0 to 10, wherein the sum of a and b is at least one, and the EO and PO groups can be randomly mixed or in discrete block form, and R 36 It is hydrogen or C1 to C6 alkyl.

[0267] R 31 Independently hydrogen or C1 to C 22 Alkyl; R 32 Independently, it is C1-C 10 Alkyl groups, --O--, amide groups --C(O)N(R6)--, polyether groups --O(EO) a (PO) b -、-R 37 -DR 37 -or-DR 37 -D-, where R 37 It is independently a C1-C6 alkyl group, and D is an -O-, -S-, or amide group -C(O)N(R)36 )- or amino group-N(R 36 )-, where R 36 a and b are defined as above, and t is independently 0 or 1.

[0268] Z is independently hydrogen, -SO3Y, -P(O)(OY)2, -COOY, -CH2COOY, -CH2CH(OH)CH2SO3Y, and when R 32 When not a polyether, Z is also --OSO3Y and --OP(O)(OY)2; where Y is hydrogen, alkali metal (such as sodium and potassium); alkaline earth metal, such as magnesium and calcium; ammonium; or organic alkali salt, such as monoethanolamine, diethanolamine, triethanolamine, triethylamine, trimethylamine, N-hydroxyethylmorpholine, etc.

[0269] A1 or A2 is independently a straight-chain or branched C1 to C6 alkyl group, O--R 5 --O-- group or aryl group; preferably phenyl; R 33 It is a bond, aryl (such as phenyl or diphenyl), C1 to C2. 10 Alkyl, preferably C1 to C4 alkyl, most preferably methylene, -C≡C-, -O-, --S--, --S----, --N(R) 36 )--、--R 35 O--、--R 35 O(EO) a (PO) b --、--D1—R 38 --D1--or-R 38 --D1—R 38 --, where R 38 Independently, it is C1-C 10 Alkyl group, --C(O)--, --R 35 O(EO) a (PO) b --、--O—R 35 --O-- or aryl (e.g., phenyl), and D1 is independently --O--, --S--, --S----, --SO2--, --C(O)--, or a polyether group --O(EO). a (PO) b --, Amide group--C(O)N(R) 36 --, amino group--N(R) 36 )-、--O--R5--O--or aryl, where R 35 R 36 a and b are defined as above.

[0270] In the general formulas of this disclosure, the term "base" includes substituted bases, particularly their hydroxyl-substituted derivatives, as well as straight-chain and branched bases. When Z is hydrogen, the twinned surfactant is nonionic.

[0271] Other twinned surfactants that are particularly useful in this disclosure include twinned anionic or nonionic surfactants of the following formula:

[0272]

[0273] Where R c Represents an aryl group, preferably a phenyl group. R 31 R 33 R 34 Z is defined as above. a and b are numbers from 0 to 100, a is preferably from about 0 to about 30, and b is preferably from about 0 to 10, wherein the sum of a and b is at least one, and the epoxy EO groups and PO groups may be randomly mixed or in discrete block form.

[0274] These surfactants can be easily phosphorylated, sulfated, or carboxylated using standard techniques.

[0275] Alternatively, the detergent or cleaning compositions disclosed herein may be free of twinned surfactants.

[0276] Additional components

[0277] The cleaning compositions or detergent compositions disclosed herein may also include one or more additional cleaning composition agents. Exemplary additional cleaning composition agents include, but are not limited to, threshold agents; crystal modifiers; hardeners; bleaching agents; peroxycarboxylic acids, peroxycarboxylic acid compositions, fillers; defoamers; anti-redeposition agents; stabilizers; dispersants; fragrances and dyes; and thickeners.

[0278] Alternatively, the cleaning compositions or detergent compositions disclosed herein may not contain one, more, or all of the additional cleaning composition reagents.

[0279] Preparation of the Compositions in this Article

[0280] In one example, the compound of Formula 1 is combined with any additional functional components and allowed to interact and harden into a solid form. The curing process can last from a few minutes to about six hours, depending on factors including, but not limited to, the size of the formed or cast composition, the composition's composition, and the composition's temperature.

[0281] Solid compositions can be formed using batch or continuous mixing systems. In one exemplary embodiment, a single or twin-screw extruder is used to combine and mix one or more cleaning agents under high shear to form a homogeneous mixture. In some embodiments, the processing temperature is at or below the melting temperature of the components. The processed mixture can be dispensed from the mixer by forming, casting, or other suitable means, thereby hardening the composition into a solid form. The structure of the matrix can be characterized according to methods known in the art, based on the matrix's hardness, melting point, material distribution, crystal structure, and other similar properties. Generally, solid compositions processed according to the methods of this disclosure have a substantially homogeneous component distribution throughout their aggregates and are dimensionally stable.

[0282] In an extrusion process, liquid and solid components are introduced into a final mixing system and continuously mixed until the components form a substantially homogeneous semi-solid mixture in which the components are distributed throughout the mass. The mixture is then discharged from the mixing system into or through a die or other forming means. The product is then packaged. In one exemplary embodiment, the molding composition begins to harden into a solid form in about 1 minute to about 3 hours. Specifically, the molding composition begins to harden into a solid form in about 1 minute to about 2 hours. More specifically, the molding composition begins to harden into a solid form in about 1 minute to about 20 minutes.

[0283] In the casting process, liquid and solid components are introduced into a final mixing system and continuously mixed until the components form a generally homogeneous liquid mixture in which the components are distributed throughout the entire mass. For example, the components may be mixed in the mixing system for at least about 60 seconds. Once mixing is complete, the product can be transferred to a packaging container for curing. In one exemplary embodiment, the casting composition begins to harden into a solid form in about 1 minute to about 3 hours. Specifically, the casting composition begins to harden into a solid form in about 1 minute to about 2 hours. More specifically, the casting composition begins to harden into a solid form in about 1 minute to about 20 minutes.

[0284] The term "solid" means that the hardened composition does not flow and will substantially retain its shape under moderate stress or pressure or gravity alone. The hardness of a solid casting composition can range from a relatively dense and hard fused solid product, such as concrete, to a consistency characterized as a hardened paste. Additionally, the term "solid" refers to the state of the composition under the conditions of its intended storage and use. Generally, the composition is expected to remain in solid form when exposed to temperatures up to about 100°F, and particularly up to about 120°F.

[0285] The resulting solid composition may take the form of (but is not limited to) cast solid products; extruded, pressed, molded, or shaped solid pellets, blocks, tablets, powders, granules, flakes; or the shaped solid may subsequently be ground or shaped into powders, granules, or flakes. For example, extruded pellet material formed from a cured matrix may have a weight of about 50 grams to about 250 grams, extruded solids formed from the composition may have a weight of greater than or equal to about 100 grams, and solid block cleaning compositions formed from said composition may have a mass of about 1 kilogram to about 10 kilograms. The solid composition provides a stable source of functional materials. In some embodiments, the solid composition may be dissolved in, for example, water or other media to produce a concentrated composition and / or a usable composition. The solution may be directed to a storage container for later use and / or dilution, or it may be applied directly to the point of use.

[0286] Solid compositions can be supplied in unit doses. A unit dose refers to a solid composition unit of a set size that allows all units to be used during a single wash cycle. When solid compositions are supplied in unit doses, they are typically supplied as cast solids, extruded granules, or tablets in sizes from about 1 gram to about 50 grams.

[0287] The solid composition may also be provided in the form of a multipurpose solid, such as blocks or multiple pellets, and can be repeatedly used to generate an aqueous composition for a variety of washing cycles. For example, the solid composition may be provided as a cast solid, extruded block, or tablet in a mass of about 5 grams to about 10 kilograms, about 1 kilogram to about 10 kilograms, or about 5 kilograms to about 8 kilograms. Alternatively, the multi-use form of the solid composition may have a mass of about 5 grams to about 1 kilogram or about 5 grams to about 500 grams.

[0288] Although the composition is discussed as forming a solid product, it may also be provided in paste or liquid form. When the concentrate is provided in paste form, sufficient water is added to the composition to prevent complete solidification. Furthermore, dispersants and other components may be incorporated into the composition to maintain the desired component distribution.

[0289] When used in the methods described below, the cleaning composition or detergent composition may be a ready-to-use solution or a concentrated composition, which may be added to an aqueous system or diluted to form a working composition. Generally, a concentrate refers to a composition intended to be added to or diluted with water, and the composition that comes into contact with the articles to be washed may be referred to as a working composition.

[0290] The composition can be prepared from a concentrate by diluting the concentrate with water at a dilution ratio that provides the desired washing properties. The water used to dilute the concentrate to form the composition can be called diluent or diluent and can vary between different locations. The composition may also contain additional functional ingredients suitable for cleaning, rinsing, and other levels.

[0291] The concentrated composition may substantially contain only one or more compounds of Formula 1, and additional components and / or functional materials may be added as separate ingredients before or at the time of use. Alternatively, the concentrated composition may contain one or more compounds of Formula 1 as well as additional components, such as, but not limited to, at least one alkali metal hydroxide.

[0292] Typical dilution ratios for cleaning or detergent compositions are from about 1 to about 10,000, but will depend on factors such as water hardness and the amount of dirt to be removed. For example, concentrates are diluted at a concentrate:water ratio of about 1:10 to about 1:1000. Specifically, concentrates are diluted at a concentrate:water ratio of about 1:100 to about 1:5000. More specifically, concentrates are diluted at a concentrate:water ratio of about 1:250 to about 1:2000.

[0293] For illustrative purposes, this document provides representative non-limiting cleaning or detergent compositions comprising compounds of formula 1, 2, or 3 that can be used in a variety of applications.

[0294]

[0295] A method for cleaning articles is also provided. The method includes contacting the articles with a detergent composition comprising a compound of formula 1, 2, or 3 as described herein. As mentioned above, the detergent composition may further comprise a builder. The builder may include enzymes, oxidants, condensed phosphates, alkali metal carbonates, alkali metal silicates, alkali metal metasilicates, phosphonates, aminocarboxylic acids, carboxylic acid polymers, or combinations thereof.

[0296] Based on the total volume of fluid in contact with the article, the article may be exposed to a cleaning composition of about 50 ppm to about 6,000 ppm.

[0297] Based on the total volume of fluid in contact with the article, the article may be exposed to about 10 ppm to about 3,000 ppm of a compound of formula 1, formula 2 or formula 3.

[0298] The article may include a metal surface, a glass surface, a fabric, a vessel, a polycarbonate surface, a polysulfone surface, a melamine surface, a ceramic surface, a porcelain surface, or a combination thereof. Preferably, the article is a fabric. More preferably, the article is a vessel.

[0299] A method for cleaning a membrane is also provided. The method involves contacting the membrane with a cleaning solution containing any compound of formula 1, 2, or 3 as described herein.

[0300] Based on the total weight of the fluid in contact with the membrane, the membrane can be contacted with a compound of formula 1, formula 2 or formula 3 at a concentration of about 10 ppm to about 5,000 ppm.

[0301] In the methods disclosed herein, the membrane may be a membrane used for dairy processing. For example, the membrane may be a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, or a combination thereof.

[0302] definition

[0303] As used herein, the terms “substantially free,” “free,” or “free of” mean a composition that is completely free of a component or contains such small amounts of a component that it does not affect the properties of the composition. A component may be present as an impurity or contaminant and should be less than 0.5 wt.%. For example, the amount of a component may be less than 0.1 wt%, or in some cases, less than 0.01 wt%.

[0304] As used herein, the terms “weight percent,” “weight %,” “percent by weight,” “% by weight,” and their variations refer to the concentration of a substance as the weight of the substance divided by the total weight of the composition and multiplied by 100. It should be understood that, as used herein, “percentage,” “%,” etc., are intended to be synonymous with “weight percent,” “weight %,” etc.

[0305] As used herein, the term "polymer" refers to a water-soluble or water-dispersible polymer. The term "polymer" encompasses and includes homopolymers, copolymers, terpolymers and polymers having more than three monomers, crosslinked or partially crosslinked polymers, and combinations or blends of these.

[0306] As used herein, the terms "polymer solution" or "polymer dispersion" mean a polymer composition that is substantially dispersed or dissolved in water, an aqueous source, or an aqueous-based solution. Aqueous-based solutions include one or more dissolved salts, buffer solutions, acids, bases, surfactants, or other dissolved, dispersed, or emulsified compounds, materials, components, or combinations thereof.

[0307] As used herein, "reverse emulsion polymer" and "reverse latex polymer" refer to a water-in-oil polymer emulsion comprising a water-soluble polymer (which may be cationic, anionic, nonionic, amphoteric, or zwitterionic) in an aqueous phase, a hydrocarbon oil for the oil phase, and a water-in-oil emulsifier. The reverse emulsion polymer is a hydrocarbon continuously containing a water-soluble polymer dispersed in a hydrocarbon matrix. The reverse emulsion polymer is then "reversed" or activated for use by shearing, dilution, and, typically, another surfactant releasing the polymer from the particles. See U.S. Patent No. 3,734,873, which is incorporated herein by reference.

[0308] As used herein, the term "water source" means a source of water that comprises, is substantially composed of, or consists of: fresh water, deionized water, distilled water, produced water, municipal water use, wastewater such as runoff or municipal wastewater, treated or partially treated wastewater, well water, brackish water, "reclaimed water," seawater, or a combination of two or more such water sources as determined by the context. A water source may include one or more salts, ions, buffer solutions, acids, bases, surfactants, or other dissolved, dispersed, or emulsified compounds, materials, components, or combinations thereof.

[0309] As used herein, the term "oil" or "hydrocarbon solvent" as applied to the oil phase of a water-in-oil emulsion means any compound or blend thereof that is substantially chemically inert in a water-in-oil emulsion as described herein and is liquid in the range of at least 20°C to 100°C, and is soluble in water at less than 0.1% by weight at 25°C.

[0310] As used herein, the term "aqueous phase" means a source of water in which at least a monomer or polymer is dispersed or dissolved, wherein the dispersion or solution is a discontinuous phase in a water-in-oil emulsion.

[0311] Unless otherwise specified, alkyl groups as described herein, either alone or as part of another group, are optionally substituted straight-chain saturated monovalent hydrocarbon substituents containing one to sixty carbon atoms and preferably one to thirty carbon atoms in the main chain, or optionally substituted branched saturated monovalent hydrocarbon substituents containing three to sixty carbon atoms and preferably eight to thirty carbon atoms in the main chain. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, etc.

[0312] As used herein, the term "aryl" or "aromatic," whether alone or as part of another group (e.g., aralkyl), refers to an optionally substituted allotropic aromatic group, preferably a monocyclic or bicyclic group containing 6 to 12 carbon atoms in the ring moiety, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. Phenyl and substituted phenyl are more preferred aryl groups. The term "aryl" also includes heteroaryl functional groups.

[0313] "Aryl group" refers to an aryl group attached to the parent molecule via an alkylene group. The number of carbon atoms in the aryl group and the alkylene group is selected such that the aryl group has a total of about 6 to about 18 carbon atoms. A preferred aryl group is benzyl.

[0314] The term "substituted" in phrases such as "substituted aryl" and "substituted alkyl" means that in the group under discussion (i.e., alkyl, aryl, or other groups following the term), at least one hydrogen atom bonded to a carbon atom is replaced by one or more of the following substituents: such as hydroxyl (-OH), alkylthio, phosphinyl, amide (-CON(R)). A (R) B ), where R A and R B Independently hydrogen, alkyl or aryl), amino (-N(R) A (R) B ), where R A and R B Independently, it can be hydrogen, alkyl, or aryl; halogen (fluorine, chlorine, bromine, or iodine); silyl; nitro (-NO2); or ether (-OR). A , where R A It is an alkyl or aryl group, an ester (-OC(O)R) A , where R A It is an alkyl or aryl group, or a ketone group (-C(O)R). A , where R A These are alkyl or aryl groups, heterocyclic groups, etc. When the term "substituted" introduces a list of groups that may be substituted, it means that the term applies to every member of that group. That is, the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted alkyl or optional substituted aryl".

[0315] As used herein, the terms "heterocyclo," "heterocycle," or "heterocyclyl" refer to a monocyclic, bicyclic, or tricyclic group containing one to four heteroatoms selected from N, O, S(O)n, P(O)n, PRz, NH, or NRz, where Rz is a suitable substituent. A heterocyclic group optionally contains one or two double bonds. Heterocyclic groups include, but are not limited to, azacyclic butyl, tetrahydrofuranyl, imidazoalkyl, pyrrolyl, piperidinyl, piperazine, oxazolyl, thiazoalkyl, pyrazolyl, thiomorpholinyl, tetrahydrothiazinyl, tetrahydrothiadiazinyl, morpholinyl, oxacyclobutyl, tetrahydrodiazinyl, oxazinyl, oxahiazinyl, indololinyl, isoindololinyl, quininecyclo, benzodihydropyranyl, isobenzodihydropyranyl, and benzoxazinyl. Examples of monocyclic saturated or partially saturated ring systems are tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, imidazolin-1-yl, imidazolin-2-yl, imidazolin-4-yl, pyrrolidine-1-yl, pyrrolidine-2-yl, pyrrolidine-3-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperazine-1-yl, piperazine-2-yl, piperazine-3-yl, 1,3-oxazolidine-3-yl, and isothiazine. The heterocyclic groups include 1,3-thiazolidin-3-yl, 1,2-pyrazolidine-2-yl, 1,3-pyrazolidine-1-yl, thiomorpholino-yl, 1,2-tetrahydrothiazin-2-yl, 1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazin-yl, morpholino-yl, 1,2-tetrahydropyridazin-2-yl, 1,3-tetrahydropyridazin-1-yl, 1,4-oxazin-2-yl, and 1,2,5-oxazin-4-yl. As defined above, the heterocyclic group may be unsubstituted or substituted with one or more suitable substituents, preferably one to three suitable substituents.

[0316] Having described this disclosure in detail, it will be apparent that modifications and variations are possible without departing from the scope of this disclosure as defined in the appended claims.

[0317] Example

[0318] The following non-limiting embodiments are provided to further illustrate this disclosure.

[0319] Example 1: Synthesis of a novel surfactant composition

[0320] The overall synthesis of the surfactants described in this paper is carried out in two steps (Scheme 1). First, acceptor molecules (C) are prepared by ring-opening reaction of alkyl epoxides (II) with aromatic amines or alcohol compounds (A). The second step involves alkoxylation of the acceptor molecule (C) with epoxides (D) to obtain a series of surfactants (E).

[0321]

[0322] X, R1, R2, R3, R4, R5, R6, R7, R8, m, and n are defined as above.

[0323] Examples 1 and 2 disclose a series of specific syntheses (Scheme 2) of ethoxylated 1-((2-ethylhexyl)oxy-3-phenoxyprop-2-ol) via the following two-step method:

[0324]

[0325] Example 1A: Synthesis of 1-((2-ethylhexyl)oxy)-3-phenoxyprop-2-ol.

[0326]

[0327] Table 1:

[0328]

[0329] Phenol (100 g, 1.06 mol) and potassium hydroxide (1 g, 0.02 mol) were added to a 500 mL three-necked round-bottom flask equipped with a temperature probe, condenser, nitrogen inlet, and magnetic stir bar, and the reaction temperature was raised to 50 °C. Then, 2-ethylhexyl glycidyl ether (200 g, 1.06 mol) was added to the molten phenol under a nitrogen blanket. The reaction temperature was further raised to 130 °C, and the mixture was stirred for 4 hours or until the reaction was complete. The reaction progress was monitored by GC-MS. Figure 1 The structure of the obtained compound was determined by NMR ( ). Figure 2 Confirmed by mass spectrometry (+ESI-MS): Calculated [M+H]+281.21, measured value 281.2109.

[0330] Example 1B: Ethylene oxide was added to 1-((2-ethylhexyl)oxy)-3-phenoxyprop-2-ol.

[0331] Following catalysis and dehydration, 505.93 g of 1-((2-ethylhexyl)oxy-3-phenoxyprop-2-ol) was added to a 2 L Parr reactor and heated to 125 °C with stirring at 300 rpm under 10 psi nitrogen. The ethoxylation reaction began when the acceptor material reached 125 °C. Ethylene oxide was added in a stepwise manner to slowly increase the working pressure range of 55–65 psi during the oxide feed. Slight exothermic reaction was observed. Once the target amount of 476.5 g (6 mol) of ethylene oxide was added to the reactor, the oxide feed was stopped, and the reaction was allowed to proceed at 125 °C for 6 hours. The material was then cooled and sampled for testing. The preparation of intermediates with progressively increasing levels of ethylene oxide (6–13 mol of EO) was completed by adding the desired amount of EO.

[0332] Example 2A: Synthesis of 3,3'-((4-hydroxyphenyl)azadiyl)bis(1-((2-ethylhexyl)oxy)prop-2-ol)

[0333]

[0334] Table 2:

[0335] reagents MW (g / mol) Mass (g) n (moles) 4-Aminophenol 109.13 176 1.612 2-Ethylhexyl glycidyl ether 186.29 600 3.22

[0336] 600 g (3.22 mol) of 2-ethylhexyl glycidyl ether was added to a 1 L three-necked round-bottom flask equipped with a temperature probe, nitrogen inlet, condenser, and magnetic stir bar. Then, 176 g (1.612 mol) of 4-aminophenol was added to the well-stirred reaction mixture. The resulting suspension was heated to 120 °C under a nitrogen blanket and stirred for 3 hours or until the reaction was complete. As the reaction proceeded to completion, the suspension became a homogeneous dark amber product. The product was characterized by NMR and ESI-MS.

[0337] Example 2B: Ethylene oxide was added to 3,3'-((4-hydroxyphenyl)azadiyl)bis(1-((2-ethylhexyl)oxy)prop-2-ol).

[0338] Following catalysis and dehydration, 481.72 g of 3,3'-((4-hydroxyphenyl)azadiyl)bis(1-((2-ethylhexyl)oxy)prop-2-ol) was added to a 2 L Parr reactor and heated to 125 °C with stirring at 300 rpm under 10 psi nitrogen. The ethoxylation reaction began when the acceptor material reached 125 °C. Ethylene oxide was added in a stepwise manner to slowly increase the working pressure range by 55–65 psi during the oxide feed. Slight exothermic reactions were observed. Once the target amount of 440.5 g (10 mol) of ethylene oxide was added to the reactor, the oxide feed was stopped, and the reaction was allowed to proceed at 125 °C for 6 hours. The material was then cooled and sampled for testing. The intermediate with progressively increasing levels of ethylene oxide (10–24 mol of O-EO) was prepared by adding the desired amount of EO.

[0339] Example 3: Physical properties of 1-((2-ethylhexyl)oxy)-3-phenoxyprop-2-ol ethoxylate

[0340] In this embodiment, the interfacial tension, cloud point, and critical micelle concentration of a series of ethoxylated surfactants (1-((2-ethylhexyl)oxy)-3-phenoxyprop-2-ol ethoxylate) with 6 to 13 moles of EO groups were determined.

[0341]

[0342] Compound A

[0343]

[0344] Interfacial tension is the surface free energy at the interface between two immiscible liquids (in this case, oil and water). Adding a surfactant reduces interfacial tension. To achieve low interfacial tension, the surfactant is evenly distributed between the two phases and has low affinity for both phases.

[0345] The interfacial tension between a 1% surfactant aqueous solution and corn oil was measured using a spin drop tensiometer at 4000 rpm. The temperature was kept constant at 25°C. This value is actually temperature-dependent. The minimum interfacial tension for different surfactants can vary depending on the selected temperature and oil phase.

[0346] The interphase tensions of ethoxylated surfactants measured using corn oil or dodecane as the light phase are shown in Table 3.

[0347] Table 3: Interphase Tension

[0348]

[0349] The cloud point is the temperature at which a nonionic surfactant solution becomes cloudy. At this point, the solution has crossed the phase boundary, and the cloudy solution is an emulsion of a condensed layer phase in a dilute phase.

[0350] A 1% by weight surfactant solution was slowly heated with stirring to ensure a constant temperature. The temperature at which the solution began to turn cloudy was taken as the cloud point, and the results are described in Table 4 for the series of ethoxylated surfactants.

[0351] Table 4: Cloud Point

[0352] Surfactant ID Cloud point (°C) (+ / -1°C) 6EO <1 7EO 1.0 8EO 12.5 9EO 27.0 10EO 37.5 11EO 48.0 12EO 58.5 13EO 77.5 NP9.5 53.0

[0353] Critical micelle concentration (CMC) is the concentration at which micelles begin to form in a solution containing a surfactant. It can be measured using several physical properties. Here, it is determined by measuring the surface tension of surfactant solutions at various concentrations. The semi-logarithmic curve of concentration versus surface temperature produces a curve with an interrupted or changing slope. The concentration at which this interruption occurs is taken as the critical micelle concentration (CMC). Table 5 summarizes the critical micelle concentration for each of the tested ethoxylated surfactants.

[0354] Table 5: Critical micelle concentration

[0355] Surfactant ID CMC (ppm) 6EO 72.45 7EO 110.84 8EO 129.02 9EO 152.75 10EO 167.80 11EO 227.52 12EO 350.73 13EO 451.00

[0356] Example 4: A surfactant that can effectively remove milk fat.

[0357] Standard butter removal test methods are used to screen the ability of surfactants to remove butter from polysulfone test pieces. Typical consumer materials are made of PES (polyethersulfone) or PVDF. Here, polysulfone test pieces are used to represent the surface of PES films.

[0358] Ethoxylated surfactants, compounds A (9EO and 10EO), were tested together with deionized (DI) water, ethylhexanol alkoxylate (Ecosurf EH-9), nonylphenol containing 9.5 mol of ethylene oxide (NPE 9.5), and laurylamine oxide (Barlox 12). Except for EH-9 (always at 1000 ppm), each surfactant was used at a concentration of 200 ppm or 600 ppm.

[0359] For each surfactant tested, brand new, unused test pieces (1×3-inch PS test pieces from Small Parts via Amazon) were used. Each sample was immersed in methanol for 30 seconds and allowed to dry, then placed on a baking sheet (lined with a Wypall towel) in a 120℉ oven for 30 minutes. After cleaning and drying, each sample was weighed on an analytical balance. A uniform layer of room temperature butter (unsalted) was then applied to the bottom 75% of each test piece using a 1” wide foam brush. In total, approximately 0.0250 g to 0.0300 g of butter was applied to each test piece. The test pieces were then returned to the baking sheet and dried overnight before a second weighing.

[0360] Prepare 600g of a test solution in deionized water containing each of the following compounds: A-9EO, A-10EO, NPE 9.5, and Barlox 12 (200ppm or 600ppm except for EH-9, which is always 1000ppm), and add it to a beaker with a stir bar. Heat the solution to 45°C, set the stirring speed to 240rpm, and test at pH 7, pH 9, or pH 11. Note that each surfactant is tested in quadruplicate using four different test pieces in a beaker containing the corresponding surfactant solution. Once prepared, suspend the test pieces in the solution with a constant distance between the test pieces and the center of the beaker, with the soiled / buttered side facing the center. Maintain the stirring speed at 240rpm and the temperature at 45°C for 10 minutes. Then remove each test piece and immerse it three times in a separate beaker of slowly overflowing deionized water (e.g., placed under a running deionized water tap). Each "immersion" consists of immersing the test piece in the water for 2 seconds and then removing it for 2 seconds. The test pieces were then dried on paper towels and returned to the baking tray to dry overnight. They were weighed again the next day.

[0361] Figure 1The percentage of dirt removed by weight is shown for compounds A-9EO, A-10EO, NPE 9.5, and EH9 cleaned at pH 7, 9, and 11 compared to dried, soiled samples.

[0362] Figure 2 The percentage of milk fat removed by weight of cleaned specimens (without pH adjustment or with pH adjusted to 11) compared to dried, soiled specimens is shown.

[0363] Example 5: Non-APE surfactants demonstrated good dirt removal from prefabricated fabric samples.

[0364] In this embodiment, alkaline detergent builders, alone or in combination with novel surfactants disclosed herein, are subjected to a standard oscillating detergent test procedure to measure the amount of dirt removed from a pre-fabricated fabric sample (e.g., terry cloth). This test measures the ability of each detergent-surfactant combination to remove cosmetics from terry cloth. The test is performed at 40°C.

[0365] Pre-fabricated cotton samples purchased from Test Fabrics, Inc. are embossed with cosmetic using a standardized method designed to reduce variability in lipstick application for repeatable and consistent cleanliness testing. In short, the embossing process involves: pouring liquid cosmetic onto a petri dish, then applying the cosmetic to the stamp using a rounded foam applicator. The applicator is tapped over the entire surface of the stamp until it is smooth. A clean edge, such as the edge of a stainless steel curtain, is then dragged across the stamp along the ridge. Ideally, the stamp is fully coated with cosmetic, with the ridge still visible. The same amount of pressure is used to emboss the fabric sample for each sample. The stamp is gently lifted to undisturb the freshly embossed material.

[0366] The pre-formed fluid cosmetic on the cotton sample (code CS-17) was purchased from Center for Testmaterials B.V.

[0367] The soiled fabric samples were then subjected to a standard vibratory detergent test to measure the effectiveness of the detergent / surfactant combination in removing dirt. A vibratory detergent model 7243ES, serial number MCC 14-813 from Test Fabrics Inc., along with 1L pots and water baths, was used. Initial values ​​for the soiled samples were read on a Mach5 colorimeter before washing to establish an initial “L” value. The vibratory detergent was set to 120℉, and 0.5 liters of 5-grain water were added to each of the six pots and equilibrated to 120℉.

[0368] Weigh out the laundry detergent and add it to the vibrating detergent dispenser pot, stirring for 30 seconds to 1 minute to mix and dissolve. Set the controller to a 1-minute run time and 100 RPM (standard RPM for most tests). Quickly add each sample to minimize differences in exposure time to the detergent system. Immediately after adding the sample, stir each sample for 10 minutes, then remove and transfer to 1L of cold 5-grid water for rinsing. Then remove the sample from the cold water and rinse further under cold 5-grid tap water. Remove excess water by squeezing and air dry the sample on Wypall paper towels. After drying, measure the final “L” value using a Mach5 colorimeter. Calculate the soil removal percentage based on the difference between the initial (before washing) L value and the final L value (after washing).

[0369] Figure 3A The percentage of dirt removed (from natural beige dirt from L'Oreal True Match Foundation) is shown, as determined by an oscillating detergent apparatus, for 500 ppm Aquanomic 2.0 low-temperature detergent and 600 ppm Aquanomic 2.0 low-temperature builder (1x), 1000 ppm Aquanomic 2.0 low-temperature detergent and 1200 ppm Aquanomic 2.0 low-temperature builder (2x), 500 ppm compound A-10EO, 500 ppm compound A-10EO plus 600 ppm Aquanomic 2.0 low-temperature builder, 500 ppm compound A-9EO, and 500 ppm compound A-9EO plus 600 ppm Aquanomic 2.0 low-temperature builder.

[0370] Figure 3B The percentage of dirt removed (from natural beige dirt from Neutrogena Healthy Skin Foundation) is shown, measured by an oscillating detergent apparatus, for 500 ppm Aquanomic 2.0 low-temperature detergent (1x), 500 ppm Aquanomic 2.0 low-temperature detergent and 600 ppm Aquanomic 2.0 low-temperature builder (1x + builder), 500 ppm compound A-9EO, and 500 ppm compound A-9EO plus 600 ppm Aquanomic 2.0 low-temperature builder, 500 ppm compound A-10EO, 500 ppm compound A-10EO plus 600 ppm Aquanomic 2.0 low-temperature builder, 500 ppm NPE, and 500 ppm NPE plus 600 ppm Aquanomic 2.0 low-temperature builder.

[0371] In describing elements of this disclosure or one or more preferred embodiments thereof, the articles “a / an” and “the / said” are intended to mean the presence of one or more elements. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that additional elements besides those listed may be present.

[0372] In view of the foregoing, it will be seen that several objectives of this disclosure have been achieved and other advantageous results have been obtained.

[0373] Since various changes can be made to the above compositions and methods without departing from the scope of this disclosure, it is intended that all subject matter contained in the foregoing description and shown in the accompanying drawings be interpreted as illustrative rather than restrictive.

Claims

1. A method for using a cleaning article, the method comprising contacting the article with a cleaning composition comprising a compound of formula 3: R1, R2, R4, R5, and Z2 are hydrogen; and Z1 has a structure with part (A): in X is -O-; n is an integer from 0 to 5; R6 is either hydrogen or methyl; R7 is -(CH2)zOR 11 ; R8 is either hydrogen or methyl; R 11 C8 to C 22 alkyl; m is an integer from 6 to 12; z is an integer from 1 to 3; Furthermore, the pH of the cleaning composition is 7 or lower.

2. Use of the cleaning composition for cleaning articles, said use comprising contacting said article with said cleaning composition comprising a compound of formula 3: R1, R2, R4, R5, and Z2 are hydrogen; and Z1 has a structure with part (A): in X is -O-; n is an integer from 0 to 5; R6 is either hydrogen or methyl; R7 is -(CH2)zOR 11 ; R8 is either hydrogen or methyl; R 11 C8 to C 22 alkyl; m is an integer from 6 to 12; z is an integer from 1 to 3; Furthermore, the pH of the cleaning composition is 7 or lower.

3. The method or use according to claim 1 or 2, wherein the pH of the cleaning composition is from 1 to 7.

4. The method or use according to claim 1 or 2, wherein R6 is hydrogen.

5. The method or use according to claim 1 or 2, wherein the compound of formula 3 has a structure corresponding to the following Where m is an integer from 6 to 12.

6. The method or use according to claim 5, wherein m is an integer of 9 or 10.

7. The method or use according to claim 1 or 2, wherein the article is a metal surface, a glass surface, a polycarbonate surface, a polysulfone surface, a melamine surface, a ceramic surface, or a combination thereof.

8. The method or use according to claim 1 or 2, wherein the article is a porcelain surface.

9. The method or use according to claim 1 or 2, wherein the cleaning composition further comprises a cleaning aid.

10. The method or use according to claim 9, wherein the detergent is an enzyme, an oxidizing agent, a condensed phosphate, an alkali metal silicate, an alkali metal metasilicate, a phosphonate, an aminocarboxylic acid, a carboxylic acid polymer, or a combination thereof.

11. The method or use according to claim 1 or 2, wherein the article is a fabric.

12. The method or use according to claim 1 or 2, wherein the article is a vessel.

13. The method or use according to claim 1 or 2, wherein the article is a membrane.

14. The method or use according to claim 13, wherein the membrane is a membrane used in dairy processing.

15. The method or use according to claim 14, wherein the membrane is a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, or a combination thereof.

16. The method or use according to claim 1 or 2, wherein the article is soiled with protein or oily dirt.

17. The method or use according to claim 1 or 2, wherein the pH of the cleaning composition is 2 to 7.

18. The method or use according to claim 1 or 2, wherein the pH of the cleaning composition is 3 to 7.

19. The method or use according to claim 1 or 2, wherein the pH of the cleaning composition is 4 to 7.

20. The method or use according to claim 1 or 2, wherein the pH of the cleaning composition is 5 to 7.

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