Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3788—Graft polymers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/12—Soft surfaces, e.g. textile

Definitions

• the present invention relates to use of a graft polymer in a laundry detergent composition that additionally comprise a detersive surfactant, to prevent dye transfer during a laundering process.
• Dye transfer can be a problem when consumers laundering dark-coloured items together with light-coloured or white items. Technically, this problem can be minimized by sorting the items by colour and washing them separately. However, some consumers may not prefer the sorting approach because this may mean more time, washes, effort, energy consumption, carbon emission, and cost to complete their laundry. In addition, consumers become increasingly aware of the impact their choices have on the environment, they seek out products that are eco-friendly and have a lower carbon footprint. Therefore, there is a need for new sustainable technologies that can effectively prevent dye transfer during laundry process.
• the inventors have surprisingly found that above need can be achieved by the use of a specific graft copolymer with improved biodegradation profile in a laundry detergent composition.
• Suitable laundry detergent compositions include laundry detergent powders, laundry beads, laundry detergent liquids, laundry detergent gel, laundry detergent sheets, fibrous articles and water-soluble unit dose laundry detergents.
• the composition comprises from 0.01% to 20%, preferably from 0.05% to 15%, more preferably from 0.1% to 10%, and most preferably from 0.5% to 5% of the graft polymer, in relation to the total weight of the laundry detergent composition.
• the composition comprises from 1.0% to 70% detersive surfactant. in relation to the total weight of the laundry detergent composition.
• the graft polymer of the present invention comprises:
• aerobic biodegradation in wastewater according to OECD 301F is expressed as a percentage of the theoretical oxygen demand (ThOD, which is measured by the elemental analysis of the compound of interest), which is needed to completely biodegrade the compound sample.
• ThOD theoretical oxygen demand
• the amount of oxygen taken up by the microbial population during biodegradation of the test substance is expressed as a percentage of ThOD.
• the obtained values are preferably measured in triplicate using the OECD 301F manometric respirometry method.
• the consumption of oxygen is determined by measuring the change in pressure in the apparatus using an OxiTop ® C (Xylem 35 Analytics Germany Sales GmbH & Co KG). Details for the tests performed are given in the experimental section below.
• the biodegradable polymers of the present invention can be non-biodegradable or biodegradable, preferably biodegradable.
• the graft polymers that are biodegradable demonstrate at least 30%, preferably at least 40%, preferably at least 45%, more preferably at least 50%, more preferably at least 55%, or most preferably at least 60% biodegradability according to standard OECD 301F at 28 days.
• the ratio of the block copolymer backbone (A) versus the polymeric side chains (B) within the graft polymers according to the present invention is not limited to specific values.
• the graft polymer comprises in percentage by weight to the total weight of the graft polymer from 40 to 98%, preferably from 50 to 96%, preferably from 60 to 95%, more preferably from 65 to 90%, more preferably from 70 to 85%, more preferably from 75 to 80%, of block copolymer backbone (A), and from 2 to 60%, preferably from 4 to 50%, preferably from 5 to 40%, preferably from 10 to 35%, preferably from 15 to 30%, more preferably from 20 to 25%, of polymeric sidechains (B).
• the graft polymer according to the present invention may have any molecular weight known to a person skilled in the art. However, it is preferred that the graft polymer has a mean molecular weight M w of from 1,000 to 100,000 g/mol, preferably from 1,200 to 50,000 g/ mol preferably from 1,500 to 10,000 g/mol, preferably from 2,000 to 8,000 g/ mol and more preferably from 2,500 to 6,000 g/mol.
• M w mean molecular weight
• M n mean molecular mass g mol / g mol ).
• the block copolymer backbone (A) comprises from 85% to 100%, by weight of the backbone (A), at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide.
• block copolymer backbone A
• Other monomers can be any types of monomers that can copolymerize with ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide.
• Other monomers can also be any type of monomers that react with the block copolymer backbone (A).
• One example of other monomers is end-capping groups that can be attached to one or both end of the block copolymer backbone (A), such as C 1 -C 25 alkyl groups.
• the total amount of other monomers is less than 15%, preferably less than 10%, more preferrable less than 5%, more preferrable less than 2%, more preferably less than 1% (by weight of the backbone (A)). However, it is more preferred that other monomers are essentially not present or only present as impurities at trace amount (less than 0.5%).
• the block copolymer backbone (A) has a number average molecular weight (Mn) in the range of from 600 to 90,000 g/mol.
• the block copolymer backbone (A) has a number average molecular weight (Mn) of less than 10,000 g/mol, more preferably less than 5,000, more preferably less than 4,000, more preferably less than 3,000 g/mol.
• the block copolymer backbone (A) has a number average molecular weight in the range of 800 and 2,750, more preferably 1,000 and 2,500, more preferably 1,200 and 2,250, most preferably 1,400 to 2,000, such as 1,500, 1,800, 1,900 g/mol.
• a particular preferred type of block copolymer backbone is a block copolymer comprising 2 to 5 blocks, such block being units derived from PEG and PPG.
• the most preferred block copolymer backbone of this type is selected a di- or triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). Even more preferably, the block copolymer backbone is a tri-block copolymer polyethylene oxide (PEG) and polypropylene oxide (PPG).
• PEG polyethylene oxide
• PPG polypropylene oxide
• Various types of such block copolymer backbones are commercially available, for example under the trademark series "Pluronic" (BASF SE, Ludwigshafen, Germany).
• Suitable block copolymer backbones (A) to be employed within the present invention are described, for example, within EPA 0 362 688. Within the present invention, it is preferred that the respective monomer to be employed for preparing the individual blocks of the block copolymer backbone (A) are added in sequence. However, it is possible at the transition of the feed from one monomer to the other to produce so called "dirty structures" wherein at the edge/border of the respective block a small number of monomers of the respective neighboring block may be contained within the individual block to be considered. However, it is preferred that the block copolymer backbones (A) according to the present invention do not contain any so called "dirty structures" or "dirty passages" at the respective border of the blocks.
• the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).
• the triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG) having the structure according to formula (A1) or formula (A2) with formula (A1) is defined as follows: with
• the triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG) having the structure according to formula (A2) as defined above.
• the graft polymer comprising polymeric sidechains grafted onto the block copolymer backbone (A), wherein said polymeric sidechains (B) comprises from 85% to 100%, by weight of the sidechains (B), N-vinyl lactam monomer (B1) and vinyl ester monomer (B2)
• the vinyl ester monomer (B2) is known to a person skilled in the art.
• the optimum amount by weight of polymeric sidechains (B2), in relation to the total weight of the graft polymer, is in the range of 5 to 15%, such as 8%, 10%, 12%.
• the amount of sidechains (B2) when the amount of sidechains (B2) is in preferred range, the graft polymer also show improved performance in the presence of hydrophobic dyes.
• N-vinyl lactam monomer (B1) versus vinyl ester (B2) may have any value known to a person skilled in the art. However, it is preferred within the context of the present invention that the polymeric sidechains (B) are obtained by free radical polymerization of, in relation to the sum of (B 1) and (B2):
• the corresponding vinyl alcohol is not suitable to be employed as monomer within the polymerization process of the polymeric sidechains (B) due to stability aspects.
• the alcohol function has to be introduced by hydrolyzing the ester function of the sidechains.
• the polymeric sidechains (B) are not hydrolyzed after polymerization.
• the inventive graft polymers maybe characterized by their degree of grafting (number of graft sites of the polymeric sidechains (B) on the polymer backbone (A)).
• the degree of graft may be high or low, depending on the reaction conditions.
• the degree of grafting is low to medium, more preferably low. "Low” in this aspect means that statistically less than 2 graft sites per 50 alkylene oxide units are present.
• This adjustment of the degree of grafting and this amount of ungrafted polymers can be used to optimize the performance in areas of specific interest.
• inventive polymers have at least one of the following properties, preferably two or more, to be successfully employed in the various fields of applications targeted with this present invention:
• the graft polymer comprises:
• the graft polymer of this embodiment demonstrates optimum balances between biodegradability, performance, solubility and processability.
• the invention also related to a laundry detergent composition
• a laundry detergent composition comprising a detersive surfactnat, and a graft polymer, wherein,
• laundry detergent composition further comprises hydrophobic cleaning polymers and hydrophilic cleaning polymers, such as other graft polymers and modified polyamine dispersing agent.
• Another subject-matter of the present invention is a process for preparing the inventive graft polymers as described above in the various embodiments and variations thereof.
• at least one monomer (B 1) and at least one monomer (B2) are polymerized in the presence of at least one polymer backbone (A).
• the polymeric sidechains (B) are obtained by radical polymerization.
• radical polymerization as such is also known to a skilled person.
• the person skilled in the art also knows that the inventive process can be carried out in the presence of a radical-forming initiator (C) and/or at least one solvent (D).
• C radical-forming initiator
• D solvent
• the skilled person knows the respective components as such.
• radical polymerization as used within the context of the present invention comprises besides the free radical polymerization also variants thereof, such as controlled radical polymerization.
• Suitable control mechanisms are RAFT, NMP or ATRP, which are each known to the skilled person, including suitable control agents.
• the process to produce a graft polymer of the invention and/or as detailed before comprises the polymerization of at least one N-vinyl lactam monomer (B1) and at least one (B2) in the presence of at least one polymer backbone (A), a free radical-forming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B1), (B2), and (C) of at least one organic solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B1) and monomer (B2) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the copolymer backbone (A).
• the amount of ((free) radical-forming) initiator (C) is preferably from 0.1 to 5% by weight, in particular from 0.3 to 3.5% by weight, based in each case on the polymeric sidechains (B).
• the steady-state concentration of radicals present at the mean polymerization temperature is substantially constant and the graft monomers (B1) and/or (B2) are present in the reaction mixture constantly only in low concentration (for example of not more than 5% by weight in total). This allows the reaction to be controlled, and graft polymers can be prepared in a controlled manner with the desired low polydispersity.
• mean polymerization temperature is intended to mean here that, although the process is substantially isothermal, there may, owing to the exothermicity of the reaction, be temperature variations which are preferably kept within the range of +/- 10°C, more preferably in the range of +/- 5°C.
• the initiator (C) and the graft monomers (B1) and/or (B2) are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and graft monomers (B1) and/or (B2) is present in the reaction mixture.
• the proportion of undecomposed initiator in the overall reaction mixture is preferably ⁇ 15% by weight, in particular ⁇ 10% by weight, based on the total amount of initiator metered in during the monomer addition.
• the laundry detergent composition additionally comprises a detersive surfactant.
• the composition comprises, by weight of the composition, from about 1% to about 70% of a detersive surfactant system.
• the detersive surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof.
• a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
• Suitable surfactants include anionic surfactants, non-ionic surfactant, cationic surfactants, zwitterionic surfactants and amphoteric surfactants and mixtures thereof.
• Suitable surfactants may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
• Preferred surfactant systems comprise both anionic and nonionic surfactant, preferably in weight ratios from 90:1 to 1:90. In some instances a weight ratio of anionic to nonionic surfactant of at least 1:1 is preferred. However, a ratio below 10:1 may be preferred.
• the total surfactant level is preferably from 0.1% to 60%, from 1% to 50% or even from 5% to 40% by weight of the subject composition.
• Anionic surfactants include, but are not limited to, those surface-active compounds that contain an organic hydrophobic group containing generally 8 to 22 carbon atoms or generally 8 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group preferably selected from sulfonate, sulfate, and carboxylate so as to form a water-soluble compound.
• the hydrophobic group will comprise a C 8 -C 22 alkyl, or acyl group.
• Such surfactants are employed in the form of water-soluble salts and the salt-forming cation usually is selected from sodium, potassium, ammonium, magnesium and mono-, with the sodium cation being the usual one chosen.
• Anionic surfactants of the present invention and adjunct anionic cosurfactants may exist in an acid form, and said acid form may be neutralized to form a surfactant salt which is desirable for use in the present detergent compositions.
• Typical agents for neutralization include the metal counterion base such as hydroxides, e.g., NaOH or KOH.
• Further preferred agents for neutralizing anionic surfactants of the present invention and adjunct anionic surfactants or cosurfactants in their acid forms include ammonia, amines, oligamines, or alkanolamines. Alkanolamines are preferred.
• Amine neutralization may be done to a full or partial extent, e.g. part of the anionic surfactant mix may be neutralized with sodium or potassium and part of the anionic surfactant mix may be neutralized with amines or alkanolamines.
• Suitable sulphonate surfactants include methyl ester sulphonates, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates, preferably C 10- C 13 alkyl benzene sulphonate.
• Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB).
• Suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem ® or those supplied by Petresa under the tradename Petrelab ® , other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene ® .
• a suitable anionic surfactant is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, although other synthesis routes, such as HF, may also be suitable.
• a magnesium salt of LAS is used.
• Suitable LAS may comprise a component obtained from waste plastic feedstock.
• LAS obtained from waste plastic feedstock comprises from 0.001 to 100% wt. of the total LAS, more preferably from 0.01 to 50 wt.%, more preferably from 0.1 to 20 wt.%, most preferably from 0.5 to 10%.
• Suitable LAS obtained from waste plastic feedstock are described for example in WO2023057604 , WO2023057531 and WO2023057530 .
• the composition may contain from about 0.5% to about 30%, by weight of the laundry composition, of a HLAS surfactant selected from alkyl benzene sulfonic acids, alkali metal or amine salts of C 10 -C 16 alkyl benzene sulfonic acids, wherein the HLAS surfactant comprises greater than 50% C 12 , preferably greater than 60%, preferably greater than 70% C 12 , more preferably greater than 75%.
• a HLAS surfactant selected from alkyl benzene sulfonic acids, alkali metal or amine salts of C 10 -C 16 alkyl benzene sulfonic acids, wherein the HLAS surfactant comprises greater than 50% C 12 , preferably greater than 60%, preferably greater than 70% C 12 , more preferably greater than 75%.
• Suitable sulphate surfactants include alkyl sulphate, preferably C 8-18 alkyl sulphate, or predominantly C 12 alkyl sulphate.
• a preferred sulphate surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate, preferably a C 8 -C 18 alkyl alkoxylated sulphate, preferably a C 8 -C 18 alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a C 8 -C 18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3 or from about 1.5 to 3 or from about 1.8 to 2.5.
• the alkyl alkoxylated sulfate may have a broad alkoxy distribution or a peaked alkoxy distribution.
• the alkyl portion of the AES may include, on average, from 13.7 to about 16 or from 13.9 to 14.6 carbons atoms.
• At least about 50% or at least about 60% of the AES molecule may include having an alkyl portion having 14 or more carbon atoms, preferable from 14 to 18, or from 14 to 17, or from 14 to 16, or from 14 to 15 carbon atoms.
• the alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, including 2 alkyl substituted or mid chain branched type, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
• the branching group is an alkyl.
• the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, cyclic alkyl groups and mixtures thereof.
• Single or multiple alkyl branches could be present on the main hydrocarbyl chain of the starting alcohol(s) used to produce the sulfated anionic surfactant used in the detergent of the invention.
• the branched sulfated anionic surfactant is selected from alkyl sulfates, alkyl ethoxy sulfates, and mixtures thereof.
• Alkyl sulfates and alkyl alkoxy sulfates are commercially available with a variety of chain lengths, ethoxylation and branching degrees.
• Commercially available sulfates include those based on Neodol alcohols ex the Shell company, Lial - Isalchem and Safol ex the Sasol company, natural alcohols ex The Procter & Gamble Chemicals company.
• alkyl ether carboxylates comprising a C 10 -C 26 linear or branched, preferably C 10 -C 20 linear, most preferably C 16 -C 18 linear alkyl alcohol and from 2 to 20, preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates.
• the acid form or salt form such as sodium or ammonium salt, may be used, and the alkyl chain may contain one cis or trans double bond.
• Alkyl ether carboxylic acids are available from Kao (Akypo ® ), Huntsman (Empicol ® ) and Clariant (Emulsogen ® ).
• rhamnolipids may have a single rhamnose sugar ring or two rhamnose sugar rings.
• Non-ionic Surfactant are selected from the group consisting of: C 8 -C 18 alkyl ethoxylates, such as, NEODOL ® non-ionic surfactants from Shell; C 6 -C 12 alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic ® from BASF; alkylpolysaccharides, preferably alkylpolyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants; and mixtures thereof.
• C 8 -C 18 alkyl ethoxylates such as, NEODOL ® non-ionic surfactants from Shell
• Suitable non-ionic surfactants are alkylpolyglucoside and/or an alkyl alkoxylated alcohol.
• Suitable non-ionic surfactants include alkyl alkoxylated alcohols, preferably C 8 -C 18 alkyl alkoxylated alcohol, preferably a C 8 -C 18 alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C 8 -C 18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7.
• the alkyl alkoxylated alcohol is a C 12- C 15 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 7 to 10.
• the alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted.
• Suitable nonionic surfactants include those with the trade name Lutensol ® from BASF.
• the alkyl alkoxylated sulfate may have a broad alkoxy distribution for example Alfonic 1214-9 Ethoxylate or a peaked alkoxy distribution for example Novel 1214-9 both commercially available from Sasol.
• Suitable cationic surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
• Preferred cationic surfactants are quaternary ammonium compounds having the general formula: (R)(R 1 )(R 2 )(R 3 )N + X - wherein, R is a linear or branched, substituted or unsubstituted C 6-18 alkyl or alkenyl moiety, R 1 and R 2 are independently selected from methyl or ethyl moieties, R 3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, preferred anions include: halides, preferably chloride; sulphate; and sulphonate.
• the fabric care compositions of the present invention may contain up to about 30%, alternatively from about 0.01% to about 20%, more alternatively from about 0.1% to about 20%, by weight of the composition, of a cationic surfactant.
• cationic surfactants include those which can deliver fabric care benefits.
• Non-limiting examples of useful cationic surfactants include: fatty amines, imidazoline quat materials and quaternary ammonium surfactants, preferably N, N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethyl ammonium chloride, N,N-bis(stearoyl-oxyethyl) N-(2 hydroxyethyl) N-methyl ammonium methyl sulfate; N,N-bis(stearoyl-isopropoxy)N,N-dimethyl ammonium methyl sulfate, N,N-bis(tallowoyl-isopropoxy)N,N-dimethyl ammonium methyl sulfate, 1, 2 di (stearoyl-oxy) 3 trimethyl ammoniumpropane chloride; dialkylenedimethylammonium salts such as dican
• Amphoteric and Zwitterionic surfactant include amine oxides, and/or betaines.
• Preferred amine oxides are alkyl dimethyl amine oxide or alkyl amido propyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide and especially coco dimethyl amino oxide.
• Amine oxide may have a linear or mid-branched alkyl moiety.
• Typical linear amine oxides include water-soluble amine oxides containing one R 1 Cs-C 18 alkyl moiety and 2 R 2 and R 3 moieties selected from the group consisting of C 1 -C 3 alkyl groups and C 1 -C 3 hydroxyalkyl groups.
• amine oxide is characterized by the formula R 1 - N(R 2 )(R 3 ) O wherein R 1 is a C 8 -C 18 alkyl and R 2 and R 3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl.
• the linear amine oxide surfactants in particular may include linear C 10 -C 18 alkyl dimethyl amine oxides and linear C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
• Other suitable surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as Phosphobetaines.
• the laundry detergent composition of the invention may comprise at least one laundry detergent ingredient different from the graft polymer and detersive surfactant.
• Suitable ingredient include, enzymes, enzyme stabilizers, builders, dispersants, structurants or thickeners, other polymers, additional amines, catalytic materials, bleaching agents, bleaching catalysts, bleach activators, polymeric dispersing agents, soil removal/ anti-redeposition agents, polymeric grease cleaning agents, amphiphilic copolymers, fluorescent brightener, fabric hueing agents, chelating agent, encapsulates, perfume, pro-perfumes, malodor reduction materials, conditioning agents, probiotics, organic acids, anti-oxidants, anti-microbial agents and/or preservatives, neutralizers and/ or pH adjusting agents, processing aids, rheology modifiers, corrosion and/or anti-tarnishing agents, hygiene Agent, pearlescent agent, pigments, opacifier, solvents, carriers, hydrotrope, suds suppressor and mixtures thereof. More details are described below:
• the composition comprises one or more enzymes.
• Preferred enzymes provide cleaning performance and/or fabric care benefits.
• suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, galactanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ß-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
• a typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase.
• the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001% to about 0.5% enzyme protein by weight of the composition.
• the composition comprises one or more proteases.
• Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62).
• Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable protease may be of microbial origin.
• the suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases.
• the suitable protease may be a serine protease, such as an alkaline microbial protease or/and a trypsin-type protease.
• suitable neutral or alkaline proteases include:
• Suitable commercially available protease enzymes include those sold under the trade names Alcalase ® , Savinase ® , Primase ® , Durazym ® , Polarzyme ® , Kannase ® , Liquanase ® , Liquanase Ultra ® , Savinase Ultra ® , Liquanase ® Evity ® , Savinase ® Evity ® , Ovozyme ® , Neutrase ® , Everlase ® , Coronase ® , Blaze ® , Blaze Ultra ® , Blaze ® Evity ® , Blaze ® Exceed, Blaze ® Pro, Esperase ® , Progress ® Uno, Progress ® Excel, Progress ® Key, Ronozyme ® , Vinzon ® and Het Ultra ® by Novozymes A/S (Denmark); those sold under the tradename Maxatase
• Amylases Preferably the composition may comprise an amylase.
• Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included.
• a preferred alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 ( USP 7,153,818 ) DSM 12368, DSMZ no. 12649, KSM AP1378 ( WO 97/00324 ), KSM K36 or KSM K38 ( EP 1,022,334 ).
• Preferred amylases include:
• Suitable commercially available alpha-amylases include DURAMYL ® , LIQUEZYME ® , TERMAMYL ® , TERMAMYL ULTRA ® , NATALASE ® , SUPRAMYL ® , STAINZYME ® , STAINZYME PLUS ® , FUNGAMYL ® and BAN ® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM ® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE ® , PURASTAR ® , ENZYSIZE ® , OPTISIZE HT PLUS ® , POWERASE ® and PURASTAR OXAM ® (Genencor International Inc., Palo Alto, California) and KAM ® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan).
• the composition comprises one or more lipases, including "first cycle lipases” such as those described in U.S. Patent 6,939,702 B1 and US PA 2009/0217464 .
• Preferred lipases are first-wash lipases.
• the composition may comprise a first wash lipase.
• First wash lipases includes a lipase which is a polypeptide having an amino acid sequence which: (a) has at least 90% identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109; (b) compared to said wild-type lipase, comprises a substitution of an electrically neutral or negatively charged amino acid at the surface of the three-dimensional structure within 15A of E1 or Q249 with a positively charged amino acid; and (c) comprises a peptide addition at the C-terminal; and/or (d) comprises a peptide addition at the N-terminal and/or (e) meets the following limitations: i) comprises a negative amino acid in position E210 of said wild-type lipase; ii) comprises a negatively charged amino acid in the region corresponding to positions 90-101 of said wild-type lipase; and iii) comprises a neutral or negative amino acid at a position corresponding to N94 or said wild-type lipase and/or has
• variants of the wild-type lipase from Thermomyces lanuginosus comprising one or more of the T231R and N233R mutations.
• the wild-type sequence is the 269 amino acids (amino acids 23 - 291) of the Swissprot accession number Swiss-Prot O59952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)).
• Other suitable lipases include: Liprl 139, e.g. as described in WO2013171241 ; TfuLip2, e.g. as described in WO2011084412 and WO2013033318 ; Pseudomonas stutzeri lipase, e.g.
• WO2018228880 Microbulbifer thermotolerans lipase, e.g. as described in WO2018228881 ; Sulfobacillus acidocaldarius lipase, e.g. as described in EP3299457 ; LIP062 lipase e.g. as described in WO2018209026 ; PinLip lipase e.g. as described in WO2017036901 and Absidia sp. lipase e.g. as described in WO2017005798 .
• Preferred lipases would include those sold under the tradenames Lipex ® and Lipolex ® and Lipoclean ® .
• Suitable enzymes include cellulases of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 and US 5,691,178 . Suitable cellulases include the alkaline or neutral cellulases having colour care benefits.
• cellulases include CELLUZYME ® , CAREZYME ® and CAREZYME PREMIUM (Novozymes A/S), CLAZINASE ® , and PURADAX HA ® (Genencor International Inc.), and KAC-500(B) ® (Kao Corporation).
• the bacterial cleaning cellulase may be a glycosyl hydrolase having enzymatic activity towards amorphous cellulose substrates, wherein the glycosyl hydrolase is selected from GH families 5, 7, 12, 16, 44 or 74. Suitable glycosyl hydrolases may also be selected from the group consisting of: GH family 44 glycosyl hydrolases from Paenibacillus polyxyma (wild-type) such as XYG1006 described in US 7,361,736 or are variants thereof.
• GH family 12 glycosyl hydrolases from Bacillus licheniformis (wild-type) such as SEQ ID NO:1 described in US 6,268,197 or are variants thereof; GH family 5 glycosyl hydrolases from Bacillus agaradhaerens (wild type) or variants thereof; GH family 5 glycosyl hydrolases from Paenibacillus (wild type) such as XYG1034 and XYG 1022 described in US 6,630,340 or variants thereof; GH family 74 glycosyl hydrolases from Jonesia sp.
• wild type such as XYG1020 described in WO 2002/077242 or variants thereof
• GH family 74 glycosyl hydrolases from Trichoderma Reesei wild type
• Suitable bacterial cleaning cellulases are sold under the tradenames Celluclean ® and Whitezyme ® (Novozymes A/S, Bagsvaerd, Denmark).
• the composition may comprise a fungal cleaning cellulase belonging to glycosyl hydrolase family 45 having a molecular weight of from 17kDa to 30 kDa, for example the endoglucanases sold under the tradename Biotouch ® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).
• a fungal cleaning cellulase belonging to glycosyl hydrolase family 45 having a molecular weight of from 17kDa to 30 kDa, for example the endoglucanases sold under the tradename Biotouch ® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).
• Pectate Lyases Other preferred enzymes include pectate lyases sold under the tradenames Pectawash ® , Pectaway ® , Xpect ® and mannanases sold under the tradenames Mannaway ® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite ® (Genencor International Inc., Palo Alto, California).
• the composition may comprise a nuclease enzyme.
• the nuclease enzyme is an enzyme capable of cleaving the phosphodiester bonds between the nucleotide sub-units of nucleic acids.
• the nuclease enzyme herein is preferably a deoxyribonuclease or ribonuclease enzyme or a functional fragment thereof.
• functional fragment or part is meant the portion of the nuclease enzyme that catalyzes the cleavage of phosphodiester linkages in the DNA backbone and so is a region of said nuclease protein that retains catalytic activity.
• Suitable DNases include wild-types and variants described in detail by WO2017162836 and WO2018108865 , and variants of the Bacillus cibi DNase including those described in WO2018011277 .
• RNase suitable RNases include wild-types and variants of DNases described in WO2018178061 and WO2020074499 .
• Hexosaminidases The composition may comprise one or more hexosaminidases.
• hexosaminidase includes "dispersin” and the abbreviation "Dsp", which means a polypeptide having hexosaminidase activity, EC 3.2.1 .- that catalyzes the hydrolysis of ⁇ -1,6-glycosidic linkages of N-acetyl-glucosamine polymers found in soils of microbial origin.
• the term hexosaminidase includes polypeptides having N-acetylglucosaminidase activity and ⁇ -N-acetylglucosaminidase activity.
• Hexosaminidase activity may be determined according to Assay II described in WO2018184873 .
• Suitable hexosaminidases include those disclosed in WO2017186936 , WO2017186937 , WO2017186943 , WO2017207770 , WO2018184873 , WO2019086520 , WO2019086528 , WO2019086530 , WO2019086532 , WO2019086521 , WO2019086526 , WO2020002604 , WO2020002608 , WO2020007863 , WO2020007875 , WO2020008024 , WO2020070063 , WO2020070249 , WO2020088957 , WO2020088958 and WO2020207944 .
• Variants of the Terribacillus saccharophilus hexosaminidase defined by SEQ ID NO: 1 of WO2020207944 may be preferred, especially
• the composition may comprise an extracellular-polymer-degrading enzyme that includes a mannanase enzyme.
• mannanase means a polypeptide having mannan endo-1,4-beta-mannosidase activity (EC 3.2.1.78) from the glycoside hydrolase family 26 that catalyzes the hydrolysis of 1,4-3-D-mannosidic linkages in mannans, galactomannans and glucomannans.
• mannan endo-1,4-beta-mannosidase are 1,4-3-D-mannan mannanohydrolase; endo-1,4-3-mannanase; endo- ⁇ -1,4-mannase; ⁇ -mannanase B; 3-1,4-mannan 4-mannanohydrolase; endo-3-mannanase; and ⁇ -D-mannanase.
• mannanase activity may be determined using the Reducing End Assay as described in the experimental section of WO2015040159 . Suitable examples from class EC 3.2.1.78 are described in WO2015040159 , such as the mature polypeptide SEQ ID NO: 1 described therein.
• the composition may comprise an extracellular polymer-degrading enzyme that includes an endo-beta-1,6-galactanase enzyme.
• endo-beta-1,6-galactanase or "a polypeptide having endo-beta-1,6-galactanase activity” means a endo-beta-1,6-galactanase activity (EC 3.2.1.164) from the glycoside hydrolase family 30 that catalyzes the hydrolytic cleavage of 1,6-3-D-galactooligosaccharides with a degree of polymerization (DP) higher than 3, and their acidic derivatives with 4-O-methylglucosyluronate or glucosyluronate groups at the nonreducing terminals.
• DP degree of polymerization
• endo-beta-1,6-galactanase activity is determined according to the procedure described in WO 2015185689 in Assay I. Suitable examples from class EC 3.2.1.164 are described in WO 2015185689 , such as the mature polypeptide SEQ ID NO: 2.
• the composition may optionally comprise from about 0.001% to about 10%, in some examples from about 0.005% to about 8%, and in other examples, from about 0.01% to about 6%, by weight of the composition, of an enzyme stabilizing system.
• the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
• a reversible protease inhibitor such as a boron compound, including borate, 4-formyl phenylboronic acid, phenylboronic acid and derivatives thereof, or compounds such as calcium formate, sodium formate and 1,2-propane diol may be added to further improve stability.
• the composition may optionally comprise a builder.
• Built compositions typically comprise at least about 1% builder, based on the total weight of the composition.
• Liquid compositions may comprise up to about 10% builder, and in some examples up to about 8% builder, of the total weight of the composition.
• Granular compositions may comprise up to about 30% builder, and in some examples up to about 5% builder, by weight of the composition.
• aluminosilicates e.g., zeolite builders, such as zeolite A, zeolite P, and zeolite MAP
• silicates assist in controlling mineral hardness in wash water, especially calcium and/or magnesium, or to assist in the removal of particulate soils from surfaces.
• Suitable builders may be selected from the group consisting of phosphates, such as polyphosphates (e.g., sodium tri-polyphosphate), especially sodium salts thereof; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri-, and tetracarboxylates, especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
• phosphates such as polyphosphates (e.g., sodium tri-polyphosphate), especially sodium salts thereof
• carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonate e.g., sodium tri-polyphosphate
• organic mono-, di-, tri-, and tetracarboxylates especially water-
• borates e.g., for pH-buffering purposes
• sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing compositions.
• Additional suitable builders may be selected from citric acid, lactic acid, fatty acid and salt thereof.
• Suitable builders may include polycarboxylate and salt thereof, for example, homopolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and copolymers of acrylic acid and/or maleic acid, and other suitable ethylenic monomers with various types of additional functionalities. More suitable polycarboxylate are described in polycarboxylate polymers section of this patent.
• crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general anhydride form: x(M 2 O) ⁇ ySiO 2 ⁇ zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0; and z/x is 0.005 to 1.0.
• the composition may be substantially free of builder.
• Suitable structurant / thickeners include:
• the compositions may include one or more other polymers.
• the level of other polymers is from about 0.01% to about 10.0 % by weight of the composition, preferably from about 0.1% to about 5%, and more preferably from about 0.2% to about 3.0% by weight of the composition.
• the level of the polymers maybe higher than 10.0%, or higher than 5.0%, by weight of the composition.
• polymers can provide various benefits for the composition, including but not limit to, hydrophobic and hydrophilic stain removal, surfactant boosting, soil suspension, whiteness maintenance, soil release, malodor control, dye transfer inhibition, enhanced softness, enhanced freshness, etc.
• Polymers are normally multi-functional, which means one specific given type of polymer may provide more than one types of benefit as mentioned above.
• a specific soil release polymer may provide soil release benefit as primary benefit, while also providing other benefits such as whiteness maintenance, malodor control, soil suspension, dye transfer inhibition.
• Suitable other polymers including, but not limited to the following: Other graft polymers based on polyalkylene oxide.
• the composition may comprise graft polymers which comprising block copolymer backbone (A) as a graft base and polymeric sidechains (B) grafted thereon.
• the polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer.
• the block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1 ,2-pentene oxide or 2,3-pentene oxide.
• Such graft polymers are known as effective soil suspension polymers for hydrophobic and hydrophilic stains, surfactant boosters, and sometimes as dye transfer inhibitors.
• Suitable graft polymers include amphilic graft co-polymer comprises polyethylene glycol backbone (A) as a graft base, and at least one pendant sidechains (B) selected from polyvinyl acetate, polyvinyl alcohol and mixtures thereof.
• a preferred graft polymer of this type is Sokalan HP22 available from BASF.
• Suitable graft polymers are also described in WO2007/138053 as amphiphilic graft polymers based on water-soluble polyalkylene oxides (A) as a graft base and side chains formed by polymerization of a vinyl ester component (B), said polymers having an average of ⁇ one graft site per 50 alkylene oxide units and mean molar masses M of from 3,000 to 100,000 g/mol.
• A water-soluble polyalkylene oxides
• B vinyl ester component
• One specific preferred graft polymer of this type is polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide as graft base and multiple polyvinyl acetate side chains.
• the molecular weight of the polyethylene oxide backbone is about 6,000 g/mol and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units.
• the most preferred polymer of this type is available from BASF as Sokalan PG101.
• Other examples of suitable amphiphilic graft polymers are described in WO2023017064 and WO2023019153 , where molecular weight (Mn) of the backbone is within 500 to 7,000, and preferably not more than 3,000 or even not more than 2,500 g/mol.
• Suitable graft polymer also include graft polymer comprising a block copolymer backbone (A) as a graft base, wherein said block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, wherein the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x is from 2 to 10 and preferably 3 to 5, and (B) polymeric sidechains grafted onto the block copolymer backbone, wherein said polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer.
• Suitable graft polymers of this type are described in WO2021160795 and WO2021160851 , these polymers have improved biodegradation profiles.
• Suitable graft polymers also include graft polymers based on random copolymer backbone, wherein the backbone is obtainable by polymerization of at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- pentene oxide or 2,3-pentene oxide. Graft polymer of this type is described in WO2023017062 and WO2023019152 .
• the composition may comprise one or more modified polyamine dispersing agent.
• the modified polyamine dispersant comprises a polyamine core structure and a plurality of alkoxylate groups attached to the core structure.
• the polyamine core structure includes polyalkyleneimine, and linear or branched oligoamine.
• the polyamine core structure and the alkoxylate groups attached to the core structure can be further derivatized.
• the polyamine core structure can be further partly or completely quaternized with C 1 -C 30 linear or branched alkyl, more preferably C 1 -C 10 or even C 1 -C 5 linear or branched alkyl, most preferably methyl.
• the alkoxylate group can be further sulphated, sulphonated and/or substituted with an amino functional group.
• Suitable modified polyamine dispersing agent includes ethoxylated polyethyleneimine (EPEI).
• EPEI are effective dispersing agent for hydrophilic stains, especially hydrophilic particulate stain such as clay.
• the EPEI has a polyethyleneimine backbone of weight average molecular weight of between 100 g/mol and 2,000 g/mol, preferably between 200 g/mol and 1,500 g/mol, more preferably between 300 g/mol and 1,000 g/mol, even more preferably between 400 g/mol and 800 g/mol, most preferably between 500 g/mol and 700 g/mol, preferably about 600.
• the ethoxylation chains within the EPEI may be from 200 g/mol to 2,000 g/mol weight average molecular weight, preferably from 400 g/mol to 1500 g/mol weight average molecular weight, more preferably from 600 g/mol to 1,000 g/mol weight average molecular weight, most preferably about 880 g/mol weight average molecular weight per ethoxylated chain.
• the ethoxylation chains within the EPEI have on average 5 to 40, preferably 10 to 30, more preferably 15 to 25, even more preferably 18 to 22, most preferably about 20 ethoxy units per ethoxylation chain.
• the EPEI may have a total weight average molecular weight of from 5,000 g/mol to 20,000 g/mol, preferably from 7,500 g/mol to 17,500 g/mol, more preferably from 10,000 g/mol to 15,000 g/mol, even more preferably from 12,000 g/mol to 13,000 g/mol, most preferably about 12,700 g/mol.
• a preferred example is polyethyleneimine core (with average molecular weight about 600 g/mol) ethoxylated to 20 EO groups per NH.
• Suitable EPEI this type includes Sokalan HP20 available from BASF, Lutensol FP620 from BASF. Examples of available polyethyleneimine ethoxylates also include those prepared by reacting ethylene oxide with Epomine SP-006 manufactured by Nippon Shokubai.
• the EPEI comprises polyethyleneimine has an average molecular weight (Mw) ranging from 1,800 to 5,000 g/mol (prior to ethoxylation), and the polyoxyethylene side chains have an average of from 25 to 40 ethoxy units per side chain bonded to the polyethyleneimine backbone.
• Mw average molecular weight
• the polyoxyethylene side chains have an average of from 25 to 40 ethoxy units per side chain bonded to the polyethyleneimine backbone.
• Suitable modified polyamine dispersing agent includes amphiphilic alkoxylated polyalkyleneimine polymer. These polymers have balanced hydrophilic and hydrophobic properties such that they remove grease and body soil particles from fabrics and surfaces, and keep the particles suspended in washing liquor.
• Suitable amphiphilic water-soluble alkoxylated polyalkyleneimine polymer is described in WO2009061990 and WO2006108857 , which comprising in polyalkyleneimine, preferable polyethyleneimine core, and alkoxylate group of below connected to the core: *-[A 2 -O] m -[CH 2 -CH 2 -O] n -[A 3 -O] p -R (V) wherein
• the polymer comprising a degree of quaterization ranging from 0 to 50, preferably from 0 to 20, and more preferably from 0 to 10.
• Suitable alkoxylated polyalkyleneimine polymer of this type includes Sokalan HP30 Booster available from BASF.
• Suitable alkoxylated polyalkyleneimine polymer also include amphiphilic alkoxylated poly(ethylene/propylene)imine, such as polymer examples disclosed in WO2021254828 .
• a particular preferred zwitterionic polyamine is available from BASF as Lutensit Z96 polymer (zwitterionic hexamethylene diamine according to below formula: 100% quaternized and about 40% of the polyethoxy (EO 24 ) groups are sulfonated).
• Another suitable zwitterionic polyamine is amphoterically-modified oligopropyleneimine ethoxylates as described in WO2021239547 .
• the composition may comprise one or more soil release polymer (SRP).
• SRP soil release polymers include terephthalate-derived polyester polymers, which comprise structure unit (1) and/or (II): (I) -[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d (II) -[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e wherein:
• the polymer further comprises one or more terminal group (III) derived from polyalkylene glycolmonoalkylethers, preferably selected from structure (III-a) -O-[C 2 H 4 -O] c -[C 3 H 6 -O] d -[C 4 H 8 -O] e -R 7 (III-a) wherein:
• the polymer further comprises one or more anionic terminal unit (IV) and/or (V) as described in EP3222647 .
• M is a counterion selected from Na + , Li + , K + , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1/3 Al 3+ , ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are C 1 -C 18 alkyl or C 2 -C 10 hydroxyalkyl, or mixtures thereof.
• the polymer may comprise crosslinking multifunctional structural unit which having at least three functional groups capable of the esterification reaction.
• the functional which may be for example acid -, alcohol -, ester -, anhydride - or epoxy groups, etc.
• polyesters such as, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6,-dicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 2,5-furandicarboxylic acid, adipic acid, sebacic acid, decan-1,10-dicarboxylic acid, fumaric acid, succinic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, glutaric acid, azelaic acid, or their salts or their (di)alkyl esters, preferably their (C 1 -C 4 )-(di)alkyl esters and more preferably their (di)methyl esters
• polyester SRPs are nonionic polyester SRP, which does not comprise above structure unit (II).
• a particular preferred nonionic terephthalate-derived soil release polymer has a structure according to formula below: wherein:
• One example of most preferred above suitable terephthalate-derived nonionic SRP has one of the R 5 and R 6 is H, and another is CH 3 ; d is 0; c is from 5-100 and R 7 is methyl, and n is from 3-10.
• terephthalate-derived polyester SRP are described in patent WO2014019903 , WO2014019658 and WO2014019659 .
• the end capping group of these SRPs are selected from X-(OC 2 H 4 ) n -(OC 3 H 6 ) m - -wherein X is C 1 -C 4 alkyl and preferably methyl, the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group, n is based on a molar average a number of from 40 to 50, m is based on a molar average a number of from 1 to 10 and preferably of from 1 to 7.
• Polyester soil release polymers may be available or convert into different forms, include powder, particle, liquid, waxy or premix. Other materials (for example, water, alcohol, other solvents, salt, surfactant, etc.) may be needed to convert the polyester soil release polymer into different forms mentioned above, the wt% of active soil release polymer in the powder, particle, liquid, waxy or premix is in the range from 10% to 100%, for example 15%, 20%, 40%, 60%, 70%, 80%, 90%, 95%, 100%.
• Useful soil release polymer premix examples are described in EP351759 and WO2022100876 .
• the premix maybe transparent or opaque, white or slightly yellowish. Premix in opaque maybe use to provide an opaque appearance for the finish product or part of the finish product.
• the polyester may or may not be biodegradable, preferred soil release polymers are readily biodegradable.
• suitable soil release polymers include TexCare ® series supplied by Clariant, including noniconic soil release polymers Texcare ® SRN 100, SRN 170, SRN 170 C, SRN 170 Terra, SRN 172, SRN 240, SRN 260, SRN 260 life, SRN 260 SG Terra, SRN UL50, , SRN UL50 Terra, SRN 300, SRN 325; and anionic soil release polymers TexCare ® SRA 100, SRA 300, SRA300 F.
• TexCare ® series supplied by Clariant including noniconic soil release polymers Texcare ® SRN 100, SRN 170, SRN 170 C, SRN 170 Terra, SRN 172, SRN 240, SRN 260, SRN 260 life, SRN 260 SG Terra, SRN UL50, , SRN UL50 Terra, SRN 300, SRN 325; and anionic soil release polymers TexCare ® SRA 100, SRA 300,
• Example of suitable soil release polymers also include REPEL-O-TEX ® line of polymers supplied by Rhodia/Solvay, including nonionic soil release polymer REPEL-O-TEX ® Crystal, Crystal PLUS, Crystal NAT, SRP6; and anionic soil release polymer REPEL-O-TEX ® SF-2.
• Other example of commercial soil release polymers also includes WeylClean ® series of soil release polymers supplied by WeylChem, including noniconic soil release polymers WeylClean ® PLN1, PLN2; and anionic soil release polymers WeylClean ® PSA1.
• Marloquest ® polymers such as Marloquest ® SL, HSCB, L235M, U, B, and G82, supplied by Sasol.
• suitable commercial soil release polymers include Sorez 100 (from ISP or Ashland, CAS: 9016-88-0 ).
• polysaccharides have proven to be useful starting material to make polymers for fabric and home care products, including cellulose, starch, guar, dextran, polyglucan, chitin, curdlan, xylose, Inulin, pullulan, locust bean gum, cassia gum, tamarind gum (xyloglucan), xanthan gum, amylose, amylopectin, scleroglucan and mixtures thereof.
• modified polysaccharide The most common type of modified polysaccharide is modified cellulose.
• Modified cellulose polymers include anionic modified cellulose polymers which been modified with functional groups that contain negative charge.
• Suitable anionic modified cellulose polymers include carboxyalkyl cellulose, such as carboxymethyl cellulose.
• the carboxymethyl cellulose may have a degree of carboxymethyl substitution of from about 0.5 to about 0.9 and a molecular weight from about 80,000 to about 300,000 g/mol.
• Suitable carboxymethylcellulose is described in WO2011031599 and WO2009154933 .
• Suitable carboxymethylcellulose include Finnfix ® series sold by CP Kelco or Nouryon, which include Finnfix ® GDA, a hydrophobically modified carboxymethylcellulose, e.g., the alkyl ketene dimer derivative of carboxymethylcellulose sold under the tradename Finnfix ® SH1, or the blocky carboxymethylcellulose sold under the tradename Finnfix ® V.
• Other suitable anionic modified cellulose polymers include sulphoalkyl group which described in WO2006117056 , sulfoethyl cellulose which described in WO2014124872 .
• Modified cellulose polymers also include nonionic modified cellulose polymers which been modified by functional group that does not contain any charge.
• Suitable nonionic modified cellulose polymers include alkyl cellulose, hydroxyalkyl cellulose, hydroxyalkyl alkylcellulose, alkylalkoxyalkyl cellulose.
• Suitable nonionic modified cellulose polymers also include nonionic cellulose carbamates which described in WO2015044061 ; nonionic 6-desoxy-6-amino-celluloses derivative which described in US20180346846 .
• Example of alkyl cellulose include methyl cellulose (MC), ethyl cellulose (EC), etc.
• Suitable ethyl cellulose are sold under tradename Ethocel TM by Dow Chemicals, DuPont, or IFF.
• Example of hydroxyalkyl cellulose include hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC).
• HEC hydroxyethyl cellulose
• HPC hydroxypropyl cellulose
• Suitable HEC are sold under tradename Natrosol TM hydroxyethylcellulose by Ashland, such as Natrosol TM 250 with different grade available which has a total molar substitution (MS) of 2.5.
• Suitable HEC are also sold under tradename CELLOSIZE TM Hydroxyethyl Cellulose by Dow Chemicals.
• Suitable HPC are sold under tradename Klucel TM by Ashland.
• hydroxyalkyl alkylcellulose examples include hydroxypropyl methylcellulose (HPMC), suitable HPMC are sold under tradename Methocel TM with different grade available by Dow Chemicals, DuPont or IFF, and under tradename Benecel TM by Ashland.
• HPMC hydroxypropyl methylcellulose
• suitable HPMC are sold under tradename Methocel TM with different grade available by Dow Chemicals, DuPont or IFF, and under tradename Benecel TM by Ashland.
• Modified cellulose polymers also include cationic modified cellulose polymers which been modified by functional group that contain cationic charge.
• Suitable cationic modified celluloses include quaternized hydroxyethyl cellulose (Polyquaternium-10), which available under the tradename of Ucare by Dow Chemical, such as Ucare LR400, Ucare LR30M, Ucare JR125, Ucare JR400, etc.
• Suitable cationic modified cellulose polymers also include quaternised hydroxyethyl cellulose (HEC) polymers with cationic substitution of trimethyl ammonium and dimethyldodecyl ammonium (Polyquaternium-67), which available under trade the tradename of SoftCAT by Dow Chemical, such as SoftCAT SK, SoftCAT SK-MH, SoftCAT SX, SoftCAT SL.
• HEC quaternised hydroxyethyl cellulose
• SoftCAT SX quaternium-67
• Other suitable cationic modified celluloses include those sold under tradename SupraCare TM by Dow Chemical, such as SupraCare TM 150, SupraCare TM 133, SupraCare TM 212.
• Suitable cationic modified cellulose polymers also include those modified with cationic group and/or a hydrophobic group and described as soil release polymers in WO2019111948 , WO2019111949 , WO2019111946 and WO2019111947 ; suitable polymers is also disclosed in WO2022060754 , WO2021242942 and WO2020091988 .
• modified polysaccharide is modified guar. Similar to modified cellulose, modified guar can be nonionic modified, and anionic modified. Suitable nonionic modified guar includes hydroxypropyl guar, such as N-Hance TM HP40 and HP40S guar available from Ashland. Suitable example of modified guar also include carboxymethyl hydroxypropyl guar (CMHPG) which is anionic and nonionic modified, such as Galactasol TM available from Ashland. Other nonionic and/or anionic modified guar include for example Jaguar ® HP 105 (Hydroxypropyl Guar gum), Jaguar ® SOFT and HP-120 COS (Carboxymethyl Hydroxypropyl Guar Gum).
• CMHPG carboxymethyl hydroxypropyl guar
• Other nonionic and/or anionic modified guar include for example Jaguar ® HP 105 (Hydroxypropyl Guar gum), Jaguar ® SOFT and HP-120 COS (Carbox
• modified polysaccharide polymers also include modified starch.
• modified starch include carboxylate ester of starch as described in WO2015144438 , esterification product of starch with e.g. C 6 -C 24 alk(en)yl succinic anhydride as described in EP0703243 ; starch maleates (starch react with maleic acid anhydride) as described US 6063914 .
• modified starch also include, but not limit to, acetylated starch, acetylated distarch adipate, distarch phosphate, hydroxypropyl starch, hydroxy propyl distarch phosphate, phosphated distarch ohosphate, acetylated distarch phosphate, starch sodium octenyl succinate.
• Suitable modified polysaccharide polymers also include polymers based on other polysaccharide, such as cationic dextran polymers described in WO2021194808 , the cationic dextran polymers are commercially available under brand name CDC, CDC-L, CD C-H by Meito Sangyo.
• Suitable modified polysaccharide polymers also include polymers based on polyglucans. Suitable modified polyglucans are based on alpha 1,3-polyglucans and/or 1,6-polyglucans.
• the modified polyglucans can be cationic modified, such as cationic modified alpha 1,3-polyglucan which described in WO2021225837 ; such as cationic modified alpha 1,6-polyglucans which described in WO2021257793 , WO2021257932 , and WO2021/257786 .
• the modified polyglucans can be hydrophobic and/or hydrophilic modified, such as those described in WO2018112187 , WO2019246228 , WO2019246171 , WO2021252558 , WO2021252560 , WO2021252561 , EP3922704 , WO2021252569 , WO2021252562 , WO2021252559 , WO2021252575 , WO2021252563 .
• the polyglucan esters which described in WO2021252562 , WO2021252559 , WO2021252575 , WO2021252563 are especially preferred due to their performance and biodegradability profiles.
• suitable polysaccharide polymers also include those based on inulin.
• modified inulin include carboxymethyl group modified inulin (CMI), suitable CMI are Carboxyline series sold by Cosun Beet Company, including Carboxyline 25-40D, Carboxyline 25 D Powder, Carboxyline 20 LS D Powder, Carboxyline 25, Carboxyline 25-30 UP.
• CMI carboxymethyl group modified inulin
• suitable CMI are Carboxyline series sold by Cosun Beet Company, including Carboxyline 25-40D, Carboxyline 25 D Powder, Carboxyline 20 LS D Powder, Carboxyline 25, Carboxyline 25-30 UP.
• modified inulin also include cationic modified inulin, suitable cationic modified inulin are as described in US20190274943 , US20180119055 ; suitable cationic modified inulin are Quatin series sold by Cosun Beet Company, including Quatin 350, Quatin 380 and Quatin 1280 which are characterized by different degree of substitution (DS), cationic density (meq/g) and molecular weight (g/mol).
• suitable cationic modified inulin are Quatin series sold by Cosun Beet Company, including Quatin 350, Quatin 380 and Quatin 1280 which are characterized by different degree of substitution (DS), cationic density (meq/g) and molecular weight (g/mol).
• Suitable modified polysaccharide polymers also include polymers based on other polysaccharide, such as xylose carbamates as described in US20210115358 ; carboxy or sulfo-alkylated pullulan as described in WO2019243072 ; carboxy- or sulfo-alkylated chitosan as described in WO2019/243108 and WO2021156093 .
• the composition may also include one or more polycarboxylate polymers which comprise at least one carboxy group-containing monomer.
• the carboxy group-containing monomers are selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and salts thereof, and anhydride thereof.
• Suitable polycarboxylate polymers include polyacrylate homopolymer having a molecular weight of from 4,000 to 9,000 g/mol, or from 6,000 to 9,000 g/mol.
• Other suitable carboxylate polymers include copolymer of acrylic acid (and/or methacrylic acid) and maleic acid having a molecular weight of from 50,000 to 120,000 g/mol, or from 60,000 to 80,000 g/mol.
• the polyacrylate homopolymer and copolymer of acrylic acid (and/or methacrylic acid) and maleic acid are commercially available as Acusol 445 and 445N, Acusol 531, Acusol 463, Acusol 448, Acusol 460, Acusol 465, Acusol 497, Acusol 490 from Dow Chemicals, and as Sokalan CP 5, Sokalan CP 7, Sokalan CP 45, and Sokalan CP 12S from BASF.
• Suitable polycarboxylate polymers also include polyitaconate homopolymers, such as Itaconix ® DSP 2K TM sold by Itaconix, and Amaze SP available from Nouryon.
• Suitable polycarboxylate polymers also include co-polymers comprising carboxy group-containing monomers and one or more sulfonate or sulfonic group-containing monomers.
• the sulfonate or sulfonic group containing monomers are selected rom 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, ally sulfonic acid, methallysulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 2-methyl-2-propenen-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropylmethacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and water soluble salts thereof.
• Suitable polymers comprise maleic acid, acrylic acid, and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, such polymers are as described in US8450261 and US8389458 .
• Suitable polymers comprise acrylic acid and 2-acrylamido-2-methyl-propane sulfonate, such as those sold under tradename Acusol 588 by Dow Chemicals, Sokalan CP50 by BASF, Aquatreat AR-545, Versaflex 310 and Versaflex 310-37 by Nouryon.
• Suitable polymers also include Poly(itaconic acid-co-AMPS) sodium salt, such as Itaconix ® TSI TM 322 and Itaconix ® CHT TM 122 available from Itaconix.
• Suitable polymer also includes those contain other structure units in addition to the sulfonate or sulfonic group group-containing monomers and carboxy group-containing monomers.
• Suitable polymer examples are described in WO2010024468 and WO2014032267 , the additional monomers herein are ether bond-containing monomers represented by formula (1) and (2) below:
• a specific preferred polymer of this type comprises structure units derived from 1 to 49 wt% of 1-(allyloxy)-3-butoxypropan-2-ol, from 50 to 98 wt% acrylic acid or methacrylic acid, and from 1 to 49 wt% of 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and the has a weight average molecular weight of from about 20,000 to about 60,000 g/mol.
• a specific preferred polymer of this type comprises structure units derived from 1 to 10 wt% of 1-(allyloxy)-3-butoxypropan-2-ol, from 70 to 89 wt% acrylic acid or methacrylic acid, and from 10 to 20 wt% of 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and the has a weight average molecular weight of from about 30,000 to about 60,000 g/mol.
• 1-(allyloxy)-3-butoxypropan-2-ol is a preferred monomer as represented by formula (2) when R 0 is H, R is CH 2 , x is 0, and R 1 is n-butyl (C 4 -alkyl).
• Suitable polycarboxylate polymers also include co-polymers comprising carboxy group-containing monomers and other suitable monomers.
• suitable monomers here are selected from esters and/or amide of the carboxy group-containing monomers, such as C 1 -C 20 alkyl ester of acrylic acid; alkylene; vinyl ethers, such as methyl vinyl ether, styrene and any mixtures thereof.
• Gantrez alternating co-polymer of methyl vinyl ether and maleic anhydride
• Gantrez S alternating co-polymer of methyl vinyl ether and maleic acid
• Gantrez ES alternating co-polymer of methyl vinyl ether and maleic acid ester
• Gantrez MS alternating co-polymer of methyl vinyl ether and maleic acid salt
• Suitable polycarboxylate polymers also include polyepoxy succinic acid polymers (PESA).
• PESA polyepoxy succinic acid polymers
• a most preferred polyepoxy succinic acid polymer can be identified using CAS number: 51274-37-4 or 109578-44-1 .
• Suitable polyepoxy succinic acid polymers are commercially available from various suppliers, such as Aquapharm Chemicals Pvt. Ltd (commercial name: Maxinol 600); Shandong Taihe Water Treatment Technologies Co., Ltd (commercial name: PESA), and Sirius International (commercial name: Briteframe PESA).
• Suitable polycarboxylate polymers also include polymer comprising a monomer having at least one aspartic acid group or a salt thereof, this polymer comprises at least 25 mol%, 40 mol%, or 50 mol%, of said monomer.
• a preferable example is sodium salt of poly(aspartic acid) having a molecular weight of from 2,000 to 3,000 g/mol which is avilable as Baypure ® DS 100 from Lanxess.
• the composition may comprise block polymers of ethylene oxide, propylene oxide and butylene oxide.
• block polymers include ethylene oxide-propylene oxide-ethylene oxide (EO/PO/EO) triblock copolymer, wherein the copolymer comprises a first EO block, a second EO block and PO block wherein the first EO block and the second EO block are linked to the PO block.
• Blocks of ethylene oxide, propylene oxide, butylene oxide can also be arranged in other ways, such as (EO/PO) diblock copolymer, (PO/EO/PO) triblock copolymer.
• the block polymers may also contain additional butylene oxide (BO) block.
• Suitable block polymers are for example Pluronic PE series from BASF, including Pluronic PE3100, PE4300, PE6100, PE6200, PE6400, PE6800, PE8100, PE9200, PE9400, PE10100, PE10500, PE10400.
• Suitable block polymers also available as Tergitol L series from Dow Chemicals, such as Tergitol L-61, L-62, L-64, L-81, L-101. Due to the hydrophobic and hydrophilic nature, such block polymer sometime is also considered as nonionic surfactant in literature.
• the composition may comprise dye transfer inhibiting polymers (also called dye transfer inhibitor, or dye fixatives), which include, but are not limited to, polyvinylpyrrolidone polymers (PVP), poly(vinylpyridine-N-oxide) polymer (PVNO), poly(vinylimidazole), polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
• dye transfer inhibiting polymers also called dye transfer inhibitor, or dye fixatives
• PVP polyvinylpyrrolidone polymers
• PVNO poly(vinylpyridine-N-oxide) polymer
• PVNO poly(vinylimidazole)
• polyamine N-oxide polymers copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles
• dye transfer inhibiting agents may be selected from the group consisting of reaction products of: i) polyamines with cyanamides and organic and/or inorganic acids, ii) cyanamides with aldehydes and ammonium salts, iii) cyanamides with aldehydes and amines, or iv) amines with epichlorohydrin.
• Suitable other polymers also include a copolymer comprising N-isopropylacrylamide units, such as described in WO2019197188 , WO2019197187 , WO2019197185 and WO2019197186 .
• Suitable other polymers also include polyester soil release polymers derived from bio-based 2,5-furandicarboxylic acid and derivatives thereof, useful examples are described in WO2019105938 , WO2019105939 , WO2019096942 and JP2015105373 .
• Additional amines may be used in the compositions described herein for added removal of grease and particulates from soiled materials.
• the compositions described herein may comprise from about 0.1% to about 10%, in some examples, from about 0.1% to about 4%, and in other examples, from about 0.1% to about 2%, by weight of the composition, of additional amines.
• additional amines may include, but are not limited to, polyamines, oligoamines, triamines, diamines, pentamines, tetraamines, or combinations thereof.
• suitable additional amines include tetraethylenepentamine, triethylenetetraamine, diethylenetriamine, or a mixture thereof.
• compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent or mixtures of bleaching agents by weight of the subject composition.
• suitable bleaching agents include:
• compositions herein can be catalyzed by means of a manganese compound.
• a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,576,282 .
• An additional source of oxidant in the composition may not be not present, molecular oxygen from air providing the oxidative source.
• Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. 5,597,936 ; U.S. 5,595,967 .
• fluorescent brighteners suitable for the present disclosure can be classified into subgroups, including but not limited to: derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents.
• the fluorescent brightener may be selected from the group consisting of disodium 4,4'-bis ⁇ [4-anilino-6-morpholino-s-triazin-2-yl]-amino ⁇ -2,2'-stilbenedisulfonate (brightener 15, commercially available under the tradename Tinopal AMS-GX by BASF), disodium4,4'-bis ⁇ [4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl]-amino ⁇ -2,2'-stilbenedisulonate (commercially available under the tradename Tinopal UNPA-GX by BASF), disodium 4,4'-bis ⁇ [4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl]-amino ⁇ -2,2'-stilbenedisulfonate (commercially available under the tradename Tinopal 5BM-GX by BASF).
• the fluorescent brightener is disodium 4,4'-bis ⁇ [4-anilino-6-morpholino-s-triazin-2-yl]-amino ⁇ -2,2'-stilbenedisulfonate or 2,2'-([1,1'-Biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt.
• the brighteners may be added in particulate form or as a premix with a suitable solvent, for example nonionic surfactant, propanediol.
• compositions may comprise a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents).
• hueing agent provides a blue or violet shade to fabric.
• Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade.
• Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof.
• acridine e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo
• the composition comprises chelating agents and/or crystal growth inhibitor.
• Suitable molecules include copper, iron and/or manganese chelating agents and mixtures thereof.
• Suitable molecules include hydroxamic acids, aminocarboxylates, aminophosphonates, succinates, salts thereof, and mixtures thereof.
• Non-limiting examples of suitable chelants for use herein include ethylenediaminetetracetates, N- (hydroxyethyl)ethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, ethanoldiglycines, ethylenediaminetetrakis (methylenephosphonates), diethylenetriamine penta(methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate (EDDS), hydroxyethanedimethylenephosphonic acid (HEDP), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), N,N-Dicarboxymethyl glutamic acid (GLDA) and salts thereof, and mixtures thereof.
• ethylenediaminetetracetates N- (hydroxyethyl)ethylenediaminetriacetates, nitrilo
• chelants of use in the present invention are found in U.S. Patent Nos. 7445644 , 7585376 and 2009/0176684A1 .
• suitable chelating agents for use herein are the commercial DEQUEST series, and chelants from Monsanto, DuPont, and Nalco, Inc.
• suitable chelants include the pyridinyl N Oxide type.
• compositions may comprise an encapsulate.
• the encapsulate comprises a core, a shell having an inner and outer surface, where the shell encapsulates the core.
• the encapsulate comprises a core and a shell, where the core comprises a material selected from perfumes; brighteners; dyes; insect repellants; silicones; waxes; flavors; vitamins; fabric softening agents; skin care agents, e.g., paraffins; enzymes; anti-bacterial agents; bleaches; sensates; or mixtures thereof; and where the shell comprises a material selected from polyethylenes; polyamides; polyvinylalcohols, optionally containing other co-monomers; polystyrenes; polyisoprenes; polycarbonates; polyesters; polyacrylates; polyolefins; polysaccharides, e.g., alginate and/or chitosan; gelatin; shellac; epoxy resins; vinyl polymers; water insoluble inorganics; silicone; aminoplasts, or mixtures thereof.
• the shell comprises an aminoplast
• the aminoplast comprises polyurea, polyurethane, and/or polyureaurethane.
• compositions of the invention comprise perfume.
• the composition comprises a perfume that comprises one or more perfume raw materials, selected from the group as described in WO08/87497 .
• any perfume useful in a laundry care composition may be used.
• a preferred method of incorporating perfume into the compositions of the invention is via an encapsulated perfume particle comprising either a water-soluble hydroxylic compound or melamine-formaldehyde or modified polyvinyl alcohol.
• the cleaning compositions of the present disclosure may comprise malodour reduction materials. Such materials are capable of decreasing or even eliminating the perception of one or more malodors. These materials can be characterized by a calculated malodor reduction value ("MORV”), which is calculated according to the test method shown in WO2016049389 .
• MORV calculated malodor reduction value
• MORV is the calculated malodor reduction value for a subject material. A material's MORV indicates such material's ability to decrease or even eliminate the perception of one or more malodors.
• the cleaning compositions of the present disclosure may comprise a sum total of from about 0.00025% to about 0.5%, preferably from about 0.0025% to about 0.1%, more preferably from about 0.005% to about 0.075%, most preferably from about 0.01% to about 0.05%, by weight of the composition, of 1 or more malodor reduction materials.
• the cleaning composition may comprise from about 1 to about 20 malodor reduction materials, more preferably 1 to about 15 malodor reduction materials, most preferably 1 to about 10 malodor reduction materials.
• One, some, or each of the malodor reduction materials may have a MORV of at least 0.5, preferably from 0.5 to 10, more preferably from 1 to 10, most preferably from 1 to 5.
• One, some, or each of the malodor reduction materials may have a Universal MORV, defined as all of the MORV values of >0.5 for the malodors tested as described herein.
• the sum total of malodor reduction materials may have a Blocker Index of less than 3, more preferable less than about 2.5, even more preferably less than about 2, and still more preferably less than about 1, and most preferably about 0.
• the sum total of malodor reduction materials may have a Blocker Index average of from about 3 to about 0.001.
• the malodor reduction materials may have a Fragrance Fidelity Index of less than 3, preferably less than 2, more preferably less than 1 and most preferably about 0 and/or a Fragrance Fidelity Index average of 3 to about 0.001 Fragrance Fidelity Index. As the Fragrance Fidelity Index decreases, the malodor reduction material(s) provide less and less of a scent impact, while continuing to counteract malodors.
• the cleaning compositions of the present disclosure may comprise a perfume.
• the weight ratio of parts of malodor reduction composition to parts of perfume may be from about 1 :20,000 to about 3,000:1, preferably from about 1:10,000 to about 1,000:1, more preferably from about 5,000:1 to about 500:1, and most preferably from about 1:15 to about 1:1.
• the malodor reduction material(s) provide less and less of a scent impact, while continuing to counteract malodors.
• Suitable conditioning agents include high melting point fatty compounds.
• the high melting point fatty compound useful herein has a melting point of 25°C or higher and is selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof.
• Suitable conditioning agents also include nonionic polymers and conditioning oils, such as hydrocarbon oils, polyolefins, and fatty esters.
• Suitable conditioning agents include those conditioning agents characterized generally as silicones (e.g., silicone oils, polyoils, silicone gums, high refractive silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty esters) or combinations thereof, or those conditioning agents which otherwise form liquid, dispersed particles in the aqueous surfactant matrix herein.
• the compositions of the present invention may also comprise from about 0.05% to about 3% of at least one organic conditioning oil as the conditioning agent, either alone or in combination with other conditioning agents, such as the silicones (described herein).
• Suitable conditioning oils include hydrocarbon oils, polyolefins, and fatty esters.
• composition may comprise probiotics, such as those described in WO2009/043709 .
• the detergent comprises one or more organic acids selected from the group consisting of acetic acid, adipic acid, aspartic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, citric acid, formic acid, glutaric acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, lactic acid, maleic acid, malic acid, malonic acid, oxydiacetic acid, oxydisuccinic acid, succinic acid, sulfamic acid, tartaric acid, tartaric-disuccinic acid, tartaric-monosuccinic acid, or mixtures thereof.
• the detergent composition may comprise an organic acid selected from the group consisting of acetic acid, lactic acid, and citric acid.
• the composition may optionally contain an anti-oxidant present in the composition from about 0.001 to about 2% by weight.
• an anti-oxidant present in the composition from about 0.001 to about 2% by weight.
• the antioxidant is present at a concentration in the range 0.01 to 0.08% by weight. Mixtures of anti-oxidants may be used.
• compositions of the present invention may also comprise components to deliver hygiene and/or malodour benefits such as one or more of zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac ® , polyethylenimines (such as Lupasol ® from BASF) and zinc complexes thereof, silver and silver compounds, especially those designed to slowly release Ag+ or nano-silver dispersions.
• hygiene and/or malodour benefits such as one or more of zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac ® , polyethylenimines (such as Lupasol ® from BASF) and zinc complexes thereof, silver and silver compounds, especially those designed to slowly release Ag+ or nano-silver dispersions.
• the cleaning compositions of the present invention may also contain antimicrobial agents.
• the anti-microbial agent is selected from the group consisting of 4-4'-dichloro-2-hydroxy diphenyl ether ("Diclosan”), 2,4,4'-trichloro-2'-hydroxy diphenyl ether (“Triclosan”), and a combination thereof.
• the anti-microbial agent is 4-4'-dichloro-2-hydroxy diphenyl ether, commercially available from BASF, under the trademark name Tinosan ® HP100.
• Non-limiting examples of pearlescent agents include: mica; titanium dioxide coated mica; bismuth oxychloride; fish scales; mono and diesters of alkylene glycol.
• the pearlescent agent may be ethyleneglycoldistearate (EGDS).
• the composition might also comprise an opacifier.
• an "opacifier” is a substance added to a material in order to make the ensuing system opaque.
• the opacifier is Acusol, which is available from Dow Chemicals.
• Acusol opacifiers are provided in liquid form at a certain % solids level.
• the pH of Acusol opacifiers ranges from 2.0 to 5.0 and particle sizes range from 0.17 to 0.45 um.
• Acusol OP303B and 301 can be used.
• the opacifier may be an inorganic opacifier.
• the inorganic opacifier can be TiO 2 , ZnO, talc, CaCO 3 , and combination thereof.
• the composite opacifier-microsphere material is readily formed with a preselected specific gravity, so that there is little tendency for the material to separate.
• the solvent system in the present compositions can be a solvent system containing water alone or mixtures of organic solvents either without or preferably with water.
• the compositions may optionally comprise an organic solvent.
• Suitable organic solvents include C 4 -C 14 ethers and diethers, glycols, alkoxylated glycols, C 6 -C 16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C 1 -C 5 alcohols, linear C 1 -C 5 alcohols, amines, C 8 -C 14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
• Preferred organic solvents include 1,2-propanediol, 2,3 butane diol, ethanol, glycerol, ethoxylated glycerol, dipropylene glycol, methyl propane diol and mixtures thereof 2 ethyl hexanol, 3,5,5,trimethyl-1 hexanol, and 2 propyl heptanol.
• Solvents may be a polyethylene or polypropylene glycol ether of glycerin.
• Other lower alcohols, C 1 -C 4 alkanolamines such as monoethanolamine and triethanolamine, can also be used.
• Solvent systems can be absent, for example from anhydrous solid embodiments of the invention, but more typically are present at levels in the range of from about 0.1% to about 98%, preferably at least about 1% to about 50%, more usually from about 5% to about 25%, alternatively from about 1% to about 10% by weight of the liquid detergent composition of said organic solvent. These organic solvents may be used in conjunction with water, or they may be used without water.
• compositions may optionally comprise a hydrotrope in an effective amount, i.e. from about 0% to 15%, or about 1% to 10% , or about 3% to about 6%, so that compositions are compatible in water.
• Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof, as disclosed in U.S. Patent 3,915,903 .
• suds supressors include monocarboxylic fatty acid and soluble salts therein, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 ketones (e.g., stearone), N-alkylated amino triazines, waxy hydrocarbons preferably having a melting point below about 100 °C, silicone suds suppressors, and secondary alcohols.
• Preferred fatty acid blends may be mixtures enriched or Fatty acid mixtures enriched with 2-alkyl fatty acid, preferably 2-methyl octanoic acid.
• antifoams are those derived from phenylpropylmethyl substituted polysiloxanes.
• the detergent composition may comprise a suds suppressor selected from organomodified silicone polymers with aryl or alkylaryl substituents combined with silicone resin and a primary filler, which is modified silica.
• the detergent compositions may comprise from about 0.001% to about 4.0%, by weight of the composition, of such a suds suppressor.
• the detergent composition comprises a suds suppressor selected from: a) mixtures of from about 80 to about 92% ethylmethyl, methyl(2-phenylpropyl) siloxane; from about 5 to about 14% MQ resin in octyl stearate; and from about 3 to about 7% modified silica; b) mixtures of from about 78 to about 92% ethylmethyl, methyl(2-phenylpropyl) siloxane; from about 3 to about 10% MQ resin in octyl stearate; from about 4 to about 12% modified silica; or c) mixtures thereof, where the percentages are by weight of the anti-foam.
• a suds suppressor selected from: a) mixtures of from about 80 to about 92% ethylmethyl, methyl(2-phenylpropyl) siloxane; from about 5 to about 14% MQ resin in octyl stearate; and from about 3 to about 7%
• Liquid laundry detergent composition Liquid laundry detergent composition.
• the fabric and home care product can be a laundry detergent composition, such as a liquid laundry detergent composition.
• Suitable liquid laundry detergent compositions can comprise a non-soap surfactant, wherein the non-soap surfactant comprises an anionic non-soap surfactant and a non-ionic surfactant.
• the laundry detergent composition can comprise from 10% to 60%, or from 20% to 55% by weight of the laundry detergent composition of the non-soap surfactant.
• the non-soap anionic surfactant to nonionic surfactant are from 1:1 to 20:1, from 1.5:1 to 17.5:1, from 2:1 to 15:1, or from 2.5:1 to 13:1.
• Suitable non-soap anionic surfactants include linear alkylbenzene sulphonate, alkyl sulphate or a mixture thereof.
• the weight ratio of linear alkylbenzene sulphonate to alkyl sulphate can be from 1:2 to 9:1, from 1:1 to 7:1, from 1:1 to 5:1, or from 1:1 to 4:1.
• Suitable linear alkylbenzene sulphonates are C 10 -C 16 alkyl benzene sulfonic acids, or C 11 -C 14 alkyl benzene sulfonic acids.
• Suitable alkyl sulphate anionic surfactants include alkoxylated alkyl sulphates, non-alkoxylated alkyl sulphates, and mixture thereof.
• the HLAS surfactant comprises greater than 50% C 12 , preferably greater than 60%, preferably greater than 70% C 12 , more preferably greater than 75% C 12 .
• Suitable alkoxylated alkyl sulphate anionic surfactants include ethoxylated alkyl sulphate anionic surfactants.
• Suitable alkyl sulphate anionic surfactants include ethoxylated alkyl sulphate anionic surfactant with a mol average degree of ethoxylation of from 1 to 5, from 1 to 3, or from 2 to 3.
• the alkyl alkoxylated sulfate may have a broad alkoxy distribution or a peaked alkoxy distribution.
• the alkyl portion of the AES may include, on average, from 13.7 to about 16 or from 13.9 to 14.6 carbons atoms.
• At least about 50% or at least about 60% of the AES molecule may include having an alkyl portion having 14 or more carbon atoms, preferable from 14 to 18, or from 14 to 17, or from 14 to 16, or from 14 to 15 carbon atoms.
• the alkyl sulphate anionic surfactant may comprise a non-ethoxylated alkyl sulphate and an ethoxylated alkyl sulphate wherein the mol average degree of ethoxylation of the alkyl sulphate anionic surfactant is from 1 to 5, from 1 to 3, or from 2 to 3.
• the alkyl fraction of the alkyl sulphate anionic surfactant can be derived from fatty alcohols, oxo-synthesized alcohols, Guerbet alcohols, or mixtures thereof.
• Preferred alkyl sulfates include optionally ethoxylated alcohol sulfates including 2-alkyl branched primary alcohol sulfates especially 2-branched C 12-15 primary alcohol sulfates, linear primary alcohol sulfates especially linear C 12-14 primary alcohol sulfates, and mixtures thereof.
• the laundry detergent composition can comprise from 10% to 50%, or from 15% to 45%, or from 20% to 40%, or from 30% to 40% by weight of the laundry detergent composition of the non-soap anionic surfactant.
• Suitable non-ionic surfactants can be selected from alcohol broad or narrow range alkoxylates, an oxo-synthesised alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl phenol alcohol alkoxylates, or a mixture thereof.
• the laundry detergent composition can comprise from 0.01% to 10%, from 0.01% to 8%, from 0.1% to 6%, or from 0.15% to 5% by weight of the liquid laundry detergent composition of a non-ionic surfactant.
• the laundry detergent composition comprises from 1.5% to 20%, or from 2% to 15%, or from 3% to 10%, or from 4% to 8% by weight of the laundry detergent composition of soap, such as a fatty acid salt.
• soap such as a fatty acid salt.
• Such soaps can be amine neutralized, for instance using an alkanolamine such as monoethanolamine.
• the laundry detergent composition can comprises an adjunct ingredient selected from the group comprising builders including citrate, enzymes, bleach, bleach catalyst, dye, hueing dye, Leuco dyes, brightener, cleaning polymers including alkoxylated polyamines and polyethyleneimines, amphiphilic copolymers, soil release polymer, surfactant, solvent, dye transfer inhibitors, chelant, diamines, perfume, encapsulated perfume, polycarboxylates, structurant, pH trimming agents, antioxidants, antibacterial, antimicrobial agents, preservatives and mixtures thereof.
• builders including citrate, enzymes, bleach, bleach catalyst, dye, hueing dye, Leuco dyes, brightener
• cleaning polymers including alkoxylated polyamines and polyethyleneimines, amphiphilic copolymers, soil release polymer, surfactant, solvent, dye transfer inhibitors, chelant, diamines, perfume, encapsulated perfume, polycarboxylates, structurant, pH trimming agents, antioxidants, antibacterial, antimicrobial agents
• the laundry detergent composition can have a pH of from 2 to 11, or from 6.5 to 8.9, or from 7 to 8, wherein the pH of the laundry detergent composition is measured at a 10% product concentration in demineralized water at 20°C.
• the liquid laundry detergent composition can be Newtonian or non-Newtonian, preferably non-Newtonian.
• the composition can comprise from 5% to 99%, or from 15% to 90%, or from 25% to 80% by weight of the liquid detergent composition of water.
• the detergent composition according to the invention can be liquid laundry detergent composition.
• the following are exemplary liquid laundry detergent formulations ( Table 1 ).
• the liquid laundry detergent composition comprises from between 0.1 to 20.0%, preferably 0.2% to 10%, preferably between 0.3% and 5.0%, preferably between 0.5% and 3%, more preferably between 1% to 2.5% by weight of the detergent composition of the polymer according to the invention.
• Table 1 Raw Material Comp. 1 %wt Comp. 2 %wt Comp. 3 %wt Comp.
• Fluorescent Brightener is disodium 4,4'-bis ⁇ [4-anilino-6-morpholino-s-triazin-2-yl]-amino ⁇ -2,2'-stilbenedisulfonate or 2,2'-([1,1'-Biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt.
• water soluble films are those supplied by Monosol under the trade references M8630, M8900, M8779, M8310.
• the detergent product comprises a detergent composition, more preferably a laundry detergent composition.
• the laundry detergent composition enclosed in the water-soluble unit dose article comprises from between 0.1% and 8%, preferably between 0.5% and 7%, more preferably 1.0% to 6.0% by weight of the detergent composition of the polymer of the present invention.
• the soluble unit dose laundry detergent composition comprises a non-soap surfactant, wherein the non-soap surfactant comprises an anionic non-soap surfactant and a non-ionic surfactant.
• Example alkyl sulphate anionic surfactant may comprise an ethoxylated alkyl sulphate anionic surfactant with a mol average degree of ethoxylation from 1 to 5, from 1 to 3, or from 2 to 3.
• Example alkyl sulphate anionic surfactant may comprise a non-ethoxylated alkyl sulphate and an ethoxylated alkyl sulphate wherein the mol average degree of ethoxylation of the alkyl sulphate anionic surfactant is from 1 to 5, from 1 to 3, or from 2 to 3.
• the laundry detergent composition comprises between 10% and 40%, or between 15% and 30% by weight of the liquid laundry detergent composition of a non-aqueous solvent selected from 1,2-propanediol, dipropylene glycol, tripropyleneglycol, glycerol, sorbitol, polyethylene glycol or a mixture thereof.
• a non-aqueous solvent selected from 1,2-propanediol, dipropylene glycol, tripropyleneglycol, glycerol, sorbitol, polyethylene glycol or a mixture thereof.
• the composition can be part of a single chamber water soluble unit dose article or can be split over multiple compartments resulting in below "averaged across compartments" full article composition.
• the composition is enclosed within a polyvinyl alcohol-based water soluble, the polyvinyl alcohol comprising a blend of a polyvinyl alcohol homopolymer and an anionic e.g. carboxylated polyvinyl alcohol copolymer.
• Table 2 Ingredients Comp.
• water-soluble unit dose article As used herein, the phrases “water-soluble unit dose article,” “water-soluble fibrous structure”, and “water-soluble fibrous element” mean that the unit dose article, fibrous structure, and fibrous element are miscible in water. In other words, the unit dose article, fibrous structure, or fibrous element is capable of forming a homogeneous solution with water at ambient conditions. "Ambient conditions” as used herein means 23°C ⁇ 1.0°C and a relative humidity of 50% ⁇ 2%.
• the water-soluble unit dose article may contain insoluble materials, which are dispersible in aqueous wash conditions to a suspension mean particle size that is less than about 20 microns, or less than about 50 microns.
• the wash liquor may comprise 40 liters or less of water, or 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or even 6 liters or less of water.
• the wash liquor may comprise from above 0 to 15 liters, or from 2 liters, and to 12 liters, or even to 8 liters of water.
• from 0.01kg to 2kg of fabric per liter of wash liquor is dosed into said wash liquor.
• from 0.01kg, or from 0.05kg, or from 0.07kg, or from 0.10kg, or from 0.15kg, or from 0.20kg, or from 0.25kg fabric per liter of wash liquor is dosed into said wash liquor.
• the fabric may comprise any fabric capable of being laundered in normal consumer or institutional use conditions, and the invention is suitable for cellulosic substrates and in some aspects also suitable for synthetic textiles such as polyester and nylon and for treatment of mixed fabrics and/or fibers comprising synthetic and cellulosic fabrics and/or fibers.
• synthetic fabrics are polyester, nylon, these may be present in mixtures with cellulosic fibers, for example, polycotton fabrics.
• the solution typically has a pH of from 7 to 11, more usually 8 to 10.5.
• the compositions are typically employed at concentrations from 500 ppm to 5,000 ppm in solution.
• the water temperatures typically range from about 5°C to about 90°C.
• the water to fabric ratio is typically from about 1:1 to about 30:1.
• nonwoven substrate can comprise any conventionally fashioned nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics.
• suitable commercially available nonwoven substrates include those marketed under the trade names SONTARA ® by DuPont and POLY WEB ® by James River Corp.
• Biomass is a renewable carbon source formed through photosynthesis in the presence of sunlight, or chemosynthesis process in the absence of sunlight.
• polymers isolated from biomass can be used directly, or further derivatized to make performance polymers.
• polysaccharide such as starch
• derivatized polysaccharide such as cellulose derivatives, guar derivatives, dextran derivatives
• biomass can be converted into basic chemicals under certain thermal, chemical, or biological conditions.
• bioethanol can be derived from biomass such as straw, and further convert to biobased polyethylene glycol.
• renewable carbon from biomass examples include plants (e.g., sugar cane, beets, corn, potatoes, citrus fruit, woody plants, lignocellulosics, hemicellulosics, cellulosic waste), animals, animal fats, fish, bacteria, fungi, plant-based oils, and forestry products. These resources can be naturally occurring, hybrids, or genetically engineered organisms.
• Carbon capture is another renewable carbon source which use various process to capture CO 2 or methane from industrial or natural processes, or directly from air (direct capture).
• Captured methane and CO 2 maybe converted into syngas, and/or further convert to basic chemicals, including but not limit to methanol, ethanol, fatty alcohols such as C 12 /C 14 or even C 16 /C 18 alcohols, other alcohols, olefins, alkanes, saturated and unsaturated organic acids, etc.
• These basic chemicals can used as or further convert to monomers for making transformed to usable chemicals by e.g. catalytic processes, such as the Fischer-Tropsch process or by fermentation by C 1 -fixing microorganisms.
• Chemical recycling is another renewable carbon source which allow plastics from waste management industry to be recycled and converted into base chemicals and chemical feedstocks.
• waste plastics which cannot be re-used or mechanical recycled are convert to hydrocarbons or basic petrochemicals through gasification, pyrolysis or hydrothermal treatment processes, the hydrocarbons and basic petrochemicals can be further convert into monomers for polymers.
• waste plastics are depolymerized into monomers to make new polymers. It is also possible that waste plastics are depolymerized into oligomers, the oligomers can be used as building blocks to make new polymers.
• waste plastic converted by various processes to a waste plastic feedstock for the above materials may either be used alone or in combination with traditional surfactant feedstocks, such as kerosene, polyolefins derived from natural gas, coal, crude oil or even biomass, or waste fat/oil-derived paraffin and olefin, to produce biodegradable surfactants for use in detergents and other industries (thereby providing a benefit to society).
• traditional surfactant feedstocks such as kerosene, polyolefins derived from natural gas, coal, crude oil or even biomass, or waste fat/oil-derived paraffin and olefin
• the surfactant, polymers and other ingredients contains renewable carbon
• the Renewable Carbon Index (RCI, a measure of sustainability by dividing the number of carbons derived from renewable sources by the total number of carbons in an active ingredient) of the polymer is above 10%, more preferably above 30%, more preferably above 50%, more preferably above 60%, more preferably between 70% to 100%, and most preferably 100%.
• the white acceptor fabrics are "de-sized” and/or “stripped” to remove any manufacturer's finish that may be present. Fabrics are dried, cut in 2 cm x 2.75 cm swatches and treated with a detergent composition containing dye extracted from test fabrics using the Wrist Shaker Dye Transfer method designed to mimic full-scale washing machine conditions. Dye transfer onto the white acceptor fabrics is measured on a spectrophotometer according to the Dye Transfer Measurement Method on treated Fabrics. Stripping of fabrics.
• New 100% cotton knit fabrics are stripped by washing five times in a high capacity front-loading washing machine such as a Milnor model number 30022X8J at 60 °C (140°F) using 0 gpg water.
• the machine is programmed to fill and drain 15 times for a total of 1420 L (375 gallons) of water.
• the first and second wash cycles use 175 g of detergent (AATCC 2003 Standard Reference Liquid Detergent without optical brightener, available from Test Fabrics Inc., West Pittston, PA), which is added to a 20-23 kg load of fabric.
• Each wash cycle is followed by two rinses, and the second wash cycle is followed by three additional wash cycles without detergent or until no suds are observed.
• Wrist Shaker Dye Transfer Method A concentrated solution of extractable dye is prepared by heating and shaking four pieces (7.6 cm x 7.6 cm) of test fabric knits (Style 460 bleached tubular cotton knit dyed with 3% dye solution, Test Fabrics, Inc. in West Pittston, PA) for a minimum 24h at 50 °C in a 38 mL of deionized water in a 40 mL scintillation vial (Qorpak VWR supplier part #18087-086).
• Vials are heated using a Multi Temperature Zone Reaction Blocks, KEM Scientific, SN: 26197 on top of an orbital Shaker at Speed: 2 (VWR Standard Analog Shaker, Model: 3500, SN: 191011001, NA CAT No: 89032-092). Vials are removed from heat, fabric swatches and solution are transferred to a disposable syringe fitted with a 1.1micron glass filter (Thermo Scientific, #722-2000) and filtered into a clean vial. The UV-VIS is measured in a1 cm disposable cuvette (VWR 97000-588) on a spectrophotometer such as Beckman Coulter DU800. Solutions are diluted to 0.25 absorbance at ⁇ max into 15 gpg water.
• the L*C*h color space is an approximately uniform scale with a polar color space.
• the CIE L*C*h color space (“CIELCh”) scale values are determined instrumentally and may also be calculated from the CIELAB scale values.
• dE2000 value includes the vector associated with the distance in the L*C*h space between the initial L*C*h value and the final L*C*h value and corrected for perception according to the procedure detailed in G.
• Feed 1 (5.10 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 39.0 g of tripropylene glycol) and 10 min upon the start of Feed 1
• Feed 2 (50.0 g of vinyl acetate) and Feed 3 (150 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.04 g/h and 00:10 h to 06:10 h: 7.22 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 8.33 g/h) and Feed 3 (00:10 h to 06:10
• Feed 4 (4.08 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 31.1 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was heated under stirring for 1:00 h at 95°C upon complete addition of the feed. Destination for 1 h at 95°C with a vacuum of 50 mbar was carried out to remove the volatiles. The yield was 1070 g of a polymer mixture.
• Feed 1 (8.16 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 46.7 g of tripropylene glycol) and 10 min upon the start of Feed 1,
• Feed 2 (200.0 g of vinyl acetate) and Feed 3 (150 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 5.03 g/h and 00:10 h to 06:10 h: 9.00 g/h) and a constant feed rate of Feed 2 (00:10 h to 06: 10 h: 33.3 g/h) and Feed 3 (00:10 h to 06: 10 h:
• Feed 4 (4.08 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 23.3 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was heated under stirring for 1:00 h at 95°C upon complete addition of the feed. Destination for 1 h at 95°C with a vacuum of 50 mbar was carried out to remove the volatiles. The yield was 1060 g of a polymer mixture.
• Example 1H hydrolysis of Example 1C
• OECD 301F Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method.
• OECD 301F is an aerobic test that measures biodegradation of a sample by measuring the consumption of oxygen.
• 100 mg/L test substance which is the nominal sole source of carbon is added along with the inoculum (30 mg/L, aerated sludge taken from Mannheim wastewater treatment plant). This is stirred in a closed flask at a constant temperature (20°C or 25°C) for 28 or 56 days, respectively.
• the consumption of oxygen is determined by measuring the change in pressure in the apparatus using an OxiTop ® C (Xylem 35 Analytics Germany Sales GmbH & Co KG).
• Evolved carbon dioxide is absorbed in a solution of sodium hydroxide.
• Nitrification inhibitors are added to the flask to prevent usage of oxygen due to nitrification.
• the amount of oxygen taken up by the microbial population during biodegradation of the test substance is expressed as a percentage of ThOD (Theoretical oxygen demand, which is measured by the elemental analysis of the compound).
• ThOD Theoretical oxygen demand, which is measured by the elemental analysis of the compound.
• a positive control Glucose/Glucosamine is run along with the test samples for each cabinet.
• Inventive polymers have high or low biodegradability, preferred polymers show higher biodegradability.
• the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity Mw/Mn of the inventive graft polymers can be determined by gel permeation chromatography in dimethylacetamide.
• the mobile phase (eluent) to be used is dimethylacetamide comprising 0.5 wt% LiBr.
• concentration of graft polymer in the solvent is 4.0 mg per mL.
• inventive or comparative detergent composition 2A to 2I can be made by mixing ingredients together (Table 5). Table 5.
• a graft copolymer according to Example 1A-1C above is added to detergent composition Example 2A above and are compared in performance to corresponding compositions that do not include the graft copolymer.
• the wrist shaker dye transfer method is used to assess the amount of dye that has transferred in one wash cycle from a detergent wash liquor containing dye previously extracted from test fabric onto a white 100% cotton knitted fabric.
• a dE2000 value is calculated comparing results from before and after the test; a higher dE2000 value corresponds to a greater color change, indicating that relatively more dye transferred to the fabric in question.
• a graft copolymer according to Example 1G above is added to detergent composition Example 2X (1.7%) above and are compared in performance to corresponding compositions that do not include the graft copolymer or include Comparative Example 1.
• Table 7 Example Dye 1 Graft Copolymer dE2000 (vs initial) ddE2000 (vs REF) 4A Red Dye 120 none 11.5 REF 4B Red Dye 120 Comparative 1 7.1 4.4 units less 4C Red Dye 120 1B 6.1 5.4 units less 1) Red dye 120 is Reactive Red 120 (Permabril Red HE3B). Cotton test fabric knit available from WfK, Testgewebe GmbH, Brüggen, Germany The data shows that the PO-EO-PO grafting base is more effective than PEG6000 since there is an incremental 1 unit less dye transfer with 4C than 4B.
• a graft copolymer according to Example 1D-1F above is added to detergent composition Example 2E and are compared in performance to corresponding compositions that do not include the graft copolymer.
• the wrist shaker dye transfer method is used to assess the amount of dye that has transferred in one wash cycle from a detergent wash liquor containing dye previously extracted from test fabric onto a white 100% cotton knitted fabric.
• a dE2000 value is calculated comparing results from before and after the test; a higher dE2000 value corresponds to a greater color change, indicating that relatively more dye transferred to the fabric in question.
• Example Dye 1 Graft Copolymer 2 B1 VP (wt %) dE2000 (vs initial) ddE2000 (vs REF) 3A Blue Dye 21 none N/A 4.5 REF 3B Blue Dye 21 1D 20 2.5 2.0 units less 3C Blue Dye 21 1E 20 2.4 2.1 units less 3D Blue Dye 21 1F 10 3.2 1.3 units less 3E Red Dye 195 none N/A 7.3 REF 3F Red Dye 195 1D 20 5.2 2.1 units less 3G Red Dye 195 1E 20 5.4 1.9 units less 3H Red Dye 195 1F 10 6.1 1.2 units less 1) Blue dye 21 is Reactive Blue 21 (Permabril Turquoise RP), Red dye 195 is Reactive Red 195 (Remazol Brill Red 3BS

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