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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • 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
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

• the present invention relates to fabric and home care composition
• a fabric and home care ingredient comprising a fabric and home care ingredient, a graft polymer and a modified polyalkyleneimine / polyamine (PAI / PA).
• PAI / PA modified polyalkyleneimine / polyamine
• fabric and home care industry there is a strong need for new biodegradable cleaning polymers to provide both excellent primary (i.e., soil removal) and secondary (i.e., whiteness maintenance) cleaning benefits for both hydrophobic and hydrophilic stains, particularly under quick and cold wash conditions.
• fabric and home care composition comprising the new biodegradable polymers should also provide beautiful sensorial experiences for consumer, including suds profile during wash, freshness profile during wash and after wash, fabric feel during wash during wash and after wash.
• the objective of the present invention is to provide a fabric and home care composition
• a fabric and home care composition comprising a fabric and home care ingredient, a graft polymer, and a modified polyalkyleneimine / polyamine (PAI / PA).
• the composition of the present inventions not only delivers strong cleaning benefit, but also delivers peaceful sensorial experience, particularly good flash suds in the presence of soil.
• the combination of the graft polymer with the modified polyalkyleneimine / polyamine (PAI / PA) improved sustainability and biodegradability profile of the fabric and home care composition.
• composition may or may not include surfactant.
• Preferred compositions are detergents and cleaning compositions.
• fabric treatment compositions even more preferred are laundry detergent compositions.
• Fabric and home care compositions are typically suitable for: (a) the care of finished textiles, cleaning of finished textiles, sanitization of finished textiles, disinfection of finished textiles, detergents, stain removers, softeners, fabric enhancers, stain removal or finished textiles treatments, pre and post wash treatments, washing machine cleaning and maintenance, with finished textiles intended to include garments and items made of cloth; (b) the care of dishes, glasses, crockery, cooking pots, pans, utensils, cutlery and the like in automatic, in-machine washing, including detergents, preparatory post treatment and machine cleaning and maintenance products for both the dishwasher, the utilized water and its contents; or (c) manual hand dish washing detergents.
• the composition comprises from 0.1 to 10.0 wt% of the graft polymer, preferably from 0.2 to 8.0 wt%, more preferably from 0.3 to 6.0 wt%, more preferably from 0.4 to 4 wt%, mostly preferably in the range of from 0.5 to 3 wt%.
• the composition comprises from 0.1 to 10.0 wt% of the modified polyalkyleneimine / polyamine (PAI/ PA), preferably from 0.2 to 8.0 wt%, more preferably from 0.3 to 6.0 wt%, more preferably from 0.4 to 4 wt%, mostly preferably in the range of from 0.5 to 3 wt%.
• PAI/ PA modified polyalkyleneimine / polyamine
• the weight ratio of the graft polymer and the modified polyalkyleneimine / polyamine (PAI / PA) in the composition is between 99:1 to 1:99, preferably between 90:10 to 10:90, more preferably between 80:20 to 20:80, more preferably between 70:30, and most preferably between 65:35 to 35:65, such as 60:40, 50:50, 40:60.
• the composition comprises at least one fabric and home care ingredient, more details are described in the description.
• the composition may comprise from 1.0wt% to 70wt% detersive surfactant.
• Fabric and home care compositions include, but not limit to: Laundry Detergent Composition: Suitable laundry detergent compositions include laundry detergent powder compositions, laundry beads, laundry detergent liquid compositions, laundry detergent gel compositions, laundry sheets, fibrous articles and water-soluble unit dose laundry detergent compositions.
• Suitable fabric enhancers are liquid fabric enhancers including compact liquid fabric enhancers, and solid fabric enhancers including fabric enhancer beads and sheets.
• Suitable dish-washing detergent compositions include hand dish-washing detergent compositions and automatic dish-washing detergent compositions. Such as automatic dish-washing powder, tablet and pouches.
• Hard Surface Cleaner Compositions include product that can be directly applied onto hard surface, eg. by a spray, and products that can be diluted in water before been applied onto hard surface.
• the graft polymer of the present invention comprises:
• the graft polymer of the present invention includes Type I, Type II and Type III depending on the type of the polyalkylene oxide backbone (A).
• Type I (Block backbone)
• the graft polymer comprising:
• 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. Any ratio known to a person skilled in the art can be employed. However, graft polymers are preferred that comprise 20 to 95% by weight of the block copolymer backbone (A) and 5 to 80% by weight of the polymeric sidechains (B) (in relation to the total weight of the graft polymer).
• the graft polymer comprises 40 to 85% by weight, more preferably 50 to 75% by weight of the block copolymer backbone (A), and preferably 15 to 60% by weight, more preferably 25 to 50% by weight of the polymeric sidechains (B) (in relation to the total weight of the graft polymer).
• Block copolymer backbones (A) as such are known to a person skilled in the art as well as methods for producing such block copolymers backbones.
• Various types of such block copolymer backbones are commercially available, for example under the trademark series "Pluronic” (BASF SE, Ludwigshafen, Germany). Specific examples are Pluronic PE 6100, Pluronic PE 6800 or Pluronic PE 3100.
• Suitable block copolymer backbones (A) to be employed within the present invention are described, for example, within EP-A 0 362 688 .
• the respective monomer to be employed for preparing the individual blocks of the block copolymer backbone (A) are added in sequence.
• 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.
• block copolymer backbone (A) of the graft polymers according to the present invention it is preferred that the block copolymer backbone (A) is obtainable, or it is preferrable that the block copolymer backbone (A) is obtained, by polymerization of
• 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 1 500 to 45 000 g/mol, more preferably from 2 000 to 30 000 g/mol, more preferably from 2 500 to 20 000 g/mol, and most preferably from 3 000 to 12 000 g/mol.
• block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).
• the graft polymer has a block copolymer backbone (A) having the structure according to formula (A1) or formula (A2) with formula (A1) is defined as follows: with
• Block copolymers (A) can contain different levels of hydrophilic ethylene glycol which influences the overall properties of the graft polymer.
• the block copolymers can be low, medium or high respective %EO which has effects on the biodegradation properties as well as the performance in laundry formulations. The ranges are defined as follows: - Low: 5 - 20 %EO - Medium: 21 - 50 %EO - High: 51 - 90 %EO
• the polymeric sidechains (B) contained within the graft polymer according to the present invention are obtained by radical polymerization and/or the at least one vinyl ester monomer (B 1) is vinyl acetate or vinyl propionate, more preferably vinyl acetate.
• vinyl ester monomer (B1) any further vinyl ester besides vinyl acetate or vinyl propionate may be employed which are known to a person skilled in the art.
• the polymeric sidechains (B) may be obtained by, preferably, radical polymerization of 5 to 99% by weight of monomer (B1), which is most preferably vinyl acetate, and 1 to 95% by weight of N-vinylpyrrolidone as optional further monomer (B2) in relation to the sum of (B1) and (B2)).
• the ratio of the mandatory vinyl ester monomer (B1) versus said further monomer (B2) may have any value known to a person skilled in the art, but preferably the amount of B2 is at most 40 weight percent, more preferably at most 30, even more preferably at most 20, such as at most 18, 15, 12, 10, 8, 5, 3, 2, or even 1, and any value in between 1 and 25 (in relation to the sum of (B 1) and (B2)). However, the amount of vinyl ester monomer (B1) is usually not smaller than 60% by weight (in relation to the sum of (B1) and (B2)).
• the polymeric sidechains (B) may be obtained by, preferably, radical polymerization of 60 to 99% by weight of monomer (B 1), which is most preferably vinyl acetate, and 1 to 40% by weight of N-vinylpyrrolidone as further monomer (B2).
• polymeric sidechains (B) are obtained by free radical polymerization of
• the polymeric sidechains (B) are obtained by radical polymerization of 100% by weight (in relation to the total amount of monomers employed) of at least one vinyl ester monomer (B 1), which is preferably vinyl acetate or vinyl propionate, more preferably vinyl acetate.
• the graft polymer comprising:
• the ratio of the random copolymer backbone (A) versus the polymeric side chains (B) within the graft polymers as exemplified in the present invention may not be limited to specific values; any ratio known to a person skilled in the art can in principle be employed. However, good results are obtained when using the ratios as detailed before.
• Copolymer backbones (A) as such are known to a person skilled in the art as well as methods for producing such copolymers backbones, e.g., in EP362688 . Such methods are typically the co-polymerization of at least two alkylene oxides using known means.
• suitable copolymer backbones (A) with the alkylene oxides arranged in random order to be employed within the present invention can be obtained easily by standard alkoxylation polymerization processes employing the required alkylene oxides in the required ratios.
• copolymer backbone (A) of the graft polymers according to the present invention it is preferred that the copolymer backbone (A) is obtainable by, or it is preferred that the copolymer is obtained by polymerization of
• the graft polymer of the invention and/or as detailed before comprises
• Copolymers (A) can contain different levels of hydrophilic ethylene glycol which influences the overall properties of the graft polymer.
• the copolymers can be low, medium or high respective %EO which has effects on the biodegradation properties as well as the performance in laundry formulations.
• the relative amount of EO in the polymer backbone (A) being within 20 to 80% (by weight in relation to the total mass of alkylene oxides in the polymer backbone (A)).
• the ratio of the mandatory vinyl ester monomer (B 1) versus said further monomer (B2) may in principle have any value known to a person skilled in the art.
• the amount of vinyl ester monomer (B 1) is usually not smaller than 5% (in relation to the sum of (B 1) and (B2)).
• the graft polymer of the invention and/or as detailed before comprises polymeric sidechains (B) which are obtained or obtainable by radical polymerization of the at least one vinyl ester monomer (B 1) and optionally at least one other monomer (B2), in the presence of the polymer backbone A, wherein preferably the vinyl ester monomer (B 1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent, and most preferably essentially only (i.e. about 100wt.% or even 100 wt.%) vinyl acetate is employed as vinyl ester (weight percent being based on the total weight of vinyl ester monomers B 1 being employed), and wherein preferably essentially no monomer (B2)
• the graft polymer of the invention and/or as detailed before comprises
• Type III (poly-ethylene oxide-polymers as backbones)
• the graft polymer comprising:
• the first subject-matter of the present invention relates to a graft polymer comprising:
• the ratio of the polymer backbone (A) versus the polymeric side chains (B) within the graft polymers as exemplified in the present invention may not be limited to specific values; any ratio known to a person skilled in the art can in principle be employed. However, good results are obtained when using the ratios as detailed before.
• Polymer backbones (A) as such are known to a person skilled in the art as well as methods for producing such copolymers backbones. Such methods are typically the polymerization of ethylene oxide using known means.
• suitable polymer backbones (A) to be employed within the present invention can be obtained easily by standard alkoxylation polymerization processes employing ethylene oxide.
• monomer (B2) is not employed for the polymerization to obtain the side chains (B).
• the graft polymer of the invention and/or as detailed before comprises:
• polymeric sidechains (B) contained within the graft polymer according to the present invention it is preferred that the polymeric sidechains (B) are obtained by radical polymerization and/or the at least one vinyl ester monomer (B1).
• vinyl ester monomer (B1) any further vinyl ester besides vinyl acetate, vinyl propionate or vinyl laurate may be employed which are known to a person skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate or vinyl benzoate.
• the amount of said additional monomers is less than 0.5% by weight, even more preferably less than 0.01% by weight, most preferably, there is a total absence of any additional monomer besides the monomers (B1) and optionally (B2).
• monomers (B2) are present in an amount of less than 1% of the total amount of monomers employed for obtaining the polymeric sidechains (B). Even more preferably, the amount of monomers (B2) is less than 0.5% by weight, even more preferably less than 0.01% by weight, most preferably, there are essentially no monomers (B2) present besides the monomers (B1). Within the present invention, it is particularly preferred that no monomers are employed comprising an acid function.
• the monomers employed for obtaining the polymeric sidechains (B) of the graft polymers according to the present invention do not comprise any acidfunctional monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinyl-acetic acid or acryloxy-propionic acid and the like.
• M w weight average molecular weight
• M n number average molecular weight
• the respective values of M w and/or M n can be determined as described within the experimental section below.
• 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 (B1) and optionally a further 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 vinyl ester monomer (B1) and optionally at least one further monomer (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), optionally (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 optional monomer (B2) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the copolymer backbone (A). In a preferred embodiment no monomer (B2) is employed.
• 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 (B 1) 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 (radical-forming) initiator (C) at the mean polymerization temperature should have a decomposition half-life of from 40 to 500 min, preferably from 50 to 400 min and more preferably from 60 to 300 min.
• the initiator (C) and the graft monomers (B 1) and/or (B2) are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and graft monomers (B 1) 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 process comprises the polymerization of at least one vinyl ester monomer (B 1) and optionally at least one other monomer (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), (B 1), optional (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 (B 1) and optional (B2) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the polymer backbone (A), wherein preferably at least 10 weight percent of the total amount of vinyl ester monomer (B 1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl
• vinyl ester weight percent being based on the total weight of vinyl ester monomers B 1 being employed
• - if (B2) is present - the weight ratio of optional monomer (B2) to monomer (B1) is less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2, and most preferably less than 0.1.
• the mean polymerization temperature is appropriately in the range from 50 to 140°C, preferably from 60 to 120°C and more preferably from 65 to 110°C.
• Suitable initiators (C) whose decomposition half-life in the temperature range from 50 to 140°C is from 20 to 500 min are those described in WO2023019153 on page 17, line 9, to page 18, line 25.
• the preferences given there are also the same preferences used here for this present invention.
• Particularly advantageous polymerization conditions can be established effortlessly by precise adjustment of initiator (C) and polymerization temperature.
• the preferred mean polymerization temperature in the case of use of tert-butyl peroxypivalate is from 60 to 80°C, and, in the case of tert-butyl peroxy-2ethylhexanoate, from 80 to 100°C.
• the inventive polymerization reaction can be carried out in the presence of, preferably small amounts of, an organic solvent (D). It is of course also possible to use mixtures of different solvents (D). Preference is given to using water-soluble or water-miscible solvents.
• a solvent (D) used as a diluent, generally from 1 to 40% by weight, preferably from 1 to 35% by weight, more preferably from 1.5 to 30% by weight, most preferably from 2 to 25% by weight, based in each case on the sum of the components (A), (B1), optionally (B2), and (C), are used.
• suitable solvents (D) include those described in WO2023019153 on page 19, line 11, to page 20, line 22. The preferences given there are also the same preferences used here for this present invention.
• polymer backbone (A), graft monomer (B1) and, if appropriate, (B2), initiator (C) and, if appropriate, solvent (D) are usually heated to the selected mean polymerization temperature in a reactor.
• the reactor types to be employed for the polymerisation, means of post-polymerization, means of polymerization such as temperatures, temperature ranges or tempertature profiules, application of pressure or reduced pressure, purification, concentration etc and any and all such means which can be adjusted, employed and/or applied are descried in detail for the grafts polymer encompassed by this invention in the literature, specifically in WO2021160795 for graft I, in WO2023019152 for graft II and WO2023019153 for graft III. Those measures and preferences thereto are also explicitly encompassed into this present invention as options and preferred embodiments. According to the invention, the polymerization is carried out in such a way that described in WO2023019153 on page 20, line 25, to page 21, line 17. The preferences given there are also the same preferences used here for this present invention.
• each ester function of the polymeric sidechain (B) may be replaced by an alcohol function (hydroxy group).
• the polymeric sidechain is fully hydrolyzed (saponified). It has to be noted that in case N-vinylpyrrolidone is employed as further monomer, no hydrolyzation takes place at those units of the polymeric sidechain (B) which originate from N-pyrrolidone employed as further monomer (B).
• the hydrolysis can be carried out by any method known to a person skilled in the art.
• the hydrolysis can be induced by addition of a suitable base, such as sodium hydroxide or potassium hydroxide.
• a suitable base such as sodium hydroxide or potassium hydroxide.
• the polymeric sidechains (B) are not hydrolyzed.
• the graft polymers of the invention may contain a certain amount of ungrafted polymers ("ungrafted side chains") made of vinyl ester(s), e.g. poly vinyl acetate in case only vinyl acetate is employed, and/or - when further monomers are employed - homo- and copolymers of vinyl ester(s) with the other monomers.
• the amount of such ungrafted vinyl acetate homo- and copolymers may be high or low, depending on the reaction conditions, but is preferably to be lowered and thus low. By this lowering, the amount of grafted side chains is preferably increased.
• suitable reaction conditions such as dosing of vinyl ester and radical initiator and their relative amounts and also in relation to the amount of backbone being present. This is generally known to a person of skill in the present field.
• the inventive graft polymers may be characterized by their degree of grafting (number of graft sites of the polymeric sidechains (B) on the copolymer 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, e.g. certain (e.g. detergent-) formulations, application areas or desired cleaning etc. performance.
• 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 examples give some guidance for the application for washing of fabrics, i.e. the general area of fabric care.
• the modified polyalkyleneimine / polyamine comprises a polyalkyleneimine / polyamine (PAI / PA) core, and at least one side chain attached to at least one NH-functionality of the polyalkyleneimine / polyamine (PAI / PA) core, such chain consisting of moieties stemming from the polycondensation or polyaddition of at least one of the following further monomers
• the polyalkyleneimine / polyamine (PAI / PA) core generally may be linear or branched, with the branching forming a tertiary amino group, and branches may be (i) relatively short alkylene amino groups as such (e.g., -(CH 2 ) 3 -NH 2 groups) up to very long side chains which may contain further amino-groups being similarly branched etc, thus leading to highly branched structures such as the typical highly branched polyethylene imine (PEI) known to date, or (ii) hydrocarbon units not bearing further amino groups.
• branching forming a tertiary amino group
• branches may be (i) relatively short alkylene amino groups as such (e.g., -(CH 2 ) 3 -NH 2 groups) up to very long side chains which may contain further amino-groups being similarly branched etc, thus leading to highly branched structures such as the typical highly branched polyethylene imine (PEI) known to date, or (ii) hydrocarbon units not bearing
• polyalkylene imine differs from the corresponding term "polyamine” (PA) especially in respect of the branching of the compounds as such as employed in the first step (to obtain an modified polyamine or modified polyalkylene iminie) as educt or within the backbone of the corresponding modified alkoxylated compounds as such as obtained within the modification steps (i.e. the following reactions with alkylene oxides and/or lactones and/or their mixtures) within the process to produce them.
• Polyethylene imines are PAI resulting from the polycondensation of ethyleneimine only.
• polyamines (PA) in the context of the present invention are (predominantly) linear compounds (in respect of its backbone without consideration of any alkoxylation), containing primary and/or secondary amino moieties but no tertiary amino moieties within its backbone
• the corresponding polyalkylene imines are, according to the present invention, (predominantly) branched molecules containing (in respect of its backbone without consideration of any alkoxylation), in addition to the primary and/or secondary amino moieties, mandatorily tertiary amino moieties, which cause the branching of the (linear) main chain into several side chains within the polymeric backbone (basic skeleton).
• the polyalkyleneimine / polyamine (PAI / PA) core comprises on average from 2 to 6 Nitrogen atoms, preferably from 2 to 4 Nitrogen atoms, more preferably from 2 to 3 Nitrogen atoms, most preferably 2 Nitrogen atoms.
• modified polyalkyleneimine / polyamine (PAI / PA) polymers with lower average number of Nitrogen atoms typically show better biodegradability.
• Polyalkylene imines both as backbone and as modified alkoxylated compounds are thus compounds falling under the definition of general formula (I), wherein z is an integer of at least 1 and/or y is an integer of at least one and at least one of the variables (residues) E 1 is C 1 -C 18 -alkyl.
• R is identical or different, linear or branched C 2 -C 12 alkylene radicals, preferably C 2 -C 6 alkylene radicals, more preferably C 2 -C 4 alkylene radicals.
• polyamines both as backbone and as modified alkoxylated compounds, are those compounds of formula (I), wherein z is 0 and E 1 is hydrogen, or wherein both z and y are 0.
• inventive modified alkoxylated polyalkylene imines (PAI) and modified alkoxylated polyamines (PA) have a basic skeleton (backbone), which comprises primary, secondary and/or tertiary amine nitrogen atoms which are joined by alkylene radicals R (as defined below) and are in the form of the following moieties in random arrangement:
• variable B indicating the branching of the polyalkylene imine backbone of compounds according to general formula (I) contains at least one fragment with at least one further amino moiety such as -[-NE 1 -R] y , H 2 N-R or combinations thereof, including a two times, three times or even higher degree of branching.
• variable E 1 with C 1 -C 18 -alkyl also provides a branching of the respective backbone and, by consequence, another type of tertiary amino moiety, but in contrast to the definition of the variable B, the variable E 1 does not contain any further amino moiety.
• the degree of branching may be determined, for example, by NMR-spectroscopy such as 1 H-NMR or preferably 13 C-NMR.
• polyalkylene imine backbone relates to those fragments of the inventive modified alkoxylated polyalkylene imines which are not alkoxylated and not further modified.
• the polyalkylene imine backbone is employed within the present invention as an educt in step a) to be reacted first with at least one first lactone (LA 1) or hydroxy carbon acid (HA1) in order to obtain a first intermediate (I1), followed by step b), wherein said first intermediate (I1) is reacted with at least one alkylene oxide (AO) in order to obtain a second intermediate (I2).
• said second intermediate (I2) is reacted with at least one second lactone (LA2) and/or a second hydroxy carbon acid (HA2) in order to obtain the inventive modified alkoxylated polyalkylene imines.
• LA2 second lactone
• HA2 second hydroxy carbon acid
• polyamine backbone relates to those fragments of the inventive modified alkoxylated polyamines which are not alkoxylated and not further modified.
• the polyamine backbone is employed within the present invention as an educt in step a) to be reacted first with at least one first lactone (LA1) or hydroxy carbon acid (HA1) in order to obtain a first intermediate (I1), followed by step b), wherein said first intermediate (I1) is reacted with at least one alkylene oxide (AO) in order to obtain a second intermediate (I2).
• said second intermediate (I2) is reacted with at least one second lactone (LA2) and/or a second hydroxy carbon acid (HA2) in order to obtain the inventive modified alkoxylated polyamines.
• LA2 second lactone
• HA2 second hydroxy carbon acid
• NH-functionality is defined as follows: In case of defined organic amines, such as di- and oligo amines like BAPMA, N4-amine or 1,6-hexamethylene diamine, the structure itself gives information about the content of primary, secondary and tertiary amines. A primary amino group (-NH 2 ) has two NH- functionalities, a secondary amino group only one NH-functionality, and a tertiary amino group, by consequence, has no reactive NH-functionality.
• polyethylene imine such as those as obtained from polymerization of the monomer ethylene imine (C 2 H 5 N)
• the respective polymer contains a mixture of primary, secondary and tertiary amino groups.
• the exact distribution of primary, secondary and tertiary amino groups can be determined as described in Lukovkin G.M., Pshezhetsky V.S., Murtazaeva G. A.: Europ. Polymer Journal 1973, 9, 559-565 and St. Pierre T., Geckle M.: ACS Polym. Prep. 1981, 22, 128-129 , or by determination of the primary, secondary and tertiary amino number, according to DIN 16945.
• this information is then used to calculate the total amount of NH functionalities in the polyalkylene imine, which serves as the basis for the amount of modification reagents to be employed in the reaction.
• the term "integer" - as defined, for example, for the number of the different repeating units such as the variables m, n and o of the residue according to general formula (IIa) - relates to the average number of each of the different repeating units of that specific residue, i.e., to the number of each of the different repeating units of the most frequent residue among all existing specific residues according to general formula (IIa), as obtained by the respective synthesis/polymerization conditions. It is clear to the person skilled in the art that a polymer composition usually contains a statistically distributed mixture of individual polymers or a statistically distributed mixture of individual residues according to, for example, general formula (IIa), respectively.
• the determination of the average number of repeating units is performed by closely monitoring the conversion rates of each of the synthetical steps a) - c) using 13 C-NMR-spectroscopy and/or 1 H-NMR-spectroscopy.
• integer denotes the number of repeating units, and these numbers are a results from a statistical distribution which stems from the way the reaction is pursued (amounts, relative amounts, duration etc)
• the number not necessarily is an "integer” in mathematical terms, but can be in principle any number between zero and the maximum amount allowed, including natural numbers but also decimal numbers.
• Polyalkyleneimine / polyamine may be predominantly linear, such as at least to 95% linear, and preferably are essentially linear ("essentially linear” being defined herein as comprising less than 1%, preferably less than 0,5% of tertiary nitrogen atoms), such as completely linear ("completely linear” being defined herein as containing no detectable amounts of tertiary amines).
• essentially linear being defined herein as comprising less than 1%, preferably less than 0,5% of tertiary nitrogen atoms
• completely linear being defined herein as containing no detectable amounts of tertiary amines.
• those nitrogen atoms are preferably substituted with hydrocarbon units only, more preferably with C 1 -C 4 -alkyl-groups, most preferably with C 1 - and/or C 2 -alkyl, most preferably C 1 -alkyl only.
• tertiary nitrogen atoms are essentially not present and thus the PAI are essentially linear.
• polyalkyleneimine / polyamine may be branched, such as moderately to highly branched or even hyperbranched, as the known PEI-structures which typically are highly branched or even hyperbranched.
• the degree of branching may be determined, for example, by NMR-spectroscopy such as 1 H-NMR or preferably 13 C-NMR.
• the amine number for primary and secondary, and tertiary amines is determined in accordance with the standard DIN EN ISO 9702.
• the biodegradation of polyalkyleneimine / polyamine (PAI / PA) itself is depending on the molecular weight: the higher the molecular weight, biodegradability decreases quickly.
• the polyalkyleneimine / polyamine (PAI / PA) has a MW less than 600, preferably less than 550
• modified alkoxylated compounds according to the present invention can be seen in their properties, which can be tuned in hydrophilicity/hydrophobicity to achieve in principle all properties from hydrophobic over amphiphilic to hydrophilic; this is especially due to the employment of alkylene oxides and the proper selection of hydrophilic and more hydrophobic alkylene oxides, their relative amounts and their order, by which one or more blocks or a totally random structure or a mixture of random and block structures can be created, thus achieving in principle each and every degree of hydrophilicity/ hydrophobicity/amphiphillicity as desired.
• linker By inclusion of ester-groups into those alkylene oxide chains a “linker” is introduced which is generally accepted as having a lower resistance to hydrolysis; thus, these linker positions are prone to hydrolytic attack and thus help to "cut” the chains into smaller sub-parts, and by this help to speed up the total biodegradation in terms of speed and also of total biodegradability of the compounds.
• the expression / term "modified” relates to the presence of a linker based on lactones or hydroxyl carbon acids within the inventive modified alkoxylated polyalkylene imines and modified alkoxylated polyamines (obtainable by a process comprising the step a)), as well as the presence of further (predominately) hydrophobic polyester blocks based on lactones or hydroxyl carbon acids obtained in step c), in addition to the alkylene oxide blocks obtained in step b)
• residues such as residues according to formula (IIa) expressed by the variables R 3 and m
• fragments with (predominately) hydrophobic polyester blocks are obtained.
• those fragments with (predominately) hydrophobic polyester blocks lead to the amphiphilic nature and thus to excellent cleaning properties of the inventive polymers in detergent applications.
• polymer refers to modified alkoxylated polyalkylene imines as described below and/or in the appended claims.
• the alkyl radical can be either linear or branched or optionally cyclic.
• Alkyl radicals which have both a cyclic component and a linear component likewise come within this definition. The same applies to other alkyl radicals such as a C 1 -C 4 -alkyl radical.
• alkyl radicals are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu/t-Bu), pentyl, hexyl, heptyl, cyclohexyl, octyl, nonyl, decyl or dodecyl.
• C2-C22 alkylene oxides and the like have their ordinary meaning as used in this field of organic chemistry.
• C 5 -C 10 -cycloalkylene refers to saturated, divalent hydrocarbons of 5, 6, 7, 8, 9 or 10 carbon atoms wherein all or at least a part of the respective number of carbon atoms form a cycle (ring). In case not all of the respective number of carbon atoms form a cycle, such remaining carbon atoms (i. e., those carbon atoms not forming a cycle) form a methane-1,1-diyl ("methylene”) fragment or an ethane-1,2-diyl ("ethylene”) fragment of the respective C 5 -C 10 -cycloalkylene radicals.
• methylene methane-1,1-diyl
• ethylene ethane-1,2-diyl
• One of the two valencies of said respective methylene or ethylene fragments is bound to a neighbouring nitrogen atom within general formula (I), whereas the second valency of said fragments is bound to the cyclic fragment of said C 5 -C 10 -cycloalkylene radical.
• a C 5 -C 10 -cycloalkylene radical may comprise, in addition to its cyclic fragment, also some non-cyclic fragments building a bridge or a linker of the cyclic fragment of the C 5 -C 10 -cycloalkylene radical to the neighbouring nitrogen atom within general formula (I).
• the number of such carbon linker atoms is usually not more than 3, preferably 1 or 2.
• a C 7 -cycloalkylene radical may contain one C 6 -cycle and one C 1 -linker.
• the respective hydrocarbon cycle itself may be unsubstituted or at least monosubstituted by C 1 -C 3 -alkyl. It has to be noted that the carbon atoms of the respective C 1 -C 3 -alkyl substituents are not considered for determination of the number of carbon atoms of the C 5 -C 10 -cycloalkylene radical. In contrast to that, the number of carbon atoms of such a C 5 -C 10 -cycloalkylene radical is solely determined without any substituents, but only by the number of carbon atoms of the cyclic fragment and optionally present carbon linker atoms (methylene or ethylene fragments).
• C 5 -C 10 -cycloalkylene examples include cyclopentane-1,2-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl, cycloheptane-1,3-diyl or cyclooctane-1,4-diyl, each of the aforementioned radicals may be at least monosubstituted with C 1 -C 3 -alkyl.
• the respective C 5 -C 10 -cycloalkylene radical is employed as a mixture of two or more individual cycloalkylene radicals having the same ring size. It is particularly preferred to employ a mixture of cyclohexane-1,3-diyl monosubstituted with methyl in position 2 or 4, respectively, of the cycle.
• the ratio of the two compounds is preferably in a range of 95 : 5 to 75 : 25, most preferably about 85 : 15 (4-methyl versus 2-methyl).
• 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl is a preferred example for a C 5 -C 10 -cycloalkylene radical having a non-cyclic fragment in addition to its cyclic fragment.
• the non-cyclic fragment is a C 1 -linker and the cyclic fragment is a C 6 -cycle resulting in a C 7 -cycloalkylene radical.
• 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl may also be substituted with at least one C 1 -C 3 -alkyl, preferably with three methyl groups, in particular 3,5,5-trimethyl. The latter one is a fragment of isophorone diamine, which may be employed as backbone with general formula (I).
• the term "aralkyl” or "C 7 -C 22 -aralkyl”, respectively, as defined below for, for example, the radical R 2 in formula (IIa), means that the substituent (radical) is an aromatic ("ar") combined with an alkyl substituent ("alkyl").
• the aromatic "ar" part can be a monocyclic, bicyclic or optionally polycyclic aromatic. In the case of polycyclic aromatics, individual rings can optionally be fully or partially saturated.
• Preferred examples of aryl are phenyl, naphthyl or anthracyl, in particular phenyl.
• the sum of the carbon atoms of the aromatic and the alkyl fragment is a radical having from 7 to 22 carbon atoms.
• -(CO)-C 1 -C 22 -alkyl as used hereinafter, for example, within the definition for the radical R 2 in formula (IIa) means that this substituent contains a carbonyl group (CO) bound to an alkyl radical having 1 to 22 carbon atoms as defined above.
• the alkyl radical can be either linear or branched or optionally cyclic. Alkyl radicals which have both a cyclic component and a linear component likewise come within this definition.
• This carbon radical is preferably monounsaturated but can optionally also be doubly unsaturated or multiply unsaturated.
• linearity, branches and cyclic constituents what has been said above for C 1 -C 30 -alkyl radicals applies analogously.
• C 2 -C 30 -alkenyl is, for the purposes of the present invention, preferably vinyl, 1-allyl, 3-allyl, 2-allyl, cis- or trans-2-butenyl, ⁇ -butenyl.
• the term "-(CO)-C 2 -C 30 -alkenyl” in turn relates to a substituent containing a carbonyl group (CO) bound to such an alkenyl radical having from 2 to 30 carbon atoms as defined above.
• substituents replace a hydrogen atom of the respective radicals (substituents) such as C 1 -C 22 -alkyl or -(CO)-C 7 -C 22 -aralkyl.
• substituents are selected from -COOH or a salt thereof, the respective salts are known to the skilled person.
• the salts are selected from alkali salts such as sodium or potassium salts, in particular a sodium salt (-COONa).
• the modified polyalkyleneimine / polyamine (PAI / PA) may comprise side chains which are attached to nitrogen atoms of the polyalkyleneimine / polyamine (PAI / PA).
• the side chains may be - and preferably are - attached by way of a polycondensation or polyaddition reaction.
• the side chains are made up from C 2 -C 22 -alkylene oxides, lactones and/or hydroxy carbon acids.
• a side chain comprises at least one alkylene oxide (AO) and at least one lactone (LA) and/or at least one hydroxy acid (HA).
• the (poly)condensation or (poly)addition reaction to prepare a side chain comprising AO, LA and HA is - by way of example for the preparation of the side chains in general - typically done by reacting the polyalkyleneimine / polyamine (PAI / PA) with the at least one AO and the at least one LA and/or HA either i) in a mixture of adding all ingredients employed at the very same time or at least shortly after each other with a preferably as short as possible timelag, ii) by adding first either the AO or the LA or the HA and then the second ingredient and then the third to obtain blocks of AO, LA and HA, iii) by adding one or two ingredients as defined for method i) before and the remaining two or one ingredient(s) according to method ii) as defined before. It is of course also possible to repeat reactions with further amounts of the same ingredient type AO, LA and/or HA at a later point in time, thereby creating block structures.
• a side chain comprises more than one, more preferably more than two, even more preferably more than 3 units per NH-functionality of the polyalkyleneimine / polyamine (PAI / PA) stemming from AO, and at least 0,5 units per NH-functionality. All such numbers are numbers "on average” meaning that such numbers refer to the average number for such unit per NH-functionality calculated based on all NH-functionalities of a polyalkyleneimine / polyamine (PAI / PA).
• those primary amino moieties of the respective backbone, which are reacted first with at least one lactone and/or at least one hydroxy carbon acid are transferred into an amido moiety wherein one of the originally two hydrogen atoms of the respective primary amino moiety is replaced by a fragment originating from the respective lactone or hydroxy carbon acid, whereas the second hydrogen atom of the primary amino moiety of the backbone does not get substituted by this reaction. Beyond that, such a second hydrogen atom of the primary amino moiety of the backbone does also not become substituted within the further reaction steps, e.g., further reactions with AO, LA and/or HA.
• a modified polyalkyleneimine / polyamine (PAI / PA) by their monomers and process of production (i.e. order of reaction steps) is a viable way of defining the structures. Also, defining the composition of the side chains by average numbers based on the numbers of NH-functionalities being present in the modified polyalkyleneimine / polyamine (PAI / PA) - such number of functionalities being themselves an average number due to this factual mixture - is a useful way of defining the overall composition of any mixture herein defined as "a modified polyalkyleneimine / polyamine (PAI / PA)".
• the values, ranges and ratios given in the specification, the numbers for a, b, c, d and e, the number of NH-functionalities, and the molecular weight (Mn) relate to the number average values of the mixture obtained as modified polyalkyleneimine / polyamine (PAI / PA) containing individual, slightly from each other deviating chemical structures of several modified polyalkyleneimine / polyamine (PAI / PA) - compounds, with "the modified PAI/PA” defining this mixture being the result from the preparation method.
• the weight-average molecular weight (Mw) is then a measure for the (in)homogeneity within the mixture of different species in "the modified polyalkyleneimine / polyamine (PAI / PA)".
• Suitable lactones and/or hydroxy carbon acids can be aliphatic, cycloaliphatic or aromatic.
• aromatic hydroxy carbon acids are hydroxy-substituted benzoic acids and naphthalene carboxylic acids, such as p-hydroxyethyl benzoic acid and 2-hydroxynaphthalene-6-carboxylic acid.
• aliphatic hydroxy carbon acids Preference is given to aliphatic hydroxy carbon acids, especially to those with hydroxyl groups in the ⁇ position, and their lactones.
• the aliphatic hydroxy carbon acids have from 1 to 22 alkylene radicals, preferably from 2 to 10 alkylene radicals, more preferably from 2 to 5 alkylene radicals.
• the alkylene radicals may be linear or branched.
• glycolic acid examples which may be mentioned are glycolic acid, lactic acid and its lactide, gamma-hydroxybutyric acid and gamma-butyrolactone, delta-hydroxyvaleric acid and gamma- and delta-valerolactone, epsilon-hydroxycaproic acid and epsilon-caprolactone, 12-hydroxystearic acid and ricinoleic acid, and also mixtures, especially including naturally occurring acids.
• glycolic acid, lactic acid, epsilon-caprolactone or lactide, or mixtures thereof are employed, even more preferably epsilon-caprolactone.M
• Modified polyalkyleneimine / polyamine (PAI / PA) thus comprises at least one of the following side chain-structures:
• the conversion rate of each reaction is monitored: Only when the previous reaction (in this example: E1 as the first reactant reacting with polyalkyleneimine / polyamine (PAI / PA)) has proceeded to a conversion rate of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99,5 % or even more has been achieved, the next reactant (in this example: D1 as the second reactant) is to be added which in turn is also monitored for its conversion rate to detect when this next reaction has proceeded to a conversion rate of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99,5 % or even more has been achieved, then the even next reaction (in this example: E2 as the third reactant) is to be added - and so on until all reactants have been reacted and the reaction of the last reactant added has proceeded to a conversion rate of at least 90%, preferably at least 95%, more preferably at least 99%,
• the conversion rate of each of the respective steps can be determined according to methods known to the skilled person, such as NMR-spectroscopy, such as 13 C-NMR-spectroscopy and/or 1 H-NMR-spectroscopy.
• At least 50 %, preferably at least 60% and most preferably at least 80%, even more preferably at least 90, and most preferably at least 95% of all side chains attached to the NH-functionalities of one specific modified polyalkyleneimine / polyamine (PAI / PA) (whatever is employed as the "core") have the same structural order, such structural order as being generally defined as "structural orders” as i), ii), iii), iv), v) or vi) in the context of "Modified polyalkyleneimine / polyamine (PAI / PA) according to this invention" as defined above.
• the modified PAI/PA as detailed herein may be further modified by quaternization using standard means, including protonation by pH-adjustment or permanent quaternization by standard means such as alkylation using standard reactants, preferably by alkylation, to a degree of from 5 to 100, preferably up to 95, more preferably up to 70, even more preferably up to 50 percent of all nitrogen-atoms within the PAI/PA.
• standard means such as alkylation using standard reactants, preferably by alkylation, to a degree of from 5 to 100, preferably up to 95, more preferably up to 70, even more preferably up to 50 percent of all nitrogen-atoms within the PAI/PA.
• a suitable degree of quaternization is up to 100%, in particular from 5 to 95%.
• the quaternization is conducted preferably by introducing C 1 -C 22 -alkyl groups, C 1 -C 4 -alkyl groups and/or C 7 -C 22 -aralkyl groups and may be undertaken in a customary manner by reaction with corresponding alkyl halides and dialkyl sulfates.
• the quaternization may be advantageous in order to adjust the inventive modified PAI/PA to the particular composition such as laundry compositions in which they are to be used, and to achieve better compatibility and/or phase stability of the formulation.
• the quaternization of the inventive modified PAI/PA is achieved preferably by introducing C 1 -C 22 alkyl, C 1 -C 4 -alkyl groups and/or C 7 -C 22 aralkyl, aryl or alkylaryl groups and may be undertaken in a customary manner by reaction with corresponding alkyl-, aralkyl - halides and dialkylsulfates, as described for example in WO 09/060059 .
• Quaternization can be accomplished, for example, by reacting an inventive modified PAI/PA with an alkylation agent such as a C 1 -C 4 -alkyl halide, for example with methyl bromide, methyl chloride, ethyl chloride, methyl iodide, n-butyl bromide, isopropyl bromide, or with an aralkyl halide, for example with benzyl chloride, benzyl bromide or with a di-C 1 -C 22 -alkyl sulfate in the presence of a base, especially with dimethyl sulfate or with diethyl sulfate.
• Suitable bases are, for example, sodium hydroxide and potassium hydroxide.
• the amount of alkylating agent determines the amount of quaternization of the amino groups in the polymer, i.e., the amount of quaternized moieties.
• the amount of the quaternized moieties can be calculated from the difference of the amine number in the non-quaternized amine and the quaternized amine.
• the amine number can be determined according to the method described in DIN 16945.
• the quaternization can be carried out without any solvent.
• a solvent or diluent like water, acetonitrile, dimethylsulfoxide, N-methylpyrrolidone, etc. may be used.
• the reaction temperature is usually in the range from 10°C to 150°C and is preferably from 50°C to 100°C.
• the quaternization may be advantageous in order to adjust the modified or unmodified PAI/PA to the particular composition such as laundry compositions in which they are to be used, and to achieve better compatibility and/or phase stability of the formulation
• a preferred process to produce preferred modified polyalkyleneimine / polyamine include the steps of modifying in a further polycondensation or polyaddition reaction to produce a modified polyalkyleneimine / polyamine (PAI / PA) comprising at least one side chain attached to at least one NH-functionality of the polyalkyleneimine / polyamine (PAI / PA), such chain consisting of moieties stemming from the polycondensation or polyaddition of at least one of the following further monomers
• those primary amino moieties of the respective backbone which are reacted within the first reaction step of modification step (b) with at least one lactone and/or at least one hydroxy carbon acid are transferred into an amido moiety wherein one of the originally two hydrogen atoms of the respective primary amino moiety is replaced by a fragment originating from the respective lactone or hydroxy carbon acid, whereas the second hydrogen atom of the primary amino moiety of the backbone does not get substituted by this reaction.
• such a second hydrogen atom of the primary amino moiety of the backbone does also not become substituted within the further reaction steps within step (b) of the process according to the present invention when the respective intermediate backbone is for example alkoxylated with at least one C 2 -C 22 -epoxide.
• the modified polyalkyleneimine / polyamine contains side chains which have a structural order being similar or - preferably - essentially identical to at least 50 %, preferably at least 60% and most preferably at least 80%, even more preferably at least 90, and most preferably at least 95% of all side chains attached to the NH-functionalities of one specific modified polyalkyleneimine / polyamine (PAI / PA), such structural order as being defined as "structural orders" as i), ii), iii), iv), v) or vi) (all as detailed before).
• variables as defined in the embodiment of the processes before are average numbers being based on mol equivalents per NH-functionality of the polyalkyleneimine / polyamine (PAI / PA) as follows:
• the sub-units are composed on average as follows:
• the resulting product mixture containing the modified polyalkyleneimine / polyamine (PAI / PA) may be further purified by standard means to reduce the content of residual monomers, but also to reduce the amount of possible by-products, reduce the amount(s) of the solvent(s) employed (i.e., to concentrate) or replace solvent(s) with other solvents.
• Such processes are known to a person of skill in this field.
• undesirable amounts of residual non-reacted monomers are removed, preferably by means of distillative processes, more preferably by thermal distillative processes, which may additionally comprise the application of reduced pressure to increase the speed and/or the effectiveness of the removal.
• the composition of the invention comprises at least one fabric and home care ingredient different from the graft polymer and the modified polyalkyleneimine / polyamine (PAI / PA).
• Suitable fabric and home care additives include surfactant system, enzymes, enzyme stabilizing system, builders, structurant, thickeners, other polymers, bleaching agents, fluorescent brightener, fabric hueing agents, chelating agent, encapsulates, perfumes, malodor reduction materials, conditioning agents, probiotics, organic acids, anti-oxidants, hygiene agent, opacifier, solvents, hydrophotrope, suds suppressor, and any combination thereof.
• compositions comprise a surfactant system in an amount sufficient to provide desired cleaning properties.
• the composition may comprise, by weight of the composition, from about 1% to about 70% of a surfactant system.
• the composition may comprise, by weight of the composition, from about 2% to about 60% of the surfactant system.
• the composition may comprise, by weight of the composition, from about 5% to about 30% of the surfactant system.
• the 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%
• 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; alkyl polysaccharides, 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 alcohol 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 methylsulfate; 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 dicano
• 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 C 8 -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.
• surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as Phosphobetaines.
• 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, ⁇ -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 WO2013/171241 ; TfuLip2, e.g. as described in WO2011/084412 and WO2013/033318 ; 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 other graft polymers, other modified polyalkyleneimine, zwitterionic polyamines and polyester soil release polymers, polymers based on polysaccharide, polycarboxylate polymers, block polymers of alkylene oxide, dye transfer inhibiting polymers,
• Suitable graft polymers are 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 5 000 to 100 000.
• 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 6000 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.
• Another preferred graft polymer of this type is Sokalan HP22 available from BASF.
• the composition may comprise one or more other modified polyalkyleneimine and polyamine.
• the one or more other modified polyalkyleneimine and polyamine comprises a polyamine core structure and a plurality of alkoxylate groups attached to the core structure.
• the polyamine core comprises more than 8 Nitrogen atoms, preferably more than 10 Nitrogen atoms.
• 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 may have a polyethyleneimine backbone of weight average molecular weight of between 340g/mol and 2500g/mol, preferably between 430g/mol and 2000g/mol, preferably between 500g/mol and 1500g/mol, more preferably between 550g/mol and 1000g/mol, even more preferably between 600g/mol and 800g/mol, more preferably about 600.
• the ethoxylation chains within the EPEI may be from 200g/mol to 2000g/mol weight average molecular weight, preferably from 400g/mol to 1500g/mol weight average molecular weight, more preferably from 600g/mol to 1000g/mol weight average molecular weight, most preferably about 880g/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 5000g/mol to 20000g/mol, preferably from 7500g/mol to 17500g/mol, more preferably from 10000g/mol to 15000g/mol, even more preferably from 12000g/mol to 13000g/mol, most preferably about 12700g/mol.
• a preferred example is polyethyleneimine core (with average molecular weight about 600g/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. Such polymers maybe also referred as PE-20 polymer.
• the EPEI may comprise polyethyleneimine has an average molecular weight (Mw) ranging from 1800 to 5000 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
• Such EPEI is described in WO2020/030760 and WO2020/030469 .
• 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 WO2009/061990 and WO2006/108857 , 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.
• alkoxylated polyalkyleneimine polymer of this type includes Sokalan HP30 Booster available from BASF.
• Suitable zwitterionic polyamine comprises zwitterionic polyamines according to the following formula:
• 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).
• Sokalan HP96 Another preferred zwitterionic polyamine is Sokalan HP96, available from BASF.
• Suitable zwitterionic polyamines are amphoterically-modified oligopropyleneimine ethoxylates as described in WO2021239547 .
• the composition may comprise one or more polyester soil release polymer (SRP).
• SRP polyester soil release polymer
• Polyester SRP typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers (such as polyester and nylon), and hydrophobic segments to enable deposition of SRP onto hydrophobic fibers and remain adhered thereto through washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
• Polyester SRP may be linear, branched, or star-shaped. Polyester SRP may comprises end capping moiety, which is especially effective in controlling the molecular weight of the polyester or altering the physical or surface-adsorption properties of the polymer. Soil release polymers may also include charged units (negative or positive). Typically, nonionic SRP or anionic SRP may be preferred when used in composition which containing anionic surfactants, in order to avoid potentially negative interactions between the SRP and anionic surfactants.
• Preferred polyester SRP comprises structural unit (I), or combination of structural unit (I) and (II): -[(O-CHR 1 -CHR 2 ) a -O-OC-Ar-CO-] c (I) -[(O-CHR 3 -CHR 4 ) b -O-OC-sAr-CO-] d (II) wherein:
• the polyester SRP further comprises one or more terminal group (III) derived from polyalkylene glycolmonoalkylethers.
• the terminal group (III) has a structure of (III-a). R 7 -O-[C 2 H 4 -O] e -[C 3 H 6 -O] f -[C 4 H 8 -O] g - (III-a) wherein:
• structure (III-a) connected to structural units -OC-Ar-CO- or -OC-sAr-CO- via an ester bond to form an end cap, as illistrated below: R 7 -O-[C 2 H 4 -O] e -[C 3 H 6 -O] f -[C 4 H 8 -O] g -OC-Ar-CO-, or R 7 -O-[C 2 H 4 -O] e -[C 3 H 6 -O] f -[C 4 H 8 -O] g -OC-sAr-CO-, or R 7 -O-[C 2 H 4 -O] e -[C 3 H 6 -O] f -[C 4 H 8 -O] g -OC-sAr-CO-
• the polymer comprises one or more anionic terminal unit (IV) and/or (V) as described in EP3222647 .
• 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 polyester SRP may comprise crosslinking structural unit derived from monomers which comprise at least three functional groups capable of forming esters.
• monomers which comprise at least three functional groups capable of forming esters include, but not limit to, trimellitic acid, citric acid, glycerine, sorbitol.
• di-carboxylic acids or their salts or their (di)alkylesters can be used in the polyesters of the invention.
• Suitable examples include furandicarboxylic acids, such as 2,5-furandicarboxylic acid; pyridine dicarboxylic acids, such as pyridine-2,5-dicarboxylic acid; cyclohexanedicarboxylic acids, such as 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, fumaric acid, succinic acid, glutaric acid, azelaic acid.
• polyester SRPs are nonionic polyester SRP, which does not comprise above structural unit (II).
• a particular preferred nonionic polyester SRP 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 ; f is 0; e 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-O-[C 2 H 4 O] n -[C 3 H 6 O] m - wherein X is C 1- C 4 alkyl and preferably methyl, the [C 2 H 4 O] groups and the [C 3 H 6 O] groups are arranged blockwise and the block consisting of the [C 3 H 6 O] groups is bound to a -CO-Ar-CO-structural unit via an ester bond , n is based on a molar average a number of from 40 to 50, m is based on a molar average a number from 1 to 10 and preferably from 1 to 7.
• anionic polyester SRP which comprise above structural unit (I) and structural unit (II).
• the anionic SRP comprise further at least one terminal group selected from (III-a), (IV) and (V). More preferably, the anionic SRP comprises structural (I) and (II), and one or two terminal group (III-a), wherein R 7 is C 1 alkyl, e is from 2 to 100, preferably from 3 to 50 such as 5, 10, 15, 20, and both f and g are 0.
• Suitable anionic polyester SRP examples are described in EP1966273B1 and EP3222647B1 .
• Polyester SRP 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.
• 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 SRP may or may not be biodegradable, preferred soil release polymers are readily biodegradable.
• polyester SRP examples 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 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 300, SRN 325; and anionic soil release polymers TexCare ® SRA 100, SRA 300, SRA300 F.
• 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.
• Other examples of commercial soil release polymers are Marloquest ® polymers, such as Marloquest ® SL, HSCB, L235M, U, B, and G82, supplied by Sasol.
• the raw materials for the preparation of the polyesters of the invention can be based on fossil carbon or renewable carbon.
• Renewable carbon includes carbon originating from biomass, carbon capture, or chemical recycling.
• the raw materials for the preparation of the polyesters of the invention are at least partly based on 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 polyesters of the invention preferably is above 40%, more preferably above 50%, even more preferably above 60%, particularly preferably from 70 to 100% (including 100%), and most preferably 100%.
• 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 Da to about 300,000 Da.
• Suitable carboxymethylcellulose is described in WO2011/031599 and WO2009/154933 .
• 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 WO2015/044061 ; 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.
• 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 WO2020/091988 .
• 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 Da to 9,000 Da, or from 6,000 Da to 9,000 Da.
• Other suitable carboxylate polymers include copolymer of acrylic acid (and/or methacrylic acid) and maleic acid having a molecular weight of from 50,000 Da to 120,000 Da, or from 60,000 Da to 80,000 Da.
• 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 WO2014/032267 , the additional monomers herein are ether bond-containing monomers represented by formula (1) and (2) below: Wherein in Formula (1)
• 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.
• 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.
• 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 2000 to 3000 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 oxideethylene 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 WO2019/105938 , WO2019/105939 , WO2019/096942 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 WO2016/049389 .
• 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 3000:1, 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. As the ratio of malodor reduction composition to parts of perfume is tightened, 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.
• the composition may comprise probiotics, such as those described in WO2009/043709 .
• Organic acids 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.
• Pearlescent Agent 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.
• the fabric and home care product can be a water-soluble unit dose article.
• the water-soluble unit dose article comprises at least one water-soluble film orientated to create at least one unit dose internal compartment, wherein the at least one unit dose internal compartment comprises a detergent composition.
• the water-soluble film preferably comprises polyvinyl alcohol homopolymer or polyvinyl alcohol copolymer, for example a blend of polyvinylalcohol homopolymers and/or polyvinylalcohol copolymers, for example copolymers selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers, for example a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer.
• 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.
• the laundry detergent composition comprises between 10% and 60%, or between 20% and 55% by weight of the laundry detergent composition of the non-soap surfactant.
• the weight ratio of non-soap anionic surfactant to nonionic surfactant preferably is 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.
• the non-soap anionic surfactants preferably comprise linear alkylbenzene sulphonate, alkyl sulphate or a mixture thereof.
• the weight ratio of linear alkylbenzene sulphonate to alkyl sulphate preferably is 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.
• Example linear alkylbenzene sulphonates are C 10 -C 16 alkyl benzene sulfonic acids, or C 11 -C 14 alkyl benzene sulfonic acids.
• 'linear' we herein mean the alkyl group is linear.
• Example alkyl sulphate anionic surfactant may comprise alkoxylated alkyl sulphate or non-alkoxylated alkyl sulphate or a mixture thereof.
• Example alkoxylated alkyl sulphate anionic surfactants comprise an ethoxylated alkyl sulphate anionic 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.
• Example alkyl fraction of the alkyl sulphate anionic surfactant are derived from fatty alcohols, oxo-synthesized alcohols, Guerbet alcohols, or mixtures thereof.
• the laundry detergent composition comprises between 10% and 50%, between 15% and 45%, between 20% and 40%, or between 30% and 40% by weight of the laundry detergent composition of the non-soap anionic surfactant.
• the non-ionic surfactant is selected from alcohol alkoxylate, an oxo-synthesised alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl phenol alcohol alkoxylates, or a mixture thereof.
• the laundry detergent composition comprises between 0.01% and 10%, or between 0.01% and 8%, or between 0.1% and 6%, or between 0.15% and 5% by weight of the liquid laundry detergent composition of a non-ionic surfactant.
• the laundry detergent composition comprises between 1.5% and 20%, between 2% and 15%, between 3% and 10%, or between 4% and 8% by weight of the laundry detergent composition of soap, in some examples a fatty acid salt, in some examples an amine neutralized fatty acid salt, wherein in some examples the amine is an alkanolamine preferably monoethanolamine.
• the liquid laundry detergent composition comprises less than 15%, or less than 12% by weight of the liquid laundry detergent composition of water.
• 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 liquid laundry detergent composition comprises from 0.1% to 10%, preferably from 0.5% to 8% by weight of the detergent composition of further soil release polymers, preferably selected from the group of nonionic and/or anionically modified polyester terephthalate soil release polymers such as commercially available under the Texcare brand name from Clariant, amphiphilic graft polymers such as those based on polyalkylene oxides and vinyl esters, polyalkoxylated polyethyleneimines, and mixtures thereof.
• the liquid detergent composition further comprises from 0.1% to 10% preferably from 1% to 5% of a chelant.
• the laundry detergent composition comprises an adjunct ingredient selected from the group comprising builders including citrate, enzymes, bleach, bleach catalyst, dye, hueing dye, brightener, cleaning polymers including (zwitterionic) alkoxylated polyamines, surfactant, solvent, dye transfer inhibitors, perfume, encapsulated perfume, polycarboxylates, structurant, pH trimming agents, and mixtures thereof.
• the laundry detergent composition has a pH between 6 and 10, between 6.5 and 8.9, or between 7 and 8, wherein the pH of the laundry detergent composition is measured as a 10% product concentration in demineralized water at 20°C.
• the laundry detergent composition may be Newtonian or non-Newtonian, preferably non-Newtonian.
• 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.
• the fabric and home care product can be a dishwashing detergent composition, such as a hand dishwashing detergent composition, more preferably a liquid hand dishwashing detergent composition.
• a dishwashing detergent composition such as a hand dishwashing detergent composition, more preferably a liquid hand dishwashing detergent composition.
• the liquid hand dishwashing detergent composition comprises from between 0.1% and 5.0%, preferably between 0.5% and 4%, more preferably 1.0% to 3.0% by weight of the detergent composition of the polymer of the present invention.
• the liquid handdishwashing detergent composition preferably is an aqueous composition, comprising from 50% to 90%, preferably from 60% to 75%, by weight of the total composition of water.
• the pH of the detergent composition of the invention is adjusted to between 3 and 14, more preferably between 4 and 13, more preferably between 6 and 12 and most preferably between 8 and 10.
• the composition of the present invention can be Newtonian or non-Newtonian, preferably Newtonian.
• the composition has a viscosity of from 10 mPa ⁇ s to 10,000 mPa ⁇ s, preferably from 100 mPa ⁇ s to 5,000 mPa ⁇ s, more preferably from 300 mPa ⁇ s to 2,000 mPa ⁇ s, or most preferably from 500 mPa ⁇ s to 1,500 mPa ⁇ s, alternatively combinations thereof.
• the viscosity is measured at 20°C with a Brookfield RT Viscometer using spindle 31 with the RPM of the viscometer adjusted to achieve a torque of between 40% and 60%.
• the composition comprises from 5% to 50%, preferably from 8% to 45%, more preferably from 15% to 40%, by weight of the total composition of a surfactant system.
• the surfactant system preferably comprises from 60% to 90%, more preferably from 70% to 80% by weight of the surfactant system of an anionic surfactant.
• Alkyl sulphated anionic surfactants are preferred, particularly those selected from the group consisting of: alkyl sulphate, alkyl alkoxy sulphate preferably alkyl ethoxy sulphate, and mixtures thereof.
• the alkyl sulphated anionic surfactant preferably has an average alkyl chain length of from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, most preferably from 12 to 13 carbon atoms.
• the alkyl sulphated anionic surfactant preferably has an average degree of alkoxylation preferably ethoxylation, of less than 5, preferably less than 3, more preferably from 0.5 to 2.0, most preferably from 0.5 to 0.9.
• the alkyl sulphate anionic surfactant preferably has a weight average degree of branching of more than 10%, preferably more than 20%, more preferably more than 30%, even more preferably between 30% and 60%, most preferably between 30% and 50%.
• Suitable counterions include alkali metal cation earth alkali metal cation, alkanolammonium or ammonium or substituted ammonium, but preferably sodium.
• Suitable examples of commercially available alkyl sulphate anionic surfactants include, those derived from alcohols sold under the Neodol ® brand-name by Shell, or the Lial ® , Isalchem ® , and Safol ® brand-names by Sasol, or some of the natural alcohols produced by The Procter & Gamble Chemicals company.
• the surfactant system preferably comprises from 0.1% to 20%, more preferably from 0.5% to 15% and especially from 2% to 10% by weight of the liquid hand dishwashing detergent composition of a co-surfactant.
• co-surfactants are selected from the group consisting of an amphoteric surfactant, a zwitterionic surfactant, and mixtures thereof.
• the anionic surfactant to the co-surfactant weight ratio can be from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1.
• the co-surfactant is preferably an amphoteric surfactant, more preferably an amine oxide surfactant.
• the amine oxide surfactant is selected from the group consisting of: alkyl dimethyl amine oxide, alkyl amido propyl dimethyl amine oxide, and mixtures thereof, most preferably C 12 -C 14 alkyl dimethyl amine oxide.
• Suitable zwitterionic surfactants include betaine surfactants, preferably cocamidopropyl betaine.
• the surfactant system of the composition of the present invention further comprises from 1% to 25%, preferably from 1.25% to 20%, more preferably from 1.5% to 15%, most preferably from 1.5% to 5%, by weight of the surfactant system, of a non-ionic surfactant.
• Suitable nonionic surfactants can be selected from the group consisting of: alkoxylated non-ionic surfactant, alkyl polyglucoside (“APG”) surfactant, and mixtures thereof.
• Suitable alkoxylated non-ionic surfactants can be linear or branched, primary or secondary alkyl alkoxylated preferably alkyl ethoxylated non-ionic surfactants comprising on average from 9 to 15, preferably from 10 to 14 carbon atoms in its alkyl chain and on average from 5 to 12, preferably from 6 to 10, most preferably from 7 to 8, units of ethylene oxide per mole of alcohol.
• the alkyl polyglucoside surfactant has an average alkyl carbon chain length between 10 and 16, preferably between 10 and 14, most preferably between 12 and 14, with an average degree of polymerization of between 0.5 and 2.5 preferably between 1 and 2, most preferably between 1.2 and 1.6.
• C 8 -C 16 alkyl polyglucosides are commercially available from several suppliers (e.g., Simusol ® surfactants from Seppic Corporation; and Glucopon ® 600 CSUP, Glucopon ® 650 EC, Glucopon ® 600 CSUP/MB, and Glucopon ® 650 EC/MB, from BASF Corporation).
• the liquid hand dishwashing detergent composition herein may optionally comprise a number of other adjunct ingredients such as builders (e.g., preferably citrate), chelants (e.g., preferably GLDA), conditioning polymers, cleaning polymers including polyalkoxylated polyalkylene imines, surface modifying polymers, soil flocculating polymers, sudsing polymers including EO-PO-EO triblock copolymers, grease cleaning amines including cyclic polyamines, structurants, emollients, humectants, skin rejuvenating actives, enzymes, carboxylic acids, scrubbing particles, bleach and bleach activators, perfumes, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, organic solvents, inorganic cations such as alkaline earth metals such as Ca/Mg-ions, antibacterial agents, preservatives, viscosity adjusters (e.g., salt such as NaCl, and other mono-, di
• carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, phosphoric and sulfonic acids, carbonates such as sodium carbonates, bicarbonates, sesquicarbonates, borates, silicates, phosphates, imidazole and alike).
• the formulation can be made through standard mixing of the individual components. Table 3.
• As 100% active Comp. 6 (wt%) C 1213 AE 0.6 S anionic surfactant (Avg. branching : 37,84%) 19.6 C 1214 dimethyl amine oxide 6.5 Alcohol ethoxylate nonionic surfactant (Neodol 91/8) 1.0 Alkoxylated polyethyleneimine (PEI 600 EO 24 PO 16 ) 0.2 Graft polymer of the present invention 1.5 Modified polyalkyleneimine / polyamine (PAI / PA) of the present invention 1.0 Ethanol 2.4 NaCl 0.7 Polypropyleneglycol (MW2000) 0.9 Water + Minor ingredients (perfume, dye, preservatives) Balance to 100 pH (at 10% product concentration in demineralized water - with NaOH trimming) 9.0
• Solid Free-flowing Particulate Laundry Detergent Composition Solid Free-flowing Particulate Laundry Detergent Composition.
• the fabric and home care product can be solid free-flowing particulate laundry detergent composition.
• the following is an exemplary solid free-flowing particulate laundry detergent composition (Table 4).
• Table 4 Ingredient Comp. 7 (wt%) Anionic detersive surfactant (such as alkyl benzene sulphonate, alkyl ethoxylated sulphate and mixtures thereof) from 8wt% to 20wt%
• Non-ionic detersive surfactant such as alkyl ethoxylated alcohol
• Cationic detersive surfactant such as quaternary ammonium compounds
• Other detersive surfactant such as zwiterionic detersive surfactants, amphoteric surfactants and mixtures thereof
• Carboxylate polymer such as co-polymers of maleic acid and acrylic acid and/or carboxylate polymers comprising ether moieties and
• fluorescent brightener 260 or C.I. fluorescent brightener 351 from 0.1wt% to 0.4wt% Protease (such as Savinase, Savinase Ultra, Purafect, FN3, FN4 and any combination thereof) from 0.1 wt% to 0.4wt% Amylase (such as Termamyl, Termamyl ultra, Natalase, Optisize, Stainzyme, Stainzyme Plus and any combination thereof) from 0wt% to 0.2wt% Cellulase (such as Carezyme and/or Celluclean) from 0wt% to 0.2wt% Lipase (such as Lipex, Lipolex, Lipoclean and any combination thereof) from 0wt% to 1wt% Other enzyme (such as xyloglucanase, cutinase, pectate lyase, mannanase, bleaching enzyme) from 0wt% to 2wt% Fabric softener (such as mont
• 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 fibrous water-soluble unit dose article may include any of the disclosures found in U.S. Patent Application No. 15/880,594 filed on January 26, 2018 ; U.S. Patent Application No. 15/880,599 filed January 26, 2018 ; and U.S. Patent Application No. 15/880,604 filed January 26, 2018 ; incorporated by reference in their entirety.
• Preferred water-soluble fibrous structure comprises particles having a ratio of Linear Alkylbenzene Sulfonate to Alkylethoxylated Sulfate or Alkyl Sulfate of greater than 1.
• These fibrous water-soluble unit dose articles can be dissolved under various wash conditions, e.g., low temperature, low water and/or short wash cycles or cycles where consumers have been overloading the machine, especially with items having high water absorption capacities, while providing sufficient delivery of active agents for the intended effect on the target consumer substrates (with similar performance as today's liquid products).
• the water-soluble unit dose articles described herein can be produced in an economical manner by spinning fibers comprising active agents.
• the water-soluble unit dose articles described herein also have improved cleaning performance.
• compositions of this invention can be used to form aqueous washing/treatment solutions for use in the laundering/treatment of fabrics.
• an effective amount of such compositions is added to water, for example in a conventional fabric automatic washing machine, to form such aqueous laundering solutions.
• the aqueous washing solution so formed is then contacted, typically under agitation, with the fabrics to be laundered/treated therewith.
• An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution, or from about 1,000 to 3,000 ppm of the laundry care compositions herein will be provided in aqueous washing solution.
• the wash liquor is formed by contacting the laundry care composition with wash water in such an amount so that the concentration of the laundry care composition in the wash liquor is from above 0g/l to 5g/l, or from 1g/l, and to 4.5g/l, or to 4.0g/l, or to 3.5g/l, or to 3.0g/l, or to 2.5g/l, or even to 2.0g/l, or even to 1.5g/l.
• the method of laundering fabric or textile may be carried out in a top-loading or front-loading automatic washing machine or can be used in a handwash laundry application. In these applications, the wash liquor formed and concentration of laundry detergent composition in the wash liquor is that of the main wash cycle. Any input of water during any optional rinsing step(s) is not included when determining the volume of the wash liquor.
• 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 composition is contacted to water to form the wash liquor.
• Such compositions are typically employed at concentrations of from about 500 ppm to about 15,000 ppm in solution.
• the wash solvent is water
• the water temperature typically ranges from about 5 °C to about 90 °C and, when the situs comprises a fabric, the water to fabric ratio is typically from about 1:1 to about 30:1.
• the wash liquor comprising the laundry care composition of the invention has a pH of from 3 to 11.5.
• such method comprises the steps of optionally washing and/or rinsing said surface or fabric, contacting said surface or fabric with any composition disclosed in this specification then optionally washing and/or rinsing said surface or fabric is disclosed, with an optional drying step.
• 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.
• the raw materials for preparation of the surfactant, polymers and other ingredients can be based on fossil carbon or renewable carbon.
• Renewable carbon is a carbon source that avoid the use of fossil carbon such as natural gas, coal, petroleum.
• renewable carbon is derived from the biomass, carbon capture, or chemical recycling.
• 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%.
• 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.
• test stains suitable for this test are:
• the stains are analysed using Image Analysis System for Laundry stain removal testing before and after the wash.
• SBL2004 test soil strips supplied by WFK Testgewebe GmbH are used to simulate consumer soil levels (mix of body soil, food, dirt etc.). Every 1 SBL2004 strip is loaded with 8g soil. The SBL2004 test soil strips were cut into 5 ⁇ 5 cm squares for use in the test.
• ballast background fabric swatches
• Ballast loads are comprised of knitted cotton swatches at 5 ⁇ 5 cm size.
• the desired amount of detergent is fully dissolved by mixing with 1L water (at defined hardness) in each tergotometer pot. 60 total grams of fabrics including stains (2 internal replicates of each stain in each pot), defined amount of 5 ⁇ 5 cm SBL2004 and ballast are washed and rinsed in the tergotometer pot under defined conditions. The test is repeated for 4 times (4 external replicates).
• Stain Removal Index are automatically calculated from the L, a, b values using the formula shown below. The higher the SRI, the better the stain removal.
• the suds profile of a laundry detergent is a very important property to consumers.
• the detergent must deliver enough suds to serve as a signal to consumers to show effective cleaning but not too much that extra rinse effort are required to remove excess suds.
• the flash suds of comparative and inventive composition are evaluated using automatic Tergotometer with 10 pots for laundry formulation testing.
• SBL2004 test soil strips supplied by WFK Testgewebe GmbH are used to simulate consumer soil levels (mix of body soil, food, dirt etc.). Every 1 SBL2004 strip is loaded with 8g soil. The SBL2004 test soil strips were cut into 5 ⁇ 5 cm squares for use in the test.
• the number average molecular weight (M n ), the weight average molecular weight (M w ) and the polydispersity M w /M n of the inventive graft polymers were determined by gel permeation chromatography in tetrahydrofuran.
• the mobile phase (eluent) used was tetrahydrofuran comprising 0.035 mol/L diethanolamine.
• the concentration of graft polymer in tetrahydrofuran was 2.0 mg per mL. After filtration (pore size 0.2 ⁇ m), 100 ⁇ L of this solution were injected into the GPC system.
• graft polymer Example 1 The following inventive graft polymer Example 1 was synthesized according to procedure described below. Graft polymer Example 1 graft polymerization of vinyl acetate in a ratio of polyalkylene oxide / VAc (60 / 40), wherein the polyalkylene oxide is triblock copolymer (PO 13 -EO 24 -PO 13 ).
• a polymerization vessel equipped with stirrer and reflux condenser was initially charged with 600 g of triblock copolymer (PO 13 -EO 24 -PO 13 ) under nitrogen atmosphere and melted at 90°C.
• Feed 1 containing 4.0 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 33.0 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90°C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90°C.
• Feeds 1 and 2 Upon completion of the Feeds 1 and 2, the temperature was increased to 95°C and Feed 3 consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 21.0 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 °C. The mixture was stirred for one hour at 95°C upon complete addition of the feed.
• Graft polymer Example 2 graft polymerization of vinyl acetate in a ratio of polyalkylene oxide / VAc (60 / 40), wherein the polyalkylene oxide is triblock copolymer (P0 6.5 EO 48 -PO 6.5 ).
• triblock copolymer PO 13 -EO 24 -PO 13
• triblock copolymer PO 6.5 -EO 48 -PO 6.5
• the resulting graft polymer had a mean molecular weight M w of 5 190 g/mol and a polydispersity of 1.5.
• graft polymer examples 3-24 can be synthesized following similar procedure.
• the structure details of graft polymer 1-24 are summarized in Table 5 below: Table 5.
• inventive alkoxylated polyamine Example 1 and 2 has been synthesized according to procedure described below.
• the synthesis of more inventive alkoxylated polyamine polymers is described in WO2022136389 and WO2021165493 .
• Example 1-a HMDA + 1 PO per mol of NH functionality
• a 21 autoclave was charged with 245.0 g hexamethylene diamine and 12.3 g water. The reactor was purged three times with nitrogen and heated to 110°C. 489.8 g propylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours at 110°C. Volatile compounds were removed in vacuo at 90°C. A viscous yellow oil (730.0 g) was obtained. 1 H-NMR in CDCl 3 indicated complete conversion.
• Example 1-b HMDA + 1 PO per mol of NH functionality + 0.25 Caprolactone per mol of NH functionality
• Example 1-c HMDA + 1 PO per mol of NH functionality + 0.25 Caprolactone per mol of NH functionality + 8 PO per mol of NH functionality
• a 2 l autoclave is filled with 139.1 g hexamethylene diamine, reacted with 1 mole caprolactone/mole and propoxylated with 12 mole propylene oxide /mole (example 6) and 0.94 g potassium tert. butoxide.
• the mixture is heated to 110°C, and the vessel is purged three times with nitrogen.
• the vessel is heated to 140°C and 418.2 g propylene oxide is added within 5 h.
• the mixture is allowed to post-react for additional 7 h at 140°C.
• the reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90°C. 556.0 g of a highly viscous brown oil is obtained (saponification value: 5.4 mgKOH/g).
• Liquid detergent composition E, F1-F4 below are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients (Table 7).
• the stain removal performance of the inventive polymers is evaluated according to the method for evaluating stain removal benefit of polymers in laundry detergent above.
• the Liquid detergent concentration is 2500ppm, fabrics are washed at 27°C for 12 minutes at 7gpg hardness, followed by 5 minutes rinse at 15°C. 11 SBL squares were added as soil to simulate consumer soil levels.
• the suds coverage is evaluated according to the method of evaluating suds.
• composition F3 and F4 show both improved cleaning and suds profile.
• Table 7 Ingredients (wt%) E (comparative) F1 (comparative) F2 (comparative) F3 (Inventive) F4 (Inventive) LAS 9.7 9.7 9.7 9.7 9.7 AES 7.0 7.0 7.0 7.0 C 12-14 EO 9 nonionic surfactant 6.1 6.1 6.1 6.1 6.1 Propylene glycol 6.0 6.0 6.0 6.0 6.0 6.0 Sodium Lauryl Sulfate 5.2 5.2 5.2 5.2 5.2 Ethanolamine 3.9 3.9 3.9 3.9 3.9 3.9 3.9 Graft Polymer Example 1 0 4.7 0 2.7 3.3 Modified polyalkyleneimine / polyamine (PAI / PA) IE1 0 0 4.7 1.2 1.4 Citric acid 2.4 2.4 2.4 2.4 2.4 2.4

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