CN117561321A

CN117561321A - Composition and method for producing the same

Info

Publication number: CN117561321A
Application number: CN202280027119.0A
Authority: CN
Inventors: A·卡明斯; 董思宇; C·W·琼斯; A·R·桑德森; 尹琴
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2021-04-15
Filing date: 2022-04-14
Publication date: 2024-02-13
Also published as: EP4323487A1; WO2022219132A1

Abstract

A surfactant comprising a C8-22 alkyl chain and a molar average of 1-40 ethoxylate units, at least one of the alkoxylate units or one of the alkyl chains comprising carbon resulting from carbon capture; and a surfactant product comprising such surfactant in a 50-95% aqueous suspension or solution.

Description

Composition and method for producing the same

The present invention relates to improved surfactants and surfactant products.

Despite the prior art, there remains a need for improved surfactants and surfactant products.

Thus, in a first aspect, there is provided a surfactant comprising a C8-22 alkyl chain and a molar average of 1-40 alkoxylate units, at least one alkoxylate unit or one alkyl chain comprising carbon resulting from carbon capture.

Surprisingly, it has been found that such surfactants have desirable fragrance performance characteristics when used in cleaning compositions. We have also found that the composition has improved foaming properties during the pre-wash stage, during the wash, and is also thicker before addition to water to form a liquid.

Improvements in fragrance performance/selection are highly desirable. Fragrance is often the most attractive sensory component of the product, and the performance behavior of the fragrance is tightly controlled to avoid excessive perfume leaving the product so that no residual perfume is deposited on the fabric during the laundering process. Insufficient fragrance leaving the product results in a lack of pleasurable feel for the product.

Improving visual effects, especially the color perception through the film when surfactants are used in water-soluble capsules, is also a sensitive formulation limiting factor. The light absorption spectrum of the product is a key factor in the color stability of the product. This can lead not only to differences in color appearance between different products (in case the different products are affected differently by external ultraviolet light (e.g. from the sun), but also to differences in physical properties, in particular physical stability.

There is a great need for ingredients that help reduce the light absorption of the composition at about 335-400nm in the product.

For surfactant-containing products as liquid unit dosage forms, improvement of the chelating agent precipitation is also a critical issue, as chelating agents are necessary for cleaning performance, while under low moisture conditions their performance is often strictly managed to avoid chelating agent precipitation. Precipitation causes the product to become cloudy and often forms a crust on the outside of the water-soluble film used to encapsulate the product. Surfactants that can enhance the ability to be formulated with powerful cleaning ingredients are highly desirable.

Viscosity in liquid formulations is also a critical physical property that may be affected by raw material variations. Higher viscosity means improved product use confidence. There is a great need for components that can provide higher viscosities without the need to add expensive viscosity modifiers.

Preferably, the alkoxylate is a propoxylate or ethoxylate group, and either or both may be present in either surfactant material.

Preferably, the surfactant is a nonionic surfactant or an anionic surfactant.

When it is a nonionic surfactant, it preferably contains 5 to 9 EO groups. From 5 to 9 EO groups means that the molar average comes from these endpoints.

Preferably, the nonionic surfactant is an alcohol ethoxylate and the alkyl chain includes from 10 to 18 carbon atoms. Preferably, the alkyl chain is obtained from a non-fossil fuel source.

Alternatively, when the surfactant is an anionic surfactant, it is preferably an alkyl ether sulfate surfactant. Preferably, such surfactants have a molar average of 1 to 5, more preferably 1 to 3 ethoxylate groups.

Carbon capture

Carbon capture means C ₁ Carbon capture, which is primarily but not exclusively a gas, and typically carbon dioxide or carbon monoxide (both of which are referred to herein as COx). Carbon is preferably captured from waste emissions (e.g., exhaust from industrial processes, known as "point sources") or from the atmosphere. The term carbon captureFossil fuels such as crude oil, natural gas, coal or peat are used directly as the carbon source and vice versa. However, carbon may be captured from waste products produced by using fossil fuels, and thus carbon captured from waste gases of burning fossil fuels in power generation, for example. Capturing CO at point sources _x Is most effective, e.g. large fossil fuel or biomass energy facilities, natural gas power plants, with primary CO _x Discharged industries, natural gas processing, synthetic fuel plants, and fossil fuel-based hydrogen production plants. Extraction of CO from air _x It is also possible, although the CO in air is much lower than the combustion source _x Concentration presents significant engineering challenges. Preferably, the carbon is captured from a point source.

Preferably, the method for carbon is selected from biological separation, chemical separation, absorption, adsorption, gas separation membranes, diffusion, rectification, or condensation, or any combination thereof.

CO collection from air _x May use a process that physically or chemically combines CO in air _x Is a solvent of (a) and (b). Solvents include strong alkaline hydroxide solutions such as sodium hydroxide and potassium hydroxide. Hydroxide solutions in excess of 0.1 molar concentration can readily remove CO from air _x . Higher hydroxide concentrations are desirable and efficient air contactors use more than 1 mole of hydroxide solution. Sodium hydroxide is a particularly convenient choice, but other solvents may also be of interest. In particular, similar processes can also be used for organic amines. Examples of carbon capture include amine washes in which CO is contained _x Through liquid amine to absorb most of CO _x . The carbon-rich gas is then pumped away. Preferably, the CO is collected from air _x The process of (2) may use a solvent selected from sodium hydroxide, potassium hydroxide or an organic amine.

Carbon capture may include post-combustion capture, whereby CO is removed from "flue" gas after combustion of a carbon fuel, such as a fossil fuel or a biofuel _x . The carbon capture may also be pre-combustion, whereby fossil fuels are partially oxidized, for example in a gasifier. From the resulting synthesis gas (CO and H ₂ ) CO of (c) with added steam (H) ₂ O) reaction and conversionIs CO _x And H ₂ . The CO obtained ₂ Can be captured from waste steam. The capture may be by oxy-fuel combustion carbon capture whereby the power plant burns fossil fuel in oxygen. This produces a mixture comprising mainly steam and CO _x Is a gas mixture of (a) and (b). Separation of steam and CO by cooling and compressing a gas stream ₂ 。

Preferably, the carbon is captured from the flue gas after combustion of the carbonized fossil fuel.

Carbon dioxide can be produced by providing CO ₂ Absorbing liquid and removing it from the atmosphere or ambient air. CO is then recovered from the liquid ₂ For use. Electrochemical methods can be used to recover carbon dioxide from an alkaline solvent for carbon dioxide capture of air, as described in US 2011/108421. Alternatively, captured CO ₂ Can be captured as a solid or liquid, for example as bicarbonate, carbonate or hydroxide, from which CO is extracted using well known chemical methods ₂ 。

Transformation

The carbon may be stored temporarily prior to use or used directly. The captured carbon undergoes a process of conversion to a chemical product.

The captured carbon may be converted into, for example, by biological or chemical means

1. Short chain intermediates, such as short chain alcohols.

2. Hydrocarbon intermediates, such as hydrocarbon chains: alkanes, alkenes, and the like.

These can be further converted into using well known chemistry, such as chain growth reactions, etc: long chain olefins/olefins (olefns), alkanes, long chain alcohols, aromatics, and ethylene, ethylene oxide, which is an excellent starting chemical for the various ingredients in the detergent composition, to produce components in the surfactant.

Preferably, the captured carbon is converted to ethylene or ethylene oxide.

Various transformation pathways through such intermediates are possible. Preferably, the captured carbon is converted by a method selected from the group consisting of: chemical conversion to ethanol by a fischer-tropsch process using a hydrogen catalyst, using a catalyst of copper nanoparticles embedded in carbon spikes (carbon spikes); reverse burning of sunlight-thermochemical alkane; or bioconversion, such as fermentation. One suitable example of conversion is a process in which a reactor converts carbon dioxide, water and electricity into methanol or ethanol and oxygen. Examples of such processes are provided by Opus 12WO21252535, WO17192787, WO20132064, WO20146402, WO19144135 and WO 20112919.

1.CO ₂ Or CO can be reacted with H using a metal catalyst ₂ Is chemically converted to liquid hydrocarbons by the fischer-tropsch (FT) reaction. CO may be captured as CO or converted to carbon monoxide by a reverse water gas shift reaction. The FT reaction is gas-based, thus solid C ₁ The carbon source may need to be gasified (the product of which is commonly referred to as "syngas". This name comes from its use as an intermediate in the production of Synthetic Natural Gas (SNG).

2. CO may be converted using a catalyst of copper nanoparticles embedded in carbon pins ₂ Chemical conversion to ethanol.

3. The reverse combustion reaction of sunlight-thermochemical alkane is to utilize a photo-thermochemical flow reactor to make CO ₂ And a one-step conversion of water to oxygen and hydrocarbons.

4. Bioconversion-biocontrol organisms convert carbon into useful chemicals NB. This does not involve plants photosynthesizing CO ₂ Biological sealing and natural process with plant as material. Bioconversion as used herein means the utilization of an organism to produce a desired feedstock (e.g., a short chain alcohol).

Preferably, bioconversion comprises passing a microorganism such as C ₁ Immobilizing bacteria will C ₁ Carbon is fermented into useful chemicals. The fermentation is preferably a gas fermentation (C ₁ The raw materials are in the form of gas).

There are a variety of microorganisms that can be used in fermentation processes, including anaerobic bacteria, such as clostridium immortalnii (Clostridium ljungdahlii) strain PETC or ERI2, etc. (see, e.g., U.S. patent No. 5,173,429;5,593,886 and 5,821,111; and references cited therein; see also WO 98/00558. WO 00/68407 discloses Clostridium immortalized strains for the production of ethanol.

The ability of microorganisms to grow CO as the sole carbon source was first discovered in 1903. This was later identified as a property of organisms using the autotrophic long acetyl-CoA (acetyl CoA) biochemical pathway (also known as the Woods-Ljungdahl pathway and the carbon monoxide dehydrogenase/acetyl CoA synthase (CODH/ACS) pathway). A large number of anaerobic organisms, including carboxydotrophic, photosynthetic, methanogenic and acetogenic organisms, have been demonstrated to metabolize CO into various end products, namely CO ₂ 、H ₂ Methane, n-butanol, acetate and ethanol. When CO is used as the sole carbon source, all of these organisms produce at least two of these end products.

Anaerobic bacteria, such as those from the genus clostridium, have been demonstrated to be biochemically derived from CO, via the acetyl CoA biochemical pathway ₂ And H ₂ Ethanol is produced. For example, various strains of Clostridium immortalized bacteria that produce ethanol from a gas are described in WO 00/68407, EP 117309, U.S. Pat. Nos. 5,173,429, 5,593,886 and 6,368,819, WO 98/00558 and WO 02/08438. Clostridium ethanogenum bacteria are also known to produce ethanol from gas (Abrini et al Archives of Microbiology 161, pp 345-351 (1994)).

The process may further comprise a catalytic hydrogenation module. In embodiments using a catalytic hydrogenation module, the acid gas depleted stream is passed to a catalytic hydrogenation module and then to a deoxygenation module, wherein at least one component from the acid gas depleted stream is removed and/or converted prior to being passed to the deoxygenation module. At least one component removed and/or converted by the catalytic hydrogenation module is acetylene (C ₂ H ₂ )。

The process may include at least one additional module selected from: particulate removal modules, chloride removal modules, tar removal modules, hydrogen cyanide removal modules, additional acid gas removal modules, temperature modules, and pressure modules.

Further examples of carbon capture techniques suitable for producing ethanol feedstocks for the manufacture of ethoxy subunits for use in surfactants described herein are described in WO 2007/117157, WO 2018/175481, WO 2019/157519 and WO 2018/231948.

Preparation of alkyl groups

The C8-22 alkyl chain of the surfactant, whether alcohol ethoxylate or alkyl ether sulfate, is preferably obtained from a renewable source, such as carbon capture, and preferably from a triglyceride if not from, or in addition to, the carbon capture source. Renewable sources refer to sources in which the material is produced by natural ecological cycle of living species, preferably by plants, algae, fungi, yeast or bacteria, more preferably by plants, algae or yeast.

Preferred vegetable oil sources are rapeseed, sunflower, corn (size), soybean, cottonseed, olive oil and tree. The oil from trees is known as tall oil. Most preferably, the sources are palm oil and rapeseed oil.

Algae oil is discussed in energy 2019,12,1920Algal Biofuels:Current Status and Key Challenges by Saad m.g. et al. Masri M.A. et al describe methods for producing triglycerides from biomass using yeast in Energy environment.Sci., 2019,12,2717A sustainable,high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents.

Non-edible vegetable oils may be used and are preferably selected from the fruits and seeds of the following plants: jatropha curcas (Jatropha curcas), calophyllum, sterculia nobilis (Sterculia feotida), cercis indicus (Madhuca indica) (cercis latifolia (mahua)), cercis fumosorosea (Pongamia glabra) (koroch seeds), flaxseed, pongamia pinnata (kangamia pinnata) (kalan Gu Shu (karanja)), rubber tree (Hevea brasiliensis) (rubber seeds), neem tree (Azadirachta indica) (neem), camelina sativa), lesquerella fendleri, tobacco (Nicotiana tabacum) (tobacco), kenaf (Deccan hemp), castor (Ricinus com l.) (castor), cerus oiliness (Simmondsia chinensis) (jojojoba)); sesame seed (Eruca sativa.l.), lime tree (Cerbera odola) (Cerbera mango), coriander (Coriandrum sativum l.), crotylon (Croton megalocarpus), pilu, cranberry (Crambe), clove (syringa), jujuba (Scheleichera triguga) (kusum), black-bone mortar (stillgia), salsa (shore robusta) (sal), fructus Terminaliae (Terminalia belerica roxb), calyx-flos (Cuphea), camellia (Camellia), gardenia (Champaca), quassia (Simarouba glauca), garcinia cambogia (Garcinia indica), rice bran, hingan (balanite), olea (Desert date), citrus grandis (degermine), cynara scolymus (cardon), calamus syringae (Asclepias syriaca) (Milk grass (Milkwet)), semen Abutili (Guizotia abyssinica), etsuba mustard (Radish Ethiopian mustard), jin Shankui (Syagrus), tung tree (Tung), idesia polycarpa var. Velutina, algae, argemone mexicana (Argemone mexicana L.) (Mexico poppy (Mexican prickly poppy)), rumex pseudolites (Putranjiva roxburghii) (lucky bean tree), sapindus mukurossi (Sapindus mukorossi) (Soapnut), chinaberry (M.azedarach) (syringe), oleander (Thevettia peruviana) (yellow oleander), yellow wine cup flower (Copaiba), white Milk wood (Milk), bay (Laurel), semen Pisi Sativi (Cumaru), sophora davidiana (Andioica), brassica napus (B.napus), zanthoxylum bungeanum (Zanthoxylum bungeanum).

Preparation of surfactants

Ethanol produced by the carbon capture process is used to produce ethoxy subunits and together with the appropriate alkyl chains form the desired surfactant. When sulfonation is desired, for example for the formation of anionic surfactants such as alkyl ether sulfates, this is likewise in accordance with standard procedures.

In the first step, ethanol (C ₂ H ₅ OH) is dehydrated to ethylene (C ₂ H ₄ ) And this is a common industrial process.

Ethylene is then oxidized to form ethylene oxide (C ₂ H ₄ O)。

Finally, ethylene oxide is reacted with a long chain alcohol (e.g., a C12/14 type fatty alcohol) via a polymerization type reaction. This process is commonly referred to as ethoxylation and produces a surfactant known as alcohol ethoxylate and which is a nonionic surfactant.

By sulfonating these alcohol ethoxylates, alkyl ether sulfate anionic surfactants may be formed.

Alkoxylate units

The surfactant according to the invention comprises on average 1 to 40 alkoxylation units on a molar basis.

The alkoxylate units in the surfactant may be selected from ethoxylate units, propoxylate (propylene oxide) units, or the surfactant may comprise a combination of ethoxylate units, propoxylate (propylene oxide) units.

If propoxylated is present, the average degree of propoxylation is preferably between 1 and 25, more preferably between 2 and 20, most preferably between 5 and 10.

In a preferred embodiment, the surfactant is the reaction product of a higher linear alcohol with a mixture of ethylene oxide and propylene oxide, comprising a mixed chain of ethylene oxide and propylene oxide terminated with hydroxyl groups.

When mixed alkoxylate groups are present, the alkoxy groups may be randomly ordered or present in blocks, preferably in blocks. For example, the mixed Ethoxy (EO)/Propoxy (PO) groups may be ordered as EO/PO blocks, PO/EO blocks, EO/PO/EO blocks, or PO/EO/PO blocks.

The alkoxylate units in the surfactant may be present in the form of block copolymers. Preferably, the block copolymer has at least one Polyoxypropylene (PO) block and at least one other polyoxyethylene (EO) block is attached to the Polyoxypropylene (PO) block. Additional polyoxyethylene or polyoxypropylene blocks may be present in the molecule. These are nonionic surfactants.

Particularly useful polyoxypropylene-polyoxyethylene block copolymers are those comprising a central block of polyoxypropylene units and blocks of polyoxyethylene units located on each side of the central block. Those comprising a central block of polyoxyethylene units and blocks of polyoxypropylene units on each side of the central block are also suitable.

PO preparation

The alkoxylate units in the surfactant may preferably comprise at least one propoxylate unit (PO) comprising carbon atoms resulting from carbon capture. More preferably, at least 50% of the propoxylate groups, particularly preferably at least 70% of the propoxylate groups comprise carbon atoms resulting from carbon capture, most preferably all of the propoxylate groups present in the surfactant comprise carbon atoms resulting from carbon capture.

Preferably, less than 90%, preferably less than 10%, of the propylene oxide groups contain carbon atoms obtained from fossil fuel-based sources.

Preferably, more than 10%, preferably more than 90%, of the propylene oxide groups contain carbon atoms obtained from a source based on carbon capture.

Preparation of EO

The ethoxylate units in the surfactant comprise at least one ethoxylate having carbon atoms that have been captured from carbon. More preferably, at least 50%, particularly preferably at least 70% of the ethoxylate groups comprise carbon atoms resulting from carbon capture, and most preferably all ethoxylate groups present in the nonionic surfactant comprise carbon atoms resulting from carbon capture.

Preferably, the ethoxylate units in the surfactant include at least one ethoxylate having two carbon atoms that are captured from carbon. More preferably, at least 10%, particularly preferably at least 70% of the ethoxylate groups contain two carbon atoms resulting from carbon capture, most preferably all ethoxylate groups present in the nonionic surfactant contain two carbon atoms resulting from carbon capture.

Preferably, less than 90%, preferably less than 10%, of the ethoxylate groups comprise carbon atoms obtained from fossil fuel-based sources.

Preferably, greater than 10%, more preferably greater than 90%, of the ethoxylate groups comprise carbon atoms obtained from sources based on carbon capture.

The surfactant is preferably disposed in the detergent composition. More preferably laundry liquid compositions, powder detergent compositions, liquid hand dishwashing compositions, and the like. When the composition is a laundry liquid, it is preferably a liquid unit dose composition. Preferably, such a composition is contained in a water-soluble pouch. Preferably, the pouch has one to four compartments. Preferably, the pouch is a unit dose product and may weigh from 10 to 50g to represent a unit dose.

When the surfactant is placed in a laundry liquid composition, it is preferred that the composition comprises from 50 to 95% by weight of the composition of water. More preferably, the composition comprises 70% to 90% water. On the other hand, when the composition is a unit dose liquid laundry composition and it is held in a water-soluble capsule, it is preferred that the water is 0-15% by weight of the unit dose product.

However, the composition may also be a gel, a powder, or a liquid. When the product is a liquid, it may be a dilutable composition or an automatic feed composition. An automatic-feeding composition is a composition contained in a cartridge or similar container and dispensed from the washing machine when needed.

If the product is dilutable, it means that the consumer can purchase the concentrated product and bring the concentrated product home, which can be diluted at home to form a conventional liquid laundry product. Dilution may require any amount of 1 part concentrate 1-10 parts water.

Alcohol ethoxylates

The surfactant preferably comprises a nonionic surfactant. Preferably, the composition comprises from 0.1 to 50 wt% of nonionic surfactant, based on the total weight of the composition. Such nonionic surfactants include, for example, the reaction products of polyoxyalkylene compounds, i.e., alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having hydrophobic groups and active hydrogen atoms reactive with the alkylene oxides. Such starter molecules include alcohols, acids, amides or alkylphenols. In the case where the starting molecule is an alcohol, the reaction product is referred to as an alcohol alkoxylate. The polyoxyalkylene compounds may have a variety of block and mixed (random) structures. For example, they may comprise a single alkylene oxide block, or they may be diblock alkoxylates or triblock alkoxylates. Within the block structure, the blocks may be all ethylene oxide or all propylene oxide, or the blocks may contain a hybrid of alkylene oxides And (3) a mixture. Examples of such materials include C ₈ To C ₂₂ Alkylphenol ethoxylates, wherein there are an average of 5 to 25 moles of ethylene oxide per mole of alkylphenol; and aliphatic alcohol ethoxylates such as C ₈ -C ₁₈ Linear or branched primary or secondary alcohol ethoxylates having an average of 2 to 40 moles of ethylene oxide per mole of alcohol.

Preferred further classes of nonionic surfactants for use in the present invention include aliphatic C ₁₂ -C ₁₅ Linear primary alcohol ethoxylates having an average of from 3 to 20, more preferably from 5 to 10, moles of ethylene oxide per mole of alcohol.

The alcohol ethoxylate may be provided as a single feed component or as a mixture of components.

Anionic surfactants

Anionic surfactants are described in H.W. Stache edited Anionic Surfactants Organic Chemistry (Surfactant Science Series Volume) 1996 (Marcel Dekker).

The non-soap anionic surfactants useful in the present invention are typically salts of organic sulfuric and sulfonic acids having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, alpha olefin sulfonates, and mixtures thereof. The alkyl group preferably contains 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates may contain from 1 to 10 ethylene oxide or propylene oxide units per molecule, preferably from 1 to 3 ethylene oxide units per molecule. The counter ion of the anionic surfactant is typically an alkali metal such as sodium or potassium; or an ammonia counterion such as Monoethanolamine (MEA), diethanolamine (DEA), or Triethanolamine (TEA). Mixtures of such counterions can also be used. Sodium and potassium are preferred.

The surfactant-containing compositions of the present invention may include alkylbenzenesulfonates, particularly Linear Alkylbenzenesulfonates (LAS) having alkyl chain lengths of 10 to 18 carbon atoms. Commercially available LAS is a mixture of closely related isomers and homologs of alkyl chains, each containing an aromatic ring sulfonated in the "para" position and attached to the linear alkyl chain at any position other than the terminal carbon. The straight alkyl chain typically has a chain length of 11 to 15 carbon atoms, with the primary material having a chain length of about C12. Each alkyl chain homolog consists of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is typically formulated into the composition in the form of an acid (i.e., HLAS), and then at least partially neutralized in situ.

Some alkyl sulfate surfactants (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulfates having alkyl chain lengths of 10-18.

Mixtures of any of the above materials may also be used.

Commonly used in laundry liquid compositions and dish cleaning compositions are alkyl ether sulfates having a linear or branched alkyl chain of 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is Sodium Lauryl Ether Sulphate (SLES), in which predominantly C12 lauryl alkyl groups are ethoxylated with an average of 3EO units per molecule mole.

The alkyl ether sulfate may be provided as a single feed component or as a mixture of components.

Modern carbon percentage

Modern carbon percentage (pMC) levels are based on measuring the level of radioactive carbon produced in the upper atmosphere in which radioactive carbon (C14) diffuses, providing a general background level in air. Once captured (e.g., by biomass), the level of C14 decreases over time in a manner such that the amount of C14 is substantially depleted after 45,000 years. Thus, the level of fossil-based carbon C14 used in the traditional petrochemical industry is almost zero.

A pMC value of 100% biobased carbon or biogenic carbon indicates that 100% of the carbon is from plant or animal byproducts (biomass) living in natural environments (or as captured from air), and a value of 0% means that all carbon is derived from petrochemical, coal, and other fossil sources. Values between 0 and 100% indicate mixtures. The higher the value, the greater the proportion of components of natural origin in the material, although this may include carbon captured from the air.

pMC levels can be determined using% biobased carbon content ASTM D6866-20 method B using the American national standards and technology Association (NIST) modern reference standard (SRM 4990C). Such measurements are known in the art and are commercially made, for example by Beta analytical inc (USA). The art of measuring C14 carbon levels has been known for decades and is mostly known from archaeological organic findings of carbon year assays.

In one embodiment, the composition comprising at least one ethoxylate unit and at least one carbon capture source carbon comprises carbon from a point source carbon capture. Preferably, these ingredients have a pMC of 0 to 10%.

In an alternative embodiment, the composition comprising at least one ethoxylate unit and at least one carbon derived from carbon capture contains carbon from direct air capture. Preferably, these ingredients have a pMC of 90 to 100%.

Liquid laundry detergent compositions

When formulating liquid detergent compositions, the following components may be mixed with the surfactant according to the present invention.

Fatty acid

Preferably, the fatty acid is present in an amount of from 4 to 20% by weight of the composition (measured with reference to the acid added to the composition), more preferably from 5 to 12% by weight, most preferably from 6 to 8% by weight.

Suitable fatty acids in the context of the present invention include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight or branched alkyl or alkenyl chain containing from 6 to 24, more preferably from 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric, myristic, palmitic or stearic acid; and fatty acid mixtures wherein 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. These mixtures may generally be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

The fatty acids may be present in the form of their sodium, potassium, ammonium salts and/or in the form of soluble salts of organic bases such as monoethanolamine, diethanolamine or triethanolamine.

Mixtures of any of the above materials may also be used.

For formulation calculation purposes, fatty acids and/or salts thereof (as defined above) are not included in the formulation at the level of surfactant or at the level of adjuvants.

Chelating agent

Preferably, the detergent composition may further comprise a chelating agent material. Examples include alkali metal citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetylcarboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid. Other examples are DEQUEST ^TM Chelating agents of the type organic phosphonates sold by Monsanto, and alkane hydroxy phosphonates.

The preferred chelating agents are Dequest (R) 2066 (diethylenetriamine penta (methylenephosphonic acid) or heptasodium DTPMP). Preferably, HEDP (1-hydroxyethylidene-1, 1-diphosphonic acid) is absent.

In a preferred embodiment, the composition comprises a fatty acid and a chelating agent.

Preservative agent

Food preservatives are discussed in Food Chemistry (beltz h. -d., grosch w., schieberle), 4 th edition Springer.

The formulation contains a preservative or a mixture of preservatives selected from benzoic acid and salts thereof, alkyl esters of parahydroxybenzoic acid and salts thereof, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and salts thereof, most preferably sodium benzoate. The preservative is present at 0.01 to 3 wt%, preferably 0.3 wt% to 1.5 wt%. The weight was calculated in protonated form.

Cleaning polymers

The anti-redeposition polymer stabilizes the soil in the wash liquor, thereby preventing redeposition of the soil. Suitable de-wrinkling for use in the present inventionSoil polymers include alkoxylated polyethyleneimines. The polyethyleneimine is composed of ethyleneimine units-CH ₂ CH ₂ NH-and when branched, hydrogen on the nitrogen is replaced by a chain of another ethyleneimine unit. Preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (M) of from about 300 to about 10000 _w ) Polyethylene imine backbone of (a). The polyethyleneimine backbone may be linear or branched. It can be branched to the extent that it is a dendrimer. Alkoxylation may generally be ethoxylation or propoxylation, or a mixture of both. When the nitrogen atom is alkoxylated, the preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25, alkoxy groups per modification. A preferred material is an ethoxylated polyethyleneimine wherein the average degree of ethoxylation of each ethoxylated nitrogen atom in the polyethyleneimine backbone is from 10 to 30, preferably from 15 to 25 ethoxy groups.

Mixtures of any of the above materials may also be used.

Preferably, the compositions of the present invention comprise from 0.025% to 8% by weight of one or more anti-redeposition polymers, such as the alkoxylated polyethylenimine described above.

Soil release polymers

Soil release polymers help improve the release of soil from fabrics by modifying the surface of the fabrics during the laundering process. Adsorption of the SRP on the fabric surface is facilitated by the affinity between the chemical structure of the SRP and the target fiber.

SRPs useful in the present invention may include a variety of charged (e.g., anionic) as well as uncharged monomeric units, and may be linear, branched, or star-shaped in structure. The SRP structure may also include end capping groups to control molecular weight or to alter polymer properties such as surface activity. Weight average molecular weight (M) of SRP _w ) May suitably be in the range of from about 1000 to about 20,000, preferably in the range of from about 1500 to about 10,000.

The SRP used in the present invention may be suitably selected from copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid, or terephthalic acid), glycols (e.g., ethylene glycol or propylene glycol), and polyglycols (e.g., polyethylene glycol or polypropylene glycol). The copolyester may also include monomer units substituted with anionic groups, such as sulfonated isophthaloyl units. Examples of such materials include oligoesters produced by transesterification/oligomerization of poly (ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and poly (ethylene glycol) ("PEG"); partially and fully anionically blocked oligoesters, such as oligomers from ethylene glycol ("EG"), PG, DMT, and Na-3, 6-dioxa-8-hydroxyoctanesulfonate; nonionic blocked block polyester oligomeric compounds, such as those prepared from DMT, me-blocked PEG and EG and/or PG, or combinations of DMT, EG and/or PG, me-blocked PEG and Na-dimethyl-5-sulfoisophthalate, and copolymerized blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate.

Other types of SRPs useful in the present invention include cellulose derivatives, such as hydroxyether cellulose polymers, C ₁ -C ₄ Alkyl cellulose and C ₄ Hydroxyalkyl cellulose; polymers having hydrophobic segments of poly (vinyl esters), e.g. graft copolymers of poly (vinyl esters), e.g. C grafted onto polyalkylene oxide backbones ₁ -C ₆ Vinyl esters (e.g., poly (vinyl acetate)); poly (vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam and polyethylene glycol.

Preferred SRPs for use in the present invention include copolyesters formed by the condensation of terephthalic acid esters and diols, preferably 1, 2-propanediol, and also include end-caps formed from repeating units of an alkyl-terminated alkylene oxide. Examples of such materials have a structure corresponding to the general formula (I):

wherein R is ¹ And R is ² X- (OC) independently of one another ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m ；

Wherein X is C _1-4 Alkyl, and preferably methyl;

n is a number from 12 to 120, preferably from 40 to 50;

m is a number from 1 to 10, preferably from 1 to 7; and

a is a number from 4 to 9.

Since they are average values, m, n and a are not necessarily integers for the overall polymer.

Mixtures of any of the above materials may also be used.

When included, the overall level of SRP may be in the range of 0.1 to 10%, depending on the level of polymer intended for use in the final diluted composition, and it is desirably 0.3 to 7%, more preferably 0.5 to 5% (by weight based on the total weight of the diluted composition).

Suitable soil release polymers are described in more detail in U.S. Pat. nos. 5,574,179;4,956,447;4,861,512;4,702,857, WO2007/079850 and WO 2016/005271. If used, the soil release polymer is typically incorporated into the liquid laundry detergent compositions herein at a concentration in the range of from 0.01% to 10%, more preferably from 0.1% to 5% by weight of the composition.

Hydrotropic substance

The compositions of the present invention may incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids, such as C1 to C5 monohydric alcohols (e.g., ethanol and n-propanol or isopropanol); c2 to C6 diols (such as monopropylene glycol and dipropylene glycol); c3 to C9 triols (such as glycerol); weight average molecular weight (M) _w ) Polyethylene glycol in the range of about 200 to 600; c1 to C3 alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (e.g., sodium and potassium xylenes, toluene, ethylbenzene, and cumene (cumene) sulfonates).

Mixtures of any of the above materials may also be used.

Preferably, a non-aqueous carrier is included, which may be present in an amount ranging from 1 to 50%, preferably from 10 to 30%, more preferably from 15 to 25% (by weight based on the total weight of the composition). The level of hydrotrope used is related to the level of surfactant, and it is desirable to use hydrotrope levels to control the viscosity of these compositions. Preferred hydrotropes are monopropylene glycol and glycerol.

Cosurfactant

In addition to the non-soap anionic and/or nonionic detersive surfactants described above, the compositions of the present invention may comprise one or more cosurfactants (e.g., amphoteric (zwitterionic) and/or cationic surfactants).

Specific cationic surfactants include C8-C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof. When included, the cationic surfactant may be present in an amount ranging from 0.1 to 5% by weight based on the total weight of the composition.

Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkylamidopropylbetaines, alkyl sulfobetaines (sulfobetaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycinates, alkylamidopropylhydroxysulfobetaines, acyl taurates, and acyl glutamates having an alkyl group containing from about 8 to about 22 carbon atoms, preferably selected from the group consisting of C12, C14, C16, C18, and C18:1, the term "alkyl" being used for alkyl moieties including higher acyl groups. When included, the amphoteric (zwitterionic) surfactant can be present in an amount ranging from 0.1 to 5% by weight, based on the total weight of the composition.

Mixtures of any of the above materials may also be used.

Fluorescent agent

It may be advantageous to include a fluorescent agent in the composition. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts (e.g., sodium salts). The total amount of the one or more fluorescent agents used in the composition is typically from 0.005 to 2% by weight of the composition, more preferably from 0.01 to 0.5% by weight.

Preferred classes of fluorescent agents are: distyrylbiphenyl compounds, e.g.CBS-X, diamine stilbenedisulfonic acid compounds, e.g. Tinopal DMS pure Xtra, tinopal 5BMGX and +.>HRH, and pyrazoline compounds, such as Blankophor SN.

Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d ] triazoles, disodium 4,4' -bis { [ (4-anilino-6- (N-methyl-N-2-hydroxyethyl) amino-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' -disulfonate, disodium 4,4' -bis { [ (4-anilino-6-morpholino-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' -disulfonate and disodium 4,4' -bis (2-sulfonylstyryl) biphenyl.

Most preferably, the fluorescent agent is a distyrylbiphenyl compound, preferably sodium 2,2' - ([ 1,1' -biphenyl ] -4,4' -diylbis (ethylene-2, 1-diyl)) diphenylsulfonate (CAS No 27344-41-8).

Shading dye

Hueing dyes may be used to improve the performance of the composition. Preferred dyes are violet or blue. It is believed that the low level of these hues of dye deposited on the fabric masks the yellowing of the fabric. Another advantage of hueing dyes is that they can be used to mask any yellow hue in the composition itself.

Hueing dyes are well known in the art of laundry liquid formulations.

Suitable and preferred dye classes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes, and dye conjugates. Preferred examples are disperse violet 28, acid violet 50, anthraquinone dyes covalently bonded to ethoxylated or propoxylated polyethylenimine as described in WO2011/047987 and WO2012/119859, alkoxylated monoazothiophenes, dyes of CAS-No72749-80-5, acid blue 59 and phenazine dyes selected from the group consisting of:

wherein:

X ₃ selected from: -H, -F, -CH ₃ 、-C ₂ H ₅ 、-OCH ₃ and-OC ₂ H ₅ ；

X ₄ Selected from: -H, -CH ₃ 、-C ₂ H ₅ 、-OCH ₃ and-OC ₂ H ₅ ；

Y ₂ Selected from: -OH, -OCH ₂ CH ₂ OH、-CH(OH)CH ₂ OH、-OC(O)CH ₃ And C (O) OCH ₃ ；

Alkoxylated thiophene dyes are discussed in WO2013/142495 and WO 2008/087497.

The hueing dye is preferably present in the composition in the range of 0.0001 to 0.1% by weight. Depending on the nature of the hueing dye, there is a preferred range of efficacy depending on the hueing dye, which depends on the species and the particular efficacy within any particular species.

External structurants

The composition of the present invention may further alter its rheology by using one or more external structurants that form a structural network within the composition. Examples of such materials include hydrogenated castor oil, microfibrillated cellulose and citrus pulp fibers. The presence of the external structurant may provide shear thinning rheology and may also provide for stable suspension of materials such as encapsulates and visual cues in the liquid.

Enzymes

The compositions of the present invention may comprise an effective amount of one or more enzymes selected from pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present together with the corresponding enzyme stabilizers.

Spice

Perfumes are well known in the art and are preferably added to the compositions described herein at levels of 1 to 5% by weight.

Preferably, the perfume component is selected from the group of benzene, toluene, xylene (BTX) feedstock. More preferably, the perfume component is selected from the group consisting of 2-phenylethanol, colestyl alcohol and mixtures thereof.

Preferably, the perfume component is selected from the cyclododecanone raw material class. More preferably, the perfume component is halololide.

Preferably, the perfume component is selected from the class of phenolic raw materials. More preferably, the perfume component is hexyl salicylate.

Preferably, the perfume component is selected from the class of heterocyclic moiety starting materials containing C5 modules or oxygen. More preferably, the perfume component is selected from gamma decalactone, methyl dihydrojasmonate, and mixtures thereof.

Preferably, the perfume component is selected from the class of terpene raw materials. More preferably, the fragrance component is selected from the group consisting of dihydromyrcenol, linalool, terpineol, camphor, citronellol, and mixtures thereof.

Preferably, the perfume component is selected from the class of alkyl alcohol raw materials. More preferably, the perfume component is ethyl-2-methylbutyrate.

Preferably, the perfume component is selected from the diacid raw material class. More preferably, the perfume component is ethylene glycol brazilate.

Preferably, the perfume component described above is present in the final detergent composition in an amount of from 0.0001 to 1% by weight of the composition.

Microcapsule

One type of microparticle suitable for use in the present invention is a microcapsule. Microencapsulation can be defined as a process of surrounding or encapsulating one substance within another substance on a very small scale, resulting in capsules ranging in size from less than one micron to several hundred microns. The encapsulated material may be referred to as a core, active ingredient or agent, filler, payload, core or internal phase. The material that encapsulates the core may be referred to as a coating, film, shell or wall material.

Microcapsules typically have at least one generally spherical continuous shell surrounding a core. The shell may contain holes, voids or interstitial openings depending on the materials and encapsulation techniques employed. The multiple shells may be made of the same or different encapsulating materials and may be arranged in layers of different thickness around the core. Alternatively, the microcapsules may be asymmetrically and variably shaped and a quantity of smaller droplets of core material embedded throughout the microcapsules.

The shell may have a barrier function that protects the core material from the environment outside the microcapsule, but it may also be used as a means of modulating the release of the core material, such as perfume. Thus, the shell may be water-soluble or water-swellable and may initiate perfume release in response to exposure of the microcapsules to a humid environment. Similarly, if the shell is temperature sensitive, the microcapsules may release a fragrance in response to an elevated temperature. The microcapsules may also release a perfume in response to shear forces applied to the surface of the microcapsules.

A preferred type of polymeric microparticles suitable for use in the present invention are polymeric core-shell microcapsules in which at least one continuous shell of polymeric material of generally spherical shape surrounds a core containing a fragrance formulation (f 2). The shell generally comprises up to 20% by weight of the total weight of the microcapsule. The perfume formulation (f 2) generally comprises from about 10% to about 60% by weight, preferably from about 20% to about 40% by weight of the total weight of the microcapsules. The amount of perfume (f 2) can be determined by taking a slurry of microcapsules, extracting into ethanol and measuring by liquid chromatography.

The polymeric core-shell microcapsules used in the present invention may be prepared using methods known to those skilled in the art such as coacervation, interfacial polymerization, and polycondensation.

The agglomeration process typically involves encapsulation of a core material, which is typically insoluble in water, by precipitation of colloidal substances on the surface of the droplets. Agglomeration may be simple, for example, using one colloid, such as gelatin, or may be complex, wherein two or possibly more oppositely charged colloids, such as gelatin and acacia or gelatin and carboxymethylcellulose, are used under carefully controlled pH, temperature and concentration conditions.

Interfacial polymerization generally proceeds with the formation of a fine dispersion of oil droplets (oil droplets containing the core material) in an aqueous continuous phase. The dispersed droplets form the core of the future microcapsules and the size of the dispersed droplets directly determines the size of the subsequent microcapsules. Microcapsule shell forming materials (monomers or oligomers) are contained in a dispersed phase (oil droplets) and an aqueous continuous phase and react together at the phase interface to build up a polymer wall around the oil droplets, encapsulating the droplets and forming core-shell microcapsules. An example of a core-shell microcapsule prepared by this method is a polyurea microcapsule having a shell formed by the reaction of a diisocyanate or polyisocyanate with a diamine or polyamine.

Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of a precondensate of the polymeric material under suitable agitation conditions to produce capsules of the desired size, and adjusting the reaction conditions to cause polycondensation of the precondensate by acid catalysis, resulting in the condensate separating from the solution and surrounding the dispersed core material to produce a coacervate film and the desired microcapsules. Examples of core-shell microcapsules produced by this method are aminoplast microcapsules having a shell formed from melamine (2, 4, 6-triamino-1, 3, 5-triazine) or the polycondensation product of urea and formaldehyde. Suitable crosslinkers (e.g., toluene diisocyanate, divinylbenzene, butanediol diacrylate) may also be used, and secondary wall polymers such as polymers and copolymers of anhydrides and derivatives thereof, particularly maleic anhydride, may also be suitably used.

One example of a preferred polymeric core-shell microcapsule for use in the present invention is an aminoplast microcapsule having an aminoplast shell surrounding a core containing a fragrance formulation (f 2). More preferably, such aminoplast shells are formed from the polycondensation product of melamine and formaldehyde.

The polymer microparticles suitable for use in the present invention typically have an average particle size of 100 nanometers to 50 micrometers. Particles larger than this size fall into the visible range. Examples of particles in the submicron range include latices and microemulsions having typical size ranges of 100 to 600 nanometers. The preferred particle size range is in the micrometer range. Examples of particles in the micrometer range include polymeric core-shell microcapsules (such as those further described above) having a typical size range of 1 to 50 micrometers, preferably 5 to 30 micrometers. The average particle size can be determined by light scattering using Malvern Mastersizer, with the average particle size being taken as the median particle size D (0.5) value. The particle size distribution may be narrow, broad or multimodal. The initially produced microcapsules can be filtered or screened if desired to produce a more uniform sized product.

The polymer particles suitable for use in the present invention may provide a deposition aid on the outer surface of the particles. Deposition aids are used to alter properties external to the particles, for example, to make the particles more compatible with the desired substrate. Desirable substrates include cellulose (including cotton) and polyester (including those used to make polyester fabrics).

The deposition aid may suitably be provided at the outer surface of the particles by means of covalent bonding, entanglement or strong adsorption. Examples include polymeric core-shell microcapsules (such as those further described above) in which a deposition aid is attached to the exterior of the shell, preferably by covalent bonding. While it is preferred to attach the deposition aid directly to the exterior of the shell, it may also be attached to the exterior of the shell via a connecting substance.

The deposition aid for use in the present invention may be suitably selected from polysaccharides having affinity for cellulose. Such polysaccharides may be naturally occurring or synthetic and may have an inherent affinity for cellulose or may be derivatized or otherwise modified to have an affinity for cellulose. Suitable polysaccharides have a 1-4 linked beta glycan (generalized saccharide) backbone structure having at least 4, preferably at least 10 beta 1-4 linked backbone residues, such as a glucan backbone (consisting of beta 1-4 linked glucose residues), a mannan backbone (consisting of beta 1-4 linked mannose residues) or a xylan backbone (consisting of beta 1-4 linked xylose residues). Examples of these beta 1-4 linked polysaccharides include xyloglucan, glucomannan, mannan, galactomannan, beta (1-3), beta (1-4) glucan and xylan families comprising glucuronic acid xylan, arabinoxylan and glucuronic acid arabinoxylan. Preferred β1-4 linked polysaccharides for use in the present invention may be selected from xyloglucan of plant origin, such as pea xyloglucan and tamarind seed xyloglucan (TXG) (which has a β1-4 linked glucan backbone and side chains of α -D xylopyranose and β -D-galactopyranosyl- (1-2) - α -D-xylopyranose, both of which are 1-6 linked to the backbone); and galactomannans of plant origin, such as Locust Bean Gum (LBG), which has a mannan backbone consisting of mannose residues linked by β1-4 and single unit galactose side chains linked to the backbone α1-6.

Polysaccharides which can suitably attain affinity for cellulose upon hydrolysis, such as cellulose monoacetate, or modified polysaccharides having affinity for cellulose, such as hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, hydroxypropyl guar gum, hydroxyethyl ethylcellulose, and methylcellulose, are also suitable.

The deposition aid used in the present invention may also be selected from phthalate-containing polymers having affinity for polyesters. Such phthalate-containing polymers may have one or more nonionic hydrophilic segments comprising alkylene oxide groups (e.g., ethylene oxide, polyoxyethylene, propylene oxide, or polyoxypropylene groups) and one or more hydrophobic segments comprising terephthalate groups. Typically, the alkylene oxide groups will have a degree of polymerization of from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. Suitable examples of phthalate-containing polymers of this type are copolymers having random blocks of ethylene terephthalate and polyethylene oxide terephthalate.

Mixtures of any of the above materials may also be used.

Weight average molecular weight (M) of deposition aid for use in the present invention _w ) Typically in the range of about 5kDa to about 500kDa, preferably about 10kDa to about 500kDa, more preferably about 20kDa to about 300 kDa.

An example of a particularly preferred polymeric core-shell microcapsule for use in the present invention is an aminoplast microcapsule having a shell formed by polycondensation of melamine with formaldehyde, said shell surrounding a core containing a fragrance formulation (f 2), wherein a deposition aid is attached to the outside of said shell by means of covalent bonding. Preferred deposition aids are selected from the group consisting of β1-4 linked polysaccharides, in particular xyloglucans of plant origin, as further described above.

The inventors have surprisingly observed that the overall level of perfume contained in the compositions of the present invention can be reduced without sacrificing the overall perfume experience delivered to the consumer at a critical stage in the laundry process. The reduction of the total level of fragrance is advantageous for cost and environmental reasons.

Thus, the total amount of fragrance formulation (f 1) and fragrance formulation (f 2) in the compositions of the present invention suitably ranges from 0.5 to 1.4%, preferably from 0.5 to 1.2%, more preferably from 0.5 to 1%, most preferably from 0.6 to 0.9% (by weight based on the total weight of the composition).

The weight ratio of fragrance formulation (f 1) to fragrance formulation (f 2) in the composition of the invention preferably ranges from 60:40 to 45:55. Particularly good results are obtained when the weight ratio of perfume formulation (f 1) to perfume formulation (f 2) is about 50:50.

Fragrance (f 1) and fragrance (f 2) are generally added at different stages of formation of the compositions of the invention. Typically, the discrete polymeric microparticles (e.g., microcapsules) surrounding the fragrance formulation (f 2) are added as a slurry to a warm base formulation comprising the other components of the composition (e.g., surfactants and solvents). Fragrance (f 1) is typically added subsequently after the base formulation has cooled.

Further optional ingredients of the liquid composition

The surfactant-containing compositions of the present invention may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include foam enhancers, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkling agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, antistatic agents, ironing aids, colorants, pearlescers and/or opacifiers and hueing dyes. Each of these ingredients is present in an amount effective to achieve its purpose. Typically, these optional ingredients are included individually in amounts up to 5% (by weight based on the total weight of the diluted composition) and are adjusted according to the dilution ratio with water.

Many of the ingredients used in embodiments of the present invention may be derived from so-called black carbon sources or more sustainable green sources. A list of alternative sources for several of these ingredients and how they can be made into the materials described herein is provided below.

In a second aspect, there is provided a surfactant product comprising the surfactant of any preceding claim in 50-95% aqueous suspension or solution.

Granular laundry detergent compositions

Preferably, the laundry composition is a powder or granule.

The term "particulate laundry detergent" in the context of the present invention refers to free-flowing or compacted solid forms, such as powders, granules, pellets, flakes, bars, briquettes or tablets, and is intended for and capable of wetting and cleaning household garments, such as clothing, linens and other household textiles. The term "linen" is commonly used to describe certain types of clothing, including bedsheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles may include wovens, nonwovens, and knits; and may include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends.

Examples of laundry detergents include heavy duty laundry detergents used in the wash cycle of automatic washing machines, as well as finish and color-protecting detergents, such as those suitable for washing delicate laundry (e.g., those made of silk or wool) by hand or in the wash cycle of automatic washing machines.

One preferred form of the composition according to the invention is a free flowing powdered solid having a bulk (unpackaged) bulk density typically in the range of about 200 g/liter to about 1,300 g/liter, preferably about 400 g/liter to about 1,000 g/liter, more preferably about 500 g/liter to about 900 g/liter.

The particulate composition of the present invention comprises from 3 to 80%, preferably from 10 to 60%, more preferably from 15 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from the group consisting of non-soap anionic surfactants, nonionic surfactants and mixtures thereof.

In the case of granular detergent formulations, the term "detersive surfactant" refers to a surfactant that provides a detersive (i.e. cleaning) effect to laundry that is treated as part of a home laundering process.

Except for sulfated ethoxylated C as described above ₁₀ In addition to Guerbet alcohol surfactants, other non-soap anionic surfactants used in the particulate compositions are typically salts of organic sulfuric and sulfonic acids having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, alpha olefin sulfonates, and mixtures thereof. The alkyl group preferably contains 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates may contain from 1 to 10 ethylene oxide or propylene oxide units per molecule and preferably from 1 to 3 ethylene oxide units per molecule. The counter ion of the anionic surfactant is typically an alkali metal, such as sodium or potassium; or an ammonia counterion, such as Monoethanolamine (MEA), diethanolamine (DEA), or Triethanolamine (TEA). Mixtures of these counterions can also be used.

Previously, a preferred class of non-soap anionic surfactants for use in the particulate compositions included alkylbenzenesulfonates, particularly Linear Alkylbenzenesulfonates (LAS) having an alkyl chain length of 10 to 18 carbon atoms. Commercial LAS are mixtures of closely related isomers and homologs of alkyl chains, each containing an aromatic ring sulfonated in the "para" position and attached to a linear alkyl chain at any position other than the terminal carbon. The linear alkyl chain typically has a chain length of 11 to 15 carbon atoms, with the chain length of the primary material being about C12. Each alkyl chain homolog consists of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is typically formulated into the composition in the acid (i.e., HLAS) form and then at least partially neutralized in situ.

Except for sulfated ethoxylated C as described above ₁₀ In addition to the Guerbet alcohol surfactant, the particulate composition according to the present invention may contain some alkylbenzene sulfonate, but preferably the composition contains less than 5% by weight. More preferably less than 1% by weight. Most preferably less than 0.1 wt% alkylbenzene sulfonate surfactant.

Mixtures of any of the above materials may also be used.

In typical particulate compositions, the total content of non-soap anionic surfactant may suitably be in the range of 5-25% by weight (based on the total weight of the composition).

Nonionic surfactants can provide enhanced removal of very hydrophobic oily soils and cleaning of hydrophobic polyester and polyester/cotton blend fabrics.

Nonionic surfactants for use in the particulate compositions are typically polyoxyalkylene compounds, i.e., the reaction product of an alkylene oxide (e.g., ethylene oxide or propylene oxide or mixtures thereof) with a starter molecule having a hydrophobic group and an active hydrogen atom reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkylphenols. In the case where the starting molecule is an alcohol, the reaction product is referred to as an alcohol alkoxylate. The polyoxyalkylene compounds may have a variety of block and mixed (random) structures. For example, they may comprise a single alkylene oxide block, or they may be diblock alkoxylates or triblock alkoxylates. Within the block structure, the blocks may be all ethylene oxide or all propylene oxide, or the blocks may contain a hybrid mixture of alkylene oxides. Examples of such materials include C ₈ To C ₂₂ Alkylphenol ethoxylates, wherein there are an average of 5 to 25 moles of ethylene oxide per mole of alkylphenol; and aliphatic alcohol ethoxylates such as C ₈ -C ₁₈ Linear or branched primary or secondary alcohol ethoxylates having an average of 2 to 40 moles of ethylene oxide per mole of alcohol.

One preferred class of nonionic surfactants for use in the particulate compositions includes aliphatic C ₈ -C ₁₈ More preferably C ₁₂ -C ₁₅ Linear primary alcohol ethoxylates have an average of 3 to 20, more preferably 5 to 10, moles of ethylene oxide per mole of alcohol.

Mixtures of any of the above materials may also be used.

The total content of nonionic surfactant in the particulate composition may suitably be in the range of 1-10% by weight, based on the total weight of the composition.

For particle setsExamples of suitable mixtures of non-soap anionic and/or nonionic surfactants of the compounds include linear alkylbenzenesulfonates (preferably C ₁₁ -C ₁₅ Linear alkylbenzene sulfonate), if present, with sulfated ethoxylated C as described above ₁₀ Guerbet alcohol surfactant, sodium lauryl ether sulfate (C ethoxylated with preferably average 1-3 EO) ₁₀ -C ₁₈ Alkyl sulphates) and/or ethoxylated aliphatic alcohols (C ethoxylated with an average of 5-10 moles of ethylene oxide per mole of alcohol ₁₂ -C ₁₅ Linear primary alcohols).

In addition to the non-soap anionic and/or nonionic detersive surfactant described above, the particulate composition may also comprise one or more cosurfactants (e.g., amphoteric (zwitterionic) and/or cationic surfactants).

Specific cationic surfactants include C wherein one or two hydroxyethyl groups replace one or two methyl groups ₈ To C ₁₈ Alkyl dimethyl ammonium halides and derivatives thereof, and mixtures thereof. When included, the cationic surfactant is present in an amount ranging from 0.1 to 5% by weight based on the total weight of the composition.

Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sulfobetaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycinates, alkyl amidopropyl hydroxysulfobetaines, acyl taurates, and acyl glutamates having an alkyl group containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. When included, the amphoteric (zwitterionic) surfactant can be present in an amount ranging from 0.1 to 5% by weight, based on the total weight of the composition.

Preferably, the particulate composition may further comprise one or more builders. Builders are mainly used to reduce the hardness of water. This is achieved by isolation or chelation (maintaining the hardness minerals in solution), by precipitation (forming insoluble materials) or by ion exchange (exchanging charged particles). Builders can also supply and maintain alkalinity, which aids in cleaning especially acidic soils; helping to prevent redeposition of the removed soil during the washing process; and emulsifying oily and greasy soils.

The builder for the particulate composition may be of the organic or inorganic type, or mixtures thereof. Non-phosphate builders are preferred.

Inorganic non-phosphate builders for use in the particulate compositions include carbonates, silicates, zeolites and mixtures thereof.

Suitable carbonate builders for use in the particulate compositions include mixed or individual, anhydrous or partially hydrated alkali metal carbonates, bicarbonates or sesquicarbonates.

Preferably the alkali metal is sodium and/or potassium, particularly preferably sodium carbonate.

Suitable silicate builders include the amorphous and/or crystalline forms of alkali metal (e.g. sodium) silicate. Preference is given to crystalline layered sodium silicate (phyllosilicate) of the general formula (I)

NaMSi _x O _2x+1 .yH ₂ O(I)

Wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2 or 3, and y is a number from 0 to 20. Particularly preferred is sodium disilicate of the above formula wherein M is sodium and x is 2. Such materials can be prepared with different crystal structures, known as the α, β, γ and δ phases, with δ -sodium disilicate being most preferred.

The zeolite is composed of (SiO ₄ ) ^4- And (AlO) ₄ ) ^5- A naturally occurring or synthetic crystalline aluminosilicate of tetrahedral composition sharing oxygen bridge vertices and forming a cage-like structure in crystalline form. The ratio of oxygen, aluminum and silicon is O (al+si) =2:1. The frame acquires a negative charge by replacing part of the silicon with aluminum. The negative charge is neutralized by cations and under normal conditions the framework is sufficiently open to contain mobile water molecules. Suitable zeolite builders for use in the present invention may be defined by the general formula (II):

Na _x [(AlO ₂ ) _x (SiO ₂ ) _y ]·zH ₂ O(II)

Wherein x and y are integers of at least 6, the molar ratio of x to y is from about 1 to about 0.5, and z is an integer of at least 5, preferably from about 7.5 to about 276, more preferably from about 10 to about 264.

Organic non-phosphate builders suitable for use in the particulate compositions include polycarboxylic acids in acid and/or salt form. When used in salt form, alkali metal (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium salts of monosuccinic acid tartrate, sodium and potassium salts of disuccinic acid tartrate, sodium and potassium ethylenediamine tetraacetate, sodium and potassium N (2-hydroxyethyl) -ethylenediamine triacetate, sodium and potassium nitrilotriacetic acid, and sodium and potassium N- (2-hydroxyethyl) -nitrilodiacetate. Polymeric polycarboxylic acids, such as polymers of unsaturated monocarboxylic acids (e.g., acrylic acid, methacrylic acid, ethylene acetic acid, and crotonic acid) and/or unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid and anhydrides thereof) may also be used. Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic acid and maleic acid. The polymer may be in acid, salt or partially neutralized form and may suitably have a molecular weight (Mw) of from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, more preferably from about 2,500 to about 75,000.

Mixtures of any of the above materials may also be used. Preferred builders for the particulate composition may be selected from the group consisting of zeolites (having formula (II) above), sodium carbonate, delta sodium disilicate and mixtures thereof.

Preferably, the content of phosphate builder in the particulate composition is less than 1% (by weight based on the total weight of the composition). The term "phosphate builder" refers to alkali metal, ammonium and alkanolammonium salts of polyphosphoric, orthophosphoric and/or metaphosphoric acids (e.g., sodium tripolyphosphate).

When included, the builder may be present in a total amount ranging from about 10 to about 80%, preferably from about 15 to 50% (by weight based on the total weight of the composition).

The particulate composition may also contain one or more fillers to help provide the composition with the desired density and volume. Suitable fillers for use in the present invention may generally be selected from neutral salts having a solubility in water of at least 1 gram per 100 grams of water at 20 ℃; such as alkali metal, alkaline earth metal, ammonium or substituted ammonium chlorides, fluorides, acetates and sulfates and mixtures thereof. Preferred fillers for use in the present invention include alkali metal (more preferably sodium and/or potassium) sulphates and chlorides and mixtures thereof, with sodium sulphate and/or sodium chloride being most preferred.

When included, the filler may be present in a total amount ranging from about 1 to about 80%, preferably from about 5 to about 50% (by weight based on the total weight of the composition).

The compositions of the present invention may comprise one or more fatty acids and/or salts thereof.

Suitable fatty acids in the context of the present invention include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight or branched alkyl or alkenyl chain containing from 6 to 24, more preferably from 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric, myristic, palmitic or stearic acid; and fatty acid mixtures, wherein 50-100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may generally be derived from natural fats and/or optionally hydrogenated natural oils (e.g. coconut oil, palm kernel oil or tallow).

The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di-or triethanolamine.

Mixtures of any of the above materials may also be used.

When included, the fatty acid and/or salt thereof is present in an amount ranging from about 0.25 to 5%, more preferably from 0.5 to 5%, most preferably from 0.75 to 4% (by weight based on the total weight of the composition).

For the purposes of formulation calculation, fatty acids and/or salts thereof (defined above) are not included in the surfactant content or builder content in the formulation.

The particulate composition may also include one or more polymeric cleaning enhancers. Such as soil release polymers, anti-redeposition polymers, and mixtures thereof.

The soil release polymer is adsorbed onto the fabric surfaceFacilitating soil removal. Soil release polymers suitable for use in the particulate composition include copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), glycols (e.g. ethylene glycol or propylene glycol) and polyglycols (e.g. polyethylene glycol or polypropylene glycol). Examples of such materials have a mid-block formed from trimethylene terephthalate repeat units and one or two end blocks of capped polyalkylene oxide, typically PEG 750-2000 with methyl caps. Weight average molecular weight (M) _w ) Typically in the range of about 1000 to about 20,000, preferably about 1500 to about 10,000.

Mixtures of any of the above materials may also be used.

When included, the compositions of the present invention preferably comprise from 0.05 to 6%, more preferably from 0.1 to 5% (by weight based on the total weight of the composition) of one or more soil release polymers, such as the copolyesters described above.

The polymer stabilizes the soil in the wash liquor, thereby preventing redeposition of the soil. Suitable anti-redeposition polymers for use in the present invention include alkoxylated polyethylenimines. The polyethyleneimine is composed of ethyleneimine units-CH ₂ CH ₂ NH-and when branched, hydrogen on the nitrogen is replaced by a chain of another ethyleneimine unit. Preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (M) of from about 300 to about 10000 _w ) Polyethylene imine backbone of (a). The polyethyleneimine backbone may be linear or branched. It can be branched to the extent that it is a dendrimer. Alkoxylation may generally be ethoxylation or propoxylation, or a mixture of both. When the nitrogen atom is alkoxylated, the preferred average degree of alkoxylation is from 10 to 50, preferably from 15 to 40, alkoxy groups per modification. A preferred material is an ethoxylated polyethyleneimine wherein the average degree of ethoxylation of each ethoxylated nitrogen atom in the polyethyleneimine backbone is from 10 to 40, preferably from 15 to 35 ethoxy groups. Another type of suitable anti-redeposition polymer for use in the present invention includes cellulose esters and ethers, such as sodium carboxymethyl cellulose.

Mixtures of any of the above materials may also be used.

When included, the particulate compositions of the present invention preferably comprise from 0.05 to 6%, more preferably from 0.1 to 5% (by weight based on the total weight of the composition) of one or more anti-redeposition polymers, such as the alkoxylated polyethylenimine and/or cellulose esters and ethers described above.

The particulate compositions of the present invention may also contain oxidizing agents to facilitate removal of difficult to remove food stains and other organic stains by chemical oxidation. The oxidizing agent may, for example, oxidize polyphenolic compounds common in coffee, tea, wine, and fruit stains. Oxidation of the oxidizing agent may also aid in bleaching, whitening and sanitizing fabrics, and may also provide additional washer cleanliness and odor protection. Oxidizing agents suitable for use in the present invention include peroxygen bleaching compounds such as sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.

When included, the particulate composition preferably comprises from 5 to 35%, preferably from 8 to 20% (by weight based on the total weight of the composition) of one or more oxidizing agents, such as the peroxygen bleaching compounds described above.

Bleach activators such as N, N, N ', N' -tetraacetylethylene diamine (TAED) or sodium nonanoyloxybenzene sulfonate (NOBS) may be included in combination with one or more oxidizing agents to improve bleaching at low wash temperatures.

Bleach catalysts may also be included in addition to or in place of bleach activators. Typical bleach catalysts include complexes of heavy metal ions such as cobalt, copper, iron, manganese or combinations thereof; with organic ligands such as 1,4, 7-Triazacyclononane (TACN), 1,4, 7-trimethyl-1, 4, 7-triazacyclononane (Me) ₃ -TACN), 1,5, 9-trimethyl-1, 5, 9-triazacyclononane, 1,5, 9-triazacyclododecane, 1,4, 7-triazacycloundecane, tris [2- (salicylideneamino) ethyl]An amine, or a combination thereof.

The particulate composition may also comprise one or more chelating agents for transition metal ions. Such chelating agents may also have calcium and magnesium chelating ability, but preferentially bind heavy metal ions, such as iron, manganese and copper. Such chelating agents can help to improve the stability of the composition and prevent decomposition of certain components, such as transition metal catalysis.

Suitable transition metal ion chelators include phosphonic acids in acid and/or salt form. When used in salt form, alkali metal (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotri (methylenephosphonic Acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP), and diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and their corresponding sodium or potassium salts. HEDP is preferred. Mixtures of any of the above materials may also be used.

The transition metal ion chelator (when included) may be present in an amount ranging from about 0.1 to about 10%, preferably from about 0.1 to about 3% (by weight based on the total weight of the composition). Mixtures of any of the above materials may also be used.

The particulate composition may further comprise an effective amount of one or more enzymes selected from pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present together with the corresponding enzyme stabilizers.

The particulate composition may comprise further optional ingredients that enhance performance and/or consumer acceptance. Examples of such ingredients include dye transfer inhibitors (e.g., polyvinylpyrrolidone), foam control agents, preservatives (e.g., bactericides), anti-shrinkage agents, anti-wrinkling agents, antioxidants, sunscreens, corrosion inhibitors, drape imparting agents, antistatic agents, ironing aids, colorants, fluorescers, pearlescers and/or opacifiers, and hueing dyes. Each of these components is present in an amount effective to achieve its purpose. Typically, these optional ingredients are individually included in amounts up to 5% (by weight based on the total weight of the composition).

Packaging and feeding

The compositions of the present invention may be packaged in unit doses in polymeric films that are soluble in wash water. Alternatively, the compositions of the present invention may be provided in multi-dose plastic packages having a top or bottom seal. The dosing device may be provided with the package as part of the lid or as an integrated system.

The method of laundering fabrics using the compositions of the present invention generally comprises diluting a dose of detergent composition with water to obtain a wash liquor and laundering the fabrics using the wash liquor so formed. In automatic washing machines, a dose of detergent composition is typically placed into a dispenser and thereby rinsed into the washing machine by water flowing into the washing machine, thereby forming a wash liquor. Depending on the washing machine configuration, 5 to about 65 liters of water may be used to form the wash liquor. The dosage of the detergent composition may be adjusted accordingly to achieve the appropriate detergent concentration.

The dilution step preferably provides a wash liquor comprising in particular about 3 to about 20 grams/wash of detersive surfactant (as further defined hereinabove). The washing liquid preferably has a pH value of above 7 to below 13, preferably above 7 to below 10.5.

Subsequent water rinsing steps and drying of the laundry are preferred.

Dishwashing composition

Tableware refers to hard surfaces intended to be cleaned with manual dishwashing compositions and includes dishes, glasses, pans, plates, bakeware, and tableware made of any material or combination of hard surface materials commonly used to make edible and/or cooked items.

Surfactant for dishwashing compositions

Surfactants (detergent actives) are generally selected from anionic and nonionic detergent actives. The cleaning composition may further or alternatively comprise cationic, amphoteric and zwitterionic surfactants.

Suitable synthetic (non-soap) anionic surfactants are water-soluble salts of organic sulfuric monoesters and sulfonic acids having branched or straight chain alkyl groups containing 6 to 22 carbon atoms in the alkyl moiety in the molecular structure.

Examples of such anionic surfactants are the water-soluble salts of alkylbenzenesulfonic acids, such as those in which the alkyl group contains 6 to 20 carbon atoms; long-chain (e.g., 6-22 carbon atoms) (primary) alcohol sulfates (hereinafter referred to as PAS), particularly those obtained by sulfating fatty alcohols produced by reduction of glycerides of tallow or coconut oil; secondary alkane sulfonates; and mixtures thereof.

Alkyl glyceryl ether sulphates are also suitable, in particular ethers of fatty alcohols derived from tallow and coconut oil; fatty acid monoglyceride sulfates; sulfates of ethoxylated aliphatic alcohols containing 1 to 12 ethoxy groups; alkylphenol ethoxylate sulfates having 1 to 8 ethoxy units per molecule and wherein the alkyl group contains 4 to 14 carbon atoms; reaction products of fatty acids esterified with isethionic acid and neutralized with a base, and mixtures thereof.

Previously, preferred water-soluble synthetic anionic surfactants were the alkali metal (e.g., sodium and potassium) and alkaline earth metal (e.g., calcium and magnesium) salts of alkyl-benzenesulfonic acids, as well as mixtures with olefin sulfonates and alkyl sulfates, and fatty acid monoglyceride sulfates.

Nonionic surfactants tend to reduce foaming when the composition is used. Consumers often associate high suds with strong cleaning, and thus it may be desirable to avoid the use of nonionic surfactants altogether. For compositions in which this problem does not exist, a suitable class of nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides (which are hydrophilic in nature) with aliphatic or alkyl-aromatic hydrophobic compounds having reactive hydrogen atoms. The length of the hydrophilic or polyoxyalkylene chain attached to any particular hydrophobic group can be readily adjusted to produce a compound having the desired balance between hydrophilic and hydrophobic elements. This enables the selection of nonionic surfactants having the appropriate HLB. Specific examples include: condensation products of aliphatic alcohols having 8 to 22 carbon atoms in a straight or branched configuration with ethylene oxide, for example coco alcohol/ethylene oxide condensates having 2 to 15 moles of ethylene oxide per mole of coco alcohol; condensates of alkylphenols having C6-C15-alkyl groups with 5-25 mol of ethylene oxide per mol of alkylphenol; and a condensate of ethylene diamine and propylene oxide, the condensate comprising 40 to 80 wt% of ethoxy groups and having a molecular weight of 5,000 to 11,000.

Other classes of nonionic surfactants are: tertiary amine oxides of the structure R1R2R 3N-O wherein R1 is an alkyl group of 8 to 20 carbon atoms, R2 and R3 are each an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms, such as dimethyldodecylamine oxide; tertiary phosphine oxides of the structure R1R2R3P-O, wherein R1 is an alkyl group of 8 to 20 carbon atoms, R2 and R3 are each an alkyl group of 1 to 3 carbon atoms or a hydroxyalkyl group, such as dimethyl-dodecylphosphine oxide; dialkyl sulfoxides of the structure r1r2s=o, wherein R1 is alkyl of 10 to 18 carbon atoms, R2 is methyl or ethyl, for example methyl-tetradecyl sulfoxide; fatty acid alkanolamides such as ethanolamides; alkylene oxide condensates of fatty acid alkanolamides; and alkyl mercaptans.

If nonionic surfactants are used, the amount present in the cleaning compositions of the present invention is generally at least 0.1 wt.%, preferably at least 0.5 wt.%, more preferably at least 1.0 wt.%, but not more than 20 wt.%, preferably at most 10 wt.%, more preferably not more than 5 wt.%.

Amphoteric, cationic or zwitterionic surfactants may also optionally be included in the composition.

Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines which contain an alkyl group of 8 to 20 carbon atoms and an aliphatic radical which is substituted by an anionic water-solubilizing group, for example sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate and sodium N-2-hydroxydodecyl-N-methyltaurine.

Examples of suitable cationic surfactants can be found in quaternary ammonium salts having one or two alkyl or aralkyl groups of 8 to 20 carbon atoms and two or three small aliphatic (e.g., methyl) groups, such as cetyltrimethylammonium chloride.

One particular group of surfactants are tertiary amines obtained by condensation of ethylene oxide and/or propylene oxide with long chain aliphatic amines. These compounds behave like nonionic surfactants in alkaline media and like cationic surfactants in acidic media.

Examples of suitable zwitterionic surfactants can be found in derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium compounds having aliphatic groups of 8 to 18 carbon atoms and aliphatic groups substituted with anionic water-soluble groups, for example betaines and betaine derivatives, such as alkyl betaines, in particular C12-C16 alkyl betaines, 3- (N, N-dimethyl-N-hexadecylammonium) -propane 1-sulfonate betaine, 3- (dodecyl methyl-sulfonium) -propane 1-sulfonate betaine, 3- (hexadecyl methyl-phosphonium) -propane 1-sulfonate betaine and N, N-dimethyl-N-dodecyl glycine. Other well known betaines are alkylamidopropylbetaines, such as those in which the alkylamide group is derived from coconut fatty acid.

Further examples of suitable surfactants are the compounds given in the well-known textbooks which are generally used as surface-active agents: "Surface Active Agents" Vol.1, schwartz and Perry, interscience 1949; "Surface Active Agents" Vol.2, schwartz, perry and Berch, interscience 1958; the current version of the "McCutcheon' sEmulsifiers and Detergents" Manufacturing Confectioners Company publication; "Tenside-Taschenbuch", H.Stache,2nd Edn., carl Hauser Verlag,1981.

The total surfactant content is preferably 3-40% by weight of the composition and typically with sulfated Guerbet surfactant the ratio of LAS to SLES is 80:20 to 30:70. Preferred ratios between SLES and CAPB are from 4:1 to 7:1, and ratios between PAS and SLES are from 1:1 to 2:1.

Optional ingredients of dishwashing compositions

The composition may include optional ingredients such as abrasives and additional ingredients to aid formulation performance, stability and cleaning performance.

The magnesium sulfate and/or sodium is desirably included in an amount of 0.5 to 5 wt.% to ensure that the desired rheological properties are achieved.

Preservative systems are also desirable, such as mixtures of CIT and MIT. BIT may also be used. The amount of preservative varies depending on the desired storage temperature and the quality of the raw material. Typically 0.0001 to 0.1 wt%.

The sodium EDTA chelating agent is advantageously included in the composition at a level of 0.01-0.5% by weight. DMDMH (glydant) may also be included in the composition in an amount of 0.005 to 1 weight percent.

When the composition comprises one or more anionic surfactants, the composition may preferably comprise detergent builder in an amount of more preferably from 0.1 to 25% by weight. Suitable inorganic and organic builders are well known to those skilled in the art. Citric acid is a preferred buffer/builder and may suitably be included in an amount of 0.01 to 0.5% by weight.

The composition may further comprise ingredients such as colorants, brighteners, optical brighteners, soil suspending agents, cleaning enzymes, compatible bleaching agents (especially peroxides and active chlorine-releasing compounds), solvents, co-solvents, gel control agents, freeze-thaw stabilizers, bactericides, preservatives, hydrotropes, polymers and perfumes.

Examples of optional enzymes include lipases, cellulases, proteases, mannanases and pectate lyases.

Viscosity of dishwashing composition

At 20s ^-1 The liquid composition according to the invention preferably has a viscosity of 100 to 10,000mpa.s, more preferably 200 to 8,000mpa.s, even more preferably 400 to 6,500mpa.s, even more preferably 800 to 5,000mpa.s, measured at a temperature of 25 degrees celsius.

Package of dishwashing composition

The liquid composition may be packaged in any suitable form of container. Preferably, the composition is packaged in a plastic bottle having a removable closure/pour spout. The bottle may be rigid or deformable. The deformable bottle allows squeezing the bottle to aid in dispensing. If transparent bottles are used, they may be formed of PET. Polyethylene or clarified polypropylene may be used. Preferably, the container is sufficiently transparent that the liquid with any visual cues therein can be seen from the outside. The bottle may provide one or more labels, or shrink wrap sleeves, which are desirably at least partially transparent, for example, 50% of the sleeve area is transparent. The adhesive used for any transparent label preferably does not adversely affect transparency.

OTNE

Preferably, the detergent composition, whether a liquid laundry detergent, a powder laundry detergent or a dishwashing composition, with the surfactant derived from carbon capture, comprises octahydrotetramethyl acetophenone (OTNE), which is an ideal synthetic fragrance component and provides particularly attractive sandalwood and cedar wood fragrance effects to the consumable.

OTNE is an abbreviation for aromatic materials with CAS numbers 68155-66-8, 54464-57-2 and 68155-67-9 and EC list number 915-730-3. Preferably, the OTNE is present in the form of a multicomponent isomer mixture comprising:

1- (1, 2,3,4,5,6,7, 8-octahydro-2, 3, 8-tetramethyl-2-naphthyl) ethan-1-one (CAS 54464-57-2)

1- (1, 2,3,5,6,7,8 a-octahydro-2, 3, 8-tetramethyl-2-naphthyl) ethan-1-one (CAS 68155-66-8)

1- (1, 2,3,4,6,7,8 a-octahydro-2, 3, 8-tetramethyl-2-naphthyl) ethan-1-one (CAS 68155-67-9)

More particularly, the present invention must be carried out with an amber-like perfume composition for perfumes consisting of octahydro-2 ',3',8',8' -tetramethyl- (2 'or 3') -naphthacene, most of which contain a double bond in the 9'-10' position.

Such OTNEs and methods of making them are described in detail in US3907321 (IFF).

Perfume molecular 01 is a specific isomer of OTNE and is commercially available from IFF. Another commercially available fragrance Escentric 01 contains OTNE, but also ambroxan, pink pepper, lime, with balsamic notes such as benzoin, olibanum and incense. Typically, commercially available perfume raw materials comprise 1-8 wt% of the perfume raw material OTNE.

Preferably, the detergent composition comprises from 0.01 to 0.2% by weight of the composition of OTNE as described above, more preferably from 0.07 to 0.15% by weight of the composition of OTNE.

With respect to additional or alternative perfume components, the following are preferred.

Preferably, the perfume component is selected from the group of benzene, toluene, xylene (BTX) raw materials. More preferably, the perfume component is selected from the group consisting of 2-phenylethanol, colestyl alcohol and mixtures thereof.

Preferably, the perfume component is selected from cyclododecanone raw materials. More preferably, the perfume component is halololide.

Preferably, the perfume component is selected from the group of phenolic raw materials. More preferably, the perfume component is hexyl salicylate.

Preferably, the perfume component is selected from the group of C5 module or oxygen containing heterocyclic moiety starting materials. More preferably, the perfume component is selected from gamma decalactone, methyl dihydrojasmonate, and mixtures thereof.

Preferably, the perfume component is selected from the class of terpene raw materials. More preferably, the perfume component is selected from the group consisting of dihydromyrcenol, linalool, terpinene, camphor, citronellol, and mixtures thereof.

Preferably, the perfume component is selected from the group of alkyl alcohol raw materials. More preferably, the perfume component is ethyl-2-methylbutyrate.

Preferably, the perfume component is selected from the group of diacid raw materials. More preferably, the perfume component is ethylene glycol brazilate.

Preferably, the perfume components listed above are present in the final detergent composition at 0.0001 to 1% by weight of the composition.

Examples

The nonionic surfactants are exemplified below and are all alcohol ethoxylates described herein. Nonionic surfactants 1 and 5 are comparative examples, while 2, 3, 4, 6, 7 and 8 are of the present invention.

	Ethoxylate (7 EO)	Alkyl (C12)
			Nonionic surfactant 1	Petroleum oil	Petroleum oil
Nonionic surfactant 2	Petroleum oil	Carbon capture
			Nonionic surfactant 3	Carbon capture	Petroleum oil
Nonionic surfactant 4	Carbon capture	Carbon capture

	Ethoxylate (7 EO)	Alkyl (C18)
			Nonionic surfactant 5	Petroleum oil	Petroleum oil
Nonionic surfactant 6	Petroleum oil	Carbon capture
			Nonionic surfactant 7	Carbon capture	Petroleum oil
Nonionic surfactant 8	Carbon capture	Carbon capture

The following anionic surfactants are the alkyl ether sulfates described herein. Anionic surfactants 1, 5, 9 and 13 are comparative examples, while the remainder are of the present invention.

	Ethoxylate (3 EO)	Alkyl (C18)
			Anionic surfactant 5	Petroleum oil	Petroleum oil
Anionic surfactant 6	Petroleum oil	Carbon capture
			Anionic surfactant 7	Carbon capture	Petroleum oil
Anionic surfactant 8	Carbon capture	Carbon capture

	Ethoxylate (1 EO)	Alkyl (C12)
			Anionic surfactant 9	Petroleum oil	Petroleum oil
Anionic surfactant 10	Petroleum oil	Carbon capture
			Anionic surfactant 11	Carbon capture	Petroleum oil
Anionic surfactant 12	Carbon capture	Carbon capture

	Ethoxylate (1 EO)	Alkyl (C18)
			Anionic surfactant 13	Petroleum oil	Petroleum oil
Anionic surfactant 14	Petroleum oil	Carbon capture
			Anionic surfactant 15	Carbon capture	Petroleum oil
Anionic surfactant 16	Carbon capture	Carbon capture

All surfactants herein are suitable for storage as 50-95% solutions or suspensions in water.

It should be appreciated that the ratio of carbon capture to petroleum derived carbon may vary within a batch. In any case, in the context of these embodiments, "carbon capture" means that at least 10% of the carbon atoms in the appropriate portion of the molecule are obtained by means of carbon capture. "Petroleum" means that at least 90% of the carbon is obtained from petrochemical means.

Ethoxylate (XEO) refers to surfactants having a molar average of X ethoxylate groups.

Alkyl (CX) means that the surfactant has a molar average of X atoms in the alkyl chain.

This is a laundry liquid formulation that may contain a surfactant of any of the carbon capture sources described below.

Composition of the components	Weight percent
		Straight chain alkylbenzenesulfonic acid	8.2
Alcohol ethoxylates	6.2
		Sodium lauryl ether sulfate with 3 moles EO	6.2
Monoethanolamine	3.5
		Citric acid	2
Sodium benzoate	1.0
		Potassium sulfite	0.2
Ethoxylate polyethylenimine	1.2
		Polyester antifouling polymers	0.4
Dequest 2010	0.5
		Spice	1.3
Fluorescent agent	0.2
		Allowance of	Water and its preparation method

This is a laundry liquid unit dose formulation and it may be used to contain any surfactant obtained by carbon capture.

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Example 2

This shows the different levels of volatile materials in the headspace of the non-perfumed detergent composition.

These values are the sum of the up to 50 peaks obtained from the GC trace.

	L	M
			Test 1	424 000 000	370 000 000
Test 2	408 000 000	372 000 000

The table shows that the volatile materials in the surfactants containing carbon-based capture are significantly higher than the petroleum derived equivalents. The test surfactant was nonionic alcohol ethoxylate 7EO comprising an ethoxylate group based on carbon capture.

Flavour assessment is a feature that allows carbon capture derived surfactants to be sweeter (sweeteer), more fruity than petroleum derived surfactant forms.

Example 3

We have also found that compositions comprising such surfactants have improved foaming characteristics during the pre-wash stage, wash process, and are also thicker before addition to water to form a liquid.

Claims

1. A surfactant comprising a C8-22 alkyl chain and a molar average of 1-40 ethoxylate units, at least one of the alkoxylate units or one of the alkyl chains comprising carbon resulting from carbon capture.

2. The surfactant of claim 1 which is an alcohol ethoxylate, an alkyl ether carboxylate, or an alkyl ether sulfate.

3. A surfactant according to claim 1 or 2, wherein carbon atoms in at least one of the alkoxylate, preferably the ethoxylate units or one of the alkyl chains are both carbon-captured.

4. A surfactant according to any preceding claim, wherein at least 10% of the alkoxylates, preferably ethoxylate groups or at least 10% of the alkyl chains comprise carbon atoms derived from carbon capture, and most preferably all of the alkoxylates, preferably ethoxylate groups or all of the alkyl chains comprise carbon atoms derived from carbon capture.

5. A surfactant according to any preceding claim, wherein substantially all of the alkoxylates, preferably ethoxylate groups or all of the alkyl chains present in the surfactant comprise carbon atoms resulting from carbon capture.

6. A surfactant according to any preceding claim, wherein at least 10% of the alkoxylate, preferably ethoxylate groups, comprise two carbon atoms from carbon capture.

7. A surfactant according to any preceding claim, wherein substantially all of the alkoxylate, preferably ethoxylate groups, comprise carbon atoms derived from carbon capture.

8. A surfactant according to any preceding claim, wherein the carbon captured from carbon is obtainable from gaseous carbon dioxide.

9. A surfactant according to any preceding claim, wherein the carbon captured from carbon is obtainable from physical or chemical incorporation of carbon dioxide in flue gas.

10. A surfactant according to any preceding claim, wherein the carbon captured from carbon is obtainable from physically or chemically binding carbon dioxide in air.

11. The surfactant of any preceding claim, wherein the carbon captured from carbon comprises converting carbon dioxide to form ethanol by a process selected from the group consisting of chemical conversions using a fischer-tropsch process with a hydrogen catalyst; chemical conversion to ethanol using a catalyst of copper nanoparticles embedded in carbon pins; reverse burning of sunlight-thermochemical alkane; or bioconversion of available carbon.

12. A surfactant according to any preceding claim, wherein less than 90%, preferably less than 10% of the alkoxylate, preferably ethoxylate groups comprise carbon atoms obtained from petroleum-based sources.

13. A surfactant according to any preceding claim, wherein the C8-22 alkyl group is obtained from a renewable source, more preferably from a plant, algae or yeast.

14. A surfactant product comprising the surfactant of any preceding claim in 50-95% aqueous suspension or solution.

15. A detergent comprising 1-50% by weight of the detergent of a surfactant according to any preceding claim, selected from laundry liquid compositions, powder detergent compositions, liquid hand dishwashing compositions and hard surface cleaning compositions.