Field of the invention

The present invention relates to hard surface cleaning compositions comprising carbon from carbon capture and methods of preparing such cleaning compositions.

Background of the invention

Cleaning products are well-known and play an important role in everyday life. Such products will contain surfactant and, if disinfection is desired, usually also a disinfecting agent like for example quaternary ammonium compound, organic acid, hydrogen peroxide or chloroxylenol. Hard surface cleaning compositions are used to clean household care hard surfaces in and around the home such as windows, floors, kitchen tops and bathroom tiles. Cleaning products for cleaning sanitary hard surfaces like toilets and other bathroom surfaces like for example floors and tiles usually comprise a disinfection agent. Household care hard surface cleaning activities are time consuming and, ideally, can be optimized when using products with excellent detergency and soil removal capacity.

Household care hard surface cleaning compositions will comprise surfactants. When cleaning hard surfaces, it may not be desired to generate a lot of foam as this will require rinsing with water. Therefore, such cleaning products will usually contain nonionic surfactant as this is a low foaming surfactant. In addition, other types of surfactants may be present. Anionic surfactant, like for example alkyl ether sulphate surfactant, will provide foam. Amphoteric surfactants such as betaines and amineoxides are sometimes used as co-surfactant to enhance detergency. Some consumers prefer hard surface cleaning products that are fragranced and coloured.

Improvement in fragrance performance/choice is highly desirable. Fragrances are often the most persuasive sensory component in a product, particularly upon first use, e.g. by squeezing or pumping product out of a bottle containing such product. The behavior of fragrances is strictly controlled such that during cleaning it is perceivable, but that, with or without rinsing, enough but not too much fragrance remains. Stability is also an important feature of hard surface cleaning products. Instability is indicated by separation, increased or decreased viscosity, a change in the fragrance, flocculation or a change in the aesthetics, such as a color change. Finally, the aesthetics of a hard surface cleaning product are important. In particular the color of the product. Aesthetics and stability are very closely linked; poor aesthetics can indicate poor stability. Equally aesthetics can be linked to the fragrance composition within a product. Nowadays, some consumers prefer cleaning products with a good environmental profile. That is, they prefer products that are ‘eco-friendly’ and have less or no impact on the environment when the product is used but also when the product is manufactured. There are cleaning products on the market that claim to be ‘eco- friendly’, but it is not always easy for consumers to understand what those positive terms really stand for or trust the credibility of such claim. Some consumers prefer such products to have certain tangible characteristics that provide trust and credibility that the product is more ‘eco-friendly’. Some consumers still associate ‘eco-friendly’ cleaning products with less efficacious cleaning products. In view of the above, there remains a need for hard surface cleaning composition with a good environmental profile without compromising consumer satisfaction in terms of fragrance, stability, aesthetics and/or cleaning performance.

Summary of the invention We have found that hard surface cleaning compositions comprising a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture provide for an improved environmental profile of the product and/or allow for a tangible reason to believe claimed environmental credentials whilst maintaining or improving consumer satisfaction.

Accordingly, in a first aspect the invention relates to a method of creating an eco- marker in an aqueous hard surface cleaning composition, wherein a. the cleaning composition comprises surfactant, perfume and at least 75 wt% water; and b. the method comprises the step of incorporating in the cleaning composition a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture.

The invention further relates to an aqueous hard surface cleaning composition comprising a. surfactant, perfume and at least 75 wt% water; and b. wherein the cleaning composition comprises a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture.

The invention also relates to use of a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture to create an eco-marker in a cleaning composition according to the present invention.

Detailed description of the invention Any feature of one aspect of the present invention may be utilized in any other aspect of the invention. The word ‘comprising’ is intended to mean ‘including’ but not necessarily ‘consisting of or ‘composed of. In other words, the listed steps or options need not be exhaustive. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word ‘about’. Numerical ranges expressed in the format ‘from x to y’ are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format ‘x to y’, it is understood that all ranges combining the different endpoints are also contemplated. Unless specified otherwise, amounts as used herein are expressed in percentage by weight based on total weight of the composition and is abbreviated as ‘wt%’. The use of any and all examples or exemplary language e.g. ‘such as’ provided herein is intended merely to better illuminate the invention and does not in any way limit the scope of the invention otherwise claimed. Room temperature is defined as a temperature of about 20 degrees Celsius. The term ‘virgin fossil fuels’ refers to fossil fuel sources (coal, crude oil, natural gas) which have not been used for any other purpose, i.e. has not been burnt for energy, or is not the waste gas from an industrial process. The compositions described herein comprise surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture. To obtain these ingredients from carbon capture, carbon must be captured, separated (where required) and utilized or transformed into an ingredient for use in a hard surface cleaning composition. The capture, separation and transformation may happen in one continuous process or may be separate steps carried out at different locations.

The surfactant is a non-ionic surfactant or an anionic surfactant. Where it is a non-ionic surfactant it preferably comprises from 5 to 9 EO groups. By from 5 to 9 EO groups means the mole average is from these end points.

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

Alternatively, where the surfactant is an anionic surfactant, it is preferred that it is an alkyl ether sulphate surfactant. Preferably, such a surfactant has a mole average of from 1 to 5, more preferably from 1 to 3 ethoxylate groups. Carbon Capture

Carbon capture means the capture of a C ₁ carbon, mostly, but not exclusively, as a gas. Carbon is preferably captured from waste emissions (e.g. exhaust gases from industrial processes, known as “point sources”) or from the atmosphere. The term carbon capture contrasts with the direct use of fossil fuels e.g. crude oil, natural gas, coal or peat as the source of carbon. However, carbon may be captured from the waste products arising from usage of fossil fuels, so for example carbon captured from the exhaust gases of the burning of fossil fuels in power generation. Capturing CO ₂ is most effective at point sources, such as large fossil fuel or biomass energy facilities, natural gas electric power generation plants, industries with major CO ₂ emissions, natural gas processing, synthetic fuel plants and fossil fuel-based hydrogen production plants. Extracting CO ₂ from air is also possible, although the far lower concentration of CO ₂ in air compared to combustion sources presents significant engineering challenges. Preferably, the carbon is captured from a point source. Preferably, the method used to carbon is selected from biological separation, chemical separation, absorption, adsorption, gas separation membranes, diffusion, rectification or condensation or any combination thereof.

Processes that collect CO ₂ from the air may use solvents that either physically or chemically bind CO ₂ from the air. Solvents include strongly alkaline hydroxide solutions like, for example, sodium and potassium hydroxide. Hydroxide solutions in excess of 0.1 molarity can readily remove CO ₂ from air. Higher hydroxide concentrations are desirable and an efficient air contactor will use hydroxide solutions in excess of 1 molar. Sodium hydroxide is a particular convenient choice, but other solvents may also be of interest. Specifically, similar processes may be useful for organic amines as well. Examples of carbon capture include amine scrubbing in which CC> ₂ -containing exhaust gas passes through liquid amines to absorb most of the CO ₂ . The carbon-rich gas is then pumped away. Preferably, the processes that collects CO ₂ from the air may use solvents selected from, sodium and potassium hydroxide or organic amines.

Carbon capture may include post combustion capture whereby the CO ₂ is removed from “flue” gases after combustion of a carbon fuel, e.g. fossil fuel or a bio-fuel.

Carbon capture may also be pre-combustion, whereby the fossil fuel is partially oxidized, for instance in a gasifier. The CO from the resulting syngas (CO and H ₂ ) reacts with added steam (H ₂ O) and is shifted into CO ₂ and H ₂ . The resulting CO ₂ can be captured from the exhaust stream. Capture may be by oxy-fuel combustion carbon capture, whereby a power plant burns fossil fuel in oxygen. This results in a gas mixture comprising mostly steam and CO ₂ . The steam and carbon dioxide are separated by cooling and compressing the gas stream.

Preferably, the carbon is captured from flue gases after combustion of a carbon fossil fuel.

Carbon dioxide may be removed from the atmosphere or ambient air, by supplying a CO ₂ absorbing liquid. The CO ₂ is then recovered from the liquid for use. Electrochemical methods for carbon dioxide recovery from alkaline solvents for carbon dioxide capture from air may be used as in US 2011/108421. Alternatively, the captured CO ₂ may be captured as a solid or liquid for example as a bicarbonate, carbonate or hydroxide from which the CO ₂ is extracted using well know chemistries.

Transformation

The carbon may be temporarily stored before usage or used directly. Captured carbon undergoes a process of transformation to chemical products.

The capture carbon may be transformed biologically or chemically to e.g. 1. Short chain intermediates such as short chain alcohols.

2. Hydrocarbon intermediates such as hydrocarbon chains: alkanes, alkenes, etc.

These can be converted further to make the components of surfactants using well known chemistries e.g. chain growth reactions etc to: longer chain alkenes/olefins, alkanes, longer chain alcohols, aromatics and ethylene, ethylene oxide which is an excellent starter chemical for various ingredients in detergent compositions.

Preferably, the carbon captured is transformed into ethylene or ethylene oxide.

Various transformation pathways via such intermediates are possible. Preferably, the carbon captured is transformed by a process selected from chemical transformation by Fischer-Tropsch using a hydrogen catalyst; conversion to ethanol chemically using a catalyst of copper nanoparticles embedded in carbon spikes; solar photo- thermochemical alkane reverse combustion; or biological transformation, for example fermentation.

1. CO ₂ or CO can be chemically transformed to liquid hydrocarbons by Fischer-Tropsch (FT) reactions with H ₂ using metal catalysts. CO can be captured as CO or converted into carbon monoxide by a reverse water gas shift reaction. FT reactions are gas- based so solid C ₁ carbon sources may require gasification (the product of which is often terms “syngas”. The name comes from its use as intermediates in creating synthetic natural gas (SNG)). 2. CO ₂ can be converted to ethanol chemically using a catalyst of copper nanoparticles embedded in carbon spikes.

3. Solar photo-thermochemical alkane reverse combustion reaction is a one-step conversion of CO ₂ and water into oxygen and hydrocarbons using a photo- thermochemical flow reactor. 4. Biological transformation - biological organisms transform the carbon to usable chemicals. NB. This excludes natural process of bio-sequestration of CO2 by plants via photosynthesis and then using the plant itself as a feedstock. Biological transformation as used here means harnessing organisms to produce a desired feedstock (such as a short chain alcohol).

Preferably biological transformation comprises fermentation of the C ₁ carbon by micro- organisms such as Crfixing bacteria to useful chemicals. Fermentation is preferably gas fermentation (the Ci feedstock is in gaseous form).

There are a variety of microorganisms that can be used in fermentation processes, including anaerobic bacteria such as Clostridium ljungdahlii strain PETC or ERI2, among others [See e.g., US Patent Nos. 5,173,429; 5,593,886 and 5,821,111; and references cited therein; see also W098/00558. WO 00/68407 discloses strains of Clostridium ljungdahlii for the production of ethanol.

The ability of micro-organisms to grow on CO as a sole carbon source was first discovered in 1903. This was later determined to be a property of organisms that use the acetyl coenzyme A (acetyl CoA) biochemical pathway of autotrophic growth (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 shown to metabolize CO to various end products, namely CO ₂ , H ₂ , methane, n-butanol, acetate and ethanol. While using CO as the sole carbon source, all such organisms produce at least two of these end products.

Anaerobic bacteria, such as those from the genus Clostridium, have been demonstrated to produce ethanol from CO, CO ₂ and H ₂ via the acetyl CoA biochemical pathway. For example, various strains of Clostridium ljungdahlii that produce ethanol from gases are described in WO 00/68407 , EP 117309 , US patent nos. 5,173,429 , 5,593,886 , and 6,368,819 , WO 98/00558 and WO 02/08438 . The bacterium Clostridium autoethanogenum sp is also known to produce ethanol from gases (Abrini et al., Archives of Microbiology 161, pp 345-351 (1994 )). The process may further include a catalytic hydrogenation module. In embodiments utilizing a catalytic hydrogenation module, the acid gas depleted stream is passed to the catalytic hydrogenation module, prior to being passed to the deoxygenation module, wherein at least one constituent from the acid gas depleted stream is removed and/or converted prior to being passed to the deoxygenation module. At least one constituent 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 the group comprising: particulate removal module, chloride removal module, tar removal module, hydrogen cyanide removal module, additional acid gas removal module, temperature module, and pressure module.

Further examples of carbon capture technologies suitable to generate the ethanol stock for use in manufacturing ethoxy sub-units for use in the surfactants described herein are disclosed in WO 2007/117157, WO 2018/175481, WO 2019/157519 and WO 2018/231948.

Manufacture of alkyl The C8-22 alkyl chain of the surfactant whether an alcohol ethoxylate or an alkyl ether sulphate is preferably obtained from a renewable source, e.g. carbon capture, and if not from a carbon capture source, or in addition to a carbon capture source then preferably from a triglyceride. A renewable source is one where the material is produced by natural ecological cycle of a living species, preferably by a plant, algae, fungi, yeast or bacteria, more preferably plants, algae or yeasts.

Preferred plant sources of oils are rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees. The oil from trees is called tall oil. Most preferably Palm and Rapeseed oils are the source.

Algal oils are discussed in Energies 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges by Saad M.G. et al. A process for the production of triglycerides from biomass using yeasts is described in Energy Environ. Sci. , 2019,12, 2717 A sustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents by Masri M.A. et al. Non-edible plant oils may be used and are preferably selected from the fruit and seeds of Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), Linseed, Pongamia pinnata (karanja), Hevea brasiliensis (Rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Jojoba), Eruca sativa. L., Cerbera odollam (Sea mango), Coriander (Coriandrum sativum L.), Croton megalocarpus, Pilu, Crambe, syringa, Scheleichera triguga (kusum), Stillingia, Shorea robusta (sal), Terminalia belerica roxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, Rice bran, Hingan (balanites), Desert date, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, Alagae, Argemone mexicana L. (Mexican prickly poppy, Putranjiva roxburghii (Lucky bean tree), Sapindus mukorossi (Soapnut), M. azedarach (syringe), Thevettia peruviana (yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, B. napus, Zanthoxylum bungeanum.

Manufacture of surfactant.

The ethanol manufactured through carbon capture processes is used to generate ethoxy subunits and, together with appropriate alkyl, chains is formed into the desired surfactant. Where sulphonation is required, for example to form an anionic surfactant such as alkyl ether sulphate, again, this is according to standard processes.

In a first step the ethanol (C ₂ H ₅ OH) is dehydrated to ethylene (C2H4) and this is a common industrial process. Then the ethylene is oxidised to form ethylene oxide (C ₂ H ₄ O).

Finally, the ethylene oxide is then reacted with a long chain alcohol (e.g. C12/14 type fatty alcohol) via a polymerisation type reaction. This process is commonly referred to as ethoxylation and gives rise to surfactants that are known as alcohol ethoxylates and which are non-ionic surfactants.

By sulphonating these alcohol ethoxylates one forms the alkyl ether sulphate anionic surfactants. Manufacture of EO

The ethoxylate units in the surfactant comprises at least one ethoxylate containing a carbon atom obtained from carbon capture. More preferably, at least 50% of the ethoxylate groups and especially preferably at least 70% comprise carbon atoms obtained from carbon capture and most preferably all the ethoxylate groups present in the non-ionic surfactant contain a carbon atom obtained from carbon capture.

Preferably, the ethoxylate units in the surfactant comprises at least one ethoxylate containing two carbon atoms obtained from carbon capture. More preferably, at least 10% of the ethoxylate groups and especially preferably at least 70% comprise two carbon atoms obtained from carbon capture and most preferably all the ethoxylate groups present in the non-ionic surfactant contain two carbon atoms obtained 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, more than 10%, preferably more than 90% of the ethoxylate groups comprise carbon atoms obtained from carbon capture based sources.

Surfactant

The hard surface cleaning compositions of the invention comprise surfactant and preferably at least part of the surfactant is nonionic surfactant as cleaning compositions of the invention preferably are low foaming compositions. In addition to nonionic surfactant other surfactants may be present. For example, anionic surfactant may be present. Preferably at least 50 wt% of total surfactant is nonionic surfactant and for certain embodiments it is preferred that the amount of nonionic surfactant is at least 80 wt%, like for example at least 90 wt%, and preferably all surfactant is nonionic surfactant calculated on total surfactant in the composition.

Preferably the total amount of surfactant in the composition is from 0.1 to 10 wt%. Hard surface cleaning compositions typically have a relatively low amount of total surfactant like for example 0.1 to 8 wt%, 0.1 to 5 wt% and 0.1 to 2 wt%. Where the product is a dilutable it means that the consumer can purchase a concentrated product and take the concentrate home where it can be diluted to form a regular hard surface cleaning product. The dilution may require anything from 1 to 10 parts water to one part concentrate. Such compositions will contain 5 to 10 wt% or even 8 to 10 wt% total surfactant.

Alcohol ethoxylates:

Preferably the nonionic surfactant is an alcohol ethoxylate. Alcohol ethoxylates have the general formula:

R-Y-(C2H ₄ 0) _Z -CH2-CH2-0H

Wherein R is an alkyl chain. When the ingredient comprising at least one ethoxylate unit and at least one carbon derived from carbon capture is an alcohol ethoxylate, the carbon obtained from carbon capture may be located in the alky chain or the ethoxylate group. Preferably both the alkyl chain and ethoxylate comprise carbon obtained from carbon capture.

R is preferably 8 to 60, more preferably 10 to 25, even more preferably 12 to 20 and most preferably 16-18.

Y is selected from:

-O- , -C(0)0- , -C(0)N(R)- or -C(0)N(R)R- and is preferably -O- Z is preferably 2 to 100, more preferably 3 to 50, even more preferably 4 to 30, still even more preferably 4 to 10, and most preferably 5 to 7, calculated as a molar average.

Particularly preferably R is 10-18 and Z is 5-7.

These ingredients are particularly advantageous in so called dilute at home products, in which they aid the spontaneous mixing on the concentrated product and water, when the consumer dilutes at home. Alkyl ether sulphates:

Alkyl ether sulphate is a preferred anionic surfactant which may be used at from 0 to 50 wt% of the total anionic surfactant used. Alkyl ether sulphates have the formula:

(R ₁ -(OR’) _n -O-SO ₃ ^' ) _x M ^x+ , wherein:

Wherein Ri is an alkyl chain. When the ingredient comprising at least one ethoxylate unit and at least one carbon derived from carbon capture is an alkyl ether sulphate, the carbon obtained from carbon capture may be located in the alky chain or the ethoxylate group. Preferably both the alkyl chain and ethoxylate comprise carbon obtained from carbon capture. R ₁ preferably is saturated or unsaturated C ₈ -C ₁₆ , preferably C ₁₂ -C ₁₄ alkyl chain; preferably, R ₁ is a saturated C ₈ -C ₁₆ , more preferably a saturated C ₁₂ -C ₁₄ alkyl chain;

R’ is ethylene; n is from 1 to 18, preferably from 1 to 15, more preferably from 1 to 10, still more preferably from 1 to 5; x is equal to 1 or 2; M ^x+ is a suitable cation which provides charge neutrality, preferably sodium, calcium, potassium, or magnesium, more preferably a sodium cation.

Preferably, the alkyl ether sulphate comprises from 1 to 5 ethoxylate groups by mole average, more preferably from 1 to 3 mole average.

Preferably the cleaning composition is free from anionic surfactant if quaternary ammonium compound is present as a hygiene active as anionic surfactants may interfere with the biocidal action thereof. Other surfactants

The cleaning composition may comprise other surfactants as part of the total surfactants present, like amphoteric surfactants. Amphoteric surfactant

If present, the composition comprises 0.1 to 5 wt% amphoteric surfactant, like for example 0.2 to 4 wt%. More preferably the amount of amphoteric surfactant is 0.3 to 3 wt% and even more preferably 0.5 to 2 wt%. Suitable amphoteric surfactants include amine oxide and betaine.

Amine oxide

Preferred amine oxides are alkyl dimethyl amine oxide and alkyl amido propyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide. Especially preferred are lauryl dimethylamine oxide, coco dimethyl amine oxide and coco amido propyl dimethyl amine oxide.

Betaine

Preferably the amphoteric surfactant is a betaine. Suitable betaines include alkyl betaine, alkyl amido betaine, alkyl amidopropyl betaine, alkyl sulphobetaine and alkyl phosphobetaine, wherein the alkyl groups preferably have from 8 to 19 carbon atoms.

Examples include cocodimethyl sulphopropyl betaine, cetyl betaine, laurylamidopropyl betaine, caprylate/caprate betaine, capryl/capramidopropyl betaine, cocam idopropyl hydroxysultaine, cocobutyramido hydroxysultaine, and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate. Preferably the betaine is cocamidopropyl betaine (CAPB).

Percent modern carbon

The percentage modern carbon (pMC) level is based on measuring the level of radiocarbon (C14) which is generated in the upper atmosphere from where it diffuses, providing a general background level in the air. The level of C14, once captured (e.g. by biomass) decreases over time, in such a way that the amount of C14 is essentially depleted after 45,000 years. Hence the C14 level of fossil-based carbons, as used in the conventional petrochemical industry is virtually zero. A pMC value of 100% biobased or biogenic carbon would indicate that 100% of the carbon came from plants or animal by-products (biomass) living in the natural environment (or as captured from the air) and a value of 0% would mean that all of the carbon was derived from petrochemicals, coal and other fossil sources. A value between 0-100% would indicate a mixture. The higher the value, the greater the proportion of naturally sourced components in the material, even though this may include carbon captured from the air.

The pMC level can be determined using the % Biobased Carbon Content ASTM D6866-20 Method B, using a National Institute of Standards and Technology (NIST) modern reference standard (SRM 4990C). Such measurements are known in the art are performed commercially, such as by Beta Analytic Inc. (USA). The technique to measure the C14 carbon level is known since decades and most known from carbondating archaeological organic findings.

In one embodiment, the ingredient comprising at least one ethoxylate unit and at least one carbon derived from carbon capture comprises carbons from point source carbon capture. These ingredients preferably have a pMC of 0 to 10%. In an alternate embodiment, the ingredient comprising at least one ethoxylate unit and at least one carbon derived from carbon capture comprises carbons from direct air capture. These ingredients preferably have a pMC of 90 to 100%.

Hard surface cleaning composition The aqueous hard surface cleaning composition of the invention comprises a. surfactant, perfume and at least 75 wt% water; and b. the cleaning composition comprises a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture.

We have found that inclusion of a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture allows for improved consumer satisfaction in terms of fragrance, stability, aesthetics and/or cleaning performance. It was surprisingly found that inclusion of such surfactant not only improves the ecological profile of the product, but also allows for the creation of tangible markers as proof of inclusion of eco friendly ingredients without negatively influencing the performance or other characteristics of the product. For the purpose of the invention such markers are defined as ‘tangible eco-marker’ or ‘eco-marker’.

For example, inclusion of such ingredient not only improves the ecological profile of the product, but also imparts a distinguishable overall fragrance perception, alone or in combination with other ingredients, that can be act as an eco-marker. Thereby providing assurance to a consumer concerning the credibility of the eco friendly ingredients and total product upon use.

Another example of such a tangible eco-marker is that inclusion of ingredient comprising at least one ethoxylate unit and at least one carbon derived from carbon capture allows for calculation of pMC (as discussed above) that as such can act as an eco-marker according to the present invention. The pMC value can for example be used on pack as a tangible eco-marker.

Aqueous cleaning composition The cleaning composition of the present invention is an aqueous cleaning composition, that is to say, the composition comprises water. The amount of water will depend on the desired concentration of the other ingredients but will at least be 75 wt%, like for example at least 85 wt% or at least 90 wt%, but typically not more than 99 wt%. The amount of water preferably is from 80 to 99 wt%, more preferably 80 to 95 wt% and even more preferably 85 to 95 wt%.

The composition is liquid, that is, it can be poured, and has viscosity at 25°C of 1 to 1000 mPa.s @ 20 s ^-1 . The viscosity is measured using an AR 1000 Rheometer (TA instruments) using a 4 cm, 2° cone-plate geometry @ 20 s ^-1 a1nd 25°C. Depending on the required use characteristics the composition may be more or less viscous. For example, a more water thin viscosity is desired if the composition is to be used in a trigger spray bottle. If dispensed from a squeeze bottle, a more viscous consistency may be desired. A more viscous viscosity may also be desired if the cleaning product is a toilet cleaning product. Preferably the composition has a viscosity of 100 to 700 mPa.s @ 20 s ^-1 and more preferably of 200 to 600 mPa.s @ 20 s ^-1 . The desired viscosity can suitably be obtained by known methods like for example the use of a viscosity modifying agent.

Hygiene active Preferably the compositions of the invention comprise a hygiene active such as quaternary ammonium compound, organic acid, hydrogen peroxide or chloroxylenol.

Preferably the cleaning composition comprises one or more hygiene actives selected from quaternary ammonium compounds, organic acids having a pKa of from 1 to 5.5, hydrogen peroxide and combinations thereof.

Quaternary ammonium compound

Preferably the cleaning composition of the present invention comprises 0.05 to 1.5 wt% quaternary ammonium compound as a disinfecting agent. Preferably the composition comprises 0.1 to 1 wt% and more preferably 0.2 to 0.8 wt% of said quaternary ammonium compound.

The combination of a quaternary ammonium compound with hydrogen peroxide provides a broader disinfectant efficacy, which is further augmented if used in combination with an organic acid.

Any quaternary ammonium compound can be used in the presently described technology. Examples of quaternary ammonium compounds include, for example, alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. One suitable type of quaternary ammonium compound includes, for example, those in which the molecules contain amine, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like. Another effective type of quaternary ammonium compound include, for example, those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as the case of lauryloxyphenyltrimehyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethylammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like. Preferably, the quaternary ammonium compound utilized in the practice of the present technology exhibit biocidal activity or are biocidal in nature.

Particularly useful quaternary ammonium compound germicides include compositions which include a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Such useful quaternary compounds are available under the EMPIGEN, BARDAC, BARQUAT, HYAMINE, LONZABAC, and ONYXIDE trademarks, which are more fully described in, for example, McCutcheon's Functional Materials (Vol. 2), North American Edition, 1998, as well as the respective product literature from the suppliers identified below.

For example, BARDAC 205M is described to be a liquid containing alkyl dimethyl benzyl ammonium chloride (Benzalkonium chloride, BKC), octyl decyl dimethyl ammonium chloride; didecyl dimethyl ammonium chloride (DDAC), and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC 208M)); described generally in McCutcheon's as a combination of alkyl dimethyl benzyl ammonium chloride and dialkyl dimethyl ammonium chloride); BARDAC 2050 is described to be a combination of octyl decyl dimethyl ammonium chloridedidecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC 2080)); BARDAC 2250 is described to be didecyl dimethyl ammonium chloride (50% active); BARDAC LF (or BARDAC LF-80), described as being based on dioctyl dimethyl ammonium chloride (BARQUAT MB-50, MX-50, OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are each described as an alkyl dimethyl benzyl ammonium chloride; BARDAC 4250 and BARQUAT 4250 Z (each 50% active) or BARQUAT 4280 and BARQUAT 4280Z (each 80% active) are each described as alkyl dimethyl benzyl ammonium chloride/alkyl dimethyl ethyl benzyl ammonium chloride. Also, HYAMINE 1622, described as diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (50% solution); HYAMINE 3500 (50% actives), described as alkyl dimethyl benzyl ammonium chloride (also available as 80% active (HYAMINE 3500-80)); and HYMAINE 2389 described as being based on methyldodecylbenzyl ammonium chloride and/or methyldodecylxylene- bis-trimethyl ammonium chloride.

(BARDAC, BARQUAT and HYAMINE are presently commercially available from Lonza, Inc., Fairlawn, N. J.). BTC 50 NF (or BTC 65 NF) is described to be alkyl dimethyl benzyl ammonium chloride (50% active); BTC 99 is described as didecyl dimethyl ammonium chloride (50% active); BTC 776 is described to be myrisalkonium chloride (50% active); BTC 818 is described as being octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (available also as 80% active (BTC 818-80%)); BTC 824 and BTC 835 are each described as being of alkyl dimethyl benzyl ammonium chloride (each 50% active);

BTC 885 is described as a combination of BTC 835 and BTC 818 (50% active) (available also as 80% active (BTC 888)); BTC 1010 is described as didecyl dimethyl ammonium chloride (50% active) (also available as 80% active (BTC 1010-80)); BTC 2125 (or BTC 2125 M) is described as alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethylbenzyl ammonium chloride (each 50% active) (also available as 80% active (BTC 2125 80 or BTC 2125 M)); BTC 2565 is described as alkyl dimethyl benzyl ammonium chlorides (50% active) (also available as 80% active (BTC 2568)); BTC 8248 (or BTC 8358) is described as alkyl dimethyl benzyl ammonium chloride (80% active) (also available as 90% active (BTC 8249)); ONYXIDE 3300 is described as n-alkyl dimethyl benzyl ammonium saccharinate (95% active). (BTC and ONYXIDE are presently commercially available from Stepan Company, Northfield, III). Benzyl-C12-14-alkyldimethylammonium chlorides benzyl C12-C16- alkyl dimethyl chlorides also available as EMPIGEN BAC 50 and EMPIGEN BAC 80. It is an aqueous solution of benzalkonium chloride at ca. 50% or 80% in water respectively. EMPIGEN BAC 50 and EMPIGEN 80 are readily biodegradable, EMPIGEN is commercially available from Innospec Performance Chemicals

Polymeric quaternary ammonium salts based on these monomeric structures are also considered desirable for the present invention. One example is POLYQUAT, described as being a 2-butenyldimethyl ammonium chloride polymer.

Preferably the quaternary ammonium compound is selected from alkyl dimethyl benzyl ammonium chloride (BKC), didecyl dimethyl ammonium chloride (DDAC) and combinations thereof.

Hydrogen peroxide

The cleaning composition of the present invention may comprise 0.5 to 4 wt% hydrogen peroxide. The amount of hydrogen peroxide is chosen such that it provides adequate disinfection in combination with the other disinfecting agents present. Preferably the composition comprising 0.9 to 3 wt% hydrogen peroxide and more preferably 1.5 to 2.5 wt%.

Organic acid The cleaning composition may comprise 0.25 to 2.5 wt% organic acid having a p K _a of from 1 to 5.5. The organic acid is one of the disinfecting agents and may also contribute to obtaining the desired acidic pH. Preferably the amount of organic acid is from 0.5 to 2 wt% and more preferably from 1 to 2 wt%. Examples of suitable organic acids that may be used in the present invention include citric acid (p K _a = 3.1), lactic acid (p K _a = 3.86), acetic acid (p K _a = 4.76), malonic acid (pK _a = 2.85), adipic acid (pK _a = 4.43), glutaric acid (pK _a = 3.76), glycolic acid (pK _a = 3.83) and maleic acid (pK _a = 1.9), succinic acid (pK _a = 4.2), malic acid (pK _a = 3.4), tartaric acid (for L+ pK _a = 2.89; and for meso pK _a = 3.22), hexanoic acid (pK _a = 4.88), cyclohexanoic acid (pK _a = 4.82), heptanoic acid (pK _a = 4.8), octanoic acid (pK _a = 4.89), 4-methyl octanoic acid (pK _a = 5.23), nonanoic acid (pK _a = 4.95), decanoic acid (pK _a = 4.9), benzoic acid (pK _a = 4.2) and 4-methoxy benzoic acid (pK _a = 4.37).

Preferably the organic acid has a pK _a of 2 to 4.8 and more preferably 3 to 4.

Preferred organic acids are citric acid, lactic acid, acetic acid, malonic acid, adipic acid, glutaric acid, glycolic acid, maleic acid and combinations thereof. More preferably the organic acid is selected from citric acid, lactic acid, glycolic acid and combinations thereof. A preferred organic acid is citric acid. pH

The aqueous cleaning composition of the present invention may be acidic, neutral or alkaline. For sanitary cleaning an acidic cleaning composition is preferred having a pH from 2 to 5. The acidic pH helps to address hard water stains. Neutral pH compositions are gaining more traction with consumers as such products are milder on hands and typically have a pH from 6.5 to 7.5. Alkaline compositions are traditionally used for kitchen cleaning and typically have a pH from 9 to 11.

The desired pH of the composition may be obtained using suitable pH adjusting agents like e.g. hydrochloric acid and sodium hydroxide, and/or organic acids if present. Perfume

The composition comprises perfume. Perfumes (sometimes referred to as fragrances) are well known in the art and are preferably incorporated into compositions described herein at level of 0.1 to 5 wt%, more preferably 0.1 to 2 wt%. Preferably the composition comprises a biodegradable fragrance.

Preferably the perfume comprises a fragrance component selected from the group consisting of ethyl-2-methyl valerate (manzanate), limonene, dihyro myrcenol, dimethyl benzyl carbonate acetate, benzyl acetate, geraniol, methyl nonyl acetaldehyde, Rose Oxide, cyclacet (verdyl acetate), cyclamal, beta ionone, hexyl salicylate, tonalid, phenafleur, octahydrotetram ethyl acetophenone (OTNE), the benzene, toluene, xylene (BTX) feedstock class such as 2-phenyl ethanol, phenoxanol and mixtures thereof, the cyclododecanone feedstock class, such as habolonolide, the phenolics feedstock class such as hexyl salicylate, the C5 blocks or oxygen containing heterocycle moiety feedstock class such as gamma decalactone, methyl dihydrojasmonate and mixtures thereof, the terpenes feedstock class such as dihydromycernol, linalool, terpinolene, camphor, citronellol and mixtures thereof, the alkyl alcohols feedstock class such as ethyl-2-methylbutyrate, the diacids feedstock class such as ethylene brassylate, and mixtures of these components.

Preferably the composition comprises linalool, citronellol, limonene or combinations thereof. Linalool and limonene are especially preferred. Preferably the composition comprises limonene. Preferably the composition comprises 0.01 to 5 wt%, more preferably 0.05 to 4 wt% and even more preferably 0.1 to 3 wt% of the aforementioned fragrance components.

We have found that performance benefits are seen with using certain fragrance components such as limonene, when using carbon capture-based surfactant raw materials. In particular, we have found that using carbon capture based surfactants in the composition means that more fragrance components are present in the headspace meaning that more fragrance is perceived by the consumer when opening the container containing the composition. Optional Ingredients

The composition according to the invention may contain other ingredients which aid in the cleaning or sensory performance. Compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as thickeners, colorants, preservatives, fatty acids, anti-microbial agents, pH adjusters, sequestrants, alkalinity agents and hydrotropes.

Organic solvents

Preferred compositions do not contain large amounts of organic solvents, usually added to boost cleaning performance, that is from 0 to 1 wt% organic solvent. Preferably the composition is free of organic solvents.

Silicones

Compositions of the present invention preferably comprise only limited amounts of silicones as these may not provide the required user characteristics for cleaning compositions of the present invention. Silicones may for example leave a ‘slippery’ feel to the hard surface. Therefore, the composition of the present invention preferably comprises from 0 to 1 wt%, more preferably from 0 to 0.5 wt% and still more preferably from 0 to 0.1 wt% silicones. Still more preferably the composition is free of silicones.

Method of preparing compositions of the invention

In one aspect of the present invention is provided a method of preparing an aqueous hard surface cleaning composition according to the present invention wherein the cleaning composition comprises surfactant, perfume and at least 75 wt% water, comprising the steps: a. obtaining a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture; b. incorporating said ingredient into an aqueous hard surface cleaning composition.

Step a. may involve any of the processes described herein or any suitable alternate routes to obtain a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture. The ingredient is preferably an ingredient as described herein. Step b. involves incorporating the C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture into an aqueous hard surface cleaning composition. Once produced, the aqueous hard surface cleaning composition is stored in suitable packaging. Preferably the packaging comprises post consumer recycled packaging or PCR.

Method of creating an eco-marker In one aspect of the present invention is provided a method of creating an eco-marker in aqueous hard surface cleaning compositions of the present invention.

Provided is a method of creating an eco-marker in an aqueous hard surface cleaning composition, wherein a. the cleaning composition comprises surfactant, perfume and at least 75 wt% water; and b. the method comprises the step of incorporating in the cleaning composition a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture.

We have found that inclusion of a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture allows for improved consumer satisfaction in terms of fragrance, stability, aesthetics and/or cleaning performance.

It was surprisingly found that inclusion of such surfactant not only improves the ecological profile of the product, but also allows for the creation of tangible markers as proof of inclusion of eco friendly ingredients without negatively influencing the performance or other characteristics of the product. For the purpose of the invention such markers are defined as ‘tangible eco-marker’ or ‘eco-marker’.

For example, inclusion of such ingredient not only improves the ecological profile of the product, but also imparts a distinguishable overall fragrance perception, alone or in combination with other ingredients, that can be act as an eco-marker. Thereby providing assurance to a consumer concerning the credibility of the eco friendly ingredients and total product upon use.

Another example of such a tangible eco-marker is that inclusion of ingredient comprising at least one ethoxylate unit and at least one carbon derived from carbon capture allows for calculation of pMC (as discussed above) that as such can act as an eco-marker according to the present invention. The pMC value can for example be used on pack as a tangible eco-marker. Use

In a further aspect, the invention relates to the use a surfactant comprising a C8-22 alkyl chain and a mole average of from 1 to 40 ethoxylate units, at least one ethoxylate unit or one alkyl chain comprising carbon obtained from carbon capture to create an eco-marker in a cleaning composition according to the present invention.

The invention will now be illustrated by means of the following non-limiting examples.

Examples

The following ingredients are illustrative of surfactants described herein.

Table 1 : Alkyl ether sulphate

Table 2: Alcohol ethoxylate Table 3: Hard surface cleaning compositions

Examples 7 and 8 are illustrative toilet cleaning compositions. Example 9 is a typical 10x concentrated general purpose cleaner that can be diluted at home by the user to create a normal strength general purpose cleaner for home storage. Example 10 is a typical general purpose spray cleaning composition.

Example 11 Sensorial testing was performed on non-ionic surfactants which were C12-alcohol ethoxylates with an average of 7EO. A C12-alcohol ethoxylate-7EO non-ionic surfactant according to the invention was obtained of which the EO-polymer moiety was derived from a process which involved gas fermentation to reduce gaseous captured CO2 to ethanol, wherein the ethanol was further converted to ethylene and used to make the EO-polymer. The alkyl-chain was obtained from a bio-source. A C12- alcohol ethoxylate-7EO non-ionic not according to the invention was obtained, also with an alkyl chain derived from a bio-source, but where the EO-polymer chain was derived from a petrochemical source. The surfactants were used to make a detergent formulation before testing. The detergent formulations were either tested at 20 degrees Celsius or heated to 40 degrees Celsius. The formulations, which otherwise contained no added perfumes were tested by a human nose. The surfactant according to the invention provided a ‘waxy/fatty’ odour whereas the petrochemically derived surfactant provided a ‘chemical’ odour. The odour perception was verified by two persons independently.

Example 12

Detergent compositions comprising fragrance components were prepared and assessed for headspace fragrance analysis. The table shows the normalised results for the petro-derived AE7EO non-ionic surfactant (M) versus the equivalent comprising carbon captured raw materials for manufacturing the EO units (L).

For the fragrance components listed, all were present in the headspace in greater concentrations for the carbon capture derived composition than for the petroleum based equivalent.