GLYCINE BETAINE ESTER

BACKGROUND

[0001] It would be advantageous to have cleaning compositions, which have a unique shear thinning profile. In particular, it may be desirable to have such compositions, which thin less after being sprayed onto a hard surface, e.g, of a shower or toilet, than conventional cleaning products. It may also be desirable for such compositions to be derived from natural products. Additionally, such compositions may advantageously exhibit sanitizing, disinfecting, biofilm prevention and disruption efficacy, and/or be compatible with a wide range of additional ingredients such as fragrance, dyes, and other cleaning agent auxiliary ingredients.

SUMMARY

[0002] The present application relates generally to the field of cleaning compositions and, in particular, cleaning compositions which may be especially useful for cleaning hard surfaces, such as the inside surface of a toilet bowl. The present application provides cleaning compositions, which may exhibit a unique shear thinning profile, such that the compositions thin less after being sprayed onto a surface and thereby provide a longer contact time than conventional cleaning products. The present cleaning compositions may include (a) a glycine betaine ester, (b) an acidifying agent, (c) polysaccharide thickener, and (d) water. Commonly, the composition has a pH of no more than about 4, a viscosity of no more than about 1,500 cP at a shear rate of 10 at 25 °C, and/or a viscosity of at least about 150 cP at a shear rate of 50 at 25 °C (where the viscosities are determined with a Brookfield Cone/Plate viscometer). In certain embodiments, composition may have a 10/50 shear rate ratio of no more than about 3.

[0003] Often, the glycine betaine ester may be a compound of formula (I):

Me ₃ N ⁺ -CH ₂ -C(0)-0-R X ^" (I) wherein R is an aliphatic group having 8 to 22 carbon atoms and X ^" represents an inorganic or organic anion. Typically, X ^" represents an alkanesulphonate anion, such as a

methanesulphonate anion.

[0004] In some embodiments, the cleaning composition may have a unique shear thinning profile, such that the composition thins less after being sprayed onto a surface and thereby provides a longer contact time than conventional products. In some embodiments, the composition may have a 10/50 shear rate ratio of no more than about 3.5, no more than about 3, or more desirably no more than about 2.5. As used herein, the term "10/50 shear rate ratio" refers to the ratio of the viscosity of the composition at a shear rate of 10 at 25 °C to the viscosity of the composition at a shear rate of 50 at 25 °C. In some embodiments, the compositions may have a 10/50 shear rate ratio of about 2 to 3. In some embodiments, the composition may have a viscosity of at least about 1000 cP at a shear rate of 10 at 25 °C. In some embodiments, the composition may have a viscosity of at least about 150 cP at a shear rate of 50 at 25 °C. In some embodiments, the composition may have a viscosity of about 250 to 1,200 cP at a shear rate of 10 at 25 °C. In some embodiments, the composition may have a viscosity of about 100 to 1000 cP, or at least about 150 cP and, in some instances, at least about 250 cP at a shear rate of 50 at 25 °C.

[0005] The acidifying agent may include mineral acid, such as hydrochloric acid, an alkanesulphonic acid, such as methanesulfonic acid and/or one or more carboxylic acids, e.g., one or more hydroxy carboxylic acids. Nonlimiting examples of suitable

hydroxycarboxylic acids include lactic acid, citric acid, tartaric acid, xylonic acid and gluconic acid. Examples of other suitable carboxylic acids include acetic acid, propionic acid, malonic acid, succinic acid and glutaric acid.

[0006] The polysaccharide thickener may include starch, modified starch, agar, carrageenan, pectin, alginate, pectin, cellulose, and/or a cellulose derivative. In some embodiments, the polysaccharide thickener may include a natural gum. In some

embodiments, the polysaccharide thickener may include agar, carob gum, guar gum, gellan gum, xanthan gum, and/or acacia gum.

[0007] The cleaning composition may include other ingredients, such as one or more of an antimicrobial agent, a bleaching agent, a fragrance, and dye component. In some embodiments, in addition to the glycine betaine amide, the composition may optionally include an additional surfactant selected from nonionic, anionic, cationic, zwitterionic, and/or amphoteric surfactants and mixtures thereof.

[0008] In some embodiments, it may be advantageous to use a "crude" or "semi-purified" form of the glycine betaine ester. As used herein the term "crude" in reference to the glycine betaine ester is understood to mean the reaction product as formed from the reaction of glycine betaine with an aliphatic alcohol (typically a fatty alcohol) in the presence of an acid (typically methanesulfonic acid), i.e., the final reaction product as is, and used without further treatment or purification. The terms "semi-pure" or "semi-purified" in reference to the glycine betaine ester are understood to mean that the reaction product as originally formed is partly purified, i.e., residual glycine betaine, aliphatic alcohol and/or

methanesulfonic acid are at least partially removed to provide a mixture which is still not a pure sample of the glycine betaine ester. Such "crude" or "semi-purified" glycine betaine ester components may be especially useful as surfactants in the present cleaning

compositions. The "crude" and "semi -purified" glycine betaine ester components employed in the present cleaning compositions typically include at least 50 wt.% and, commonly, at least 60 wt.% of the glycine betaine ester.

[0009] In one embodiment, the cleaning compositions may include a mixture of a glycine betaine ester of Formula (I):

Me ₃ N ⁺ -CH ₂ -C(0)-0-R X ^" (I)

wherein R is an aliphatic group having 8 to 22 carbon atoms and X ^" represents an inorganic or organic anion, and one or more of Me ₃ N ⁺ -CH ₂ -C0 ₂ H X ^" ("a glycine betaine salt"), an aliphatic alcohol ROH, where R is as defined, and an acid HX. Typically, X ^" represents an alkanesulphonate anion, such as a methanesulphonate anion and the acid HX is an alkanesulphonic acid, such as a methanesulphonic acid. As used herein, the term "glycine betaine salt" refers to the ionic compound Me ₃ N ⁺ -CH ₂ -C0 ₂ H X ^" , where X ^" represents an inorganic or organic counterion, typically a methanesulphonate counterion. For example, a "crude" or "semi-purified" glycine betaine ester may include a glycine betaine ester of Formula (I) where R is a lauric group and one of more of glycine betaine methanesulphonate, lauric alcohol (ROH where R is a lauric group), and methanesulph acid.

[0010] In some embodiments, the compositions may be exhibit properties such as sanitizing, disinfecting, and/or biofilm prevention and disruption efficacy.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIG. 1 is a graph illustrating the rheology profiles of several of the present thickened cleaning compositions (Formula 7 - "4a"; Formula 8 - "5a") in comparison to a standard benchmark cleaning product (Standard 3 - "control"), which contains a combination of a natural gum with an ethoxylated oxo alcohol and sodium lauryl ether sulfate.

DETAILED DESCRIPTION

[0012] In one aspect, the composition may be a liquid cleaning composition that includes (a) a glycine betaine ester of formula (I):

Me ₃ N ⁺ -CH ₂ -C(0)-NH-R X (I)

wherein R is an aliphatic group having 8 to 22 carbon atoms and X ^" represents an inorganic or organic anion; (b) an acidifying agent; (c) polysaccharide thickener; and (d) water. The composition may have a pH of no more than about 4, a viscosity of no more than about 1,500 cP at a shear rate of 10 at 25 °C and/or a viscosity of at least about 250 cP at a shear rate of 50 at 25 °C (viscosities determined with a Brookfield Cone/Plate viscometer). In some embodiments, the composition may include at least about 85 wt.%, at least about 90 wt.%, or often at least about 95 wt.% water.

[0013] Glycine betaine is a natural material derived from sugar beet molasses. The present glycine betaine esters may be derived from natural glycine betaine, providing a green (eco-friendly) and multifunctional material. Particularly of use is a glycine betaine ester of formula (I):

X ^" Me ₃ N ⁺ -CH ₂ -C(0)-0-R (I), wherein R may be an aliphatic group having 8 to 22 carbon atoms and X ^" represents an inorganic or organic counterion. The glycine betaine ester component of the present compositions may include one or more glycine betaine esters of formula (I). In some embodiments, R may be a linear or branched aliphatic group. In some embodiments, R may be a linear aliphatic group. In some embodiments, R may be an alkyl or an alkenyl group. In some embodiments, R may be an aliphatic group having 10 to 18 carbon atoms. In some embodiments, R may be a linear primary aliphatic group having 8 to 18 carbon atoms, e.g. an R group that is part of a fatty alcohol compound. In another embodiment, R may be an aliphatic group having 10 to 16 carbon atoms, such as the R group present in a C ₁₀ -C ₁₆ linear primary alkyl alcohol. The R group may be a C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , and/or C ₁₈ aliphatic group, e.g., a C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , and/or C ₁₈ linear primary alkyl and/or alkenyl group. In some embodiments, R may be a C ₁₀ , C ₁₂ , C ₁₄ , and/or C ₁₆ aliphatic group. In some embodiments, R may be a lauric, mystric, palmitic, stearic, and/or oleic group. In certain embodiments, R may include a lauric and/or mystric group. In some embodiments, R may be a C ₁₂ and/or C ₁₄ alkyl and/or alkenyl group. Examples of suitable inorganic or organic anions which may be present as the counterion, X ^" , include halide, carboxylic acid, alkylcarbonate, alkyl sulfonate, aryl sulfonate, alkylsulfate, sulfate, nitrate, phosphate, and phosphite anions. In some embodiments, X ^" represents CI ^" , Br ^" , T, CH ₃ CO ₂ ^" ,

CH ₃ CH(OH)C0 ₂ ^" , CH ₃ S0 ₃ ^" , ArS0 ₃ ^" , CH ₃ C ₆ H ₄ S0 ₃ ^" , CH ₃ OS0 ₃ ^" , H ₂ P0 ₄ ^" , and/or H ₂ P0 ₃ ^" anion. X ^" may be a halide or alkyl sulfonate anion. In some embodiments, X ^" may be a chloride or methanesulfonate anion. As noted above, in glycine betaine esters derived from natural glycine betaine, X ^" may commonly be a methane sulfonate anion.

[0014] In some embodiments, X ^" represents CI ^" , Br ^" , T, CH ₃ C0 ₂ ^" , CH ₃ CH(OH)C0 ₂ ^" , CH ₃ S0 ₃ ^" , ArS0 ₃ ^" , CH ₃ C ₆ H ₄ S0 ₃ ^" , CH ₃ OS0 ₃ ^" , H ₂ P0 ₄ ^" , and/or H ₂ P0 ₃ ^" anion. X ^" may be a halide or alkyl sulfonate anion. In some embodiments, X ^" may be a chloride or

methanesulfonate anion. As noted above, in glycine betaine esters derived from natural glycine betaine, X ^" may commonly be a methane sulfonate anion.

[0015] In many embodiments of the present compositions, the glycine betaine ester may be present in combination with an aliphatic alcohol (i.e., ROH) thereof, wherein R is as defined above. Often, aliphatic alcohol may be present as an unreacted starting material of the reaction used to produce the glycine betaine ester. In such cases, the "R group" of the aliphatic alcohol is commonly the same as the "R group" of the glycine betaine ester. The weight ratio of the glycine betaine ester to the aliphatic alcohol in the compositions may be about 10: 1 to 1 :5, more commonly about 5: 1 to 1 :2. In some embodiments, the glycine betaine ester may include a mixture of glycine betaine esters having R groups with 12 to 14 carbon atoms. The composition may also include one or more fatty alcohols with 12 to 14 carbon atoms in combination with such a glycine betaine ester. In some embodiments, the glycine betaine ester component may be an unpurified reaction product, which also includes glycine betaine and/or salt thereof. In some embodiments, such an unpurified reaction product may include methanesulfonic acid and/or salt thereof. In addition to the glycine betaine ester, in some embodiments the composition may further include an aliphatic amine, e.g. aliphatic C ₈ -C ₂₂ amine, more typically a C ₈ -Ci ₅ amine such as a C ₈ -Ci ₄ fatty amine. For example, the composition may include a linear aliphatic C ₈ -Ci ₈ amine in combination with the glycine betaine ester.

[0016] In some embodiments, in addition to the glycine betaine ester, the composition may also include a glycine betaine amide, e.g. a glycine betaine amide of formula (II):

X ^" Me ₃ N ⁺ -CH ₂ -C(0)- H-R (II),

wherein R and X ^" are as defined above.

[0017] The polysaccharide thickener may include starch, modified starch, agar, carrageenan, pectin, alginate, cellulose, and/or a cellulose derivative. In some

embodiments, the polysaccharide thickener may include starch or a modified starch. In some embodiments, the polysaccharide thickener may include natural gum. Non-limiting examples of natural gum include agar, carob gum, guar gum, gellan gum, xanthan gum, and/or acacia gum. In some embodiments, the polysaccharide may desirably include xanthan gum and/or guar gum. In some embodiments, the composition may include about 0.1 to 5 wt.% , about 0.5 to 4 wt.%, or about 0.1 to 2 wt.% of one or more polysaccharide thickeners. For example, when the composition includes a natural gum as a thickener, the polysaccharide thickener may include about 0.1 to 1.5 wt.% and, more commonly about 0.2 to 1 wt.%) xanthan gum and/or guar gum. When the composition includes starch and/or modified starch as a thickener, the composition may include about 2 to 4 wt.%> of the polysaccharide thickener. [0018] In some embodiments, composition may include other thickeners, such as rheology modifiers based on polyacrylates (including carbomers) and polyacrylamides;

acrylamidomethylpropane sulfate including acryloyldimethyltaurates; PEG and polyol thickeners; cationic thickeners; cyclodextrin-based rheology modifiers; star polymers and dendrimers; polypeptide/protein thickeners; silicone thickeners; amphipathic polymers, synthetic associative thickeners, polymeric emulsifiers, gums from seaweed, gums produced by fermentation; chitin and derivatives and mineral thickeners. These other thickeners may be used in place of or in addition to the polysaccharide thickeners.

[0019] The acidifying agent may include mineral acid, such as hydrochloric acid, and/or one or more organic acids. For example, the acidifying agent may include an organic acid, such as lactic acid, glycolic acid, citric acid, acetic acid, malonic acid, succinic acid, tartaric acid gluconic acid, glutaric acid and/or methanesulfonic acid. In some embodiments, the acidifying agent may include a carboxylic acid, e.g., one or more hydroxy carboxylic acids. Non-limiting examples of suitable hydroxycarboxylic acids include lactic acid, citric acid, tartaric acid and gluconic acid. In some embodiments, the acidifying agent may include mineral acid, such as hydrochloric acid. In some embodiments, the acidifying agent may include methanesulfonic acid. In some embodiments, the acidifying agent may include lactic acid and/or citric acid. In some embodiments, the acidifying agent may include lactic acid. In some embodiments, the composition may include about 0.1 wt.% to 10 wt.% , about 0.5 wt.% to 10 wt.%, about 1 wt.% to 10 wt.%, or about 0.5 wt.% to 5 wt.% of one or more acidifying agents. In some embodiments, the composition may include at least about 1 wt.%) of a mineral acid, such as hydrochloric acid, and may commonly include up to about 10 wt.%) of the mineral acid (e.g., hydrochloric acid). In some embodiments, the composition may include at least about 1 wt.%> and commonly about 1 to 5 wt.%> of an organic acid. For example, the composition may include about 1 to 5 wt.%> of an organic acid, which includes lactic acid, glycolic acid, citric acid, acetic acid, malonic acid, succinic acid, tartaric acid gluconic acid, glutaric acid and/or methanesulfonic acid. In many embodiments, the composition may include about 1 to 5 wt.%> lactic acid. In other embodiments, the composition may include about 1 to 5 wt.%> citric acid.

[0020] The cleaning composition may include one or more additional surfactants that are different from the glycine betaine ester selected from nonionic, anionic, cationic, zwitterionic, and/or amphoteric surfactants and mixtures thereof. In some embodiments, the composition may include one or more anionic and/or cationic surfactants. In some embodiments, the surfactants may be detersive surfactants. In some embodiments, the composition may include up to about 5 wt.%, about 0.1 wt.% to 3 wt.%, or about 0.1 to 2 wt.% of the additional surfactant.

[0021] The surfactants may include one or more alkoxylated alcohols. The alkoxylated alcohol may include one or more ethoxylated alcohols. Ethoxylated alcohols may be linear or branched. In some embodiments, the ethoxylated alcohol may include a C ₈ -Ci ₆ alcohol having an average of 2 to 20 ethylene oxide units, more commonly 2 to 12 ethylene oxide units. Typically, when present, the ethoxylated alcohol includes a C ₉ -C ₁₅ linear and/or branched alcohol having an average of 5 to 12 ethylene oxide units. A non-limiting example is Genapol® X-100 (available from CLARIANT), which is a branched iso-Cn alcohol ethoxylate having an average of 10 ethylene oxide units. Other ethoxylated alcohols that may be present in the cleaning compositions as a nonionic surfactant include linear or branched ethoxylated alcohols including a C ₅ -C ₁₅ alcohol having an average of 4 to 12 ethylene oxide units. Nonlimiting examples include Tomadol® 91-6 - a C ₉ -C ₁₁ ethoxylated alcohol having an average of 6 ethylene oxide units (available from Air Products and Chemicals, Inc.), LUTENSOL® AO-8 - a synthetic C ₁₃ -C ₁₅ ethoxylated oxo alcohol having an average of 8 ethylene oxide units (available from BASF), Genapol® LA 070S - an ethoxylated lauryl alcohol having an average of 7 ethylene oxide units (available from CLARIANT), and TERGITOL™ 15-S-7, a branched secondary ethoxylated alcohol with 7 ethylene oxide units (available from DOW Chemical). Other examples of suitable ethoxylated linear alcohols include ethoxylated linear alcohols having a C ₁₀ -C ₁₅ n-alkyl group, e.g., having an average of 2 to 12 ethylene oxide units. Nonlimiting examples include LUTENSOL® TDA 10 (available from BASF) - an ethoxylated tridecyl alcohol having an average of 10 EO groups. Triglyceride derivatives such as ethoxylated triglycerides having an average of 2 to 10 ethylene oxide units may also be used (e.g., such compounds are available from BASF or Rhodia).

[0022] Other nonionic surfactants which may be present include, but are not limited to, secondary ethoxylated alcohols, such as C ₁₁ -C ₁₅ secondary ethoxylated alcohols. Secondary ethoxylated alcohols suitable for use are sold under the tradename TERGITOL® (available from Dow Chemical). For example TERGITOL® 15-S, more particularly TERGITOL® 15-S-12 is a Cn-C ₁₅ secondary ethoxylate alcohol having an average of about 12 ethylene oxide groups.

[0023] Additional suitable nonionic surfactants include linear alkyl amine oxides. Typical linear alkyl amine oxides include water-soluble amine oxides of the formula R ¹ -N(R ² )(R ³ )0 where R ¹ is typically a C ₈ -Ci ₈ alkyl moiety and the R ² and R ³ moieties are typically selected from the group consisting of hydrogen, C ₁ -C ₃ alkyl groups, and C ₁ -C ₃ hydroxyalkyl groups. Quite often, R ¹ is a C ₈ -Ci ₈ n-alkyl and R ² and R ³ are methyl, ethyl, propyl, isopropyl, 2- hydroxethyl, 2-hydroxypropyl, and/or 3-hydroxypropyl. The linear amine oxide surfactants in particular may include linear C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and linear C ₈ -Ci ₂ alkoxy ethyl di(hydroxyethyl) amine oxides. Particularly suitable amine oxides include linear C ₁₀ , linear C ₁₀ -C ₁₂ , and linear C ₁₂ -C ₁₄ alkyl dimethyl amine oxides. Other examples of amine oxide nonionic surfactants include alkyl amidopropyl amine oxides, such as lauiyl/myristyl amidopropyl amine oxides (e.g., lauiyl/myristyl amidopropyl dimethylamine oxide).

[0024] In some embodiments, the cleaning composition may include one or more bases. In some embodiments, the base may be an organic base such as an alkylamine including triethylamine and heterocyclic amines such as pyrrole, pyridine, and piperdine. In some embodiments, the base may be an inorganic base including alkali metals and alkaline earth metal bases such as NaOH, Li OH, KOH, Mg(OH) ₂ , and Ca(OH) ₂ . The cleaning

composition may include up to about 5 wt.% of one or more bases. In some embodiments, the cleaning composition may include about 0.001 wt.% to 3 wt.%, about 0.01 wt.% to 1 wt.%), or more preferably about 0.05 wt.% to 0.5 wt.% of one or more bases.

[0025] The cleaning composition may include other ingredients including adjuvants. As used herein, adjuvants include components or agents, such as additional functional materials. In some embodiments, the functional materials may be included to provide desired properties and functionalities to the cleaning composition. For the purpose of this application, the term "functional materials" include a material that when dispersed or dissolved in a concentrate and/or use solution, such as an aqueous solution, provides a beneficial property in a particular use. The present compositions may optionally include other soil-digesting components, surfactants, disinfectants, detergent fillers, sanitizers, acidulants, complexing agents, biocides and/or antimicrobial agents, corrosion inhibitors, anti-redeposition agents, foam inhibitors, opacifying agents such as titanium dioxide, dyes, bleaching agents (e.g., hydrogen peroxide and other peroxides), enzymes, enzyme stabilizing systems, builders, thickening or gelling agents, wetting agents, dispersants, stabilizing agents, dispersant polymers, cleaning compounds, pH adjusting agents (acids and alkaline agents), stain preventers, and/or fragrances. In some embodiments, the

composition may include one or more of an antimicrobial agent, a bleaching agent, a fragrance, and/or dye component. In some embodiments, the composition may include up to about 1 wt.%, about 0.05 to 0.5 wt.%, or about 0.1 to 0.3 wt.% of a fragrance component. In some embodiments, the composition may include up to about 1 wt.%, about 0.001 to 0.5 wt.%), or about 0.01 to about 0.1 wt.% of one or more dye components.

[0026] In some embodiments, the composition may include: about 0.1 - 3 wt.% of the glycine betaine ester; about 0.5 - 10 wt.% of the acidifying agent; about 0.5 - 5 wt.% of the polysaccharide thickener; and at least about 85 wt.%, more commonly at least about 90 wt.%) water.

[0027] In some embodiments, the composition may include: (a) about 0.1 - 3 wt.%> of the glycine betaine ester; (b) about 0.5 - 5 wt.%> of the acidifying agent; (c) about 0.5 - 3 wt.%> of the polysaccharide thickener; and (d) at least about 90 wt.%, more commonly at least about 95 wt.%) water.

[0028] In some embodiments, the composition may include: about 0.1 - 3 wt.% of the glycine betaine ester; about 0.5 - 5 wt.% of an acidifying agent, which may include a hydroxycarboxylic acid, e.g. lactic and/or citric acid, and/or acetic acid; about 0.1 - 1 wt.% of the polysaccharide thickener, which may include a natural gum; and at least about 90 wt.%), more commonly at least about 95 wt.% water.

[0029] In some embodiments, the composition may include: about 0.1 - 3 wt.% of the glycine betaine ester; about 0.5 - 10 wt.% of the acidifying agent, which may include a mineral acid; about 0.1 - 1 wt.% of the polysaccharide thickener, which may include a natural gum; and at least about 90 wt.%, more commonly at least about 95 wt.% water.

[0030] In some embodiments, the composition may include: about 0.1 - 3 wt.% of the glycine betaine ester; about 0.5 - 10 wt.% of the acidifying agent, which may include a mineral acid; about 0.5 - 4 wt.% of the polysaccharide thickener, which may include starch and/or a modified starch; and at least about 90 wt.%, more commonly at least about 95 wt.% water.

[0031] In some embodiments, the composition may include: about 0.1 - 3 wt.% of the glycine betaine ester; about 0.5 - 5 wt.% of the acidifying agent, which may include a hydroxy carboxylic acid, e.g. lactic and/or citric acid; about 0.5 - 4 wt.% of the

polysaccharide thickener, which may include starch and/or a modified starch; and at least about 90 wt.%), more commonly at least about 95 wt.%> water.

[0032] As used herein, "composition" refers to any liquid, foam, solid, gel, and/or paste substance having more than one component.

[0033] As used herein, "fragrance" refers to any perfume, odor-eliminator, odor masking agent, the like, and combinations thereof. In some embodiments, a fragrance is any substance which may have an effect on a consumer, or user's, olfactory senses.

[0034] As used herein, "wt. %>" refers to the weight percentage of an ingredient in the total formula. For example, an off-the-shelf commercial composition of Formula X may only contain 70%> active ingredient X. Thus, 10 g of the off-the-shelf composition only contains 7 g of X. If 10 g of the off-the-shelf composition is added to 90 g of other ingredients, the wt. %> of X in the final formula is thus only 7%>.

[0035] As used herein, "hard surface" refers to any porous and/or non-porous surface. In one embodiment, a hard surface may be selected from the group consisting of: ceramic, glass, metal, polymer, stone, and combinations thereof. For the purposes of this application, a hard surface does not include silicon wafers and/or other semiconductor substrate materials. Nonlimiting examples of ceramic surfaces include: toilet bowl, sink, shower, tile, the like, and combinations thereof. A non-limiting example of a glass surfaces includes: window and the like. Nonlimiting examples of metal surfaces include: drain pipe, sink, the like. Nonlimiting examples of a polymeric surface includes: PVC piping, fiberglass, acrylic, Corian®, the like. A non-limiting example of a stone hard surface includes: granite, marble, and the like. [0036] A hard surface may be any shape, size, or have any orientation that is suitable for its desired purpose. In one non-limiting example, a hard surface may be oriented in a vertical configuration. In another non-limiting example, a hard surface may be the surface of a curved surface, such as a ceramic toilet bowl. In yet another non-limiting example, a hard surface may be the inside of a pipe, which has vertical and horizontal elements, and also may have curved elements. It is thought that the shape, size and/or orientation of the hard surface will not affect the compositions of the present invention, because of the unexpectedly strong transport properties of the compositions under the conditions described infra.

[0037] As used herein, "surfactant" refers to any agent that lowers the surface tension of a liquid, for example water. Exemplary surfactants which may be suitable for use with the present invention are described herein. In one embodiment, surfactants may be selected from the group consisting of anionic, non-ionic, cationic, amphoteric, zwitterionic, and combinations thereof.

[0038] As used herein, "viscosity" refers to the resistance to gradual deformation by shear stress or tensile stress of a composition. The rheology profiles (determined at shear rates from 1-100 sec ^"1 ) of all viscous formula were measured at 25 °C using a TA AR 2000 rheometer equipped with a 4cm stainless steel parallel plate and Peltier plate at a shear of 1 to 100 sec ^"1 . In other instances, viscosity values were measured using a Brookfield rheometer at 25 °C using a spindle of 2 and 12 RPM.

EXAMPLES

[0039] The following examples are intended to more specifically illustrate the present cleaning compositions according to various embodiments described above. These examples should in no way be construed as limiting the scope of the present technology.

[0040] A number of exemplary formulations of the present cleaning compositions were prepared and are presented in Tables 1-4 below. For all formulations, the balance of the formulation was water. The ability of the test formulations to remove lime scale and organic soil from a hard surface was determined using the procedures described below. Lime Scale Removal Test

[0041] The effectiveness of the present cleaning compositions to remove lime scale from a hard surface was determined using the following procedure. Marble chips were used to simulate lime scale. Testing procedures are designed to provide a simulation of conditions that would commonly be found in toilets containing lime scale. The time required to complete this test is 48 hours. Total time required for test, including preparation of materials is 3 days. Approximately 5 grams of marble chips are rinsed with Deionized water for 3 minutes and drained. The marble chips are baked in oven set at 40 +/- 2 °C for 48 hours and cool at room conditions for 2 hours +/- 15 minutes. The formulation being tested (100 g of per 5.00 g of marble chips) are stored at room conditions in contact with the marble chips undisturbed for eighteen hours. The marble chips are then drained and rinsed under deionized water for 30 seconds to remove excess formula. The marble chips are then dried again in an oven at 40° +/- 2 °C for 48 hours, cooled to room temperature (~ 2 hours +/- 15 min) and weighed. The percentage weight loss is calculated according to the formula below and report as % lime scale removal. The value reported is an average of 3 separate results.

(Wi-Wf x looywi. where; Wi =initial weight of marble chips; W _f =final weight of marble chips. Organic Soil Removal Test

[0042] The effectiveness of the present cleaning compositions to remove organic soil from a hard surface was determined using the following procedure. To measure the ability of a liquid toilet bowl cleaner to remove organic stains, colorimeter readings ( L, a, b values) are taken on clean ceramic tiles through a piece of glass that is mounted on a jig. A silkscreen is used to apply the organic soil to the ceramic tiles. Colorimeter readings are taken immediately after the organic soil is applied (organic soil should be wet). Product is allowed to dwell on the surface of the soiled tile for 1 minute. A scrubber with a brush attachment is then used to scrub the tile three times (3 passes). Cleaning efficacy or percent soil removed is determined by using the measured colorimeter readings before and after treatment with the liquid toilet bowl cleaner in the equation below. V (( L _s -L _c ) ² +( a _s -a _c ) ² +( b _s -b _c ) ² ) Percent Soil Removal = 100* — —

(( L _s -L _n ) ² ₊ ( a _s -a _n ) ² ₊ ( b _s -b _n ) ² ) where s = soiled tile reading; n = non-soiled tile reading; and c = cleaned tile reading. Example 1

[0043] Table 1 lists several exemplary formulations of the present cleaning product and demonstrates that the present compositions (with lactic acid as an acidifying agent) are more effective at removing lime scale and organic soil compared to a standard benchmark formulation. A standard thickened cleaning product which contains a combination of 59 wt.% of a synthetic C ₁₃ .C ₁₅ ethoxylated oxo alcohol having an average of 8 ethylene oxide units (LUTENSOL® AO-8) and 41 wt.% sodium lauryl ether sulfate ("SLES") as the surfactant component.

Table 1

* 66% C ₁₂ /C14-GB Ester / 3% Ci ₂ /Ci ₄ -Alcohol / 31% Methane Sulfonic Acid [0044] Table 1 includes a standard benchmark formulations (Standard 1) that does not include glycine betaine ester and three formulations with a varying amount of crude glycine betaine C ₁₂ /C ₁₄ ester, lactic acid (as an acidifying agent), and a natural gum thickener (xanthan gum or guar gum). Table 1 demonstrates that the formulations of the present compositions are considerably better at removing both organic soil and lime scale.

Particularly notable is Formula 1, which is about 3 times better at removing lime scale than the standard benchmark formulation as well as substantially more effective at organic soil removal. Formula 1 contains the same amount of surfactant, lactic acid, and xanthan gum as the standard formulation. These formulas demonstrate that glycine betaine ester cleaning formulations with lactic acid and either xanthan gum or guar gum as a thickener provide more efficient cleaning compositions with the same or decreased amount of surfactant compared to the standard benchmark formulation.

Example 2

[0045] Table 2 lists several additional exemplary formulations of the present cleaning product. A standard thickened cleaning product which contains a combination of

LUTENSOL® AO-8 and Na LES as the surfactant component was tested for comparison purposes. The results demonstrate that the present compositions (with lactic acid as an acidifying agent) are more effective at removing lime scale and organic soil compared to a standard benchmark formulation. The performance of Formula 6, which includes a comparable amount of surfactant compared to the standard formulation with hydrochloric acid as an acidifying agent, was particularly effective.

Table 2

* 66% C ₁₂ /C14-GB Ester / 3% Ci ₂ /Ci ₄ -Alcohol / 31% Methane Sulfonic Acid

Example 3

[0046] Table 3 lists several additional exemplary formulations of the present cleaning product in comparison to a standard thickened cleaning product containing a combination of LUTENSOL® AO-8 and Na LES as the surfactant component.

Table 3

* 66% C ₁₂ /C14-GB Ester / 3% Ci ₂ /Ci ₄ -Alcohol / 31% Methane Sulfonic Acid [0047] Figure 1 shows the rheology profiles of the two GB Ester-based compositions listed in Table 3. These two formulations exemplifying the present cleaning products containing a combination of GB Ester and natural gum (Formula 7 - "4a"; Formula 8 - "5a") have rheology profiles which exhibit less shear thinning than observed with the standard benchmark cleaning product (Standard 3 - "control"), which contains a combination of a natural gum with an ethoxylated oxo alcohol and sodium lauryl ether sulfate.

Example 4

[0048] Table 4 lists several additional exemplary formulations of the present cleaning product containing starch as the polysaccharide thickening agent in comparison to a standard thickened cleaning product containing a combination of LUTENSOL® AO-8 and Na LES as the surfactant component.

Table 4

* 66% C ₁₂ /C14-GB Ester / 3% Ci ₂ /Ci ₄ -Alcohol / 31% Methane Sulfonic Acid ILLUSTRATIVE EMBODIMENTS

[0049] Reference is made in the following to a number of illustrative embodiments of the subject matter described herein. The following embodiments describe illustrative embodiments that may include various features, characteristics, and advantages of the subject matter as presently described. Accordingly, the following embodiments should not be considered as being comprehensive of all of the possible embodiments or otherwise limit the scope of the methods, materials and compositions described herein.

[0050] In one aspect, the present technology provides a liquid cleaning composition including (a) a glycine betaine ester of formula (I):

Me ₃ N ⁺ -CH ₂ -C(0)-0-R X ^" (I) wherein R is an aliphatic group having 8 to 22 carbon atoms; (b) an acidifying agent; (c) polysaccharide thickener; and (d) water; wherein the composition may have a pH of no more than about 4, a viscosity of no more than about 1,500 cP at a shear rate of 10 at 25 °C, and a viscosity of at least about 250 cP at a shear rate of 50 at 25 °C (viscosities determined with a Brookfield Cone/Plate viscometer); and X ^" represents an inorganic or organic counterion.

[0051] In some embodiments, the composition may further include an aliphatic alcohol

ROH, wherein the R group is as defined herein. In some embodiments, the weight ratio of the glycine betaine ester to the aliphatic alcohol may be about 20: 1 to 1 :2, more commonly about 10: 1 to 2: 1. The glycine betaine ester may include a mixture of glycine betaine esters having R groups with 12 carbon atoms and 14 carbon atoms; and the composition may further include a mixture of fatty alcohols (ROH) having R groups with 12 carbon atoms and 14 carbon atoms. In some embodiments, the R group is the aliphatic group of a fatty alcohol. In some embodiments, the R group may be an aliphatic group of a Cio, Ci ₂ , Ci ₄ , and/or Ci ₆ alkyl group. In some embodiments, the R group may be a Cio-Ci ₆ aliphatic group. In some embodiments, the R group may be a C ₈ -C ₂₂ linear aliphatic group. In some embodiments, the R group may be a C ₈ , Ci ₀ , C _i2 , C _i4 , Ci ₆ and/or C _i8 alkyl group and/or an oleic group. In some embodiments, the R group may be a lauric, myristic, palmitic, stearic, and/or oleic group. In some embodiments, the R group may be an aliphatic group of a linear primary amine having 8 to 18 carbon atoms. In some embodiments, the X ^" represents a methanesulfonate anion. In some embodiment, the X ^" represents a methanesulfonate anion and the R group includes a lauric and/or myristic group.

[0052] The polysaccharide thickener may include xanthan gum and/or guar gum. In some embodiments, the polysaccharide may include starch or a modified starch. In some embodiments, the polysaccharide thickener includes starch, modified starch, agar, carrageenan, pectin, alginate, pectin, cellulose, and/or a cellulose derivative. The polysaccharide thickener may include a natural gum. In some embodiments, the natural gum may include agar, carob gum, guar gum, gellan gum, xanthan gum, and/or acacia gum.

[0053] In some embodiments, the acidifying agent may include a mineral acid, such as hydrochloric acid. In some embodiments, the acidifying agent may include a carboxylic acid, e.g., acetic acid and/or a hydroxycarboxylic acid. The hydroxycarboxylic acid may include lactic acid, citric acid, tartaric acid, gluconic acid, and/or glutaric acid. In some embodiments, the acidifying agent may include lactic acid and/or citric acid.

[0054] In some embodiments, the composition may include: about 0.1 - 15 wt.% of the glycine betaine ester; about 0.5 - 10 wt.% of the acidifying agent; about 0.5 - 5 wt.% of the polysaccharide thickener; and at least about 90 wt.% water. In some embodiments, the composition may include: (a) about 0.1 - 5 wt.% of the glycine betaine ester; (b) about 0.5 - 10 wt.%) of the acidifying agent; (c) about 0.5-5 wt.%> of the polysaccharide thickener; and (d) at least about 90 wt.%> water. In some embodiments, the composition may include: about 0.1 - 3 wt.%) of the glycine betaine ester; about 0.5 - 5 wt.%> of the acidifying agent, which may include a hydroxycarboxylic acid; about 0.5 - 3 wt.%> of the polysaccharide thickener, which may include a natural gum; and at least about 90 wt.%> water. In some embodiments, the composition may include: about 0.1 - 3 wt.%> of the glycine betaine ester; about 0.5 - 10 wt.%> of the acidifying agent, which may include a mineral acid; about 0.5 - 5 wt.%) of the polysaccharide thickener, which may include starch and/or a modified starch; and at least about 90 wt.%> water. In some embodiments, the composition may include: about 0.1 - 3 wt.%) of the glycine betaine ester; about 0.5 - 5 wt.%> of the acidifying agent, which may include a hydroxycarboxylic acid; about 0.5 - 5 wt.%> of the polysaccharide thickener, which may include starch and/or a modified starch; and at least about 90 wt.%> water. [0055] In some embodiments, in addition to the glycine betaine ester, the composition may further include a glycine betaine amide of formula (II):

Me ₃ N ⁺ -CH ₂ -C(0)-NH-R Y ^" (II) wherein R is an aliphatic group having 8 to 22 carbon atoms; and Y ^" represents an inorganic or organic counterion.

[0056] In some embodiments, the composition may further include methanesulfonic acid and/or glycine betaine and/or a salt thereof.

[0057] In some embodiments, the composition may have a viscosity of about 250 to 1,200 cP at a shear rate of 10 at 25°C. The composition may have a viscosity of about 150 to 1000 cP at a shear rate of 50 at 25°C. In some embodiments, the composition may have a 10/50 shear rate ratio of no more than about 3. In some embodiments, the composition may have a 10/50 shear rate ratio of no more than about 2.5.

[0058] In some embodiments, the composition may include: (a) about 0.1 - 1 wt.% of the glycine betaine ester; (b) about 1 - 4 wt.% of the acidifying agent, which may include lactic and/or citric acid; (c) about 0.2 - 1 wt.% of a natural gum thickener; and (d) at least about 95 wt.%) water. Such a composition may have a pH of no more than about 3, a 10/50 shear rate ratio of no more than about 3, and/or a viscosity of at least about 250 at a shear rate of 50 at 25 °C.

[0059] In some embodiments, the composition may include: (a) about 0.1 - 1 wt.%> of the glycine betaine ester; (b) about 1 - 10 wt.%> of the acidifying agent, which may include lactic and/or citric acid; (c) about 1 - 4 wt.%> of a thickener, which may include starch and/or a modified starch; and (d) at least about 90 wt.%> water. Such a composition may have a pH of no more than about 3, a 10/50 shear rate ratio of no more than about 3, and/or a viscosity of at least about 250 at a shear rate of 50 at 25 °C.

[0060] In some embodiments, the composition may include: (a) about 0.1 - 1 wt.%> of the glycine betaine ester; (b) about 1 - 10 wt.%> of an acidifying agent, which may include hydrochloric acid; (c) about 0.2 - 1 wt.%> of a natural gum thickener; and (d) at least about 90 wt.%) water. Such a composition may have a pH of no more than about 1.5 (typically no more than about 1), a 10/50 shear rate ratio of no more than about 3, and/or a viscosity of at least about 250 at a shear rate of 50 at 25 °C.

[0061] In some embodiments, the present liquid cleaning composition may comprise

(a) a glycine betaine ester of formula (I):

Me3N ⁺ -CH2-C(0)-0-R X ^" (I)

wherein R is an aliphatic group having 8 to 22 carbon atoms; and X- represents an inorganic or organic counterion;

(b) about 1 - 10 wt.% acidifying agent, which includes a mineral acid;

(c) polysaccharide thickener; and

(d) water; wherein the composition has a pH of no more than about 1. The mineral acid typically comprises hydrochloric acid, e.g., at least about 1 wt.% hydrochloric acid.

[0062] In some embodiments, the composition may include: (a) about 0.1 - 1 wt.% of the glycine betaine ester; (b) about 1 - 10 wt.% of the acidifying agent, which may include hydrochloric acid; (c) about 1 - 4 wt.% of a thickener, which may include starch and/or a modified starch; and (d) at least about 85 wt.% water. Such a composition may have a pH of no more than about 1.5, typically no more than about 1, a 10/50 shear rate ratio of no more than about 3, and/or a viscosity of at least about 250 at a shear rate of 50 at 25 °C.

[0063] In some embodiments, the present composition may be a liquid cleaning composition which includes (a) a glycine betaine ester of formula (I):

Me ₃ N ⁺ -CH ₂ -C(0)-0-R X ^" (I) wherein R is an aliphatic group having 8 to 22 carbon atoms; and X ^" represents an inorganic or organic counterion; (b) an acidifying agent; (c) polysaccharide thickener; and (d) water. The composition may have a pH of no more than about 3, a 10/50 shear rate ratio of no more than about 3, and/or a viscosity of at least about 250 at a shear rate of 50 at 25 °C. In certain embodiments, the composition may include about 0.1 - 3 wt.% of the glycine betaine amide; about 0.1 - 3 wt.% of the acidifying agent; about 0.1 - 4 wt.% of the polysaccharide thickener; and at least about 90 wt.% water. The acidifying agent may include an organic acid, such as lactic acid, glycolic acid, citric acid, acetic acid, malonic acid, succinic acid, tartaric acid gluconic acid, glutaric acid and/or methanesulfonic acid. [0064] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects.

[0065] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase "consisting essentially of will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of excludes any element not specified.

[0066] As used herein, "about" will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, "about" will mean up to plus or minus 10% of the particular term.

[0067] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0068] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0069] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof.