BR112015003775A2 - cleaning formulation - Google Patents

Abstract

Summary "Cleaning Formulation" The present invention provides water based cleaning formulations comprising one or more organic solvents having low water solubility and an alkylene glycol dilevulinate for coupling the organic solvent with water. 1/1

Description

CLEANING FORMULATION

Field of the invention [001] The present invention relates to cleaning formulations comprising water, one or more organic solvents having low water solubility, such as aliphatic hydrocarbons, aromatic hydrocarbons, or other organic compounds, and an alkylene glycol dilevulinate. Alkylene glycol dilevulinate is an excellent solvent for coupling organic solvents with water.

Background of the invention [002] Organic solvents are compounds that can be used to dissolve, soften, melt, or extract another compound, such as grease, earth, oil, paint, glue, stains, etc. and, therefore, are commonly used in cleaning formulations. Typical organic solvents include aliphatic hydrocarbons, isoparaffins, aromatic hydrocarbons, dormant hydrocarbons, terpenes and d-limonene, among others. Unfortunately, many organic solvents have limited solubility, or practically zero solubility, in water that severely limits the amount that can be added to aqueous based cleaning formulations, sometimes the point where their beneficial effects cannot be realized.

[003] Coupling agents are compounds that facilitate the dissolution and dispersion of organic solvents, in water-based formulations, in greater quantities than the other possible ones, while the formulations retain their transparency, viscosity and homogeneity. Various coupling agents are known for use in cleaning formulations including propylene glycol, diethylene glycol, ethers

2/31 glycol, and surfactants, among others. See U.S. Patent No. US 4,511,488. However, lower glycol ethers are volatile organic compounds (VOCs) that are environmentally undesirable. Some higher glycol ethers have less solubility in water-based systems, which limits their usefulness as a coupling agent.

[004] Levulinic acid esters are well known and described in the art as plasticizers and solvents. For example, English patent No. GB423919 describes the production of esters of levulinic acid with modified polyhydric alcohols which are useful as plasticizers for cellulose derivatives in coating applications.

[005] For example, U.S. Patent No. US 2,654,723 describes the preparation of diethylene glycol dilevulinate by heating a mixture of levulinic acid and diethylene glycol, in a solvent such as toluene and in the presence of an acid catalyst.

[006] International patent application No. WO 2010/102203 describes the preparation of alkyl levulinate by an acid-catalyzed reaction of furfuryl alcohol with other alcohols including methanol, ethanol, propanol, isopropanol, butanol and isobutane.

[007] In U.S. Patent No. US 3,203,964, a process is described for making levulinic acid esters by heating furfuryl alcohol with another alcohol selected from the group consisting of unsubstituted primary and secondary carbon chain and aliphatic carbon-oxygen and cycloaliphatic oxygen-carbon ring and alcohol containing from 1 to 10

3/31 carbon atoms, in the presence of an acid catalyst. United States Patent No. US 3,203,964 declares that levulinic acid esters are useful as plasticizers or solvents.

[008] The publication of international patent application No. WO 2007/094922 describes the use of levulinic acid ester derivatives to replace traditional plasticizers and coalescent solvents in polymeric compositions, plastics and water-based coatings, thus decreasing, your VOC content.

[009] The GB478854 patent describes the use of lower alkylene glycol dilevulinate (e.g., propylene glycol dilevulinate, diethylene glycol, ethylene glycol, trimethylene glycol (1,3-propanediol), 1,3-butylene glycol and dimethyl-dimethylol ) as high boiling softening agents suitable for cellulosic films. U.S. Patent No. US 2,581,008 describes the preparation of mono-, di- and tri-ethoxylated diol dilevulinate and its uses as plasticizers for polyvinyl acetals and other polymers.

[010] Furfuryl alcohol and levulinic acid are two of the reagents that can be used to make levulinic acid esters, for example, alkylene glycol dilevulinate. They are both economically renewable raw materials available from biomass. Thus, the use of levulinate as solvents in water-based cleaning formulations would be economically and environmentally beneficial.

[011] A solvent that could facilitate the use of organic solvents having low water solubility in water-based systems, such as aqueous cleaning formulations, would provide

4/31 a significant advantage over solvents traditionally used as coupling agents. The present invention provides for the use of alkylene glycol dilevulinate as new solvent alternative coupling agents in water based formulations.

Summary of the invention

The present invention provides a cleaning formulation comprising: (A) an aqueous solvent comprising water; (B) an active component comprising an organic solvent; and (C) a coupling agent comprising an alkylene glycol dilevulinate. The alkylene glycol dilevulinate has the general formula, CH ₃ C (0) CH ₂ CH ₂ C (0) ORO (0) CCH ₂ CH ₂ C (0) CH ₃ , where R is a linear C ₂ -C ₃ chain or a branched alkylene moiety, and the two levulinate groups (CH ₃ C (0) CH ₂ CH ₂ C (0) 0-) can be attached to the adjacent, or non-adjacent, carbon atoms of the alkylene moiety. In some embodiments, for example, R may be a C2-C3 alkylene moiety, and the alkylene glycol dilevulinate may be selected from the group consisting of: ethylene glycol dilevulinate, 1,2-propylene glycol dilevulinate and dilevulinate 1, 3-propylene glycol. The organic solvent can have a solubility of no more than 10% or no more than 5% by weight, in water at 25 ° C and atmospheric pressure, based on the total weight of the organic solvent and water in the solution. In addition, the organic solvent can be at least one compound selected from the group consisting of: an aliphatic hydrocarbon, an aromatic hydrocarbon, a dorado hydrocarbon, a terpene, a lemon oil, pine oil, methyl and so- limonene.

In one embodiment of the cleaning formulation of this

5/31 invention, the aqueous solvent comprising water (A) can be present in an amount from 90% to 98% by weight, the active component comprising an organic solvent (B) can be present in an amount from 0 , 1% to 5.0% by weight, and the coupling agent comprising an alkylene glycol (C) dilevulinate can be present in an amount from 0.1% to 6.0%, all percentages by weight with based on the total weight of the cleaning formulation.

Brief description of the drawings [012] A more complete understanding of the present invention will be acquired from the embodiments discussed below and with reference to the figures accompanying the application and in which:

[013] Figure 1 illustrates a schematic grid diagram of the general presentation of the sample formulations, each containing various types of glycol ether as a coupling agent, various amounts of d-limonene fragrance, and 1% lauryl surfactant sodium sulfate (SLS), which were tested for coupling effectiveness as shown in figures 2-4;

[014] Figures 2, 3 and 4 are diagrams according to the general presentation of figure 1 showing the coupling efficiency of glycol ether at 25 ° C, 40 ° C and 5 ° C, respectively;

[015] Figure 5 illustrates a schematic grid diagram of the general presentation of the sample formulations, each containing various types of ether glycol as a coupling agent, various amounts of d-limonene fragrance, and 0% SLS surfactant, which were tested for coupling effectiveness as shown in figures 6-8;

6/31 [016] Figures 6, 7, and 8 are diagrams according to the general presentation of figure 5, showing the coupling efficiency of glycol ether at 25 ° C, 40 ° C and 5 ° C, respectively;

[017] Figure 9 illustrates a schematic grid diagram of the general presentation of the sample formulation, each containing various types of alkylene glycol dilevulinate as a coupling agent, various quantities of the d-limonene fragrances, and 1% of the SLS surfactant , and tested for stability as shown in figures 10-12;

[018] Figures 10, 11 and 12 are diagrams according to the general presentation of Figure 9, showing the stability of formulations containing the dilevulinato alkylene glycol at 25 ° C, 40 ° C and 5 respectively;

[019] Figure 13 is a schematic grid diagram of the general presentation of the sample formulations, each containing various types of alkylene glycol dilevulinate as coupling agents, various amounts of the d-limonene fragrance, and 0% of the SLS surfactant. , and tested for stability as shown in figures 14-15; and [020] Figures 14, 15 and 16 are diagrams according to the overview of figure 13, showing the stability of formulations containing the dilevulinato alkylene glycol at 25 ° C, 40 ° C and 5 respectively.

Detailed description of the invention [021] The present invention relates to the use of alkylene glycol dilevulinate or alkylene glycol dilevulinate mixtures in a water-based cleaning formulation to couple the active component comprising organic compounds such as solvents or fragrances, having low or zero solubility in

7/31 water, with water. Alkylene glycol dilevulinate can be economically produced from levulinic acid and a glycol. Levulinic acid is available from biomass and is, therefore, a renewable-friendly source. In addition, glycols such as 1,2-propylene glycol and 1,3-propylene glycol are bio-renewable and therefore also environmentally friendly materials.

[022] Alkylene glycol dilevulinate are high-boiling, cleaning liquids with minimal odor and are not volatile organic compounds (VOCs). These particular characteristics provide the benefits and advantages to its use as alternative coupling agents in water-based cleaning formulations. For example, additional coupling agents such as propylene glycol, diethylene glycol and lower ether glycol are volatile organic compounds (VOCs) that are environmentally undesirable. In addition, with the exception of dipropylene glycol methyl ether, glycol ether is not as effective couplers as alkylene glycol dilevulinate. Alkylene glycol dilevulinate is partially completely soluble in water and are not VOCs. Since it is widely understood by those skilled in the relevant subject of the art that diesters are typically not soluble in water, the fact that alkylene glycol dilevulinate is soluble in water and therefore useful as coupling agents in d-based systems 'water is a surprising and unexpected benefit. In addition, the depositor found that the alkylene glycol dilevulinate provides better coupling performance that allows the use of more organic solvents having low or zero water solubility, in addition to those traditional coupling agents that are

8/31 used. The inclusion of larger amounts of organic solvents increases cleaning efficiency while maintaining the preferred formulation of characteristics such as homogeneity, clarity, stability and viscosity.

[023] It is believed that alkylene glycol dilevulinate could be particularly useful in aerosol products such as hair care, sanitizing, and insecticide and spray products, and spray applied to consumer products. These dilevulinate solvents allow for the most efficient, safe and most environmentally friendly formulations and can facilitate the development of many new formulations suitable for cleaning, coatings, pigment dispersants, pesticides, and agricultural applications.

[024] As used below, the terms an alkylene glycol dilevulinate and alkylene glycol dilevulinate have both meanings, include the presence of one or more compounds having the general formula, CH ₃ C (O) CH ₂ CH ₂ C (O) O-R0 (O) CCH2CH2C (O) CH ₃ , where R is a C2-C8 linear chain or a branched alkylene moiety, and the two levulinate groups (CH ₃ C (O) CH2CH2C (Ο) 0-) carbon atoms of the alkylene moiety may be attached to the adjacent or non-adjacent. Thus, an alkylene glycol dilevulinate can be a compound that meets the general formula above or a mixture of such compounds. Where a mixture of alkylene glycol dilevulinate is synthesized or otherwise available, it is not necessary for the various species from one another before using the mixture in a cleaning formulation according to the present invention.

[025] As also used here, the term components

9/31 organic assets means including organic materials that play a particular role in cleaning formulations, such as organic solvents, fragrances, etc. Organic solvents as the term is used here, mean compounds that dissolve, soften, melt, or extract another compound, such as grease, earth, oil, paint, glue, stains, etc., and which are therefore commonly used in formulations cleaning. Typical organic solvents include, without limitation, aliphatic hydrocarbons, isoparaffin, aromatic hydrocarbons, dormant hydrocarbons, and terpenes, among others. Fragrances, as the term is used here, means organic compounds that impart a particular odor to the cleaning formulation, and may or may not also provide the same function as organic solvents. Typical fragrances include, for example, d-limonene, lemon oil and pine oil.

[026] The term coupling agent as used here means compounds that facilitate the dissolution and dispersion of organic solvents in water-based formulations, in greater quantities than other possible ones, while the formulations retain their preferred characteristics of transparency, viscosity and homogeneity. Traditional coupling agents used in cleaning formulations include, without limitation, propylene glycol, diethylene glycol, glycol ether, and some surfactants, among others.

[027] It is observed that in the following description, the extreme points of ranges are considered as defined and are recognized for incorporating within their tolerance other values within the knowledge of a technician in the subject, including, but not limited to those that are

10/31 insignificantly different from the respective extreme points as reported in this invention (in other words, the extreme points must be constructed to incorporate values of about or close to or in proximity to each of the respective extreme points). The range and limit ratio, quoted here, are combinable. For example, if the range 1-20 and 5-15 is quoted for a particular parameter, it should be understood that ranges 1-5, 1-15, 5-20, or 15-20 are also contemplated and covered here .

[028] All percentages declared here are percentages by weight, unless otherwise stated. The cleaning formulations of the present invention comprise an aqueous solvent comprising water, an active component comprising at least one organic solvent, and at least one alkylene glycol dilevulinate.

[02 9] The aqueous solvent can comprise up to 100% in water. In addition, the cleaning formulation may comprise the aqueous solvent comprising water in an amount between 70 and 98% by weight, based on the total weight of the formulation. For example, the aqueous solvent comprising water can be present in an amount between 94 and 98% by weight.

[030] The organic active component may be an organic solvent or fragrance and may have a solubility in water of not more than 10% by weight at 25 ° C and atmospheric pressure or, for example, not more than 5% or even 1% in weight at 25 ° C and atmospheric pressure, based on the total weight of the organic solvent or fragrance and water in the solution. Typical examples include, without limitation, d-limonene, lemon oil, pine oil, methyl soiate, and terpenes.

[031] According to the present invention, formulations of

The cleaning may comprise an organic active component in an amount between 0.1 to 20.0% by weight, based on the total weight of the formulation. For example, without limitation, the active organic component can be present in an amount between 0.5 to 3.0% by weight.

[032] The alkylene glycol dilevulinate suitable for use in the present invention are lower alkylene glycol dilevulinate of the general formula CH ₃ C (O) CH ₂ CH ₂ C (O) O-R0 (O) CCH ₂ CH ₂ C (O ) CH ₃ , derived from alkylene glycol having the general formula HO-R-OH, where R is a straight chain C ₂ -Cs or a branched alkylene moiety, and the two hydroxyl groups can be on adjacent carbons, for example, ethylene glycol and 1,2-propylene glycol, or on non-adjacent carbons, for example, 1,3-propanediol or 1,6-hexanediol. Particularly suitable are alkylene glycol dilevulinate of the aforementioned general formula, where R is C ₂ -C ₃ alkylene, such as ethylene, 1,2-propylene, or 1,3propylene.

[033] In particular, the depositor noted that ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol diesters with levulinic acid are surprisingly good solvents for coupling aromatic and aliphatic hydrocarbons and other organic materials with water. Ethylene glycol dilevulinate (EGDL) is 100% water-soluble while 1,2-propylene glycol dilevulinate (1,2-PGDL) is 10% water-soluble by weight, and 1,3-propylene glycol dilevulinate (1 , 3-PGDL) is 25% soluble. All three compounds also dissolve aromatic hydrocarbon compounds such as toluene in xylene, while having limited solubility for simple aliphatic hydrocarbons such as

12/31 hexane and cyclohexane. Thus, C2-C3 alkylene glycol dilevulinate appears to provide the greatest benefit when used as coupling agents in water-based cleaning formulations.

[034] Cleaning formulations may appropriately comprise alkylene glycol dilevulinate in an amount between 0.1 and 6.0% by weight, based on the total weight of the formulation. For example, without limitation, alkylene glycol dilevulinate can be present in cleaning formulations in an amount between 0.5 and 3.0% by weight. The processes for preparing levulinate esters are well known and commercially practiced. For example, the publication of international patent application No. WO 2010/102203 describes the reaction of furfuryl alcohol with other alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, and isobutane), in equimolar amounts, in the presence of an acid catalyst, to produce corresponding alkyl levulinates.

[035] The alkylene glycol dilevulinate suitable for use according to the cleaning formulation of the present invention can be prepared by any process known now or in the future is not particularly limited. For example, U.S. Patent No. US 2,654,723 describes the preparation of diethylene glycol dilevulinate to involve the appropriate mixture of amounts of levulinic acid, diethylene glycol and toluene (as the reaction solvent), heating the mixture to react with the levulinic acid and diethylene glycol and to remove water produced by the reaction, followed by the removal of toluene by removing the yield in an amount of dilevulinate of

13/31 diethylene glycol, which has a boiling point above 200 ° C. From this source it is observed that the production of a dilevulinate from levulinic acid and an alkylene glycol requires the provision of these reagents in a molar ratio of (levulinic acid): (alkylene glycol) of at least 2: 1.

[036] Laboratory quantities of glycol dilevulinate can be conveniently prepared, for example, using the methods described in the examples provided below. [037] Thus, alkylene glycol dilevulinate suitable for use in the present invention includes, without limitation, those prepared from any linear or branched C2-C8 mono-, di- or tri-alkylene glycol and levulinic acid.

[038] With other known cleaning formulations, the cleaning formulations according to the present invention may contain ingredients in addition to water, an active organic component and a coupling agent. For example, cleaning formulations can also comprise one or more surfactants, buffers, chelating agents, biocides, fragrances, viscosity modifiers, colorants, and polymers, among other things.

[039] Suitable surfactants include, for example, without limitation, linear sodium sulfonated alkylbenzene, alkyl sulfates, alpha-olefin sulfonates, acyl sarcosinates, coconut fatty acid sodium salt, sulfonated alkyl esters, alkyl polyglucoside, alcohol primary ethoxylate, alkyl polypentaside, secondary ethoxylated alcohol, EO-PO and EO-BO block polymers, and sodium 3dodecylamino-propionate.

[040] Appropriate plugs include, for example, without

14/31 limitation, sodium hydroxide (NaOH), alkanolamine, amines, ammonia, alkali metal carboxylates, citric acid, sodium citrate, and lactic acid.

[041] Suitable chelators include, for example, without limitation, diamino-N acid, ethylene Ν'-tetraacetic acid, mono-, di-, tri- and tetra sodium salts (EDTA), nitriloacetic acid, trisodium salt ( NTA), hydroxyethyl iminodiacetic acid, disodium salt (HEIDA), methyl glycinodiacetic acid, trisodium salt (MGDA), glutamic acid, tetrasodium salt of N, N-diacetic acid (GLDA), iminodiacetic acid, tetrasodium salt, ( IDS), tri (hydroxymethyl) amino methane (TRIS), 2-maino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, and polyamines.

[042] The dyes appropriate, per example, include without limitation, dry. [043] Polymers appropriate for use in formulations in cleaning this invention, per example, include without

limitation, polyacrylate homopolymers and copolymers, METHOCELS, ETHOCELs, hydroxyethyl cellulose, POLYOXs, polyethylene glycol, polypropylene glycol, polyvinylpyrrolidones, and polyvinyl alcohols.

[044] The use, application and benefits of the present invention will be clarified by the following discussion and description of the exemplary embodiments and applications of cleaning formulations of the present invention.

EXAMPLES

Preparation of ethylene glycol dilevulinate:

[045] In the laboratory, we prepare glycol dilevulinates using an acid catalyst (Dowex DR-2030 beads

15/31 resin, a strong cation exchange resin) and the procedure described below:

[046] Ethylene glycol (9.17 g, 1.598 moles), levulinic acid (378.4 g, 3.259 moles), and 8.08 g of Dowex DR-2030 resin beads were placed in a 1-liter round bottom flask . The flask was connected to a Rotovapor Büchi and heated in a 95 ° C bath while a vacuum cleaner for water was applied. The water produced by the reaction was collected in the Rotavapor capture bottle. After 14 hours, the Dowex DR-2030 beads were filtered from the orange solution which was placed in a 500 ml round bottom flask. A Vigreux-coated 1-foot column surmounted by a standard vacuum distillation head with a thermometer and a water-cooled condensation indicator was attached to the flask, and the distillation at about 0.5 mm Hg at elevated temperature was started. Six fractions were then harvested at increased distillation temperatures. Fractions 3 to 5 varied from 95 to 98% of purity area based on gas chromatography analysis and represented a total of 67% yield based on the ethylene glycol used. The identity of the product as ethylene glycol dilevulinate was confirmed by ¹ H and ¹³ C NMR spectroscopy.

[047] 1,3-Propanediol dilevulinate and 1,2-propanediol dilevulinate were prepared in a similar manner with total yields of 70% and 59% respectively.

Examples 1-24 - Relative coupling effectiveness with fragrances:

[048] The following study was carried out to evaluate the stability and the coupling capacity of alkylene glycol dilevulinate in different formulations containing one of

16/31 three fragrances, open air, orange, and lemon.

[049] To speed up the preparation of cleaning formulations for testing, we created stock solutions that contained the main components that did not change throughout Examples 1-24, along with stock solutions with surfactant combinations. These stock solutions were used together with the other components to formulate the samples in percentage by weight. 20 grams of samples from each formulation were prepared. Each formulation contained the following ingredients in the amounts shown below in the Standard Ingredient Table of Examples 1-24:

Standard Ingredients Table - Examples 1-24

Name Quantity (% by weight) Description / Comment VERSENE HEIDA 1.00 Chelating agent, commercially available from Dow Chemical Company of Midland, Michigan, USA. An aqueous solution of ethanoldiglycine dissociates which is easily biodegradable. It is particularly useful for iron chelation in intermediate alkaline solutions Diisopropanolamine (DiPA) 0.50 A buffer replaces the traditional monoethanolamine (MEA) buffer Sodium hydroxide (NaOH) 0.20 Buffer, pH adjuster Water Variable Aqueous solvent Fragrance 0.50 One of the following listed in Table 1 free range lemon orange

Coupling agents / solvents tested:

[050] Each formulation containing 2.00% by weight of one of the following solvents / couplers, as shown in Table 1:

17/31 [051] PG-dilevulinate = 1,2-propylene glycol dilevulinate;

[052] 1,3-PG-dilevulinate = 1,3-propylene glycol dilevulinate;

[053] EG-dilevulinate - ethylene glycol dilevulinate;

[054] DOWANOL DPnP = dipropylene glycol propyl ether (a glycol ether of the P series).

[055] After the desired formulations with the fragrances were prepared, their stability was checked at 5 ° C, 20 ° C and 50 ° C and observed if the samples were clear / clear, cloudy, or cloudy. To assess light turbidity, we take a piece of paper with black text on it, and leave it behind the bottle containing the formulation. If it is possible to see the black text clearly, we note the wording as clear / transparent. If we could not see the text as a whole, we note the wording as cloudy. Finally, if we could see the text, as it was not a vibrant black, the wording was described as blurred. The less cloudy, or foggy, the better coupling achieved between water and fragrance (organic solvent).

[056] Table 1 below shows the results of the various tests of formulations containing fragrances difficult to couple (organic active ingredients), ie free air, orange, and lemon, using the test procedure mentioned above.

18/31

Table 1

Green surfactants ** Stability Fragrance (0.5%) Solvent/ Coupler (2.00% by weight) TERGI- TOL ECO— SURF ECO— SURF % of water 5 ° C 20 ° C 50 ° C 1 Open air PG-dilevulinate 0.50 0.25 0.25 95.30 cloudy cloudy Cloudy 2 Open air PG-dilevulinate 1.00 0.50 0.50 94.30 transparent transparent Cloudy 3 Orange PG-dilevulinate 0.50 0.25 0.25 95.30 Cloudy Transparent Cloudy 4 Orange PG-dilevulinate 1.00 0.50 0.50 94.30 Transparent Transparent Cloudy 5 Lemon PG-dilevulinate 0.50 0.25 0.25 95.30 Transparent Transparent Cloudy 6 Lemon PG-dilevulinate 1.00 0.50 0.50 94.30 Transparent Transparent transparent 7 Open air 1,3-PGdilevulinate 0.50 0.25 0.25 95.30 Cloudy cloudy Cloudy 8 Open air 1,3-PGdilevulinate 1.00 0.50 0.50 94.30 transparent transparent transparent 9 Orange 1,3-PGdilevulinate 0.50 0.25 0.25 95.30 Transparent Transparent Cloudy 10 Orange 1,3-PGdilevulinate 1.00 0.50 0.50 94.30 Transparent Transparent transparent 11 Lemon 1,3-PGdilevulinate 0.50 0.25 0.25 95.30 Transparent Transparent cloudy 12 Lemon 1,3-PGdilevulinate 1.00 0.50 0.50 94.30 Transparent Transparent transparent 13 Open air EG-dilevulinate 0.50 0.25 0.25 95.30 Transparent Transparent Cloudy 14 Open air EG-dilevulinate 1.00 0.50 0.50 94.30 Transparent Transparent transparent 15 Orange EG-dilevulinate 0.50 0.25 0.25 95.30 Transparent Transparent Cloudy 16 Orange EG-dilevulinate 1.00 0.50 0.50 94.30 Transparent Transparent transparent 17 Lemon EG-dilevulinate 0.50 0.25 0.25 95.30 Transparent Transparent cloudy 18 Lemon EG-dilevulinate 1.00 0.50 0.50 94.30 Transparent Transparent transparent

18/31

19/31

19 Open air DOWANOL DPnP 0.50 0.25 0.25 95.30 Cloudy cloudy transparent 20 Open air DOWANOL DPnP 1.00 0.50 0.50 94.30 Transparent Transparent transparent 21 Orange DOWANOL DPnP 0.50 0.25 0.25 95.30 Transparent Cloudy Cloudy 22 Orange DOWANOL DPnP 1.00 0.50 0.50 94.30 Transparent Transparent transparent 23 Lemon DOWANOL DPnP 0.50 0.25 0.25 95.30 Transparent Cloudy transparent 24 Lemon DOWANOL DPnP 1.00 0.50 0.50 94.30 Transparent transparent transparent

** green surfactants: each formulation also contained one of two possible combinations of three environmentally friendly surfactants, each of which is commercially available from the Dow Chemical Company of Midland, Michigan, USA;

TERGITOL 15-S-15 = a highly hydrophilic-lipophilic and dispersing balance emulsifier;

ECOSURF EH-6 = A water-soluble nonionic surfactant; and

ECOSURF EH-9 = a water-soluble nonionic surfactant.

19/31

20/31

Example of Arrangement I (Comparative) & Arrangement II (work) Figures 1-16 [057] Two arrangements of experiments (I & II) were performed to determine the effectiveness of the relative coupling of aqueous formulations containing fragrances (d-limonene) having various traditional coupling agents (ether glycol) and those having various alkylene glycol dilevulinate as the coupling agent, at various temperatures (5 ° C, room temperature (25 ° C) and 40 ° C). Details are provided below and the results are illustrated in the diagrams provided in figures 1-16 and explained below: Table of Standard Ingredients - Arrangement I & II

Name Quantity (% by weight) Description / comment Sodium lauryl sulfate (SLS) None or 1% Surfactant Water Variable Aqueous solvent D-limonene (fragrance) Various Fragrance amounts were varied between 0.5%; 0.75%; 1.5% and 3% by weight

[058] More particularly, the cleaning formulations were both:

Arrangement I - Comparative examples (see figure 1-8), which included a known coupling agent selected from one of the ether glycols below, in an amount of 1.5; 10 or 20 weight percent as indicated in the figures;

BuCb = n-butyl diethylene glycol ether

BTG = n-butyl triethylene glycol ether

HxCb = diethylene glycol n-butyl ether

ETG = triethylene glycol ethyl ether

MTG = triethylene glycol methyl ether

TPM = tripropylene glycol methyl ether [059] Or Arrangement II - Working examples (see figures

21/31

9-16) which included an alkylene glycol dilevulinate according to the present invention, or DOWANOL DPM, monomethyl ether dipropylene glycol, in an amount of 1, 5, 10 or 20 weight percent, and selected from the following compounds :

1.2- EGDL = ethylene glycol dilevulinate,

1.2- PGDL = 1,2-propylene glycol dilevulinate,

1.3- PGDL = 1,3-propylene glycol dilevulinate,

1.2- EGDL + 1,2-PGDL = 50/50 mixture of dilevulinate of

1.2- ethylene glycol + 1,2-propylene glycol dilevulinate, DPM = methyl dipropylene glycol ether.

[060] Referring now to the figures, figures 1-8 refer to the arrangement of comparative examples. Each circle represents a formulation sample. More particularly, each of Figures 1 & 5 provides a schematic grid diagram of the general presentation of the formulation sample having various types of ether glycol as the coupling agent and various amounts of d-limonene fragrance, in the presence of 1% of the SLS surfactant and absence (0%) of the SLS surfactant.

[061] For example, the arrows A & B of the grid in figure 1 were formulations that each had 0.25% by weight of d-limonene. Thus, arrows A & B in each of figures 2-4 and 5-8 represent formulations that had 0.25% by weight of dlimonene.

[062] Columns 1 & 2 of the grid in Figure 1 form formulations that contained various amounts of BuCb, a glycol ether, as the coupling agent. More specifically, column 1 of the grid in figure 1 illustrates that for each vertical pair of formulations, the top formulation had 1 wt% BuCb and one at the bottom had 10 wt% BuCb. Similarly, the

22/31 column 2 of the grid in figure 1 shows that for each vertical pair of formulations, the top formulation had 5% by weight of BuCb and one at the bottom had 20% by weight of BuCb. This information can be similarly translated into columns 1 & 2 of figures 2-4.

[063] Thus, to provide a random example, the sample formulation in arrow D, column 6 contained the standard ingredients listed in the Table above for arrangements I and II, as well as 0.75% by weight of d-limonene and 20 % by weight of HxCb as the coupling agent based on the weight of the formulation.

[064] Figures 2-4 and 6-8 illustrate the results (transparency / light or cloudy / dark) for the samples of the formulations identified in the grids of figures 1 and 5 at 5 ° C, room temperature (25 ° C), and 40 ° C, respectively. Transparency indicates successful coupling of d-limonene and cloudy indicates little or no coupling.

[065] Generally speaking, a review of figures 68 seems to indicate that ether glycol has had some success in coupling d-limonene in aqueous formulations, but only when the amount of d-limonene was relatively low, that is, 0.25% by weight.

[066] More specifically, the sample of the formulation in arrow D, column 6, which contained 0.75% by weight of d-limonene and 20% by weight of HxCb, was cloudy at 5 ° C (figure 2), transparent at temperature (Figure 3), and cloudy at 40 ° C.

[067] Figures 9-16 refer to arrangement II of the working examples. As in figures 1-8, each circle represents a sample of the formulation. More particularly, figure 9 provides a diagram of the schematic grid of the general presentation of the samples of the formulations having several

23/31 types of alkylene glycol dilevulinate as coupling agent in various amounts of the dlimonene fragrance. For example, the arrows A & B of the grid in figure 9 were formulations that had 0.25% by weight of d-limonene. Thus, arrows A & B in each of figures 10-12 & 14-16 represent formulations that had 0.25% by weight of dlimonene.

[068] In addition, columns 1 & 2 of the grid in figure 9 were formulations that contained varying amounts of dilevulinate

1,2-ethylene glycol (1,2-EGDL) as the coupling agent according to the present invention. More specifically, column 1 of the grid in figure 9 represents each of the vertical pairs of the formulations, the top formulation had 1% by weight of 1,2-EGDL and one at the bottom had 10% by weight of 1,2-EGDL . Similarly, column 2 of the grid in figure 9 shows that for each vertical pair of formulations, the top formulation had 5% by weight of 1,2-EGDL and one at the bottom had 20% by weight of 1,2-EGDL. This information can be similarly translated into columns 1 & 2 of figures 10-12-14-16.

[069] Thus, to provide a random example, the formulation sample in arrow f, column 6 contained the standard ingredients listed in the table above for arrangements I & II, as well as 1.5% by weight of d-limonene and 20 % by weight of 1,2-EGDL as the coupling agent, based on the total weight of the formulation.

[070] Figures 10-12 & 14-16 illustrate the results (transparency / light or cloudy / dark) for the samples of the formulations identified in the grids of figures 9 & 13 at 5 ° C, room temperature (25 ° C) and 40 ° C, respectively. Transparency indicates the successful coupling of d-limonene and

24/31 cloudy indicates little or no coupling.

[071] Generally speaking, a review of figures 10-12 & 14-16 seems to indicate that dilevulinate and alkylene glycol are more successful in coupling d-limonene in aqueous formulations over a wide range of temperatures and concentrations of d- limonene in addition to those commonly used in ether glycol.

[072] More specifically, samples of formulations in arrow F, column 6 that contained 1.5% by weight of d-limonene and 20% by weight of 1,2-EGDL, were clear at 5 ° C (figure 2) , transparent / clear at room temperature (figure 3), and cloudy at 40 ° C.

[073] Figures 1-16 show the phase stability data of ether glycol and alkylene glycol dilevulinate with varying levels of d-limonene in the presence of 1% of the surfactant SLS and absence of (0% of SLS) of the surfactant .

[074] In the absence of the added SLS surfactant, many of the tested glycol ether solvents were unable to couple more than 0.25% d-limonene in an aqueous mixture. The only exception was DOWANOL DPM. In contrast, the experimental solvents of dilevulinate glycol were quite effective in coupling d-limonene in the absence of the surfactant. Ethylene glycol dilevulinate and 1,3propylene glycol dilevulinate were better than 1,2propylene glycol dilevulinate. This is in accordance with its observed water solubility.

[075] In the presence of 1% SLS, all solvents tested showed an improvement in the probability of being clear / transparent. The solvents Hexil CARBITOL, DOWANOL DPM, and dilevulinate glycol at a level of 20% were able to couple with

25/31 success even at the highest levels tested with d-limonene, 3%.

Examples A - FF = Relative cleaning performance of formulations:

[076] These experiments are intended to measure how much the cleaning formulations containing various solvent / coupling agents, as well as the different combinations of surfactants, played in terms of leaving films or bands / streaks, and how efficiently they cleaned.

[077] Again, we created stock formulations that contained the main components that do not change during each formulation arrangement, along with stock solutions with combinations of surfactants, both 0.5% and 1.0% of the total surfactant, as shown in Table 2 below. These stock solutions were used together with other components to formulate the samples in percentage by weight. None of these formulation samples contained any fragrance, since the objective was to see how much cleaning formulations containing different coupling agents and surfactant combinations cleaned. 20 grams of each formulation were prepared.

[078] Each formulation containing the following ingredients in the amounts shown below in the Standard Ingredient Table - Examples A - FF:

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Table of standard ingredients - Examples A-FF

Name Quantity (% by weight) Description / comment VERSENE HEIDA 0.5 Chelating agent, commercially available from Dow Chemical Company of Midland, Michigan, USA. An aqueous solution of disodium ethanoldiglycine that is easily biodegradable. It is particularly useful for chelation and iron in intermediate alkaline solutions Diisopropanolamine (DiPA) 0.50 A buffer replaces the traditional monoethanolamine (MEA) buffer. Sodium hydroxide (NaOH) 0.20 Buffer, pH adjuster Water Variable Aqueous solvent

Coupling agent / Solvents tested:

[079] Each formulation containing 1.00% by weight of one of the following solvents / couplers below, as shown in Table 2:

PGDL = PG-dilevulinate = 1,2-propylene glycol dilevulinate;

1,3-PGDL = 1,3-PG-dilevulinate = 1,3-propylene glycol dilevulinate;

EGDL = EG-dilevulinate - ethylene glycol dilevulinate;

DPnP = DOWANOL DPnP = dipropylene glycol propyl ether (a glycol ether of the P series).

Surfactant and combinations of the same tested:

[080] Each formulation containing a total of both 0.5% and 1.0% surfactants, as follows and shown in Table 2 below:

[081] Different combinations of the three ecologically friendly surfactants (green), but always totaling

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0.5 or 1.0% by weight, were tested between cleaning formulations. Each of the following surfactants is commercially available from Dow Chemical Company of Midland, Michigan, USA:

TERGITOL 15-S-15 = a highly hydrophilic-lipophilic and dispersing balance emulsifier;

ECOSURF EH-6 = A water-soluble nonionic surfactant; and ECOSURF EH-9 = a water-soluble non-ionic surfactant. [082] For some formulations, one of the other products below, less environmentally friendly materials (both commercially available from Shell Chemical LP in Houston, Texas, USA) has been replaced by surfactant in amounts of either 0.5 or 1.0% in Weight.

NEODOL 25-7 = one mixture of C12-C15 alcohol containing an average of 7 mol of oxide of ethylene per mol of alcohol. NEODOL 45-7 = one alcohol mixture C14-C15 containing an average of 7 mol of oxide of ethylene per mol of alcohol.

[083] After the desired formulations with various coupling agents and surfactant combinations were prepared, their performance was tested with respect to cleaning efficiency (film and strips / streaks) and stability (appearance at 5 ° C, 20 ° c and 60 ° C), as follows.

Film and Streaks / Streaks:

[084] To test the residue left by the cleaning formulation, the film and strip tests were performed on glass tiles. Ten drops in a circular pattern were applied to a glass tile and cleaned with a folded piece of cleaning cloth with five steps. No downward pressure was applied to the tile, just pressure to create a forward and backward motion. The tiles

28/31 were allowed to dry for 30 minutes. The tiles were rated on a scale of 1-10 for both film and strips compared to standards where WINDEX®: Film = 1, streaks + 1 and FANTASTIK®: Film = 10, streak = 10. All tiles classified by the same operator to minimize discrepancy in classification and to eliminate differences by operator.

Hard surface cleaning: spring compression device (SCiD):

[085] The cleaning energy of the hard surface of the formulations was tested by removing soil from a vinyl tile. The vinyl tiles were cut to match the sample size of 11.5 cm x 7.5 cm and 500 μΐ of Brazil soil carbon black 3% was applied to the grooved side of the tile using a foam applicator. The tiles were set to dry for approximately 24 hours, and then the tile was placed on the SCiD plate and represented on an orbital shaker. 400 μΕ of the cleaning solutions were dispensed into each well along with a carpet mop, and the samples were run on the shaker for five minutes. For each sample, 3 wells were tested, and the samples were run side by side with a good and bad cleaning pattern. The samples were scanned on a computer and analyzed using image software. The cleaning power was measured using an average value of five wells, and the cleaning power of the sample was measured using the average gray value of the three wells. A higher gray value corresponds to a lighter circle and greater cleaning power, while a lower gray value corresponds to a darker circle and low cleaning power.

29/31 [086] Table 2 below shows the results of the various tests of the formulations containing different coupling agents and surfactant combinations, using the test procedure mentioned above. It was observed that the values for film and streaks / bands of each run from 1 to 10, with smaller numbers representing at least one film or streak / spot and, therefore, being the preferred values. For the average gray performance characteristic, larger values are considered more preferred.

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Table 2

Solvent / Coupler Green surfactant Other surfactants Cleaning performance Stability DPnP PGDL EGDL 1.3- PDGL ECOSURF EH-6 ECOSURF EH-9 TERGITOL 15-S-15 NEODOL 25-7 NEODOL 45-7 Water (%) Film (1-10) Stretch marks (1-10) 60 ° C 5 ° C Average gray values THE 1.00 0.13 0.13 0.25 97.3 3 2 clear sure 6 9.66 B 1.00 0.25 0.25 0.50 96, 8 4 4 clear sure 93.52 Ç 1.00 0.17 0.17 0.17 97.3 4 4 clear sure 82.96 D 1.00 0.33 0.33 0.33 96, 8 5 5 clear sure 94.82 AND 1.00 0.50 97.3 5 6 Cloudy Cloudy 83, 67 F 1.00 1, 0 96, 8 3 2 Cloudy Cloudy 91.09 G 1,001.00 0.50 97.3 4 3 cloudy Cloudy 73.13 H 1.00 96, 8 5 5 Cloudy Cloudy 85, 96 I 1.00 0.13 0.13 0.25 97.3 4 5 clear sure 99.50 J 1.00 0.25 0.25 0.50 96, 8 6 6 clear sure 126, 84 K 1.00 0.17 0.17 0.17 97.3 5 5 clear sure 114.50 L 1.00 0.33 0.33 0.33 96, 8 6 6 clear sure 164.02 M 1.00 0.50 97.3 5 6 Cloudy Cloudy 86.77 N 1.00 1.00 96, 8 5 5 Cloudy Cloudy 115.17 0 1.00 0.50 97.3 5 6 Cloudy Cloudy 61.33 P 1.00 1.00 96, 8 6 6 Cloudy Cloudy 63,716 Q 1.00 0.13 0.13 0.25 97.3 5 5 clear clear 79.37 R 1.00 0.25 0.25 0.50 96, 8 7 7 sure clear 97.50 s 1.00 0.17 0.17 0.17 97.3 5 5 sure clear 84.14 T 1.00 0.33 0.33 0.33 96, 8 6 6 sure clear 119.47 u 1.00 0.50 97.3 6 6 cloudy cloudy 84.88 V 1.00 1.00 96, 8 7 7 cloudy Cloudy 129.51 w 1.00 0.50 97.3 7 7 cloudy cloudy 60.44 X 1.00 1.00 96, 8 8 8 Cloudy cloudy 92.77

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Y 1.00 0.13 0.13 0.25 97.3 3 4 cloudy Cloudy 104.54 z 1.00 0.25 0.25 0.50 96, 8 6 5 clear sure 121.08 AA 1.00 0.17 0.17 0.17 97.3 4 5 clear clear 129, 60 BB 1.00 0.33 0.33 0.33 96, 8 5 5 clear clear 138.14 CC 1.00 0.50 97.3 5 5 cloudy clear 121.33 DD 1.00 1.00 96, 8 6 5 cloudy clear 143.99 AND IS 1.00 0.50 97.3 4 5 cloudy cloudy 97.69 FF 1.00 1.00 96, 8 5 5 cloudy cloudy 114.68

* Note: All formulations remained clear at 20 ° C.

Claims (10)

1. Cleaning formulation, characterized by the fact that it comprises: (A) an aqueous solvent comprising water; (B) an active component comprising an organic solvent; and (C) a coupling agent comprising an alkylene glycol dilevulinate having the general formula, CH ₃ C (0) CH ₂ CH ₂ C (0) 0-R0 (0) CCH ₂ CH ₂ C (0) CH ₃ , where R is a straight C ₂ -C ₃ chain or a branched alkylene moiety, and the two levulinate groups (CH ₃ C (0) CH ₂ CH ₂ C (0) 0-) can be attached to the adjacent, or non-adjacent, carbon atoms of the alkylene moiety. 2. Cleaning formulation according to claim 1, characterized in that said organic solvent has a solubility of no more than 10% by weight, in water at 25 ° C and atmospheric pressure based on the total weight of the organic solvent and water in solution. 3. Cleaning formulation according to claim 1, characterized in that said organic solvent is at least one compound selected from the group consisting of: an aliphatic hydrocarbon, an aromatic hydrocarbon, a dorado hydrocarbon, a terpene, oil lemon, pine oil, methyl somalate and dlimonene. 4. Cleaning formulation according to claim 1, characterized in that R is a C ₂ -C ₃ alkylene moiety. 5. Cleaning formulation according to claim 4, characterized in that said alkylene glycol dilevulinate is one or more compounds selected from the group consisting of: ethylene glycol dilevulinate, 1,2-propylene glycol dilevulinate, and dilevulinate 1,3propylene glycol. 2/2 6. Cleaning formulation according to claim 1, characterized in that the aqueous solvent comprises (A) present in an amount from 90% to 98% by weight, the active component comprising an organic solvent (B) present in an amount from 0.1% to 5.0% by weight, and the coupling agent comprising an alkylene glycol dilevulinate (C) present in an amount from 0.1% to 6.0%, all weight percentages based on the total weight of the cleaning formulation. 7. Cleaning formulation according to claim 6, characterized in that the aqueous solvent comprises water (A) present in an amount from 94% to 98% by weight. 8. Cleaning formulation according to claim 6, characterized in that the active component comprises an organic solvent (B) present in an amount from 0.5% to 3.0% by weight. Cleaning formulation according to claim 6, characterized in that the coupling agent comprises an alkylene glycol (C) dilevulinate present in an amount from 0.5% to 3.0% by weight. 10. Cleaning formulation according to claim 1, characterized in that it additionally comprises one or more of the following additional components: (D) surfactants; (E) chelating agents; (F) pH buffers / adjusters; (G) biocides; (H) fragrances; (I) viscosity modifiers; (J) dyes; and (K) polymers.