Patent Grant
6851433
This invention relates to all purpose spray cleaners and to concentrates which can be diluted to produce the all purpose spray cleaners.
Typical all purpose spray cleaners contain from 4 to 5% by weight of glycol ether, as well as alkaline builders and surfactants. Due to the above components, single phase, uniform, and stable concentrates having more than a 5 or 10 times concentration have not been possible, since incompatibility and insufficient solubility of these three components will occur in higher concentrations. For example, in order to produce a single phase, uniform, and stable 50× concentrate, the glycol ether component would either have to be removed or at least drastically reduced, resulting in a marked reduction in the cleaning performance of the use dilution.
This invention relates to organic solvent-free all purpose spray cleaner compositions and concentrates therefor which are highly concentrated, e.g. to from 25 to 50 times, without any change in the formulation, and wherein the concentrates are single phase, uniform, and stable free flowing liquids, and can be readily diluted with water without any tendency to gel.
The organic solvent-free concentrates of the invention are comprised of the following components:
provided that the total quantity of nonaqueous components is from 25 to 60% by weight, preferably from 40 to 50% by weight.
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term “about”.
The Surfactant 1 component is at least one base-catalyzed reaction product of reactants comprising:
The mole ratio of the linking compound (I) to (II) is from 0.1:1 to 5:1, preferably from 0.6:1 to 2:1, more preferably from 0.8:1 to 2:1, and most preferably from 1.0:1 to 1.5:1.
In the above compounds of component A), the linking compound of formula I is preferably epichlorohydrin or another epihalohydrin. Also, trihaloalkanes can be used, such as 1,2,3-trichloropropane, 1,2,4-trichlorobutane, 1,3,6-trichlorohexane, and the like. Instead of chlorine in the epichlorohydrins and the trihaloalkanes, the corresponding bromine and iodine compounds can also be used, including compounds containing two or even all three of the above halogens.
The component B) compounds of formula II are organic (optionally alkoxylated) alcohols or the corresponding sulfhydryl or amine compounds.
The R2 group can be a substituted or unsubstituted, saturated or unsaturated hydrocarbon group having from 1 to 36 carbon atoms. Examples of such hydrocarbon groups include linear or branched alkyl groups having from 1 to 36 carbon atoms, preferably from 4 to 22 carbon atoms, linear or branched alkenyl or alkynyl groups having from 2 to 36 carbon atoms, preferably from 4 to 22 carbon atoms, aryl groups having from 6 to 22 carbon atoms, and arenyl groups having from 7 to 36 carbon atoms. Arenyl groups are alkyl-substituted aromatic radicals having a free valance at an alkyl carbon atom such as a benzylic group.
The R2 group can also be a saturated carbocyclic group, an unsaturated carbocyclic group having one or more multiple bonds, a saturated heterocyclic group, or an unsaturated heterocyclic group having one or more multiple bonds. Any of the above R2 groups can be substituted groups, i.e. the groups can be single or multiple substituents such as one or more halogen substituents, for example Cl, F, I, and Br; a sulfur functionality such as a mercaptan or thio group; a nitrogen functionality such as an amine or amide functionality; an alcohol functionality, a silicon functionality, e.g., a siloxane; an ether functionality, e.g. a C1-C6 alkoxy group; or any combination thereof.
The R2 group in formula II is preferably a branched chain alkyl group containing from 4 to 36 carbon atoms, preferably from 4 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms.
When the X group of formula II is an —S—group, the R2 group will preferably have from about 4 to about 22 carbon atoms, examples of which include but are not limited to, dodecyl mercapto and 1-hexadecanethio.
When the R2X—group of formula H is a secondary or tertiary amino group, the group preferably contains from 4 to 22 carbon atoms, and n is preferably a number of from 4 to 50. Examples of primary and secondary amines useful for obtaining the R2X—group include, but are not limited to, dibutyl amine, cyclohexyl amine, isodecyl amine, and dioctylamine.
When Y in formula II is an amine or sulfhydryl group, the resulting compounds can be readily prepared from the corresponding alcohols wherein the terminal hydroxy group is replaced by an —SH group or by an amine nitrogen. For example, a compound of formula II where Y is —OH can be subjected to a catalyzed ammoniation (with ammonia, or a lower alkylamine) for replacement of the hydroxyl.
In the compounds of formula II, the AO groups when present are preferably all ethyleneoxy groups. However, as stated above, each OA group can be independently an ethyleneoxy (EO), 1,2-propyleneoxy (PO), 1,2-butyleneoxy (BO) group, i.e. any one or more of such groups can be present, and they can be present in any order, as well as be present in blocks, e.g. compounds of formula III:
R2O(EO)m(PO)p(BO)qH (III)
wherein R2 has the meaning given above, m is a number of from 0 to 100, preferably from 1 to 50, p is a number of from 0 to 50, and q is a number of from 0 to 50. Compounds of formula III in which R2 is a branched chain alkyl group having from 4 to 12 carbon atoms, m is a number of from 2 to 20, and p and q are 0 are preferred. The most preferred compound is the reaction product of epichlorohydrin and isodecyl alcohol—4EO, marketed by Cognis Corporation Ambler, PA, 19002 as DEHYPOUND® ST-15.
The degree of hydrophilic and hydrophobic properties of the reaction products of components A) and B) can be readily controlled by controlling the type and number of alkyleneoxy groups in component B). For example, the greater the number of ethyleneoxy groups present, the greater the water solubility, while the presence of 1,2-propyleneoxy groups and/or 1,2-butyleneoxy groups for example, will decrease water solubility.
In general, the compounds of formula III wherein the sum of n, m, and p is at least 1, and especially at least 2 or 3 are preferred for use herein.
The above reaction products can be prepared by the process disclosed in U.S. Pat. No. 5,827,453, the disclosure of which is expressly incorporated herein by reference.
In general, the component A) and B) reactants are reacted together, preferably in the presence of an inert organic solvent such as toluene that will azeotrope water, and in the presence of a base, such as aqueous sodium hydroxide, at a temperature of from 60° to 125° C. Preferably component B) is first mixed with the base and the organic solvent, and water is removed by azeotropic distillation. Then component A) is slowly added and the reaction continued until the reaction is completed. The reaction mixture is filtered and vacuum stripped to remove the organic solvent.
Surfactant 2 is at least one alkyl polyglycoside having formula IV below:
R1O(R2O)b(Z)a (IV)
wherein R1 is a monovalent organic radical having from about 6 to about 30 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably having an average of from 10 to 10.5 carbon atoms; R2 is a divalent alkylene radical having from 2 to 4 carbon atoms; Z is saccharide residue having 5 or 6 carbon atoms; b is a number having a value from 0 to about 12; a is a number having a value from 1 to about 6, preferably from 1.2 to 2.2, and more preferably from 1.5 to 1.7. Preferred alkyl polyglycosides which can be used in the compositions according to the invention have the formula I wherein Z is a glucose residue and b is zero. Such alkyl polyglycosides are commercially available, for example, as APG®, GLUCOPON®, or PLANTAREN® surfactants from Cognis Corporation, Ambler, PA, 19002. Examples of such surfactants include but are not limited to:
The most preferred alkyl polyglycosides for use in the present invention are GLUCOPON® 425 or 425N, which are alkyl polyglycosides in which the alkyl group contains an average of 10.3 carbon atoms, and the average degree of polymerization is 1.5.
The builders that can be used in the concentrates of the invention include one or more of the following: bases, polycarboxylic acid salts, and solubilizers.
The bases that can be used as builders include alkali metal hydroxides, e.g. sodium or potassium hydroxide, alkaline earth metal hydroxides, and amines, especially mono-, di-, or tri-ethanolamine.
The polycarboxylic acid salts that can be used as builders include tetrasodium ethylenediamine tetraacetic acid, (tertasodium EDTA), which is preferred for use herein, or an alkali metal citrate, especially sodium citrate, although other polycarboxylic acid salts can be used instead of, or in addition to, the above, such as other aliphatic di- or tri-carboxylic acid salts, e.g. sodium tartrate, sodium succinate, sodium maleate, sodium malonate, and the like. Also, alkaline earth metal salts or alkanolamine salts, e.g. mono-, di-, or triethanolamine salts of the above polycarboxylic acids can be used instead of the alkali metal salts, provided they possess adequate water solubility and are otherwise compatible with the other components of the concentrate.
The alkali metal hydroxide is preferably sodium or potassium hydroxide.
The solubilizers that can be used as builders include salts, especially alkali metal, e.g. sodium salts, of fatty acid alcohol sulfates, e.g. C6-C12 fatty alcohol sulfates. The preferred solubilizer is the sodium salt of n-decyl alcohol sulfate.
The preferred builder for use in the concentrates of the invention is a combination of triethanolamine, tetrasodium EDTA, and the sodium salt of n-decyl alcohol sulfate.
The above concentrates can then be diluted with water to obtain in-use dilutions, e.g. by adding 1 part of the concentrate to from 25 to 60 parts by weight of water.
The concentrates of the invention provide reduced storage and shipping space and expense, since they are highly concentrated. In addition, they contain no volatile organic solvents and hence present no fire or explosion risks. The in-use dilutions have no objectionable odors to consumers, are easy to fragrance, using less fragrance since there are no solvent odors to mask, and exhibit excellent cleaning ability on oily soil, without the use of organic solvents. In addition, the formulation cost of obtaining the in-use dilution from the concentrates is extremely low. They can also be used as all-purpose concentrates, and in hard surface wet wipes.
The invention will be illustrated but not limited to the following examples.
A free flowing liquid highly concentrated organic solvent-free all-purpose spray cleaner concentrate was prepared by mixing together the following components:
1 part by weight of the concentrate of Example 1 was added to 50 parts by weight of water resulting in the use dilution (test solutions) set forth below, which was obtained without any tendency to gel:
The use dilution composition of Example 2 was evaluated for hard surface cleaning performance in a side-by-side comparison with the national brand all purpose spray cleaner FANTASTIK® (test solution) using H7 test soil on Armstrong tiles according to the following method. FANTASTIKO contains 4-5% by weight of the volatile glycol ether solvent, an alkaline builder, and one or more surfactants.
H7 Test Soil composition coated onto 3″×3″ Armstrong 56830 Chalk II Vinyl Composite Tiles. The H7 Test Soil Composition was composed of the following components:
Procedure For Soil Application:
0.4 Ml of the above soil composition was applied to the rough side of the above vinyl composite tiles (test panels). The soil was applied with the grain on the panel, using a nylon brush. The panels were dried for 20 minutes at room temperature, then for 20 minutes at 100° C., and then for a final 20 minutes at room temperature.
Cleaning operation (after measuring the reflectance of both the unsoiled tiles and the soiled tiles):
The results obtained are set forth below:
The 90% confidence interval for the method is 2.7% soil removal.
It can be seen that the cleaning performance of the composition of Example 2 of the invention was as good as that of the commercial product FANTASTIK®, despite the fact that the actives content of Example 2 was less than 1% by weight. The actives content of commercial ready to use all purpose spray cleaners such as FANTASTIK® is typically in the range of 6 to 10% by weight.
The following volatile organic compound free all purpose cleaner concentrate was prepared by mixing together the following components:
The above concentrate had a specific gravity of 1.130 and a pH of 11.8.
The concentrate of Example 4 was diluted 1 part in 4 parts of water. This 20% solution at 2 ounces per gallon was compared to the commercial brands “MR CLEAN® antibacterial” and “MR. CLEAN® Top Job” at 2 ounces per gallon using the test method set forth in Example 3. The results obtained are set forth below:
Reflectance data from the hard surface detergency evaluation (washed tiles):
The concentrate of Example 4 was diluted to 5% in water and 2.5% in water and compared to the commercial brand “FANTASTIK®”. The results are given below:
Reflectance data from the hard surface detergency evaluation (washed tiles):
The concentrate of Example 4 was diluted to 0.32% in water and compared to the commercial brand glass cleaner “WINDEX™”. The results are set forth below:
Reflectance data from the hard surface detergency evaluation (washed tiles):
This application claims the benefit of copending provisional application Ser. No. 60/335,911, filed on Nov. 2, 2001, the entire contents of which are incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 5827453 | Gross et al. | Oct 1998 | A |
| 5895605 | Gross et al. | Apr 1999 | A |
| 6110977 | Gross et al. | Aug 2000 | A |
| 6532973 | Gross et al. | Mar 2003 | B1 |
| Number | Date | Country | |
|---|---|---|---|
| 60335911 | Nov 2001 | US |
