WO2002031094A2

WO2002031094A2 - Clear softening formulations including alkoxylated additives

Info

Publication number: WO2002031094A2
Application number: PCT/US2001/028533
Authority: WO
Inventors: Pierre Marie Lenoir; Irene Siegrist
Original assignee: Dow Chemical Co; Dow Global Technologies LLC
Current assignee: Dow Chemical Co; Dow Global Technologies LLC
Priority date: 2000-10-06
Filing date: 2001-09-12
Publication date: 2002-04-18
Anticipated expiration: 2003-04-06
Also published as: AU2001289039A1; WO2002031094A3

Abstract

The present invention relates to softening formulations, and especially fabric softening formulations, which remain clear at relatively low temperatures and at relatively low concentrations of the active fabric softening ingredient. The formulations comprise an active fabric softening composition, an additive corresponding to the formula: R1-Q-(AO)n-R3; where R1 is C1-18 alkyl; Q is O, C(O)0, or NR1; A is CH2CHR2; R2 and R3 are independently at each occurence H or C1-4 alkyl; and n is 2 to 13, an aliphatic alcohol, a supplemental organic solvent, wherein the supplemental organic solvent is a glycol ether made from a C1 to C6 mono- or di-alcohol which has been alkoxylated with a C2-C4 alkylene oxide, or a C1 to C6 diol having a Clog P value less than 0.15 or mixtures thereof, and water.

Description

CLEAR SOFTENING FORMULATIONS INCLUDING ALKOXYLATED ADDITIVES FIELD OF THE INVENTION

The present invention relates to softening formulations, and especially fabric softening formulations, which remain clear at relatively low temperatures and at relatively low concentrations of the active fabric softening ingredient. More particularly the invention relates to a formulation comprising an active fabric softening ingredient, water, an alkoxylated species having a mono function H, such as alcohols, fatty acids and amines, and additional solvents. The formulations may optionally contain other additives generally used in fabric softening or detergent compositions. 0 BACKGROUND AND SUMMARY OF THE INVENTION

Fabric softening formulations have long been used to render washed clothing or other articles softer to the touch. It is believed, however, that many consumers avoid the use of fabric softeners due in part to the typical fabric softener's cloudy appearance. Some consumers perceive that the cloudiness will leave a residue on the laundered articles, dulling 5 the colors, and perhaps irritating skin which may come into contact with it. Thus, there is a need for fabric softening compositions having a water-like clear appearance.

Many attempts at clear fabric softening formulations have been reported in the literature. For example, US-A-5,490,944, teaches a clear fabric softening composition containing an amido imidazolinium compound. This reference also teaches that the o inclusion of solvents may aid in the formulation of clear softeners. US-A-5,525,245 and

US-A-5,656,585 teach clear fabric softening formulations having diester and/or diamido ammonium active ingredients together with relatively high levels of organic solvents. WO 97/03169 teaches clear formulations having relatively high concentrations of fabric softener with relatively high amounts of specific principle solvents. WO 98/23808 teaches clear 5 fabric softener compositions comprising an imidazolinium salt, a quaternary ammonium salt, a solvent, and a polyoxyethylene alkylether, having from 9 to 60 EO units. WO 99/09122 teaches using a principal solvent as taught in WO 97/03169 together with a nonionic preferably ethoxylated surfactant.

It is desired to improve upon these reported formulations by allowing lower o concentrations of active fabric softening ingredients if desired, by allowing less concentration of the odorous solvents, by allowing the use of more readily available and hence economical additives, and by allowing the formulations to be more stable and to remain clear at lower temperatures.

The formulations of the present invention improve on some or all of these aspects of the prior art. 5 The Applicants have found that many of these objectives can be facilitated by the use of an additive selected from the group corresponding to the formula: R₁-Q-(AO)_n— R3, where R is C_1-18 alkyl, cylcloalkyl or aryl; Q is O, C(O)0, or NR^ A is CH₂CHR₂; R₂ and R₃ are independently at each occurrence H or CM alkyl; and n is 2 to 13, together with lower aliphatic alcohols and other organic solvents. l o These additives can be combined with known detergent or fabric softening active ingredients and water as well as other ingredients typically used in fabric softening formulations. DETAILED DESCRIPTION OF THE INVENTION

The formulations of the present invention comprise: 15 A. an active fabric softening composition;

B. an additive corresponding to the formula:

Rι-Q-(AO)_n-R₃, where Ri is C_1-18 alkyl, cylcloalkyl or aryl; Q is O, C(O)0, or NRu A is CH₂CHR ; R and R₃ are independently at each occurrence H or C_1-4 alkyl; and n is 2 to 13; 20 C. water;

D. aliphatic monol;

E. a supplemental organic solvent, wherein the supplemental organic solvent is a glycol ether made from a to C₆mono- or di-alcohol which has been alkoxylated with a C₂-C₄ alkylene oxide, or a C_\ to C₆ diol having a Clog P value less than 0.15 or mixtures

25 thereof

The formulations may also include salts or other additives typically found in detergent or fabric softening compositions.

The active fabric softening ingredient used in the formulations of the ingredient can be selected from any of those known in the art, such as those described in the review article 3 o "Rinse- Added Fabric Softener Technology at the Close of the Twentieth Century", Matthew I. Levinson, Journal of Surfactants and Detergents. Vol 2, No.2, pages 223-235 (April, 1999). Typically the active ingredient will be chosen from the group consisting of quaternary ammonium compounds, especially ester quaternary ammonium compounds ("ester quats"), diamido amines and diamido ammonium compounds, and amido imidazolinium compounds.

Non ester quaternary ammonium compounds are characterized by having a quaternized ammonium where at least one of the branches attached to the nitrogen contains a long (C₈-C ₂) alkyl chain. Preferably there are two such long alkyl chains. Suitable non ester quaternary ammonium compounds are described for example in WO 99/09122.

In general the ester quat class of compounds is characterized by having a central nitrogen being joined to four organic groups, at least one of which contains an organic acid 0 moiety, that is a C(O)OR group, where R is the remaining portion of the fatty acid used to make the ester. It is preferred that two of the organic groups joined to the nitrogen contain esters. It is also preferred that 50 to 100 percent of the ammonium compounds present be quaternized. Suitable ester quats are described for example in WO 00/06678, WO 99/09122, US-A-5 ,490,944, US-A-5 ,656,585, WO 98/45394, or WO 97/03169. Suitable but non 5 limiting examples of diesterquats are: methyl bis(oleoyl-oxy-ethyl)-(2-hydroxyethyl) ammonium methyl sulfate (TEA diesterquat); N,N-di(oleoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride (MDEA diesterquat); l,2-dioleoyloxy-3-N,N,N- trimethylammoniopropane chloride (DMAPD diesterquat); diester quat of monoisopropanol diethanolamme based on oleic acid and dimethylsulfate: the monoisopropanol o diethanolamme can be made by reacting diethanolamme (DEA) and propylene oxide (PO) (DEA+1PO) or by reacting monoisopropanolamine (MIPA) and ethylene oxide (EO) (MIPA + 2 EO). Esterquats based on trialkanolamines are generally preferred.

Suitable, but non limiting, examples of diamido ammonium compounds are described, in US-A-5,525,245, 5,656,585, and WO 99/09122. Some specific examples 5 (which may or may not be included in these references) include diamido (oleic type) amines which may be alkoxylated (EO, PO, and or BO) or not and their quaternary ammonium salts (DETA based) of the formula: [R⁴-(CO)-NR⁶-(CH₂CH₂)-N(R⁵)(R⁸)-(CH₂CH₂)-NR⁶-(CO)-R⁴]⁺, A-

Wherein R⁴ together with (CO) is an oleoyl group; R⁵ is H, -C₄ alkyl or (CH - o CR⁷HO)_t-H, with t being from 1-7; R⁶ is H, or CH₂-CR⁷HOH;and R⁷ is H or -C₄ alkyl; R⁸ is not present or C_xH_2x+_l5 where x is 0 to 4 and A- is an inorganic or organic acid anion (such as methyl sulfate, or a chloride anion) or not present when R⁸ is not present. It will be readily understood by those in the art that if R⁸ and A^" are not present then, the "+" designation in the formula will also disappear.

Suitable amido imidazolinium compounds are described, for example in 99/09122, WO 98/23808, and US-A-5,490,944. Other materials which may be used as the fabric softening active ingredient in the formulations of this invention include the amido esterquats of US-A-5,580,481 and their respective amido esteramines.

It is preferred that whenever a fatty acid or derivative (i.e a material containing a moiety corresponding to the formula RC(O)O-) is used to prepare the active fabric softening ingredient, such as in the quaternary ester compounds, then the fatty acid has an iodine value of between 20 and 140, especially for fatty acids having a predominant chain length in the range of C₁₆-C₁₈. For fatty acids having a chain length in the range of C_{1 -14}, iodine values of 0 to 100 are preferred. Preferred fatty acids are described in WO 97/03169, see for example, pages 18-21. As is taught in the art, there may be situations where a preponderance of either the cis or the trans isomer of a particular unsaturated fatty acid may be preferred. It should be understood that mixtures of fatty acids may also be advantageously used. It is generally preferred that the fatty acid contain more than 40 percent oleic acid.

The fatty acid used is typically derived from a triglyceride source. Suitable and non limiting examples of triglyceride source are those derived from tallow, partially hardened tallow, lard, partially hardened lard, vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, sunbean oil, tall oil, rice bran oil, coconut oil, palm oil, cotton seed oil, olive oil, rapeseed oil, cod liver oil etc., and mixtures of these oils

One of the observed advantages of the formulations of the present invention is that in general they tend to remain clear at relatively lower concentrations of the fabric softening active ingredient. Thus, the fabric softening active ingredient may be present in the formulation in an amount of from 1 to 85 percent based on weight of the total formulation. Preferably it is added in a range of from 5 to 70 and more preferably from 10 to 65.

The additive to be used in the formulations of the present invention correspond to the formula:

R!-Q-(AO)_n-R₃ where R_! is C_1-18 alkyl, cycloalkyl or aryl; Q is preferably O, but can also be C(O)0, or NRj; A is CH₂CHR₂; R and R₃ are independently at each occurrence H or Cμ alkyl; and n is 2 to 13. It should be understood that although this application will mention specific moles of the various oxides for convenience, in practice, a pure additive in which each molecule has the 5 given number of moles of alkyl oxides will not be used. Rather the alkoxylated additive used will be a distribution of different alkoxylated additive molecules whose average number is represented by the formula.

These additives tend to be liquid at room temperature, making them ideal for the manufacturing and handling of fabric softener formulations. 0 It is preferred that Ri is an alkyl group and the alkyl group may be branched or linear, saturated or unsaturated. It is preferred that R_\ contain from 2 to 17 carbon atoms, more preferably from 4 to 15, and most preferably from 7 to 9 carbon atoms. R₁ may be linear or branched.

It is preferred that R₃ be H. The preferred AO units are those derived from EO, PO, 5 and BO. It is generally preferred that R₂ be H (that is, that the additives be ethoxylates).

When mixed additives are used, however, the alkylene oxide portion of the additive may be added by random or block addition or a mixture thereof. Due to the relative reactivities of EO vs. higher oxides, if the addition is random, the EO will tend to be added first. It is also possible to add the oxide units in a mixed block/random fashion, for example, by adding a o few moles of PO or BO first and then by adding a mixed feed of EO with PO or BO.

Similarly, it is possible to add the mixed feed first and then cap the additive with higher AO units by the addition of pure higher alkylene oxide.

The additives can be added in an amount of from 1 to 60 percent by weight based on the total formulation. Preferably it is added in an amount of from 3 to 50, more preferably 5 from 5 to 35. When R\ is linear, it may be desirable to add more than 10 percent of the additive.

The additives of the present invention can be prepared by alkoxylating a starting material having the formula RrQ-H where Rι and Q are as defined before. Any method of alkoxylation may be used. The alkoxylation reaction may be carried out in the presence of 0 an alkaline catalyst, such as sodium, potassium, calcium, barium and strontium hydroxide, in an amount of from 0.01 to 5, preferably 0.1 to 0.5, percent by weight based on the total weight of the mixture at the completion of the reaction. Temperature and pressures are not critical, but conveniently the alkoxylation reaction is carried out at an elevated temperature, preferably at a temperature from 50°C to 200°C, more preferably from 80°C to 140°C and a pressure of from 1 to 80 bars. The alkaline catalysts suitable for use in this reaction are well known to a person skilled in the art. After completion of the reaction, that is, for example, 5 when the pressure does not change anymore, the catalyst is removed by a suitable method, such as by filtration over an absorbing clay, for example, magnesium silicate, or neutralized with an inorganic acid such as, for example, hydrochloric acid, or an organic acid such as, for example, acetic acid.

In addition to the facilitation of clear fabric softening formulations from low o temperature to 50°C or more, the cost-effective additives of the present invention offer many other advantages. As these additives are not traditional solvents, they avoid many of the problems associated with the traditional solvents. Thus, by using the additives of the present invention instead of some or all of the solvents specified in the prior art, odor and flammability issues are reduced. Furthermore, the additives of the present invention are 5 surfactants and thus may offer additional cleaning properties. It is also believed that the formulations including the additives may facilitate or even eliminate the need for ironing the clothes after the wash.

The formulation of the present invention also includes aliphatic alcohols, and a supplemental organic solvent, wherein the supplemental organic solvent is a glycol ether o made from a C_\ to C₆ mono- or di-alcohol which has been alkoxylated with a C -C₄ alkylene oxide, or a C\ to C₆ diol having a Clog P value less than 0.15 or mixtures thereof. These solvents can help reduce the viscosity of the formulations and help clarity, especially at lower temperatures. In general, the lower the concentration of these solvents present in the formulation the better, so long as the formulation remains clear. Typically the aliphatic 5 alcohol is present in an amount from 0.1 to 25 percent by weight of the formulation, but it is preferred that there be less than 10 percent, more preferably less than 7 percent of the formulation. The supplemental organic solvents can be added in an amount of from 0.1 to 40 percent by weight of the formulation, but it is preferred that they be less than 30 percent, more preferably less than 25 percent of the formulation. o Suitable solvents are generally known in the art, and are listed for example in

US-A-5,525,245 or WO 99/09122. Preferred aliphatic alcohol solvents include propanol, isopropyl alcohol, ethanol, and butanol. Preferred d to C₆ diols having Clog P values less than 0.15 include ethylene glycol, 1,3- propane diol, 1,4-butanediol, propylene glycol, butylene glycol, diethylene glycol, dipropyleneglycol (DPG), tripropyleneglycol (TPG), polyethylene glycol, and polypropylene glycol. Preferred glycol ethers include materials such as DOWANOL™ (trademark of The Dow Chemical Company) P and E series including, ethylene glycol mono n-butyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol mono n-butyl ether (PnB), dipropylene glycol monomethyl ether, dipropylene glycol mono propyl ether (DPnP), dipropylene glycol mono n-butyl ether (DPnB), , and diethylene glycol butyl ether (DB). The formulations of the present invention may also advantageously include low levels (generally less than 3 percent by weight) of salts of the sort occasionally found in detergent or fabric softening compositions. In general suitable salts can be mono or divalent and can be inorganic or organic. Some examples of suitable salts include potassium acetate, calcium chloride, Magnesium chloride, sodium acetate, sodium chloride, and potassium chloride.

Other ingredients typically used in fabric softeners and detergents may also be used in the formulations of the present invention. These are known in the art (see for example WO 99/09122, US 5,656,585, WO-97/31889, WO 98/35002, WO-A-95/19951, WO-A-93/25648, WO-A-93/23510, WO-A-96/21715, WO-A-96/09436, WO-A-94/29521, GB 2 197 66 A, EP 0413 249 Al, WO 98/41604, WO 97/03169, WO 98/18890, WO 96/33800 and EP-A-0580245) and include things such as brighteners; dispersibility aids such as cationic surfactants (for example monoalkyl quaternary ammonium compounds), nonionic surfactants and amine oxides; stabilizers; soil-release agents; scum dispersant; perfumes; chelating agents; enzymes; colorants; preservatives; anti-shrinking agents; viscosity modifiers such as polyethylene glycols and polypropylene glycols; bactericides and germicides; anti-corrosion agents; pH adjusters (for example HC1, or organic acids such as acetic acid, lactic, fumaric acid, or maleic acid); fatty acids, fatty alcohols, fatty esters, fatty amines, amidoamines, permanent press agents (such as silicones) and the like.

Finally, the formulations of the present invention contain water. The amount of water contained in the formulation largely depends on user needs. It may be that concentrated or superconcentrated formulations are sought in which case the formulation may contain as little as 1 percent water to help stabilize the formulation. In other situations the formulation may contain a majority of water such that it is ready to use by the consumer. It may be advantageous to prepare somewhat concentrated formulations such that the water content together with the aliphatic alcohol represents no more than 60, 55 or 50 percent of the total formulation, depending on the user's need. It should be understood that the formulations of the present invention will turn turbid at very high concentrations of water 5 such as when diluted in the rinse cycle.

The formulations of the present invention can be made in several ways, as should be readily understood in the art. For example, the individual components (that is fabric softening active ingredient, the additive, water, aliphatic alcohol, supplemental organic solvent and any optional ingredients) can be simply blended together (at elevated o temperatures if required) in any order. In the case where the fabric softener active ingredient is based on fatty acid, however, it may be advantageous to add at least a portion the additive of the present invention at any point after the chemical reaction of the fatty acid (esterification and/or amidation). For example, in the synthesis of an ester quat, the additive could be added after the esterification and either before, during or after the quaternization 5 step, enabling the reduction or even the elimination of the traditional solvents used in such process. EXAMPLES

The following examples (including comparative example 7) are provided for illustration purposes and should not be interpreted as limiting the scope of the invention or o the claims. The Examples were prepared by first melting the active fabric softener and then mixing in the additive and the solvent. Water was then added to reach the final reported concentrations. The mixtures were then chilled to temperatures below 10°C and visually inspected to see if it was clear and had an appropriate viscosity. The components of each Example are presented in Table 1. In the table, all percentages are by weight (with the 5 balance being water) and the following items have the following meanings:

TEA + EQ is a triethanolamine diesterquat based on oleic acid, and DEA + IPO EQ is a methyldiethanolamine diesterquat based on diethanolamme which is reacted with an equimolar amount of PO and then esterified with oleic acid, and quaternized with dimethylsulfate. IPA is iso-propyl alcohol, DPG is dipropylene glycol, and DPnB is o dipropylene n-butyl glycol ether. C8+5EO means n-octanol reacted with 5 moles EO. 2EH

+EO means 2-ethylhexanol reacted with 5 moles EO. Table 1

Examples 1-6 all resulted in clear formulations. Comparative example 7, which did not contain the supplemental organic solvent, resulted in a turbid formulation.

It should be realized by those skilled in the art that the invention is not limited to the exact configuration or methods illustrated above, but that various changes and modifications may be made without departing from the spirit and scope of the invention as described within the following claims:

Claims

CLAIMS:

1. A fabric softening formulation comprising:

A. an active fabric softening composition;

B. an additive corresponding to the formula: R₁-Q-(AO)_n— R₃; where Ri is C _S 5 alkyl, cylcloalkyl or aryl; Q is O, C(O)0, or NRu A is CH₂CHR₂; R₂ and R₃ are independently at each occurrence H or C_1- alkyl; and n is 2 to 13;

C. water;

D. aliphatic alcohol;

E. a supplemental organic solvent, wherein the supplemental organic solvent is a o glycol ether made from a to C₆ mono- or di-alcohol which has been alkoxylated with a

C -C₄ alkylene oxide, or a to C₆ diol having a Clog P value less than 0.15 or mixtures thereof.

2. The formulation of Claim 1 wherein Q is O.

3. The formulation of Claim 2 wherein the aliphatic alcohol is of propanol, 5 butanol, isopropyl alcohol, or ethanol.

4. The formulation of Claim 2 wherein the supplemental organic solvent is ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, tripropylene glycol, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol mono n-butyl ether o (PnB), dipropylene glycol monomethyl ether, dipropylene glycol mono propyl ether (DPnP), dipropylene glycol mono n-butyl ether (DPnB), or diethylene glycol butyl ether (DB).

5. The formulation of Claim 2 wherein Ri is C₄ to Cis, R₂ is H, and R₃ is H.

6. The formulation of Claim 5 wherein Ri is not linear.

7. The formulation of Claim 5 wherein Ri is linear. 5

8. The formulation of Claim 7 wherein the additive is more than 10 percent of the total formulation.

9. The formulation of Claim 7 wherein the water and the aliphatic alcohol is less than 60 percent by weight of the formulation.

10. The formulation of Claim 7 wherein the water and the aliphatic alcohol 0 is less than 55 percent by weight of the formulation.

11. The formulation of Claim 2 wherein the active fabric softening composition is based on a trialkanolamine esterified with a fatty acid mixture comprising at least 40 percent oleic acid.

12. The formulation of Claim 2 wherein the active fabric softening

5 composition is prepared from a mixture of fatty acids having predominantly 16-18 carbon atoms and an Iodine Value of from 20-140.

13. The formulation of Claim 2 wherein the active fabric softening composition is prepared from a mixture of fatty acids having predominantly 12-14 carbon atoms and an Iodine Value of from 0-100. o

14. The formulation of Claim 2 wherein the active fabric softening composition is prepared from a mixture of fatty acids having 16-18 carbon atoms and Iodine Values of from 20-140 and fatty acids having 12-14 carbon atoms and Iodine Values of

15. The formulation of Claim 2 wherein the active fabric softening 5 composition includes an esterified quaternary ammonium compound.

16. The formulation of Claim 2 wherein the active fabric softening compositions comprise from 5 to 65 percent by weight of the total formulation, and the additives comprise 5 to 40 percent by weight.

17. The formulation of claim 2 further comprising from 0.1 to 10 percent by o weight of a fabric co-softener selected from the group consisting of fatty alcohols, fatty acids, fatty esters, fatty amines and amide/amides.

18. The formulation of claim 2 further comprising brighteners; dispersibility aids; stabilizers; soil-release agents; scum dispersant; perfumes; chelating agents; enzymes; colorants; perfumes, preservatives; anti-shrinking agents; viscosity modifiers; bactericides 5 and germicides; anti-corrosion agents; permanent press agents or pH adjusters