EP0197578B1

EP0197578B1 - Textile treatment compositions

Info

Publication number: EP0197578B1
Application number: EP86200430A
Authority: EP
Inventors: Axel König; Francesco De Buzzaccarini
Original assignee: Procter and Gamble European Technical Center; Procter and Gamble Co
Current assignee: Procter and Gamble European Technical Center; Procter and Gamble Co
Priority date: 1985-03-28
Filing date: 1986-03-19
Publication date: 1991-06-26
Anticipated expiration: 2006-03-19
Also published as: TR23492A; GB2174422B; AU5535386A; HK103892A; EG17723A; DE3679927D1; MY100080A; CA1279447C; EP0197578A2; FI861341A0; MX165248B; FI861341A; IE59115B1; KR930008698B1; JPH0768668B2; KR860007415A; MA20655A1; CN1005735B; CN86102993A; DK139886A

Description

This invention relates to textile treatment compositions. More particularly it relates to textile treatment compositions suitable for use in the rinse cycle of a textile laundering operation to provide fabric softening/static control benefits, the compositions being characterized by excellent softening, water dispersibility and storage properties after prolonged storage at both elevated and sub-normal temperatures.
Textile treatment compositions suitable for providing fabric softening and static control benefits during laundering are well known in the art and have found widespread commercial application. Conventionally, rinse-added fabric softening compositions contain, as the active component, substantially water-insoluble cationic materials having two long alkyl chains. Typical of such materials are di-hardened tallow dimethylammonium chloride, and imidazolinium compounds substituted with two tallow groups. These materials are normally prepared in the form of a dispersion in water and it is generally not possible to prepare such aqueous dispersions with more than about 10 % of cationic softener without encountering severe product viscosity and storage-stability problems. Although more concentrated dispersions of softener materials can be prepared as described in European Patent Application No. 0 000 406 and British Patent No. 1 601 360 by incorporating certain nonionic adjunct softening materials therein, such compositions tend to be relatively inefficient in terms of softening benefit/unit weight of active; moreover, product viscosity and stability problems become increasingly unmanageable in more concentrated aqueous dispersions and effectively limit the commercial range of applicability to softener active levels in the range from about 15% to about 20%.
U.S. Patent 4 454 049, issued June 12, 1984 to MacGilp et al discloses concentrated liquid fabric softeners comprising substantial amounts at least 10%, more typically about 30 - 40%, of water miscible organic solvent.
U.S. Patent 2 995 520, issued August 8, 1961 to Luvisi et al discloses the use of the acid salts of certain imidazoline derivatives for softening of fibrous materials such as cotton and paper. The treatment baths used for treating textiles contain from 0.001% to 1% of an acid salt of an imidazoline derivative. For shipment, it is said to be desirable to place the materials in a low molecular weight aliphatic alcohol to prevent freezing.
Other patents, more recent than U.S. 2 995 520, also disclose the use of an acid salt of an imidazoline derivative for the softening of fabrics, such as FR-A-2 322 963;
FR-A-2 391 312 describes compositions for industrual treatment of textiles wherein imidazoline derivatives are used as sole softening agents, together with an organic fluidizer.
However, according to the state of the art, quaternary ammonium salts are, in the context of fabric softening, preferred over acid salts of, e.g., acyclic tertiary amines or cyclic amines.
It is therefore an object of the present invention to provide liquid fabric softening compositions that can be formulated as both diluted and concentrated aqueous dispersions without the need of significant amounts of organic solvents. The compositions of the present invention have excellent stability at both elevated and sub-normal temperatures, even under prolonged storage conditions. These compositions further provide excellent softening, anti-static and fabric rewettability characteristics across a broad range of fabric types.

Summary of the Invention

The present invention provides a stable aqueous dispersion comprising:

(a) from 1% to 40% by weight of an amine selected from the group consisting of the di(higher alkyl) cyclic amines of formula I herein; and mixtures thereof; and
(b) a compound selected from the group of conventional quaternary ammonium softening agents having two higher alkyl groups, each comprising from 8 to 30 carbon atoms. The weight ratio of (a) to (b) being in the range of from 3:1 to 1:10; and
(c) from 1% to 50% by weight of the amine, of a dispersing aid selected from the group of Bronstedt acids having a pKa value of not greater than 6, provided that the pH of the dispersion is not greater than 5.

DETAILED DESCRIPTION OF THE INVENTION

The compositions of the present invention are based upon the discovery that stable aqueous dispersion can be formulated with certain cyclic amines, even at high amine concentration, and a conventional di(higher alkyl) quaternary ammonium salt, without the use of substantial amounts of organic solvent.

a) The amine

The amines used in the compositions of the present invention are selected from the group consisting of compounds of the formula I.
wherein n is 2 or 3, preferably 2; R₁ and R₂ are, independently, a C₈-C₃₀ alkyl or alkenyl, preferably c₁₁_,-c₂₂ alkyl, more preferably C₁₅-C₁₈ alkyl, or mixtures of such alkyl radicals. Examples of such mixtures are the alkyl radicals obtained from coconut oil, "soft" (non-hardened) tallow, and hardened tallow. Q is CH, CH₂, NH, or N, preferably N.
wherein T is NR₅, R₅ being H or C₁-C₄ alkyl, preferably H, and R₄ is a divalent C₁-C₃ alkylene group or (C₂H₄O)_m, wherein m is an number of from 1 to 8; or X is R₄.
The compositions of the present invention comprise from 1% to 40% by weight of the amine, preferably from 2% to 35%, and more preferably from 2% to 20%.
Detergent carryover, as may take place in a laundry process, particularly under conditions as prevail in U.S. washing machines, tends to negatively affect the softening performance of rinse added softeners. It has been found that the amines of formula I are less sensitive to detergent carryover than, e.g. ditallowdimethylammonium chloride.

b) Quaternary ammonium salt

As a second component, the dispersions herein contain a conventional di(higher alkyl) quaternary ammonium softening agent. By "higher alkyl" as used in the context of the quaternary ammonium salts herein is meant alkyl groups having from 8 to 30 carbon atoms, preferably from 11 to 22 carbon atoms. Examples of such conventional quaternary ammonium salts include (i) acyclic quaternary ammonium salts having the formula:
wherein R₂ is an acyclic aliphatic C₁₅-C₂₂ hydrocarbon group. R₃ is a C₁-C₄ saturated alkyl or hydroxyalkyl group, R₄ is selected from R₂ and R₃, and A is an anion.

(ii) diamido quaternary ammonium salts having the formula:

wherein R₁ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group, R₂ is a divalent alkylene group having 1 to 3 carbon atoms, R₅ and R₈ are C₁-C₄ saturated alkyl or hydroxyalkyl groups, and A^- is an anion:

(iii) diamido alkoxylated quaternary ammonium salts having the formula:

wherein n is equal to 1 to about 5, and R₁, R₂, R₅ and A^- are as defined above ;

(vi) quaternary imidazolinium compounds.

Examples of Component (i) are the well-known dialkyldimethylammoniums salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methylsulfate, di(hydrodrogenated tallow) dimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride.
Examples of Component (ii) are methylbis(tallowamidoethyl) (2-hydroxyethyl) ammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl) (2-hydroxyethyl) ammonium methylsulfate wherein R₁ is an acyclic aliphatic C₁₅-C₁₇ hydrocarbon group, R₂ is an ethylene group, R₅ is a methyl group, R₈ is a hydroxyalkyl group and A is a methylsulfate anion; these materials are available from Sherex Chemical Company under the trade names Varisoft (R) 222 and Varisoft (R) 110, respectively.
Examples of (iv) are 1-methyl-1-tallowamido-ethyl-2-tallowimidazolinium methylsulfate and 1-methyl-1-(hydrogenated tallowamidoethyl)-methylsulfate.
The quaternary ammonium salt (b) preferably comprises from 1% to 20%, more preferably 2% to 20% by weight of the composition herein.
The weight ratio amine (a); quaternary ammonium salt (b) is in the range from 3:1 to 1:10, preferably from 3:1 to 1:3.
The di(higher alkyl)imidazolinium compounds are preferred for use herein, in particular the 1- (lower alkyl)-1-(higher alkyl)amidoethyl-2-(higher alkyl) imidazolinium compounds, wherein "lower alkyl" signifies alkyl having from 1 to 4 carbon atoms, and "higher alkyl" signifies alkyl having from 11 to 22 carbon atoms.

c) Bronstedt acid

The dispersion further comprises Bronstedt acids having a pKa value of 6 or less.
The amount of acid should be such that the pH of the dispersion, after mixing, is not greater than 5, preferably not greater than 4, and most preferably in the range of from 2.5 - 4. The amount of acid is from 1% to 50% by weight of the amine, preferably from 2% to 30%, most preferably from 3 to 15%.
Examples of suitable acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C₁-C₅) carboxylic acids, aromatic carboxylic acids, like benzoic acid, and alkylsulfonic acids.
Suitable ionorganic acids include HCl, HBr, H₂SO₄, HNO₃ and H₃PO₄. Suitable organic acids include benzoic acid, formic, acetic, methylsulfonic and ethylsulfonic acid. Preferred acids are phosphoric, formic and methylsulfonic acid.

d) Organic solvent

The compositions of the present invention can be formulated without the use of any organic solvent. However, the presence of organic solvents (for example, low molecular weight, water miscible aliphatic alcohols,) does not harm the storage stability, the viscosity, or the softening performance of the compositions of this invention.
Typically, the amine will be obtained from a supplier of bulk chemicals in solid form of as a solution in an organic solvent, e.g. isopropanol. There is no need, whatsoever, to remove such a solvent in making the compositions of this invention. Indeed, additional solvent may be added, if this is deemed desirable.
However, compared to water, organic solvents are expensive, and difficult to handle because of their flammability and, sometimes, toxicity. It is therefore desirable to formulate the present compositions with low levels of organic solvent, i.e., less than 10%, preferably less than 2%.

e) Optional silicone Component

The compositions herein can optionally contain an aqueous emulsion of a predominantly linear polydialkyl or alkyl, aryl siloxane in which the alkyl groups can have from one to five carbon atoms and may be wholly or partially fluorinated. Suitable silicones are polydimethyl siloxanes having a viscosity at 25°C in the range from 100 to 100,000 centistokes (mm²/s) preferably in the range from 300 to 6,000 centistokes (mm²/s).
It has been found that the ionic charge characteristics of the silicone as used in the combination are important in determining both the extent of deposition and the evenness of distribution of the silicone and hence the properties of a fabric treated therewith.
Silicones having cationic character show an enhanced tendency to deposit. Silicones found to be of value in providing fabric feel benefits have a predominantly linear character and are preferably polydialkyl siloxanes in which the alkyl group is most commonly methyl. Such silicone polymers are frequently manufactured commercially by emulsion polymerisation using a strong acid or strong alkali catalyst in the presence of a nonionic or mixed nonionic-anionic emulsifier system.
In the present invention, the optional silicone component embraces a silicone of cationic character which is defined as being one of

(a) a predominantly linear di C₁-C₅ alkyl or C₁-C₅ alkyl, aryl siloxane, prepared by emulsion polymerisation using a cationic surfactant as emulsifier;
(b) an alpha-omega-di quaternised di C₁-C₅ alkyl or C₁-C₅ alkyl, aryl siloxane polymer or
(c) an amino-functional di C₁-C₅ alkyl or alkyl aryl siloxane polymer in which the amino group may be substituted and may be quaternised and in which the degree of substitution (d.s.) lies in the range 0.001 to 0.1, preferably 01-0.075;

The silicone component suitable for use herein are more fully disclosed in British Patent No. 1.549.180.

f) Optional nonionics

The compositions optionally contain nonionics as have been disclosed for use in softener compositions. Such nonionics and their usage levels, have been disclosed in U.S. Patent 4.454.049, issued June 12,1984 to Mac Gilp et al.
Specific examples of nonionics suitable for the compositions herein include glycerol esters (e.g., glycerol monostearate), fatty alcohols (e.g.,stearyl alcohol), and alkoxylated fatty alcohols. The nonionics, if used, are typically used at a level in the range of from 0.5 - 10% by weight of the composition.

g) Other Optional Ingredients

In order to further improve the stability of the compositions herein, and further adjust their viscosities, these compositions can contain relatively small amounts of electrolyte. A highly preferred electrolyte is CaCl₂. It has been found that the Brookfield viscosities of highly concentrated dispersions can be reduced to less than 100 cps,(100 mPas) using relatively small amounts of CaCl₂ (e.g., 600 ppm).
The compositions herein can optionally contain other ingredients known to be suitable for use in textile softeners. Such adjuvants include perfumes, preservatives, germicides, colorants, dyes, fungicides, stabilizers, brighteners and opacifiers. These adjuvants, if used, are normally added at their conventional levels. However, in the case of composition ingredients utilized for a fabric treatment effect, e.g., perfumes, these materials can be added at higher than normal levels, corresponding to the degree of concentration of the product.

EXAMPLES I-IV

The following compositions are prepared :

1) ditallow imidazolinium (1-methyl-1-tallow-amido-ethyl-2-imidazolinium chloride)
2) ditallowdimethylammonium chloride
3) polydimethyl siloxane, viscosity 500 centistokes (mm²/s)
4) formic acid
5) methylsulfonic acid
6) glycerolmonostearate
7) 1-tallowamidoethyl-2-tallowimidazoline

Some hydrolysis of the ditallow imidazolinium component is observed to take place during processing. This is not found to markedly affect the softening performance of the compositions.

EXAMPLES V - VIII

The following examples are prepared, each having pH values in the range 2.5 to 5.

1. DTDMAC - As in Examples II, III and IV.
2. PDMS - Polydimethylsiloxane, viscosity 5000 cs. (mm²/s)
3. Amine - 1-(2-C₁₄-C₁₈-Amidoethyl)-2-C₁₃-C₁₇-alkyl - 4,5 dihydro-imidazoline; CAS number 72623-82-6.
4. Emulsifier - As "Sapogenat T 100" (Trade Mark) for triisobutylphenol decaglycolether, Hoechst.

Claims

A stable aqueous dispersion comprising :
(a) from 1% to 40% by weight of an amine selected from the group consisting of the cyclic amines of the formula:
wherein n is 2 or 3, R₁ and R₂ are, independently, a C₈-C₃₀ alkyl or alkenyl radical , Q is CH, CH₂, NH or N.
X is
wherein T is NR₅, R₅ being H or C₁-C₄ alkyl, and R₄ is a divalent C₁-C₃ alkylene group or (C₂H₄O)m, wherein m is a number of from 1 to 8; or X is R₄,
and mixtures thereof;

(b) a compound selected from the group of conventional quaternary ammonium salt softening agents having two alkyl groups each comprising from 8 to 30 carbon atoms. The weight ratio of (a) to (b) being in the range of from 3:1 to 1:10; and

(c) from 1% to 50% by weight of the amine of a dispersing aid selected from the group of Bronstedt acids having a pKa value of not greater than 6; provided that the pH of the dispersion is not greater than 5.
A dispersion according to claim 1 wherein the weight ratio (a):(b) is in the range from 3:1 to 1:3.
A dispersion according to any of the preceding 7 claims which comprises from 2% to 35% by weight of the amine.
A dispersion according to any of the preceding claims wherein the amine is a 1-(C_11-22 alkyl) amidoethyl-2-(C_11-22 alkyl) imidazoline.
A dispersion according to any of the preceding claims which further comprises an emulsion of predominantly linear di(C₁-C₅) alkyl or C₁-C₅ alkylaryl siloxane in which the alkyl groups may be partially or wholly fluorinated and which may be substituted with cationic nitrogen groups, the siloxane having a viscosity at 25°C of at least 100 centistokes (mm²/s) and up to 100000 centistokes (mm²/s); the weight ratio of the siloxane content of the emulsion to the amine component being in the range of from 5:1 to 1:100, preferably 2:1 to 1:10.
A dispersion according to claim 6 wherein the siloxane is a polydimethyl siloxane.
A dispersion according to any of the preceding claims which further comprises from 0.5% to 10% by weight of a nonionic, preferably a glycerol ester, a fatty alcohol, or an alkoxylated fatty alcohol.