NO169661B - Liquid detergent mixture for simultaneous cleaning and softening of fabrics - Google Patents

Description

The present invention relates to new liquid detergent mixtures where the amount of alkyl glycoside present acts to improve washing strength and softening properties and is sufficient to offset the reduction in washing strength due to the amount of quaternary ammonium compound present, as well as the use of such a liquid detergent mixture for simultaneous cleaning and softening of substances.

The use of different and disparate chemical substances and in particular cationic quaternary ammonium compounds as plasticizers for textile products is very well known in the art. It is also well known to use such substances because of the softening effects during the laundry and especially during the rinsing period of the washing process. This latter technique has been necessitated by the fact that the previously mentioned, hitherto used quaternary compounds which are mainly cationic in nature, are not compatible with the anionic detergents, one of the main types of detergents used in the washing period. Furthermore, cationic quaternary compounds are relatively ineffective in the presence of non-ionic detergents.

It is also well known that there is a tendency for washed articles of clothing to yellow or discolor when treated with the aforementioned quaternary compounds.

Another disadvantage associated with the use of the cationic agents in the washing of fabrics is the effect on the deposition of optical whitening agent on fabrics, thereby reducing the optical whitening effect of a detergent mixture containing the optical whitening agent.

Yet another disadvantage of the antistatic softeners of the cationic quaternary ammonium type is the effect on the cleaning properties of the detergent in that the soil removal

caused by the detergent is reduced, resulting in reduced washing efficiency. The presence of the anionic detergent substance largely negates the fabric softening properties of the cationic quaternary ammonium compounds.

Accordingly, the previously mentioned quaternary agents have been combined with several compounds designed to counteract the unfavorable properties with respect to detergency, or the quaternary softeners have been replaced by other softeners to improve cleaning power.

Higher alkyl mono- and -polyglycosides which can be used as detergents, fabric softeners, surfactants, gel-forming agents, food emulsifiers and lubricants, and methods for the production of these have been described in US Patents Nos. 3,598,865, 3,707,535, 3,839,318, 3,772,269 and 3,219,656.

Higher alkyl polyglycosides have been used as nonionic surfactants in a variety of detergent compositions together with anionic surfactants, as shown in US Patent No. 3,721,633, European Patent Nos. 70,074, 70,075, 70,076 and 92,877, and together with an anionic and a other nonionic surfactant as shown in US Patent Nos. 4,483,779, 4,483,780 and 4,483,787,

and in European patent documents no. 75,994, 75,995, 75,996 and 105,556, whereby a good washing effect is obtained.

In the prior art, detergent mixtures containing an alkyl polyglycoside are also described,

a conventional non-ionic surface-active agent and a cationic fabric softening compound, whereby both softening and detergent-active properties are obtained during laundry washing, as shown in US Patent No. 4,493,773 and European Patent Nos. 94,118 and 106,692. However, according to these patents, anionic surfactants are expressly omitted as these are harmful to the mixture.

US Patent No. 4,014,808 discloses an aqueous detergent composition for cleaning hard surfaces, such as floors, containing alkaline builders, a mixture of higher alkyl mono- and polyglycosides, a nonionic ethoxylate or any anionic modified ethoxylate in acid form,

and a cationic flocculating agent, such as sqm polydiallyldimethylammonium chloride, which causes fouling to agglomerate into small particles which float up, and optionally a flotation agent which is sodium alkylaryl sulphonate.

However, none of the aforementioned literature sources describe a liquid softener and detergent mixture for simultaneous cleaning and softening of fabrics containing four essential components, an effective amount of an alkyl glycoside to improve wash strength and softening properties in the presence of a softening quaternary ammonium compound and anionic and nonionic surfactants.

It has now been discovered that the addition of an alkylpolyglycoside surfactant to a liquid softener and detergent mixture containing a softening cationic quaternary compound in a mixture of nonionic and anionic surfactant enhances the washing effect and provides increased softening properties to fabrics treated with it. Accordingly, it is a primary object of the present invention to provide a liquid detergent composition with improved cleaning power in the presence of softening cationic quaternary ammonium compounds.

Another object of the invention is to provide

a liquid detergent mixture that simultaneously cleans and softens fabrics during the washing process, containing an alkyl glycoside, a softening quaternary ammonium compound, a non-ionic surfactant and an anionic surfactant as the four essential ingredients.

Yet another object of the invention is to provide a liquid softener and detergent composition with improved cleaning and softening properties due to the presence of an alkyl glycoside in a detergent composition containing a mixture of anionic, nonionic and cationic surfactants.

The present invention thus relates to a liquid detergent mixture where the amount of alkyl glycoside present acts to improve the washing strength and the softening properties and is sufficient to offset the reduction in washing strength due to the amount of quaternary ammonium compound present, which is characterized by the fact that it contains four basic components: 1 -30% by weight of an alkyl glycoside with one or more hydrophobic groups containing 1-30 carbon atoms per hydrophobic group, and a hydrophilic glycoside group containing 1-10 reducing saccharide radicals; 2-8% by weight of a softening, quaternary ammonium compound where at least one of the four groups bound to the nitrogen atom is a C10~C20 <a>lkY19ruPPe'°9 at least two of the groups are C.-C, alkyl groups and the fourth group can be either another C10~C20 alkyl group or a C1~C3 alkyl group;

1-12% by weight of an anionic surfactant; and 8-25% by weight of a nonionic surfactant selected from the group consisting of ethoxylates of primary, aliphatic

isic alcohols, ethoxylates of secondary aliphatic alcohols, ethoxylates of alkylphenols, ethylene oxide/propylene oxide condensates of alcohols and mixtures thereof;

in an aqueous carrier, optionally together with conventional laundry detergent additives. Furthermore, the invention relates to the use of such a detergent mixture for simultaneous cleaning and softening of substances.

The alkyl glycosides act as a softening agent and enhance fabric softening in the presence of cationic surfactants. It is assumed that the alkyl glycosides cover the surface of the fabric and/or change the fabric structure, so that softening benefits are obtained. It is believed that the alkyl glycosides can break up hydrogen bonding and thereby increase softening properties. The alkyl glycosides do not affect the washing effect and/or the deposition of bleach, which is another problem with fabric softeners and detergents.

The alkyl glycosides used in the present new detergent mixture are defined in that they have one or more hydrophobic groups containing 1-30 carbon atoms per hydrophobic group, and preferably 8-15 carbon atoms, and a hydrophilic glycoside group containing 1-10, and preferably from 1 to 3 reducing saccharide radicals. The alkyl glycosides can be represented by the following formula: R0(R'0) Z , where

x n

R is a C^-C^q alkyl radical, (R'O) is an ethoxy, propoxy or glyceryl group, x has a numerical value from 0 to 10, and preferably 0, Z is a reducing saccharide containing 5 or 6 carbon atoms, and n has a numerical value of 1 - 10 and preferably 1.0 - 3. The hydrophobic alkyl group can be saturated or unsaturated, branched or straight-chain, preferably saturated and straight-chain, and contain 1-30 carbon atoms, preferably 8-23 carbon atoms. Suitable alkyl polyglycosides include methyl, ethyl, propyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecylog mixtures thereof, monoglycosides, diglycosides, triglycosides, tetraglycosides, pentaglycosides, hexaglycosides, etc. The glycoside units can be glucose, galactose, mannose, lactose and/or fructose. Methods for producing the aforementioned glycosides are described in US Patent Nos. 3,598,865, 3,707,535, 3,839,318, 3,772,269 and 3,219,656. The addition of the alkyl glycoside to softeners and detergents improves cleaning power. The amount of glycoside should be sufficient to counteract the loss in washing effect due to the presence of the cationic quaternary ammonium softeners in the softener and detergent. Accordingly, the glycoside content improves the washing effect of the softener and detergent mixture and constitutes 1 to 30% by weight, and preferably 2 to 25% by weight, of the mixture.

The softening quaternary ammonium compounds are commercially well known and include quaternary ammonium compounds where at least one of the four groups attached to the nitrogen atom is an alkyl group of 10-20 carbon atoms, and at least two of the groups attached to the nitrogen atom are alkyl groups containing 1-3 carbon atoms, and the quaternary group can be either another cio~C20 alkyl group or a C-^-C^ alkyl group, and where an anion is present, such as halogen, acetate, methosulfate, etc. Typical quaternary ammonium compounds are ethyl-dimethyl-distearyl- ammonium chloride, trimethyl-stearyl-ammonium chloride, trimethylcetyl-ammonium bromide, dimethyl-ethyl-dilauryl-ammonium chloride, dimethyl-propyl-myristyl-ammonium chloride, tallow-trimethyl-ammonium chloride, (dihydrogenated tallow)-dimethyl-1-ammonium chloride, dicocos-dimethyl-ammonium chloride, di -steary1-dimethy1-ammonium chloride, disteary1-dimethy1-ammonium chloride, octadecyl-trimethy1-ammonium chloride, dodecyl-trimethyl-or -triethylammonium chloride, and the equivalent the methosulphates and acetates.

Other suitable quaternary compounds include "duo-quats", polyethoxylated "quats" and amido-alkylated "quats".

The amount of the quaternary ammonium compounds used in the present detergent mixture is 2 - 8% by weight

of the detergent mixture.

In accordance with the invention, the nonionic surfactants for use in the detergent composition are commercially well known and include the ethoxylates of primary aliphatic alcohols, the ethoxylates of secondary aliphatic alcohols, the ethoxylates of alkylphenol and the ethylene oxide/propylene oxide condensates of alcohols, such as Plurafac< ®>, and mixtures thereof. The nonionic synthetic organic detergents are usually the condensation product of an organic aliphatic or alkylaromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound that has a carboxyl, hydroxyl, amide or amine group with a free hydrogen atom attached to the nitrogen atom can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, whereby a nonionic surfactant is obtained medium. Furthermore, the length of the poly-ethenoxy chain can be regulated to achieve the desired equilibrium between the hydrophobic and hydrophilic elements.

The nonionic detergents comprise the polyethylene oxide condensate of 1 mole of alkylphenol containing from 6 to 12 carbon atoms in a straight chain or branched configuration with 5-30 moles of ethylene oxide, e.g. nonylphenol condensed with 9 mol ethylene oxide, dodecylphenol condensed with 15 mol ethylene oxide. Condensation products of the corresponding alkylthiophenols with 5 - 30 mol of ethylene oxide are also suitable.

Also included in the nonionic detergent class are the condensation products of a higher alcohol (eg, an alkanol containing 8-18 carbon atoms in a straight-chain or branched configuration) condensed with 5-30 moles of ethylene oxide, e.g. lauryl-myristyl alcohol condensed with approx. 16 moles of ethylene oxide.

A preferred group of nonionic surfactants are the "Neodol" ethoxylates, which are higher aliphatic alcohol ethoxylates with 5-20 ethylene oxide groups per moles of aliphatic alcohol containing 10 - 18 carbon atoms, such as C]_ 2~^ 13 alkane°l condensed with 6.5 moles of ethylene oxide, Ci2-C15 alkane°l condensed with 12 moles of ethylene oxide,

C^-C^t- alkanol condensed with 13 moles of ethylene oxide and the like.

- Ethoxamers with an HLB (hydrophobic/lipophilic balance) value of

8-15 give good O/W emulsification, while ethoxamers with low HLB values (below 8) contain less than 5 ethyleneoxy groups and are poor emulsifiers and poor nonionic detergents. This nonionic surfactant is present in the fabric softener and detergent mixture in an amount equal to

or greater than the alkyl polyglycoside content, and amounts to 8-25% by weight. The total amount of nonionic surfactant, namely the glycoside, which is also a nonionic surfactant, and the nonionic alcohol ethoxylates defined above constitute the main detergent component of the detergent composition, 25-40% by weight and preferably 30-40% by weight of the mixture.

The anionic surfactants used in the detergent mixture according to the invention are commercially well known and include alkylbenzenesulfonic acid and salts thereof, e.g. compounds with the formula alkyl-phenyl-SO^-M, where alkyl is an alkyl radical with cq~ C22' °^ preferably C]lø~C18' °<9>

M is hydrogen or an alkali metal, compounds which constitute a well-known class of anionic detergents and include sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, sodium cetylbenzenesulfonate. Others include alkane sulfonates, alkyl sulfates, alcohol ether sulfates, olefin sulfonates and the alkylphenol ethoxylate sulfates (eg sodium dinonylphenoxynonaethoxyethanol sulfate), and other equivalent water-soluble salts, especially of the alkali metal series.

Among the above-mentioned alkylbenzenesulfonic acids and salts thereof, preferred compounds include those which are biologically degradable and which are particularly characterized by a straight-chain alkyl substituent with C1~C22°9 preferably from C12~C15' It should of course be understood that the carbon chain length generally constitutes an average chain length since alkylating reagents with mixed chain length are usually used in the process for the production of such products. However, it is clear that practically pure olefins as well as alkylating compounds used in other techniques can and do give alkylated benzene sulphonates where the alkyl residue is essentially (i.e. at least 99%) of one chain length, i.e.

C12' C13' C14 or C15* The straight-chain alkylbenzenesulfonates are further characterized by the position of the benzene ring in the straight-chain alkyl radical, any of the positional isomers (ie a tilu3) can be used and are meant to be included.

In addition to the benzene sulphonates, one can also use them

the lower alkyl (C₁-C₂) analogues of benzene, such as toluene, xylene, the trimethylbenzenes, the ethylbenzenes, isopropylbenzene and the like. The sulphonates are generally used in the water-soluble salt form which includes, as cation, the alkali metals, ammonium and lower amine, and alkanolamine cations.

Examples of suitable straight chain alkylbenzenesulfonates include: sodium n-decylbenzenesulfonate

sodium n-dodecylbenzenesulfonate

sodium n-tetradecylbenzenesulfonate

sodium n-pentadecylbenzenesulfonate

sodium n-hexadecylbenzenesulfonate

and the corresponding lower alkyl substituted homologues of benzene, as well as the salts of the cations previously referred to. Mixtures of these sulfonates can of course also be used together with mixtures that may include compounds where the straight-chain alkyl residue is smaller or larger than what is stated here, provided that the average chain length in the mixture corresponds to the specific requirements for c^q-C22*

The straight chain alkanesulfonates are also well known

groups of compounds and includes water-soluble salts (alkali metal, amine, alkanolamine and ammonium) of:

1-decanesulfonic acid

1-dodecanesulfonic acid

1-tridecanesulfonic acid

1-tetradecanesulfonic acid

1-pentadecanesulfonic acid

1-hexadecanesulfonic acid

as well as other positional isomers of the sulfonic acid group.

In addition to the alkanesulphonates illustrated above, others with the general range of C]_q-<~22 a^-ky-'- residues may be used, the most preferred range being from C1- to C20*

The straight-chain alkyl sulfates that are contemplated by the present invention comprise the range ciø~C20* Certain examples include sodium-n-decyl sulfate, sodium-n-dodecyl sulfate, sodium-n-hexadecyl sulfate, sodium-n-heptadecyl sulfate, sodium-n -octadecyl sulfate and the ethoxylated (1 - 100 mol ethylene oxide) derivatives, such as the ethoxylated alcohol sulfates, and of course the other water-soluble salt-forming cations mentioned above.

Included in the group of anionic detergents that have been described above as suitable in the present invention are the olefin sulfates, including long-chain alkenesulfonates, long-chain hydroxyalkanesulfonates, as well as disulfonates. Examples of suitable olefin sulfonates which are only illustrative of the general class are sodium dodecenyl-l-sulfonate, sodium tetradecenyl-l-sulfonate, sodium hexadecenyl-l-sulfonate,

and sodium octadecenyl-1-sulfonate. The amount of anionic surfactant used in the present mixture is less than the weight content of nonionic (ethoxylated aliphatic alcohol) surfactant, and preferably less than 50% by weight of the total amount of .. nonionic surfactant (alkylglycoside plus ethoxylated aliphatic alcohol) and make up 1-12% by weight of the mixture.

The liquid detergent mixture according to the present invention can also include conventional laundry additives, such as optical brighteners, germicides, dirt-repelling agents, anti-redeposition agents, antioxidants, coloring substances (dyes and pigments), perfume and water-soluble alcohols, foam enhancers, hydrotropic compounds, such as sodium and potassium xylene sulphonates, sodium and potassium toluene sulphonates, cumene sulphonates, ethyl benzene sulphonate and the like. Enzymes and enzyme stabilizers, provided they do not affect the washing effect and softening activity of the mixture.

The following examples illustrate the invention in more detail.

Example 1

Softener and detergent

15% C]_2~ci5 alcohol: 7 moles of ethylene oxide

15% alkyl polyglycoside, ci2~13<:3> m°l glycoside

0.25% triethanolamine

8.0% monoalkyltrimethylammonium chloride

12% Cj2-15 <a>alcohol:3 mol ethyleneoxyd-

sulfate, sodium salt

4.0% sodium xylene sulfonate

0.5% bleach

Q.S. water

^ tallow-trimethyl-ammonium chloride.

The liquid detergent is prepared by mixing the above-mentioned ingredients until homogeneity, whereby a stable liquid mixture is obtained.

The washing performance of this product was tested in a tergotometer containing 1 liter of water with 150 ppm calcium at 49°C and 21°C and with a concentration of 0.18% softener and detergent, and it was compared to commercial detergents. intermediate products that do not contain the alkylglycoside component. A fabric load of standard soiled samples of "Test Fabric" nylon (TFN) and cotton (TFC), a 65/35% blend of polyester/cotton (PC) and 50/50% dacron/cotton (DC) and EMPA

101 fabric samples were washed with the test detergents and dried in electric tumble dryers. Reflectance of the soiled test pieces was read as a measure of washing effect (Rd). The soil removal (SR) is the sum of the Rd readings on all the test pieces, and the soil removal number (SRI) is the average of the total Rd readings divided by the number of fabric samples.

Example 1 shows excellent washing effect for Dynamo<®>, Solo and Bold® 3. No statistically significant difference with regard to washing effect was observed between example 1 and

liquid Tide<®> at 4 9°C and 21°C.

Removal of skin grease at 49°C was equal to liquid Tide<®> on cotton and D/C 50/50, and better than most competitors on D/C 50/50. At 21°C liquid Tide<®> was slightly better, while most other competitors were equal to the product

according to example 1.

A multi-spot test at 49°C and 20°C gave the following results using liquid Tide<®> as a control.

The greatest losses in washing efficiency were obtained compared to liquid Tide<®> in the case of enzyme at 49°C. This was to be expected as the mixture according to example 1 does not contain any enzymes. However, loss was also observed with the oxidizable stains (grapefruit juice and cranberry juice). In example 1, large gains were made for DDK in the case of oily dirt (barbecue sauce and French dressing).

At 21°C, losses due to enzyme spots were significantly reduced. This is due to the fact that enzymes are generally more effective at higher temperatures. At 21°C, the product according to example 1 is a much more effective detergent than liquid Tide<® >in the case of oily dirt (Spangler skin fat/drops, barbecue sauce, "Red Crisco" margarine and French dressing).

Bold<®> 3 and SOLO did not perform better at any temperature.

The five period softening/static/whitening test gave the following results:

Fluorescence on the cotton samples was read as a measure

for effectiveness as a bleaching agent (Rb).

The mixture according to example 1 was equal to Bold<®> 3 in controlling static cling and better than SOLO. The mixture of Example 1 was judged to be somewhat less effective in terms of softening compared to SOLO, but showed improved softening compared to the mixture of Example 1 without the alkyl glycoside.

Example 2

Softener and detergent

21% "Neodol 25-7"

6% sodium dodecylbenzene sulfonate

4% tallow-trimethyl-(quaternary) ammonium sulfate 2% methylglucoside

0.4% bleach

8% ethanol

5% sodium xylene sulfonate

0.5% dye

Q.S. water

^ C12~<C>15 <a>lkon°l:7 mol ethylene oxide.

Example 3

Softener and detergent

21% "Neodol 25-7"

4% sodium dodecylbenzenesulfonate

4% tallow-trimethyl-ammonium sulfate

2% methylglycoside

0.4% bleach

8% ethanol

5% sodium xylene sulfonate

0.5% dye

Q.S. water

This blend was tested in a five period softness test with 2.7 kg of clean laundry using SOLO as the highest softness control (10). The softness rating of this mixture which was 6.8 (the average of these readings after the 1st, 3rd and 5th periods) measures up nicely with the SOLO. The softness rating lies within a range of 1 (the hardest) to 10 (the softest). Adding 3% of a tallow:15 ethylene oxide to this mixture reduces the softness rating to 6.0. Omitting the quaternary compound and increasing the methylglycoside content to 6% increases the softness rating to 7.2.

The following Table IV summarizes the whitening and static results of the five period test on five test products and two controls.

The above results indicate that methylglycoside provides softening benefits to fabric. The laboratory tests also indicate that the glucoside provides whitening benefits in liquid mixtures. In the absence of a quaternary compound, however, no control of static electricity is achieved.

The fabric softeners and detergents containing an alkyl glycoside were unexpectedly found not only to overcome the reduction in washing performance due to the presence of the quaternary softener, but also to have improved the washing performance and softening properties of the fabric softener and detergent mixture. This is clearly shown in table V by product 4 which contains only 2% methylglycoside, the mixture according to example 3 exhibits a greater degree of softness (6.8) than products 1 (5.9), 2 (5.8) and 3 ( 6.0) which does not contain any alkyl glycoside. Likewise, product 4 shows a greater degree of whiteness after the 1st, 3rd and 5th washing period than products 1, 2 and 3, as well as an increased SRI value compared to the products that do not contain any alkyl glycoside.

Amounts as small as 2% alkyl glycoside are effective when that

applies to improving both the washing effect and the softening properties of a softening and detergent mixture used when washing fabrics. In addition, the present compositions exhibit better cleaning and softening power than other surfactant and/or softener compositions currently on the market, as shown by the comparative results in

tables I, II, IV and V.

Claims (11)

1. Liquid detergent mixture for simultaneous cleaning and softening of fabrics, where the amount of alkyl glycoside present acts to improve washing strength and softening properties and is sufficient to offset the reduction in washing strength due to the amount of quaternary ammonium compound present, characterized by the fact that it contains four basic components: 1-30% by weight of an alkyl glycoside with one or more hydrophobic groups containing 1-30 carbon atoms per hydrophobic group, and a hydrophilic glycoside group containing 1- 10 reducing saccharide radicals; 2-8% by weight of a softening, quaternary ammonium compound where at least one of the four groups bound to the nitrogen atom is a <C>^0~C20 alkY19ruPPe'°? at least two of the groups are C1~C3 alkY1(?ruPPer °g the fourth group can be either another <C>1Q-C20 alkyl group or a C^-Cg alkyl group; 1-12% by weight of an anionic surfactant; and 8-25% by weight of a non-ionic surfactant selected from the group consisting of ethoxylates of primary aliphatic alcohols, ethoxylates of secondary aliphatic alcohols, ethoxylates of alkylphenols, ethylene oxide/propylene oxide condensates of alcohols and mixtures thereof; in an aqueous carrier, optionally together with conventional laundry detergent additives. 2. Mixture according to claim 1, characterized in that the alkyl glycoside amount constitutes 2-25% by weight of the mixture. 3. Mixture according to claims 1-2, characterized in that the alkylglycoside is a C12~C±2 alkyltriglycoside. 4. Mixture according to claims 1-2, characterized in that the alkyl glycoside is a methyl monoglycoside. 5. Mixture according to claim 1, characterized in that the total content of non-ionic surfactant consisting of the mixture of the alcohol ethoxylate and the alkyl glycoside constitutes the main detergent component in an amount of 25 - 40% by weight of the mixture. 6. Mixture according to claim 1, characterized in that the non-ionic surfactant is a ci2~C15 aliphatic alcohol with 7 ethylene oxide groups per moles of alcohol. 7. Mixture according to claim 1, characterized in that the anionic surfactant is selected from the group consisting of alkyl benzene sulphonates, alcohol ether sulphates, olefin sulphonates, alkanes sulphonates, alkyl sulphates and ethoxylated alcohol sulphates. 8. Mixture according to claim 7, characterized in that the content of anionic surfactant is less than the content of non-ionic surfactant. 9. Mixture according to claim 7, characterized in that the anionic surfactant is the sodium salt of the ethoxylated C12~<C>15 alcohol sulphate which contains 3 mol of ethylene oxide per moles of alcohol. 10. Mixture according to claim 7, characterized in that the anionic surfactant is sodium dodecylbenzene sulphonate. 11. Use of a liquid detergent mixture according to claims 1-10 for simultaneous cleaning and softening of substances.