DE3783352T2 - CLEANER CONTAINING POLYAMIDE SOFTENER. - Google Patents

Abstract

Detergent compositions capable of providing through-the-wash softeness and other fabric-care benefits are disclosed, which contain specific polyamide softening agents.

Description

Technical area

The present invention relates to softening detergent compositions containing a well-defined polyamide as a softener.

In addition to showing good cleaning performance, the compositions of the invention exhibit exceptional softening properties during washing and provide additional fabric care benefits such as static control, crease resistance, ease of ironing, color fastness and anti-felt properties in wool.

Basis of the invention

Those who formulate fabric treatment compositions have long sought means for simultaneously washing and softening fabrics. Among the various approaches proposed are processes employing clay softeners or amine materials or both in combination, as described, for example, in German Patent Specifications 24 39 541, 23 34 899 and European Patent Specifications 0 026 528 and 0 028 432.

Amines have also been used in conjunction with soaps (GB-PS 1 514 276), fatty acids (published EP-A-0 133 804) or phosphate esters (published EP-A-0 168 889) as softeners during washing.

However, the formulation of the in-wash softening detergent compositions known in the art can be subject to flexibility problems, often arising as a result of incompatibility between certain ingredients (for example, between peroxyacid bleaches and softeners).

Carboxyamides have been used as antistatic agents for industrial fabric treatment (German Patent 30 43 618) and N-alkylisostearamides have been used as antistatic agents in laundry applications (French Patent 2 531 447).

In the Japanese patent specification J5 8144-175-A, the industrial Treatment of fabric by cationic softening agents and ethoxylated fatty acid amides is described.

Diamides with long-chain alkyl groups as substituents are described in EP-A-87 233, EP-A-94 250 and EP-A-258 500, which was published on March 9, 1988.

Alkoxylated fatty amides are known as surfactants (EP-A-0 000 595) and as viscosity regulating agents (EP-A-0 112 719).

The German patent application 19 59 007 describes the use of a monoethanolamide as a plasticizer. The German patent application 33 10 417 contains the use of fatty acid diethanolamides as antistatic/anti-yellowing agents.

None of the above documents disclose the use of the specific amides of the present invention in softening detergent compositions.

It is an object of the present invention to provide detergent compositions capable of providing outstanding cleaning, softening and fabric care properties.

It is a further object of the invention to provide softening detergent compositions which can be formulated with increased flexibility, particularly in the presence of peroxyacid bleach compounds.

In fact, it has now been found that the use of a well-defined class of amides as softeners in detergent compositions provides outstanding results in cleaning and softening fabrics as well as other "fabric care" benefits, optionally in the presence of peroxyacid bleaches.

Summary of the invention

The present invention relates to detergent compositions capable of providing fabric care benefits including softness during washing, containing detersive surfactants, a nitrogen-containing fabric softener and optionally detersive additives, which are characterized in that the nitrogen-containing softener is selected from the group consisting of:

i) Diamides of the formula:

wherein R₁, R₂, R₃, R₄ represent coconut alkyl or tallow alkyl groups;

ii) Diamides of the formula:

wherein R₁, R₂, R₃, R₄ represent coconut alkyl or tallow alkyl groups, R₅ is selected from the group consisting of alk(en)ylene groups having 1 to 10 carbon atoms, arylene groups, substituted arylene groups, heteroaromatic groups, substituted heteroaromatic groups, polyaromatic groups, and R₅ optionally has hydroxy groups, ester groups and/or ether linkages;

iii) Triamides of the formula:

wherein

R₁, R₂, R₃, R₄ are independently selected from the group consisting of C₁₂₋₂₂-alk(en)yl, aryl or alkyl-aryl groups, which optionally contain hydroxy groups, ester groups and/or ether bonds,

R₅ is selected from the group consisting of alk(en)ylene groups having 1 to 10 carbon atoms, arylene groups, substituted arylene groups, heteroaromatic groups, substituted heteroaromatic groups, polyaromatic groups, and R₅ optionally has hydroxy groups, ester groups and/or ether linkages;

iv) sulfonamides corresponding to the amides described in i) to iii),

consists.

Detailed description of the invention

The plasticizer - The plasticizers for use in the present invention are selected from the amides or sulfonamides of formulae i) to iv) contained hereinabove.

Preferably, all R₁, R₂, R₃ and R₄ in formulae iii) or iv) are selected from tallow and coconut alkyl groups.

Preferred compounds have the formula ii) wherein R5 represents either a C1-5 alkylene or alkenylene group or a phenylene or substituted phenylene group.

When R5 represents an alk(en)ylene group, preferred compounds include the tetracoconut and tetratallow diamides obtained from the following carboxylic acids: malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid.

The most preferred compound of the above category is tetracoconut adipamide.

When R₅ represents an aromatic group, the amide group carrying the R₃ and R₄ chains may be in any of the ortho, meta or para positions to the amide group carrying the R₁ and R₂ chains.

When R5 is a phenylene or substituted phenylene group, preferred compounds are tetratallow terephthalic acid diamide and tetracoconut terephthalic acid diamide.

A preferred polyaromatic group for R5 is biphenylene.

The plasticizer is generally used in amounts of from 0.1 wt% to 15 wt%, preferably from 1 wt% to 10 wt%, most preferably from 3 wt% to 6 wt%.

In a highly preferred embodiment, the amide plasticizer is premixed (predispersed) with a dispersing agent and the resulting mixture is then added to the remainder of the composition.

Any conventional dispersing agent can be used for this purpose. Examples of suitable dispersing agents include nonionic surfactants resulting from the condensation of primary or secondary aliphatic alcohols, e.g. tallow alcohol or alkylphenol, with from 5-12 ethylene oxide units; and phosphate esters as described in European Patent Application 0 168 889, having the formula:

R'-O(CH₂-CH₂O)mPO(OH)₂,

wherein R' is C₁₂₋₁₄alkyl and m is from 1 to 5, which are available under the trade name "Servoxyl VPAZ".

In a particularly preferred embodiment, fatty acids are used as dispersing agents for the amide plasticizer. Fatty acids having from 10 to 20 carbon atoms in the alkyl chain, such as lauric, myristic, palmitic, stearic, oleic acid and mixtures thereof can be advantageously used in the present context. A mixture of palmitic and stearic acid is particularly preferred.

Fatty acid dispersants are most preferably used in a weight ratio of 1/1 to 10/1 of amide plasticizer to fatty acid.

Detersive Surfactants - The compositions of this invention will typically contain organic surfactants ("surfactants") to provide the traditional cleaning benefits associated with the use of such materials.

Detersive surfactants useful herein include the well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkylbenzene sulfonates, alkyl and alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkylphenols, amine oxides and alpha-sulfonates of fatty acids and of fatty acid esters, which are well known in the detergent art. In general, such detersive surfactants contain an alkyl group in the C9-C18 range; the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from 5 to 17 ethylene oxide groups. Detailed listings of such typical detersive surfactants are contained in U.S. Patent No. 4,111,855. C11-C16 alkylbenzenesulfonates, C12-C18 paraffinsulfonates and alkylsulfates and the ethoxylated alcohols and alkylphenols are particularly preferred in compositions of the present type.

Also useful as surfactants here are the water-soluble soaps, e.g. the usual sodium and potassium coconut or tallow soaps, which are well known in the art.

The surfactant component may comprise as little as 1% of the compositions of the invention, but preferably the compositions will comprise from 5% to 40%, more preferably from 10% to 30%, of the surfactant. Mixtures of the ethoxylated nonionics with anionics such as the alkylbenzene sulfonates, the alkyl sulfates and the paraffin sulfonates are preferred in fabrics for cleaning a wide range of soils and stains during the wash.

Detersive Additives - The amide plasticizer is preferably used in conjunction with a detergent-compatible clay plasticizer, although this is not an essential requirement. Such clay plasticizers are They are well known in the detergent art and are in extensive commercial use in both Europe and the United States of America. Such clay plasticizers include various heat treated kaolins and various multilayer smectites. Preferred clay plasticizers are smectite plasticizing clays described in German Patent Application 23 34 899 and in GB-PS 1 400 898. Plasticizing clays are used in the preferred compositions in amounts of at least 1%, generally 1 to 20%, preferably 2 to 10%.

The compositions of the invention may contain other ingredients that assist their cleaning performance. For example, the compositions of the invention may advantageously contain a bleach, particularly a peroxyacid bleach, thanks to the compatibility of the amide softener of the invention with peroxyacid bleaches without any detriment to stability or overall performance. In the context of the present invention, peroxyacid bleach includes both a peroxyacid "per se" and systems capable of delivering peroxyacids in situ.

Peroxyacids "per se" are intended herein to include the alkali and alkaline earth metal salts thereof. Peroxyacids and diperoxyacids are frequently used; examples are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.

Systems capable of delivering peracids in situ consist of a peroxygen bleach and an activator therefor.

Peroxygen bleaches are those capable of providing hydrogen peroxide in an aqueous solution; these compounds are well known in the art and include hydrogen peroxide, alkali metal peroxides, organic peroxide bleaches such as urea peroxide, and inorganic persalt bleaches such as the alkali metal perborates, percarbonates, perphosphates or persilicates.

Preferred are sodium perborate, commercially available in the form of mono- and tetrahydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.

The released hydrogen peroxide reacts with the Bleach activator to form the peroxyacid bleach. Classes of bleach activators include esters, imides, imidazoles, oximes and carbonates. In these classes, preferred materials are methyl o-acetoxybenzoates; sodium p-acetoxybenzenesulfonates such as sodium 4-nonanoyloxybenzenesulfonate; sodium 4-octanoyloxybenzenesulfonate and sodium 4-decanoyloxybenzenesulfonate; bisphenol A diacetate; tetraacetylethylenediamine; tetraacetylhexamethylenediamine; tetraacetylmethylenediamine.

Other highly preferred peroxygen bleach activators, which are described in U.S. Patents 4,483,778 and 4,539,130, are alpha-substituted alkyl or alkenyl esters such as sodium 4-(2-chlorooctanoyloxy)benzenesulfonate, sodium 4-(3,5,5-trimethylhexanoyloxy)benzenesulfonate. Suitable peroxyacids are also peroxygen bleach activators as described in published European patent application No. 0 166 571, i.e. compounds of the general type RXAOOH and RXAL, where R is a hydroxycarbyl group, X represents a heteroatom, A represents a carbonyl bridging group and L represents a leaving group, particularly oxybenzenesulfonate.

The compositions of the invention may alternatively contain any other type of bleaching agent conventionally used in detergent compositions. It is also highly preferred that the detergent compositions applied during washing contain a detergent builder and/or a metal ion complexing agent. Compounds classifiable as detergent builders and well known in the art as such include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tripolyphosphate and sodium ortho- and pyro-phosphates, silicates and mixtures thereof. Metal ion complexing agents include all of the above compounds as well as materials such as ethylenediaminetetraacetate, the amino-polyphosphonates and phosphates (DEQUEST®) and a wide variety of other polyfunctional organic acids and salts too numerous to be mentioned in detail herein. See US Patent 3,579,454 for typical examples of the use of such materials in various cleaning compositions. Generally, the builder/chelating agent will comprise from 0.5% to 45% of the composition. The Zeolite builders of 1-10 micrometers in size (eg zeolite A), which are described in German Patent Specification 24 22 655, are particularly preferred for use in compositions which have a low phosphate content or contain no phosphate.

The laundry compositions herein preferably also contain enzymes to enhance their cleaning performance during the wash for a variety of soils and stains, such as amylase and protease enzymes and cellulase enzymes. Amylase and protease enzymes suitable for use in detergents are well known in the art and in commercially available liquid and granular detergents. Commercial detersive enzymes (preferably a mixture of amylase and protease) are typically used in the present compositions in amounts of 0.001% to 2% and more. Other detergent ingredients which are highly desirable for use in the detergent compositions of the present invention are quaternary ammonium compounds of the form R4 R5 R6 R7 N+ X-, wherein R4 is an alkyl of 10 to 20, preferably 12 to 18 carbon atoms, and R5, R6 and R7 are each C1-C4 alkyl, preferably methyl, X- is an anion, e.g. chloride. Examples of such quaternary ammonium compounds include C12-C14 alkyl trimethyl ammonium chloride and coco alkyl trimethyl ammonium methosulfate. The quaternary ammonium compounds can be used in amounts of 0.5% to 5%, preferably 1% to 3%.

Moreover, the compositions of the invention may contain, in addition to the ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical ingredients include pH adjusting agents, perfumes, dyes, optical brighteners, soil suspending agents, hydrotropes and gel controlling agents, freeze-thaw stabilizers, bactericides, preservatives, foam controlling agents, bleach stabilizers.

When applied during washing, the compositions are typically used at a concentration of at least 500 ppm, preferably 0.10% to 1.5%, in an aqueous laundry bath at a pH of 7-11 is used to wash fabrics. Washing can be carried out over a range from 5ºC to boiling with excellent results.

Form and Preparation of the Compositions - The detergent compositions of the present invention may be in any suitable physical state, such as granular, liquid or sheet form. They may be prepared in any manner appropriate to their physical form, such as by mixing the components, coagglomerating them, microencapsulating them, dispersing them in a liquid carrier, releasably adsorbing them, or applying them to a non-particulate substrate such as a nonwoven or paper sheet.

Preferably, the compositions are in granular form.

A preferred method of preparing the said granular compositions consists of preparing a melt of the dispersant and the amide, dispersing the molten mixture in a stirred aqueous crutcher mixture comprising the remainder of the detersive ingredients and spray drying in standard fashion. In an equally preferred embodiment, the melt can be finely sprayed onto the detergent granules. The compositions of the invention can also be sprayed onto particles of, for example, sodium perborate mono- or tetrahydrate, sodium sulfate, sodium carbonate, sodium silicate, sodium phosphate or onto clay of the type described above.

Industrial application

The following examples are typical of preferred uses of the invention, but are not intended to limit the scope.

EXAMPLE 1

A mixture of tetracoconut terephthalic acid diamide (total 5% of the complete formulation after spray drying) and lauric acid (1.5% of the complete formulation) are mixed, melted and stirred until homogeneous. A standard aqueous Crutcher mixture comprising the following ingredients is prepared (the percentages given refer to the percentage of components in the total formulation after spray drying). Ingredients Percent C₁₁-C₁₂ Alkylbenzenesulfonate Tallow alcohol ethoxylate (E011) Sodium tripolyphosphate Sodium sulfate Sodium silicate Smectite clay * Carboxymethylcellulose Polyacrylate (soil suspending agent) Enzymes Optical brightener Sulfonated zinc phthalocyanine ** EDTA Parfum/copper salts/minor ingredients C₁₂-C₁₄ Alkyltrimethylammonium chloride Moisture

The crutcher mixture is then treated in the standard manner and spray dried. After drying, sodium perborate (20%) and bleach activator (3% 3,5,5-trimethylhexanoic acid, sulfaphenyl ester, sodium salt***) are dry mixed with the granules.

The mixture of tetracoconut terephthalic acid diamide and lauric acid was then sprayed onto the finished product.

* Natural smectite: ion exchange capacity more than 50 milliequ./100 g clay

** US Patent 3 927 967

*** US Pat. Nos. 4,483,778 and 4,539,130.

The composition of Example 1 was compared with an identical composition which did not contain the tetracoconut terephthalic acid diamide/lauric acid premix (reference) in terms of the softness it provided during washing. The purpose of the test was to determine the softness of fabric pieces which had been washed once (monocycle) and washed four times (multicycle) with the invention and reference composition.

The test conditions were as follows:

- Automatic drum washing machine MIELE 423

- Heating from 15ºC to 90ºC; 50' at 90ºC

- 1% product concentration in the wash liquor

- 18 grains/gallon (0.31 g/l) water hardness (3:1 Ca/Mg ratio).

The washed and line dried rags were compared by a panel of two experienced professionals working independently, by a paired comparison technique using a 9-point Scheffe scale. Differences were recorded in panel rating units (psu), with a positive value corresponding to better softness performance, and the least significant difference (LSD) with 95% confidence interval was also calculated.

The test results were as follows: Softness (Example 1 vs. reference) 1 cycle 4 cycles Terry fabric (12) Polyester fabric (12) * The value between brackets is the LSD value (see text)

These results demonstrate the significant wash-through softness benefits achievable by the composition of Example 1.

EXAMPLE 2

A low phosphate spray dried detergent formulation is as follows: Ingredients Percent Zeolite A (1-10 µm) Sodium Nitrilotriacetate Smectite Clay * Tetracoconut Adipamide/Lauric Acid (3:1 wt ratio) C₁₁-C₁₂ Alkylbenzene Sulfonate Tallow Ethoxylate (EO 9-11) Sodium Perborate 4H₂O *** Tetraacetylethylenediamine (TAED) *** Sodium Silicate CMC Sodium Sulphate Enzymes (1:1 Amylase/Protease) *** Optical Brightener Water, Minor * As Gelwhite GP (Trade Mark): CaCO₃ Ion Exchange Capacity 70 millieq/100 g ** Prepared as in Example 1 and sprayed onto the finished product *** Dry-mixed with the composition.

The composition of Example 2 is prepared in the manner described for Example 1. The composition of Example 2 provides better softness than the composition wherein the amide/lauric acid complex has been replaced with additional sodium sulfate.

Claims (10)

1. A detergent composition comprising a surfactant, a nitrogen-containing fabric softener and optionally detersive additives, characterized in that the nitrogen-containing softener is selected from the group consisting of: i) Diamides of the formula: wherein R₁, R₂, R₃, R₄ represent coconut alkyl or tallow alkyl groups; ii) Diamides of the formula: wherein R₁, R₂, R₃, R₄ represent coconut alkyl or tallow alkyl groups, R₅ is selected from the group consisting of alk(en)ylene groups having 1 to 10 carbon atoms, arylene groups, substituted arylene groups, heteroaromatic groups, substituted heteroaromatic groups, polyaromatic groups, and R₅ optionally has hydroxy groups, ester groups and/or ether linkages; iii) Triamides of the formula: wherein R₁, R₂, R₃, R₄ are independently selected from the group consisting of C₁₂₋₂₂-alk(en)yl, aryl or alkyl-aryl groups, which optionally contain hydroxy groups, ester groups and/or ether bonds, R₅ is selected from the group consisting of alk(en)ylene groups having 1 to 10 carbon atoms, arylene groups, substituted arylene groups, heteroaromatic groups, substituted heteroaromatic groups, polyaromatic groups, and R₅ optionally has hydroxy groups, ester groups and/or ether linkages; iv) sulfonamides corresponding to the amides described in i) to iii), consists. 2. Composition according to claim 1, wherein the amide plasticizer is predispersed with a dispersant which is - non-ionic surfactants resulting from the condensation of primary or secondary aliphatic alcohols; - Phosphate esters of the formula R'-O(CH₂-CH₂O)mPO(OH)₂, wherein R' is C₁₂-C₁₄alkyl and m is from 1 to 5, - fatty acids with 10 to 20 carbon atoms in the alkyl chain is selected. 3. A composition according to claim 2, wherein the dispersant is a fatty acid having 10 to 20 carbon atoms in the alkyl chain and in a weight ratio of amide plasticizer to fatty acid of 1:1 to 10:1. 4. A composition according to claims 1 to 3, wherein the nitrogen-containing plasticizer is i) or ii) or has the formula iii) or iv) where R₁, R₂, R₃, R₄ are a coconut alkyl or a tallow alkyl group. 5. A composition according to claims 1 to 4, wherein the nitrogen-containing plasticizer has the formula ii) wherein R5 is an alkylene group having 1 to 5 carbon atoms. 6. A composition according to claims 1 to 5, wherein the nitrogen-containing plasticizer has the formula ii) wherein R5 is a phenylene group or a substituted phenylene group. 7. A composition according to claim 6, wherein the nitrogen-containing plasticizer is tetratallow terephthalic acid diamide or tetracoconut terephthalic acid diamide. 8. Composition according to claims 1 to 7, wherein the amount of nitrogen-containing plasticizer is from 0.1 wt% to 15 wt%. 9. A composition according to claims 1 to 8, which additionally contains a peroxyacid bleaching compound. 10. A composition according to claim 9, wherein the peroxyacid bleach compound consists of a peroxygen bleach compound and an activator therefor.