WO1995035361A1

WO1995035361A1 - Hand wash laundry compositions

Info

Publication number: WO1995035361A1
Application number: PCT/US1995/006948
Authority: WO
Inventors: John Downing Curry
Original assignee: The Procter & Gamble Company
Priority date: 1994-06-17
Filing date: 1995-06-02
Publication date: 1995-12-28
Also published as: CN1155295A; CN1082998C; MX9606567A

Abstract

The subject invention involves detergent compositions comprising, by weight: (a) from about 10 % to about 40 % anionic surfactant comprising one or more anionic surfactants selected from the group consisting of about C10-C14 linear or branched alkylbenzene sulfonate and about C10-C18 alkyl sulfate; (b) from about 3 % to about 30 % nonionic polymeric mildness aid material comprising nonionic homopolymers of ethylene oxide, or nonionic copolymers of ethylene oxide and propylene oxide having a HLB of greater than about 18; (c) from about 1 % to about 15 % mild non-anionic lather builder having the structure RX, wherein R is a hydrophobic group having from about 10 to about 22 carbon atoms, the group being selected from the group consisting of alkyl, alkyl aryl, and aryl alkyl, and wherein X is a non-polymeric moiety comprising at least one oxygen or nitrogen atom.

Description

HAND WASH LAUNDRY COMPOSITIONS TECHNICAL FIELD

This invention relates to mild, high-lathering hand laundry compositions. BACKGROUND OF THE INVENTION

This invention relates to mild, high-lathering laundry compositions. These compositions are preferably in granular or bar form. The compositions of this invention comprise selected anionic surfactants, water-soluble nonionic polymers such as polyethylene glycol (PEG) for mildness enhancement, and mild non- anionic lather builders to counteract the lather depressing effects of the nonionic polymers.

Detergent compositions are frequently used for laundering clothes by hand in situations in which mechanical washing machines are not accessible. In the process of hand laundering, the hands and arms may be exposed to aqueous solutions of laundry detergent. Such exposure can lead to skin damage, such as irritation or lesions. An objective of this invention is to provide compositions that ameliorate the detrimental effects of hand laundering on the skin condition of the exposed hands and arms.

During the hand laundering process, detergent materials may be depleted from the washing liquor. This depletion is evidenced by a reduction in cleaning efficacy of the washing liquor and a corresponding reduction in lather volume. Therefore, the lathering of the washing liquor is commonly used as an indicator of cleaning efficacy. For this and other reasons, there is wide-spread preference for hand wash laundry detergent compositions that are high lathering at normal washing liquor concentrations. A further objective of this invention is to provide compositions that produce high-lathering washing liquors while maintaining mildness.

SUMMARY OF THE INVENTION

The laundry compositions of this invention comprise, by weight, a) from about 10% to about 40% of anionic surfactant mixture comprising one or more anionic surfactants selected from the group consisting of about C10-C1 linear or branched alkyl benzene sulfonate and about C10-I8 ^alky' sulfate; b) from about 3% to about 30% nonionic polymeric mildness aid material comprising nonionic homopolymers of ethylene oxide, or nonionic copolymers of ethylene oxide and propylene oxide having a HLB of greater than about 18; c) from about 1% to about 15% mild non-anionic lather builder having the structure RX, wherein R is a hydrophobic group having from about 10 to about 22 carbon atoms, the group being selected from the group consisting of alkyl, alkyl aryl, and aryl alkyl, and wherein X is a non-polymeric moiety comprising at least one oxygen or nitrogen atom;

In addition to the essential materials of the invention, other materials may be included in the detergent compositions of this invention to provide desired performance and aesthetic features.

The compositions of this invention are useful for laundry products, particularly for those produced in granular or bar form, or other solid or semisolid (paste or gel) form.

Polyethylene glycol (PEG) is the preferred nonionic polymeric material. The preferred PEG has an average molecular weight in the range of 2,000- 25,000.

The preferred mild non-anionic lather builders are betaines, fatty acid amides including fatty acid monoethanol amides and polyhydroxy fatty acid amides, amine oxides, and fatty alcohols.

DETAILED DESCRIPTION OF THE INVENTION Anionic Surfactant

The compositions of this invention comprise from about 10% to about 40% of an anionic surfactant comprising, preferably consisting essentially of, one or more anionic surfactants selected from the group consisting of about C-ιrj-C-14 linear or branched alkyl benzene sulfonate and about C-JO-18 ^a'^kvl sulfate. These anionic surfactants are broadly used in commercial hand laundry products and have demonstrated desirable performance properties and are available in large volumes.

This invention provides improved mildness, relative to currently used anionic surfactant-comprising compositions while maintaining equivalent lather. Currently used products that may be improved through the use of this invention typically comprise from about 10% to about 40% anionic surfactant, and therefore this is the anionic surfactant concentration range for the compositions of this invention. The preferred amount of anionic surfactant is from about 12% to about 35% by weight of the compositions, more preferred is from about 15% to about 30%.

Alkyl benzene has a hydrocarbon chain substituted for one of the hydrogens in the benzene ring. The alkyl designations for alkylbenzene refer to the hydrocarbon chain substituent. Suitable alkylbenzene sulfonates include the alkali (lithium, sodium, and/or potassium), ammonium and/or alkanolammonium salts of straight or branched chain alkylbenzene sulfonic acids. Alkylbenzene sulfonic acids useful as precursors for these surfactants include decyl benzene sulfonic acid, undecyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tridecyl benzene sulfonic acid, tetradecyl benzene sulfonic acid, tetrapropylene benzene sulfonic acid, and mixtures thereof. Typically, mixtures are used and the chain length designation, such as C-13, indicates the average number of carbons in the alkyl chains of the mixture; average chain lengths of from about 11 to about 14 carbons are preferred. Alkylbenzene sulfonates having linear alkyl chains (LAS) are also preferred.

The alkyl sulfates of this invention include the sodium, potassium, lithium, ammonium, and alkanoiammonium salts of alkyl sulfuric acids having average chain lengths in the range of from about C<ιo to about C13. Especially preferred are the alkyl sulfates made by sulfating primary alcohols derived from coconut oil (CFAS).

Although washing liquors containing the above surfactants, particularly CFAS or LAS, can provide effective cleaning and desirable lathering, they can be harsh to the skin. Skin can be irritated by exposure to harsh washing liquors, and/or by abrasion during the laundry scrubbing process.

This invention provides compositions that ameliorate harshness and/or abrasion to the skin while maintaining effective cleaning and desirable lathering. Nonionic Polymeric Mildness Aid Material

Cationic and nonionic polymeric skin mildness aids are used in cosmetic and personal cleansing products. Such products are typically applied to the skin in high concentrations, either directly or in the form of an aqueous lather or foam having high concentrations of the polymeric mildness aid material. It has now been discovered that certain nonionic polymeric mildness aid materials can ameliorate the skin-damaging effects of harsh surfactants, even in the dilute solutions used in laundering. Such material can also provide lubricity which reduces abrasion to the skin during the hand washing process.

The amount of the nonionic mildness aid depends on the concentration and harshness of the anionic surfactant used in the composition. At low concentrations of anionic surfactant, desired mildness improvements may be achieved using as little as about 3% nonionic polymeric mildness aid, whereas at higher concentrations of anionic surfactant, as much as about 30% nonionic polymeric mildness aid may be required to achieve a desired mildness improvement. Preferred level of mildness aids in the subject compositions is from about 4% to about 15%, also preferred is from about 5% to about 10%. In the compositions of this invention, it is preferred that the weight ratio of nonionic polymeric mildness aid material to anionic surfactant be in the range of about 1 :8 to about 3:1; more preferred is from about 1:6 to about 1:1; also preferred is from about 1:5 to about 1:2.

Although certain cationic polymers might, in some detergent compositions, provide desirable mildness effects, nonionic polymeric mildness aid materials are used in the compositions of this invention to avoid any reaction of cationic polymers with the anionic surfactant component.

Classes of nonionic polymeric mildness aid useful in the subject invention compositions comprise nonionic homopolymers of ethylene oxide or copolymers of ethylene oxide and propylene oxide. Good water solubility of the nonionic polymeric mildness aid is desirable, making copolymers high in ethylene oxide content generally preferred. Such materials that comprise copolymers of ethylene oxide and propylene oxide have a HLB of more than about 18, preferably more than about 24. Regarding such copolymers, block copolymers are preferred.

Especially preferred nonionic polymeric mildness aids are polyethylene glycols. Polyethylene glycol (PEG) has the general formula:

HO(C₂H O)_nH wherein n represents the degree of polymerization, for example, for tetraethyleneglycol, n=4. PEG can be characterized by degree of polymerization (n or DP) or by molecular weight (MW). The relationship between n and MW is defined by the equation:

MW = 44n +18 for PEG

By the nature of polymer-forming reactions the products obtained under any one set of conditions comprise a mixture of polymers having a range of molecular weights. The range of molecular weights of the individual polymers in a PEG or copolymer product are clustered about an average value. This average molecular weight is used to characterize PEG and copolymer products and is commonly referred to as the molecular weight of the product. As used herein in reference to PEG or copolymer products, the term "molecular weight" refers to the average molecular weight of the polymeric mixture. PEG is commonly available in molecular weights ranging from about 200 to about 25,000.

Nonionic polymeric mildness aids useful in the subject invention preferably have a molecular weight of from about 1000 to about 30,000, more preferably from about 1500 to about 20,000, more preferably still from about 2000 to about 15,000, still more preferably from about 3,000 to about 12,000, also preferably from about 4,000 to about 10,000. Mild Non-Anionic Lather Builders The incorporation of the nonionic polymeric mildness aid material generally depresses the lathering of the anionic surfactant. The function of the mild non- anionic lather builder is to counteract anionic surfactant lather depression resulting from the incorporation of the nonionic polymeric material, while maintaining or further improving mildness of the subject compositions.

The amount of the non-anionic lather builder used in the compositions of this invention depends on the concentration and type of nonionic polymeric mildness aid, the non-anionic lather builder selected, and the lathering performance sought. Specific appropriate concentrations may be determined, without undue experimentation, using the lather evaluation method disclosed in the examples below. At low concentrations of nonionic polymeric mildness aid, as little as about 1% non-anionic lather builder may provide a desired lathering performance, whereas at high concentrations of nonionic polymeric mildness aid, as much as about 15% non-anionic lather builder may be required to achieve a desired lathering performance. Preferred amount of non-anionic lather builder in the subject compositions is from about 2% to about 12%; more preferred is from about 3% to about 10%; also preferred is from about 4% to about 8%.

Non-anionic lather builders are defined as materials having the general formula RX, wherein R is an alkyl chain having from about 10 to about 22 carbon atoms and X is a non-polymeric moiety comprising oxygen and/or nitrogen atoms which, taken as a whole, is non-anionic.

Although the definition given for mild non-anionic lather builder does not specifically exclude cationic materials, such cationic materials are not preferred for incorporation into compositions of this invention because of the potential for reaction with the components of the anionic surfactant mixture comprised in compositions of this invention.

EΞxamples of preferred non-anionic lather builders include betaines, fatty acid amides including fatty acid monoethanol amides and poiyhydroxy fatty acid amides, amine oxides, fatty alcohols, and mixtures thereof.

The betaine surfactant has the general formula:

(+) R-N(R⁶)₂R⁷COO (-) wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbons atoms with a benzene ring being counted as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether iinkages; each R⁶ is an alkyl group containing one to about 3 carbon atoms; and R⁷ is an alkylene group containing from one to about 6 carbon atoms.

Examples of preferred materials are dodecylamidopropyldimethylbetaine, dodecyldimethylbetaine, tetradecyldimethylbetaine, cetyldimethylbetaine, cetylamidopropyldimethylbetaine, tetradecylamidopropyldimethylbetaine, docosyldimethylammonium hexoanate, and mixtures thereof. Especially preferred is coconut amidopropylbetaine, such as Tego®-Betaine L-7 sold by Goldschmidt Chemical Corporation.

The fatty acid amides useful as non-anionic lather builders in the compositions of this invention include fatty acid monoethanol amides which have the general formula:

R CONHC₂H OH wherein R¹ is a saturated or unsaturated, aliphatic hydrocarbon radical having from about 9 to about 21, preferably from about 11 to about 17, carbon atoms. The acyl moieties may be derived from naturally occurring glycerides, such as coconut oil, palm oil, or tallow, or they may be synthesized from petroleum stocks. The monoethanol amides of about C12-14 fatty acids are preferred, particularly coconut monoethanol amide.

Other fatty acid amides useful as non-anionic lather builders in this invention are poiyhydroxy fatty acid amides, which comprise compounds of the structural formula:

O R²

R¹ - C - N - Z wherein: R¹ is about C9-C21 hydrocarbyl, preferably straight chain about C9-C19 alkyl or alkenyl, more preferably straight chain about C9-C17 alkyl or alkenyl, most preferably straight chain about C-j -J-C-IQ alkyl or alkenyl, or mixtures thereof; R² is H, about C-J-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, 3-methoxy propyl, 2-methoxy ethyl or mixtures thereof, preferably about C1-C4 alkyl, more preferably C-_j or C₂ alkyl, most preferably C-| alkyl (i.e. methyl); and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkyoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. Preferably Z will be selected from the group consisting of -CH₂-(CHOH)_nCH₂OH, -CH(CH₂OH)(CHOH)_n.₁CH₂OH, and -CH₂-(CHOH)₂(CHOR^*)(CHOH)CH₂OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH (CHOH)4CH₂OH. R¹-CO-N< can be, for example, cocamide, stearamide, oieamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Methods for making poiyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Poiyhydroxy fatty acid amides and processes for making them are disclosed in U.S. Patent No. 5,194,639, incorporated herein by reference.

Amine oxide semi-polar nonionic surface active agents comprise compounds and mixtures of compounds having the general formula:

R² R1-N-O

'_R3 wherein R¹ is about C-*o_-|6 ^a,kv|. preferably about C10-C-14 alkyl, and R² and R³ are methyl or ethyl, preferably methyl.

Fatty alcohol has the general formula ROH, wherein R is an alkyl chain having from about 10 to about 20 carbons. The preferred coconut fatty alcohol is made commercially both by hydrogenation of fatty acids produced by hydrolysis of coconut oil and by hydrogenation of methyl esters produced by methanolysis of coconut oil. Most preferred are lauryl alcohol-rich materials, such as 95% lauryl alcohol fractions produced by distillation of coconut fatty alcohol. OPTIONAL INGREDIENTS Other Surfactants

Other anionic surfactants useful in the subject invention compositions include sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10, preferably from about 2 to about 4, units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates (R(EO)_xS) containing about 1 to about 10 (x), preferably from about 2 to about 4, units of ethylene oxide (EO) per molecule and wherein the alkyl group (R) contains from about 10 to about 20 carbon atoms.

Also included are water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1 -sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to about 20 carbon atoms in the alkyl group and from about 1 to about 30 moles of ethylene oxide; water- soluble salts of olefm sulfonates containing from about 12 to about 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to about 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.

Other nonionic surfactants can also be incorporated in the subject invention compositions. Examples of such other nonionic surfactants are disclosed in U.S. Patent No. 4,844,821, incorporated herein by reference.

The amount of such other surfactants incorporated in the subject invention compositions is from 0% to about 10%, preferably from about 2% to about 6%. Detergent Builders

Optional detergent ingredients employed in the present invention are inorganic and/or organic detersive builders. Inorganic detersive builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripoiyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales.

Examples of silicate builders are the alkali metal silicates, particularly those having a SiO₂:Na₂O weight ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, available from Hoechst under the trademark "SKS"; SKS-6 is an especially preferred layered silicate builder. Carbonate builders, especially a finely ground calcium carbonate with surface area greater than 10 m²/g, are preferred builders that can be used in granular compositions. The density of such alkali metal carbonate built detergents can be in the range of 450-850 g/l with the moisture content preferably below 4%. Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Calcium carbonate is often used as a component of laundry bars at levels up to 40%, preferably from about 5% to about 25%.

Aluminosilicate builders are especially useful in the present invention. Preferred aluminosilicates are zeolite builders which have the formula:

Na_z[(AIO₂)_z(SiO₂)_y] xH₂O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally- occurring aluminosilicates or synthetically derived. Methods for producing aluminosilicate ion exchange materials are disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, and U.S. Patent 4,605,509, Corkill et al., issued August 12, 1986. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B) (including those disclosed in EPO 384,070), and Zeolite X. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic detersive builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds, such as ether polycarboxylates, including oxydisuccinate, and disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972. See also TMSTDS" builders of U.S. Patent 4,663,071, issued to Bush et al., on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

Other useful detersive builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5- trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt) are preferred polycarboxylate builders that can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.

In situations where phosphorus-based builders can be used, they are preferred, especially in the formulation of bars used for hand-laundering operations. The various alkali metal phosphates such as the well-known sodium tripolyphosphates (STPP), sodium pyrophosphate, especially tetrasodium pyrophosphate (TSPP), and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137) can also be used.

If detergent builders are used in the present compositions, they are used at levels from about 5% to about 60% by weight, preferably from about 10% to about 50% by weight. Phosphate-based builders in laundry bars are preferably at a level of from about 5% to about 30%, more preferably from about 7% to about 20%. Phosphate builders in hand laundry granules are preferably at a level of from about 10% to about 50%, more preferably from about 15% to about 35%. Other Optional Components

The subject invention compositions can contain other optional ingredients, including fillers and water, in an amount of from 0% to about 50%, preferably from about 5% to about 25%, also from about 2% to about 10%.

Another component of the compositions of the present invention may be a chelant. Such chelants are able to sequester and chelate heavy metal cations (such as iron). The chelant is preferably a phosphonate chelant, particularly one selected from the group consisting of diethylenetriamine penta(methylene phosphonic acid), ethylene diamine tetra(methylene phosphonic acid), and mixtures and salts and complexes thereof, and an acetate chelant, particularly one selected from the group consisting of diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinate (EDDS), and mixtures and salts and complexes thereof. The detergent chelant is included in the compositions of this invention at concentrations up to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to about 2%, most preferably from about 0.5% to about 1.5%. Such detergent chelants can be used to counteract the detrimental effects of heavy metal cations on washing liquor cleaning efficacy.

Another particularly preferred component is a detergent enzyme. Non- limiting types of enzymes include cellulase, lipase, amylase, and protease, and mixtures thereof. Enzymes are advantageously used at levels up to 5%.

Another optional component of the compositions of this invention is a soil release polymer. A soil release polymer can be incorporated at concentrations up to 5%, preferably at from about 0.05% to about 3%, more preferably from about 0.2% to about 1.0%, to improve the cleaning of clothes after multiple wear-wash cycles.

A preferred soil release polymer is a water-soluble or water-dispersible soil release polymer comprising at least about 10% by weight (preferably at least about 50% by weight) of a substantially linear sulfonated poly-ethoxy/propoxy end-capped ester having a molecular weight ranging from about 500 to about 8,000, the ester consisting essentially of on a molar basis: i) from about 1 to about 2 moles of sulfonated poly-ethoxy/propoxy end- capping units of the formula: (MO3S)(CH₂)_m(CH₂CH₂O)(RO)_n- wherein M is a salt-forming cation such as sodium or tetraalkylammonium, m is 0 or 1, R is ethylene, propylene or a mixture thereof, and n is from 0 to 2; and mixture thereof; ii) from about 0.5 to about 66 moles of units selected from the group consisting of: a) oxyethyleneoxy units; b) a mixture of oxyethyleneoxy and oxy-1 ,2-propyleneoxy units wherein said oxyethyleneoxy units are present in an oxyethyleneoxy to oxy- 1,2-propyleneoxy mole ratio ranging from 0.5:1 to about 10:1; and c) a mixture of a) or b) with poly(oxyethylene)oxy units wherein said poly(oxyethylene)oxy units have a degree of polymerization of from 2 to 4; provided that when said poly(oxyethylene)oxy units have a degree of polymerization of 2, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to about 0.33:1; and when said poly(oxyethyiene)oxy units have a degree of polymerization of 3, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to about 0.22:1; and when said poly(oxyethylene)oxy units have a degree of polymerization of 4, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to about 0.14:1; iii) from about 1.5 to about 40 moles of terephthaloyl units; and iv) from 0 to about 26 moles of 5-sulfoisophthaloyl units of the formula -(O)C(C6H3)(SO3M)C(O)- wherein M is a salt forming cation.

Other preferred soil release polymers are disclosed in the following patents: U.S. 4,569,772 to Ciallella, issued February 11, 1986; U.S. 4,721,580 to Gosselink, issued January 26, 1988; U.S. 4,818,569 to Trinh et al., issued April 4, 1989; U.S. 4,956,447 to Gosselink et al., issued September 11, 1990; U.S. 4,976,879 to Maldonado et al., issued December 11, 1990; U.S. 4,834,895 to Cook et al., issued May 30, 1989; and U.S. 5,256,168 to Monrall et al., issued October 26, 1993 (all incorporated by reference herein).

Other preferred optional components in the laundry compositions are dye transfer inhibiting (DTI) ingredients that can reduce or prevent the detrimental effects of laundering on the color fidelity and color intensity of laundered articles. Effective DTI ingredients include materials that inhibit deposition of fugitives dyes on fabrics and materials that decolorize fugitives dyes. Examples of dye- decolorizing materials are oxidizing agents such as hydrogen peroxide or sources of hydrogen peroxide, such as percarbonate or perborate. EΞxamples of dye-deposition inhibiting materials are certain polymeric materials. Especially useful are polymeric DTI materials such as polyvinylpyrrolidone, polyamine N- oxide containing polymer (preferably poly(4-vinylpyridine)-N-oxide), and N- vinylimidazole N-vinylpyrrolidone copolymer, and mixtures thereof. The DTI materials may be advantageously used at levels up to about 10%, preferably from about 0.05% to 5%, more preferably from about 0.2% to about 2% by weight of the laundry compositions.

Fabric softening agent is another optional component in the compositions of this invention. Preferred fabric softening agents can include softening clay, such as montmorillonite, bentonite, and hectorite clay, as well as an acid-treated bentonite or other softening clay. Compositions of this invention containing a softening clay may also advantageously include a polymeric clay-flocculating agent such as polyethylene oxide having molecular weight in the range of about 300,000 to about 5,000,000. Care must be taken to make sure that these fabric softening agents are compatible with the polymeric mildness aid. The fabric softening agent may be comprised in the compositions of this invention at concentrations up to 20%, preferably from about 2% to about 15%. Bleaching agent is yet another optional component in the compositions of this invention. The bleaching component can be a source of "OOH group, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate.

These peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.

Preferred bleach activators incorporated into compositions of the present invention have the general formula:

O

II

R-C-L wherein R is an alkyl group containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbons atoms and L is a leaving group, the conjugate acid of which has a pK_a in the range of from about 6 to about 13. An example of such a preferred bleach activator is nonanoyi oxybenzene sulfonate (NOBS). Another widely used bleach activator is tetraacetyl ethylene diamine ("TAED"). .

Also suitable are manganese-containing bleach catalysts, particularly where the catalyst is a water-soluble complex of manganese (II), (III) or (IV). Such manganese-containing catalysts are disclosed in the following U.S. patents assigned to Lever Brothers Co. (all incorporated by reference herein): 5,114,606; 5,114,611; 5,153,161; 5,194,416; 5,227,084; 5,244,594; 5,246,612; 5,246,621; 5,256,779; 5,274,147; 5,280,117; and 5,284,944. They are also disclosed in Lever's European Patent Applications EP 306,089 and EP 549,271.

The bleaching component may be a peracid having the general formula: CH3(CH2)wNH-C(O)-(CH₂)₂CO3H wherein z is from 2 to 4 and w is from 4 to 10.

The bleach components can be added to the compositions of this invention at concentrations up to 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 6%.

Bleaching agents other than oxygen bleaching agents are known in the art and can be used herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited on clothes during the washing process. Upon irradiation with light, such as when the clothes are exposed to sunlight when they are hung out to dry, the sulfonated zinc phthalocyanine is activated and the clothes are bleached. Desirable bleaching results may be achieved using detergents having sulfonated zinc phthalocyanine concentrations in the range of about 0.005% to about 1.25%.

Alkali carbonates, such as sodium carbonate, are useful in the compositions of this invention. Such materials provide alkalinity and may reduce the detrimental effects of water hardness.

Sodium sulfate is a well-known material that is compatible with the compositions of this invention. It can be a by-product of the surfactant sulfation and sulfonation processes, or it can be added separately.

When the compositions of this invention are produced in bar form, it is preferred to incorporate binding agents such as natural and synthetic starches, gums, thickeners, and mixtures thereof. Some binding agents can also serve as soil suspending agents, and can include such materials as water-soluble salts of carboxymethylcellulose and carboxyhydroxymethylcellulose.

A preferred soil suspending agent which can optionally be used is an acrylic/maleic copolymer, commercially available as Sokolan®, from BASF Corp. Another preferred soil suspending agent is a sodium salt of polyacrylic acid, having a molecular weight between about 2,000 and about 9,000. Other soil suspending agents include ethoxylated mono- and polyamines, and quaternary salts thereof. Dyes, pigments, optical brighteners, germicides, and perfumes can also be added to the compositions of this invention.

The compositions of this invention may be produced in the form of low density granules, such as may be made by spray drying, or in the form of high density granules, such as may be made using commercially available agglomeration and mixing equipment, such as that sold by Loedige.

The detergent laundry bar form of the present invention can be produced using conventional soap or detergent bar making equipment which may include some or all of the following: blender/mixer, mill or refining plodder, two-stage vacuum plodder, logo printer/cutter, cooling tunnel and wrapper. TEST METHODS

Suds heights are the average of the suds height for two tests using a tumbling tube method. Solutions, having typical usage concentrations of detergent, are agitated in a tumbling tube to produce a layer of foam. The height of this foam layer is measured and reported as "inches of suds" in the following examples. EXAMPLES The following Examples 1 & 2 demonstrate the lather-depressing effect of nonionic polymer using PEG as the example nonionic polymer.

Example Test Formula Anionic PEG Inches of Surfactant (MW 20,000) Suds

1 A 21% LAS 0% 7.25

2 B 21% LAS 10.5% 0.35

The following Examples 3-8 demonstrate the effect of the incorporation of 2% non-anionic lather builders in counteracting the lather-depressing effects of PEG.

Example Test Formula Lather Builder Inches of Suds

3 B None 0.35

4 B Fatty Alcohol (95% C₁₂) 3.25

5 B Coco Monoethanol Amide 2.25

6 B Coco Amine Oxide (C12-14) 7.00

7 B Coco Amidopropylbetaine 6.30

8 B Coco N-methylglucamide 2.40 (^c12-14>

Examples 9 & 10 demonstrate the lather boosting ineffectiveness of certain nonionic and anionic materials.

Example 11

Laundry bars of this invention are made from the materials in the table below, using the conventional steps of blending in a mixer, transferring to a feed hopper, and then plodding using a two-stage vacuum plodder. The mixer is charged with sodium coconut fatty alkyl sulfate (CFAS, as dried noodle or flake), sodium tripolyphosphate (STPP), coco amidopropylbetaine, tetrasodium pyrophosphate (TSPP), sodium carbonate, calcium carbonate, and the acid form of LAS (HLAS). The polyethylene glycol (PEG, MW 8,000) and colorants are dissolved in the water and held at about 160°F (71°C) to melt the PEG and maximize solubility. The water with dissolved colorants and PEG is added and blended with the ingredients in the mixer to form a dough. Dry minors are then added - Zeolite A, sodium sulfate, brighteners, Sokalan CP-5 polymer - and mixed until the composition changes from a dough to a coarse granular mix. Molten coconut fatty alcohol (CFA) is then added, and perfume is added last. A mixer jacket is often used with approximately 160°F (71 °C) water, and the mix is roughly 120°F (49°C) when unloaded.

The moist granular mix is unloaded with little further mixing and is transferred (with 5-10 minutes delay) to the feed hopper for the two-stage vacuum plodder. Jacketing of the plodder can be adjusted to give a range of bar temperatures at the exit die, ideally 125-150°F (52-66°C). The ability of the hot water jacketing to heat the mix in mixer and/or plodder is often limited, so the heat contributed by preheated feedstocks such as surfactant paste is often very important for achieving minimum temperatures for plodding.

The following laundry bar composition is produced:

Ingredient Weight % Active Material

CFAS 24.5

LAS 3.5

STPP 5.0

Coco Amidopropylbetaine 4.0

TSPP 5.0

Sodium Carbonate 20.0

Sodium Sulfate 5.0

Calcium Carbonate 16.5

Zeolite A 2.0

PEG-8000 5.0

Water 5.0

Sokalan Polymer 0.4

CFA (total) 2.5

Minors (perfume, brighteners, and 1.6 colorants)

Example 12 Laundry granules of this invention, having the following composition are made using a conventional spray drying or agglomeration process.

Component Weight %

LAS 25.0

Coco Amidopropylbetaine 8.0

PEG 4000 8.0

STPP 19.0

Sokalan Polymer 1.0

Zeolite A 5.5

EDTA Chelant 0.4

Sodium Carbonate 12.0

Sodium Sulfate 5.2

Sodium Perborate Monohydrate 4.5

Bleach Activator (NOBS) 3.2

Enzyme(s) 1.0

Minors (brighteners, perfume etc.) 1.4

Moisture 5.8

Example 13

Laundry granules of the subject invention having the following composition are made using a conventional process.

Carboxymethylcellulose 0.4

Sodiuπ Carbonate 4.0

Sodium Silicate 3.0

Sodium Bicarbonate 3.0

Bri htener 0.2

Photobleach 0.005

Magnesium Sulfate 2.2

Diethylene Triamine Pentamethylene Phosphonic Acid 1.6

Enzymes 1.67

Sodium Sulfate balance

Example 14

Gel-form products using compositions of this invention, may be produced by a process whereby the composition is kept above its liquification temperature until all the components have been mixed into a homogeneous liquid blend. The homogeneous blend is then cooled to a temperature below its liquification temperature, taking care that there is no agitation of the blend that would interfere with gel formation during cooling.

The following is an example of a composition of this invention suitable for production in gel form.

Component Weiαht %

Magnesium LAS 20.0

Sodium LAS 16.0

Coco Amidopropyl Betaine 5.0

PEG 4000 10.0

Urea 17.0

Minors (brighteners, perfume, etc.) 3.0

Water 29.0

While particular embodiments of the subject invention have been described, it would be obvious to those skilled in the art that various changes and modifications to the subject invention can be made without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all such modifications that are within the scope of this invention.

WHAT IS CLAIMED IS:

Claims

Claims:

1. Detergent compositions comprising, by weight: a. from 10% to 40% anionic surfactant comprising one or more anionic surfactants selected from the group consisting of C10-C-J4 linear or branched alkylbenzene sulfonate and Cιo-C-]g alkyl sulfate, b. from 3% to 30% nonionic polymeric mildness aid material, and c. from 1% to 15% non-anionic lather builder.

2. The composition of Claim 1 wherein the nonionic polymeric mildness aid material is selected from the group consisting of nonionic homopolymers and copolymers comprising ethylene oxide and/or propylene oxide.

3. The composition of Claim 2 wherein the nonionic polymeric mildness aid is polyethylene glycol having a molecular weight between 2,000 and 25,000.

4. The composition of Claim 1 wherein the anionic surfactant comprises coconut alkyl sulfate.

5. The composition of Claim 1 wherein the non-anionic lather builder comprises a material selected from the group consisting of betaines, fatty acid amides including poiyhydroxy fatty acid amides, amine oxides, fatty alcohols, and mixtures thereof.

6. The composition of Claim 1 wherein the non-anionic lather builder comprises a material selected from the group consisting of betaines, fatty acid amides, including poiyhydroxy fatty acid amides, amine oxides, and mixtures thereof.

7. The composition of Claim 1 wherein the non-anionic lather builder is a fatty acid amide, and wherein the fatty acid amide is a monoethanol amide.

8. The composition of Claim 1 wherein the composition is in granular form.

9. The composition of Claim 1 wherein the composition is in bar form.

10. The composition of Claim 1 wherein the composition is in gel form.