Ethoxylated amine polymers having clay soil removal/anti-redeposition properties useful in detergent compositions.

TECHNICAL FIELD

The present application relates to ethoxylated amine polymers having clay-soil removal/anti-redeposition properties when used in detergent compositions.

A- particularly important property of a detergent composition is its ability to remove particulate type soils from a variety of fabrics during laundering. Perhaps the most important particulate soils are the clay-type soils. Clay soil particles generally comprise negatively charged layers of aluminosilicates and positively charged cations (e.g. calciunt)- which are positioned between and hold together the negatively charged layers.

A variety of models can be proposed for compounds which would have clay soil removal properties. One model requires that the compound have two distinct characteristics. The first is the ability of the compound to adsorb onto the negatively charged layers of the clay particle. The second is the ability of the compound, once adsorbed, to push apart (swell) the negatively charged layers so that the clay particle loses its cohesive force and can be removed in the wash water.

One class of clay-soil removal compounds which appears to work according to this model are the polyethoxy zwitterionic surfactants disclosed in U.S. Patent 4,301,044 to Wentler et al., issued November 17, 1981. Representative of such compounds are those having the formula: <chemistry id="chem0001" num="0001"><img file="EP0111984A2_D0001.tif" /></chemistry>wherein R is a C₁₄-C₂₀ alkyl group, x is 1 or an integer of from 3 to 5, and y is from 6 to 12. See also U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975 (detergent composition containing polyethoxy zwitterionic surfactant plus other detergent surfactants); U.S. Patent 3,925,262 to Laughlin et al., issued December 9, 1975 (detergent composition containing polyethoxy zwitterionic surfactants with detergent builders); U.S. Patent 4,157,277 to Gosselink et al., issued June 26, 1979 (C₄ polyoxyalkylene zwitterionic surfactants useful in detergent compositions); U.S. Patent 4,165,334 to Gosselink et al., issued August 21, 1979 (sulfonium-type polyethoxy zwitterionic surfactants).

These polyethoxy zwitterionic surfactants are generally compatible with other detergent surfactants such as the nonionic, zwitterionic and.ampholytic types. However, as suggested in the Wentler et al. patent, most anionic surfactants interfere with the particulate soil removal performance of these compounds; anionic soils such as fatty acids likewise interfere. Because anionic detergent surfactants form the most important class of such materials for use in detergent -compositions, the lack of compatibility between these polyethoxy zwitterionic surfactants and anionic surfactants poses a significant handicap where particulate (clay) soil removal is desired.

In addition to clay_soil removal, one of the other properties mentioned in the Laughlin et al. patents with regard to these polyethoxy zwitterionic surfactants is the ability to keep the removed soil in suspension during the laundering cycle. Soil which is removed from the fabric and suspended in the wash water can redeposit onto the surface of the fabric. This redeposited soil causes a dulling or "graying" effect which is especially noticeable on white fabrics. Because soil is normally hydrophobic, this graying effect is a particularly important problem for those fabrics made in total or in part from hydrophobic fibers, e.g. polyester.

To minimize this problem, anti-redeposition or whiteness maintenance agents can be included in the detergent composition. Besides the previously mentioned polyethoxy zwitterionic surfactants, there are a variety of other compounds which can be used as anti-redeposition agents. One class of agents are the water-soluble copolymers of acrylic or methacrylic acid with acrylic or methacrylic acid-ethylene oxide condensates disclosed in U.S. Patent 3,719,647 to Hardy et al., issued March 6, 1973. Another class of anti-redeposition agents are the cellulose and carboxymethylcellulose derivatives disclosed in U.S. Patent 3,597,416 to Diehl, issued August 3, 1971 (ionic combination of dodecyltrimethyl phosphonium chloride and sodium carboxymethylcellulose), and U.S. Patent 3,523,088 to Dean et al., issued August 4, 1970 (combination of alkali metal carboxymethylcellulose and hydroxypropylcellulose). A mixture of compounds has also been used to provide not only anti-redeposition, but also clay soil removal properties. See U.S. Patent 4,228,044 to Cambre, issued October 14, 1980, which discloses detergent compositions having anti-redeposition and clay soil removal properties which can comprise a nonionic alkyl polyethoxy surfactant, a polyethoxy alkyl quaternary cationic surfactant and a fatty amide surfactant.

These anti-redeposition agents do have a number of significant handicaps. While effective-to keep soil suspended, these compounds may lack additional clay soil removal properties. Moreover, as disclosed in the Diehl and Dean et al. patents, mixtures of compounds can be required to achieve the anti-redeposition benefit. To the extent that there are combined anti-rede- position/clay soil removal benefits as disclosed in the Cambre patent, mixtures of compounds are also required.

It is therefore an object of the present invention to provide compounds useful in detergent compositions which provide particulate soil, especially clay soil, removal benefits.

It is a further object of the present invention to provide compounds useful in detergent compositions which provide clay soil removal benefits and are anionic detergent surfactant compatible.

It is yet another object of the present invention to provide compounds useful in detergent compositions having anti-redeposition properties.

It is yet a further object of the present invention to provide compounds useful in detergent compositions which combine both clay soil removal and anti-redeposition properties.

These and further objects of the present invention are hereinafter disclosed.

These and further objects of the present invention are- hereinafter disclosed.

BACKGROUND ART

U. S. Patent 3,301,783 to Dickson^-, et al., issued January 31, 1967, discloses oxyalkylated, acylated, alkylated, carbonylated and olefinated derivatives of polyalkyleneimines, in particular polyethyleneimines (PEIs). For the oxyalkylated derivatives, the alkylene oxide (e.g. ethylene oxide) is reacted with the polyalkyleneimine in a mole ratio of from 1:1 to 1000:1, and preferably in a ratio of from 1:1 to 200:1. Among the ethoxylated PEIs disclosed are Examples 1-0₇ and 1-0₈ formed by condensing 105 and 200 moles, respectively, of ethylene oxide with a 900 M.W. PEI. The degree of ethoxylation calculates out to about 4.5 and about 8 ethoxy groups per reactive site, respectively. See also Examples 27-0₅ and 27-0₆ which disclose ethoxylated polypropyleneimines (M.W. 500) which have about 4 and about 8 ethoxy units per reactive site, respectively. Amongst the numerous disclosed uses of these polyalkyleneimine derivatives is a teaching that they are useful as detergents, softening agents, and anti-static agents. Preferred uses disclosed by this patent are as chelating agents, lubricating oil additives, emulsifying agents, and cutting oils.

U.S. Patent 2,792,371 to Dickson, issued May 14, 1957, - teaches a process for breaking petroleum emulsions with oxyalkylated tetraethylene pentaamines (TEPA). Ethoxylated TEPAs specifically disclosed include those having about 5 (Example 3aa), about 7 (Example 4aa), about 8.5 (Example 5a) and about 15.5 (Example Bc) ethoxy units per reactive site. Similarly, U.S. patent 2,792,370 to Dickson issued May 14, 1957, teaches a process- for breaking petroleum emulsions with oxyalkylated triethylene tetramines (TETAs) including those having about 5.5 (Example 3aa), about 7.5 (Example 4aa), about 9 (Example 5a) and about 16.5 (Example Bc) ethoxy units per reactive site. See also U. S. patent 2,792,372 to Dickson, issued May 14, 1957, (oxyalkylated- higher PEAs used to break petroleum emulsions); U. S. patent 2,792,369 to Dickson, issued May 14, 1957 (oxyalkylated diethylene triamines used to break petroleum emulsions).

U. S. Patent 4,171,278 to Andree et al., issued October 16, 1979, discloses cold water detergent compositions containing a detergent surfactant (e.g. anionic) and a hydroxyalkyl amine in a weight ratio of 100:1 to 1:1. The amine can have the formula: <chemistry id="chem0002" num="0002"><img file="EP0111984A2_D0002.tif" /></chemistry>wherein R₁ is C₁-C₁₆ alkyl; R₂-is H or C₁-C₁₆ alkyl; R₁⁺ R₂have 6-20 carbon atoms; R₄ is H or methyl; m, n, and o, are each 0 to 3 and A is bridging group such as <chemistry id="chem0003" num="0003"><img file="EP0111984A2_D0003.tif" /></chemistry>wherein R₃ is H or methyl; x is 2 to 6; y is 1 to 3; and p is 0 to 3; the sum of m to p being 1 to 5.5, and preferably 1 to 2. See also German Patent Document 2,165,900 to Henkel, published July 5, 1973, which discloses a washing agent for graying prevention formed by the reaction product of a PEI with an alkylglycidylether and ethylene oxide (2-hydroxyethyl moiety at each reactive site when ethoxylated).

U. S. Patent 3,838,057 to Barnes et al., issued September 24, 1974, discloses toilet bars containing ethoxylated quaternary ammonium compounds, including ethoxylated, quaternized PEIs taught to be useful in the detergent, textile, and polymer industries, as anti-static and softening agents. These ethoxylated quaternized PEIs have the formula: <chemistry id="chem0004" num="0004"><img file="EP0111984A2_D0004.tif" /></chemistry> wherein R₁ is a compatible quaternary nitrogen substituent; n is at least 2; x is from 3 to 40; and X^- is a compatible anion. Preferred compounds are those where R₁ is a C₈- C₂₂ alkyl group or the group: <chemistry id="chem0005" num="0005"><img file="EP0111984A2_D0005.tif" /></chemistry>where R' is a C₈- C₂₂ alkyl group and y is from 3 to 40. See also U. S. Patent 4,179,382 to Rudkin et al., issued December 18, 1979; U. S. Patent 4,152,272 to Young, issued May 1, 1979; and European Patent Application 2,085 to Rudkin et al., published May 30, 1979, which disclose ethoxylated quaternized polyamines having C₁₀ to C₂₄ alkyl or alkenyl groups attached to one of the nitrogen atoms useful as fabric softeners.

There are several patents which disclose detergent compositions, shampoo compositions and the like containing slightly ethoxylated PEIs (ethylene oxide:PEI weight ratio of 4:1 or less) to enhance the deposition and retention of particulate substances such as antimicrobials. See, for example, U.S. Patent 3,489,686 to Parran, issued January 13, 1970; U.S. Patent 3,580,853 to Parran, issued May 25, 1971; British Patent Specification 1,111,708 to Procter &amp; Gamble published May 1, 1968, U.S. Patent 3,549,546 to Moore, issued December 22, 1970; and U.S. Patent 3,549,542 to Holderby, issued December 22, 1970.

DISCLOSURE OF THE INVENTION

The present invention relates to water-soluble ethoxylated amine polymers having clay soil removal/anti-redeposition properties useful in detergent compositions. These polymers comprise a polymer backbone other than a polyalkyleneamine backbone, at least 2 M groups and at least one L-X group, wherein M is a tertiary amine group attached to or integral with the backbone; X is a nonionic group, anionic group or mixture thereof; and L is a hydrophilic chain connecting groups M and X or connecting X to the backbone. L also contains the polyoxyalkylene moiety -[(R'O)_m(CH₂CH₂O)_n]-, wherein R' is C₃-C₄ alkylene or hydroxyalkylene, m and n are numbers such that the moiety -(CH₂CH₂0)_n- comprises at least about 50% by weight of said polyoxyalkylene moiety, and n is at least about 3, except when the polymer backbone is a polyethyleneimine backbone, and n is at least about 12 when the polymer backbone is a polyethyleneimine backbone.

The ethoxylated amine polymers of the present invention provide clay soil removal benefits while being anionic detergent surfactant compatible. At most wash pHs, it is believed nitrogen atoms of the polymer are protonated to form positively charged centers which, together with the remaining polar nitrogen atoms, cause adsorption of the polymer onto the negatively charged layers of the clay particle. It is also believed that the hydrophilic ethoxy units attached to the polymer backbone swell the clay particle so that it loses its cohesive character and is swept away in the wash water.

The anti-redeposition benefits provided by these ethoxylated amine polymers are also believed to be due to the positively charged centers which, together with the remaining polar nitrogen atoms, cause it to be adsorbed onto soil suspended in the wash water. As more and more of these polymers adsorb onto the suspended soil, it becomes encased within a hydrophilic layer provided by the attached ethoxy units. As such, the hydrophilically encased soil is prevented from redepositing on fabrics, in particular hydrophobic fabrics such as polyester, during the laundering cycle.

Ethoxylated Amine Polymers

The water-soluble ethoxylated amine polymers of the present invention comprise a polymer backbone other than a polyalkyleneamine backbone, and at least 2 M groups and at least one :L-X group, wherein M is a tertiary amine group attached to or integral with the backbone; X is a nonionic group, an anionic group or mixture thereof; and L is a hydrophilic chain connecting groups M and X, or connecting X to the polymer backbone.

As used herein, the term "polymer backbone" refers to the polymeric moiety to which groups M and L-X are attached to or integral with. Included within this term are oligomer backbones (2 to 4 units), and true polymer backbones (5 or more units).

As used herein, the term "attached to" means that the group is pendent from the polymer backbone, examples of which are represented by the following general structures A and B: <chemistry id="chem0006" num="0006"><img file="EP0111984A2_D0006.tif" /></chemistry>

As used herein, the term "integral with" means that the group forms part of the polymer backbone, examples of which are represented by the following general structures C and D: <chemistry id="chem0007" num="0007"><img file="EP0111984A2_D0007.tif" /></chemistry>

Any polymer backbone (other than a polyalkyleneamine backbone) can be used as long as the ethoxylated amine polymer formed is water-soluble and has clay soil removal/anti-redeposition properties. Suitable polymer backbones can be derived from the polyurethanes, the polyesters, the polyethers, the polyamides, the polyimides and the like, the polyacrylates, the polyacrylamides, the polyvinyl ethers, the polyethylenes, the polypropylenes and like polyalkylenes, the polystyrenes and like polyalkarylenes, the polyalkyleneimines, the polyvinylamines, the polyallylamines, the polydiallylamines, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes and mixtures thereof.

As used herein, the term "polyalkyleneamine backbone" refers to polymer backbones having the following general formula: <chemistry id="chem0008" num="0008"><img file="EP0111984A2_D0008.tif" /></chemistry>wherein R is C_Z-C₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C₂-C₃ oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N or 0-0 bonds are formed; w is 1 or 0; x + y + z is from 2 to 9; and y + z is from 2 to 9. Such polymer backbones are particularly represented by the polyethyleneamines (PEAs) where R is ethylene, and x + y + z is from 3 to 7. These PEAs can be obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEAs obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372 to Dickson, issued May 14, 1957, which describes the preparation of PEAs.

As used herein, the term "polyalkyleneimine backbone" refers to a polymer backbones having the following general formula: <chemistry id="chem0009" num="0009"><img file="EP0111984A2_D0009.tif" /></chemistry>wherein R is defined as abôve; x + y +z is at least 10,

M can be any compatible tertiary amine group. The tertiary amine group can be represented by the following general structures E and F: <chemistry id="chem0010" num="0010"><img file="EP0111984A2_D0010.tif" /></chemistry>Particularly preferred M groups are those represented by general structure E. The tertiary amine group M is also preferably positioned close to or integral with the polymer backbone.

In the preceding formula, X can be any compatible nonionic group, anionic group or mixture thereof. Suitable nonionic groups include C₁-C₄ alkyl or hydroxyalkyl, ester or ether groups, preferably acetate or methyl ether, respectively; hydrogen (H); or mixtures thereof. The particularly preferred nonionic group is H. With regard to anionic groups, P0₃^-2 and S0₃^- are suitable. The particualrly preferred anionic group is SO₃^-. It has been found that the relative percentage of anionic groups to nonionic groups can be important to the clay soil removal/anti-redeposition properties provided by the ethoxylated amine polymer. A mixture of from 0 to about 30% anionic groups and from about 70 to 100% nonionic groups provides preferred properties. A mixture of from about 5 to about 10% anionic groups and from about 90 to about 95% nonionic groups provides the most preferred properties. Usually, a mixture of from 0 to about 80% anionic groups and from about 20 to 100% nonionic groups provides suitable clay soil removal/anti-redeposition properties.

The ethoxylated amine polymers of the present invention normally have a ratio of groups M to groups X of 1:1. However, by appropriated copolymerization of tertiary amine, anionic (nonionic) (i.e. containing the group L-X), or mixed tertiary amine/ anionic (nonionic) monomers, the ratio of cationic groups M to groups X can be varied. The ratio of groups M to groups X can usually range from about 2:1 to about 1:10. In preferred polymers, the ratio is from about 1:1 to about 1:5. The polymers formed from such copolymerization are typically random, i.e. the tertiary amine, anionic (nonionic), or mixed cationic/anionic (nonionic) monomers copolymerize in a nonrepeating sequence.

The units which contain groups M and groups L-X most preferably comprise 100% of the ethoxylated amine polymers of the present invention. However, inclusion of other units (preferably nonionic) in the polymers is also permissible. Examples of other units include the acrylamides and the vinylethers. These other units can comprise from 0 to about 90% of the polymer (from about 10 to 100% of the polymer being units containing M and L-X groups): Typically, these other units comprise from 0 to about 50% of the polymer (from about 50 to 100% of the polymer being units containing M and L-X groups).

The number of groups M and L-X usually ranges from about 2 to about 200. Typically,- the number of groups M and L-X is from about 3 to about 100. Preferably, the number of groups M and L-X is from about 3 to about 40.

Other than moieties for connecting groups M and X, or for attachment to the polymer backbone, hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R'O) - (CH₂CH₂O)_n]-. The moieties -(R'O)_m- and -(CH₂CH₂0)_n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of -(R'O)_m- and -(CH₂CH₂O)_n- moieties. R' is preferably C₃ H₆ (propylene); m is preferably from 0 to about 5, and most preferably 0, i.e. the polyoxyalkylene moiety consists entirely of the moiety _-(_CH2CH20)_n-_. The moiety -(_CH2CH20)_n- preferably comprises at least about 85% by weight of the polyoxyalkylene moiety, and most preferably 100% by weight (m is 0). For the moiety -(CH₂CH₂O)-_n, n is usually from about 3 to about 100. Typically n is from about 12 to about 42.

A plurality (2 or more) of moieties -L-X can also be hooked together and attached to group M or to the polymer backbone, examples of which are represented by the following general structures G and H: <chemistry id="chem0011" num="0011"><img file="EP0111984A2_D0011.tif" /></chemistry>

Structures G and H can-be formed, for example, by reacting glycidol- with group M or the polymer backbone, and then ethoxylating the subsequently formed hydroxy groups.

The level at which the ethoxylated amine polymers of the present invention can be present in the detergent compositions can vary widely depending upon the polymer used, the type of detergent formulation (liquid, granular), and the benefits desired. These compositions can be used as laundry detergents, laundry additives, or laundry pretreatments. Generally, these polymers can be included in an amount of from about 0.05 to about 95% by weight of the composition, with a usual range of from about 0.1 to about 10% by weight for laundry detergents. Preferred detergent compositions comprise from about 0.5 to about 5% by weight of the polymer of the present invention. For these preferred compositions, the polymer is typically present at from about 1 to about 3% by weight. The polymer is normally present at a level that provides from about 2 ppm to about 200 ppm, preferably from about 10 ppm to about 100 ppm, of the polymer in the wash solution at recommended U.S. usage levels, and normally from about 30 ppm to about 1000 ppm, preferably from about 50 ppm to about 500 ppm for European usage levels.

Representative classes of ethoxylated amine polymers of the present invention are as follows:

A. Polyurethane, Polyester, Polyether, Polyamide or Like Polymers

One class of suitable ethoxylated amine polymers are derived from polyurethanes, polyesters, polyethers, polyamides and the like. These polymers comprise units selected from those having formulas I, II and III: <chemistry id="chem0012" num="0012"><img file="EP0111984A2_D0012.tif" /></chemistry><chemistry id="chem0013" num="0013"><img file="EP0111984A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP0111984A2_D0014.tif" /></chemistry>wherein <chemistry id="chem0015" num="0015"><img file="EP0111984A2_D0015.tif" /></chemistry>x is 0 or 1; R is H or C₁-C₄ alkyl or hydroxyalkyl; R is C₂-C₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C₂-C₃ oxyalkylene moiety having from 2 to about 20 oxyalkylene units, provided that no 0-0 or 0-N bonds are formed with A¹; when x is 1, R² is -R⁵- except when A <chemistry id="chem0016" num="0016"><img file="EP0111984A2_D0016.tif" /></chemistry>or is -(OR⁷)_x- or -_OR^5- provided that no 0-0 or N-0 bonds are formed with A , and R³ is -_R^5- except when A is <chemistry id="chem0017" num="0017"><img file="EP0111984A2_D0017.tif" /></chemistry>or is -(R⁷O)_x- or -R⁵O- provided that no 0-0 or 0-N bonds are formed with A¹; when x is 0, R² is -(OR⁷)_y-, -OR⁵-, <chemistry id="chem0018" num="0018"><img file="EP0111984A2_D0018.tif" /></chemistry>or <chemistry id="chem0019" num="0019"><img file="EP0111984A2_D0019.tif" /></chemistry>and R³ is -R⁵-; R⁴is C₁-C₄ alkyl or hydroxyalkyl; R⁵ is C₁-C₁₂ alkylene, hydroxyalkylene, cycloalkylene, alkenylene, arylene, or alkarylene; R⁶ is H or R⁴; R⁷ is C₂-C₃ alkylene or hydroxyalkylene; X is R, SO₃^-, or a mixture thereof; k is 0 or 1; m is from 0 to about 5; n is at least about 3; m and n are numbers such that the moiety -(CH₂CH₂O)_n- comprises at least about 85% by weight of the moiety -[(C₃H₆O)_m(CH₂CH₂O)_n]-; y is from 2 to about 20; the number of u + v and w are such that there are at least 2 N groups and at least 2 X groups.

In the above formulas, A is preferably <chemistry id="chem0020" num="0020"><img file="EP0111984A2_D0020.tif" /></chemistry>A² is preferably -0-; x is preferably 1; and R is preferably H. R¹ can be linear (e.g. -CH₂-CH₂-CH₂-, <chemistry id="chem0021" num="0021"><img file="EP0111984A2_D0021.tif" /></chemistry>or branched <chemistry id="chem0022" num="0022"><img file="EP0111984A2_D0022.tif" /></chemistry>alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or oxyalkylene; when R is a C₂-C₃ oxyalkylene moiety, the number of oxyalkylene units is preferably from 2 to about 12; R¹ is preferably C₂-C₆ alkylene or phenylene, and most preferably C₂-C₆ alkylene (ethylene, propylene, hexamethylene). R² is preferably -OR^5- or -(OR⁷)_y; R³ is preferably -R⁵0- or -(R⁷0) _y -; R⁴ is preferably methyl. Like R¹, R⁵ can be linear or branched, and is preferably C₂-C₃ alkylene; R is preferably H or C₁-C₃ alkyl; R is preferably ethylene; X is preferably H or methyl; k is preferably 0; m is preferably 0; r and s are each preferably 2; y is preferably from 2 to about 12.

In the above formulas, n is preferably at least about 6 when the number of N and X groups are each 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of u + v + w. For homopolymers (v and w are 0), u is preferably from about 3 to about 40, and is most preferably from about 3 to about 20. For random copolymers (u is at least 1 or preferably 0), v and w are each preferably from about 3 to about 40.

B. Polyacrylate, Polyacrylamide, Polyvinylether or Like Polymers

Another class of suitable ethoxylated amine polymers are derived from polyacrylates, polyacrylamides, polyvinylethers and the like. These polymers comprise units selected from those having formulas IV, V and VI. <chemistry id="chem0023" num="0023"><img file="EP0111984A2_D0023.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP0111984A2_D0024.tif" /></chemistry>wherein <chemistry id="chem0025" num="0025"><img file="EP0111984A2_D0025.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP0111984A2_D0026.tif" /></chemistry>R is H or C₁-C₄ alkyl or hydroxyalkyl; R¹ is substituted C₂-C₁₂ alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene or C₂-C₃ oxyalkylene; each R² is C₁-C₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; R³ is C_I-C₄ alkyl or hydroxyalkyl, or the moiety -(R₂)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X; each R⁴ is C₁-C₄ alkyl or hydroxyalkyl, or together form the moiety -(CH₂)_r-A²-(CH₂)_s-, wherein A² is -O- or -CH₂-; R⁵ C₂-C₃ alkylene or hydroxyalkylene; X is R, SO₃^-, or a mixture thereof; j is 1 or 0; k is 1 or 0; m is from 0 to about 5; n is at least about 3; m and n are numbers such that the moiety -(CH₂CH₂O)_n- comprises at least about 85% by weight of the moiety -[(C₃H₆O)_m(CH₂CH₂O)_n]-; ^r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; the number u, v and w are such that there are at least 2 N groups and at least 2 X groups.

In the above formulas, A is preferably <chemistry id="chem0027" num="0027"><img file="EP0111984A2_D0027.tif" /></chemistry>or -0-; _A² is preferably -0-, R is preferably H. R¹ can be linear (e.g. <chemistry id="chem0028" num="0028"><img file="EP0111984A2_D0028.tif" /></chemistry>alkenylene, alkarylene or oxyalkylene; R is preferably C₂-C₆ alkylene and most preferably -CH₂<img file="EP0111984A2_D0029.tif" />H- or <chemistry id="chem0029" num="0029"><img file="EP0111984A2_D0030.tif" /></chemistry>. Each R² is preferably C2-C3 alkylene; R is preferably methyl; each R is preferably methyl; X is preferably H or methyl; j is preferably 1; k is preferably 0; m is preferably 0; r and s are each preferably 2.

In the above formulas, n, u, v and w can be varied according to the n, u, v and w for the polyurethane and like polymers.

C. Polyalkyleneimine or Like Polymers

Another class of suitable ethoxylated amine polymers are derived from polyalkyleneimines and the like. These polymers have the general formula VII: <chemistry id="chem0030" num="0030"><img file="EP0111984A2_D0031.tif" /></chemistry>wherein R is C₂- C₁₂ alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C₂-C₃ polyoxyalkylene moiety having from 2 to about 20 oxyalkylene units; each R² is C₁-C₄ alkyl or hydroxyalkyl, the moiety -(R₃)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X, or two R² together form the moiety -(CH₂)_r-A-(CH₂)_s-, wherein A is -0- or -CH₂-; R³ is C₁-C₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; X is H, SO₃^-, or mixture thereof; k is 1 or 0; m is from 0 to about 5; n is at least about 12; m and n are numbers usch that the moiety -(CH₂CH₂O)_n- comprises at least about 85% by weight of the moiety -[(C₃H₆O)_m(CH₂CH₂O)_n]-; _{x +} y _{+ z} is at least ^10.

In the above formulas, A is preferably -0-; R can be varied like R¹ of the polyurethane and like polymers; R² is preferably methyl or the moiety -(R³)-_k[(C₃H₆O)_m(CH₂CH₂O)_n]-X; each R³ is preferably C₂-C₃ alkylene; X is preferably H; k is preferably 0; m is preferably 0; r and s are each preferably 2.

In the above formulas, n has a typical range of from about 12 to about 42 for all ranges of y + z.

.Preferred ethoxylated amine polymers of this class are the ethoxylated C₂-C₃ polyalkyleneimines. Particularly - preferred ethoxylated polyalkyleneimines are the ethoxylated ethyleneimines (PEIs). These preferred polymers have the general formula: <chemistry id="chem0031" num="0031"><img file="EP0111984A2_D0032.tif" /></chemistry>wherein X, x, y, z and n are defined as before.

The PEIs used in preparing the polymers of the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units. Preferred PEIs used- in preparing these compounds have a molecular weight of from about 600 to about 1800. The polymer backbone of these PEIs can be represented by the general formula: <chemistry id="chem0032" num="0032"><img file="EP0111984A2_D0033.tif" /></chemistry>wherein the sum of x, y and z represents a number of sufficient magnitude to yield a polymer having the molecular weights previously specified. Although linear polymer backbones are possible, branch chains can also occur. The relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. The distribution of amine groups is typically as follows: <chemistry id="chem0033" num="0033"><img file="EP0111984A2_D0034.tif" /></chemistry><chemistry id="chem0034" num="0034"><img file="EP0111984A2_D0035.tif" /></chemistry><chemistry id="chem0035" num="0035"><img file="EP0111984A2_D0036.tif" /></chemistry>Each hydrogen atom attached to each nitrogen atom of the PEI represents an active site for subsequent ethoxylation. These PEIs can be prepared, for example by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEIs are disclosed in U.S. Patent 2,182,306 to Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746 to Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095 to Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839 to Crowther, issued September 17, 1957; and U.S. Patent 2,553,696 to Wilson, issued May 21, 1951 (all herein incorporated by reference).

As -defined in the preceding formulas, n is at least about 12 for the ethoxylated PEIs. However, it should be noted that the minimum degree of the ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the molecular weight of the PEI increases, especially much beyond about 1800. Also, the degree of ethoxylation for preferred compounds increases as the molecular weight of the PEI increases. For PEIs having a molecular weight of at least about 600, n is preferably at least about 12, with a typical range of from about 12 to about 42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24,. with a typical range of from about 24 to 42.

D. Diallylamine Polymers

Another class of suitable ethoxylated amine polymers are those derived from the diallylamines. These polymers comprise units selected from those having formulas IX and X: <chemistry id="chem0036" num="0036"><img file="EP0111984A2_D0037.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP0111984A2_D0038.tif" /></chemistry>wherein R is C₁-C₄ alkyl or hydroxyalkyl; R² is C₁-C₁₂ alkylene, hydroxyalkylene, alkylene, arylene or alkarylene; X is H, SO₃^-, or mixture thereof; k is 1 or 0; m is from 0 to about 5; n is at least about 3; m and n are numbers such that the moiety -(CH₂CH₂O)_n- comprises at least about 85% by weight of the moiety -[(C₃H₆O)_m(CH₂CH₂O)_n-]; x is 1 or 0; y is 1 when x is 0 and 0 when x is 1; the number of u and v is such that there are at least 2 N groups and at least 2 X groups.

In the above formulas, R ¹ is preferably methyl; each R² is preferably C₂-C₃ alkylene; X is preferably H; k is preferably 0; m is preferably 0.

In the above formulas, n is preferably at least about 6 when the number of N and X groups are each 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of u + v. Preferably v is 0, and u is from about 3 to about 40.

Methods for Making Ethoxylated Amine Polymers

A. Polyurethane

The polyurethane versions of the present invention can be prepared according to the following general scheme: <chemistry id="chem0038" num="0038"><img file="EP0111984A2_D0039.tif" /></chemistry>

Step 1: Ethoxylation

The monotetrahydropyronyl ether of diethylene glycol (1.77 moles) [Compt. Rend., 260, 1399-1401 (1965)] is ethoxylated using 5 mole % NaH to generate a catalytic amount of the corresponding alkoxide. Ethoxylation is conducted at 90°-120°C until about 22 moles (n = 22) of ethylene oxide is taken up for each mole of the starting alcohol to form the ethoyxlated compound.

Step 2: Tosylation

The ethoxylated compound from step 1 is dissolved in 1000 ml. of acetonitrile and then cooled to about 10°C. To this solution is added 2.6 moles of tosyl chloride dissolved in 500 ml. of acetonitrile and cooled to 10°C and then 2.9 moles of triethylamine is added. After the reaction is complete, H₂0 is added to decompose the remaining tosyl chloride.

Step 3: Amination

To the reaction mixture from step 3 is added 3.4 moles of diethanolamine. After heating for 18 hrs. at 80°C, the reaction mixture is cooled and carefully acidified with HC1, keeping the pH just above 7, and then extracted with ether. The aqueous phase is then extracted with a mixture of ether:acetonitrile (ratio of about 5:2) twice. The aqueous phase is separated and then made basic with 50% NaOH. This aqueous phase is extracted with dichloromethane (2000 ml.). The lower layer is separated and then extracted 3 times with 2000 ml. portions of 1/4 saturated NaCl solution while.adding enough 50% NaOH to make the aqueous phase strongly basic (pH of about 11). The lower organic layer is stripped to give the desired aminated compound. Toluene (200 ml.) is added and the mixture stripped again to give the desired aminated monomer.

Step 4: Polymerization and Removal of Protecting Groups

The aminated monomer from step 3 is dissolved in chloroform free of ethanol stabilizer. The monomer; is previously evacuated in a Kugelrohr at 80°-90°C under a vacuum (pressure of 1 mm.) for at least 18 hours. The monomer in the chloroform is then dried overnight with 3A molecular sieves and then transferred to a dry flask (equipped with mechanical stirrer) under argon. To the monomer is added dibutyltin dilaurate catalyst (0.058 mole equiv.) in chloroform under argon. To the stirred reaction mixture is then added 0.7 moles of hexamethylenediisocyanate per mole of aminated monomer over a 5 minute period. The reaction mixture is stirred at room temperature for 18 hours. The chloroform is removed under a vacuum at about 70°C to give the resulting polymer. This polymer is dissolved in methanol, the pH is adjusted to about 4 with aqueous HC1 and is then allowed to stand overnight to solvolyze the tetrahydropyranyl protecting group. The solution is then neutralized with NaOH and stripped to give the crude polyurethane. This crude polyurethane is dissolved in chloroform and filtered to remove any salts. The chloroform is stripped away to give the desired, largely salt-free polymer.

B. Random Copolymer of Ethoxylated Acrylate and an Amino Methacrylamide

The random copolymer versions of the present invention can be prepared according to the following general scheme: <chemistry id="chem0039" num="0039"><img file="EP0111984A2_D0040.tif" /></chemistry>

The synthesis of one such random copolymer is described as follows: <ul id="ul0001" list-style="none"><li>Decaethyleneglycol monomethacrylate monomer (0.008 moles) and N-(3-dimethylaminopropyl)-methacrylamide monomer (0.011 moles) are dissolved in 40 ml. of acetonitrile. The reaction mixture is purged of oxygen by bubbling argon through it. A 0.23 g. portion of benzoyl peroxide is separately dissolved in acetonitrile and similarly purged. The reaction mixture is heated to reflux and the benzoyl peroxide solution then added dropwise over 0.5 hours. Next, 0.28 g. of azobisisobutyronitrile in 5 ml. of acetonitrile is added to the reaction mixture and heating continued overnight. The desired random copolymer is isolated by stripping off the solvent.</li></ul>

C. Ethoxylated PEI

The ethoxylated PEIs of the present invention can be prepared by standard methods for ethoxylating amines. There is preferably an initial step of condensing sufficient ethylene oxide to provide 2-hydroxyethyl groups at each reactive site. The appropriate amount of ethylene oxide is then condensed with these 2-hydroxyethylamines using an alkali metal (e.g., sodium, potassium) hydride of hydroxide as the catalyst to provide the respective ethoxylated amines. The total degree of ethoxylation per reactive site (n) can be determined according to the following formula: <ul id="ul0002" list-style="none"><li>Degree of Ethoxylation = E/(A x R) wherein E is the total number of moles of ethylene oxide condensed (including hydroxyethylation), A is the number of moles of the starting PEi, and R is the number of reactive sites (typically 3 + y + z) for the starting PEI.</li></ul>

A representative synthesis of an ethoxylated PEI of the present invention is as follows:

Example 3

Dried PEI (M.W. 600, 14.19 g., 0.0236 moles) was hydroxy- ethylated with ethylene oxide at 130°-140°C for 3 hours with stirring. 0.5 g. (0.0125 moles) of 60% sodium hydride in mineral oil was then added and the reaction mixture swept with argon. After hydrogen evoluation ceased, EO was then added under atmospheric pressure with stirring at 130°-140°C. After 14 hours, 711.6 g. of EO had been added to give a calculated total degree of ethoxylation of 41.5. The ethoxylated PEI 600 obtained was a tan waxy solid.

D. Diallylamine Polymers

Diallylamine polymer versions of the present invention can be prepared according to the following general scheme. <chemistry id="chem0040" num="0040"><img file="EP0111984A2_D0041.tif" /></chemistry> The synthesis of one such polymer is described as follows:

Example 4

Step 1: Ethoxylation

Diallylamine (1.7 moles) is dissolved in methanol (160 ml.) under argon and then heated to 45°C. Ethylene oxide is then added for 2.5 hours. Methanol is then removed by heating the reaction mixture to 100°C in vacuo. To the residue is added sodium hydride (0.17 moles) with stirring until the evolution of hydrogen ceased. Ethylene oxide is then added until the degree of ethoxylation (n) is about 7.

Step 2: Polymerization

A portion of the ethoxylated monomer from step 1 (25 g.) is mixed with D₂0 (20 ml.) and heated to 95°C under argon for 1 hour. Tertbutylhydroperoxide (0.5 ml.) is then added dropwise and the reaction continued at 90°C for 18 hours. Then additional hydroperoxide (0.5 ml.) is added dropwise. After heating 3 more days, water is then removed in vacuo (50°-60°C at pressure of 0.1 mm) to yield the crude polymer.

Clay Soil Removal/Anti-Redeposition Properties of

Various Ethoxylated Amine Polymers

A. Experimental Method

1. Clay Soil Removal

Clay soil removal comparisons were conducted in a standard 1 liter Tergotometer employing water of 7 grain hardness (3:1 Ca :Mg ) and a temperature of 100°F. Soiled swatches were washed in the Tergotometer for 10 minutes and rinsed twice with water (7 grain hardness) at 70°F for 2 minutes.

65% polyester/35% cotton blend fabric was used for the swatches. The swatches were 5 inches by 5 inches in size and were soiled by dipping in an aqueous slurry of local clay and subsequently baked to remove the water. The dipping and baking was repeated 5 times.

One wash employed 2000 ppm of a control liquid detergent composition containing the following surfactants: <tables id="tabl0001" num="0001"><img file="EP0111984A2_D0042.tif" /></tables>

A second wash used the same detergent composition but also con- .taining an ethoxylated amine polymer at 20 ppm. Neither composition contained optical brighteners. The product washes approximated a conventional home use laundry situation. After laundering, the swatches were dried in a mini-dryer.

The swatches were graded before and after washing on a Gardner Whiteness meter reading the L, a, and b coordinates. Whiteness (W) was calculated as: W = <maths id="math0001" num=""><img file="EP0111984A2_D0043.tif" /></maths>

The clay soil removal performance of each detergent composition was determined by finding the difference in whiteness (AW) before and after washing as: ΔW = W after - W before

The improvement in clay soil removal performance of the composition containing the ethoxylated amine polymer was measured as the difference in W values (Δ²W) relative to the control composition.

2. Anti-Redeposition

Anti-redeposition comparisons were conducted in a 5 pot Automatic Miniwasher (AMW) employing 7 grain hardness water and temperature of 95°F. Test swatches were washed for 10 minutes and rinsed twice with water (7 grain hardness) at 75°F for 2 minutes.

After the AMW pots were filled with 6 liters of water each, the detergent composition to be tested (control or containing 20 ppm ethoxylated amine polymer as in clay soil removal test) was added and agitated for 2 minutes. A background soil mixture (200 ppm artificial body soil, 100 ppm vacuum cleaner soil and 200 ppm clay soil) was then added and agitated for an additional 3 minutes. Three 5 inch square test swatches (50% polyester/50% cotton T-shirt material) were then added, along with two 80% cotton/20% polyester terry clothes and two 11 inch square swatches of 100% polyester knit fabric. The 10 minute wash cycle commenced at this point.

Following the rinse cycle, the test swatches were dried in a .mini-dryer... Gardner Whiteness meter readings (L, a and b) were then determined for the three test swatches. Anti-redeposition performance (ARD) was then calculated according to the following equation. <chemistry id="chem0041" num="0041"><img file="EP0111984A2_D0044.tif" /></chemistry>

The ARD values for the three test swatches were then averaged. The improvement in anti-redeposition performance of the composition containing the ethoxylated amine was measured as the difference in ARD values (AARD) relative to the control composition.

B. Test Results

The results from testing the clay-soil removal and anti-redeposition performance of various ethoxylated amine polymers is shown in the following Table: <tables id="tabl0002" num="0002"><img file="EP0111984A2_D0045.tif" /></tables>

For comparison, PEG 6000 (polyethylene glycol having M.W. of 6000) has a 62W value of 4.9 and a Δ ARD value of 8.9.

Detergent Surfactants

The amount of detergent surfactant included in the detergent compositions of the present invention can vary from about 1 to about 75% by weight of the composition depending upon the detergent surfactant(s) used, the type of composition to be formulated (e.g. granular, liquid) and the effects desired. Preferably, the detergent surfactant(s) comprises from about 10 to about 50% by weight of the composition. The detergent surfactant can be nonionic, anionic, ampholytic, zwitterionic, cationic, or a mixture thereof:

A. Nonionic Surfactants

Suitable nonionic surfactants for use in detergent compositions of the present invention are generally disclosed in U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975 at column 13, line 14 through column 16, line 6 (herein incorporated by reference). Classes of nonionic surfactants included are: <ul id="ul0003" list-style="none"><li>1. The polyethyleneoxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630, marketed by the GAF Corporation, and Triton X-45, X-114, X-100, and X-102, all marketed by the Rohm &amp; Haas Company.</li><li>2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms). Examples of commercially available nonionic surfactants of this type include Tergitol 15-S-9, marketed by Union Carbide Corporation, Neodol 45-9, Neodol 23-6.5, Neodol 45-7, and Neodol 45-4, marketed by Shell Chemical Company, and Kyro EOB, marketed by The Procter &amp; Gamble Company.</li><li>3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from about 1500 to 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic surfactants, marketed by Wyandotte Chemical Corporation.</li><li>4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, the moiety having a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic compounds, marketed by Wyandotte Chemical Corporation.</li><li>5. Semi-polar nonionic detergent surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2. moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.</li></ul>

Preferred semi-polar nonionic detergent surfactants are the amine oxide detergent surfactants having the formula <chemistry id="chem0042" num="0042"><img file="EP0111984A2_D0046.tif" /></chemistry>wherein R is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ is an alkyl or hydroxyalkyl group containing from 1 to about 3 carbon atoms or a polyethylene oxide group containing from one to about 3 ethylene oxide groups. The R⁵ groups can-be attached to each other, e.g., through an oxygen or nitrogen atom to form a ring structure.

Preferred amine oxide detergent surfactants are C₁₀-C₁₈ alkyl dimethyl amine oxide and C₈-C₁₂ alkoxy ethyl dihydr^qxy ethyl amine oxide. - <ul id="ul0004" list-style="none"><li>6. Alkylpolysaccharides disclosed in European patent _Applica- tion n° 82200868.6, filed July 12, 1982, R.A. Llenado, having a hydrophobic group containing from about 6 to about 30 carbon _'atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about li to about 10, preferably from about 1½ to about 3, most preferably from about 1.6 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g. glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2, 3, 4, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6 positions on the preceding saccharide units.</li></ul>

Optionally, and less desirably, there can be a polyalkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, most preferably 0, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses, and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.

The preferred alkylpolyglycosides have the formula <chemistry id="chem0043" num="0043"><img file="EP0111984A2_D0047.tif" /></chemistry>wherein R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from 1½ to about 10, preferably from about 1½ to about 3, most preferably from about 1.6 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl- polyethoxy alcohol is formed first and then reacted with' glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position. <ul id="ul0005" list-style="none"><li>7. Fatty acid amide detergent surfactants having the formula: <chemistry id="chem0044" num="0044"><img file="EP0111984A2_D0048.tif" /></chemistry>wherein R is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R is selected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, and -(C₂H₄O)_xH where x varies from about 1 to about 3.</li></ul>

Preferred amides are C₈-C₂₀ ammonia amides, monoethanolamides, diethanolamides, and isopropanol amides.

B. Anionic Surfactants

Anionic surfactants suitable in detergent compositions of the present invention are generally disclosed in U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975 at column 23, line 58 through column 29, line 23 (herein incorporated by reference). Classes of anionic surfactants included are: <ul id="ul0006" list-style="none"><li>1. Ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms.</li><li>2. Water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.)</li></ul>

Examples of this group of anionic surfactants are the sodium and potassium alkyl sulfates, especiall-y those obtained by sulfating the higher alcohols (C₈-C₁₈ carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C₁₁-C₁₃LAS.

Preferred anionic surfactants of this type are the alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from about 10 to about 22, preferably from about 12 to about 18 carbon atoms, and wherein the polyethoxylate chain contains from about 1 to about 15 ethoxylate moieties preferably from about 1 to about 3 ethoxylate moieties. These anionic detergent surfactants are particularly desirable for formulating heavy-duty liquid laundry detergent compositions.

. Other anionic surfactants of this type 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 ethylerie oxide ether sulfates containing from about 1 to about 10 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 containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group 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 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-.acyloxy-alkane-l-sulfonic acids containing from about 2 to 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 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety. <ul id="ul0007" list-style="none"><li>3. Anionic phosphate surfactants.</li><li>4. N-alkyl substituted succinamates.</li></ul>

C. Ampholytic Surfactants

Ampholytic surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See-U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.

D. Zwitterionic Surfactants

Zwitterionic surfactants can be broadly described as derivatives of-secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1-975 at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.

E. Cationic Surfactants

Cationic surfactants can also be included in detergent compositions of the present invention. Suitable cationic surfactants include the quaternary ammonium surfactants having the formula: <chemistry id="chem0045" num="0045"><img file="EP0111984A2_D0049.tif" /></chemistry>wherein R is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each R³ is selected from the group consisting of -CH₂CN₂-, -CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, -CN₂CH₂CH₂-, and mixtures thereof; each R⁴ is selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl, ring structures formed by joining the two R⁴ groups, -CH₂CNOHCHOHCOR⁶CHONCH₂OH wherein R⁶ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R⁵ is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R² plus R is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Preferred of the above are the alkyl quaternary ammonium surfactants, especially the mono-long chain alkyl surfactants described in the above formula when R is selected from the same groups as R⁴. The most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C₈-C₁₆ alkyl trimethylammonium salts, C₈-C₁₆ alkyl di(hydroxyethyl)methylammonium salts, the C₈-C₁₆ alkyl hydroxyethyldimethylammonium slats, and C₈-C₁₆ alkyloxypropyl trimethylammonium salts. Of the above, decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate are particularly preferred.

Detergent Builders

Detergent compositions of the present invention can optionally-comprise inorganic or organic detergent builders to assist in mineral hardness control. These builders can comprise from 0 to about 80% by weight of the composition. When included, these builders typically comprise up to about 60% by weight of the detergent composition. Built liquid formulations preferably comprise from about 10 to about 25% detergent builder while built granular formulations preferably comprise from about 10 to about 50% by weight detergent builder.

Suitable detergent builders include crystalline aluminosilicate ion exchange materials having the formula: <chemistry id="chem0046" num="0046"><img file="EP0111984A2_D0050.tif" /></chemistry>wherein z and y are at least about 6, the mole ratio of z to y is from about 1.0 to about 0.5; and x is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula <chemistry id="chem0047" num="0047"><img file="EP0111984A2_D0051.tif" /></chemistry>wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC0₃ hardness per gram of anhydrous aluminosilicate.

The aluminosil_icate ion exchange builder materials are in hydrated form and contain from about 10%. to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The preferred crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. More preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope. The crystalline aluminosilicate ion exchange materials are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaC0₃ water hardness/g. of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg. eq./g. to about 352 mg. eq./g. The aluminosilicate ion exchange -materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca⁺⁺/gallon/min- ute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness. Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.

The amorphous aluminosilicate ion exchange materials usually have a Mg exchange capacity of at least about 50 mg. eq. CaC0₃/g. (12 mg. Mg⁺⁺/g.) and a Mg⁺⁺ exchange rate of at least about I grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).

.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. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669 to Krummel, et al. issued October 12, 1976 (herein incorporated by reference). Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (8), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula <chemistry id="chem0048" num="0048"><img file="EP0111984A2_D0052.tif" /></chemistry>wherein x is from about 20 to about 30, especially about 27.

Other examples of detergency builders include the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene-1,1-diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphos- phonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148 Call herein incorporated by reference).

Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a mole ratio of Si02 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.

Useful water-soluble, nonphosphorus organic builders include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.

Highly preferred polycarboxylate builders are disclosed in U.S. Patent No. 3,308,067 to Diehl, issued March 7, 1967 (herein incorporated by reference). Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322 to Diehl issued March 28, 1973 (herein incorporated by reference).

Other useful builders are sodium and potassium carboxymethyl- oxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacar- boxylate, cis-cyclopentanetetracarboxylate phloroglucinol trisul- fonate, water-soluble polyacrylates (having molecular weights of from about 2,000 to about 200,000 for example), and the copolymers of maleic-anhydride with vinyl methyl ether.or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, to Crutchfield et al. issued March 13, 1979, and U.S. Patent 4,246,495, to Crutchfield et al., issued March 27, 1979 (both herein incorporated by reference). These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.

Other useful detergency builder materials are the "seeded builder" compositions disclosed in Belgian Patent No. 798,856, issued October 29, 1973, (herein incorporated by reference). Specific examples of such seeded builder mixtures are: 3:1 wt. mixtures of sodium carbonate and calcium carbonate having 5 micron particle diameter; 2.7:1 wt. mixtures of sodium sesquicarbonate and calcium carbonate having a particle diameter of 0.5 microns; 20:1 wt. mixtures of sodium sesquicarbonate and calcium hydroxide having a particle diameter of 0.01 micron; and a 3:3:1 wt. mixture of sodium carbonate, sodium aluminate and calcium oxide having a particle diameter of 5 microns.

Other Optional Detergent Ingredients

Other optional ingredients which can be included in detergent compositions of the present invention, in their conventional art-established levels for use (i.e., from 0 to about 20%), include solvents, bleaching agents, bleach activators, soil-suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents (monoethanolamine, sodium carbonate, sodium hydroxide, etc.), enzymes, enzyme-stabilizing agents, perfumes, fabric softening components, static control agents, and the like.

Detergent Formulations

Granular formulations embodying the detergent compositions of the present invention can be formed by conventional techniques, i.e., by slurrying the individual components in water and then atomizing and spray-drying the resultant mixture, or by pan or drum granulation of the ingredients. Granular formulations preferably comprise from about 10 to about 30% detergent surfactant, usually anionic.

Liquid formulations embodying the detergent compositions can be built or unbuilt. If unbuilt, these compositions conventionally contain approximately 15 to 50% total surfactant, from 0 to 10% of an organic base such as a mono-, di-, or tri-alkanol amine, a neutralization system such as an alkali metal hydroxide and a lower primary alcohol such as ethanol or isopropanol, and approximately 20 to 80% water. Such compositions are normally homogeneous single phase liquids of low viscosity (approximately 100 to 150 centipoise at 75°F).

Built liquid detergent compositions can be in the form of single phase liquids provided that the builder is solubilized in the mixture at its level of use. Such liquids conventionally contain 10 to 25% total surfactant, 10 to 25% builder which can be organic or inorganic, 3 to 10% of a hydrotrope system and 40 to 77% water. Liquids of this type also have a low viscosity (100 to 150 centipoise at 75°F). Built liquid detergents incorporating components that form heterogeneous mixtures (or levels of builder that cannot be completely dissolved) can also comprise detergent compositions of the present invention. Such liquids conventionally employ viscosity modifiers to produce systems having plastic shear characteristics to maintain stable dispersions and to prevent phase separation or solid settlement.

Near Neutral Wash pH Detergent Formulations

While the detergent compositions of the present invention are operative within a wide range of wash pHs (e.g. from about 5 to about 12), they are particularly suitable when formulated to provide a near neutral wash pH, i.e. an initial pH of from about 6.0 to about 8.5 at a concentration of from about 0.1 to about 2% by weight in water at 20°C. Near neutral wash pH formulations are better for enzyme stability and for preventing stains from setting. In such formulations, the wash pH is preferably from about 7.0 to about 8.5, and more preferably from about 7.5 to about 8.0.

Preferred near neutral wash pH detergent formulations are disclosed in European Patent Application n° 83200688.6, filed on May 16, 1983, J.H.M. Wertz and P.C.E. Goffinet. These preferred formulations comprise: <ul id="ul0008" list-style="none"><li>(a) from about 2 to about 60% (preferably from about 10 to about 25%) by weight of an anionic synthetic surfactant as previously defined;</li><li>(b) from about 0.25 to about 12% (preferably from about 1 to about 4%) by weight of a cosurfactant selected from the group consisting of: <ul id="ul0009" list-style="none"><li>(i) quaternary ammonium surfactants having the formula: <chemistry id="chem0049" num="0049"><img file="EP0111984A2_D0053.tif" /></chemistry>wherein R , each R³, R , R , X and y are as previously defined; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion;</li><li>(ii) diquaternary ammonium surfactants having the formula: <chemistry id="chem0050" num="0050"><img file="EP0111984A2_D0054.tif" /></chemistry>wherein R², R³, R⁴, y and X are as defined above; particularly preferred are the C₈-C₁₆ alkyl pentamethylethylene- diamine chloride, bromide and methylsulfate salts;</li><li>(iii) amine surfactants having the formula: <chemistry id="chem0051" num="0051"><img file="EP0111984A2_D0055.tif" /></chemistry>wherein R², R³, R⁴, R and y are as defined above; particularly preferred are the C₁₂-C₁₆ alkyl dimethyl amines;</li><li>(iv) diamine surfactants having the formula: <chemistry id="chem0052" num="0052"><img file="EP0111984A2_D0056.tif" /></chemistry>wherein R², R³, R⁴, R^5Jand y are as defined above; particularly preferred are the C₁₂-C₁₆ alkyl dimethyl diamines;</li><li>(v) amine oxide surfactants having the formula: <chemistry id="chem0053" num="0053"><img file="EP0111984A2_D0057.tif" /></chemistry>wherein R², R³, R⁴, R⁵ and y are as defined above; particularly preferred are the C₁₂-C₁₆ alkyldimethyl amine oxides; and</li><li>(vi) di(amine oxide) surfactants having the formula: <chemistry id="chem0054" num="0054"><img file="EP0111984A2_D0058.tif" /></chemistry>wherein R², R³, R⁴, R and y are as defined above; preferred are the C₁₂-C₁₆ alkyl trimethylethylene di(amine oxides) and</li></ul></li><li>(c) from about 5% to about 40% by weight (preferably 7 to about 30% by weight, and most preferably from about 10 to 20% by weight) of a fatty acid containing from about 10 to about 22 carbon atoms (preferably a C₁₀-C₁₄ saturated fatty acid or mixture thereof); the mole ratio of the anionic surfactant to the cosurfactant being at least 1 and preferably from about 2:1 to about 20:1.</li></ul>

Such compositions also preferably contain from about 3 to about 15% by weight of an ethoxylated alcohol or ethoxylated alkyl phenol (nonionic surfactants) as previously defined. Highly preferred compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, antioxidants, bactericides, dyes, perfumes and brighteners, such as those described in U.S. Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference).

Specific Embodiments of Detergent Compositions According to the Present Invention

Embodiment I

The following embodiments illustrate, but are not limiting of, detergent compositions of the present invention: <ul id="ul0010" list-style="none"><li>A granular detergent composition is as follows:<img file="EP0111984A2_D0059.tif" /></li></ul>

The components are added together with continuous mixing to form an aqueous slurry which is then spray dried to form the composition. Instead of the polyurethane, the random copolymer of Example 2, the PEI of Example 3 or the diallylamine polymer of Example 4 can be substituted therefor.

Embodiment II

A liquid detergent composition is as follows: <tables id="tabl0003" num="0003"><img file="EP0111984A2_D0060.tif" /></tables>

The components are added together with continuous mixing to form the composition. Instead of the random copolymer, the polyurethane of Example 1, the PEI of Example 3 or the diallylamine polymer of Example 4 can be substituted therefor.

Embodiments III and IV

Liquid detergent compositions are as follows: <tables id="tabl0004" num="0004"><img file="EP0111984A2_D0061.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0111984A2_D0062.tif" /></tables>

Embodiment IV is prepared by adding the components together with continuous mixing, in the following order to produce a clear liquid: a paste premix of the alkylbenzene sulfonic acid, 0.9 parts of the sodium hydroxide, propylene glycol, and 2.3 parts of the ethanol; a paste premix of the alkylpolyethoxysulfuric acid, 1.1 parts of the sodium hydroxide and 3.1 parts of the ethanol; alcohol polyethoxylate; premix of monoethanolamine, triethanolamine and brighteners, 1.5 parts potassium hydroxide; balance of the ethanol; citric acid; formate; 1.4 parts potassium hydroxide; fatty acid; pentaacetic acid; alkyl trimethylammonium chloride; adjust pH to about 8.4 with potassium hydroxide, water or citric acid; enzymes; PEI (50% aqueous solution); and perfume. Embodiment III can be prepared in a similar manner.

Embodiment V

A liquid detergent composition is formulated as follows: <tables id="tabl0006" num="0006"><img file="EP0111984A2_D0063.tif" /></tables>

The components are added together with continuous mixing to form the composition. Instead of the PEI, the polyurethane of Example 1, the random copolymer of Example 2, or the diallylamine polymer of Example 4 can be substituted therefor.