CN1308668A - Surfactant agglomerates - Google Patents

Abstract

A high active surfactant agglomerate is disclosed which has a reduced tendency to gel upon contact with water, and has an improved dissolution profile in water. The surfactant agglomerate comprises a surfactant and a carrier and a water-soluble cationic compound.

Description

Surfactant agglomerates

Technical Field

The present invention relates to surfactant agglomerates suitable for formulating detergent products. The agglomerates of the invention have a reduced tendency to gel when contacted with water and the dissolution profile is improved.

Background

Surfactants are important components of detergent compositions. The surfactant starting material is generally available as a liquid. When formulated in solid detergent compositions, they are typically sprayed onto the solid components of the composition, or provided to the composition in the form of agglomerates. Agglomerates are obtained by agglomerating a liquid or pasty surfactant with a powdered carrier. Agglomerates have the advantage that they allow the formulation of high active compositions, since they contain a higher amount of surfactant by weight of the total composition. Surfactant agglomerates are known in the art.

A problem encountered with surfactant agglomerates in use is that they tend to gel when contacted with water and they have poor dissolution profiles. Both of these problems tend to increase with increasing activity of the agglomerates and are particularly acute for nonionic surfactants. It is therefore an object of the present invention to provide surfactant agglomerates having a reduced tendency to gel when contacted with water and an improved dissolution profile in water.

It has now been found that the above objects are met by formulating surfactant agglomerates comprising a surfactant and a carrier, further comprising a water-soluble cationic compound. The present invention thus provides surfactant agglomerates having a better dissolution profile for a given activity, or agglomerates having a higher activity for a given dissolution profile.

Summary of The Invention

The present invention includes a surfactant agglomerate comprising a surfactant and a carrier, further comprising a water soluble cationic compound. The invention also includes a granular or tablet detergent composition comprising the agglomerates. The invention also includes a process for making the agglomerates.

Detailed Description Agglomerates

The agglomerates of the present invention comprise at least three components which are a surfactant, a carrier and a water-soluble cationic compound.

The agglomerates of the present invention may be prepared with any surfactant, but the preferred surfactant for use in the present invention is a nonionic surfactant.

Suitable nonionic surfactants include compounds resulting from the condensation of oxyalkylene groups (hydrophilic) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The chain length of the polyoxyalkylene group condensed with any particular hydrophobic group can be readily adjusted to give a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic moieties.

Particularly preferred for use herein are nonionic surfactants such as polyoxyethylene condensates of alkyl phenols such as the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 16 carbon atoms in either a straight chain or branched chain configuration with from about 4 to about 25 moles of ethylene oxide per mole of alkylphenol.

Preferred nonionic surfactants are water soluble condensation products of aliphatic alcohols containing 8 to 22 carbon atoms in a straight or branched chain configuration with up to 25 moles of ethylene oxide on average per mole of alcohol. Particularly preferred are the condensation products of about 2 to 10 moles of ethylene oxide per mole of alcohol having an alkyl group containing about 9 to 15 carbon atoms; and condensation products of propylene glycol and ethylene oxide. Most preferred are the condensation products of an average of about 3 moles of ethylene oxide per mole of alcohol having an alkyl group containing from about 12 to about 15 carbon atoms.

Another suitable class of nonionic surfactants are polyhydroxy fatty acid amides, which can be prepared by reacting a fatty acid ester with an N-alkyl polyhydroxy amine. The preferred amine for use in the present invention is N- (R)¹)-CH₂(CH₂OH)₄-CH₂-OH, wherein R¹Typically alkyl groups such as methyl; preferred esters are C12-C20 fatty acid methyl esters.

The preparation of polyhydroxy fatty acid amides is described in WO926073 published on 16.4.1992. This application describes the preparation of polyhydroxy fatty acid amides in the presence of a solvent. In a highly preferred embodiment of the present invention, N-methylglucamine is reacted with a C12-C20 methyl ester. It is also stated that formulators of granular detergent compositions find it easy to perform amidation reactions in the presence of solvents comprising alkoxylated, especially ethoxylated (EO3-8) C12-C14 alcohols (page 15, lines 22-27). This directly leads to the preferred nonionic surfactant systems of the present invention, for example those comprising N-methylglucamide and a C12-C14 alcohol having an average of 3 ethoxy groups per molecule.

Other nonionic surfactants that may be used as components of the surfactant system of the present invention include glyceryl ethers, glucamides, glyceryl amides, glyceryl esters, fatty acids, fatty acid esters, fatty amides, alkyl polyglycosides, alkyl polyglycol ethers, polyethylene glycols, ethoxylated alkyl phenols, and mixtures thereof.

Although the invention is preferably practiced with a nonionic surfactant, preferably an ethoxylated alcohol or a mixture of nonionic surfactants, it can also be practiced with the following anionic or other surfactants.

Anionic surfactants suitable for use in the present invention include:

alkyl ester sulfonate surfactants comprising gaseous SO according to The method of Journal of The American Oil Chemists Society, 52(1975), pages 323-329₃Sulfonated straight chain C₈-C₂₀Carboxylic acid (i.e., fatty acid) esters. Suitable starting materials include natural fatty materials such as those derived from tallow, palm oil, and the like.

Preferred alkyl ester sulfonate surfactants, particularly for laundry applications, include alkyl ester sulfonate surfactants having the following structural formula:wherein R is³Is C₈-C₂₀Hydrocarbyl, preferably alkyl, or mixtures thereof, R⁴Is C₁-C₆A hydrocarbyl group, preferably an alkyl group, or mixtures thereof, M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolAmines and triethanolamine. Preferably R³Is C₁₀-C₁₆Alkyl radical, R⁴Is methyl, ethyl or isopropyl. Particularly preferred are the methyl ester sulfonates wherein R³Is C₁₄-C₁₆An alkyl group. An alkyl sulfate surfactant of the formula ROSO₃Water soluble salts or acids of M, wherein R is preferably C₁₀-C₂₄Hydrocarbyl, preferably alkyl or having C₁₀-C₂₀Hydroxyalkyl of alkyl moieties, more preferably C₁₂-C₁₈Alkyl or hydroxyalkyl, M is H or a cation, such as an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl, dimethyl, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Generally for lower wash temperatures (e.g., below about 50 ℃), C is preferred₁₂-C₁₆Alkyl chains, while C is preferred for higher wash temperatures (e.g., greater than about 50 deg.C)₁₆-C₁₈An alkyl chain. An alkyl alkoxylated sulphate surfactant of the formula RO (A)_mSO₃Water soluble salts or acids of M, wherein R is unsubstituted C₁₀-C₂₄Alkyl or having C₁₀-C₂₄Hydroxyalkyl of alkyl moietiesOr preferably C₁₂-C₂₀Alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈Alkyl or hydroxyalkyl, a is an ethoxy or propoxy unit, M has a value greater than 0, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated for use in the present invention. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethyl ammonium, and quaternary ammonium cations such as tetramethyl ammonium, dimethyl piperdinium, and those derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C₁₂-C₁₈Alkyl ether (1.0) sulfates, C₁₂-C₁₈Alkyl radicalEther (2.25) sulfate, C₁₂-C₁₈Alkyl ether (3.0) sulfates and C₁₂-C₁₈Alkyl ether (4.0) sulphate, where the counterion is suitably selected from sodium and potassium. Other anionic surfactants useful for detersive purposes may also be included in the laundry detergent compositions of the present invention. These may include salts of soap (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di-and triethanolamine salts), C₉-C₂₀Straight chain alkyl benzene sulfonate, C₈-C₂₂Primary or secondary alkanesulfonates, C₈-C₂₄Alkene sulfonates, sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis product of alkaline earth metal citrates, such as described in british patent specification No.1,082,179; c₈-C₂₄Alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); methyl Ester Sulfonate (MES); acyl glycerol sulfonates, fatty oil-based glycerol sulfates, alkylphenol ethoxylate sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinic acid monoesters (in particular saturated and unsaturated C's)₁₂-C₁₈Monoesters) and sulfosuccinic acid diesters (in particular saturated and unsaturated C)₆-C₁₄Diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as alkyl polyglucoside sulfates, branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those having the formula RO (CH)₂CH₂O)_kCH₂COO^-M⁺Salts wherein R is C₈-C₂₂Alkyl, k is an integer from 0 to 10, and M is a cation forming a soluble salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.

Other examples are given in the book "surfactants and detergents" (volumes I and II, by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678 to LaughLin et al, issued 1975, 12, 30, at column 23, line 58 to column 29, line 23 (incorporated herein by reference).

The agglomerates of the present invention may also contain cationic, amphoteric, zwitterionic, and semi-polar surfactants. Cationic detersive surfactants suitable for use in the laundry detergent composition of the present invention are those having one long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium salt surfactants such as alkyl dimethyl ammonium halides, and those having the formula:

[R²(OR³)_y][R⁴(OR³)_y]₂R⁵N⁺X^-wherein R is²Is an alkyl or alkylbenzyl group containing from about 8 to about 18 carbon atoms in the alkyl chain, each R³Is selected from-CH₂CH₂-、-CH₂CH(CH₃)-、-CH₂CH(CH₂OH)-、-CH₂CH₂CH₂-and mixtures thereof; each R⁴Is selected from C₁-C₄Alkyl radical, C₁-C₄Hydroxyalkyl radical, by linking two R⁴Benzyl ring structure formed by the radicals, -CH₂COH-CHOHCOR⁶CHOHCH₂OH, wherein R⁶Is any hexose or hexose polymer having a molecular weight of less than about 1000, and hydrogen (when y is other than 0); r⁵Is with R⁴The same group, or an alkyl chain, wherein R²Adding R⁵No more than about 18 total carbon atoms; each y is 0 to about 10 and the sum of the values of y is 0 to about 15; x is any compatible anion.

Other cationic surfactants useful in the present invention are also described in Cambre, U.S. patent No. US4,228,044, issued 10/14 1980, which is incorporated herein by reference.

Amphoteric surfactants are also suitable for use in the agglomerates of the invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic radical can be straight or branched chain. One aliphatic substituent contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains a water-solubilizing anionic group, e.g., carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al, issued 1975, 12, 30, column 19, lines 18-35 (incorporated herein by reference) for examples of amphoteric surfactants.

Zwitterionic surfactants are also suitable for use in the agglomerates of the present invention. These surfactants can be broadly described as derivatives of secondary or tertiary amines, derivatives of heterocyclic secondary or tertiary amines, or derivatives of quaternary ammonium salts, quaternary phosphonium salts, or tertiary sulfonium compounds. See, U.S. Pat. No. 3,929,678 to Laughlin et al, issued on 30/12/1975, column 19, line 38 to column 22, line 48 (incorporated herein by reference) for examples of zwitterionic surfactants.

Semi-polar nonionic surfactants are a particular class of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides comprising one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include amine oxide surfactants having the formula:

wherein R is³Is an alkyl, hydroxyalkyl or alkylphenyl group containing from about 8 to about 22 carbon atoms, or mixtures thereof; r⁴Is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is 0 to about 3; each R⁵Is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyoxyethylene group containing from about 1 to about 3 oxyethylene groups. R⁵The groups may be linked to each other, for example through oxygen or nitrogen atoms, to form a cyclic structure.

Amine oxide surfactants include in particular C₁₀-C₁₈Alkyl dimethyl amine oxide and C₈-C₁₂Alkoxyethyl dihydroxyethyl amine oxide.

The above surfactants need to be agglomerated with a powdered carrier. The sticky surfactant system is contacted with a finely divided powder carrier such that the powders are bound together (i.e., agglomerated). The result is a particulate composition having a particle size distribution of generally 250-1200 microns and having a bulk density of at least 650 g/l. Suitable mixers for carrying out the agglomeration are well known to those skilled in the art. Any suitable carrier may be selected as one or a mixture of the components listed below, which are suitable for handling in powder form. Suitable materials include zeolites, bentonite, carbonates, silicas, silicates, sulfates, phosphates, citrates and citric acid.

The agglomerates of the present invention also comprise a water-soluble cationic compound. In fact, the use of even small amounts of water-soluble cationic compounds allows the formulation of more active agglomerates, i.e. which contain a greater amount of surfactant, without any significant effect on the solubility of the agglomerates in water, or without increasing their tendency to gel when in contact with water. It is believed that premixing the compound and surfactant causes the surfactant paste to structure, resulting in dough with high stickiness and reduced stickiness. This in turn allows the use of lower amounts of carrier, which overall results in higher activity agglomerates.

Suitable water-soluble cationic compounds include compounds selected from:

(1) ethoxylated cationic monoamines having the formula:

(2) an ethoxylated cationic diamine having the formula:

wherein M is¹Is N⁺Or a N group; each M²Is N⁺Or a N group, at least one M²Is N⁺A group.

(3) Ethoxylated cationic polyamines having the formula:

(4) ethoxylated cationic polymer comprising a polymer backbone, at least 2M groups and at least one L-X group, wherein M is a cationic group attached to or integral with the backbone and contains N⁺A center of positive charge; and L links the radicals M andx or linking a group X to the polymer backbone; and

(5) mixtures thereof; wherein A is¹Is thator-O-, R is H or C₁-_C4Alkyl or hydroxyalkyl radical, R¹Is C₂-C₁₂Alkylene, hydroxyalkylene, alkenylene, arylene or alkylarylene, or C having from 2 to about 20 oxyalkylene units₂-C₃An oxyalkylene segment, provided that no O-N bond is formed; each R²Is C₁-C₄Alkyl or hydroxyalkyl, the segment-L-X or two R²Combine to form- (CH)₂)_r-A²-(CH₂)_s-, wherein A²is-O-or-CH₂-r is 1 or 2, s is 1 or 2, r + s is 3 or 4; each R³Is C₁-C₈Alkyl or hydroxyalkyl, benzyl, the chain segment L-X, or two R³Or a R²And one R³Combined to form a chain segment- (CH)₂)_r-A²-(CH₂)_s-；R⁴Is substituted C with a p-substitution site₃-C₁₂Alkyl, hydroxyalkyl, alkenyl, aryl or alkylaryl groups; r⁵Is C₁-C₁₂Alkylene, hydroxyalkylene, alkenylene, arylene or alkylarylene, or C having from 2 to about 20 oxyalkylene units₂-C₃Alkylene oxide segments, provided that no O-O or O-N bonds are formed; x is selected from H, C₁-C₄Nonionic groups of alkyl or hydroxyalkyl ester or ether groups and mixtures thereof; l is a hydrophilic segment containing a polyoxyalkylene moiety: - [ (R)⁶O)_m(CH₂CH₂O)_n]-; wherein R is⁶Is C₃-C₄Alkylene or hydroxyalkylene, m and n being such that the segment- (CH)₂CH₂O)_n-a value of at least about 50% of said polyoxyalkylene segments; when M is²Is N⁺When d is 1, when M²When N, d is 0; for said cationic monoamines, n is at least about 12; n is at least about 6 for said cationic diamine, and for said cationic poly(s)An amine and a cationic polymer, n is at least about 3; p is 3 to 8; q is 1 or 0; t is 1 or 0, with the proviso that when q is 1, t is 1.

In the above cationic amine formula, R¹May be branched (for example:annular (e.g. of) Or most preferably straight chain (e.g. -CH)₂CH₂-，-CH₂CH₂-CH₂-，

) Alkylene, hydroxyalkylene, alkenylene, alkylarylene or oxyalkylene. For ethoxylated cationic diamines, R¹Is preferably C₂-C₆An alkylene group. Each R²Preferably methyl or the segment-L-X; each R³Is preferably C₁-C₄Alkyl or hydroxyalkyl, most preferably methyl.

N⁺The positive charge of the group is offset by an appropriate number of counter anions. Suitable counter anions include Cl^-、Br^-、SO₃ ^-2、SO₄ ^-2、PO₄ ^-2、MeOSO₃-and the like. A particularly preferred counter anion is Cl^-And Br^-。

X may be a non-ionic group selected from hydrogen (H), C₁-C₄Alkyl or hydroxyalkyl ester or ether groups, or mixtures thereof. Preferred esters or ethers are acetate and methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether.

In the above formula, the hydrophilic chain L is usually composed entirely of polyoxyalkylene segments- [ (R)⁶O)_m(CH₂CH₂O)_n-]And (4) forming. Of the polyoxyalkylene segment- (R)⁶O)_m-and- (CH)₂CH₂O)_nThe segments may be mixed together or preferably form- (R)⁶O)_m-and- (CH)₂CH₂O)_n-blocks of segments. R⁶Is preferably C₃H₆(propylene); m is preferably from 0 to about 5, most preferably 0, i.e.the polyoxyalkylene segment consists entirely of the segment- (CH)₂CH₂O)_n-composition. Chain segment- (CH)₂CH₂O)_nPreferably at least about 85% by weight of the polyoxyalkylene segment, most preferably 100% by weight (m is 0).

In the above formula, for cationic diamines and polyamines, M¹And each M²Is preferably N⁺A group.

Preferred ethoxylated cationic monoamines and diamines have the formula:

wherein X and n are as defined above, a is 0-4 (e.g., ethylene, propylene, hexamethylene) and b is 1 or 0. For the preferred cationic monoamines (b ═ 0), n is preferably at least about 12, and generally ranges from about 15 to 35. For the preferred cationic diamines (b ═ 1), n is at least about 12, and typically ranges from about 12 to about 42.

In the ethoxylated cationic polyamines of the above formula, R⁴(straight, branched or cyclic) is preferably substituted C₃-C₆Alkyl, hydroxyalkyl or aryl; a. the¹Preferably:n is preferably at least about 12, and generally ranges from about 12 to about 42; p is preferably 3 to 6. When R is⁴When substituted aryl or alkaryl, q is preferably 1, R⁵Is preferably C₂-C₃An alkylene group. When R is⁴Is a substituted alkyl, hydroxyalkyl or alkenyl group and q is 0, R⁵Is preferably C₂-C₃An oxyalkylene segment; when q is 1, R⁵Is preferably C₂-C₃An alkylene group.

These ethoxylated cationic polyamines can be derived from polyaminoamides, for example:these ethoxylated cationic polyamines can also be derived from polyaminooxypropylene derivatives, for example:wherein each c has a value of from 2 to about 20.

Process for preparing cationic aminesA.Method 1

Cation of the inventionThe amines can be prepared according to the following route:

the synthesis of such a cationic amine is described below:

example 1 Step 1: ethoxylation reaction

N-2-hydroxyethyl morpholine (0.8 mol) was placed in a flask equipped with a mechanical stirrer, condenser, argon inlet, ethylene oxide sparge and internal thermometer. After purging with argon, NaH (0.2 mol) was added to the flask. The reaction mixture was stirred until the NaH reacted. Ethylene oxide was then added with vigorous stirring while maintaining the temperature at about 80-120 ℃. The reaction was stopped when the degree of ethoxylation of the ethoxylated compound was about 11.Step 2: quaternization reaction

The ethoxylated compound of step 1 (0.03 mol) was mixed with 1, 6-dibromohexane (0.015 mol). The reaction mixture was mixed, sealed in a jar and heated to 80 ℃ over 10 days to give crude quaternized 1, 6-bis [ (-N-morpholinopolyethoxylate (11)) ] -hexane dibromide.

B.Method 2

The ethoxylated cationic amines of the present invention can also be prepared using standard methods for ethoxylating and quaternizing amines. Preferably, the initial step is to condense sufficient ethylene oxide at each active site to give 2-hydroxyethyl groups (hydroxyethylation). The use of 2-hydroxyethylamine as starting material makes it possible to omit this initial step. Appropriate amounts of ethylene oxide are then condensed with these 2-hydroxyethylamines using alkali metals (e.g., sodium, potassium) or their hydrides or their hydroxides as catalysts to give the corresponding ethoxylated amines. The total degree of ethoxylation (n) per active site can be determined according to the following formula:

degree of ethoxylation ═ E/(a × R) where E is the total moles of ethylene oxide condensed (including hydroxyethylation), a is the moles of starting amine, R is the number of active sites of the starting amine (typically 3 for monoamines, 4 for diamines, and 2 × p for polyamines). The ethoxylated amine may then be quaternized with an alkyl halide such as methyl bromide to produce an ethoxylated cationic amine.

Representative examples of ethoxylated cationic amines of the present invention synthesized by this method are as follows:

example 2a Step 1: ethoxylation reaction

1, 6-hexamethylenediamine (100g, 0.86 mole) was placed in a flask and heated to 85 ℃ under argon. Ethylene Oxide (EO) was bubbled into the flask. Over about 7.5 hours, the reaction temperature was gradually increased to 120 ℃ and then briefly increased to 158 ℃ and cooled back to 100 ℃. H-NMR indicated that about 4 moles of EO were incorporated at this point.

Sodium pellets (1.24g, 0.05 mol) were added and the reaction stirred overnight, after which the sodium was consumed. EO addition was resumed and the reaction temperature rose to 120 ℃. After about 3 hours, H-NMR indicated about 10 moles of EO incorporated per mole of diamine. Another portion of sodium spherulites (3.6g, 0.15 moles) was added and the ethoxylation continued. The temperature was allowed to rise to 125-130 ℃. Ethoxylation was continued for about 22 hours. When about 96 moles of EO have been accepted per mole of diamine, the reaction is terminated, yielding a total degree of ethoxylation of about 24.Step 2: quaternization reaction

A portion of the ethoxylated diamine of step 1 (25g, 0.0057 moles) was first dissolved in methanol (100ml) containing a small amount of NaOH and quaternized. Using a dry ice condenser, excess methyl bromide was added. The reaction mixture was allowed to stand overnight, after which the pH was lowered to about 4. NaOH in methanol was added to raise the pH to about 9. The quaternary ammonium compound is isolated by stripping off the methanol and retaining the methyl bromide. The resulting moist mass was washed with several portions of dichloromethane. The combined dichloromethane washes were filtered, the solids removed and stripped to give 27.5g of a yellow oil which solidified at room temperature. The oil bodies contain ethoxylated quaternized diamines.

Example 2b Step 1: ethoxylation reaction

Anhydrous Triethanolamine (TEA) (16.01g, 0.107 moles) was catalyzed with 0.5g (0.0125 moles) of 60% NaH in mineral oil. Then stirring and adding the epoxy at the temperature of 150 ℃ and 170 ℃ under atmospheric pressureEthane (EO). After 23 hours, 36.86g (8.38 moles) of EO were added, giving a calculated total degree of ethoxylation of 26.1. The ethoxylated TEA (PEI 17) was a pale brown waxy solid.Step 2: quaternization reaction

A portion of the ethoxylated TEA of step 1 (31.68g, 0.0088 moles) was dissolved in H₂O, to give an approximately 50% solution. The solution was heated to 60-70 ℃ while stirring with a magnetic bar. Methyl bromide gas was purged through the reactor for 8 hours, and sodium bicarbonate was added as needed to maintain a pH of 7 or greater. After quaternization, the solution was dialyzed for 3 hours to remove the salts. The solution was then eluted to give a 10% slightly cloudy, golden aqueous solution containing ethoxylated quaternized TEA.

Cationic polymers

The water-soluble cationic polymers of the present invention comprise a polymer backbone, at least 2M groups, wherein M is a cationic group attached to or integral with the backbone, and at least one L-X group; x is a nonionic group selected from H, C₁-C₄Alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; and L is a linking group M and X or a hydrophilic chain linking X to the polymer backbone.

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

As used herein, the term "attached" means that the group is attached to the polymer backbone, examples of which are represented by the following general structural formulae A and B:

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 structural formulae C and D:

any polymer backbone can be used as long as the cationic polymer formed is water soluble and has soil removal/anti-redeposition properties. Suitable polymer backbones can be derived from polyurethanes, polyesters, polyethers, polyamides, polyimides and the like, polyacrylates, polyacrylamides, polyvinyl ethers, polyethylenes, polypropylenes and similar polyolefins, polystyrenes and similar polyalkylene arylenes, polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyallylamines, polydiallylamines, polyvinylpyridines, polyaminotriazoles, polyvinylalcohols, aminopoly 1, 3-ureenes, and mixtures thereof.

M may be any compatible cationic group including N⁺(quaternary), positively charged centers. The quaternary positively charged center can be represented by the following general structures E and F:

particularly preferred M groups are those containing a four-membered center represented by general structure E. The cationic groups are preferably located next to or integral with the polymer backbone.

N⁺The positive charge of the center is offset by an appropriate number of counter anions. Suitable counter anions include Cl^-、Br^-、SO₃ ^2-、SO₄ ^2-、PO₄ ^2-、MeOSO₃ ^-And the like. A particularly preferred counter anion is Cl^-And Br^-。

X may be a non-ionic group selected from hydrogen (H), C₁-C₄Alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof. Preferred ester or ether groups are acetate and methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether.

The cationic polymers of the present invention generally have a ratio of cationic groups M to nonionic groups X of from about 1: 1 to about 1: 2. However, the ratio of cationic groups M to nonionic groups X can be varied, for example, by appropriate copolymerization of cationic, nonionic (i.e., containing groups L-X) and mixed cationic/nonionic monomers. The ratio of M to X groups may generally range from about 2: 1 to about 1: 10. In preferred cationic polymers, the ratio is from about 1: 1 to about 1: 5. The polymers resulting from such copolymerization are generally random, i.e., cationic, nonionic, and mixed cationic/nonionic monomers are copolymerized in a non-repeating sequence.

The units containing M and L-X groups make up 100% of the cationic polymers of the invention. However, it is also possible to include other units (preferably nonionic) in the polymer. Examples of other units include acrylamides, vinyl ethers and compounds containing non-quaternized tertiary amine groups (M)¹) Those units (containing N centers). These other units may comprise from 0% to about 90% of the polymer (from about 10% to 100% of the units of the polymer being units containing M and L-X groups, including M¹-L-X group). Typically, these other units comprise from 0% to about 50% of the polymer (about 50% to 100% of the units of the polymer are units containing M and L-X groups).

The number of each M and L-X group is generally in the range of from about 2 to about 200. Typically, the number of each M and L-X group is from about 3 to about 100. Preferably, the number of each M and L-X group is from about 3 to about 40.

Unlike the linking groups M and X or the segments linking the polymer backbone, the hydrophilic chain L is generally composed entirely of polyoxyalkylene segments- [ (R' O)_m(CH₂CH₂O)_n]-composition. Of the polyoxyalkylene segment- (R' O)_m-and- (CH)₂CH₂O)_n-can be mixed together or preferably form- (R' O)_m-and- (CH)₂CH₂O)_n-blocks of segments. R' is preferably C₃H₆(propylene); m is preferably from 0 to about 5, most preferably 0; that is, the polyoxyalkylene segment consists entirely of- (CH)₂CH₂O)_n-a chain segment composition. Chain segment- (CH)₂CH₂O)_nPreferably at least about 85%, most preferably 100% by weight of the polyoxyalkylene segment (m is 0). For- (CH)₂CH₂O)_n-a segment, n generally being from about 3 to about 100. Preferably, n is from about 12 to about 42.

Multiple (2 or more) segments-L-X may also be linked together and to the group M or to the polymer backbone, examples of which are represented by the following general structures G and H:

for example, structures such as G and H can be obtained by reacting glycidol with the group M or with the polymer backbone and ethoxylating the subsequently formed hydroxyl groups.

Representative types of cationic polymers of the invention are as follows: A.polyurethanes, polyesters, polyethers, polyamides, or similar polymers

One suitable class of cationic polymers is derived from polyurethanes, polyesters, polyethers, polyamides, and the like. These polymers comprise units selected from the group consisting of those having formulas I, II and III:

wherein A is¹The method comprises the following steps:x is 0 or 1; r is H or C₁-C₄An alkyl or hydroxyalkyl group; r¹Is C₂-C₁₂Alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkylarylene, or C having 2 to about 20 oxyalkylene units₂-C₃Alkylene oxide segment, with the proviso that A¹In which no O-O orAn O-N bond; when x is 1, R²is-R⁵-, except when A¹The method comprises the following steps:

OR is- (OR)⁸)_y-OR-OR⁵With the exception of A¹In which no O-O or O-N bond is formed, and R³is-R⁵-, except when A¹The method comprises the following steps:

or is- (R)⁸O)_y-or-R⁵With the exception of O-, provided that A¹Wherein no O-O or O-N bond is formed; when x is 0, R²The method comprises the following steps:and R³is-R⁵-；R⁴Is C₁-C₄Alkyl or hydroxyalkyl, or segments- (R)⁵)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X；R⁵Is C₁-C₁₂Alkylene, hydroxyalkylene, alkenylene, arylene, or alkylarylene; each R⁶Is C₁-C₄Alkyl or hydroxyalkyl radicals, or segments- (CH)₂)_r-A₂-(CH₂)_s-, wherein A²is-O-or-CH₂-；R⁷Is H or R⁴；R⁸Is C₂-C₃Alkylene or hydroxyalkylene; x is a hydrogen atom(s) in the formula,-R⁹or mixtures thereof, wherein R⁹Is C₁-C₄An alkyl or hydroxyalkyl group; k is 0 or 1; the values of m and n are such that- (CH)₂CH₂O)_n-segmental occupation of- [ (C)₃H₆O)_m(CH₂CH₂O)_n]-at least about 85% by weight of the segment; m is 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; y is 2 to about 20; the values of u, v and w are such that there are at least 2 of N⁺A center and at least 2X groups.

In the above formula, A¹Preferably, the method comprises the following steps:

A²preferably is-O-; x is preferably 1; r is preferably H. R¹Can be linear (e.g. linear)Or branched (e.g.

Alkylene, hydroxyalkylene, alkenylene, cyclic alkylene, alkylarylene, or oxyalkylene; when R is¹Is C₂-C₃When alkylene oxide segments are used, the number of alkylene oxide units is preferably from about 2 to about 12; r¹Is preferably C₂-C₆Alkylene or phenylene radicals, most preferably C₂-C₆Alkylene (e.g., ethylene, propylene, hexamethylene). R²Preferably is-OR⁵-OR- (OR)⁸)_y-；R³Is preferably-R⁵O-or- (R)⁸O)_y-；R⁴And R⁶Preferably methyl. Such as R¹Same, R⁵May be straight-chain or branched, and is preferably C₂-C₃An alkylene group; r⁷Preferably H or C₁-C₃An alkyl group; r⁸Preferably an ethylene group; r⁹Preferably methyl; 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 formula, when the center N⁺And the number of X groups is 2 or 3, n is preferably at least about 6; most preferably, n is at least about 12, and all ranges of values for u + v + w generally range from about 12 to about 42. For homopolymers (v and w are 0), u is preferably from about 3 to about 40, 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.Polyacrylates, polyacrylamides, polyvinyl ethers, or like polymers

Another class of suitable cationic polymers is derived from polyacrylates, polyacrylamides, polyvinyl ethers, and the like. These polymers comprise units selected from the group consisting of those having the formulas IV, V and VI:wherein A is¹The method comprises the following steps:

-CO-, or

R is H or C₁-C₄An alkyl or hydroxyalkyl group; r¹Is substituted C₂-C₁₂Alkylene, hydroxyalkylene, alkenylene, arylene or alkylarylene, or C₂-C₃An alkylene oxide; each R²Is C₁-C₁₂Alkylene, hydroxyalkylene, alkenylene, arylene, or alkylarylene; each R³Is C₁-C₄Alkyl or hydroxyalkyl, segment- (R)²)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X, or combine to form a segment- (CH)₂)_r-A²-(CH₂)_s-, wherein A²is-O-or-CH₂-; each R⁴Is C₁-C₄Alkyl or hydroxyalkyl, or two R⁴Combine to form- (CH)₂)_r-A²-(CH₂)_s-a segment; x is a hydrogen atom(s) in the formula,-R⁵or mixtures thereof, wherein R⁵Is C₁-C₄An alkyl or hydroxyalkyl group; j is 1 or 0; k is 1 or 0; m and n have the valuesTo obtain- (CH)₂CH₂O)_n-segmental occupation of- [ (C)₃H₆O)_m(CH₂CH₂O)_n]-at least about 85% by weight of the segment; m is 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; the values of u, v and w are such that there are at least 2 of N⁺A center and at least 2X groups.

In the above formula, A¹Preferably, the method comprises the following steps:

A²preferably is-O-; r is preferably H. R¹Can be linear (e.g. linear)Or branched

Substituted alkylene, hydroxyalkylene, alkenylene, alkylarylene, or oxyalkylene; r¹Preferably substituted C₂-C₆Alkylene or substituted C₂-C₃Alkylene oxides, most preferably:each R²Is preferably C₂-C₃Alkylene radical, each R³And R⁴Preferably methyl; r⁵Preferably 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 formula, n, u, v and w may vary depending on n, u, v and w in polyurethane and similar polymers. C.Polyalkyleneamines, polyalkyleneimines, or similar polymers

Another suitable class of cationic polymers is derived from polyalkyleneamines, polyalkyleneimines, and the like. These polymers comprise units selected from the group having formulas VII, VIII and IX:wherein R is¹Is C₂-C₁₂Alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkylarylene, or C having 2 to about 20 oxyalkylene units₂-C₃An oxyalkylene segment, provided that no O-N bond is formed; each R²Is C₁-C₄Alkyl or hydroxyalkylene, or segment- (R)³)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X；R³Is C₁-C₁₂Alkylene, hydroxyalkylene, alkenylene, arylene, or alkylarylene; m' is N⁺Or an N center; x is H,-R⁴Or mixtures thereof, wherein R⁴Is C₁-C₄An alkyl or hydroxyalkyl group; when M' is N⁺When M' is N, d is 0; when M' is N⁺When M' is N, e is 1; k is 1 or 0; the values of m and n are such that- (CH)₂CH₂O)_n-segmental occupation of- [ (C)₃H₆O)_m(CH₂CH₂O)_n]-at least about 85% by weight of the segment; m is 0 to about 5; n is at least about 3; the values of x, y and z are such that at least 2M' groups, at least 2N groups are present⁺A center and at least 2X groups.

In the above formula, R¹Can be as in polyurethanes and similar polymers¹As such, vary; each R²Preferably methyl or a segment- (R)³)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X；R³Is preferably C₂-C₃An alkylene group; r⁴Preferably methyl; x is preferably H; k is preferably 0; m is preferably 0.

In the above formula, when the number of M' and X groups is 2 or 3, n is preferably at least about 6; most preferably, n is at least about 12, and all ranges of values for x + y + z generally range from about 12 to about 42. Generally, x + y + z is from 2 to about 40, preferably from 2 to about 20. For short chain polymers, x + y + z may range from 2 to 9, and have 2 to 9N⁺A center and 2-11X groups. For long chain polymers, x + y + z is at least 10, preferably in the range of 10 to about 42. For short and long chain polymers, the M' groups will generally have about 50-100% N⁺A mixture of centers and 0 to about 50% N centers.

Preferred cationic polymers of this class are derived from C₂-C₃Polyalkyleneamines (x + y + z is from 2 to 9) and polyalkyleneimines (x + y + z is at least 10, preferably from 10 to about 42).Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are cationic Polyethyleneamines (PEA) and Polyethyleneimines (PEI). These preferred cationic polymers comprise units having the general formula:

wherein R is²(preferably methyl), M', X, d, X, y, z and n are as defined above; a is 1 or 0.

The PEA used in the preparation of the cationic polymer of the invention, prior to ethoxylation, has the following general formula:wherein x + y + z is 2 to 9 and a is 0 or 1 (molecular weight about 100 to about 400). Each hydrogen atom attached to each nitrogen atom represents a reactive site for subsequent ethoxylation. For the preferred PEA, x + y + z is from about 3 to about 7 (molecular weight about 140 to about 310). These PEAs can be obtained by reacting ammonia with dichloroethane and then subjecting to fractional distillation. The common PEAs obtained are triethylenetetramine (TETA) and Tetraethylenepentamine (TEPA). Above the pentamines, i.e. hexamines, heptamines, octamines and possibly nonamines, these congeners are apparently not separable by distillation and may include other substances such as cyclic amines and especially piperazines. May also be present in the beltCyclic amines having side chains of nitrogen atoms. See U.S. patent No. US 2792372 to Dickson, 5/14/1957, which describes the preparation of PEA.

The minimum degree of ethoxylation required for preferred clay-removal/anti-redeposition performance can vary depending on the number of units in the PEA. Where y + z is 2 or 3, n is preferably at least about 6. Where y + z is 4 to 9, suitable effects may be obtained when n is at least about 3. For the preferred cationic PEAs, n is at least about 12, and generally ranges from about 12 to about 42.

The PEI used in the preparation of the polymers of the present invention has a molecular weight of at least about 440, which represents at least about 10 units, prior to ethoxylation. Preferred PEI's for use in making these polymers have a molecular weight of about 600 to about 1800. The polymer backbone of these PEI's can be represented by the following general formula:wherein the sum of x, y and z represents a sufficiently large value to obtain a product having the above-specified valuesA polymer of molecular weight. Although a linear polymer backbone is possible, branches may also be present. The relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary depending on the method of preparation. The distribution of amine groups is generally as follows: -CH₂CH₂-NH₂ 30％-CH₂CH₂-NH- 40％

Each hydrogen atom attached to each nitrogen atom of the PEI represents an active site for subsequent ethoxylation. These PEI's can be prepared, for example, by polymerizing aziridine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for making PEI are disclosed in U.S. Pat. No. 5/12 1939 to Ulrich et al, US 2182306; U.S. Pat. No. 5,47,48 to Mayle et al, issued 5/8/1962; US patent US2208095 to Esselmann et al, issued 7, 16, 1940; crowther's US 2806839 issued on 9/17.1957; and Wilson, U.S. Pat. No. 3, 2553696, 5/21 of 1951 (all incorporated herein by reference).

As defined by the formula above, n is at least about 3 for cationic PEI. It should be noted, however, that the minimum degree of ethoxylation required for suitable soil removal/anti-redeposition performance can increase with increasing molecular weight of PEI, particularly molecular weights in excess of about 1800. In addition, the preferred polymers have an increasing degree of ethoxylation as the molecular weight of the PEI increases. For PEI's having a molecular weight of at least about 600, n is preferably at least about 12, and generally ranges from about 12 to about 42. For PEI having a molecular weight of at least 1800, n is preferably at least about 24 and generally ranges from about 24 to about 42. D.Diallylamine polymers

Another class of suitable cationic polymers are those derived from diallylamine. These polymers comprise units selected from the group having the formulae X and XI:wherein R is¹Is C₁-C₄Alkyl or hydroxyalkyl, or segments- (R)²)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X；R²Is C₁-C₁₂Alkylene, hydroxyalkylene, alkenylene, arylene, or alkylarylene; each R³Is C₁-C₄Alkyl or hydroxyalkyl radicals, or combinations thereof to form segments- (CH)₂)_r-A-(CH₂)_s-, wherein A is-O-or-CH₂-; x is a hydrogen atom(s) in the formula,

-R⁴or mixtures thereof, wherein R⁴Is C₁-C₄An alkyl or hydroxyalkyl group; k is 1 or 0; the values of m and n are such that- (CH)₂CH₂O)_n-segmental occupation of- [ (C)₃H₆O)_m(CH₂CH₂O)_n]-at least about 85% by weight of the segment; m is 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; x is 1 or 0; y is 1 when x is 0, and y is 0 when x is 1; u and v are such that there are at least 2N⁺A center and at least 2X groups.

In the above formula, A is preferably-O-; r¹Preferably methyl; each R²Is preferably C₂-C₃An alkylene group; each R³Preferably methyl; r⁴Preferably methyl; x is preferably H; k is preferably 0; m is preferably 0; r and s are each preferably 2.

In the above formula, when N⁺Where the number of centers and X groups is 2 or 3 each, n is preferably at least about 6, n is preferably at least 12, and u + v is generally in the range of about 12 to about 42. Generally, v is 0 and u is from 2 to about 40, preferably from 2 to about 20.

Process for preparing cationic polymersA.Polyurethane

The polyurethane types of the present invention can be prepared according to the following general route. Step 1: ethoxylation reaction

Diethyl of the Monotetrahydropyranyl Ether with 5 mol% NaH yielding a catalytic amount of the corresponding alkoxideDiol (1.77 moles) [ comp.rend.,260，1399-1401(1965)]and (4) ethoxylating. Ethoxylation is carried out at 90-120 c until about 22 moles (n-22) of ethylene oxide are absorbed per mole of starting alcohol to form the ethoxylated compound.Step 2: tosylation reaction

The ethoxylated compound of step 1 was dissolved in 1000ml of acetonitrile and then cooled to about 10 ℃. To this solution was added 2.67 moles of phenylmethanesulfonyl chloride dissolved in 500ml of acetonitrile, cooled to 10 ℃, and then 2.9 moles of triethylamine was added. After the reaction is complete, H is added₂And O, decomposing the residual phenylmethanesulfonyl chloride.And step 3: amination reaction

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

The monomer of step 3 was dissolved in chloroform without ethanol stabilizer. The monomers were evacuated beforehand in a Coulomb apparatus at 80-90 ℃ under reduced pressure (1mm pressure) for at least 18 hours. The monomer in chloroform was then dried overnight over 3A molecular sieves and then transferred to a dry flask (equipped with a mechanical stirrer) under argon atmosphere. Dibutyltin dilaurate catalyst (0.058 molar equivalents) in chloroform was added to the monomers under argon atmosphere. Then 0.7 mole of hexamethylene diisocyanate per mole of aminated monomer was added to the stirred reaction mixture over 5 minutes. The reaction mixture was stirred at room temperature for 18 hours. The chloroform was removed under reduced pressure and at about 70 ℃ to obtain the resulting polymer.And 5: quaternization and removal of protecting groups

Polymerizing the step 4The material was dissolved in methanol and excess methyl bromide was bubbled through. After about 5 hours, the pH is adjusted to about 4 with aqueous HCl, then allowed to stand overnight and the tetrahydropyran protecting group is solvated. The solution was then neutralized with NaOH and stripped to give a crude polyurethane. The crude polyurethane was dissolved in chloroform and filtered to remove any salts. The chloroform was stripped off to give the desired polymer which was essentially free of salt. B.Random copolymers of ethoxylated acrylates and cations Methacrylamide

Random copolymer types of the invention were prepared according to the following general route:

the synthesis of such a random copolymer is described below:

example 4

Decaethylene glycol monomethacrylate monomer (0.008 mol) and N- (3-dimethylaminopropyl) -methacrylamide monomer (0.011 mol) were dissolved in 40ml of acetonitrile. Argon was bubbled through the reaction mixture, sweeping out the oxygen. A portion of 0.23g of benzoyl peroxide was dissolved separatelyThe solution was taken up in 10ml of acetonitrile and purged similarly. The reaction mixture was heated to reflux and the benzoyl peroxide solution was then added dropwise over 0.5 hours. Then, 0.28g of azobisisobutyronitrile in 5ml of acetonitrile was added to the reaction mixture, and heating was continued overnight. The methyl bromide stream was then passed into the reaction mixture and then warmed slightly for 1 hour. The solvent is stripped off and the desired random copolymer is isolated. C.Quaternized polyethyleneamines and polyethyleneimines

Quaternized polyethyleneamines and polyethyleneimines can be prepared using standard methods of ethoxylating and then quaternizing amines. The following are representative synthetic examples of such polyethyleneamines and polyethyleneimines:

example 5a Step 1: ethoxylation reaction

Tetraethylenepentamine (TEPA) (M.W.189, 13.5g, 0.071 moles) was placed in a standard dry flask and heated at 100 ℃ and 120 ℃ -And stirred under reduced pressure (pressure less than 1mmHg) for 0.5 hour for drying. Ethylene Oxide (EO) was drawn from a pre-purged trap connected to the feed tank and the vacuum released. Once the flask was filled with EO, the outlet stopcock leading to the trap connected to the exhaust diffuser was carefully opened. After stirring at 115 ℃ and 125 ℃ for 3 hours, H-NMR analysis showed a degree of ethoxylation of 1 per active site. The reaction mixture was cooled while purging with argon, then 0.5g (0.0125 mol) of 60% sodium hydride in mineral oil was added. The stirred reaction mixture was purged with argon until hydrogen production ceased. EO is then added to the mixture under moderate rapid stirring at 117 ℃ and 135 ℃ under atmospheric pressure to purge. After 31 hours 459g (10.43 moles) of EO have been added, giving a calculated total degree of ethoxylation of 21.Step 2: quaternization reaction

A portion of 34.8g (0.0052 moles) of ethoxylated TEPA as a brown waxy solid from step 1 was dissolved in D₂O, to give a 50% solution. The pH of the solution was about 8. The solution was heated to 60 ℃ and the methyl bromide gas was purged through the reaction vessel, the outlet of which was connected to a diffuser. During the reaction the pH became acidic several times and NaHCO was added to the reaction₃The pH was maintained at about 8. After about 20 hours, a purge diffuser was placed below the surface of the reaction mixture, allowing methyl bromide to bubble through the mixture while increasing the stirring rate. After a total of 22 hours, the reaction mixture was diluted to 25% and dialyzed to remove salts. The reaction mixture was then freeze dried to give a beige crystalline solid as quaternized ethoxylated TEPA.

Example 5b Step 1: ethoxylation reaction

PEI (21.5g, M.W.600, 0.5 mole) was dried at 120 ℃ under reduced pressure using a procedure similar to example 3a and purged with EO until hydroxyethylation was complete (3 hours). The hydroxyethylated compound was cooled under argon and 0.1g (0.0022 mol) 50% NaH in mineral oil was added. The reaction mixture was heated to about 70 ℃ and purged with EO for 13 hours until a total of 88.5g of EO had been added, giving the calculated degree of ethoxylation of 3.4.

53g (0.0173 mol) portions of this compound were placed in a similar apparatus, heated to 120 ℃ and evacuated for 0.5 hour, then cooled under argon and an additional 0.5g (0.010 mol) of 50% NaH was added. EO was purged for 11 hours until 103g of EO was added. This resulted in a total degree of ethoxylation of 11.6.

74g portions (0.0082 mole) of 11.6 ethoxylated PEI were placed in a similar apparatus and purged with EO at 170 ℃ for 6 hours until 70g EO was added, giving a total degree of ethoxylation of 23.4.Step 2: quaternization reaction

Using a procedure similar to example 3a, 20g (0.00114 moles) of 23.4 ethoxylated PEI from step 1 were dissolved in D₂O, heated to 50-60 ℃ and purged with methyl bromide for a total of 9 hours to give quaternized ethoxylated PEI.D. Diallylamine polymers

The diallylamine polymer types of the present invention may be prepared according to the following general route:

the synthesis of such a polymer is described below:

example 6

Step 1:ethoxylation reaction

Diallylamine (1.7 moles) was dissolved in methanol (160ml) under argon and then heated to 45 ℃. Ethylene oxide was then added for 2.5 hours. The reaction mixture was then heated to 100 ℃ under vacuum to remove the methanol. Sodium hydride in mineral oil (6.6g, 0.165 moles) was added to the residue with stirring until hydrogen production ceased. Ethylene oxide was then added until the degree of ethoxylation (n) was about 7.

Step 2:quaternization reaction

The crude ethoxylated diallylamine of step 1 was dissolved in approximately equal volume of 1N methanol NaOH, followed by the addition of methyl bromide. The addition of methyl bromide was continued until H-NMR analysis indicated complete disappearance of the hydrogen from the methylene group adjacent to the tertiary nitrogen. Another portion of 1N methanol NaOH was added as needed to maintain the pH of the reaction mixture at about 9. Methanol was removed to give a moist mass. The moist mass was washed with several portions of dichloromethane. The combined washings were concentrated to give the desired quaternized compound.

And step 3:polymerisation reaction

Reacting the quaternized monomer of step 2 with D₂O (20ml) was mixed and heated to 95 ℃ under argon for 1 hour. Tetrabutyl hydroperoxide (25 drops) was then added and the reaction continued at 90 ℃ for 18 hours. Then more than 20 drops of hydrogen peroxide were added. After heating for more than 3 days, the water was then removed under vacuum (50-60 ℃ C., pressure 0.1mm) to give the crude polymer. The cationic compounds used in the present invention are water soluble. Water solubility as used herein preferably means that at least 30g of the compound is dissolved in 100g of water at 20 ℃. In fact, the use of such lower temperatures inhibits or reduces the absorption of moisture.

It should be noted that an advantage of citrate is that it acts as a builder in the wash.

Suitable zeolites for use in the present invention are zeolites, crystalline aluminosilicate ion exchange materials having the formula:

Na_z[(AlO₂)_z.(SiO₂)_y].xH₂o wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4, and z is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful in the present invention have the empirical formula:

M_z(zAlO₂.ySiO₂) Wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2, y is 1, said material having a magnesium ion exchange capacity of at least about 50 milliequivalents CaCO₃Hardness per gram of anhydrous aluminosilicate.

The crystalline aluminosilicate ion exchange material is further characterized by a particle size diameter of from about 0.1 to about 10 microns. Amorphous materials are generally small, e.g., having particle sizes less than about 0.01 microns in diameter. Preferred ion exchange materials have a particle size diameter of about 0.2 to about 4 microns. The term "particle size diameter" herein denotes the give-up determined by conventional analytical techniques, e.g. microscopy using a scanning electron microscopeThe average particle size diameter is determined by weight of the ion exchange material. According to the inventionCrystalline aluminosilicate ion exchange materials are also generally characterized by their calcium ion exchange capacity, calculated on an anhydrous basis, of at least about 200 milliequivalents of CaCO₃Water hardness per gram of aluminosilicate, typically in the range of from about 300 milliequivalents/g to about 352 milliequivalents/g. The aluminosilicate ion exchange materials of the invention are further characterized by their calcium ion exchange rate of at least about 2 grains Ca⁺⁺(ii) gallons per minute per gram per gallon of aluminosilicate (anhydrous), typically in the range of about 2 grains per gallon per minute per gram per gallon to about 6 grains per gallon per minute per gram per gallon, based on the hardness of calcium ions. For builder applications, the optimum aluminosilicate exhibits a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.

Amorphous aluminosilicate ion exchange materials generally have Mg⁺⁺The exchange capacity is at least about 50 milliequivalents CaCO₃/g(12mgMg⁺⁺Per g) and Mg⁺⁺The exchange rate is at least about 1 grain/gallon/minute/gram/gallon. The amorphous material showed no observable derivatization pattern when measured with Cu radiation (1.54 angstrom units).

Aluminosilicate ion exchange materials useful in the practice of the present invention are commercially available. The aluminosilicates useful in the present invention may be of crystalline or amorphous structure and may be naturally occurring aluminosilicates or synthetically derived. A process for preparing aluminosilicate ion exchange materials is disclosed in U.S. Pat. No. 5,17,1976 issued to Krummel et al, U.S. Pat. No. 3985669, which is incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are commercially available as registered Zeolite A, Zeolite B and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂o wherein x is from about 20 to about 30, particularly about 27, and generally has a particle size of less than about 5 microns.

The agglomerates of the present invention comprise from 10% to 50%, preferably from 20% to 40%, most preferably from 25% to 35% by weight of the agglomerates of surfactant. The agglomerates of the present invention comprise from 10% to 50%, preferably from 20% to 40%, most preferably from 25% to 35% by weight of the agglomerate of carrier. The agglomerates of the present invention comprise from 0% to 40%, preferably from 2% to 30%, most preferably from 3% to 15% by weight of the agglomerates of a water-soluble cationic compound. Finally, the agglomerates of the present invention comprise from 0% to 50%, preferably from 20% to 40%, most preferably from 25% to 35%, by weight of the agglomerates, of the mixture of citrate and acetate salts. The mixture of citrate and acetate may comprise 0-100% by weight citrate, more preferably 40-60% citrate.

Another preferred optional component of the surfactant agglomerates is a polymer having a melting point greater than 35 c, preferably greater than 45 c, more preferably greater than 55 c, and most preferably greater than 60 c, including for example PEG (polyethylene glycol), most preferably PEG 4000. Such a said component has been found to be particularly useful when the agglomerate contains a surfactant, more preferably a nonionic surfactant, having a melting point below 35 c, whereby such surfactant having a melting point below 35 c may melt when the agglomerate is exposed to a high temperature environment, in which case the addition of a polymer having a melting point above 35 c will raise the melting point of the mixture, thereby avoiding the formation of a liquid phase. Such polymers are preferably treated simultaneously with the surfactant during the preparation of the agglomerates and are preferably present in a ratio of at least 3% and up to 20%, more preferably in a ratio of at least 4% and up to 6%, by weight of the agglomerates.

Process for preparing agglomerates

A key aspect of the process of the invention is that the surfactant must be mixed with the water-soluble cationic compound and then mixed with the carrier. If acetate or citrate is used, it must be in close proximity to the surfactant. Close proximity cannot be achieved by dry addition of acetate or citrate. Rather, this close proximity is achieved by a variety of methods including the following two embodiments.

In a first embodiment, the acetate and/or citrate, or a portion thereof, is intimately mixed with the surfactant and then agglomerated with the carrier. In a variation of this first embodiment, the acetate and/or citrate is intimately mixed with the carrier, and then the surfactant is agglomerated therewith.

If the acetate and/or citrate is mixed with the surfactant, it is preferred to first mix the surfactant and the water-soluble cationic compound, then mix the acetate and/or citrate, and then agglomerate the mixture with the carrier.

In a second embodiment, the surfactant and the water-soluble cationic compound are mixed together, then pre-agglomerated with the carrier, and the acetate and/or citrate is sprayed onto the pre-agglomerate to form the final agglomerate. A combination of these two approaches is possible, with only a portion of the acetate and/or citrate being intimately mixed with the surfactant/water-soluble cationic polymer or carrier. The surfactant/water-soluble cationic polymer and carrier and a portion of the acetate salt and/or citrate salt are then pre-agglomerated, with the remainder of the acetate salt and/or citrate salt being ultimately sprayed onto the pre-agglomerate to form the final agglomerate.

In addition to those specific examples, the process of the invention comprises mixing the fluid (surfactant) with the powder (acetate and/or citrate, carrier), the fluid (surfactant) with the fluid (water-soluble cationic compound), the powder (acetate and/or citrate) with the powder (carrier), which can be preformed by any method known to the skilled person. Suitable equipment for carrying out these steps includes Fukae manufactured by Fukae Powtech industries, Inc. of Japan^RFS-G series of blendsA machine; the apparatus is substantially in the form of a tub accessible through an upper opening, equipped, near its bottom, with a stirrer having a substantially vertical axis, equipped with a cutting blade at the side wall. The agitator and cutter may be operated independently of each other and at independently variable speeds. The vessel may be fitted with a cooling jacket or, if desired, a cryogenic device.

Other similar mixers which find use in the process of the present invention include those available from Dierks, Germany&Diosna of S Ö ohne^RA V series; and Pharma Matrix from T K Fielder ltd. of uk^R. It is believed that other mixers suitable for use in the process of the present invention are available from JapanFuji of Fuji Sangyo Co., Ltd^RVG-C series and Zanchetta from Italy&Roto of Co srl^R。

Other suitable preferred apparatus may include Eirich produced by Gustau Eirich Hardheim, Germany^RRV series, L Ö dige for batch mixing produced by L Ö dige machiennbau GmbH, Paderborn, Germany^RFM series, Baud KM series for continuous mixing/agglomeration; drais manufactured by Mannheim, Delisy, Germany^RA T160 series; and Winkworth manufactured by Berkshire, Winkworth Machinery Ltd^RRT 25 series.

A Littleford Mixer model # FM-130-D-12 with an internal cutter and a Cuisinart food processor model # DCX-Plus with a 7.75 inch (19.7cm) cutter are two examples of suitable mixers. Any other mixer having finely divided mixing and pelletizing capability with a residence time of about 0.1 to 10 minutes may be used. Preferably a "turbine type" impeller mixer with several cutters on the rotating shaft. The present invention may be practiced in a batch or continuous process.

In embodiments of the invention where the acetate and/or citrate salt is sprayed onto the pre-agglomerate of surfactant and carrier and optional water-soluble cationic compound, it is necessary to first form a solution of the acetate and/or citrate salt powder into a sprayable solution. Suitable sprayable solutions comprise from 30g/l to 60g/l of acetate and/or citrate, preferably from 40g/l to 50g/l of acetate and/or citrate. In this embodiment, any spraying equipment may be used, preferably the agglomerates are dried after spraying with the acetate and/or citrate solution. In addition, any conventional drying equipment may be used for this purpose.

Once the surfactant agglomerates have been formed, they are preferably subjected to a heating and/or drying step, followed by a cooling step. This enables removal of excess water.

Further, it is preferred that the pre-mixture of surfactant and water-soluble cationic compound has a viscosity of about 15000-35000cps, preferably 20000-25000cps, before mixing the pre-mixture with the carrier. This can be achieved by controlling the temperature of the premix. This can facilitate mixing of the surfactant or the dissolution behavior of the surfactant agglomerates can be measured as follows: 1. a Sotax beaker was charged with 1 liter of deionized water and placed in a constant temperature bath fixed at 10 ℃. In the beaker, a stirrer with a marine propeller was placed in such a way that the marine propeller was ± 1mm below the water surface. The rotational speed of the mixer was fixed at 200 rpm. 2. 10g of surfactant agglomerates to be measured were added to a Sotax beaker. 3. 30 seconds after the surfactant agglomerate addition, a 2ml sample of the solution was aspirated using a syringe equipped with a filtration device (mesh size 0.45 microns). Filters are used to avoid undissolved particles from being analyzed and affecting the results. 4. Step 3 was repeated after 1 minute, 2.5 minutes, 5 minutes, 10 minutes after the addition of the agglomerates.

All samples were analyzed for active content and compared to a larger theoretical calculated amount of surfactant in the sample.Compositions in which agglomerates may be formulated

The agglomerates according to the invention can be formulated into granular or tablet detergent compositions, but there is usually no difference between the two. Depending on their end use, typically dishwashing or laundry, these detergent compositions may contain a variety of components including, but not limited to, other surfactants, builders, chelating agents, bleaches, bleach activators, soil release polymers, suds controlling or sudsing boosters, pH adjusters, enzymes, enzyme stabilizers, perfumes, brighteners, dye transfer inhibitors, and the like. In preferred compositions of the invention, at least 40%, preferably at least 60%, most preferably at least 90% of the surfactant is incorporated in the form of agglomerates.Granular detergent composition

In preparing the granular detergent composition, the surfactant agglomerates may simply be mixed with the remaining granular components or subjected to the further processing steps of spraying the liquid and coating with the fine powder in sequence.

Although the performance of the granules described herein remains excellent, independent of the remaining product matrix, it may be advantageous to make granular detergent compositions in the following manner: to optimize the properties of various products and to allow their formulation with high flexibility without major process variations. This can be achieved by constructing the final product substrate using a modulus method.

The modulus method is based on preparing granules of one or at most two components of high character in the formulation, which are then mixed in the required proportions to form the finished product. These particles, which are components intended to provide a high degree of specificity, can be used in a wide range of products which do not require modification. The particles are prepared from an optimal combination of components to optimize the properties of the components, and are fully formulatedThe product formula is irrelevant.Detergent composition in tablet form

Detergent tablets may be prepared by simply mixing the solid components together and compressing the mixture using a conventional tablet press as used in the pharmaceutical industry, for example.

The detergent tablets may be prepared in any size or shape and may be coated if desired.

The particulate materials used to make the tablets (other than those of the agglomerates of the present invention) may be prepared by any granulation or prilling process. An example of such a process is spray drying (in a co-current or counter-current spray drying tower), which generally results in a low bulk density of 600g/l or less. By granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g. using Lodige)^®CB and/or Lodige^®KM mixer) can produce higher density particulate materials. Other suitable processes include fluidized bed processes, compression processes (e.g., roller compression), extrusion, and the preparation of any particulate material by chemical processes such as flocculation, crystallization sensing, and the like. Each particle may also be any other particulate, granule, pellet or granule.

The particulate materials may be mixed together using any conventional equipment, with batch processes being suitable for example for concrete mixers, nauta mixers, ribbon mixers or any other equipment. Alternatively, the mixing process may be carried out continuously by metering the weight of the components onto a moving belt and mixing them by stirring in one or more drums or mixers. A non-gelling binder may be sprayed onto some or all of the mixture of particulate materials. Other liquid components may also be sprayed onto the mixture of particulate materials, either alone or pre-mixed. For example, perfume and optical brightener slurries can be sprayed. Preferably, towards the end of the process, the binder is sprayed, after which finely divided flow aids (release agents such as 57 zeolite, carbonate, silica) are added to the particulate material to make the mixture low-viscous.

The tablets may be prepared by any compression method, for example tabletting, briquetting or extrusion, preferably tabletting. Suitable equipment includes standard single stroke or rolling presses (e.g., Courtoy)^®，Korch^®，Manesty^®Or Bonals^®). The tablets prepared should preferably have a diameter of 40mm to 60mm and a weight of between 25 and 100 g. The ratio of the height to the diameter (or width) of the tablet is preferably greater than 1: 3, more preferably greater than 1: 2. The pressure used for preparing the tablets does not exceed 5000kN/m²Preferably not more than 3000kN/m²Most preferably not more than 1000kN/m²。

Suitable non-gelling binders include synthetic organic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyacrylates, and water-soluble acrylate copolymers. The pharmaceutical excipients handbook, second edition, lists the following types of binders: gum arabic, alginic acid, carboxyvinyl polymer (Carbomer), sodium carboxymethylcellulose, dextrin, ethylcellulose, gelatin, guar gum, hydrogenated vegetable oil type 1, hydroxyethyl cellulose, hydroxypropyl methylcellulose, liquid glucose, magnesium aluminum silicate, maltodextrin, methylcellulose, polymethacrylates, povidone, sodium alginate, starch, and zein. Most preferred binders also have a cleaning action active in laundry, for example cationic polymers, i.e. ethoxylated hexamethylenediamine quaternary ammonium compounds, dihexaethylenetriamine or other substances such as pentamines, ethoxylated polyethyleneamines, maleic acrylic polymers.

Preferably sprayed with a non-gelling binder material, whereby it has a suitable melting point below 70 c, preferably below 50 c, so as not to destroy or degrade other active ingredients in the matrix. Most preferred are non-aqueous liquid binders (i.e., not in aqueous solution) which can be sprayed in molten form. They may also be solid adhesives which are incorporated into the matrix by dry addition, but which have adhesive properties in the sheet.

The non-gelling binder material is preferably used in an amount of from 0.1% to 15%, more preferably less than 5%, especially less than 2% by weight of the tablet if it is a non-laundry active. The sheet may be coated so that the sheet does not absorb moisture or only absorbs moisture at a very slow rate. The coating is also strong such that the tablets are subjected to moderate mechanical impact during use, packaging and shipping resulting in no more than a very low amount of breakage or wear. Finally, the coating is preferably crumbly, so that the sheet breaks when subjected to strong mechanical impact. In addition, it is advantageous if the coating material dissolves under alkaline conditions or is easily emulsified by surfactants. This helps to avoid the problem of visible residues adhering to the window of the front-loading washing machine during the washing phase and also to avoid undissolved particles or lumps of coating material being deposited on the washed load.

Water solubility was determined using the following ASTM E1148-87, test protocol entitled "Standard test methods for determining Water solubility".

Suitable coating materials are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof.

The coating material has a melting point preferably in the range of 40 ℃ to 200 ℃. The coating may be applied in a variety of ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material.

In a), the coating material is applied and cured on the sheet at a temperature above its melting point. In b), the coating material is applied as a solution and the solvent is dried, leaving a coherent coating. The substantially insoluble material may be applied to the sheet by, for example, spraying or dipping. Typically, when the molten material is sprayed onto the sheet, it quickly solidifies to form an adherent coating. Rapid solidification of the coating material can be caused when the sheet is dipped into the molten material and then removed and rapidly cooled. It is clear that substantially insoluble materials having a melting point below 40 ℃ are not sufficiently curable at room temperature and that materials having a melting point above about 200 ℃ are found to be unsuitable for practical use. Preferably, the melting point of the material is between 60 ℃ and 160 ℃, more preferably between 70 ℃ and 120 ℃.

By "melting point" is meant the temperature at which the material becomes a transparent liquid when heated slowly in, for example, a capillary.

Any desired thickness of the coating may be applied according to the present invention. For most purposes, the coating will comprise from 1% to 10%, preferably from 1.5% to 5% by weight of the tablet.

Suitable tablet coatings are very hard and provide tablet superstrength.

In a preferred embodiment, the cracking of the coating in the wash is improved by the addition of a disintegrant to the coating. The disintegrant swells upon contact with water and breaks the coating into small pieces. This will improve the dissolution of the coating in the wash solution. The amount of disintegrant suspended in the coating melt is up to 30%, preferably 5% to 20%, most preferably 5% to 10% by weight. Possible disintegrants are described in the handbook of pharmaceutical excipients (1986). Examples of suitable disintegrants include starch: native, modified or pregelatinized starches; starch sodium gluconate; a gum; agar gum; guar gum; locust bean gum; karaya gum; pectin; yellow good glue; croscarmylose sodium, polyvinyl polypyrrolidone, cellulose, carboxymethylcellulose, alginic acid and salts thereof, including sodium alginate, silica, clay, polyvinyl pyrrolidone, soybean polysaccharide, ion exchange resins, and mixtures thereof.

Depending on the raw material composition and the shape of the tablet, the pressure used can be adjusted without affecting the strength (diametral rupture stress) and disintegration time in the washing machine. The process can be used to prepare uniform or layered tablets of any size or shape.

In another preferred embodiment of the invention, the laundry tablet further comprises a sudsing agent.

Foaming, as defined herein, means the generation of carbon dioxide gas as a result of a chemical reaction between a soluble acid source and an alkali metal carbonate, with the result that bubbles are emitted from the liquid,

namely:

the tablets are also useful in a washing process which comprises preparing an aqueous solution of a laundry detergent for use in a front-loading washing machine having a dispensing chamber and a washing drum, wherein the tablets are placed in the dispensing chamber and water is passed through the dispensing chamber to form an aqueous solution of the laundry detergent, such that the tablets are dispensed as an aqueous solution of the laundry detergent which then passes into the washing drum.

In a preferred embodiment, the surfactant agglomerates comprise anionic surfactant in combination with acetate, in combination with any other structurant. Whereby the components are brought into close proximity by using a method that produces high shear, such as extrusion. In fact, it has been found that such surfactant agglomerates have a high activity, while having a satisfactory processability, which is provided by the hardness and low viscosity of the resulting paste. The structuring agent used may be, for example, zeolites, silicates or mixtures of these. It should be noted that satisfactory processability can be obtained with exceptionally low amounts of acetate, preferably anhydrous sodium acetate, preferably less than 10% by weight of the agglomerate. The agglomerates also preferably comprise more than 40% by weight anionic surfactant, more preferably more than about 50% by weight.

The invention is illustrated by the following examples.

Examples

Examples A and B

The surfactant granule compositions given in table 1 were prepared as follows: 1. a mixture comprising two parts of zeolite and 20 parts of finely divided sodium carbonate (average particle size below 200 μm) was charged to a high shear mixer/agglomerator (Lodige FM 130). 2. A pre-mix comprising 26 parts of an ethoxylated nonionic surfactant (C14-C15 EO7) and 6 parts of the cationic polymer Lutensit KHD96 (ethoxylated hexamethylenediamine quaternary ammonium compound) from BASF was then added to the carbonate/acetate dry blend. 3. The surfactant-polymer pre-mixture and dry powder were agglomerated in a mixer-agglomerator with the plow speed set at 175rpm and its cutter set at 3000rpm until discrete particles were formed. 4. The agglomerates were then transferred to a rotating concrete mixing drum and atomized with 8 parts of the flow aid zeolite for 30 seconds.

TABLE 1

	Example A composition according to Weight meter	Example B composition according to Weight meter
			Zeolite	40	40
Sodium carbonate	20	20
			Nonionic surfactant (C45 AE7)	26	-
Nonionic surfactant (C45 AE5)	-	26
			Lutensit KHD96	6	6
Flow aid (zeolite)	8	8

Example C

The surfactant granule compositions given in table 2 were prepared as follows:

the procedure of example A was repeated using quaternized ethoxylated bis-hexamethylene triamine (BHMT E30Q) instead of LutensitKHD 96.

TABLE 2

	Example C, wt.%
		Zeolite	40
Sodium carbonate	20
		Nonionic surfactant (C45 AE7)	26
BHMT E30Q	6
		Flow aid (zeolite)	8

Examples D to E

The process of example a was repeated using different proportions of cationic polymer instead of the nonionic surfactant EO7 to produce the surfactant granules of table 3.

TABLE 3

	Example D composition according to Weight meter	Example E composition according to Weight meter
			Zeolite	40	40
Sodium carbonate	20	25
			Nonionic surfactant EO7	15	10
Lutensit KHD96	15	5
			Flow aid (zeolite)	10	10

Example F

The base powder of the finished laundry detergent was mixed together by mixing the ingredients shown in table 4 below, except that the polyethylene glycol and perfume were sprayed on.

TABLE 4

Composition of	Example F (% by weight)
		Nonionic surfactant of example A Agglomerates	9.9
Anionic surfactant agglomerates	28.1
		Compact particles of layered silicate	9.0
Granular carbonate	13.4
		Granular percarbonate	14.2
Anhydrous citric acid	7.0
		Suds suppressor agglomerates	1.9
Soap powder	1.4
		Particulate soil release agent polymers	4.5
Bleach activator agglomerates	5.5
		Miscellaneous items (minor ingredients)	1.1
Enzyme	2.2
		Sodium sulfate	-
Sprayed polyethylene glycol	1.3
		Spray-on fragrance	0.5

The anionic agglomerates comprise 38% anionic surfactant, 22% zeolite and 40% carbonate. The bleach activator agglomerate comprises 81% TAED (tetraacetylethylenediamine), 17% acrylic acid/maleic acid copolymer (acid form) and 2% water.

The zinc phthalocyanine sulfonate encapsulate was 10% active.

The suds suppressor agglomerate comprises 11.5% silicone oil (from Dow Corning) and 88.5% starch.

The compact particles of layered silicate comprise 78% SKS-6 from Hoechst, 22% citric acid.

Example G

1. 80 parts of the base powder of composition F are mixed in a mixing drum with 11 parts of anhydrous citric acid and 11 parts of sodium carbonate.

2. Then, tablets were prepared, and 55g of the mixture in 1) was added to a circular mold having a diameter of 5.5cm and pressed to obtain tablets having a height of 2 cm. The tensile strength (or diametral fracture stress) of the sheet was 9 kPa.

Example H

After preparation of the tablets of example G, the tablets were immersed in a bath heated at 140 ℃ containing 90 parts dodecanedioic acid mixed with 10 parts of Nymcel zsb 16. The time for which the tablet was immersed in the heated bath was adjusted to allow 5g of the mixture to be applied thereto. The sheet was then left to cool at room temperature of 25 ℃ for 24 hours. The tensile strength of the sheet wrapped by the coating layer is increased to more than 27 kPa.

Example I

i) A detergent base powder of composition J was prepared as follows: all the granular materials of the base composition J were mixed together in a mixing drum to form a uniform granular mixture. During the mixing process, spraying was performed. After spraying, sodium diisoalkylbenzene sulfonate (DIBS) was added to the remaining matrix.

ii) then tablets were prepared as follows. 43g of the mixture was charged into a circular mold having a diameter of 5.5cm, and the tensile strength (or diameter rupture stress) of the tablet obtained by pressing was 15 kPa.

	Composition J (%)
		Anionic agglomerates 1	9.1
Anionic agglomerates 2	22.5
		Nonionic agglomerates	9.1
Cationic agglomerates	4.6
		Layered silicate	9.7
Sodium percarbonate	12.2
		Bleach activator agglomerates	6.1
Sodium carbonate	7.27
		EDDS/sulfate particles	0.5
Hydroxy ethane diphosphonic acid tetrasodium salt	0.6
		Soil release agent polymers	0.3
Fluorescent agent	0.2
		Zinc phthalocyanine sulfonate encapsulates	0.03
Soap powder	1.2
		Suds suppressor	2.8
Citric acid	5.5
		Protease enzyme	1
Lipase enzyme	0.35
		Cellulase enzymes	0.2
Amylase	1.1
		Adhesive dispensing system	3.05
Perfume on spray	0.5
		DIBS	2.1

The anionic agglomerate 1 comprises 40% anionic surfactant, 27% zeolite and 33% carbonate.

The anionic agglomerate 2 comprises 40% anionic surfactant, 28% zeolite and 32% carbonate.

The nonionic agglomerates comprise 26% nonionic surfactant, 6% lutenst K-HD96, 40% anhydrous sodium acetate, 20% carbonate, and 8% zeolite.

The cationic agglomerate comprises 20% cationic surfactant, 56% zeolite and 24% sulfate.

The layered silicate comprises 95% SKS 6 and 5% silicate.

The bleach activator agglomerate comprises 81% TAED, 17% acrylic acid/maleic acid copolymer (acid form) and 2% water.

The ethylenediamine N, N-disuccinic acid sodium salt/sulfate particles comprised 58% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate, and 19% water.

The zinc phthalocyanine sulfonate encapsulate was 10% active.

The suds suppressor comprises 11.5% silicone oil (available from Dow Corning); 59% zeolite and 29.5% water.

The binder spray system comprised 0.5 parts Lutensit K-HD96 and 2.5 parts PEG.

Claims (13)

1. A surfactant agglomerate comprising a surfactant and a carrier, characterised in that it further comprises a water soluble cationic compound.

2. An agglomerate according to claim 1, wherein the surfactant is a nonionic surfactant.

3. Agglomerates according to claim 1 or 2, further comprising a polymer having a melting point of more than 35 ℃.

4. An agglomerate according to claim 2 or 3, wherein the non-ionic surfactant is an ethoxylated alcohol.

5. An agglomerate according to any one of claims 1 to 4, further comprising a water soluble acetate and/or citrate in close proximity to the surfactant.

6. An agglomerate according to any preceding claim, comprising from 15% to 55% by weight of the agglomerate of surfactant, from 10% to 40% by weight of the agglomerate of carrier and from 0% to 40% of acetate and/or citrate, and from 0% to 20% by weight of the agglomerate of water-soluble cationic compound.

7. An agglomerate according to claim 6, comprising from 25% to 35% by weight of the agglomerate of surfactant, from 25% to 35% by weight of the agglomerate of carrier, from 25% to 35% by weight of the agglomerate of acetate and/or citrate, and from 0% to 15% by weight of the agglomerate of water-soluble cationic compound.

8. A process for preparing agglomerates according to the preceding claim, wherein the surfactant is mixed with the water-soluble cationic compound and then agglomerated with the carrier.

9. A process according to claim 8 for the preparation of agglomerates according to claims 5 to 7, wherein the surfactant and the water-soluble cationic compound are first mixed, the acetate and/or citrate salt or a part thereof is then mixed, and the mixture is then agglomerated with the carrier.

10. A process according to claims 8 and 9 wherein the acetate and/or citrate salt, or a portion thereof, is sprayed onto the pre-agglomerates of surfactant, water-soluble cationic compound, carrier and optionally the remainder of the acetate and/or citrate salt.

11. A granular detergent composition comprising an agglomerate according to any of claims 1 to 7 and other detersive ingredients.

12. A detergent composition in tablet form comprising an agglomerate according to any of claims 1 to 7 and other detersive ingredients.

13. A composition according to claim 11 or 12 wherein at least 40%, preferably 60%, most preferably at least 90% of the surfactant is incorporated into the composition via the agglomerates.