CN1334858A - Process for producing particles of amine reaction product - Google Patents

Abstract

There is provided a process for producing particles of amine reaction product by means of a carrier having a melting point between 30 DEG C and 135 DEG C, optionally followed by a coating step. Processed amine reaction products and finished compositions incorporating such processed product are also herein provided.

Description

Process for preparing particles of amine reaction product

Technical Field

The present invention relates to a process for preparing particles of an amine reaction product.

Background

Perfumed products are known in the art. However, consumer acceptance of such perfumed products, such as laundry and cleaning products, is determined not only by the performance achieved by these products, but also by the aesthetics associated therewith. Perfume ingredients are therefore an important aspect of the successful formulation of such commercial products.

Consumers also desire that the treated fabrics retain a pleasant fragrance for an extended period of time. In fact, perfume additives make such compositions more aesthetically pleasing to the consumer, and in some cases, perfumes impart a pleasing fragrance to fabrics treated therewith. However, the amount of perfume carried out of the wash water bath that is deposited onto the fabric is usually small and not durable on the fabric. In addition, perfumes are often very expensive, they are not effectively used in laundry and cleaning compositions and cannot be effectively delivered to fabrics, which results in very high costs to the consumer and laundry and cleaning manufacturer. Accordingly, there is an urgent need in the industry to continue to seek more effective fragrance donors for use in laundry and cleaning products, particularly to improve the long-lasting fragrance delivery to fabrics.

It has recently been discovered that compounds containing primary amine functionality and amine reaction products containing an active ketone or aldehyde component satisfy this need. The disclosure of such compounds can be found in the recent applications EP98870227.0, EP98870226.2, EP99870026.4 and EP99870025.6, all of which are incorporated herein by reference.

However, a problem with these compounds is that they are easily incorporated into fully formulated compositions. In fact, such amine reaction products are often sticky, which makes them less convenient to incorporate into these fully formulated compositions.

It is therefore an object of the present invention to provide an amine reaction product in a suitable form which is easily incorporated into a fully formulated composition.

It has now been found that mixing the amine reaction product with a carrier having a specific melting point to form granules satisfies this need. Preferably, the resulting particles are then treated to form coated particles.

In addition, it has also been advantageously found that both the sticky and non-sticky amine reaction products exhibit better deposition and sustained release when processed by the present invention than amine reaction products not processed according to the present invention. Without being limited by theory, it is believed that mixing with such a carrier, acts as a shell surrounding the amine reaction product, thereby avoiding contact with aggressive detergent solutions and enhancing its fabric deposition properties.

By "viscous" is meant that the product has a viscosity greater than 1000 cps. The viscosity is measured by rheometer, TA instruments CSL² ₁₀₀The gap was set at 500 microns, measured at a temperature of 25 ℃.

The supports used in the present invention have a melting point, measured at atmospheric pressure, of from 30 to 135 ℃.

Summary of The Invention

The present invention is a process for preparing particles of an amine reaction product between a compound containing primary and/or secondary amine functional groups and an active ketone or aldehyde-containing component comprising the steps of:

a) providing an amine reaction product, and

b) mixing with carrier with melting point of 30-135 deg.C.

In a preferred embodiment of the invention, the particles produced are further processed to form coated particles.

Detailed description of the invention starting materials 1) -amine reaction products

The amine reaction products useful in the present invention are the products of the reaction between a compound containing primary and/or secondary amine functional groups and an active ketone or aldehyde-containing component, hereinafter referred to as "amine reaction products".

General disclosures of amine reaction products suitable for use in the present invention may be found in the more recent applications EP98870227.0, EP98870226.2, EP99870026.4 and EP99870025.6, all of which are incorporated herein by reference. A-primary and/or secondary amines

"primary and/or secondary amine" means a component having at least one primary and/or secondary amine and/or amide functional group.

Preferably, the primary and/or secondary amine compound is further characterized by an odor intensity index that is lower than the odor intensity index of a 1% solution of methyl aminobenzoate in dipropylene glycol.

Odor intensity index method

Odor intensity index, meaning dilution of pure chemical to a 1% solution of dipropylene glycol, an odorless solvent used in the fragrance industry. This percentage is more representative of the amount used. A sniff strip, or so-called "blotting paper", is impregnated and submitted to the panelist for evaluation. Panelists were trained for at least 6 months on odor ratings by panellists, verifying the accuracy and reproducibility of their ratings relative to a reference on an existing basis. For each amine compound, two blotters were submitted to the panelists: one reference (methyl aminobenzoate, unknown to panelists) and one sample. Panelists were asked to classify the two smells on a 0-5 odor intensity scale, with 0 being no odor detected and 5 being very strong odor present.

Results

The odor intensity index of the amine compound suitable for use in the present invention according to the above procedure is shown below. In each case, the values are the arithmetic mean of 5 panelists, with statistically significant differences at 95% confidence:

1% (reference) 3.4% methyl aminobenzoate

Ethyl 4-aminobenzoate (EAB) 1% 0.9

The general structure of the primary amine compounds of the present invention is as follows:

B-(NH₂)_nwherein B is a support material and n is an index having a value of at least 1.

The compound containing a secondary amine group has a structure similar to that described above except that the compound contains one or more-NH-groups in place of-NH₂. In addition, the structure of the compound also has one or more NH₂and-NH-groups.

Preferred B carriers are inorganic or organic carriers.

By "inorganic support" is meant a support that is free or substantially free of a carbon-based backbone.

Preferred primary and/or secondary amines in the inorganic carrier are those selected from the group consisting of: amino-derived monomers or polymers of organosilanes, siloxanes, silazanes, alumones, siloxane aluminum or aluminum silicate compounds or organo-organosilicon copolymers. Typical examples of such supports are those having at least one primary amine moiety such as a diaminoalkylsiloxane [ H ]₂NCH₂(CH₃)₂Si]O or organicAmino silane (C)₆H₅)₃SiNH₂Described in polysiloxane Chemistry and Technology of Silicone, w.noll, academic press inc.1998, london, p.209, 106.

In organic carriers, preferred primary and/or secondary amines are those selected from the group consisting of: aminoaryl derivatives, polyamines, amino acids and derivatives thereof, substituted amines and amides, glucosamine, dendrimers, polyvinylamine with MW of 600-50K, amino-substituted polyvinylalcohol with MW of 400-300000, polyoxyethylene bis [ amine ], polyoxyethylene bis [ 6-aminohexyl ], linear or branched N, N' -bis (3-aminopropyl) -1, 3-propanediamine, 1, 4-bis- (3-aminopropyl) piperazine and/or mixtures thereof.

Preferred aminoaryl derivatives are aminobenzene derivatives including alkyl 4-aminobenzoate compounds, more preferably selected from ethyl 4-aminobenzoate, phenethyl 4-aminobenzoate, phenyl 4-aminobenzoate, 4-amino-N' - (3-aminopropyl) benzamide and mixtures thereof.

Polyamines suitable for the present invention are polyethyleneimine polymers, poly [ oxo (methyl-1, 2-ethanediyl) ], α - (2-aminomethylethyl) - ω - (2-aminomethyl-ethoxy) - (═ c.a.s. No. 9046-10-0), poly [ oxo (methyl-1, 2-ethanediyl) ], ethers of α -hydrogen- ω - (2-aminomethylethoxy) -, 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol (═ c.a.s. No. 39423-51-3), commercially available under the trade name Jeffamines T-403, D-230, D-400, D-2000, 2 ', 2 ″ -triaminotriethylamine, 2' -diaminodiethylamine, 3 '-diamino-dipropylamine, commercially available from mitsubishi 1, 3-diaminoethylcyclohexane and commercially available from clariaphas, e, e.g. tail amines such as C12 tail amine (FG 25), commercially available under the trade name PR, 2, 3' -diamino-dipropylamine, commercially available under the trade name luffs, G, PR, f-100G, preferably mixtures thereof, such as lufff, G, pp, dlichi.

Preferred amino acids for use in the present invention are selected from the group consisting of tyrosine, tryptophan, lysine, glutamic acid, glutamine, aspartic acid, arginine, asparagine, phenylalanine, proline, glycine, serine, histidine, threonine, methionine and mixtures thereof, most preferably from the group consisting of tyrosine, tryptophan and mixtures thereof. Preferred amino acid derivatives are selected from the group consisting of tyrosine ethyl ester, glycine methyl ester, tryptophan ethyl ester and mixtures thereof.

Preferred substituted amines and amides for use in the present invention are selected from piperidine carboxamide, N-coco-1, 3-propanediamine; n-oleyl-1, 3-propanediamine; n- (tallowalkyl) -1, 3-propanediamine; 1, 4-diaminocyclohexane; 1, 2-diaminocyclohexane; 1, 12-diaminododecane and mixtures thereof.

Other primary amine compounds suitable for use in the present invention are glucosamine, preferably selected from 2, 3, 4,5, 6-pentamethoxyglucamine; 6-acetylglucosamine, glucosamine, and mixtures thereof.

Also preferred are polyethyleneimines and/or polypropyleneimine dendrimers, commercially available as Starburst^®Polyamidoamine (PAMAM) dendrimers, modified G0-G10 from Dendritech and dendrimers Aatomols^®Improved 1-5 from DSM, which is diaminobutanepolyamine DAB (PA) x dendrimer, x ═ 2ⁿX 4, n is generally 0 to 4.

Other preferred primary and/or secondary amine-containing compounds are amino-functional polymers. Preferred amino-functional polymers for use in the present invention are selected from the group consisting of polyvinylamines, derivatives thereof, copolymers thereof, alkylenepolyamines, polyaminoacids and copolymers thereof, crosslinked polyaminoacids, amino-substituted polyvinylalcohols, polyoxyethylene diamines or bisaminoalkyl, aminoalkylpiperazines and derivatives, straight or branched chain N, N' -bis (3-aminopropyl) -1, 3-propanediamine (TPTA) and mixtures thereof.

Polyamino acids are a suitable and preferred type of amino-functional polymer. Polyamino acids are compounds composed of amino acids or chemically modified amino acids. They may contain alanine, serine, aspartic acid, arginine, valine, threonine, glutamic acid, leucine, cysteine, histidine, lysine, isoleucine, tyrosine, asparagine, methionine, proline, tryptophan, phenylalanine, glutamine, glycine or mixtures thereof. In chemically modified amino acids, the amine or acid functional group of the amino acid reacts with a chemical reagent. This is often used to protect these chemical amine and acid functionalities of the amino acid or to provide special properties to the amino acid, such as improved solubility, in subsequent reactions. Examples of such chemical modifications are benzyloxycarbonyl, aminobutyric acid, butyl ester, pyroglutamic acid. Further examples of common modifications of amino acids and small amino acid fragments can be found in Bachem, 1996, peptide and Biochemical catalogues.

Preferred polyamino acids are polylysine, polyarginine, polyglutamine, polyasparagine, polyserine, polytryptophan or mixtures thereof. Most preferred are polylysines or polyamino acids in which more than 50% of the amino acids are lysine, since the primary amine function of the lysine side chain is the most active amine of all amino acids.

The preferred polyamino acids have a molecular weight of 500-.

The polyamino acid may be crosslinked. The crosslinking may be obtained, for example, by condensing the amino groups on the side chains of amino acids, such as lysine, with carboxyl functions on the amino acids or with protein crosslinking agents such as PEG derivatives. The crosslinked polyamino acids also need to have free primary and/or secondary amino groups that are reactive with the active ingredient.

The molecular weight of the preferred crosslinked polyamino acid is 20000-.

The polyamino acid or amino acid may be copolymerized with other reagents such as acids, amides, acid chlorides. More specifically with aminocaproic acid, adipic acid, ethylhexanoic acid, caprolactam or mixtures thereof. The molar ratio used in these copolymers is from 1: 1 (reagent/amino acid (lysine)) to 1: 20, more preferably from 1: 1 to 1: 10.

Polyamino acids such as polylysine may be partially ethoxylated.

Examples and suppliers of polyamino acids containing lysine, arginine, glutamine, asparagine are given in Bachem, 1996, peptide and biochemical catalog.

The polyamino acid may be obtained in salt form before reaction with the active ingredient. For example, polylysine may be provided as polylysine hydrobromide. Polylysine hydrobromide is commercially available from Sigma, Applichem, Bachem and Fluka.

Examples of suitable amino-functional polymers containing at least one primary and/or secondary amino group for the purposes of the present invention are:

-polyvinylamine with MW of about 300-2.10E 6;

-an alkoxylated polyvinylamine having a MW of about 600, 1200 or 3000, a degree of ethoxylation of 0.5;

-polyvinylamine vinylalcohol-mole ratio of 2: 1, polyvinylamine vinylformamide-mole ratio of 1: 2 and polyvinylamine vinylformamide-mole ratio of 2: 1;

triethylenetetramine, diethylenetriamine, tetraethylenepentamine;

-bisaminopropylpiperazine;

-polyamino acids (L-lysine/lauric acid, molar ratio 10/1), polyamino acids (L-lysine/aminocaproic acid/adipic acid, molar ratio 5/5/1)), polyamino acids (L-lysine/aminocaproic acid/ethylhexanoic acid, molar ratio 5/3/1), polyamino acids (polylysine-co-caprolactam); polylysine hydrobromide; the cross-linked polylysine is a polymer,

-amino substituted polyvinyl alcohol, MW 400-300000;

polyoxyethylene bis [ amine ] available from e.g. Sigma;

polyoxyethylene bis [ 6-aminohexyl ] available from e.g. Sigma;

-linear or branched N, N' -bis (3-aminopropyl) -1, 3-propanediamine (TPTA); and

-1, 4-bis- (3-aminopropyl) piperazine (BNPP).

More preferred compounds are ethyl 4-aminobenzoate, polyethyleneimine polymers commercially available under the following trade names: lupasol, such as Lupasol FG, G20, wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA; glucosamine; diaminobutane dendrimer Astramol^®Polyvinylamine with MW of 600, 1200, 3K, 20K, 25K or 50K; amino-substituted polyvinyl alcohols with MW of 400-300000; polyoxyethylene bis [ amine](ii) a Polyoxyethylene bis[ 6-Aminohexyl group](ii) a Polyamino acids, crosslinked polyamino acids, straight or branched chain N, N' -bis (3-aminopropyl) -1, 3-propanediamine; 1, 4-bis- (3-aminopropyl) piperazine and mixtures thereof. The most preferred primary and/or secondary amine compound is selected from ethyl 4-aminobenzoate, polyethyleneimine polymers commercially available under the following trade names: lupasol, such as Lupasol FG, G20, wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA; diaminobutane dendrimer Astramol^®Straight or branched chain N, N' -bis (3-aminopropyl) -1, 3-propanediamine; 1, 4-bis- (3-aminopropyl) piperazine and mixtures thereof. Even the most preferred compounds are those selected from the group consisting of: 4-aminobenzoic acid ethyl ester, canPolyethyleneimine polymers commercially available under the following trade names: lupasol, such as Lupasol fg, G20, wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA; linear or branched N, N' -bis (3-aminopropyl) -1, 3-propanediamine; 1, 4-bis- (3-aminopropyl) piperazine, polylysine, cross-linked polylysine and mixtures thereof.

Advantageously, such most preferred primary and/or secondary amine compounds also provide fabric appearance effects, particularly color appearance effects, thereby providing the resulting amine reaction product with dual properties: fabric appearance effect and delayed release of actives. In addition, when the primary and/or secondary amine compound has more than one free primary and/or secondary amino group, several different active ingredients (aldehydes and/or ketones) can be attached to the amine compound.

B-active ketones and/or aldehydes

Preferably, with respect to the above compounds, a reactive ketone or a reactive aldehyde means any chain having at least 1 carbon atom, preferably at least 5 carbon atoms.

Preferably the active ketone or aldehyde is selected from the group consisting of a scented ketone or aldehyde component, a pharmaceutical ketone or aldehyde component, a biocontrol ketone or aldehyde agent, a scented ketone or aldehyde component, and mixtures thereof; most preferred are perfume ketones and/or aldehydes.

The aroma component includes a fragrance, a flavoring agent that contributes to the overall aroma sensation.

Pharmaceutically active substances include drugs.

Biological control agents include biocides, antimicrobials, bactericides, fungicides, algicides, mildewcides, disinfectants, cleaning agents such as bleaches, antiseptics, insecticides, insect and/or moth protectants, insect repellents, plant growth hormones.

Typical antimicrobial agents include glutaraldehyde, cinnamaldehyde, and mixtures thereof. Typical insect and/or moth repellents are perfume ingredients such as citronellal, citral, N-diethyl-m-toluamide, Rotundail, 8-acetoxy carvone and mixtures thereof. Further examples of insect and/or moth repellents for use in the present invention are disclosed in U.S. Pat. Nos. 4449987, 4693890, 4696676, 4933371, 5030660, 5196200 and "symptomatic activity of fragrance and fragrance molecules against various insects", B.D. Mokherjee et al, published in Bioactive Volatile Compounds from Plants (Bioactive Volatile Compounds from Plants), ASC proceedings 525, R.Teranishi, R.G. Buttery and H.Sugisawa, 1993, pages 35-48.

A general disclosure of suitable ketones and/or aldehydes which are conventionally used in the perfumery industry can be found in "perfumery and fragrance chemicals", I and II, S.arctander, Allwred Publishing, 1994, ISBNO-931710-35-5.

The perfume ketone component includes a component having fragrance properties.

Preferably, for the above compounds, the flavor ketone is selected from buccodexime, isomerone, methyl β naphthyl ketone, musk indanone, tonane/musk, a-dihydrodamascenone, β -dihydrodamascenone, delta-dihydrodamascenone, isodihydrodamascenone, damascenone, damarone, methyl dihydrojasmonate, menthone, carvone, camphor, fenchone, a-ionone, β -ionone, so-called gamma-methyl ionone, 2-heptyl cyclopentanone, dihydrojasmone, cis-jasmone, iso-E-supreme, methyl-cedronone or methyl cedronone (cedrylone), acetophenone, methylacetophenone, p-methoxyacetophenone, methyl- β -naphthyl ketone, benzyl acetone, benzophenone, p-hydroxyphenyl butanone, apione or livescone, 6-iso-propyldodecahydro-2-naphthalenone, dimethylcinenone, fressoment, 4- (1-ethoxyvinyl) -3, 5-menthone, 3, 5-tetramethyl-3, 5-menthone, 3-tert-menthyl cyclohexanone, 4-3, 3, 5-tetramethyl-menthone, 3, 5-methyl-menthone, 3, 3, 3, 5-tert-butyl ketone, 3, 5-menthone, 3, 5-methyl-menthyl-menthone, 3, 3, 3, 5-tert-menthyl-menthone, 3, 3, 5-menthyl-menthone, 5-menthone, 3, 5-menthyl-menthone, 3, 5-methyl-menthone, 3, 3, 3-menthone, 5-methyl-tert-menthyl-menthone, 3, 7-menthone, 3-methyl-menthone, 3-tert-menthyl-methyl-menthyl-menthone, 3-menthone, 7-methyl-menthone, 3-methyl-menthone, 7-methyl-tert-menthone, 3-methyl-menthone, 3-tert-menthyl-menthone, 3-menth.

More preferably, with respect to the above compounds, preferred ketones are selected from the group consisting of a-damascone, δ -damascone, isodamascone, carvone, γ -methylionone, iso-E-Super, 2, 4, 4, 7-tetramethyl-oct-6-en-3-one, benzyl acetone, β -damascone, methyl dihydrojasmonate, methyl cedryl ketone, methyl dihydrojasmonate and mixtures thereof.

The perfume aldehyde component comprises a component having odor properties.

With regard to the above compounds, preferably the perfume aldehyde is selected from 2, 6, 10-trimethylundecene-9-aldehyde-1; anisic aldehyde; cymal; ethyl vanillin; florydral; piperonyl propionaldehyde; piperonal; hydroxycitronellal; koavone; laurinaldehyde; lyral; methyl nonyl acetaldehyde, p.t. p-tert-butyl-a-methylhydrocinnamaldehyde; phenyl acetaldehyde; undecenal; vanillin; 2, 6, 10-trimethyl-9-undecene aldehyde, 3-dodecene-1-aldehyde, a-n-pentylcinnamaldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) propionaldehyde, 2-methyl-3- (p-methoxyphenyl) propionaldehyde, 2-methyl-4- (2, 6, 6-trimethyl-2 (1) cyclohexen-1-yl) butyraldehyde, 3-phenyl-2-propenal, cis/trans-3, 7-dimethyl-2, 6-octadiene-1-aldehyde, 3, 7-dimethyl-6-octene-1-aldehyde, [ (3, 7-dimethyl-6-octene) oxy ] acetaldehyde, 4-isopropylbenzaldehyde, 1,2, 3, 4,5, 6, 7, 8-octahydro-8, 8-dimethyl-2-naphthaldehyde, 2, 4-dimethyl-3-cyclohexene-1-formaldehyde, 2-methyl-3- (isopropylphenyl) propionaldehyde and 1-decanal; decanal, 2, 6-dimethyl-5-heptenal, 4- (tricyclo [5.2.1.0(2, 6) ] -decylidene-8) -butanal, octahydro-4, 7-methylene-1H-indene formaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, p-ethyl-a, a-dimethylhydrocinnamaldehyde, a-methyl-3, 4- (methylenedioxy) hydrocinnamaldehyde, 3, 4-methylenedioxybenzaldehyde, a-n-hexylcinnamaldehyde, isopropylbenzene-7-formaldehyde, a-methylphenylcarbaldehyde, 7-hydroxy-3, 7-dimethyloctanal, undecenal, 2, 4, 6-trimethyl-3-cyclohexene-1-formaldehyde, 4- (3) (4-methyl-3-pentenyl) -3-cyclohexene carboxaldehyde, 1-dodecanal, 2, 4-dimethylcyclohexene-3-carbaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde, 7-methoxy-3, 7-dimethyloctan-1-al, 2-methylundecanal, 2-methyldecanal, 1-nonanal, 1-octanal, 2, 6, 10-trimethyl-5, 9-undecadinaldehyde, 2-methyl-3- (4-tert-butyl) propanal, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carbaldehyde, a salt thereof, a hydrate thereof, a salt thereof, a hydrate thereof, 5 or 6 Methoxyhexahydro-4, 7-methano-1, 2-indan-1 or 2-carbaldehyde, 3, 7-dimethyloctan-1-al, 1-undec-al, 10-undecene-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexenealdehyde, 7-hydroxy-3, 7-dimethyloctanal, trans-4-decenal, 2, 6-nonadienal, p-tolylacetaldehyde, 4-methylphenylacetal, 2-methyl-4- (2, 6, 6-trimethyl-1-cyclohexen-1-yl) -2-butenal, 2-methylbutenal, 2-butenal, 5-butenylaldehyde, 6-butenylaldehyde, 2-butenylaldehyde, 5-butenylaldehyde, 6-butenylaldehyde, 1, N-methoxycinnamaldehyde, 3, 5, 6-trimethyl-3-cyclohexenealdehyde, 3, 7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5, 9-dimethyl-4, 8-decadienal, paeonifloraldehyde, (6, 10-dimethyl-3-oxa-5, 9-undecadiene-1-al), hexahydro-4, 7-methylene-1, 2-indan-1-carbaldehyde, 2-methyloctanal, a-methyl-4- (1-methylethyl) phenylacetaldehyde, 6-dimethyl-2-norpinene-2-propionaldehyde, p-methylphenoxyacetal, 2-methyl-3-phenyl-2-propen-1-al, p-methyloxypropanal, n-methyloxa-2-propen, 3, 5, 5, -trimethylhexanal, hexahydro-8, 8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo [2.2.1] -hept-5-ene-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonyl acetaldehyde, 1-p-menthene-q-carbaldehyde, citral, lilial and mixtures thereof.

The most preferred aldehydes are selected from the group consisting of citral, 1-decanal, benzaldehyde, florydral, 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde, cis/trans-3, 7-dimethyl-2, 6-octadien-1-al, piperonal, 2, 4, 6-trimethyl-3-cyclohexene-1-carbaldehyde, 2, 6-nonadienal, a-n-pentylcinnamaldehyde, a-n-hexylcinnamaldehyde, p.t. p-tert-butyl-a-methylhydrocinnamaldehyde, lyral, cymal, methylnonylacetaldehyde, trans-2-nonenal, lilial, trans-2-nonenal and mixtures thereof.

Some of the perfume ingredients listed above are conventional trade names well known to those skilled in the art and also include isomers. Such isomers are also suitable for use in the present invention.

In another embodiment, particularly suitable for the purposes of the present invention are perfume compounds, preferably perfume ketones or active aldehydes, characterized by a low odor detection threshold. Such Odor Detection Threshold (ODT) should be less than 1ppm, preferably less than 10ppb, as determined under controlled Gas Chromatography (GC) conditions, e.g., as described below. Such parameters are assigned to the values conventionally used in the perfumery field, which are the lowest concentrations of some odorous substances present at which a clear perception occurs. Reference is made to, for example, "Odor and Taste Threshold data compilation (ASTM DS 48A)" (compatibility of Odor and Taste Threshold Value data (ASTM DS 48A) ", by f.a. fazzalari, International Business Machines, hopwell junction, NY editions and examples in Calkin et al (Perfumery, Practice and Principles), John Willey & Sons, inc. page 243 and below (1994). for the purposes of this invention, Odor detection thresholds are determined according to the following method:

gas chromatography is characterized by the ability to determine the exact volume of material injected by the injector, the precise split ratio, and hydrocarbon sensitivity using standard hydrocarbons of known concentration and chain length distribution. The air flow rate was accurately measured and the sample volume was calculated assuming a human inhalation duration of 0.02 minutes. Since at any time the exact concentration in the detector is known, the amount inhaled per unit volume is known and therefore the concentration of the material is also known. To determine the ODT of the fragrance material, the solution was delivered to the air entry port at the later calculated concentration. An expert panel sniffs the GC gas stream and determines the residence time when the odor was perceived. The threshold for perceptibility was determined by the average of all panelists in the panel. The required amount of analyzer is injected into the column to obtain a determined concentration, e.g. 10ppb, on the detector. Typical gas chromatography parameters that determine the threshold for odor detection are as follows:

GC: 5890 series II with FID detector

7673 automatic sampler

Column: j & W Scientific DB-1

Length 30 m, ID0.25mm, film thickness 1 micron

The method comprises the following steps:

shunting injection: 17/1 split ratio

An automatic sampler: 1.13 microliter/injection

Column flow rate: 1.10 ml/min

Air flow rate: 345 ml/min

Inlet temperature: 245 DEG C

Detector temperature: 285 deg.C

Temperature information

An initial temperature; 50 deg.C

Speed: 5 ℃ per minute

Final temperature: 280 deg.C

The final time is as follows: 6 minutes

The main premise is as follows: each sample dilution of GC air was aspirated for 0.02 minutes

Examples of such preferred fragrance components are those selected from the group consisting of 2-methyl-2- (p-isopropylphenyl) propanal, 1- (2, 6, 6-trimethyl-2-cyclohex-1-yl) -2-butenone and/or p-methoxyacetone, even more preferred are compounds having ODT ≦ 10ppb of undecenal, gamma undecalactone, piperonal, gamma dodecanolactone, p-anisaldehyde, p-hydroxyphenylbutanone, cymal, benzyl acetone, a-ionone, P.T. p-tert-butyl-a-methylhydrocinnamaldehyde, damascenone, β ionone and methylnonyl ketone, as determined by the method described above.

Typically, the active will be present in an amount of from 10% to 90%, preferably from 30% to 85%, more preferably from 45% to 80% by weight of the amine reaction product.

Preferred amine reaction productsThe articles are those having the dry surface odor index given in the pending application EP98870155.3, page 29, line 26 to page 32, line 29, wherein the specified unperfumed binders for textile surfaces and hard surfaces are respectively as follows:

composition for fabric surface testing	% by weight
		LAS	16
NaSKS-6	6
		PB1	8
TAED	2.4
		Carbonate salt	1
Sodium carbonate	1
		HEDP	0.4
SRP1	0.2
		Photobleaches	0.013
Citric acid	1.0
		Protease enzyme	0.3
Lipase enzyme	0.1

Cellulase enzymes	0.1
		Amylase	0.3
Zeolite	3.0
		TFAA	3.0
QAS1	2.5
		Polysiloxane antifoaming agent	1.0
Balance of other/auxiliary substances to 100%

Composition for hard surface testing	% by weight
		C12-14EO21	2
C12-14EO5	2.5
		C9-11EO5	2.5
LAS	0.8
		Na2CO3	0.2
Citric acid	0.8
		Caustic acid	0.5
Fatty acids	0.5
		SCS	1.5
Water (W)&Other/auxiliary substances are balanced to100％

The most preferred amine reaction products are those obtained from the reaction of polyethyleneimine polymers such as Lupasol polymers, BNPP or TPTA with one or more of the following compounds: a-damascone, delta-damascone, carvone, gamma-methyl ionone, methyl dihydrojasmonate, florydral, lilial, piperonal and 2, 4-dimethyl-3-cyclohexene-1-formaldehyde. Other yet preferred amine reaction products are those resulting from the reaction of Astramol dendrimer with carvone and those resulting from the reaction of ethyl 4-aminobenzoate with one or more of 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde and trans-2-nonenal. Another preferred amine reaction product is that resulting from the reaction of polylysine with one or more of a-damascone, delta-damascone, carvone, and 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde.

Even the most preferred amine reaction products are those obtained by reacting Lupasol HF with delta-damascone, Lupasol G35 with alpha-damascone, Lupasol G100 with 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde, BNPP or TPTA with α and delta-damascone, ethyl 4-aminobenzoate with 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde.

2) -a vector

Another essential component of the process of the invention is a carrier having a melting point of from 30 ℃ to 135 ℃, preferably from 45 ℃ to 85 ℃. By the action of the carrier, particles of the amine reaction product will be produced.

Suitable carriers for use in the process of the invention are components such as: organic polymeric compounds, waxes, paraffins, oils, glycerides, monoglycerides, diglycerides, triglycerides, anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures thereof, preferably selected from the group consisting of organic polymeric compounds, nonionic surfactants and mixtures thereof.

Preferred organic polymeric compounds suitable for mixing with the primary and/or secondary amine compounds of the present invention include polyethylene glycols and derivatives thereof, particularly those having a molecular weight of 1000-10000, more preferably 2000-8000, and most preferably about 4000.

Essentially any nonionic surfactant useful for detersive purposes can be included in the composition, provided that its melting point is in the range of 30 ℃ to 135 ℃.

Illustrative, non-limiting types of useful nonionic surfactants are listed below: nonionic polyhydroxy fatty acid amide surfactants

Polyhydroxy fatty acid amides suitable for use in the present invention are those having the following structural formula: r²CONR¹Z, wherein R¹Is H, C₁-C₄Hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, preferably C₁-C₄Alkyl, more preferably C₁Or C₂Alkyl, most preferably C₁Alkyl (i.e., methyl); r²Is C₅-C₃₁Hydrocarbyl, preferably straight chain C₅-C₁₉Alkyl or alkenyl, more preferably straight-chain C₉-C₁₇Alkyl or alkenyl, most preferably straight chain C₁₁-C₁₇Alkyl or alkenyl, or mixtures thereof; z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl group with at least 3 hydroxyl groups directly attached, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycosyl group. Nonionic alkylphenol condensates

Polyoxyethylene, polyoxypropylene and polyoxybutylene condensates of alkyl phenols are suitable for use in the present invention. In general, polyoxyethylene condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 18 carbon atoms in either a straight or branched chain configuration with alkylene oxide, condensed with from about 1 to about 150 moles of alkylene oxide per mole of alcohol. Nonionic ethoxylated alcohol surfactants

Alkyl ethoxylated condensation products of fatty alcohols with from about 1 to about 150 moles of ethylene oxide are suitable for use in the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, may be primary or secondary, and typically contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 25 to about 150 moles of ethylene oxide per mole of alcohol, preferably from 50 to 100 moles, more preferably 80 moles, of ethylene oxide per mole of alcohol.

Preferred nonionic ethoxylated alcohol surfactants are selected from tallow (C16-C18) alcohols ethoxylated with 25, 50, 80 or 100 moles of ethylene oxide, commercially available from BASF under the trade name Lutensol, from Albright and Wilson under the trade name Empilan, and from Clariant under the trade name Genapol. The most preferred nonionic ethoxylated alcohol surfactants are tallow (C16-C18) alcohols ethoxylated with 80 moles of ethylene oxide and are commercially available from BASF under the trade name Lutensol80/80, from Albright and Wilson under the trade name Empilan KM80, or from Clariant under the trade name Genapol T800. Nonionic ethoxylated/propoxylated fatty alcohol surfactants

Ethoxylated C6-C22 fatty alcohols and C6-C22 mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use in the present invention, particularly where water soluble. Preferably, the ethoxylated fatty alcohol is a C10-C22 ethoxylated fatty alcohol having a degree of ethoxylation of from 25 to 150, and most preferably a C12-C18 ethoxylated fatty alcohol having a degree of ethoxylation of from 50 to 80. Preferably, the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30, and a degree of propoxylation of from 1 to 30. Nonionic EO/PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of compounds of this type include some commercially available pluronics^TMSurfactant, sold by BASF. Nonionic EO condensation products with propylene oxide/ethylenediamine adducts

Products of the condensation of ethylene oxide with the product obtained by the reaction of propylene oxide and ethylenediamine are suitable for use in the present invention. The hydrophobic portion of these products is comprised of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of from about 2500 to about 3000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic surfactants^TMCompound, sold by BASF. Nonionic alkyl polysaccharide surface activitySex agent

Suitable alkylpolysaccharides for use in the present invention are disclosed in U.S. Pat. No. 4,565,647 to Llenado issued on 21.1.1986 and 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 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example the glucosyl moiety can be substituted with glucose, galactose and galactosyl moieties (the hydrophobic group is optionally attached at the 2-, 3-, 4-, etc. position, thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide linkage may be, for example, between the 2-, 3-, 4-and/or 6-position of the preceding saccharide unit and a position of another saccharide unit.

Preferred alkylpolyglycosides have the formula:

R²O(C_nH_2nO)_t(sugar base)_xWherein R is²Selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is 0 to 10, preferably 0; x is 1.3 to 8, preferably 1.3 to 3, most preferably 1.3 to 2.7. The glycosyl is preferably derived from glucose. Nonionic fatty acid amide surfactants

Fatty acid amide surfactants suitable for use in the present invention are those having the formula: r⁶CON(R⁷)₂Wherein R is⁶Is an alkyl group containing 7 to 21, preferably 9 to 17, carbon atoms, each R⁷Selected from hydrogen, C₁-C₄Alkyl radical, C₁-C₄Hydroxyalkyl and- (C)₂H₄O)_xH, wherein x is 1-3.

Preferred carrier materials are selected from nonionic ethoxylated alcohol surfactants.

Typically, when the amine reaction product is merely admixed with the carrier without further processing, the amine reaction product is present in the resulting particles in an amount of from 1% to 75%, preferably from 10% to 60%, more preferably from 15% to 45% by weight of the processed reaction product. In this case, the amount of carrier will be sufficient to add up to 100%. Of course, the particles may also contain auxiliary substances, but in amounts not exceeding the amount of carrier material. Generally, the carrier will be present in the processed amine reaction product in an amount of from 3% to 95%, preferably from 15% to 80%, most preferably from 25% to 75% by weight of the particles produced.

The processing of the amine reaction product with the support is accomplished by thoroughly mixing the amine reaction product with the support. Advantageously, no additional components are required to facilitate obtaining a substantially homogeneous mixture. This mixing is carried out at the lowest possible temperature, i.e. just above the melting point of the carrier. The mixing step is carried out until a completely homogeneous mixture is obtained. By "homogeneous" is meant that the composition has a similar appearance to a composition made from 20 grams of the amine reaction product mixed with 80 grams of TAE80 by an Ultra Turrax for 5 minutes at a mixing temperature of about 70 ℃. Film coating agent

When a carrier having a melting point of 35 ℃ to 135 ℃ is used to mix with the amine reaction product, the mixture is then preferably further processed into encapsulated particles, for example by adsorbing the mixture into a solid, preferably porous, coating agent. The resulting encapsulated particles may be in any form suitable for incorporation into a liquid or powder, preferably a powder such as an agglomerate, pellet, tablet or mixture thereof.

For solids, including pastes, and liquid mixtures, suitable film-forming agents are substantially water-soluble solid binders or agglomerating agents.

By "substantially water soluble" is meant that the material is dissolved in distilled (or equivalent) water at 25 ℃ to a concentration of 0.2% by weight, preferably 1.0% by weight.

"solid" is defined as a material that is solid at room temperature, so the substantially water-soluble solid binder or agglomerating agent must have a melting point of at least 30 ℃, preferably at least 40 ℃.

Suitable water-soluble binders or agglomerating agents include water-soluble organic polymeric compounds, water-soluble monomeric polycarboxylates or acid forms thereof, homo-or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by no more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, sulfates such as sodium sulfate and magnesium sulfate, inorganic perhydrate salts, including perborates such as perborate monohydrate, percarbonates, silicates, starches, cyclodextrins and mixtures of any of the foregoing.

Organic polymeric compounds suitable as coating agents include cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and hydroxyethyl cellulose, and carbohydrates such as pectin and gums. Other compounds are carbohydrates and derivatives such as polymers based on fructose, xylose, galactose, galacturonic acid or glucose such as inuline, dextran, xyloglucose, pectin or gums.

Suitable carboxylic acid salts containing one carboxyl group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, glyoxylic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxyl groups include especially the water soluble citrates, aconitates and citraconates, and succinate derivatives such as the carboxymethoxysuccinate salt described in UK 1,379,241, the lactyloxy succinate salt described in UK 1389732, the aminosuccinate salt described in Netherlands 7205873, and the oxypolycarboxylate material described in UK 1,387,447, for example 2-oxa-1, 1, 3-propane tricarboxylate.

Polycarboxylates containing four carboxy groups include oxydisuccinates as described in British patent 1,261,829, as well as 1, 1,2, 2-ethane tetracarboxylates, 1,3, 3-propane tetracarboxylates and 1, 1,2, 3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include sulfosuccinate derivatives as described in british patents 1,398,421 and 1,398,422 and U.S. patent 3,936,448, and sulfonated pyrolized citrates as described in british patent 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis-tetracarboxylates, cyclopentadiene pentacarboxylates, 2, 3, 4, 5-tetrahydrofuran-cis, cis-tetracarboxylates, 2, 5-tetrahydrofuran-cis-dicarboxylates, 2, 5, 5-tetrahydrofuran-tetracarboxylates, 1,2, 3, 4,5, 6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include derivatives of melilite, 1,2, 4, 5-benzenetetracarboxylic and phthalic acids as disclosed in British patent No.1,425,343.

Of these compounds, the preferred polycarboxylates are hydroxycarboxylic acid salts containing up to three carboxyl groups per molecule, more particularly citrates.

Borates and borate-forming builder materials which produce borates under detergent storage or wash conditions may also be used, but are not preferred under wash conditions of less than about 50 ℃, especially less than about 40 ℃.

Examples of carbonates are alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof, and the ultrafine calcium carbonate disclosed in german patent application 2321001 published in 1973 on 11-15.

Specific examples of water-soluble phosphates are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate having a degree of polymerization of about 6 to 21, and phytates.

Suitable silicates include water-soluble sodium silicate, SiO thereof₂∶Na₂The O ratio is 1.0 to 2.8, preferably 1.6 to 2.4, most preferably 2.0. The silicate may be in the form of an anhydrous salt or a hydrated salt. The most preferred silicate is SiO₂∶Na₂Sodium silicate with an O to 2.0 ratio.

General disclosures of cyclodextrin derivatives are disclosed in WO 96/05358; U.S. patent 3426011 to Parmerter, issued on 2, 4, 1969; 3453257, respectively; 3453258, respectively; 3453259 and 3453260, all of which are signed Parmerter et al and were issued on 7/1/1969; 3459731 by Gramera et al, granted 8/5/1969; 3553191 by Parmerter, granted on 5.1.1971; 3565887 by Parmerter et al, entitled 2/23/1971; 4535152 of Szejtli et al, granted 8/13/1985; 4616008 by Hirai et al, granted 10/7/1986; 4678598 of Ogino et al, granted 7.7.1987; 4638058 issued to Brandt et al, on 20.1.1987; and 4746734 by Tsuchiyama et al, entitled 24/5/1988; all of which are incorporated herein by reference.

Partially water soluble film coating agents, although less preferred in the present invention because of their lower solubility, may also be used as film coating agents. These compounds are in fact less preferred, since the amine reaction product is still at least partially encapsulated during the washing stage and therefore does not show its full efficacy in maintaining a lasting freshness on dry or hard surfaces. Examples of partially water-soluble film coating agents include crystalline layered silicates. Examples of substantially water-insoluble builders include sodium aluminosilicate.

The crystalline layered sodium silicate has the following general formula

NaMSi_xO_x＋1-yH₂O, wherein M is sodium or hydrogen, x is 1.9-4, and y is 0-20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and processes for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above formula is 2, 3 or 4, preferably 2. The most preferred material is delta-Na₂Si₂O₅Commercially available from Hoechst AG as NaSKS-6.

Suitable aluminosilicate zeolites have the unit cell formula Na_z[(AlO₂)_z(SiO₂)_y]-xH₂O, wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.5, and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material may be in hydrated form, preferably crystalline, containing 10 to 28%, preferably 18 to 22% bound water.

The aluminosilicate ion exchange material may be a natural product, but is preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available as registered zeolites A, B, P, X, MAP, HS and mixtures thereof. Zeolite a has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]-xH₂o wherein x is 20 to 30, especially 27. Zeolite X has the formula: na (Na)₈₆[(AlO₂)₈₆(SiO₂)₁₀₆]-276H₂O。

Typically, when the amine reaction product is mixed with a carrier and further processed to form an encapsulated particle, the amine reaction product is present in the resulting particle in from 1% to 75%, preferably from 5% to 30%, more preferably from 6% to 25% by weight of the processed reaction product.

Generally, the coating agent will be present at a level of from 10% to 95%, preferably from 30% to 90%, more preferably from 50% to 70% by weight of the processed amine reaction product particles. In this case, the amount of carrier will be sufficient to add up to 100%. Of course, the encapsulated particles may also contain adjuvants, but in amounts not exceeding the amount of carrier material or film coating agent.

Preferred coating materials are selected from the group consisting of carbonates, starches, cyclodextrins and mixtures thereof.

The surface treatment of the particles can be carried out in a number of ways using equipment known in the art, and the process can be carried out in a batch or continuous manner.

One method of applying the coating material includes an agglomeration process. Any conventional agglomerator/mixer may be used, but is not limited to kettle, drum and vertical stirrer types. The molten coating composition can also be applied by pouring or atomized spraying onto a moving bed of the mixture of amine reaction product and carrier.

Another method of applying the film-coating agents is to pour the resulting mixtures (so-called granules) into the film-coating material and agglomerate them in a Braun mixer, as described above. Care is also taken that the temperature during the mixing and/or film coating step does not substantially exceed the melting point of the carrier material. For example, 150g of a mixture containing TAE80 and 20% amine reaction product was poured into a Braun mixer containing 300g of carbonate at 60 ℃. The components were mixed for about 5 minutes. Care is taken to ensure that the temperature during coating does not exceed 65 ℃. The agglomerated particles are then incorporated into the finished composition.

Thus, there is provided a processed amine reaction product resulting from the process of the present invention.

If desired, the encapsulated particles may also contain one or more additional components, such as surfactants, for improved solubility or dispersibility. Such surfactants are typically anionic, nonionic or cationic surfactants. Preferably, the weight ratio of such additional components to the film coating agent is up to 1: 1.

In another preferred embodiment, an additional coating film can be provided on the encapsulated particles, which, depending on the nature of the additional coating film, leads to improved storage stability, flowability and/or improved affinity of the fabric for the encapsulated particles. A typical example is polyvinyl alcohol. Incorporated into finished compositions

The finished compositions of the present invention, including laundry compositions, hard surface cleaning compositions, personal cleansing compositions, comprise the processed amine reaction product described herein above and one or more laundry or cleaning ingredients incorporated into the finished composition.

As noted above, depending on the final form of the processed amine reaction product, it may be conveniently incorporated by spraying when in a sprayable liquid form, and by dry blending when in an encapsulated form.

Laundry compositions include laundry detergent compositions, including liquid, solid forms such as powders, tablets, and softening compositions, including rinse-added softening compositions and dryer-added softening compositions.

Conventional disclosures of softening components for use in the softening compositions of the present invention may be found in EP98870227.0, which is incorporated herein by reference.

Preferably, the finished composition is a detergent composition, more preferably in solid form.

The finished composition incorporating the processed amine reaction product typically contains from 0.1% to 25%, more preferably from 0.2% to 10%, most preferably from 0.5% to 5% by weight of the composition of the processed product.

Preferred detergent compositions in embodiments of the present invention preferably comprise a bleach precursor required to form a peroxyacid bleach material in the wash solution, a source of alkaline hydrogen peroxide, and preferably further comprise other conventional components of detergent compositions. Thus, preferred detergent compositions will incorporate one or more surfactants, organic and inorganic builders, soil suspending and anti-redeposition agents, suds suppressors, enzymes, optical brighteners, photoactivated bleaches, perfumes, dyes, clay softeners, sudsing agents and mixtures thereof.

A general disclosure of such components is found in EP-A-0659876 and European patent application 98870226.2, both of which are incorporated herein by reference. Clay clay

The compositions of the present invention may preferably contain clay, preferably in an amount of from 0.05% to 40%, more preferably from 0.5% to 30%, most preferably from 2% to 20% by weight of the composition. For clarity, it should be noted that the term clay mineral compound as used herein excludes sodium aluminosilicate zeolite builder compounds, which, however, may be included as an optional component in the compositions of the present invention.

One preferred clay may be bentonite. Highly preferred are smectites, such as those disclosed in U.S. Pat. Nos. 3862058, 3948790, 3954632 and 4062647 and in European patents EP-A-299575 and EP-A-313146, all of which are assigned to the Procter and Gamble company.

The term smectite herein includes clays with alumina present in the silicate lattice and clays with magnesia present in the silicate lattice. Smectites tend to adopt an expandable three-layer structure.

Specific examples of suitable smectites include those selected from the following types: montmorillonite, hectorite, volkonskoite, nontronite, saponite and sauconite, especially those having alkali metal or alkaline earth metal ions in the crystal lattice structure. Sodium or calcium montmorillonite is particularly preferred.

Suitable smectites, particularly montmorillonite, are sold by various suppliers, including EnglissHina Clays, Laviosa, Georgia Kaolin and Colin Stewartminerals.

The clay used in the present invention preferably has a particle size of 10nm to 800nm, more preferably 20nm to 500mm, most preferably 50nm to 200 mm.

The clay mineral compound particles may be included as a component of agglomerated particles containing other detergent compounds. When such components are present, the term "maximum particle size" of the clay mineral compound refers to the maximum size of such clay mineral components, and not to the size of the total agglomerated particles.

Substitution of small cations, such as protons, sodium ions, potassium ions, magnesium ions, and calcium ions, and certain organic molecules including those functional groups having a positive charge, can generally occur in the crystal lattice structure of the smectite. Clays are selected for their ability to preferentially adsorb one type of cation, as measured by relative ion exchange capacity. Smectites suitable for the present invention have a cation exchange capacity of at least 50meq/100 g. Us patent 3954632 describes a method for determining the cation exchange capacity.

The crystal lattice structure of the clay mineral compound, in a preferred embodiment, may have substituted cationic fabric softeners therein. Such substituted clays are referred to as 'hydrophobically activated' clays. The cationic fabric softener is generally present in a weight ratio to clay of from 1: 200 to 1: 10, preferably from 1: 100 to 1: 20. Suitable cationic fabric softeners include water-insoluble tertiary amine or di-long chain amide materials such as those disclosed in GB-A-1514276 and EP-B-0011340.

A preferred commercially available "hydrophobically activated" clay is bentonite clay containing about 40% by weight dimethyl ditallow quaternary ammonium salt, which is sold under the trade name Claytone EM by English Chinacales International.

In a highly preferred embodiment of the invention, the clay is present in an intimate mixture or particle with the wetting agent and the hydrophobic compound, preferably paraffin or oil, e.g. paraffin oil. Preferred humectants are organic compounds including propylene glycol, ethylene glycol, dimers or trimers of ethylene glycol, most preferably glycerol. The particles are preferably agglomerates. Alternatively, the particles may be such that the wax or oil and optionally the wetting agent form an encapsulation on the clay, or alternatively, the clay is an encapsulation of the wax or oil and the wetting agent. Preferably, the particles comprise an inorganic salt or silica or silicate.

However, in another embodiment of the invention, the clay is preferably mixed with one or more surfactants and optionally with builders and optionally with water, in which case the mixture is preferably subsequently dried. Preferably, this mixture is further processed by spray drying to give spray dried granules comprising clay.

Preferably, a flocculating agent is also included in the clay-containing particles or granules.

It is also preferred that the intimate mixture comprises a chelating agent. Flocculating agent

The compositions of the present invention may contain clay flocculating agents, preferably in an amount of from 0.005% to 10%, more preferably from 0.05% to 5%, most preferably from 0.1% to 2% by weight of the composition.

Clay flocculants function, for example, to aggregate clay compound particles in a wash solution, thus aiding their deposition onto the surface of the fabrics being washed. The requisite for this function is therefore different from clay dispersant compounds, which are typically added to laundry detergent compositions to aid in the removal of clay soils from fabrics and to disperse them in the wash solution.

Preferred as the clay flocculant of the present invention are organic polymeric materials having an average molecular weight of 100000-10000000, preferably 150000-5000000, more preferably 200000-2000000.

Suitable organic polymeric materials include homopolymers or copolymers containing monomer units selected from: alkylene oxides, in particular ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinylpyrrolidone and ethyleneimine. Particular preference is given to homopolymers of ethylene oxide, and also homopolymers of acrylamide and acrylic acid.

European patents EP-A-299575 and EP-A-313146, both of the Procter and Gamble Company, describe preferred organoclay flocculants for use in the present invention.

The weight ratio of clay to flocculating polymer is preferably from 1000: 1 to 1: 1, more preferably from 500: 1 to 1: 1, most preferably from 300: 1 to 1: 1, or even more preferably from 80: 1 to 10: 1, or in some applications, even from 60: 1 to 20: 1.

Inorganic clay flocculants are also suitable for use in the present invention, typical examples of which include lime and Ming's rock.

The flocculating agent is preferably present in a detergent base particle, such as a detergent agglomerate, extrudate or spray-dried particle, typically comprising one or more surfactants and builders. Foaming agent

Foaming agents may also optionally be used in the compositions of the present invention.

Foaming, as defined herein, means that carbon dioxide gas is generated as a result of a chemical reaction between a soluble acid source and an alkali metal carbonate, resulting in gaseous bubbles emanating from the liquid,

namely:

additional examples of acid and carbonate sources and other blowing agent systems can be found in: (pharmaceutical dosage form: TablePail 1, p 287-291). Carbonate salt

Suitable alkali metal and/or alkaline earth metal inorganic carbonates herein include potassium, lithium, sodium carbonates and bicarbonates and the like, with sodium carbonate and potassium carbonate being preferred. Suitable bicarbonates for use in the present invention include any alkali metal bicarbonate such as lithium, sodium, potassium and the like, with sodium and potassium bicarbonates being preferred. However, depending on the desired pH in the aqueous medium in which the particles are dissolved, a carbonate or bicarbonate salt or a mixture thereof may be selected. For example, when a relatively high pH is desired in the aqueous medium (e.g., above pH9.5), it may be preferred to use carbonate alone or a mixture of carbonate and bicarbonate, where the amount of carbonate is higher than the amount of bicarbonate. The inorganic alkali and/or alkaline earth metal carbonate of the composition of the present invention preferably comprises potassium or more preferably sodium carbonate and/or bicarbonate. Preferably, the carbonate salt comprises sodium carbonate, optionally also sodium bicarbonate.

The inorganic carbonate is preferably present in an amount of at least 20% by weight of the composition. Preferably, they are present in an amount of at least 23% or even 25% or even 30%, preferably up to about 60% by weight, or more preferably up to 55% or even 50% by weight.

They may be incorporated wholly or in part as separate powder or granular components, as composite particles with other detergent components such as other salts or surfactants. In the solid detergent compositions of the present invention they may also be present wholly or partly in detergent particles such as agglomerates or spray-dried granules.

In one embodiment of the invention, a source of blowing agent is present, preferably including an organic acid such as a carboxylic acid or amino acid, and a carbonate. It is preferred that some or all of the carbonate herein is premixed with the organic acid and is therefore present in a separate particulate component.

Preferred sources of foaming agent are selected from citric acid and carbonate salts, optionally with a binder, compressed granules; and particles of carbonate, bicarbonate and malic or maleic acid in a weight ratio of 4: 2: 4. Preferably, a dry additive form of citric acid and carbonate is used.

The carbonate may have any particle size. In one embodiment, especially when the carbonate is present in the particles and not as a separately added compound, the carbonate preferably has a volume average particle size of 5-375 microns, whereby preferably at least 60%, preferably at least 70% or even at least 80%, or even at least 90% by volume has a particle size of 1-425 microns. More preferably, the carbon dioxide source has a volume average particle size of 10 to 250, whereby preferably at least 60%, or even at least 70%, or even at least 80%, or even at least 90% by volume has a particle size of 1 to 375 microns; or even preferred is a volume average particle size of 10 to 200 microns, whereby preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume has a particle size of 1 to 250 microns.

Especially when the carbonate is added as a separate component, that is "dry added" or mixed into other detergent components, the carbonate may have any particle size, including the particle sizes specified above, but preferably has a volume average particle size of at least 200 microns or even 250 microns or even 300 microns.

Preferably, the source of carbon dioxide having the desired particle size is obtained by grinding a larger particle size material, optionally followed by selection of the material having the desired particle size by any suitable method.

Although percarbonates may be present in the compositions of the present invention as bleaching agents, they are not included in the carbonates as defined herein.

Other preferred optional ingredients include enzyme stabilizers, polymeric soil release agents, effective materials to inhibit dye transfer from one fabric to another during laundering (i.e., dye transfer inhibitors), polymeric dispersing agents, suds suppressors, optical brighteners or other brightening or whitening agents, antistatic agents, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, and solid fillers for bar compositions.

In another aspect of the present invention, there is provided a packaged composition comprising a processed product or composition of the present invention. Preferably, the packaging composition is a closed packaging system having a moisture vapor transmission rate of less than 20g/m²And/24 hours. A general disclosure of such a package can be found in WO 98/40464.

In another embodiment of the invention, the package is a spray device. A general disclosure of such sprinklers can be found in WO96/04940, page 19, line 21 to page 22, line 27. Application method

The invention also provides a method of delaying the release of an active ketone or aldehyde comprising the step of contacting the surface to be treated with a compound or composition of the invention, followed by contacting the treated surface with a substance, preferably an aqueous-based medium such as water or any other means capable of releasing a fragrance from an amine reaction product.

By "surface" is meant any surface on which a compound may be deposited. Common examples of such materials are fabrics, hard surfaces such as dishware, floors, bathrooms, toilets, kitchens and other surfaces where delayed release of perfume ketones or aldehydes is desired, for example, where waste such as animal waste is desired. Preferably, the surface is selected from the group consisting of fabric, tile, porcelain; more preferably a fabric.

By "delayed release" is meant release of the active ingredient (e.g., perfume) over a longer period of time than by use of the active (e.g., perfume) itself.

In a further aspect of the invention there is provided the use of a product of the invention for the preparation of a laundry and cleaning composition which provides residual fragrance and fabric care, especially dye care, to fabrics to which it is applied.

The following are examples of the synthesis of compounds defined in the present invention:

synthesis reaction of ethyl I.4-aminobenzoate and 2, 4-dimethyl-3-cyclohexene-1-formaldehyde

To an ice-cold stirred solution of 10g of 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde (0.07 mol) in 35ml of EtOH and molecular sieves (4 , 20g) was added 1 equivalent of amine via the addition funnel. The reaction mixture was stirred under nitrogen atmosphere and protected from light. After 6 days, the mixture was filtered and the solvent was removed. The yield of imine formed was about 90%.

Similar results were obtained by replacing 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde with bourgeonal, trans-2-nonenal or trans-2-hexenal.

Synthesis reaction of II, 1, 4-bis- (3-aminopropyl) piperazine and α -dihydrodamascenone

To replace the primary amine group with perfume, 1 equivalent of amino functional polymer was used 2 equivalents of perfume to an ice cold stirred solution of 1mmol α -damascone and molecular sieve (4 , 20g) in 6ml EtOH, 0.5 equivalent of 1, 4-bis- (3-aminopropyl) piperazine was added through an addition funnel the reaction mixture was stirred under nitrogen and protected from light illumination the mixture was filtered and the solvent removed by vacuum distillation after disappearance of the absorption peak of the free perfume on the NMR spectrum (3-16 hours) yielding β -aminoketone of about 90%.

Similar results were obtained when α -dihydrodamascone was replaced with 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde, vertectral, bourgeonal, delta-dihydrodamascone or citronellal.

III synthesis reaction of Lupasol, damascenone and 2, 4-dimethyl-3-cyclohexene-1-formaldehyde

β -aminoketones were prepared from Lupasol G100 (commercially available from BASF, containing 50% water, 50% Lupasol G100(Mw5000)) and a-damascone (or delta-damascone) using any of these three different methods as described below:

1. commercial Lupasol G100 was dried using the following method: 20g of Lupasol solution are dried on a rotary evaporator for several hours. The residue obtained still contained about 4.5gH₂O, using toluene on a rotary evaporatorAnd (4) performing azeotropic distillation. The residue was then placed in a desiccator (using P) which was dried at 60 deg.C₂O₅As a water absorbing material). From the weights obtained, we deduced that the oil bodies contained less than 10% H₂And O. From the NMR-spectra we deduce that water may be below 5%.The dried sample was then used in the preparation of β -aminoketones.

1.38G of the dried Lupasol G100 obtained above was dissolved in 7ml of ethanol. The solution was gently stirred with a magnetic stir bar for a few minutes, then 2gNa was added₂SO₄(anhydrous). After stirring for a few more minutes, 2.21g a-damascone was added over 1 minute. After 2 days of reaction, the mixture was filtered through a celite filter (see above) and the residue was washed thoroughly with ethanol. About 180ml of slightly foamed filtrate was obtained. The filtrate was concentrated using a rotary evaporator until dry and dried over P in the desiccator at room temperature₂O₅And (5) drying. About 3.5g of colorless oil was obtained.

2. 4.3G of Lupasol G100 solution which was not dried were dissolved in 10ml of ethanol. The solution was stirred with a magnetic stir bar for several minutes, then 3.47g a-damascone was added over 1.5 minutes. After 2 days at room temperature, the reaction mixture was filtered through celite (see above) and the residue was washed thoroughly with ethanol. The filtrate (200ml, slightly foamed) was concentrated in an evaporator and dried at room temperature (P)₂O₅As a desiccant). About 5.9g of colorless oil was obtained.

3. To 3.0G of Lupasol G100 solution (used as such) was added 2.41G a-damascone. The mixture was stirred without the use of a solvent. After stirring for 4 days, the resulting oil was dissolved in 100ml THF over MgSO₄Dry, filter and concentrate the filtrate on a rotary evaporator. Desiccant (P) at room temperature₂O₅) After drying, about 4g of colorless oil was obtained. The oil bodies still contained about 13% (w/w) THF, even after long drying (3 days).

The products obtained from the three methods have identical NMR spectra.

Similar results were obtained when Lupasol G35 or Lupasol HF was used instead of Lupasol G100.

Similar results were obtained when 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde was used instead of α -damascone.

Another possible synthetic route is to use Lupasol P. β -aminoketones are prepared from Lupasol P and α -damascone using the procedure described below:

1.8g of Lupasol P solution (50% H)₂O, 50% Lupasol Mw.750000 from BASF) in 7ml of ethanol, stirring the solution with a magnetic stir bar for a few minutes, then adding 1.44g α -damascone after 3 days, filtering the reaction mixture through a celite filter (see above), washing the residue thoroughly with ethanol, concentrating the filtrate and drying at room temperature (P)₂O₅) About 3g of reaction product between Lupasol and α -damascone was obtained after drying the obtained oil bodies.

Processing method

The processing of the amine reaction product with the support is carried out as described above. In particular, 20g of the amine reaction product synthesized as described above is mixed in an Ultra Turrax containing 80g of support, such as TAE80, for 5 minutes, at a mixing temperature of about 70 ℃ and at a speed of the mixer sufficient to keep this temperature substantially constant. The temperature and time will depend on the nature of the support, but this is a routine procedure for the skilled person. The resulting mixture is maintained at a temperature substantially equal to the melting point of the support material. Once the mixture is at a suitable temperature, it is poured into a film coating material and agglomerated in an electric mixer, such as a Braun mixer. Care is also taken that the temperature during mixing does not substantially exceed the melting point of the carrier material. For example, 150g of a mixture containing TAE80 and 20% amine reaction product was poured into a Braun mixer containing 300g of carbonate salt at 60 ℃. The components were mixed for about 5 minutes. Care is also taken that the temperature during mixing does not exceed 65 ℃. In addition, the temperature and time will depend on the nature of the coating agent, but this is a routine procedure for the skilled person. Abbreviations used in the following examples of laundry and cleaning compositions

In laundry and cleaning compositions, the abbreviated component symbols have the following meanings: DEQA: (tallowoyloxyethyl) dimethylammonium chloride DTDMAC: tallow dimethyl ammonium chloride DEQA (2): methyl sulfated bis (soft tallowoyloxyethyl) hydroxyethylmethylammonium DTDMAMS: tallow dimethyl ammonium methosulfate SDASA: 1: 2 stearyl dimethylamine: stearic acid fatty acid triple pressed: stearic acid electrolyte with IV ═ 0: calcium chloride PEG: polyethylene glycol 4000Neodol 45-13: ethoxylation of C14-C15 Linear Primary alcohols sold by Shell Chemicals

Silicone defoamer: polydimethylsiloxane foam control agents and siloxane oxidation as dispersants

Mixture of olefin copolymers, ratio of foam control agent to dispersing agent

PEI in a ratio of 10: 1 to 100: 1: polyethyleneimine, average molecular weight 1800, average ethoxy groups per nitrogen

Degree of conversion is 7 oxyalkylene residues HEDP: 1, 1-hydroxyethane diphosphate LAS: straight chain C_11-13Sodium alkylbenzenesulfonate TAS: tallow alkyl sodium sulfate C_xyAS ：C_1X-C_1YAlkyl sodium sulfateC46SAS ：C₁₄-C₁₆Sodium secondary (2, 3) alkylsulfate C_xyE_zS: c condensed with Z moles of ethylene oxide_1X-C_1YSodium alkyl sulfate C_XYE_Z: predominantly linear C condensed with an average of Z moles of ethylene oxide_1X-C_1YPrimary alcohol QAS: r₂N⁺(CH₃)₂(C₂H₄OH)，R₂＝C₁₂-C₁₄QAS1 ：R₂N⁺(CH₃)₂(C₂H₄OH)，R₂＝C₈-C₁₁APA ：C₈-C₁₀Acylamidopropyl dimethylamine soap: sodium linear alkyl carboxylate from 80/20 mixture of tallow and coconut fatty acid

To STS: sodium toluenesulfonate CFAA: c₁₂-C₁₄(coconut) alkyl N-methylglucamide TFAA: c₁₆-C₁₈Alkyl N-methylglucamide TPKFA: c₁₂-C₁₄Topping full-distillate fatty acids STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite a: formula Na₁₂(AlO₂SiO₂)₁₂·27H₂Hydrated sodium aluminosilicate of O, primary particle size

0.1-10 microns (weight expressed on a dry basis) NaSKS-6: of the formula delta-NaSi₂O₅Citric acid, crystalline layered silicate of (2): anhydrous citric acid borate salt: sodium borate carbonate: particle size 200-900 μm anhydrous sodium carbonate bicarbonate: anhydrous sodium bicarbonate silicate with particle size distribution of 400-: amorphous sodium Silicate (SiO)₂∶Na₂O ratio 2.0: 1) sulfate: anhydrous sodium sulfate magnesium sulfate: anhydrous magnesium sulfate citrate: trisodium citrate dihydrate with activity of 86.4% and particle size distribution of 425-

Micron MA/AA: 1: 4 maleic/acrylic copolymer having an average molecular weight of about 70000MA/AA (1): 4: 6 maleic/acrylic copolymer, average molecular weight about 10000 AA: sodium polyacrylate polymer CMC with average molecular weight of 4500: sodium carboxymethylcellulose cellulose ether: methylcellulose ether having a degree of polymerization of 650, produced by Shin Etsu Chemicals

The protease was purchased: proteins sold under the trade name Savinase by Novo Industries A/S

Hydrolase with 3.3% by weight of active enzyme protease I: the proteolytic enzymes described in WO95/10591, having 4% by weight of active enzyme,

alcalase sold by Genencor int.inc: proteolytic enzymes sold by Novo Industries A/S have a 5.3% content

Weight active enzyme cellulase: fibers sold under the trade name Carezyme by Novo Industries A/S

Cellulase, amylase with 0.23% wt active enzyme: sold under the trade name Termamyl 120T by Novo Industries A/S

With 1.6% by weight of active enzyme lipase: lipolysis sold under the trade name Lipolase by Novo Industries A/S

Enzyme, lipase with 2.0% wt active enzyme (1): sold under the trade name Lipolase Ultra by Novo Industries A/S

With 2.0% by weight of the active enzyme endosase: endoglucanase sold by Novo Industries A/S having a 1.5

% weight active enzyme PB 4: standard NaBO₂·3H₂O·H₂O₂Sodium perborate tetrahydrate PB 1: standard NaBO₂·H₂O₂Anhydrous sodium perborate bleach percarbonate: standard formula 2NaCO₃·3H₂O₂Sodium percarbonate NOBS: nonanoyloxybenzene sulfonate, sodium salt form NAC-OBS: (6-nonanoylhexanoyl) oxybenzenesulfonate TAED: tetraacetylethylenediamine DTPA: diethylenetriaminepentaacetic acid DTPMP: diethylene triamine penta (methylene phosphonic acid) under the trade name Dequest from Monsanto

2060 marketing EDDS: ethylenediamine-N, N' -disuccinic acid, (S, S) isomer, sodium salt form photosensitized bleach (1): sulfonated zinc phthalocyanine photosensitized bleach encapsulated with dextrin soluble polymer (2): sulfonated aluminum phthalocyanine brightener encapsulated with dextrin-soluble polymer 1: 4, 4' -bis (2-sulfostyryl) biphenyl disodium brightener 2: 4, 4' -bis (4-phenylamino-6-morpholino-1, 3, 5-triazin-2-yl) amino) stilbene

-2: 2' -disodium disulfonate HEDP: hydroxy ethane 1, 1-diphosphonic acidPEG_x: polyethylene glycol, molecular weight x (typically 4000) PEO: polyoxyethylene, average molecular weight 50000 TEPAE: ethoxylated tetraethylenepentamine PVI: polyvinylimidazole, average molecular weight 20000 PVP: polyvinylpyrrolidone polymer, average molecular weight 60000 PVNO: polyvinylpyridine N-oxide, average molecular weight 50000 PVPVI: copolymers of polyvinylpyrrolidone and vinylimidazole having average molecular weights

20000 QEA: two ((C)₂H₅O)-(C₂H₄O)_n)(CH₃)-N⁺-C₆H₁₂-N⁺-(CH₃) II

((C₂H₅O)-(C₂H₄O))_nWherein n-20-30 SRP 1: anionic end-capped polyester SRP 2: diethoxylated poly (1, 2-propylene phthalate) short block copolymer PEI: polyethyleneimine, average molecular weight 1800, average ethoxy groups per nitrogen atom

Polysiloxane antifoam with a degree of chemistry of 7 oxyethylene residues: dimethicone foam control agents with polysiloxane-alkylene oxide as dispersing agent

A mixture of polymers, the weight ratio of the foam control agent to the dispersing agent being

10: 1-100: 1 sunscreen agent: aqueous based mixtures of monostyrene latexes from BASF Aktiengesellschaft

Wax is sold under the trade name Lytron 621: paraffin wax PA 30: polyacrylic acid 480N having an average molecular weight of about 4500-: random copolymer with acrylate/methacrylate ratio of 7: 3, average molecule

Amount of about 3500 polygel/carbopol: high molecular weight crosslinked polyacrylate metasilicate: sodium metasilicate (SiO)₂∶Na₂O ═ 1.0) nonionic: c with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5₁₃-

C₁₅Mixed ethoxylated/propoxylated fatty alcohol Neodol 45-13: ethoxylation of C14-C15 Linear Primary alcohols sold by Shell Chemical company

A material MnTACN: manganese 1,4, 7-trimethyl-, 1,4, 7-triazacyclononane PAAC: pentaethanamine cobalt (III) acetate salt paraffin: paraffin oil NaBz sold by Wintershall under the trade name Winog 70: sodium benzoate BzP: benzoyl peroxide SCS: sodium cumene sulfonate BTA: benzotriazole pH: PARP1 as determined in 1% distilled water solution at 20 ℃: ethyl 4-aminobenzoate prepared according to Synthesis example I with 2, 4-dimethyl-3-

Processed amine reaction product of cyclohexene-1-carbaldehyde admixed with TAE80 carrier and

agglomeration with coating Agents according to the processing method described above PARP2 preparation of Lupasol G35 and α -Dihydrodamascenone from Synthesis example III

Processed amine reaction product incorporating TAE100 carrier and processed according to the above process

The method is used for agglomerating the coating agent. PARP 3: addition of Lupasol HF to delta-damascone from Synthesis example III

An amine reaction product of step (ii) incorporating TAE80 carrier and processed according to the process described above

The film coating agent is agglomerated. PARP 4: processed amines of BNPP with delta-damascone prepared from Synthesis example II

Reaction product mixed with PEG4000 carrier and coated film according to the above processing method

The agent is agglomerated. PARP 5: lupasol G100 and 2, 4-dimethyl-3-Ring prepared according to Synthesis example III

Processed amine reaction product of hexene-1-carbaldehyde mixed with TAE80 carrier

Agglomerated with the film coating agent according to the above processing method. PARP 6: ethyl 4-aminobenzoate and trans-2-nonenal prepared according to Synthesis example I

Mixed with TAE80 carrier and processed according to the above process

The method is used for agglomerating the coating agent. PARP 7: ethyl 4-aminobenzoate and trans-2-hexenal prepared according to Synthesis example I

Mixed with TAE80 carrier and processed according to the above process

The method is used for agglomerating the coating agent. Clay I: bentonite clay II: smectite flocculant I: polyoxyethylene flocculant II with the average molecular weight of 200000-400000: polyoxyethylene flocculant III with average molecular weight of 400000 and 1000000: of acrylamide and/or acrylic acid having an average molecular weight of 2000000-400000

Polymer DOBS: decanoyloxybenzene sulfonate SRP3 in sodium salt form: polysaccharide soil release agent polymer SRP 4: non-ionic end-capped polyester polymer: polyvinyl pyridine available from BASF under the trade name Luviskol K90

Pyrrolidone K90 dye fixative: dye solid commercially available from Clariant under the tradename Cartafix CB

Dosing polyamine: 1, 4-bis- (3-aminopropyl) piperazine baysibit AM: 2-phosphinobutane-1, 2, 4-tricarboxylic acid fabric softener active commercially available from Bayer: methyl sulfated bis (canola acyloxy ethyl) hydroxyethyl methyl

Alkylammonium HPBDC hydroxypropyl β -Cyclodextrin RAMEB random methylation β -Cyclodextrin Bardac2050 Dioctyl dimethyl ammonium chloride, 50% solution Bardac22250 didecyl dimethyl ammonium chloride, 50% solution Genamin C100 ethoxylated with 10 moles of ethylene oxide commercially available from Clariant

Coconut fatty amine Genapol V4463: ethoxylated with 10 moles of ethylene oxide commercially available from Clariant

Coconut oil alcohol Silwet 7604: it is available from Osi Specialties in the group,

commercially available formula (MW) 4000 from Inc., Danbury, Connecticut

R-(CH₃)₂SiO-[(CH₃)₂SiO]_a-[(CH₃)(R)SiO]_b-

Si(CH₃)₂Polyoxyalkylene polysiloxanes of the formula (I) wherein the average of a + b

The value was 21. Silwet 7600: it is available from Osi Specialties in the group,

commercially available formula (MW) 4000 from Inc., Danbury, Connecticut

R-(CH₃)₂SiO-[(CH₃)₂SiO]_a-[(CH₃)(R)SiO]_b-

Si(CH₃)₂Polyoxyalkylene polysiloxanes of the formula (I) wherein the average of a + b

The value is 11.

In the following formulation examples, all levels are expressed as% by weight of the composition, unless otherwise indicated, and the processed amine reaction product (hereinafter "PARP") is incorporated by dry blending (d) into the fully formulated composition as defined herein. The terminology in parentheses of PARP in the formulation examples refers to the coating type (c) of the carbonate coating agent and the coating type(s) of the starch coating agent. Example 1

The following high density granular laundry detergent compositions a-G were prepared according to the present invention:

	A0	A1	A	B	C	D	E	F	G
										LAS	6.0	6.0	8.0	8.0	8.0	2.0	6.0	6.0	5.0
TAS	1.0	0.1	-	0.5	-	0.5	1.0	0.1	1.5
										C46(S)AS	-	-	2.0	2.5	-	-	-	-	-
C25AS	4.5	5.5	-	-	-	7.0	4.5	5.5	2.5
										C68AS	-	-	2.0	5.0	7.0	-	-	-	0.2
C25E5	4.6	4.6	-	-	3.4	10.0	4.6	4.6	2.6
										C25E7	-	-	3.4	3.4	1.0	-	-	-	-
C25E3S	5.0	4.5	-	-	-	2.0	5.0	4.5	0.5
										QAS	-	-	-	0.8	-	-	-	-	-
QAS(1)	0.5	1.0	-	-	-	0.8	0.5	1.0	1.5
										zeolite A	20.0	18.1	18.1	18.0	14.1	18.1	20.0	18.1	16.2
Citric acid	-	2.5	-	-	-	2.5	-	2.5	1.5
										Carbonate salt	10.0	13.0	13.0	13.0	25.0	10.0	10.0	13.0	20.6
SKS-6	-	10.0	-	-	-	10.0	-	10.0	4.3

Silicates of acid or alkali	0.5	0.3	1.4	1.4	3.0	0.3	0.5	0.3	-
										Citric acid salt	-	-	-	1.0	-	3.0	-	-	1.4
Sulfates of sulfuric acid	-	-	26.1	26.1	26.1	6.0	-	-	-
										Magnesium sulfate	-	0.2	0.3	-	-	0.2	-	0.2	0.03
MA/AA	1.0	1.0	0.3	0.3	0.3	4.0	1.0	1.0	0.6
										CMC	0.4	0.4	0.2	0.2	0.2	0.2	0.4	0.4	0.3
PB4	-	-	9.0	9.0	5.0	-	-	-	-
										Percarbonate salts	18.0	18.0	-	-	-	-	18.0	18.0	9.0
TAED	3.9	4.2	1.5	0.4	1.5	-	3.9	4.2	3.2
										NAC-OBS	-	-	-	2.0	1.0	-	-	-	-
DTPMP	-	-	0.25	0.25	0.25	0.25	-	-	-
										SRP2	-	0.2	-	-	-	0.2	-	0.2	-
EDDS	0.5	0.5	-	0.25	0.4	-	0.5	0.5	0.1
										TFAA	-	-	-	1.0	-	2.0	-	-	1.1
CFAA	-	-	-	1.0	-	2.0	-	-	-
										HEDP	0.4	0.4	0.3	0.3	0.3	0.3	0.4	0.4	0.3
QEA	-	0.5	-	-	-	0.2	-	0.5	-

Protease I	-	-	-	-	0.26	1.0	-	-	0.3
										Protease enzyme	1.5	1.0	0.26	0.26	-	-	1.5	1.0	-
Cellulase enzymes	0.3	0.3	0.3	-	-	0.3	0.3	0.3	0.3
										Amylase	0.5	0.5	0.1	0.1	0.1	0.4	0.5	0.5	0.1
Lipase (1)	0.5	0.5	0.3	-	-	0.5	0.5	0.5	0.1
										Photoactivated float Whitening agent (ppm)	20 ppm	20 ppm	15 ppm	15 ppm	15 ppm	-	20 ppm	20 ppm	20 ppm
PVNO/PVP VI	-	-	-	-	-	0.1	-	-	-
										Brightener 1	0.09	0.09	0.09	0.09	0.09	-	0.09	0.09	0.01
Whitening agent 2	-	-	-	-	-	-	-	-	0.09
										Spray-on fragrance	0.4	0.4	0.3	0.3	0.3	0.4	0.4	0.4	0.4
PARP 3	-	-	10 (c)	5 (s)	-	-	5(c)	1(c)	4(c)
										PARP5	-	-	-	-	2(c)	8(c)	4(s)	-	-
PARP6	5(c)	1(c)	-	-	-	-	-	-	-
										PARP 7	4(s)	-	-	-	-	-	-	-	-
Polysiloxanes Defoaming agent	0.3	0.3	0.5	0.5	0.5	-	0.3	0.3	0.3
										Clay II	-	-	-	-	-	-	-	-	12.0
Flocculating agent I	-	-	-	-	-	-	-	-	0.3

Glycerol	-	-	-	-	-	-	-	-	0.6
										Paraffin wax	-	-	-	-	-	-	-	-	0.4
Other/auxiliary objects To 100 percent
										Density g/l	850	850	850	850	850	850	850	850	850

Example 2

The following granular laundry detergent compositions are prepared according to the present invention, particularly suitable for use in european washing machine conditions:

	A	B	C	D	E	F
							LAS	5.5	7.5	5.0	5.0	6.0	7.0
TAS	1.25	1.86	-	0.8	0.4	0.3
							C24AS/C25AS	-	2.24	5.0	5.0	5.0	2.2
C25E3S	-	0.76	1.0	1.5	3.0	1.0
							C45E7	3.25	-	-	-	-	3.0
TFAA	-	-	2.0	-	-	-
							C25E5	-	5.5	-	-	-	-
QAS	0.8	-	-	-	-	-
							QASII	-	0.7	1.0	0.5	1.0	0.7
STPP	19.7	-	-	-	-	-
							zeolite A	-	19.5	25.0	19.5	20.0	17.0
NaSKS-6/citric acid (79∶21)	-	10.6	-	10.6	-	-
							NaSKS-6	-	-	9.0	-	10.0	10.0
Carbonate salt	6.1	10.0	9.0	10.0	10.0	18.0

Bicarbonate salt	-	2.0	7.0	5.0	-	2.0
							Silicates of acid or alkali	6.8	-	-	0.3	0.5	-
Citric acid salt	-	-	4.0	4.0	-	-
							Sulfates of sulfuric acid	39.8	-	-	5.0	-	12.0
Magnesium sulfate	-	-	0.1	0.2	0.2	-
							MA/AA	0.5	1.6	3.0	4.0	1.0	1.0
CMC	0.2	0.4	1.0	1.0	0.4	0.4
							PB4	5.0	12.7	-	-	-	-
Percarbonate salts	-	-	-	-	18.0	15.0
							TAED	0.5	3.1	-	-	5.0	-
NAC-OBS	1.0	3.5	-	-	-	2.5
							DTPMP	0.25	0.2	0.3	0.4	-	0.2
HEDP	-	0.3	-	0.3	0.3	0.3
							QEA	-	-	1.0	1.0	1.0	-
Protease 1	-	-	-	0.5	1.2	-
							Protease enzyme	0.26	0.85	0.9	1.0	-	0.7
Lipase (1)	0.15	0.15	0.3	0.3	0.3	0.2

Cellulase enzymes	0.28	0.28	0.2	0.2	0.3	0.3
							Amylase	0.1	0.1	0.4	0.4	0.6	0.2
PVNO/PVPVI	-	-	0.2	0.2	-	-
							PVP	0.9	1.3	-	-	-	0.9
SRP1	-	-	0.2	0.2	0.2	-
							Photoactivated bleaching agents (1)(ppm)	15 ppm	27 ppm	-	-	20 ppm	20 ppm
Photoactivated bleaching agents (2)(ppm)	15 ppm	-	-	-	-	-
							Brightener 1	0.08	0.19	-	-	0.09	0.15
Whitening agent 2	-	0.04	-	-	-	-
							Perfume	0.3	0.3	0.4	0.3	0.4	0.3
PARP1	1.0(c)	10.0(c)	5.0(c)	-	-	-
							PARP2	-	-	2.0(c)	4.0(s)	8.0(c)	2.0(c)
Polysiloxane antifoaming agent	0.5	2.4	0.3	0.5	0.3	2.0
							Auxiliary/other to 100％
Density g/l	750	750	750	750	750	750

Example 3

The following detergent formulations were prepared according to the invention, particularly suitable for use in european washing machine conditions:

	A	B	C	D
					blown powder	-	-	-	-
LAS	6.0	5.0	11.0	6.0
					TAS	2.0	-	-	2.0
Zeolite A	24.0	-	-	20.0
					STPP	-	27.0	24.0	-
Sulfates of sulfuric acid	4.0	6.0	13.0	-
					MA/AA	1.0	4.0	6.0	2.0
Silicates of acid or alkali	1.0	7.0	3.0	3.0
					CMC	1.0	1.0	0.5	0.6
Brightener 1	0.2	0.2	0.2	0.2
					Polysiloxane antifoaming agent	1.0	1.0	1.0	0.3
DTPMP	0.4	0.4	0.2	0.4
					Spray on
Whitening agent	0.02	-	-	0.02
					C45E7	-	-	-	5.0
C45E2	2.5	2.5	2.0	-
					C45E3	2.6	2.5	2.0	-
Perfume	0.5	0.3	0.5	0.2
					Polysiloxane antifoaming agent	0.3	0.3	0.3	-
Dry additives	-	-	-	-
					QEA	-	-	-	1.0
EDDS	0.3	-	-	-
					Sulfates of sulfuric acid	2.0	3.0	5.0	10.0
Carbonate salt	6.0	13.0	11.0	14.0
					Citric acid	2.5	-	-	2.0
QASII	0.5	-	-	0.5
					SKS-6	10.0	-	-	-
Percarbonate salts	18.5	-	-	-
					PB4	-	18.0	10.0	21.5
TAED	2.0	2.0	-	2.0

NAC-OBS	3.0	2.0	4.0	-
					Protease enzyme	1.0	1.0	1.0	1.0
Lipase enzyme	-	0.4	-	0.2
					Lipase (1)	0.4	-	0.4	-
Amylase	0.2	0.2	0.2	0.4
					Brightener 1	0.05	-	-	0.05
PARP3	2.0(c)	1.0(c)	4.0(s)	2.0(c)
					Other/auxiliary substances to 100%

Example 4

The following granular detergent formulations were prepared according to the invention:

	A	B	C	D	E	F
							blown powder
LAS	23.0	8.0	7.0	9.0	7.0	7.0
							TAS	-	-	-	-	1.0	-
C45AS	6.0	6.0	5.0	8.0	-	-
							C45AES	-	1.0	1.0	1.0	-	-
C45E35	-	-	-	-	2.0	4.0
							Zeolite A	10.0	18.0	14.0	12.0	10.0	10.0
MA/AA	-	0.5	-	-	-	2.0
							MA/AA(1)	7.0	-	-	-	-	-
AA	-	3.0	3.0	2.0	3.0	3.0
							Sulfates of sulfuric acid	5.0	6.3	14.3	11.0	15.0	19.3
Silicates of acid or alkali	10.0	1.0	1.0	1.0	1.0	1.0
							Carbonate salt	13.0	19.0	8.0	20.7	8.0	6.0
PEG4000	0.4	1.5	1.5	1.0	1.0	1.0
							DTPA	-	0.9	0.5	-	-	0.5
Whitening agent 2	0.3	0.2	0.3	-	0.1	0.3
							Spray on
C45E7	-	2.0	-	-	2.0	2.0
							C25E9	3.0	-	-	-	-	-
C23E9	-	-	1.5	2.0	-	2.0
							Perfume	0.3	0.3	0.3	2.0	0.3	0.3
Agglomerates	-	-	-	-	-	-
							C45AS	-	5.0	5.0	2.0	-	5.0
LAS	-	2.0	2.0	-	-	2.0
							Zeolite A	-	7.5	7.5	8.0	-	7.5
Carbonate salt	-	4.0	4.0	5.0	-	4.0
							PEG4000	-	0.5	0.5	-	-	0.5
Others (water, etc.)	-	2.0	2.0	2.0	-	2.0
							Dry additives

QAS(I)	-	-	-	-	1.0	-
							Citric acid	-	-	-	-	2.0	-
PB4	-	-	-	-	12.0	1.0
							PB1	4.0	1.0	3.0	2.0	-	-
Percarbonate salts	-	-	-	-	2.0	10.0
							Carbonate salt	-	5.3	1.8	-	4.0	4.0
NOBS	4.0	-	6.0	-	-	0.6
							Methyl cellulose	0.2	-	-	-	-	-
SKS-6	8.0	-	-	-	-	-
							STS	-	-	2.0	-	1.0	-
Isopropylbenzene sulfonic acid	-	1.0	-	-	-	2.0
							Lipase enzyme	0.2	-	0.2	-	0.2	0.4
Cellulase enzymes	0.2	0.2	0.2	0.3	0.2	0.2
							Amylase	0.2	-	0.1	-	0.2	-
Protease enzyme	0.5	0.5	0.5	0.3	0.5	0.5
							PVPVI	-	-	-	-	0.5	0.1
PVP	-	-	-	-	0.5	-
							PVNO	-	-	0.5	0.3	-	-
QEA	-	-	-	-	1.0	-
							SRP1	0.2	0.5	0.3	-	0.2	-
PARP3	2.0(c)	1.0(c)	4.0(c)	0.5(c)	3.5(c)	1.0(s)
							Polysiloxane antifoaming agent	0.2	0.4	0.2	0.4	0.1	-
Magnesium sulfate	-	-	0.2	-	0.2	-
							Other/auxiliary substances to 100%

	G	H	I	J
					Blown powder
Clay I or II	7.0	10.0	6.0	2.0
					LAS	16.0	5.0	11.0	6.0
TAS	-	5.0	-	2.0
					Zeolite A	-	20.0	-	10.0
STPP	24.0	-	14.0	-
					Sulfates of sulfuric acid	-	2.0	-	-

MA/AA	-	2.0	1.0	1.0
					Silicates of acid or alkali	4.0	7.0	3.0	-
CMC	1.0	-	0.5	0.6
					Brightener 1	0.2	0.2	0.2	0.2
Carbonate salt	10.0	10.0	20.0	-
					DTPMP	0.4	0.4	0.2	-
Spray on
					Brightener 1	0.02	-	-	0.02
C45E7 or E9	-	-	2.0	1.0
					C45E3 or E4	-	-	2.0	4.0
Perfume	0.5	-	0.5	0.2
					Polysiloxane antifoaming agent	0.3	-	-	-
Dry additives
					Flocculating agents I or II	0.3	1.0	1.0	0.5
QEA	-	-	-	1.0
					HEDP/EDDS	0.3	-	-	-
Sulfates of sulfuric acid	2.0	-	-	-
					Carbonate salt	20.0	13.0	15.0	24.0
Citric acid	2.5	-	-	2.0
					QAS	-	-	0.5	0.5
NaSKS-6	3.5	-	-	5.0
					Percarbonate salts	-	-	-	9.0
PB4	-	-	5.0	-
					NOBS	-	-	-	1.3
TAED	-	-	2.0	1.5
					Protease enzyme	1.0	1.0	1.0	1.0
Lipase enzyme	-	0.4	-	0.2
					Amylase	0.2	0.2	0.2	0.4
Whitening agent 2	0.05	-	-	0.05
					Perfume	1.0	0.2	0.5	0.3
Color particle	1.2	0.5	2.0	-
					PARP 3	1.0(s)	1.5(c)	3.0(c)	0.8(s)
PARP 1	3.0(c)	3.0(s)	2.0(c)	1.0(c)
					Other/auxiliary substances to 100%

Example 5

The following bleach-free detergent formulations, in particular for washing coloured laundry, were prepared according to the invention:

	A	B	C
				blown powder
Zeolite A	15.0	15.0	-
				Sulfates of sulfuric acid	0.0	5.0	-
LAS	3.0	3.0	-
				DTPMP	0.4	0.5	-
CMC	0.4	0.4	-
				MA/AA	4.0	4.0	-
Agglomerates
				C45AS	-	-	11.0
LAS	6.0	5.0	-
				TAS	3.0	2.0	-
Silicates of acid or alkali	4.0	4.0	-
				Zeolite A	10.0	15.0	13.0
CMC	-	-	0.5
				MA/AA	-	-	2.0
Carbonate salt	9.0	7.0	7.0
				Spray on
Perfume	0.3	0.3	0.5
				C45E7	4.0	4.0	4.0
C25E3	2.0	2.0	2.0
				Dry additives
MA/AA	-	-	3.0
				NaSKS-6	-	-	12.0
Citric acid salt	10.0	-	8.0
				Bicarbonate salt	7.0	3.0	5.0
Carbonate salt	6.0	-	7.0
				PVPVI/PVNO	0.5	0.5	0.5
Alcalase	0.5	0.3	0.9

Lipase enzyme	0.4	0.4	0.4
				Amylase	0.6	0.6	0.6
Cellulase enzymes	0.6	0.6	0.6
				PARP1	7.0(c)	10(c)	5.0(c)
Polysiloxane antifoaming agent	5.0	5.0	5.0
				Dry additives
Sulfates of sulfuric acid	0.0	9.0	0.0
				Other/auxiliary substances to 100%	100.0	100.0	100.0
Density (g/liter)	700	700	700

Example 6

The following granular detergent formulations were prepared according to the invention:

	A	B	C	D
					elementary particles
Zeolite A	30.0	22.0	24.0	10.0
					Sulfates of sulfuric acid	10.0	5.0	10.0	7.0
MA/AA	3.0	-	-	-
					AA	-	1.6	2.0	-
MA/AA(1)	-	12.0	-	6.0
					LAS	14.0	10.0	9.0	20.0
C45AS	8.0	7.0	9.0	7.0
					C45AES	-	1.0	1.0	-
Silicates of acid or alkali	-	1.0	0.5	10.0
					Soap	-	2.0	-	-
Brightener 1	0.2	0.2	0.2	0.2
					Carbonate salt	6.0	9.0	10.0	10.0
PEG4000	-	1.0	1.5	-
					DTPA	-	0.4	-	-
Spray on
					C25E9	-	-	-	5.0
C45E7	1.0	1.0	-	-
					C23E9	-	1.0	2.5	-
Perfume	0.2	0.3	0.3	-

Dry additives
					Carbonate salt	5.0	5.0	15.0	6.0
PVPVI/PVNO	0.5	-	0.3	-
					Protease enzyme	1.0	1.0	1.0	0.5
Lipase enzyme	0.4	-	-	0.4
					Amylase	0.1	-	-	0.1
Cellulase enzymes	0.1	0.2	0.2	0.1
					NOBS	-	4.0	-	4.5
PB1	1.0	5.0	1.5	6.0
					Sulfates of sulfuric acid	4.0	5.0	-	5.0
SRPI	-	0.4	-	-
					PARP1	10(c)	5.0(c)	8.0(c)	-
PARP3	-	1.0(s)	-	2.0(s)
					Suds suppressor	-	0.5	0.5	-
Other/auxiliary substances to 100%

Example 7

The following granular detergent compositions were prepared according to the present invention:

	A	B	C
				blown powder
Zeolite A	20.0	-	15.0
				STPP	-	20.0	-
Sulfates of sulfuric acid	-	-	5.0
				Carbonate salt	-	-	5.0
TAS	-	-	1.0
				LAS	6.0	6.0	6.0
C68AS	2.0	2.0	-
				Silicates of acid or alkali	3.0	8.0	-
MA/AA	4.0	2.0	2.0
				CMC	0.6	0.6	0.2
Brightener 1	0.2	0.2	0.1
				DTPMP	0.4	0.4	0.1
STS	-	-	1.0
				Spray on
C45E7	5.0	5.0	4.0
				Polysiloxane antifoaming agent	0.3	0.3	0.1
Perfume	0.2	0.2	0.3
				Dry additives
QEA	-	-	1.0
				Carbonate salt	14.0	9.0	10.0
PB1	1.5	2.0	-
				PB4	18.5	13.0	13.0
TAED	2.0	2.0	2.0
				QAS(I)	-	-	1.0
Photoactivated bleaching agents	15ppm	15ppm	15ppm
				SKS-6	-	-	3.0
Protease enzyme	1.0	1.0	0.2
				Lipase enzyme	0.2	0.2	0.2
Amylase	0.4	0.4	0.2

Cellulase enzymes	0.1	0.1	0.2
				Sulfates of sulfuric acid	10.0	20.0	5.0
PARP3	5.0(c)	2.0(c)	4.0(s)
				Other/auxiliary substances to 100%
Density (g/liter)	700	700	700

Example 8

The following detergent compositions were prepared according to the present invention:

	A	B	C
				blown powder
Zeolite A	15.0	15.0	15.0
				Sulfates of sulfuric acid	0.0	5.0	0.0
LAS	3.0	3.0	3.0
				QAS	-	1.5	1.5
DTPMP	0.4	0.2	0.4
				EDDS	-	0.4	0.2
CMC	0.4	0.4	0.4
				MA/AA	4.0	2.0	2.0
Agglomerates
				LAS	5.0	5.0	5.0
TAS	2.0	2.0	1.0
				Silicates of acid or alkali	3.0	3.0	4.0
Zeolite A	8.0	8.0	8.0
				Carbonate salt	8.0	8.0	4.0
Spray on
				Perfume	0.3	0.3	0.3
C45E7	2.0	2.0	2.0
				C25E3	2.0	-	-
Dry additives
				Citric acid salt	5.0	-	2.0
Bicarbonate salt	-	3.0	-
				Carbonate salt	8.0	15.0	10.0

TAED	6.0	2.0	5.0
				PB1	14.0	7.0	10.0
PEO	-	-	0.2
				PARP3	2.0(c)	1.0(c)	0.75(c)
Bentonite clay	-	-	10.0
				Protease enzyme	1.0	1.0	1.0
Lipase enzyme	0.4	0.4	0.4
				Amylase	0.6	0.6	0.6
Cellulase enzymes	0.6	0.6	0.6
				Polysiloxane antifoaming agent	5.0	5.0	5.0
Dry additives
				Sodium sulfate	0.0	3.0	0.0
Other/auxiliary substances to 100%	100.0	100.0	100.0
				Density (g/l)	850	850	850

	A	B	C	D	E
						Blown powder
STPP/Zeolite A	9.0	15.0	15.0	9.0	9.0
						Flocculant II Or III	0.5	0.2	0.9	1.5	-
LAS	7.5	23.0	3.0	7.5	7.5
						QAS	2.5	1.5	-	-	-
DTPMP	0.4	0.2	0.4	0.4	0.4
						HEDP or EDDS	-	0.4	0.2	-	-
CMC	0.1	0.4	0.4	0.1	0.1
						Sodium carbonate	5.0	20.0	20.0	10.0	-
Whitening agent	0.05	-	-	0.05	0.05
						Clay I or II	-	10.0	-	-	-
STS	0.5	-	-	0.5	0.5
						MA/AA	1.5	2.0	2.0	1.5	1.5
Agglomerates
						Suds suppressors (siloxanes)	1.0	1.0	-	2.0	0.5
Agglomerates

Clay clay	9.0	-	-	4.0	10.0
						Paraffin wax	0.5	-	-	0.5	1.5
Glycerol	0.5	-	-	0.5	0.5
						Agglomerates
LAS	-	5.0	5.0	-	-
						TAS	-	2.0	1.0	-	-
Silicates of acid or alkali	-	3.0	4.0	-	-
						Zeolite A	-	8.0	8.0	-	-
Carbonate salt	-	8.0	4.0	-	-
						Spray on
Perfume	0.3	-	-	0.3	0.3
						C45E7 or E9	2.0	-	-	2.0	2.0
C25E3 or E4	2.0	-	-	2.0	2.0
						Dry additives
Citrate or citric acid	2.5	-	2.0	2.5	2.5
						Clay I or II	-	5.0	5.0	-	-
Flocculating agent I Or II	-	-	-	-	0.2
						Bicarbonate salt	-	3.0	-	-	-
Carbonate salt	15.0	-	-	25.0	31.0
						TAED	1.0	2.0	5.0	1.0	-
Sodium perborate or percarbonate	6.0	7.0	10.0	6.0	-
						SRP1, 2, 3 or 4	0.2	0.1	0.2	0.5	0.3
CMC or non-ionic fiber Vegetable ethers	1.0	1.5	0.5	-	-
						Protease enzyme	0.3	1.0	1.0	0.3	0.3
Lipase enzyme	-	0.4	0.4	-	-
						Amylase	0.2	0.6	0.6	0.2	0.2
Cellulase enzymes	0.2	0.6	0.6	0.2	0.2
						Polysiloxane antifoaming agent	-	5.0	5.0	-	-
Spice (starch)	0.2	0.3	1.0	0.2	0.2
						Color particle	0.5	0.5	0.1	-	1.0
NaSKS-6 (silicate) 2R)	3.5	-	-	-	3.5

Photobleaches	0.1	-	-	0.1	0.1
						Soap	0.5	2.5	-	0.5	0.5
Sodium sulfate	-	3.0	-	-	-
						PARP3	1.5(c)	1.0(c)	0.75(s)	3.0(s)	1.0(c)
Other/auxiliary substances to 100％	100.0	100.0	100.0	100.0	100.0
						Density (g/liter)	850	850	850	850	850

Example 9

The following detergent compositions were prepared according to the inventionAn object:

	A	B	C	D
					LAS	18.0	14.0	24.0	20.0
QAS	0.7	1.0	-	0.7
					TFAA	-	1.0	-	-
C23E56.5	-	-	1.0	-
					C45E7	-	1.0	-	-
C45E3S	1.0	2.5	1.0	-
					STPP	32.0	18.0	30.0	22.0
silicates of acid or alkali	9.0	5.0	9.0	8.0
					Carbonate salt	9.0	7.5	-	5.0
Bicarbonate salt	-	7.5	-	-
					PB1	3.0	1.0	-	-
PB4	-	1.0	-	-
					NOBS	2.0	1.0	-	-
DTPMP	-	1.0	-	-
					DTPA	0.5	-	0.2	0.3
SRP1	0.3	0.2	-	0.1
					MA/AA	1.0	1.5	2.0	0.5
CMC	0.8	0.4	0.4	0.2
					PEI	-	-	0.4	-
Sodium sulfate	20.0	10.0	20.0	30.0
					Magnesium sulfate	0.2	-	0.4	0.9

Protease enzyme	0.8	1.0	0.5	0.5
					Amylase	0.5	0.4	-	0.25
Lipase enzyme	0.2	-	0.1	-
					Cellulase enzymes	0.15	-	-	0.05
Photoactivated bleaching agents (ppm)	30ppm	20ppm	-	10ppm
					PARP4	2.0(c)	4.0(s)	8.0(c)	0.8(c)
Spray-on fragrance	0.3	0.3	0.1	0.2
					Whitening agent 1/2	0.05	0.2	0.08	0.1
Other/auxiliary substances to 100％	-	-	-	-

Example 10

The following liquid detergent formulations (contents given in parts by weight) were prepared according to the invention:

	A	B	C	D	E
						LAS	11.5	8.8	-	3.9	-
C25E2.5S	-	3.0	18.0	-	16.0
						C45E2.25S	11.5	3.0	-	15.7	-
C23E9	-	2.7	1.8	2.0	1.0
						C23E7	3.2	-	-	-	-
CFAA	-	-	5.2	-	3.1
						TPKFA	1.6	-	2.0	0.5	2.0
citric acid (50%)	6.5	1.2	2.5	4.4	2.5
						Calcium formate	0.1	0.06	0.1	-	-
Sodium formate	0.5	0.06	0.1	0.05	0.05
						Sodium cumene sulfonate	4.0	1.0	3.0	1.18	-
Borate salt	0.6	-	3.0	2.0	2.9
						Sodium hydroxide	5.8	2.0	3.5	3.7	2.7
Ethanol	1.75	1.0	3.6	4.2	2.9
						1, 2-propanediol	3.3	2.0	8.0	7.9	5.3

Monoethanolamine	3.0	1.5	1.3	2.5	0.8
						TEPAE	1.6	-	1.3	1.2	1.2
Protease enzyme	1.0	0.3	1.0	0.5	0.7
						Lipase enzyme	-	-	0.1	-	-
Cellulase enzymes	-	-	0.1	0.2	0.05
						Amylase	-	-	-	0.1	-
SRP1	0.2	-	0.1	-	-
						DTPA	-	-	0.3	-	-
PVNO	-	-	0.3	-	0.2
						PARP1	8.0(c)	-	-	-	-
PARP2	-	2.0(c)	-	-	-
						PARP3	-	-	1.0(c)	-	-
PARP4	-	-	-	4.0(s)	-
						PARP5	-	-	-	-	10.0(s)
Brightener 1	0.2	0.07	0.1	-	-
						Polysiloxane antifoaming agent	0.04	0.02	0.1	0.1	0.1
Water/adjuvant to 100%	-	-	-	-	-

Example 11

The following liquid detergent formulations (contents given in parts by weight) were prepared according to the invention:

	A	B	C	D	E	F	G	H
									LAS	10.0	13.0	9.0	-	25.0	-	-	-
C25AS	4.0	1.0	2.0	10.0	-	13.0	18.0	15.0
									C25E3S	1.0	-	-	3.0	-	2.0	2.0	4.0
C25E7	6.0	8.0	13.0	2.5	-	-	4.0	4.0
									TFAA	-	-	-	4.5	-	6.0	8.0	8.0
APA	-	1.4	-	-	3.0	1.0	2.0	-
									TPKFA	2.0	-	13.0	7.0	-	15.0	11.0	11.0
citric acid	2.0	3.0	1.0	1.5	1.0	1.0	1.0	1.0
									Dodecenyl/tetradecenyl Succinic acid	12.0	10.0	-	-	15.0	-	-	-
Rapeseed fatty acid	4.0	2.0	1.0	-	1.0	-	3.5	-
									Ethanol	4.0	4.0	7.0	2.0	7.0	2.0	3.0	2.0

1,2 propylene glycol	4.0	4.0	2.0	7.0	6.0	8.0	10.0	13.0
									Monoethanolamine	-	-	-	5.0	-	-	9.0	9.0
Triethanolamine	-	-	8.0	-	-	-	-	-
									TEPAE	0.5	-	0.5	0.2	-	-	0.4	0.3
DTPMP	1.0	1.0	0.5	1.0	2.0	1.2	1.0	-
									Protease enzyme	0.5	0.5	0.4	0.25	-	0.5	0.3	0.6
Alcalase	-	-	-	-	1.5	-	-	-
									Lipase enzyme	-	0.10	-	0.01	-	-	0.15	0.15
Amylase	0.25	0.25	0.6	0.5	0.25	0.9	0.6	0.6
									Cellulase	-	-	-	0.05	-	-	0.15	0.15
Endolase	-	-	-	0.10	-	-	0.07	-
									SRP2	0.3	-	0.3	0.1	-	-	0.2	0.1
Boric acid	0.1	0.2	1.0	2.0	1.0	1.5	2.5	2.5
									Calcium chloride	-	0.02	-	0.01	-	-	-	-
Bentonite clay	-	-	-	-	4.0	4.0	-	-
									Brightener 1	-	0.4	-	-	0.1	0.2	0.3	-
Suds suppressor	0.1	0.3	-	0.1	0.4	-	-	-
									Light-shading agent	0.5	0.4	-	0.3	0.8	0.7	-	-
PARP1	8(s)	-	5(c)	-	3(c)	-	4(s)	2(s)
									PARP3	-	2(c)	-	1(c)	-	8(c)	1(c)	0.7(c)
Water/auxiliary substances to 100％
									NaOH to pH	8.0	8.0	7.6	7.7	8.0	7.5	8.0	8.2

Example 12

The following liquid detergent compositions (contents are given in parts by weight) were prepared according to the present invention:

	A	B
			LAS	27.6	18.9
C45AS	13.8	5.9
			C13E8	3.0	3.1
oleic acid	3.4	2.5
			Citric acid	5.4	5.4
Sodium hydroxide	0.4	3.6

Calcium formate	0.2	0.1
			Sodium formate	-	0.5
Ethanol	7.0	-
			Monoethanolamine	16.5	8.0
1.2 propylene glycol	5.9	5.5
			Xylene sulfonic acidAcid(s)	-	2.4
TEPAE	1.5	0.8
			Protease enzyme	1.5	0.6
PEG	-	0.7
			Whitening agent 2	0.4	0.1
Spray-on fragrance	0.5	0.3
			PARP2	2.0(c)	-
PARP4	2.0(c)	1.0(c)
			Water/adjuvant to 100%

Example 13 the following is a composition according to the invention in the form of a tablet, a bar, an extrudate or a granulate:

	A	B	C	D	E	F	G
								C11-C13sodium alkyl benzene sulfonate	12.0	16.0	23.0	19.0	18.0	20.0	16.0
C14-C15Sodium alcohol sulfate	-	4.5	-	-	-	-	4.0
								C14-C15Alcohol ethoxylates (3) Sulfates of sulfuric acid	-	-	2.0	-	1.0	1.0	1.0
C14-C15Alcohol ethoxylate sodium salt	2.0	2.0	-	1.3	-	-	5.0
								C9-C14Alkyl dimethyl hydroxyethyl Quaternary ammonium salts			-	-	1.0	0.5	2.0
Tallow fatty acid			-	-	-	-	1.0
								Sodium tripolyphosphate/zeolite	23.0	25.0	14.0	22.0	20.0	10.0	20.0
Sodium carbonate	25.0	22.0	35.0	20.0	28.0	41.0	30.0

Polyacrylamide sodium salt (45％)	0.5	0.5	0.5	0.5	-	-	-
								Polyacrylic acid/sodium maleate polymer	-	-	1.0	1.0	1.0	2.0	0.5
Sodium silicate (1: 6 ratio) NaO/SiO2)(46％)	3.0	6.0	9.0	8.0	9.0	6.0	8.0
								Sodium sulfate	-	-	-	-	-	2.0	3.0
Sodium perborate/percarbonate	5.0	5.0	10.0	-	3.0	1.0	-
								Poly (ethylene glycol), MW ～4000(50％)	1.5	1.5	1.0	1.0	-	-	0.5
Sodium carboxymethylcellulose	1.0	1.0	1.0	-	0.5	0.5	0.5
								NOBS/DOBS	-	1.0	-	-	1.0	0.7	-
TAED	1.5	1.0	2.5	-	3.0	0.7	-
								SRP1	1.5	1.5	1.0	1.0	-	1.0	-
Clay I or II	5.0	6.0	12.0	7.0	10.0	4.0	3.0
								Flocculating agents I or III	0.2	0.2	3.0	2.0	0.1	1.0	0.5
Moisture-retaining agent	0.5	1.0	0.5	1.0	0.5	0.5	-
								Paraffin wax	0.5	0.5	1.0	-	-	0.5	0.5
Water content	7.5	7.5	6.0	7.0	5.0	3.0	5.0
								Magnesium sulfate	-	-	-	-	-	0.5	1.5
Chelating agents	-	-	-	-	0.8	0.6	1.0
								Enzymes, including amylases, cellulases, protease and lipase	-	-	-	-	2.0	1.5	2.0
Color particle	2.5	4.1	4.2	4.4	5.6	5.0	5.2
								The presence of an adjunct, such as a perfume, PVP，PVPVI/PVNO， whitening agent and photobleaching agent	2.0	1.0	1.0	1.0	2.5	1.5	1.0
PARP5(c)	3.0	3.0	-	-	-	-	-
								PARP3(c)	0.08	0.1	0.2	0.1	0.05	0.08	0.05
aggl	1.0	1.5	3.0	1.5	0.75	1.0	0.75
								Salt (salt)	0.16	0.2	0.4	0.2	0.1	0.16	0.1

	H	I	J	K
					C11-C13 Sodium alkyl benzene sulfonate	23.0	13.0	20.0	18.0
C14-C15Sodium alcohol sulfate	-	4.0	-	-
					Clay I or II	5.0	10.0	14.0	6.0
Flocculating agents I or II	0.2	0.3	0.1	0.9
					Paraffin wax	0.5	0.5	1.0	-
Humectant (Glycerol/silicon dioxide)	0.5	2.0	1.5	-
					C14-C15Alcohol ethoxylated sulfates	-	-	-	2.0
C14-C15Alcohol ethoxylate sodium salt: (	2.5	3.5	-	-
					C9-C14Alkyl dimethyl hydroxyethyl quaternary ammonium salt	-	-	-	0.5
Tallow fatty acid	0.5	-	-	-
					Tallow alcohol ethoxylate (50)	-	-	-	1.3
Sodium tripolyphosphate	-	41.0	-	20.0
					Zeolite A hydrate (0.1-10 microns)	26.3	-	21.3	-
Sodium carbonate	24.0	22.0	35.0	27.0
					Polysodium acrylate (45%)	2.4	-	2.7	-
Polysodium acrylate/sodium maleate polymer	-	-	1.0	2.5
					Sodium silicate (1.6 or 2 or 2.2 ratio) NaO/SiO2)(46％)	4.0	7.0	2.0	6.0
Sodium sulfate	-	6.0	2.0	-
					Sodium perborate/percarbonate	8.0	4.0	-	12.0
Poly (ethylene glycol) MW-4000 (50%)	1.7	0.4	1.0	-
					Sodium carboxymethylcellulose	1.0	-	-	0.3
Citric acid	-	-	3.0	-
					NOBS/DOBS	1.2	-	-	1.0
TAED	0.6	1.5	-	3.0
					Perfume	0.5	1.0	0.3	0.4
SRP1	-	1.5	1.0	1.0
					Water content	7.5	3.1	6.1	7.3
Magnesium sulfate	-	-	-	1.0
					Chelating agents	-	-	-	0.5
Color particle	1.0	0.5	0.2	2.7

Enzymes, including amylases, cellulases, proteases And lipase	-	1.0	-	1.5
					Auxiliaries, e.g. bleaches, photobleaches	1.0	1.0	1.0	1.0
PARP3(c)	1.5	3.0	1.0	4.5

Example 14

According to the inventionThe following laundry bar detergent compositions (contents are given in parts by weight) were prepared:

	A	B	C	D	E	F	G	H
									LAS	-	-	19.0	15.0	21.0	6.75	8.8	-
C28AS	30.0	13.5	-	-	-	15.75	11.2	22.5
									sodium laurate (NaLaurus acid)	2.5	9.0	-	-	-	-	-	-
Zeolite A	2.0	1.25	-	-	-	1.25	1.25	1.25
									Carbonate salt	10.0	-	11.0	5.0	2.0	7.0	13.0	9.0
Calcium carbonate	27.5	39.0	35.0	-	-	40.0	-	40.0
									Sulfates of sulfuric acid	5.0	5.0	3.0	5.0	3.0	-	-	5.0
TSPP	5.0	-	-	-	-	5.0	2.5	-
									STPP	5.0	15.0	10.0	-	-	7.0	8.0	10.0
Bentonite clay	-	10.0	-	-	5.0	-	-	-
									DTPMP	-	0.7	0.6	-	0.6	0.7	0.7	0.7
CMC	-	1.0	1.0	1.0	1.0	-	-	1.0
									Talc	-	-	10.0	15.0	10.0	-	-	-
Silicates of acid or alkali	-	-	4.0	5.0	3.0	-	-	-
									PVNO	0.02	0.03	-	0.01	-	0.02	-	-
MA/AA	0.4	1.0	-	-	0.2	0.4	0.5	0.4
									SRP1	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
Protease enzyme	-	0.12	-	0.08	0.08	-	-	0.1
									Lipase enzyme	-	0.1	-	0.1	-	-	-	-
Amylase	-	-	0.8	-	-	-	0.1	-
									Cellulase enzymes	-	0.15	-	-	0.15	0.1	-	-
PEO	-	0.2	-	0.2	0.3	-	-	0.3
									Perfume	1.0	0.5	0.3	0.2	0.4	-	-	0.4
Magnesium sulfate	-	-	3.0	3.0	3.0	-	-	-

PARP1	10(c)	-	-	-	-	8(c)	-	-
									PARP2	-	4(c)	-	-	-	-	2(c)	-
PARP3	-	-	2(c)	-	-	-	-	1(c)
									PARP4	-	-	-	4(s)	-	-	-	-
PARP5	-	-	-	-	10(c)	-	-	4(c)
									Whitening agent	0.15	0.10	0.15	-	-	-	-	0.1
Photoactivated bleaching agents (ppm)	-	15.0	15.0	15.0	15.0	-	-	15.0

Example 15 the following detergent additive compositions were prepared according to the invention:

a B CLAS-5.05.0 STPP 30.0-20.0 zeolite a-35.020.0 PB120.015.0-TAED 10.08.0-PARP 110.0 (c) -5.0 (c) PARP 3-4.0 (c) 2.0(c) protease-0.30.3 amylase-0.060.06 adjunct, water and other to 100% example 16 the following compact high density (0.96Kg/l) dishwashing detergent compositions were prepared in accordance with the present invention:

a B C D E F G HSTPP- -54.351.451.4- -50.9 citrate 35.017.0- - -46.140.2-carbonate-15.012.014.04.0-7.031.1 bicarbonate- - -25.4- -silicate 32.014.814.810.010.01.025.03.1

Metasilicate-2.5-9.09.0-

PB1 1.9 9.7 7.8 7.8 7.8 - - -

PB4 8.6 - - - - - - -

Percarbonate- -6.711.84.8

Non-ionic 1.52.01.51.71.52.61.95.3

TAED 5.2 2.4 - - - 2.2 - 1.4

HEDP - 1.0 - - - - - -

DTPMP - 0.6 - - - - - -

MnTACN - - - - - - 0.008 -

PAAC - - 0.008 0.01 0.007 - - -

BzP - - - - 1.4 - - -

Paraffin 0.50.50.50.50.50.6-

PARP3 2(c) 4(c) 2(c) 1(c) - - - 0.5(c)

PARP1 - - - - 10(c) 3(s) 2(c) -

Protease 0.0720.0720.0290.0530.0460.0260.0590.06

Amylase 0.0120.0120.0060.0120.0130.0090.0170.03

Lipase-0.001-0.005-

BTA 0.3 0.3 0.3 0.3 0.3 - 0.3 0.3

MA/AA - - - - - 4.2 -

480N 3.3 6.0 - - - - - 0.9

Fragrance 0.20.20.20.20.20.20.10.1

Sulfate 7.020.05.02.20.812.04.6-

pH 10.8 11.0 10.8 11.3 11.3 9.6 10.8 10.9

Others and water to 100%

Example 17

The following granular dishwashing detergent compositions having a bulk density of 1.02Kg/l were prepared according to the present invention:

A B C D E F G H

STPP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6

carbonate 29.530.029.024.015.036.02.138.0

Silicate 7.47.47.57.213.33.443.712.4

Metasilicate-4.55.1- -

Percarbonate- -4.0- -

PB14.44.24.54.5- -NADCC- - -2.0-1.61.0 non-ionic 1.21.00.70.81.90.70.60.3 TAED 1.0- - -0.8- -PAAC-0.0040.0040.004- - -BzP- - -1.4- - -paraffin 0.250.250.250.25- - -PARP 31.0 (c) 0.5(c) 4.0(s) 8.0(c) - -, 1.0(c) 0.5(c) PARP 1- - -10 (c) 5.0(c) 2.0(c) 8.0(s) protease 0.0360.0150.030.028-0.03- -amylase 0.0030.0030.010.006-0.01- -lipase 0.005-0.001- - -BTA 0.150.150.150.15- - -perfume 0.20.20.20.20.10.20.2-sulphate 23.425.022.018.530.119.323.123.6 pH 10.810.811.311.310.711.512.710.9 and water to 100% example 18

The following bar detergent compositions were prepared according to the present invention by extruding the granular dishwashing detergent composition at a pressure of 13KN/cm2 using a standard 12-head rotary press:

ab C D E F STPP-48.849.238.0-46.8 citrate 26.4- - -31.1-carbonate-4.012.014.410.020.0 silicate 26.414.815.012.617.72.4 PARP 13.0 (C) - - -5.0 (C) - -PARP 2-2.0 (C) - - -4.0 (C) PARP 3- -2.0 (C) 1(s) - - -protease 0.0580.0720.0410.0330.0520.013 amylase 0.010.030.0120.0070.0160.002 lipase 0.005- - -PB11.67.712.210.615.7-PB 46.9- - -14.4 non-ionic 1.52.01.51.650.86.3 PAAC- -0.020.009- -MnTACN- - -0.007-TAED 4.32.5- -1.31.8 HEDP 0.7- -0.7-0.4 DTPMP 0.65- - -paraffin 0.40.50.50.55- -BTA 0.20.30.30.3- -PA 303.2- - -MA/AA- - -4.50.55 perfume- -0.050.050.20.2 sulfate 6-10.73.4 tablet weight 259259209309189209 pH 29 and others Water to 100% example 19

The following liquid dishwashing detergent compositions having a density of 1.40Kg/l were prepared according to the present invention:

a B C DSTPP 17.517.517.216.0 carbonate 2.0-2.4-silicate 5.36.114.615.7 NaOCI 1.151.151.151.25 polygel/carbopol 1.11.01.11.25 non-ionic-0.1-NaBz 0.750.75-PARP 34.0 (C) 2.0(C) 1.0(C) 0.5(C) NaOH-1.9-3.5 KOH 2.83.53.0-pH 11.011.710.911.0 sulfate other and water to 100% example 20 the following rinse aid liquid compositions were prepared according to the invention:

ab C nonionic 12.0-14.5 nonionic mixture-64.0-citric acid 3.2-6.5 HEDP 0.5-PEG-5.0-SCS 4.8-7.0 ethanol 6.08.0-PARP 56.0 (C) -3.0 (C) PARP 3-2.0 (C) pH 2.07.5 of the liquid 1.0(C) example 21 the following liquid dishwashing compositions were prepared according to the present invention:

AB C D EC17ES 28.527.419.234.134.1 amine oxide 2.65.02.03.03.0C 12 glucamide- -6.0- -betaine 0.9- -2.02.0 xylenesulfonate 2.04.0-2.0-Neodol C11E 9- -5.0- -polyhydroxy fatty acid amide- - -6.56.5 sodium diethylenepentaacetate- -0.03- - (40%) TAED- - -0.060.06 sucrose- - -1.51.5 ethanol 4.05.55.59.19.1 alkyldiphenyloxide disulfonate- - -2.3 calcium formate- - -0.51.1 ammonium citrate 0.060.1- - -sodium chloride-1.0- - -magnesium chloride 3.3-0.7- - -calcium chloride- -0.4- -sodium sulfate- -0.06- -magnesium sulfate 0.08- - -magnesium hydroxide- - -2.22.2 sodium hydroxide- - -1.11.1 hydrogen peroxide 200ppm 0.160.006- -PARP 34.0 (C) -2.0 (c) -0.25 (c) PARP 1-6.0 (c) -4.0(s) 3(c) protease 0.0170.005.00350.0030.002 perfume 0.180.090.090.20.2 water and adjuncts to 100% example 22 the following liquid hard surface cleaning compositions were prepared according to the present invention:

aBC D EPARP 18.0 (C) -6.0(s) -4.0 (C) PARP 3-2.0 (C) -1.0 (C) 0.5(C) amylase 0.010.0020.005-protease 0.050.010.02-hydrogen peroxide 6.06.8 acetyl triethyl citrate-2.5-DTPA-0.2-butylhydroxytoluene-0.05 EDTA^* 0.05 0.05 0.05 - -citric acid/citrate 2.92.92.91.0-LAS 0.50.50.5-C12 AS 0.50.50.5-C10 AS- - -1.7C 12(E) S0.50.50.5-C12, 13E 6.5 non-ionic 7.07.07.0- -Neodol 23-6.5- - -12.0-Dobanol 23-3- - -1.5 Dobanol 91-10- - -1.6 C25AE1.8S- - -6.0Sodium Paraffinsulfonate 6.0 fragrance 1.01.01.00.50.2 propylene glycol 1.5 ethoxylated tetraethylene 1.0-Pentaylimine 2-Butyloctanol 0.5 Hexylcarbitol^**1.01.01.0- -SCS 1.31.31.3- -pH adjusted to 7-127-124- -other and water to 100%^*Na4 Ethylenediaminediacetic acidTetrasodium dihexyl glycol ether example 23 the following spray-type compositions for cleaning hard surfaces and removing household mold were prepared according to the present invention: PARP 34.0 (c) Amylase 0.01 protease 0.01 octyl sodium sulfate 2.0 sodium dodecyl sulfate 4.0 sodium hydroxide 0.8 silicate 0.04 butyl Carbitol^*4.0 fragrance 0.35 Water/adjuvant to 100%^*Diethylene glycol monobutyl ether example 24 the following toilet cleaning bar composition was prepared according to the present invention.

AB CC16-18 fatty alcohol/50 EO 70.0- -LAS- -80.0 nonionic- -1.0- -oleamide surfactant- -25.0- -copolymer of partially esterified vinyl methyl ether and maleic anhydride 5.0- -viscosity 0.1-0.5.

Polyethylene glycol MW 8000-38.0-Water soluble K-polyacrylate MW 4000-8000-12.0-Low MW acrylamide (70%) and acrylic acid-19.0- (30%) water soluble Na copolymer sodium tripolyphosphate 10.0- -carbonate- - -PARP 58.0 (c) -6.0 (c) PARP 3-2.0 (c) 0.5(c) dye 2.51.01.0 fragrance 3.0-7.0 KOH/HCL solution pH6-11 example 25 the following toilet bowl cleaning compositions were prepared in accordance with the present invention.

A BC14-15 straight chain alcohol 7EO 2.010.0 citric acid 10.05.0 PARP 22.0 (c) -PARP 3-4.0 (c) DTPMP-1.0 dye 2.01.0 perfume 3.03.0 NaOH pH6-11 water and adjunct to 100% example 26 the following are fabric softening compositions according to the invention:

composition of

A

B

C

D

E

F

DTDMAC	-	-	-	-	4.5	15.0
							DEQA	2.6	2.9	18.0	19.0	-	-
Fatty acids	0.3	-	1.0	-	-	-
							HCl	0.02	0.02	0.02	0.02	0.02	0.02
PEG	-	-	0.6	0.6	-	0.6
							Perfume	1.0	1.0	1.0	1.0	1.0	1.0
Polysiloxane antifoaming agent	0.01	0.01	0.01	0.01	0.01	0.01
							PARP 3	4.5(c)	1.0(c)	3.0(s)	3.0(c)	1.0(s)	6.0(c)
Electrolyte (ppm)	-	-	600	1200	-	1200
							Dye (ppm)	10	10	50	50	10	50
The water and the auxiliary substances are balanced to 100%

Example 27

The following fabric conditioner compositions added to the dryer were prepared according to the present invention:

	A	B	C	D
					DEQA(2)	-	-	-	50.0
DTMAMS	-	-	26.0	-
					SDASA	70.0	70.0	42.0	35.0
Neodol45-13	13.0	13.0	-	-
					ethanol	1.0	1.0	-	-
PARP 3(c)	1.5	-	1.5	3.0
					PARP 3(s)	-	1.5	-	-
Perfume	0.75	0.75	1.0	1.5
					Glycoperse S-20	-	-	-	10.0
Glyceryl monostearate	-	-	26.0	-
					Geranyl succinate	0.38	0.38	-	-
Clay clay	-	-	3.0	-
					Dye material	0.01	0.01	-	-
The auxiliary substances are balanced to 100%

Example 28

The following are non-limiting examples of pre-soak fabric conditioning and/or fabric benefit compositions according to the invention

Example, it may be applicable to the laundry rinse stage:

composition of	A	B	C	D	E	F
							Polymer and method of making same	3.5	3.5	3.5	3.5	3.5	3.5
Dye fixative	2.3	2.3	2.4	2.4	2.5	2.5
							Polyamines	15.0	15.0	17.5	17.5	20.0	20.0
Bayhibit AM	1.0	1.0	1.0	1.0	1.0	1.0
							Chlorination of C12-C14 Dimethyl hydroxyethyl quaternary ammonium salt	-	5.0	5.0	-	-	-
Fabric softener actives	-	-	2.5	2.5	-	-
							Genamin C100	0.33	-	0.33	0.33	0.33	-
Genapol V4463	0.2	-	0.2	0.2	0.2	-
							PARP3(c)	15	30	1.5	7.5	0.75	1.0
Water and auxiliary substances	Balance weight	Balance weight	Balance weight	Balance weight	Balance weight	Balance weight

Example 29

The following are non-limiting examples of odor-absorbing compositions suitable for spray applications:

Examples	A	B	C	D	E
						HPBCD	1.0	-	1.0	-	1.2
RAMEB	-	1.0	-	0.8	-
						Tetronic901	-	-	0.1	-	-
Silwet L-7604	-	-	-	0.1	-
						Silwet L-7600	0.1	-	-	-	0.1
Bardac 2050	-	-	-	0.03	-
						Bardac 2250	-	0.2	-	-	0.1
diethylene glycol	-	1.0	-	-	0.2
						Triethylene glycol	-	-	0.1	-	-
Ethanol	-	-	-	-	2.5

Fragrance 1	0.1	-	-	-	-
						Fragrance 2	-	0.05	-	0.1	-
Fragrance 3	-	-	0.1	-	0.1
						Kathon	3ppm	3ppm	3ppm	3ppm	-
HCl	to pH4.5	to pH4.5	to pH3.5	to pH3.5	to pH3.5
						PARP3(c)	10.0	10.0	5.0	1.0	0.8
Distilled water	Balance weight	Balance weight	Balance weight	Balance weight	Balance weight

Fragrances 1,2 and 3 have the following composition:

perfume	1	2	3
				Perfume ingredients	Wt.％	Wt.％	Wt.％
	-	-	-
				Anisaldehyde	-	-	2
Benzophenones as fungicides	3	5	-
				Acetic acid benzyl ester	10	15	5
Salicylic acid benzyl ester	5	20	5
				Cedarwood jelly	2	-	-
Citronellol	10	-	5
				Coumarin compound	-	-	5
Cymal	-	-	3
				Dihydromyrcenol	10	-	5
Flor acetate	5	-	5
				Jiale Musk	10	-	-
Lilial aldehyde	10	15	20
				Nopyl acetate	4	-	5
Linalool	6	15	5
				Dihydromenthyl ketonic acid methyl ester	3	10	5
Phenylethyl acetate	2	5	1
				Phenylethanolic acid	15	15	20
alpha-terpineol	5	-	8
				Vanillin	-	-	1
Total of	100	100	100

Claims (24)

1. A process for preparing particles of an amine reaction product between a compound containing primary and/or secondary amine functional groups and an active ketone or aldehyde-containing component comprising the steps of:

a) providing an amine reaction product, and

b) mixing with carrier with melting point of 30-135 deg.C.

2. A method according to claim 1, wherein the particles are treated to form coated particles.

3. The process according to claim 1 or 2, wherein the amine reaction product has a viscosity of greater than 1000 cps.

4. A process according to any of claims 1 to 3, wherein the primary and/or secondary amine is selected from: aminoaryl derivatives, polyamines, amino acids and derivatives thereof, polyamino acids, crosslinked polyamino acids, substituted amines and amides, glucosamine, dendrimers, polyvinylamine with MW 600-50K, amino-substituted polyvinylalcohol with MW 400-300000, polyoxyethylene bis [ amine ], polyoxyethylene bis [ 6-aminohexyl ], linear or branched N, N' -bis (3-aminopropyl) -1, 3-propanediamine, 1, 4-bis- (3-aminopropyl) piperazine and mixtures thereof; preferably selected from the group consisting of ethyl 4-aminobenzoate, polyethyleneimine polymers, glucosamine, diaminobutane dendrimers, polyvinylamine with MW of 600, 1200, 3K, 20K, 25K or 50K, amino-substituted polyvinylalcohol with MW of 400-300000, polyoxyethylene bis [ amine ], polyoxyethylene bis [ 6-aminohexyl ], linear or branched N, N' -bis (3-aminopropyl) -1, 3-propanediamine, 1, 4-bis- (3-aminopropyl) piperazine and mixtures thereof; more preferably selected from ethyl 4-aminobenzoate, polyethyleneimine polymers, diaminobutane dendrimers, linear or branched N, N' -bis (3-aminopropyl) -1, 3-propanediamine, 1, 4-bis- (3-aminopropyl) piperazine and mixtures thereof, most preferably selected from: ethyl 4-aminobenzoate, polyethyleneimine polymers, polylysine, crosslinked polylysine, linear or branched N, N' -bis (3-aminopropyl) -1, 3-propanediamine, 1, 4-bis- (3-aminopropyl) piperazine and mixtures thereof.

5. A method according to any of claims 1-4, wherein the active is selected from the group consisting of a scented ketone or aldehyde component, a pharmaceutical ketone or aldehyde active, a biological control ketone or aldehyde agent, a scented ketone or aldehyde component, a cooling ketone or aldehyde agent, and/or mixtures thereof.

6. A method according to any one of claims 1 to 4 wherein the active ingredient is an insect and/or moth repellent, preferably selected from citronellal, citral, N-diethyl-m-toluamide, Rotundail, 8-acetoxy carvone and mixtures thereof.

7. A method according to any of claims 1-4, wherein the active ingredient is an antibacterial agent, preferably selected from glutaraldehyde, cinnamaldehyde, and mixtures thereof.

8. A method according to any of claims 1-4, wherein the active is a perfume, preferably selected from the group consisting of a-damascone, δ -damascone, carvone, γ -methylionone, damascone, methyl dihydrojasmonate, 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde, florydral, lilial, piperonal, trans-2-nonenal, citral and mixtures thereof.

9. The process according to any one of claims 1 to 8, wherein the amount of amine reaction product is from 1% to 75%, preferably from 5% to 30%, by weight of the processed amine reaction product.

10. A process according to any one of claims 1 to 9 wherein the carrier has a melting point of from 45 ℃ to 85 ℃.

11. A process according to any of claims 1 to 10, wherein the carrier is selected from organic polymeric compounds, waxes, paraffins, oils, glycerides, monoglycerides, diglycerides, triglycerides, anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures thereof, preferably from organic polymeric compounds, nonionic surfactants and mixtures thereof, more preferably the nonionic surfactants are selected from nonionic ethoxylated alcohols.

12. A process according to any one of claims 1 to 11 wherein the amount of support material is from 3% to 95%, preferably from 15% to 80%, most preferably from 25% to 75% by weight of the processed amine reaction product particles produced.

13. A process according to any one of claims 1 to 12, wherein the coating film is made from a water-soluble agglomerating agent.

14. A process according to claim 13, wherein the water-soluble agglomerating agent is selected from the group consisting of water-soluble organic polymeric compounds, water-soluble monomeric polycarboxylates or acid forms thereof, homo-or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by not more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, sulphates, inorganic perhydrate salts, silicates, starches, cyclodextrins and mixtures thereof, preferably selected from the group consisting of starches, carbonates, cyclodextrins and mixtures thereof.

15. A process according to any one of claims 1 to 14 wherein the amount of amine reaction product is from 1% to 75%, preferably from 5% to 30% by weight of the coated particles.

16. A processed amine reaction product produced by the process of any of claims 1-15.

17. A process for incorporating an amine reaction product according to claim 15 into a finished product.

18. A finished composition comprising one or more laundry or cleaning ingredients and a processed amine reaction product according to claim 16.

19. A composition according to claim 18, wherein the composition is selected from laundry compositions, hard surface cleaning compositions, personal cleansing compositions.

20. A composition according to claim 19, wherein the composition is a detergent composition comprising clay.

21. A method of imparting residual fragrance to a surface comprising contacting the surface with a processed product according to claim 16 or a composition according to any of claims 18 to 20, and thereafter contacting the treated fabric with a substance such that perfume is released.

22. Use of a product as defined in claim 16 for the preparation of a laundry and/or cleaning composition which provides residual fragrance on the surface to which it is applied.

23. Use of a product as defined in claim 16 for the preparation of a laundry and/or cleaning composition providing residual fragrance and fabric care on fabrics to which it is applied.

24. A packaged composition comprising the processed product of claim 14 or the composition of any of claims 18-20.