There is provided a process for producing particles of amine reaction product by means of an acid carrier. Processed amine reaction products and finished compositions incorporating such processed product are also herein provided.

The present invention relates to a process for producing particles of amine reaction product.
Perfumed products are well-known in the art. However, consumer acceptance of such perfumed products like laundry and cleaning products is determined not only by the performance achieved with these products but also by the aesthetics associated therewith. The perfume components are therefore an important aspect of the successful formulation of such commercial products.
It is also desired by consumers for treated fabrics to maintain the pleasing fragrance over time. Indeed, perfume additives make such compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasant fragrance to fabrics treated therewith. However, the amount of perfume carried-over from an aqueous laundry bath onto fabrics is often marginal and does not last long on the fabric. Furthermore, fragrance materials are often very costly and their inefficient use in laundry and cleaning compositions and ineffective delivery to fabrics results in a very high cost to both consumers and laundry and cleaning manufacturers. Industry, therefore, continues to seek with urgency for more efficient and effective fragrance delivery in laundry and cleaning products, especially for improvement in the provision of long-lasting fragrance to the fabrics.
It has recently been found that an amine reaction product of a compound containing a primary amine functional group and an active ketone or aldehyde containing component fulfills such a need. Disclosure of such compounds can be found in recently filed applications EP 98870227.0, EP 98870226.2, EP 99870026.4, and EP 99870025.6, all incorporated herein by reference.
However, a problem now encountered with the use of these compound is their ease of incorporation into fully formulated compositions. Indeed, such amine reaction products are often viscous which renders their incorporation into these fully formulated compositions more cumbersome.
It is therefore an object of the invention to provide amine reaction product in a form suitable for easy incorporation into fully formulated composition.
It has now been found that the mixing of the amine reaction product with an acid carrier fulfills such a need.
Further, it has also been advantageously found that such viscous amine reaction product when processed by the present invention exhibit better deposition and long lasting release than amine reaction product which have not been processed according to this process. Not to be bound by theory, it is believed that the mixing with such carrier acts as a shell around the amine reaction product, thus protecting it from the aggressive wash liquor as well as enhancing its fabric deposition properties.
By xe2x80x9cViscousxe2x80x9d, it is meant a product which has a viscosity higher than 1000 cps. The viscosity is measured on a rheometer, TA Instrument CSL2100 at a temperature of 25xc2x0 C. with a gap setting of 500 microns.
By xe2x80x9cacid carrierxe2x80x9d, it is meant a carrier which forms a salt with the amine reaction product. Not to be bound by theory, it is believed that the salt formation occurs by reacting the amine reaction product with an acid. The salt formation takes place via a reaction of the acid at the nitrogen of the xcex2-aminoketone or imine function. Still, and also preferred, the salt formation may also take place at other nucleophilic centers of the amine or amine reaction product. Indeed, it is believed that when the salt formation takes place at the nucleophilic center of the primary amine, the link nitrogen-active tends to be more labile and therefore may liberate the perfume in-situ. Typical examples of such other suitable nucleophilic centers are the tertiary and secondary amine functions in polyethylenimine polymers.
The present invention is a process for making particles of amine reaction product of a compound containing a primary and/or secondary amine functional group and an active ketone or aldehyde containing component, and which comprises the steps of:
a)-providing the amine reaction product, and
b)-mixing therewith an acid carrier.
In a preferred embodiment of the invention, the obtained amine reaction product is further processed to form a coated particle.
In another aspect of the invention, the obtained particle or coated particle is incorporated in a finished composition.
1)-Amine Reaction Product
The amine reaction product for use herein is a product of reaction between a compound containing a primary and/or secondary amine functional group and an active ketone or aldehyde containing component, so called hereinafter xe2x80x9camine reaction productxe2x80x9d.
A typical disclosure of amine reaction product suitable for use herein can be found in recently filed applications EP 98870227.0, EP 98870226.2, EP 99870026.4, and EP 99870025.6, all incorporated herein by reference.
Axe2x80x94Primary and/or Secondary Amine
By xe2x80x9cprimary and/or secondary aminexe2x80x9d, it is meant a component which carries at least one primary and/or secondary amine and/or amide function.
Preferably, the primary and/or secondary amine compound is also characterized by an Odour Intensity Index of less than that of a 1% solution of methylanthranilate in dipropylene glycol.
Odour Intensity Index Method
By Odour Intensity Index, it is meant that the pure chemicals were diluted at 1% in Dipropylene Glycol, odor-free solvent used in perfumery. This percentage is more representative of usage levels. Smelling strips, or so called xe2x80x9cblottersxe2x80x9d, were dipped and presented to the expert panellist for evaluation. Expert panellists are assessors trained for at least six months in odor grading and whose gradings are checked for accuracy and reproducibility versus a reference on an on-going basis. For each amine compound, the panellist was presented two blotters: one reference (Me Anthranilate, unknown from the panellist) and the sample. The panellist was asked to rank both smelling strips on the 0-5 odor intensity scale, 0 being no odor detected, 5 being very strong odor present.
Results:
The following represents Odour Intensity Index of an amine compound suitable for use in the present invention and according to the above procedure. In each case, numbers are arithmetic averages among 5 expert panellists and the results are statistically significantly different at 95% confidence level:
A general structure for the primary amine compound of the invention is as follows:
Bxe2x80x94(NH2)n;
wherein B is a carrier material, and n is an index of value of at least 1.
Compounds containing a secondary amine group have a structure similar to the above excepted that the compound comprises one or more xe2x80x94NHxe2x80x94 groups instead of xe2x80x94NH2. Further, the compound structure may also have one or more of both xe2x80x94NH2 and xe2x80x94NHxe2x80x94 groups.
Preferred B carriers are inorganic or organic carriers.
By xe2x80x9cinorganic carrierxe2x80x9d, it is meant carrier which are non-or substantially non carbon based backbones.
Preferred primary and/or secondary amines, among the inorganic carriers, are those selected from mono or polymers or organic-organosilicon copolymers of amino derivatised organo silane, siloxane, silazane, alumane, aluminum siloxane, or aluminum silicate compounds. Typical examples of such carriers are: organosiloxanes with at least one primary amine moiety like the diaminoalkylsiloxane [H2NCH2(CH3) 2Si]O, or the organoaminosilane (C6H5) 3SiNH2 described in: Chemistry and Technology of Silicone, W. Noll, Academic Press Inc. 1998, London, pp 209, 106).
Preferred primary and/or secondary amines, among the organic carriers, are those selected from aminoaryl derivatives, polyamines, amino acids and derivatives thereof, substituted amines and amides, glucamines, dendrimers, polyvinylamines and derivatives thereof, and/or copolymer thereof, alkylene polyamine, polyaminoacid and copolymer thereof, cross-linked polyaminoacids, amino substituted polyvinylalcohol, polyoxyethylene bis amine or bis aminoalkyl, aminoalkyl piperazine and derivatives thereof, bis (amino alkyl) alkyl diamine linear or branched, and mixtures thereof.
Preferred aminoaryl derivatives are the aminabenzene derivatives including the alkyl esters of 4-amino benzoate compounds, and more preferably selected from ethyl-4-amino benzoate, phenylethyl-4-aminobenzoate, phenyl-4-aminobenzoate, 4-amino-Nxe2x80x2-(3-aminopropyl)-benzamide, and mixtures thereof.
Polyamines suitable for use in the present invention are polyethyleneimines polymers, poly[oxy(methyl-1,2-ethanediyl)], xcex1-(2-aminomethylethyl)-xcfx89-(2-aminomethyl-ethoxy)- (=C.A.S No. 9046-10-0); poly[oxy(methyl-1,2-ethanediyl)], xcex1-hydro)-xcfx89-(2-aminomethylethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (=C.A.S. No. 39423-51-3); commercially available under the tradename Jeffamines T-403, D-230, D-400, D-2000; 2,2xe2x80x2,2xe2x80x3-triaminotriethylamine; 2,2xe2x80x2-diamino-diethylamine; 3,3xe2x80x2-diamino-dipropylamine, 1,3 bis aminoethyl-cyclohexane commercially available from Mitsibushi and the C12 Sternamines commercially available from Clariant like the C12 Sternamin(propylenamine)n with n=3/4, and mixtures thereof. Preferred polyamines are polyethyleneimines commercially available under the tradename Lupasol like Lupasol FG (MW 800), G20wfv (MW 1300), PR8515 (MW 2000), WF (MW 25000). FC (MW 800), G20 (MW 1300), G35 (MW 1200), G100 (MW 2000), HF (MW 25000), P (MW 750000), PS (MW 750000), SK (MW 2000000), SNA (MW 1000000).
Preferred amino acids for use herein are selected tyrosine, tryptophane, lysine, glutamic acid, glutamine, aspartic acid, arginine, asparagine, phenylalanine, proline, glycine, serine, histidine, threonine, methionine, and mixture thereof, most preferably selected from tyrosine, tryptophane, and mixture thereof. Preferred amino acid derivatives selected from tyrosine ethylate, glycine methylate, tryptophane ethylate, and mixture thereof.
Preferred substituted amines and amides for use herein are selected from nipecotamide, N-coco-1,3-propenediamine; N-oleyl-1,3-propenediamine; N-(tallow alkyl)-1,3-propenediamine; 1,4-diamino cyclohexane; 1,2-diamino-cyclohexane; 1,12-diaminododecane, and mixtures thereof.
Other primary amine compounds suitable for use herein are the glucamines, preferably selected from 2,3,4,5,6-pentamethoxy-glucamine; 6-acetylglucamine, glucamine, and mixture thereof.
Also preferred compounds are the polyethylenimine and/or polypropylenimine dendrimers and the commercially available Starburst(copyright) polyamidoamines (PAMAM) dendrimers, generation G0-G10 from Dendritech and the dendrimers Astromols(copyright), generation 1-5 from DSM being DiAminoButane PolyAmine DAB (PA)x dendrimers with x=2nx4 and n being generally comprised between 0 and 4.
Still 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 polyvinylamines, derivatives thereof, copolymer thereof, alkylene polyamine, polyaminoacids and copolymer thereof, cross-linked polyaminoacids, amino substituted polyvinylalcohol, polyoxyethylene bis amine or bis aminoalkyl, aminoalkyl piperazine and derivatives, N,Nxe2x80x2-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA), and mixtures thereof.
Polyamino acid is one suitable and preferred class of amino-functional polymer. Polyaminoacids are compounds which are made up of amino acids or chemically modified amino acids. They can 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 acidic function of the amino acid has reacted with a chemical reagent. This is often done to protect these chemical amine and acid functions of the amino acid in a subsequent reaction or to give special properties to the amino acids, like improved solubility. Examples of such chemical modifications are benzyloxycarbonyl, aminobutyric acid, butyl ester, pyroglutamic acid. More examples of common modifications of amino acids and small amino acid fragments can be found in the Bachem, 1996, Peptides and Biochemicals Catalog.
Preferred polyamino acids are polylysines, polyarginine, polyglutamine, polyasparagine, polyhistidine, polytryptophane or mixtures thereof. Most preferred are polylysines or polyamino acids where more than 50% of the amino acids are lysine, since the primary amine function in the side chain of the lysine is the most reactive amine of all amino acids.
The preferred polyamino acid has a molecular weight of 500 to 10.000.000, more preferably between 5,000 and 750,000.
The polyamino acid can be cross linked. The cross linking can be obtained for example by condensation of the amine group in the side chain of the amino acid like lysine with the carboxyl function on the amino acid or with protein cross linkers like PEG derivatives. The cross linked polyamino acids still need to have free primary and/or secondary amino groups left for reaction with the active ingredient.
The preferred cross linked polyamino acid has a molecular weight of 20,000 to 10,000,000, more preferably between 200,000 and 2,000,000.
The polyamino acid or the amino acid can be co-polymerized with other reagents like for instance with acids, amides, acyl chlorides. More specifically with aminocaproic acid, adipic acid, ethylhexanoic acid, caprolactam or mixture thereof. The molar ratio used in these copolymers ranges from 1:1 (reagent/amino acid (lysine)) to 1:20, more preferably from 1:1 to 1:10.
The polyamino acid like polylysine can be partially ethoxylated.
Examples and supply of polyaminoacids containing lysine, arginine, glutamime, asparagine are given in the Bachem 1996, Peptides and Biochemicals catalog.
The polyaminoacid can be obtained before reaction with the active ingredient, under a salt form. For example polylysine can be supplied 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 amine group for the purpose of the present invention are:
Polyvinylamine with a MW of about 300-2.10E6;
Polyvinylamine alkoxylated with a MW of about 600, 1200 or 3000 and an ethoxylation degree of 0.5;
Polyvinylamine vinylalcoholxe2x80x94molar ratio 2:1, polyvinylaminevinylformamidexe2x80x94molar ratio 1:2 and polyvinylamine vinylformamide-molar ratio 2:1;
Triethylenetetramine, diethylenetriamine, tetraethylenepentamine;
Bis-aminopropylpiperazine;
Polyamino acid (L-lysine/lauric acid in a molar ratio of 10/1), Polyamino acid (L-lysine/aminocaproic acid/adipic acid in a molar ratio of 5/5/1),), Polyamino acid (L-lysine/aminocaproic acid/ethylhexanoic acid in a molar ratio of 5/3/1) Polyamino acid (polylysine-cocaprolactam); Polylysine; Polylysine hydrobromide; cross-linked polylysine,
amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
polyoxyethylene bis [amine] available from e.g. Sigma;
polyoxyethyl ne bis [6-aminohexyl] available from e.g. Sigma;
N,Nxe2x80x2-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA); and
1,4-bis-(3aminopropyl) piperazine (BNPP).
The more preferred compounds are selected from ethyl-4-amino benzoate, polyethyleneimine polymers commercially available under the tradename Lupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA; the diaminobutane dendrimers Astramol(copyright), polylysine, cross-linked polylysine, N,Nxe2x80x2-bis-(3-aminopropyl-1,3-propanediamine linear or branched; 1,4-bis-(3-aminopropyl) piperazine, and mixtures thereof. Even most preferred compounds are those selected from ethyl-4-amino benzoate, polyethyleneimine polymers commercially available under the tradename Lupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA; polylysine, cross-linked polylysine, N,Nxe2x80x2-bis-(3-aminopropyl)-1,3-propanediamine linear or branched, 1,4-bis-(3-aminopropyl) piperazine, and mixtures thereof.
Advantageously, such most preferred primary and/or secondary amine compounds also provide fabric appearance benefit, in particular colour appearance benefit, thus providing a resulting amine reaction product with the dual properties of both fabric appearance benefit and delayed release of the active. Further, when the primary and/or secondary amine compound has more than one free primary and/or secondary amine group, several different active ingredients (aldehyde and/or ketone) can be linked to the amine compound.
B-Active Ketone and/or Aldehyde
Preferably, for the above mentioned compounds, by active ketone or active aldehyde, it is meant any chain containing at least 1 carbon atom, preferably at least 5 carbon atoms.
Preferably, the active ketone or active aldehyde is respectively selected from a flavour ketone or aldehyde ingredient, a pharmaceutical ketone or aldehyde active, a biocontrol ketone or aldehyde agent, a perfume ketone or aldehyde component and mixtures thereof; most preferably a perfume ketone and/or aldehyde.
Flavour ingredients include spices, flavor enhancers that contribute to the overall flavour perception.
Pharmaceutical actives include drugs.
Biocontrol agents include biocides, antimicrobials, bactericides, fungicides, algaecides, mildewcides, disinfectants, sanitiser like bleach, antiseptics, insecticides, insect and/or moth repellant, vermicides, plant growth hormones.
Typical antimicrobials include Glutaraldehyde, Cinnamaldehyde, and mixtures thereof. Typical insect and/or moth repellants are perfume ingredients, such as citronellal, citral, N,N diethyl meta toluamide, Rotundial, 8-acetoxycarvotanacenone, and mixtures thereof. Other examples of insect and/or moth repellant for use herein are disclosed in U.S. Pat. Nos. 4,449,987, 4,693,890, 4,696,676, 4,933,371, 5,030,660, 5,196,200, and xe2x80x9cSemio Activity of Flavor and Fragrance molecules on various Insect Speciesxe2x80x9d, B. D. Mookherjee et al., published in Bioactive Volatile Compounds from Plants, ASC Symposium Series 525, R. Teranishi, R. G. Buttery, and H. Sugisawa, 1993, pp. 35-48.
A typical disclosure of suitable ketone and/or aldehydes, traditionally used in perfumery, can be found in xe2x80x9cperfume and Flavor Chemicalsxe2x80x9d, Vol. I and II, S. Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5.
Perfume ketones components include components having odoriferous properties.
Preferably, for the above mentioned compounds, the perfume ketone is selected from buccoxime; iso jasmone; methyl beta naphthyl ketone; musk indanone; tonalid/musk plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-lonone, Beta-lonone, Gamma-Methyl so-called Ionone, Fleuramone, Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl-Cedrenyl-ketone or Methyl-Cedrylone, Acetophenone, Methyl-Acetophenone, Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone, Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone or Livescone, 6-Isopropyldecahydro-2-naphtone, Dimethyl-Octenone, Freskomenthe, 4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethyl-Cyclohexanone, Methyl-Heptenone, 2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)cyclopentanone, 1-(p-Menthen-6(2)-yl)-1-propanone, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanone, 2-Acetyl-3,3-Dimethyl-Norbornane, 6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-Damascol, Dulcinyl or Cassione, Gelsone, Hexalon, Isocyclemone E, Methyl Cyclocitrone, Methyl-Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone, Verdone, Delphone, Muscone, Neobutenone, Plicatone, Veloutone, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Tetrameran, hedione, and mixtures thereof.
More preferably, for the above mentioned compounds, the preferred ketones are selected from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-lonone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, hedione, and mixtures thereof.
Perfume aldehyde components include components having odoriferous properties.
Preferably, for the above mentioned compounds, the perfume aldehyde is selected from adoxal; anisic aldehyde; cymal, ethyl vanillin; florhydral; helional; heliotropin; hydroxycitronellal; koavone; lauric aldehyde; lyral; methyl nonyl acetaldehyde; P. T. bucinal; phenyl acetaldehyde; undecylenic aldehyde; vanillin; 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamic aldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3-(4-tert butylphenyl)propanal, 2-methyl-3-(para-methoxyphenyl propanal, 2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-octadien-1-al, 3,7-dimethyl-6-locten-1-al, [(3,7-dimethyl-6-octenyl)oxy] acetaldehyde, 4-isopropylbenzyaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, 2-methyl-3-(isopropylphenyl)propanal, 1-decanal; decyl aldehyde, 2,6-dimethyl-5-heptenal, 4-(tricyclo[220.127.116.11(2,6)]-decylidene-8)-butanal, octahydro-4,7-methano-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxy benzaldehyde, para-ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde, alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde, m-cymene-7-carboxaldehyde, alpha-methyl phenyl acetaldehyde, 7-hydroxy-3,7-dimethyl octanal, Undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde, 1-dodecanal, 2,4-dimethyl cyclohex ne-3-carboxaldehyde, 4-(4-hydroxy-4-methyl pentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal, dihydrocinnamic aldehyde, 1-methyl-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5 or 6 methoxy0hexahydro-4,7-methanoindan-1 or 2- carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-methoxy benzaldehyde, 1-methyl-3-(4-methylpentyl)-3-cyclhexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde; 4-methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexene carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyl octanal, alpha-methyl-4-(1-methyl ethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxy acetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl hexanal, 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-carboxaldehyde, citral, lilial and mixtures thereof.
Most preferred aldehydes are selected from citral, 1-decanal, benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde; cis-trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P. T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, trans-2-nonenal, lilial, trans-2-nonenal, and mixture thereof.
In the above list of perfume ingredients, some are commercial names conventionally known to one skilled in the art, and also includes isomers. Such isomers are also suitable for use in the present invention.
In another embodiment, especially suitable for the purpose of the present invention are the perfume compounds, preferably the perfume ketones or aldehydes, charactensed by having a low Odor Detection Threshold. Such Odor Detection Threshold (ODT) should be lower than 1 ppm, preferably lower than 10 ppbxe2x80x94measured at controlled Gas Chromatography (GC) conditions such as described here below. This parameter refers to the value commonly used in the perfumery arts and which is the lowest concentration at which significant detection takes place that some odorous material is present, as referred to for example in xe2x80x9cCompilation of Odor and Taste Threshold Value Data (ASTM DS 48 A)xe2x80x9d, edited by F. A. Fazzalari, International Business Machines, Hopwell Junction, N.Y. and in Calkin et at., Perfumery, Practice and Principles, John Willey and Sons, Inc., page 243 et seq (1994). For the purpose of the present invention, the Odor Detection Threshold is measured according to the following method: The gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution. The air flow rate is accurately measured and, assuming the duration of a human inhalation to last 0.02 minutes, the sampled volume is calculated. Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of material. To determine the ODT of a perfume material, solutions are delivered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is noticed. The average over all panelists determines the threshold of noticeability. The necessary amount of analyte is injected onto the column to achieve a certain concentration, such as 10 ppb, at the detector. Typical gas chromatograph parameters for determining odor detection thresholds are listed below.
GC: 5890 Series II with FID detector
7673 Autosampler
Column: JandW Scientific DB-1
Length 30-meters ID 0.25 mm film thickness 1 micron
Method:
Split Injection: 17/1 split ratio
Autosampler 1.13 microliters per injection
Column Flow: 1.10 mL/minute
Air Flow: 345 mL/minute
Inlet Temp. 245xc2x0 C.
Detector Temp. 285xc2x0 C.
Temperature Information
Initial Temperature: 50xc2x0 C.
Rate: 5C/minute
Final Temperature: 280xc2x0 C.
Final Time: 6 minutes
Leading assumptions: 0.02 minutes per sniff
GC air adds to sample dilution
Examples of such preferred perfume components are those selected from: 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde, 1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one and/or para-methoxy-acetophenone. Even more preferred are the following compounds having an ODTxe2x89xa610 ppb measured with the method described above: undecylenic aldehyde, undecalactone gamma, heliotropin, dodecalactone gamma, p-anisic aldehyde, para hydroxy-phenyl-butanone, cymal, benzyl acetone, ionone alpha, p.t.bucinal, damascenone, ionone beta and methyl-nonyl ketone.
Typically the level of active is 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 products are those resulting from the reaction of polyethyleneimine polymer like Lupasol polymers, BNPP, or TPTA with one or more of the following Alpha Damascone, Delta Damascone, Carvone, Gamma-Methyl-Ionone, Hedione, Florhydral, Lilial, Heliotmpine, and 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde. Still other preferred amine reaction products are those resulting from the reaction of Astramol Dendrimers with Carvone as well as those resulting from the reaction of ethyl-4-amino benzoate with one or more of the following 2,4-dimethyl-3-cydohexen-1-carboxaldehyde, and trans-2-nonenal. Still another preferred amine reaction products are those resulting from the reaction of polylysine with one or more of the following Alpha Damascone, Delta Damascone, Carvone, and 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.
Most preferred amine reaction products are those from the reaction of Lupasol HF with Delta Damascone; LupasolG35 with Alpha Damascone: LupasolG100 with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, BNPP or TPTA with Alpha and Delta Damascone; ethyl-4-amino benzoate with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.
Even most preferred amine reaction products are those fulfilling the Dry Surface Odor Index as per given in co-pending application EP 98870155.3 given at page 29, line 26 to page 32 line 29, in which the specified unperfumed base for fabric sufaces and hard surfaces are respectively as follow:
2)-Carrier
Another essential ingredient of the process invention is an acid carrier. By means of this carrier, particles of amine reaction product will be easily and quickly produced. In a preferred aspect, the amine reaction product and the carrier material are in close physical proximity, more preferably in close contact, most preferably in intimate admixture within said obtained particle.
Typical of these acid carrier for use herein are the commonly known organic acids or inorganic acids, which fall under the description of Bronsted or Lewis acids.
Definition of an acid can be found in March J., Advanced Organic Chemistry, Chapter 8, page 248 for definition of a Bronsted acid and page 260 for the definition of a Lewis acid, John Wiley and Sons, New York, 1992.
Suitable acid carrier for use herein have a pKa relative to water of from minus 9 to 16, more preferably from minus 2 to 10, most preferably from 0 to 7. For example, alcohols like phenol derivatives are suitable acid carrier for use herein. A typical example of such phenol derivative is picric acid which has a pKa of 0.25.
Preferred organic or inorganic acids include those conventionally known as solid binders or agglomerating agents. More preferred organic acids are substantially water soluble solid binders or agglomerating agents. Most preferred are organic acids used in detergent applications, for example as builders.
xe2x80x9cSubstantially water solublexe2x80x9d shall refer to a material that is soluble in distilled (or equivalent) water, at 25xc2x0 C., at a concentration of 0.2% by weight, and are preferably soluble at 1.0% by weight.
A xe2x80x9csolidxe2x80x9d is defined as a material that is a solid at ambient temperatures, and so solid substantially water-soluble binder or agglomerating agent must have a melting point of at least 30xc2x0 C., and preferably of at least 40xc2x0 C.
Suitable water-soluble binders or agglomerating agents as organic acid carriers include monocarboxylic acids, monomeric polycarboxylic acids, homo or copolymeric polycarboxylic acids, inorganic acids, and mixtures thereof.
Suitable example of monocarboxylic acids containing one carboxy group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof.
Still other suitable monocarboxylic acids are the monocarboxylic acids substituted by any of the following groups: CH3xe2x80x94 (CH2)n, wherein n is an integer of value of at least 1, CH3, OH, NH2, Cl, Br, F, I, ORxe2x80x3, NHRxe2x80x3, NRxe2x80x32, NO2, SO3, cyclic rings like cyclopentane, cyclohexane, phenyl, benzyl, or a mixture of these substituents; wherein Rxe2x80x3 is selected from saturated or unsaturated alkyl chains. Preferred examples are 1-methylcyclohexanecarboxylic acid, glycolic acid, mandelic acid, lactic acid, salicylic acid, benzoic acid, and derivatives thereof. The substituents may also be anywhere in the alkyl chain attached to the acidic function. The alkyl chain can be saturated or non saturated.
Still other typical of organic acids suitable for use herein as acid carrier includes the polycarboxylic acids containing two carboxy groups. Typical of these ingredients are selected from succinic acid, matonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, fumaric acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, or sebacic acid, as well as the ether carboxylic acid and the sulfinyl carboxylic acids, and mixtures thereof.
Other dicarboxylic adds suitable for use herein are the dicarboxylic acids substituted by CH3xe2x80x94 (CH2)n, wherein n is an integer of value of at least 1, CH3, OH, NH2, Cl, Br, F, I, ORxe2x80x3, NHRxe2x80x3, NRxe2x80x32, NO2, SO3, cyclic rings like cyclopentane, cydohexane, phenyl, benzyl, or a mixture of these substituents; wherein Rxe2x80x3 is selected from saturated or unsaturated alkyl chain. Preferred examples of such substituted dicarboxylic acids are phtalic acid, isophtalic acid, terephtalic acid, malic acid, fumaric acid, tartaric acid, or mixtures thereof. The substituents may also be anywhere in the alkyl chain attached to the acidic functions. The alkyl chains can be saturated or non saturated.
Other polycarboxylic acids suitable for use herein are the polycarboxylic acids containing three carboxy groups and include, in particular, water-soluble citric acid, aconitric and citraconic acid as well as succinic derivatives such as the carboxymethyloxysuccinic described in British Patent No. 1,379,24I, lactoxysuccinic described in British Patent No. 1,389,732, and aminosuccinic described in Netherlands Application 7205873, and the oxypolycarboxylic materials such as 2-oxa-1,1,3-propane tricarboxylic described in British Patent No. 1,387,447.
Other polycarboxylic acids suitable for use herein are the polycarboxylic acids containing four carboxy groups and include oxydisuccinic disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylic, 1,1,3,3-propane tetracarboxylic and 1,1,2,3-propane tetracarboxylic. Polycarboxylic containing sulfo substituents include the sulfosuccinic derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed citratic described in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylic include cyclopentane-cis,cis,cis-tetracarboxylic, cyclopentadienide pentacarboxylic, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylic, 2,5-tetrahydrofuran-cis-dicarboxylic, 2,2,5-tetrahydrofuran-tetracarboxylic, 1,2,3,4,5,6-hexane-hexacarboxylic, polyacrylic acid, polymaleic acid, polymaleic-acrylic acids, sugar-acids like glucose-phosphonic acid, gluconic acid, glucuronic acid, mannanic acid, galactonic acid, arabinamic acid, and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylic include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Other suitable carriers are amino acids like, glycine, lysine, alanine, valine, leucine, isoleucine, proline, phenylalanine, tyrosine, tryptophan, serine, threonine, cysteine, methionine, asparagine, glutamine, aspartate, glutamate, arginine, histidine, and mixtures thereof.
Other suitable acid carriers are the so called inorganic acids like for example HF, HCl, HBr, HI, H2SO4, H2SO3, H2CO3, HNO2, HNO3, HClO4, HClO3, HClO2, HClO, or H3PO4, H4P2O7, or H5P3O10 or mixture thereof. Also useful herein as acid carriers are the protonated forms of the anionic surfactants, like the protonated form of the linear C11-13 alkyl benzene sulfonate anionic surfactant.
Other suitable carriers are acid anhydrides and acyl halides. Acid anhydrides react in the presence of water to acids. Sometimes, the production of the amine reaction product is followed by the incomplete removal of the water in the amine samples. It may then be desired to remove the remaining water by reacting it with the acid anhydrides to form acids which in turn make the salt with the amine reaction product.
Other suitable carriers are acids, where the acidic proton is linked to C, N, S, Si or other non-oxygen atoms. Example of such acids is 2,4-pentanedione.
Preferably, to avoid possible hydrolysis of the amine reaction product in-situ due to the eventual additional water coming from the acid carrier, the acid carrier is used in its anhydrous forms. For example, citric acid is available under anhydrous form or as a monohydrate.
Of the above, the preferred acid carriers are polycarboxylic acids selected from citric acid, tartaric acid, malonic acid, succinic acid, oxalic acid, adipic acid, maleic acid, malic acid, phtalic acid, succinic acid, hydroxysuccinic acid, polyacrylic acid, and mixtures thereof.
Typically when the amine reaction product is mixed with such acid carrier, the amine reaction product will be present in an amount of from 10 to 85%, preferably 20 to 80%, more preferably 45 to 75% by weight of the processed reaction product in the produced particle. In this instance, the amount of carrier will be sufficient to add up to 100%. Of course, the particle may also contain minors but in quantities which will not exceed the amount of carrier material. Hence, if desired, the processed particle may contain one or more additional ingredients like a surfactant for improved solubility or dispersability. Typical of such surfactant are the anionic, nonionic, or cationic surfactants. Preferably, the weight ratio of such additional ingredient(s) to the carrier is of up to 1:1. Typically the acid carrier will be present in an amount of from 5 to 90%, preferably from 15 to 80% and most preferably from 20 to 70%, by weight of the produced particles in the processed amine reaction product.
Processing of the amine reaction product with the acid carrier is done by first dissolving the amine reaction product in anhydrous solvent, preferably ethanol. Separately, the acid carrier is also dissolved in the same solvent that is used for the amine reaction product. The two solutions are then slowly added together, by adding the solution of the acid carrier to the solution of the amine reaction product whilst maintaining the temperature upon the addition to room temperature. During the addition the salt of the amine reaction product and the acid carrier precipitate resulting a solid powder. The solvent is removed by either filtering off the salt and drying or by evaporation of the solvent. Preferably the salt is obtained by filtering off.
Accordingly, there is provided a processed amine reaction product as obtainable by the process of the invention.
In a preferred marketing execution, a coating on the particle can be provided, which depending on the nature of this coating will give ease of dispersion, improved storage stability, flowability and/or improved fabric substantivity of the coated particle.
Suitable coating materials suitable for use herein are those having a melting point between 30xc2x0 C. and 135xc2x0 C., preferably between 45xc2x0 C. and 85xc2x0 C.
Suitable additional coating materials for use in the process invention are components like organic polymeric compounds, waxes, paraffins, oils, glycerides, monoglycerides, diglycerides, triglycerides, fatty acids, anionic surfactants; nonionic surfactants, cationic surfactants, zwitterionic surfactants, and mixtures thereof, preferably are selected from organic polymeric compound, nonionic surfactants, and mixtures thereof.
Preferred organic polymeric compounds suitable for mixing with primary and/or secondary amine compound herein include polyethylene glycols, and derivatives thereof, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Essentially any nonionic surfactants useful for detersive purposes can be included in the compositions provided it has a melting point between 30xc2x0 C. and 135xc2x0 C.
Exemplary, non-limiting classes of useful nonionic surfactants are listed below.
Nonionic Polyhydroxy Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic Condensates of Alkyl Phenols
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein. In general, the polyethylene oxide 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 chain or branched chain configuration with the alkylene oxide with from about 1 to about 150 moles of alkylene oxide per mole of alcohol.
Nonionic Ethoxalated Alcohol Surfactant
The alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 150 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally 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 50 to 100, more preferably 80 moles of ethylene oxide per mole of alcohol.
Preferred nonionic ethoxylated alcohol surfactants are selected from tallow (C16-C18) alcohol ethoxylated with 25, 50, 80, or 100 moles of ethylene oxide commercially available from under the tradename of Lutensol from BASF, Empilan from Albright and Wilson, and Genapol from Clariant. The most preferred nonionic ethoxylated alcohol surfactant is tallow (C16-C18) alcohol ethoxylated with 80 moles of ethylene oxide and commercially available under the tradename of Lutensol 80/80 from BASF, Empilan KM 80 from Albright and Wilson, or Genapol T800 from Clariant.
Nonionic Ethoxylated/propoxylated Fatty Alcohol Surfactant
The ethoxylated C6-C22 fatty alcohols and C6-C22 mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the C10-C22 ethoxylated fatty alcohols with a degree of ethoxylation of from 25 to 150, most preferably these are the C12-C18 ethoxylated fatty alcohols with a degree of ethoxylation 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 herein. 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 certain of the commercially-available Pluronic(trademark) surfactants, marketed by BASF.
Nonionic EO Condensation Products with Propylene Oxide/ethylene Diamine Adducts
The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic moiety of these products consists 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 certain of the commercially available Tetronic(trademark) compounds, marketed by BASF.
Nonionic Alkylpolysaccharide Surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, 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 saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula
R2O((CnH2n)O)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10, preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose.
Nonionic Fatty Acid Amide Surfactant
Fatty acid amide surfactants suitable for use herein are those having the formula: R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and xe2x80x94(C2H4O)xH, where x is in the range of from 1 to 3.
Preferred coating materials from those above mentioned are the nonionic ethoxylated alcohol surfactants having a melting point between 30xc2x0 C. and 135xc2x0 C.
Other materials suitable for the coating are those above described as water-soluble binder or agglomerating agents. Of course, for the purpose of the invention it is preferred when a coating is provided that this is of a different nature to that of the carrier.
As above described, suitable water-soluble binders or agglomerating agents include the water soluble organic polymeric compounds, water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms.
Suitable organic polymeric compounds suitable as coating agents include cellulose derivatives such as methylcellulose, carboxymethylcellulose. hydroxypropylcellulose and hydroxyethylcellulose, as well as carbohydrates like pectins, and gums. Further compounds are carbohydrates and derivatives such as fructose, xylose, galactose, galacturonic acid or glucose based polymers like inuline, dextran, xyloglucan, pectin or gums.
Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxytate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-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 mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
Still other suitable water-soluble binders or agglomerating agents as coating materials include, carbonates, bicarbonates, borates, phosphates, sulfate salts like sodium and magnesium sulfate, inorganic perhydrate salts including perborate like perborate monohydrate, percarbonate, silicates, starch, cyclodextrin, clay as defined hereinafter like smectite and bentonite clay and mixtures of any of the foregoing.
Borate, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50xc2x0 C., especially less than about 40xc2x0 C.
Examples of carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Specific examples of water-soluble phosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Suitable silicates include the water soluble sodium silicates with an SiO2: Na2O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt Sodium silicate with an SiO2: Na2O ratio of 2.0 is the most preferred silicate.
Typical disclosure of cyclodextrin derivatives are disclosed in WO96/05358, U.S. Pat. Nos: 3,426,011, Parmerter et al., issued Feb. 4, 1969; 3,453,257; 3,453,258; 3,453,259; and 3,453,260, all in the names of Parmerter et al., and all issued Jul. 1, 1969; 3,459,731, Gramera et al., issued Aug. 5, 1969; 3,553,191, Parmerter et al., issued Jan. 5, 1971; 3,565,887, Parmerter et al., issued Feb. 23, 1971; 4,535,152, Szejtli et al., issued Aug. 13, 1985; 4,616,008, Hirai et al., issued Oct. 7, 1986; 4,678,598, Ogino et al., issued Jul. 7, 1987; 4,638,058, Brandt et al., issued Jan. 20, 1987; and 4,746,734, Tsuchiyama et al., issued May 24, 1988; all of said patents being incorporated herein by reference.
Although less preferred for use herein because of their lower solubility, partially water soluble coating agents may also be used as coating agent. These compounds are indeed less preferred because during the wash cycle the amine reaction product will still be at least partially coated and therefore can not display its full functionality of long lasting freshness on dry fabrics or hard surfaces. Examples of partially water soluble coating agents include the crystalline layered silicates. Examples of largely water insoluble builders include the sodium aluminosilicates.
Crystalline layered sodium silicates have the general formula
NaMSixOx+1.yH2O
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. The most preferred material is xcex4-Na2Si2O5, available from Hoechst AG as NaSKS-6.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(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 are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate ion exchange materials can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula
Na12[AlO2)12(SiO2)12].xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(AlO2)86(SiO2)106].276 H2O.
Typically when the amine reaction product is mixed with an acid carrier and further processed to form a coated particle, the amine reaction product will be present in an amount of from 1 to 85%, preferably 5 to 24% by weight of the processed reaction product in the produced particle.
Typically the coating agent will be present in an amount of from 10% to 95%, preferably from 30 to 90%, more preferably, 50 to 75% by weight of the particle of the processed amine reaction product. In this instance, the amount of carrier will be sufficient to add up to 100%. Of course, the coated particle may also contain minors but in quantities which will not exceed either of the amount of carrier material or coating agent.
Preferred coating materials are selected from nonionic ethoxylated alcohol surfactants having a melting point between 30xc2x0 C. and 135xc2x0 C., carbonate, starch, cyclodextrin, and mixtures thereof.
The surface treatment of the particle can be carried out in a number of ways using equipment known in the art and the process may be taken in batch wise or continuous fashion.
One method for applying the coating material involves agglomeration. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of the mixture of amine reaction product with carrier.
Another method for applying the coating is to pour the obtained mixture (so-called particle), as herein before described, onto the coating material and agglomerate it in a Braun Mixer. Care is also taken that the temperature during the mixing and/or coating step does not substantially exceed the melting point of the carrier material. For example, 130 g of a mixture containing the citric acid salt of the amine reaction product and 39 g of PEG 4000 is poured at 60xc2x0 C. into a Braun Mixer containing 50 g of carbonate. The mixing of the ingredients is carried out for about 5 minutes. Care is also taken that the temperature during the coating does not exceed 60xc2x0 C. The agglomerated particle can then be used as is for incorporation into the finished composition.
Still another preferred marketing execution is by mixing the particle with a solvent capable of dissolving the particle, thereby enabling the spraying of the resulting mixture.
Incorporation Into Finished Composition
The finished compositions aspect of the invention, including laundry compositions, hard surface cleaning compositions, personal cleaning compositions, spray-on products like odor-absorbing composition, dewrinkling composition, comprises the incorporation of the hereinbefore described processed amine reaction product together with one or more laundry or cleaning ingredient in a finished composition. Finished compositions incorporating the processed amine reaction product will normally contain from 0.01 to 25%, more preferably from 0.02 to 10%, and most preferably from 0.05 to 5% of the processed product on a composition weight basis.
Laundry compositions of the invention, which also encompass compositions providing color care, are suitable for use in any steps of the domestic treatment, that is as a pre-treatment composition, as a wash additive as a composition suitable for use in the rinse-cycle of the laundry cycle or applied on a dryer-sheet. Obviously, multiple applications can be made such as treating the fabric with a pre-treatment composition of the invention and also thereafter with a composition of the invention suitable for use in the rinse cycle and/or suitable for use as a dryer-sheet.
The liquid finished compositions of the invention may also be in a spray, foam, or aerosol form which for example can be suitable for use while ironing, or applied on the surfaces of the tumble dryer.
As mentioned hereinbefore, the incorporation of the processed amine reaction product is conveniently made depending on its end form by dry-addition, as is or in coated form.
Laundry compositions encompass laundry detergent compositions, including liquid, solid form like powdered, tablets as well as softening compositions including rinse added softening composition as well as dryer added softening compositions.
A conventional disclosure of softening ingredients to be used in the softening composition of the invention can be found in EP 98870227.0, incorporated herein by reference.
Preferably, the finished composition is a detergent composition, more preferably in solid form.
In particular, it is preferred that the detergent composition comprises a clay.
Clay
The compositions of the invention may preferably contain a clay, preferably present at a level 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 is noted that the term clay mineral compound, as used herein, excludes sodium aluminosilicate zeolite builder compounds, which however, may be included in the compositions of the invention as optional components.
One preferred clay may be a bentonite clay. Highly preferred are smectite clays, as for example disclosed in the U.S. Pat. No.s 3,862,058 3,948,790, 3,954,632 and 4,062,647 and European Patents No.s EP-A-299,575 and EP-A-313,146 all in the name of the Procter and Gamble Company.
The term smectite days herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice. Smectite clays tend to adopt an expandable three layer structure.
Specific examples of suitable smectite clays include those selected from the classes of the montmorillonites, hectorites, volchonskoites, nontronites, saponites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure. Sodium or calcium montmorillonite are particularly preferred.
Suitable smectite clays, particularly montmorillonites, are sold by various suppliers including English China Clays, Laviosa, Georgia Kaolin and Colin Stewart Minerals.
Clays for use herein preferably have a particle dimension of from 10 nm to 800 nm more preferably from 20 nm to 500 mm, most preferably from 50 nm to 200 mm.
Particles of the clay mineral compound may be included as components of agglomerate particles containing other detergent compounds. Where present as such components, the term xe2x80x9clargest particle dimensionxe2x80x9d of the clay mineral compound refers to the largest dimension of the clay mineral component as such, and not to the agglomerated particle as a whole.
Substitution of small cations, such as protons, sodium ions, potassium ions, magnesium ions and calcium ions, and of certain organic molecules including those having positively charged functional groups can typically take place within the crystal lattice structure of the smectite clays. A clay may be chosen for its ability to preferentially absorb one cation type, such ability being assessed by measurements of relative ion exchange capacity. The smectite clays suitable herein typically have a cation exchange capacity of at least 50-meq/100 g. U.S. Pat. No. 3,954,632 describes a method for measurement of cation exchange capacity.
The crystal lattice structure of the clay mineral compounds may have, in a preferred execution, a cationic fabric softening agent substituted therein. Such substituted clays have been termed xe2x80x98hydrophobically activatedxe2x80x99 clays. The cationic fabric softening agents are typically present at a weight ratio, cationic fabric softening agent to clay, of from 1:200 to 1:10, preferably from 1:100 to 1:20. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B0 011 340.
A preferred commercially available xe2x80x9chydrophobically activatedxe2x80x9d clay is a bentonite clay containing approximately 40% by weight of a dimethyl ditallow quaternary ammonium salt sold under the tradename Claytone EM by English China Clays International.
In a highly preferred embodiment of the invention, the clay is present in an intimate mixture or in a particle with a humectant and a hydrophobic compound, preferably a wax or oil, such as paraffin oil. Preferred humectants are organic compounds, including propylene glycol, ethylene glycol, dimers or trimers of glycol, most preferably glycerol. The particle is preferably an agglomerate. Alternatively, the particle may be such that the wax or oil and optionally the humectant form an encapsulate on the clay or alternatively, the clay be a encapsulate for the wax or oil and the humectant. It may be preferred that the particle comprises an organic salt or silica or silicate.
However, in another embodiment of the invention, the clay is preferably mixed with one or more surfactants and optionally builders and optionally water, in which case the mixture is preferably subsequently dried. Preferably, such a mixture is further processed in a spray-drying method to obtain a spray dried particle comprising the clay.
It may be preferred that the flocculating agent is also comprised in the particle or granule comprising the clay.
It may also be preferred that the intimate mixture comprises a chelating agent.
Flocculating Agent
The compositions of the invention may contain a clay flocculating agent, preferably present at a level 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.
The clay flocculating agent functions such as to bring together the particles of clay compound in the wash solution and hence to aid their deposition onto the surface of the fabrics in the wash. This functional requirement is hence different from that of clay dispersant compounds which are commonly added to laundry detergent compositions to aid the removal of clay soils from fabrics and enable their dispersion within the wash solution.
Preferred as clay flocculating agents herein are organic polymeric materials having an average weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000.
Suitable organic polymeric materials comprise homopolymers or copolymers containing monomeric units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Homopolymers of, on particular, ethylene oxide, but also acrylamide and acrylic acid are preferred.
European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gambl Company describe preferred organic polymeric clay flocculating agents for use herein.
The weight ratio of clay to the 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 certain applications even from 60:1 to 20:1.
Inorganic clay flocculating agents are also suitable herein, typical examples of which include lime and alum.
The flocculating agent is preferably present in a detergent base granule such as a detergent agglomerate, extrudate or spray-dried particle, comprising generally one or more surfactants and builders.
Effervescent
Effervescent means may also be optionally used in the compositions of the invention.
Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas,
i.e. C6H8O7+3NaHCO3xe2x86x92Na3C6H5O7+3CO2↑3H2O
Further examples of acid and carbonate sources and other effervescent systems may be found in: (Pharmaceutical Dosage Forms: Tablets Volume 1 Page 287 to 291).
Carbonate Salts
Suitable alkali and/or earth alkali inorganic carbonate salts herein include carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like amongst which sodium and potassium carbonate are preferred. Suitable bicarbonates to be used herein include any alkali metal salt of bicarbonate like lithium, sodium, potassium and the like, amongst which sodium and potassium bicarbonate are preferred. However, the choice of carbonate or bicarbonate or mixtures thereof may be made depending on the pH desired in the aqueous medium wherein the granules are dissolved. For example where a relativ high pH is desired in the aqueous medium (e.g., above pH 9.5) it may be preferred to use carbonate alone or to use a combination of carbonate and bicarbonate wherein the level of carbonate is higher than the level of bicarbonate. The inorganic alkali and/or earth alkali carbonate salt of the compositions of the invention comprises preferably a potassium or more preferably a sodium salt of carbonate and/or bicarbonate. Preferably, the carbonate salt comprises sodium carbonate, optionally also a sodium bicarbonate.
The inorganic carbonate salts herein are preferably present at a level of at least 20% by weight of the composition. Preferably they are present at a level of at least 23% or even 25% or even 30% by weight, preferably up to about 60% by weight or more preferably up to 55% or even 50% by weight.
They may be added completely or partially as separate powdered or granular component, as co-granules with other detergent ingredients, for example other salts or surfactants. In solid detergent compositions of the invention, they may also completely or partially be present in detergent granules such as agglomerates or spray dried granules.
In one embodiment of the invention, an effervescence source is present, preferably comprising an organic acid, such as carboxylic acids or aminoacids, and a carbonate. Then it may be preferred that part or all of the carbonate salt herein is premixed with the organic acid, and thus present in an separate granular component.
Preferred effervescent source are selected from compressed particles of citric acid and carbonate optionally with a binder, and particle of carbonate, bicarbonate and malic or maleic acid in weight ratios of 4:2:4. The dry add form of citric acid and carbonate are preferably used.
The carbonate may have any particle size. In one embodiment, in particular when the carbonate salt is present in a granule and not as separately added compound, the carbonate salt has preferably a volume median particle size from 5 to 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 from 1 to 425 microns. More preferably, the carbon dioxide source has a volume median 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 from 1 to 375 microns; or even preferably a volume median particle size from 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 from 1 to 250 microns.
In particular when the carbonate salt is added as separate component, so to say xe2x80x98dry-addedxe2x80x99 or admixed to the other detergent ingredients, the carbonate may have any particle size, including the above specified particle sizes, but preferably at least an volume average particle size of 200 microns or even 250 microns or even 300 microns.
It may be preferred that the carbon dioxide source of the required particle size is obtained by grinding a larger particle size material, optionally followed by selecting the material with the required particle size by any suitable method.
Whilst percarbonate salts may be present in the compositions of the invention as a bleaching agent, they are not included in the carbonate salts as defined herein.
The preferred detergent composition, embodiment of the invention, will, preferably contain a bleach precursor, a source of alkaline hydrogen peroxide necessary to form a peroxyacid bleaching species in the wash solution and preferably will also contain other components conventional in detergent compositions. Thus, preferred detergent compositions will incorporate one or more of surfactants, organic and inorganic builders, soil suspending and anti-redeposition agents, suds suppressors, enzymes, fluorescent whitening agents, photoactivated bleaches, perfumes, colours, and mixtures thereof.
Typical disclosure of such components can be found in EP-A-0,659,876 and European patent application No. 98870226.2 which are both incorporated herein by reference.
Form of the Composition
The composition of the invention may take a variety of physical form including liquid, gel, foam in either aqu ous or non-aqueous form, granular and tablet forms.
Still in another aspect of the invention, there is provided a packaged composition comprising the processed product of the invention or composition of the invention. Preferably, the packaged composition is a closed packaging system having a moisture vapour transmission rate of less than 20 g/m2/24 hours. Typical disclosure of such a package can be found in WO 98/40464.
Still another preferred package is a spray dispenser.
Spray Dispenser
The present invention also relates to such compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabric articles and/or surfaces with said compositions containing the amine reaction product and other ingredients (examples are cyclodextrin, polysaccharides, polymers, surfactant, perfume, softener) at a level that is effective, yet is not discernible when dried on the surfaces. The spray dispenser comprises manually activated and non-manual powered (operated) spray means and a container containing the treating composition. Typical disclosure of such spray dispenser can be found in WO 96/04940 page 19 line 21 to page 22 line 27. The articles of manufacture preferably are in association with instructions for use to ensure that the consumer applies sufficient ingredient of the composition to provide the desired benefit. Typical compositions to be dispensed from a sprayer contain a level of amine reaction product of from about 0.01% to about 5%, preferably from about 0.05% to about 2%, more preferably from about 0.1% to about 1%, by weight of the usage composition.
Method of Use
Also provided herein is a method for providing a delayed release of an active ketone or aidehyde which comprises the step of contacting the surface to be treated with a a compound or composition of the invention, and thereafter contacting the treated surface with a material, preferably an aqueous medium like moisture or any other means susceptible of releasing the active from the amine reaction product.
By xe2x80x9csurfacexe2x80x9d, it is meant any surface onto which the compound can deposit. Typical examples of such material are fabrics, hard surfaces such as dishware, floors, bathrooms, toilet, kitchen, paper, skin, and other surfaces in need of a delayed release of a perfume ketone and/or aldehyde such as that with litter like animal litter. Preferably, the surface is selected from a fabric, a tile, a ceramic; more preferably is a fabric.
By xe2x80x9cdelayed releasexe2x80x9d is meant release of the active component (e.g perfume) over a longer period of time than by the use of the active (e.g., perfume) itself.
Still in another aspect of the invention, there is provided the use of the product of the invention for the manufacture of a laundry and/or cleaning composition for delivering residual fragrance and fabric care, in particular color care, onto the fabrics on which it is applied.
The following are synthesis examples of compounds as defined in the present invention:
Ixe2x80x94Synthesis of 1,4-bis-(3-aminopropyl)-piperazine (BNPP) with xcex1-Damascone
In order to substitute both primary amine groups with a perfume, 2 eq of perfume were used for 1 eq of amino functional polymer. To an ice cooled stirred solution of 1 mmol of xcex1-Damascone in 6 mL EtOH and molecular sieves (4 xc3x85, 20 g), 0.5 eq of 1,4-bis-(3-aminopropyl)-piperazine was added via an addition funnel. The reaction mixture was stirred under nitrogen atmosphere and protected from light. After the disappearance of the absorption peak from the NMR spectrum of the free perfume raw material (from 3 to 16 hours), the mixture was filtrated and the solvent was removed by vacuum distillation. The yield of xcex2-aminoketone formation is about 90%.
Similar results were obtained where the xcex1-Damascone was replaced by xcex4-Damascone, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, vertocitral, bourgeonal, or citronellal. In these instances, excepted xcex4-Damascone which forms xcex2-amino ketone, Schiff-bases are formed.
II-Synthesis of Lupasol with Damascones and 2,4-dimethyl-3-cyclohexen-1-carboxald Hyd
The xcex2-amino ketone from Lupasol G100 (commercially available from BASF with a content of 50% water, 50% Lupasol G100 (Mw. 5000)) and xcex1-Damascone (or xcex4-Damascone) was prepared using any one of these three different procedures described as follows:
1. Commercially available Lupasol G100 was dried using the following procedure: 20 g of the Lupasol solution was dried at the rotating evaporator during several hours. The obtained residue, still containing about 4.5 g of H2O, was azeotropically distilled at the rotating evaporator using toluene. The residue was then placed in the desiccator dried at 60xc2x0 C. (using P2O5 as water absorbing material). On basis of the obtained weight we concluded that the oil contained less then 10% H2O. On basis of the NMR-spectra we concluded that this is probably less then 5%. This dried sample was then used in the preparation of xcex2-amino ketones.
1.38 g of the dried Lupasol G100 obtained above was dissolved in 7 ml. ethanol. The solution was stirred gently with a magnetic stirrer during a few minutes before 2 g Na2SO4 (anhydrous) was added. After stirring again for a few minutes 2.21 g xcex1-Damascone was added over a period of 1 minute. After two days reaction, the mixture was filtrated over a Celite filter (vide supra), and the residue washed thoroughly with ethanol. About 180 ml. of a light foaming filtrate was obtained. This was concentrated until dryness using a rotating evaporator and dried over P2O5 in an desiccator at room temperature. About 3.5 of a colorless oil was obtained.
2. 4.3 g Lupasol G100 solution was without drying dissolved in 10 ml. ethanol. The solution was stirred with a magnetic stirrer during a few minutes before 3.47 g xcex1-Damascone was added over a 1.5 minutes period. After two days reaction at room temperature the reaction mixture was filtrated over Celite (vide supra) and the residue washed thoroughly with ethanol. The filtrate (200 ml., light foaming) was concentrated at the evaporator and dried in an desiccator (P2O5 as drying agent) at room temperature. About 5.9 g of a colorless oil was obtained.
3. To 3.0 g of Lupasol G100 solution (used as such) was added 2.41 g xcex1-Damascone. The mixture was stirred without using solvent. After stirring for 4 days the obtained oil was dissolved in 100 ml. THF, dried with MgSO4, filtrated and the filtrate concentrated at the rotating evaporator. After drying in the desiccator (P2O5) at room temperature about 4 g of a colorless oil was obtained. This oil still contained about 13% (w/w) of THF, even after a prolonged drying (3 days).
The product obtained from the three procedures had identical NMR-spectra.
Similar results are obtained where Lupasol G35 or Lupasol HF is used instead of Lupasol G100.
Similar results were obtained where the xcex1-Damascone was replaced by 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.
Still another possible route of synthesis is by using Lupasol P. The xcex2-amino ketone from Lupasol P and xcex1-Damascone was prepared using the procedure described as follows:
1.8 g Lupasol P solution (50% H2O, 50% Lupasol Mw. 750000, as obtained from BASF) was dissolved in 7 ml ethanol, the solution was stirred for a few minutes with a magnetic stirrer before 1.44 g xcex1-Damascone was added. After three days the reaction mixture was filtrated over a celite filter (vide supra) and the residue washed thoroughly with ethanol. After concentrating of the filtrate and drying of the obtained oil in the desiccator (P2O5) at room temperature, about 3 g of the reaction product between Lupasol and xcex1-Damascone was obtained.
Processing Method for the Salt Formation
Processing of the amine reaction product with the acid carrier is done as hereinbefore described. In particular, 10 g of the xcex4-Damascone-Lupasol HF, as synthesized above, was dissolved in 70 ml of dry ethanol. Separately, 5 g of anhydrous citric acid was dissolved in 80 ml of dry ethanol. The solution were added slowly together in glass container while mixing, by addition of the Lupasol HF-xcex4-Damascone solution to the citric acid solution. The temperature during the mixing is kept at room temperature. After the addition is complete, 1 g anhydrous citric acid is added till a complete precipitation of the Lupasol HF-xcex4-Damascone is obtained. The precipitation is filtered off and dried. About 16 g of the salt is obtained. Total time for the experiment is about 1 hour.
Processing Method for the Coating
If a coating is desired, the obtained mixture (so-called particle), as herein before described, is pour onto the coating material and agglomerated it in a Braun Mixer. Care is taken that the temperature during the mixing and/or coating step does not substantially exceed the melting point of the carrier material. For example, 130 g of a mixture containing the citric acid salt of the amine reaction product and 39 g of PEG 4000 is poured at 60xc2x0 C. into a Braun Mixer containing 50 g of carbonate. The mixing of the ingredients is carried out for about 5 minutes. Care is also taken that the temperature during the coating does not exceed 60xc2x0 C.
Abbreviations Used in the Following Laundry and Cleaning Composition Examples
In the laundry and cleaning compositions, the abbreviated component identifications have the following meanings:
In the following formulation examples all levels are quoted as % by weight of the composition unless otherwise stated, and incorporation of the processed amine reaction product so called herein after xe2x80x9cPARPxe2x80x9d in the fully formulated composition is carried out by dry addition in the composition as defined herein before.

Process for producing particles of amine reaction products


A solid-state image pickup device comprises a pixel array having static induction transistors disposed in a line for constituting pixels and integrating charges corresponding to amounts of received light, a readout circuit for scanning the static induction transistors to read out a pixel signal representing the amount of charges integrated in each of the transistors, and a photometric circuit coupled to sources of the static induction transistors for controlling the integral times thereof. The photometric circuit has a plurality of MOS transistors having their gates connected to the sources of the static induction transistors, and a source follower having a load resistor connected to sources of the MOS transistors.

1. Field of the Invention
The present invention relates to a solid-state image pickup device and, more particularly, to the control of an integral time of charges in the line sensor.
2. Description of the Related Art
Conventionally, electronic still cameras, video cameras, facsimiles and the like use a solid-state image pickup device composed of semiconductor photoelectric conversion elements. For example, charge-transfer elements such as CCD or BBD or MOS transistors are disposed in a matrix form or in a line to implement an image pickup device or an in-focus detecting sensor.
The problems with those devices are the leakage of charges at a time of transfer of signal charges and low light-detecting sensitivity.
To solve these problems a solid-state image pickup device has been developed which uses static induction transistors (hereinafter referred to as SITs). The SITs are one type of phototransistors which have functions of photoelectric conversion and amplification. In contrast with field effect transistors and junction transistors, the SITs have features of high input impedance, high-speed operation, nonsaturation characteristic, low noise and low power dissipation. Accordingly, by using the SITs as light-receiving elements it will be possible to implement a solid-state image pickup device of great sensitivity, high-speed response and wide dynamic range.
A conventional application of a solid-state image pickup device using the SITs to a line sensor will be described. There is a method in which, when the level cf light amount of the image of an object is small, an integral time is increased, while, when the level of light amount is large, the integral time is decreased, in order to keep an output level approximately constant independently of the level of light amount and thus extend the dynamic range for light amount. As an example, an automatic focus detecting device is disclosed in a Japanese laid-open Patent publication No. 57-64711 in which a photodiode (hereinafter referred to as photometric photodiode) adapted for controlling the integral time is provided adjacent to a CCD or MOS line sensor.
FIG. 1 shows a simplified circuit diagram of the device, and FIG. 2 shows a waveform diagram of signals associated with the device.
A photometric photodiode 2 is disposed adjacent to a photodiode array 1 having photodiodes arranged in a line. Photometric photodiode 2 has a length equal to the length of photodiode array 1. Output of photometric photodiode 2 is taken out through an output buffer 3. Outputs of photodiode array 1 are in parallel applied to a CCD shift register 5 via transfer gates 4 and then transferred through shift register 5 to be serially taken out via an output buffer 6. This arrangement forms a CCD line sensor.
The operation of the line sensor will be described with reference to the signal waveforms shown in FIG. 2. When an integral-start pulse is applied, voltages in photodiode array 1 and photometric photodiode 2 are initialized.
When photodiode array 1 and photometric photodiode 2 are irradiated with a light, photoelectric charges are integrated in the capacitance of photometric photodiode 2, and the output of photometric photodiode 2 decreases. The change .DELTA.V in output potential of photometric photodiode 2 is Qph/C where C stands for the capacitance and Qph represents the photoelectric charge integrated in the capacitance.
When the output potential of photometric photodiode 2 reaches a predetermined voltage Vref, a transfer pulse is produced. As a result, transfer gate 4 is turned on to terminate the integration, and the photoelectric charges stored in the capacitances of photodiode array 1 are transferred to CCD shift register 5 to be sequentially read out therefrom.
By changing the reference voltage Vref it is possible to change the integral time and hence the CCD output level. The reference voltage Vref may be set so that the CCD output level becomes a predetermined value. That is, in order to keep the exposure (=illuminance.times.integral time) constant, the reference voltage Vref is changed in accordance with illuminance.
An area sensor formed of SITs is described in a Japanese Patent application No. 61-176290 filed by the assignee of the present application. If only a part of the area sensor is driven, the area sensor can be used as a line sensor. The operation of the line sensor which is realized by picking up only one line component from the area sensor, will be described with reference to FIGS. 3A to 7.
FIG. 3A is a perspective view representing a structure of an SIT forming one pixel, and FIG. 3B is a circuit diagram of the line sensor.
As shown in FIG. 3A, on an n.sup.+ -type silicon substrate 11 acting as the drain of the SIT deposited is an n.sup.- -type epitaxial layer 12 forming a channel region. A shallow n.sup.+ -type source region 13 is formed into epitaxial layer 12. Source region 13 is surrounded with a p.sup.+ -type gate region 14 within epitaxial layer 12. A MOS capacitor 15 is formed over gate region 14 to which a gate pulse .phi.g is applied through the capacitor.
When gate region 14 is reverse-biased, a depletion layer is formed on the outside of the gate region. Hole-electron pairs are produced by a light incident on the depletion layer. The electrons are drained into source region 13 and drain region 11, while holes are stored in gate region 14. Thus, the potential of the gate is raised, and a current flowing between the drain and the source is modulated with a change in the gate voltage so that a light-dependent amplified current is obtained. Reference numeral 16 denotes an isolation region adapted for isolating the SIT from other SITs.
For description of the line sensor, FIG. 3B shows one row of pixels. Pixel SITs 20-1, 20-2, . . . 20-n each having the structure shown in FIG. 3A are arranged in a line to form a row 20 of pixel SITs. The SITs have their sources coupled to lines 21-1, 21-2, . . . 21-n which are coupled to an output line 23 via MOS transistors 22-1, 22-2, . . . 22-n acting as select switches in a readout circuit 22. Transistors 22-1, 22-2, . . . 22-n have their gates coupled to a scanning circuit 24 to receive scan pulses .phi.s1, .phi.s2, . . . .phi.sn therefrom.
The SITs have their gates coupled via capacitors 19-1, 19-2, . . . 19-n to a line 26 which in turn is coupled to a mix circuit 27. Mix circuit 27 applies gate pulse .phi.g to the gate of each SIT through line 26.
A reset circuit 28 comprises MOS transistors 28-1, 28-2, . . . 28-n whose gates are supplied with a reset pulse .phi.r and drains are coupled to lines 21-1, 21-2, . . . 21-n, respectively.
Mix circuit 27 sets the voltage of gate pulse .phi.g to Vrd when a drive pulse .phi.rd is at a "1" level, while to Vrs when .phi.rs is at a "1" level. When pulse .phi.g is applied to line 26, the pixels of SITs are enabled to read out stored charges, so that, when the pixels are sequentially selected by the scan pulses .phi.s1, .phi.s2, . . . .phi.sn, photoelectric signals are sequentially read out from the pixels.
FIG. 4 is a timing diagram of pulses for operating the line sensor, and FIG. 5 is a circuit diagram of one pixel of SIT and the associated peripheral circuit.
In FIG. 4, the pulse .phi.g has two types of a "1" level, i.e., Vrd and Vrs. More specifically, the pulse .phi.g has the readout level Vrd during a readout period t.sub.rd and the reset level Vrs during the following reset period t.sub.rs.
The scan pulses .phi.s1, .phi.s2, . . . .phi.sn sequentially go to a logic "1" level during the readout time t.sub.rd so that the pixels of SITs arrayed in the line are sequentially scanned.
The reset pulse .phi.rs goes to a "1" level for each of reset periods to reset the pixels of SITs from which signals have been read out.
In FIG. 5, Tp denotes an SIT, Tr a resetting MOSFET, Ts a selecting MOSFET, Cgd a parasitic capacitance across the gate and drain, Cgs a parasitic rapacitance across the gate and source, Cs a stray capacitance of a source line 21, and Ron an on resistance of selecting MOS transistor Ts.
Changes with time in the gate potential Vg and source potential Vs of the pixel Tp will be described with reference to FIG. 6, which illustrates the changes with time in the gate potential Vg and source potential Vs in the pixel SIT when the pulse .phi.s, the pulse .phi.g and the reset pulse .phi.r are applied to the pixel SIT. .phi.b stands for a built-in voltage between the gate and source which will be described later.
When the pulses .phi.g (=Vrs>.phi.b) and .phi.r go to a "1" level (at a time t1), the source potential Vs is reset to ground potential and Vg becomes .phi.b (the built-in potential between the gate and source).
When the pulse .phi.g and .phi.r go to the ground level (at a time t2), the SIT is reverse-biased so that an integration is initiated. The gate voltage Vg (represented as Vg2 for time t2) is represented as follows: EQU Vg2=-(Cg/(Cg+Cj)).times.Vrs+.phi.b (1)
where Cj=Cgs+Cgd.
At a time t3 in an integration period, charges Qph produced by irradiation with a light are being stored in the gate capacitance (Cg+Cj). Qph is represented as follows: EQU Qph=Gl.times.A.times.P.times.t.sub.int =Gl.times.A.times.E (2)
where Gl stands for a generation rate (.mu.A/.mu.W), A an area (cm2) of a light-receiving surface, P an irradiance of light (.mu.W/cm2), t.sub.int an integration time (seconds), and E an exposure (E=P.times.t.sub.int).
By substituting equation (2) into equation (1) the gate voltage Vg3 at time t3 will be expressed as follows: EQU Vg3=-(Cg/(Cg+Cj)).times.Vrs+.phi.b+(Qph/(Cg+Cj)) (3)
At a time t4, since .phi.g=Vrd, the gate voltage Vg4 is represented by EQU Vg4=Vg3+(Cg/(Cg+Cj)).times.Vrd=(Cg/(Cg+Cj)).times.(Vrd-Vrs)+.phi.b+(Qph/(Cg +Cj)) (4)
When Vg4>Vp (Vp is the gate-to-source potential difference at which the drain current of the SIT begins to flow and referred to as the pinch-off voltage), the drain current of the SIT flows so that the source line capacitance Cs is charged. This charging continues until the potential difference Vgs between the gate and source becomes Vp. Thus, the source potential Vs4 will be represented by EQU Vs4=(Cg/(Cg+Cj)).times.(Vrd-Vrs)+.phi.b+(Qph/(Cg+Cj))-Vp (5)
Since Vp<.phi.b, a current hardly flows from the p.sup.+ -type gate to the n.sup.+ -type source of the SIT.
When the pulse .phi.s goes to a "1" level, (at a time t5), source line 21 is connected to a load resistor Rl via MOS transistor Ts (on resistance Ron). The output Vout (t) varies with time and represented as follows: EQU Vout (t)=(Rl/(Ron+Rl)).times.Vs(t) (6)
FIG. 7 illustrates the changes of gate voltage Vg, source voltage Vs and output Vout with time when the pulse .phi.s is at a "1" level.
When the pulse .phi.s goes to a "1" level, the p.sup.+ -type gate and n.sup.+ -type source of the SIT are biased in the forward direction with the result that a current flows through the pn junction diode, and signal charges stored in the gate capacitance flow into the source. Photoelectric signal charges are destroyed, and the gate voltage Vg and the source voltage Vs both decrease. The value of output Vout represented by equation (6) becomes smaller than a value obtained by substituting equation (5) into Vs(t) of equation (6).
As described above, the circuit of FIG. 3B can operate as a line sensor.
In addition to the sensor described above, the assignee of the present application has developed various improvements in the solid-state image pickup device and claimed an area sensor in a Japanese Patent application No. 61-277346.
FIG. 8 is a circuit diagram of the area sensor used as a line sensor, and FIG. 9 is a timing diagram therefor.
In the example of FIG. 3B, the integration time differs for each of the pixels. That is, the integration time is determined by the reset pulse .phi.rs and the scan pulse .phi.si (i=1.about.n). The reset pulse .phi.rs is commonly used for all the pixels. But, the scan pulses .phi.si for respective pixels are sequentially produced. In the circuit of FIG. 8, on the other hand, the same integration time is set to all the pixels. In FIG. 8, source voltages of all the SITs are transferred to the gate capacitances of transistors 31-i through transfer transistors 30-i at the same time. In addition, in the FIG. 3B circuit, a channel current of the SIT is taken out, while, in the FIG. 8 circuit, a source potential of an SIT which has been brought to a readout state is taken out.
Transfer switches 30-1, 30-2, . . . 30-n in a readout circuit 29 transfer source potentials of pixel SITs 20-1, 20-2, . . . 20-n to MOS transistors 31-1, 31-2, . . . 31-n through lines 21-1, 21-2, . . . 21-n. MOS transistors 31-1, 31-2, . . . 31-n are connected to a load resistor Rl via select switches 22-1, 22-2, . . . 22-n and a line 23, thereby forming a source follower circuit.
In operation, during a reset period trs a pulse .phi.g is set to Vrs in level, and pulses .phi.t and .phi.r are set to a "1" level, thereby resetting pixel SITs. The following operations during an integration period tint are the same as those of the SIT line sensor shown in FIGS. 3A through 7.
After the lapse of an integration period t.sub.int, when the pulse .phi.g is set to Vrd in level and the pulse .phi.t is set to a "1" level, the potentials (represented by equation (5)) on lines 21-1, 21-2, . . . 21-n are transferred to MOS transistors 31-1, 31-2, . . . 31-n. When pixel SITs 20-1, 20-2, . . . 20-n are selected by scan pulses .phi.s1, .phi.s2, . . . .phi.sn, the following output Vout is taken out from output line 23. EQU Vout=A.times.((Cg/(Cg+Cj)).times.(Vrd-Vrs)+Qph/(Cg+Cj)+.phi.b-Vp-Vt)(7)
where A is a voltage gain of the source follower circuit constituted by MOS transistors 31-1, 31-2, . . . 31-n, select switches 22-1, 22-2, . . . 22-n and load resistor Rl, and Vt is a threshold voltage of MOS transistors 31-1, 31-2, . . . 31-n.
This circuit arrangement permits a nondestructive read of the pixel SITs. If the pixel is not reset after the signal is read out from the pixel and the integration is continued to read out the signal from the pixel once more, it is necessary to change the timings of the pulses .phi.g and .phi.r. In order not to reset the pixel, the pulses .phi.g and .phi.r are set to a "0" level after the read period t.sub.rd.
Furthermore, another SIT sensor is shown in FIG. 10. In order for the SIT line sensor to have an integration-time control function, a photometric photodiode 41 is disposed adjacent to a pixel SIT 42. Reference numeral 43 denotes a readout circuit, 44 a scanning circuit, and 45 an output buffer circuit.
The above-described solid-state image pickup devices using SITs can overcome the drawbacks of the solid-state image pickup devices using MOS transistors, CCD, BBD or the like. The feature of the improved solid-state image pickup devices is that the integration time can be controlled in accordance with the amount of light by provision of a photometric photodiode adjacent to photodiode array and monitoring the potentials of the photodiode array.
However, with those devices, because the overall length of the pixel array is covered by one photometric photodiode an average measurement of light will be performed. Consequently, an accurate measurement of light cannot necessarily be obtained in some cases. For example, even if light is incident on only some of the pixels or on one pixel, the average photometric level is lower than the incident light level. Therefore, if the integration is stopped when the photometric output coincides with Vref, the output of the pixel onto which light is incident becomes larger than the predetermined level. Thus the integration time may not accurately be controlled.

Solid-state image pick-up device including static induction transistors with photometric function