There is provided a process for producing particles of amine reaction product by means of a carrier having a melting point of less than 30xc2x0 C. optionally followed by a coating step. 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 a carrier having specific melting point to form a particle fulfills such a need. Depending on the property of the carrier, the obtained particle is thereafter treated to form a coated particle.
Further, it has also been advantageously found that both viscous and non-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 25C with a gap setting of 500 microns.
The carrier for use herein has a melting point, measured at atmospheric pressure, of less than 30xc2x0 C.
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 a carrier having a melting point of less than 30xc2x0 C.
In a preferred embodiment of the invention, the processed amine reaction product is further processed to form a coated particle.
In another aspect of the invention, the processed amine reaction product 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.
A-Primary 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 methyl anthranilate in dipropylene glycol.
Odour Intensity Index Method
By Odour Intensity Index, it 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:
B-(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 inorganic carrier, 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 carrers 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 amino-benzene derivatives including the alkyl esters of 4-amino benzoate compounds, and more preferably selected from ethyl-4-amino benzoate, phenylethyl-4-aminobenzoate, phenylaminobenzoate, 4-amino-Nxe2x80x2-(3-aminopropyly)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 T403, D-230, D400, D-2000; 2,2xe2x80x2,2xe2x80x3-triaminotriethylamine; 2,2xe2x80x2-diamino-diethylamine; 3,3xe2x80x2-diamino-dipropylamine, 1,3 bis aminoethylyclohexane commercially available from Mitsibushi and the C12 Stemamines commercially available from Clariant like the C12 Stemamin(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-cydohexane; 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=2nxc3x974 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 vinylformamidexe2x80x94molar 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 lethylhexanoic acid in a molar ratio of 5/3/1) Polyamino acid (polylysine-coraprolactam); 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;
polyoxyethylene bis [6-aminohexyl] available from e.g. Sigma;
N,Nxe2x80x2-bis(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA); and
1,4-bis-(3-aminopropyl) piperazine (BNPP).
The more preferred compounds are selected from ethylamino benzoate, polyethyleneimines 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 0-93171035-5.
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; tonalidimusk 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 lonone, 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-PhenylButanone, Celery Ketone or Livescone, 6-Isopmpyldecahydro-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-Norbomane, 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-tertbutylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyl propanal, 2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cistrans-3,7-dimethyl-2,6-octadien-1-al, 3,7-dimethyl-6-octen-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-cydohexen-1-crboxaldehyde, 2-methyl-3-(isopropylphenyl)propanal, 1-decanal; decyl aldehyde, 2,6-dimethyl-5-heptenal, 4-(trcyclo[22.214.171.124(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 cydohexene-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-(4-methyl-3-pentenyl)-3-cycohexene-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, 1ecanal, benzaldehyde, florhydral, 2,4-dimethyl-3-cylohexen-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, alphan-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, characterised 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 al., 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-propylphenylypropionaldehyde, 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 which have a Dry Surface Odour 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:
Most 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-lonone, Hedione, Florhydral, Lilial, Heliotropine, and 2,4-dimethyl-3-cydohexen-larboxaldehyde. 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 ethylamino benzoate with one or more of the following 2,4-dimethyl-3-cyclohexen-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.
Even 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-ydohexen-1-carboxaldehyde.
Most preferred amine reaction products are those fulfilling the Dry Surface Odor Index as per given in copending application EP 98870155.3 given at page 29, line 26 to page 32 line 29.
2)-Carrier
Another essential ingredient of the process invention is a carrier having a melting point of less than 30xc2x0 C., preferably between minus 150xc2x0 C. and less than 30xc2x0 C. By means of this carrier, particles of amine reaction product, suitable for spray-on application, will be produced.
Typical of such carrier includes liquid as well as solid carrier material. The liquid carrier can be in any suitable physical form like hydrophobic or hydrophilic form.
As used herein in relation to carrier materials, xe2x80x9chydrophobicxe2x80x9d means substantially water insoluble: xe2x80x9chydrophilicxe2x80x9d means substantially water soluble. In this regard, xe2x80x9csubstantially water insolublexe2x80x9d shall refer to a material that is not soluble in distilled (or equivalent) water, at 25.degree. C., at a concentration of 0.2% by weight, and preferably not soluble at 0.1% by weight (calculated on a water plus carrier weight basis). xe2x80x9cSubstantially water solublexe2x80x9d shall refer to a material that is soluble in distilled (or equivalent) water, at 25.degree. C., at a concentration of 0.2% by weight, and are preferably soluble at 1.0% by weight. The terms xe2x80x9csolublexe2x80x9d, xe2x80x9csolubilityxe2x80x9d and the like, for purposes hereof, corresponds to the maximum concentration of carrier, as applicable, that can dissolve in water or other solvents to form a homogeneous solution, as is well understood to those skilled in the art.
Typical of materials that are in hydrophobic form include ingredients useful in perfumery. Typical of such ingredients are the perfume raw materials, solvents, and mixtures thereof. Typical hydrophobic raw materials include the ketones or aldehydes like hexyl cinnamic aldehyde, hydrocarbons like Limolene, d-Limonene, esters like Hercolyn D, benzyl salicylate, hexyl salicylate, triethyl citrate, iso propyl myristate, or mixtures thereof, or hydrophobic perfume composition preferably incorporating one or more of these raw materials.
Typical hydrophobic solvents include diethyl phthalate, ethers like butoxypropoxypropanol, and mixtures thereof.
Also suitable for use herein are the finished perfume compositions which have hydrophobic properties.
Typical of materials that are in hydrophilic form include alcohols like methanol, ethanol, dipropyleneglycol, water, nonionic surfactants as above described but having a melting point below 30C, or mixtures thereof.
Preferred carrier materials are selected from benzyl salicylate, diethyl phatalate, dipropylene glycol, methanol, ethanol, and mixtures thereof.
Typically when the amine reaction product is only mixed with a carrier but not further processed, the amine reaction product will be present in an amount of from 1 to 75%, preferably 10 to 60%, more preferably 15 to 45% by weight of the processed reaction product. In this instance, the amount of carrier will be sufficient to add up to 100%. Of course, the processed amine reaction product may also contain minors but in quantities which will not exceed the amount of carrier material. Typically the carrier will be present in an amount of from 3 to 95%, preferably from 15 to 90% and most preferably from 45 to 85%, by weight of the processed amine reaction product.
By processed amine reaction product, it is meant the resulting product of the amine reaction product with the carrier material.
Processing of the amine reaction product with the carrier is done by thoroughly mixing the amine reaction product with the carrier. Advantageously, there is no need for additional ingredients to provide a resulting substantially homogenous mixture. This mixing is done at the lowest possible temperature, i.e. just above the melting point of the carrier or at mom temperature. The mixing step is carried out until a complete homogeneous mixture is obtained. By xe2x80x9chomogeneousxe2x80x9d, it is meant compositions which have similar appearance to the resulting composition of a 20 g of amine reaction product mixed with 20 g of methanol or 80 g of diethylphtalate for 5 minutes by means of an Ultra Turrax, the temperature of mixing being room temperature.
The obtained processed amine reaction product may then be suitable for spray on applications when use of a liquid carrier is made.
When use of a carrier with a melting point of less than 30xc2x0 C. is made for the mixing with the amine reaction product, it may then be preferred to further process the mixture to form a coated particle like e.g. by adsorption of the mixture onto a solid, preferably porous coating. The coating will advantageously protect the processed amine reaction product from the aggressive chemicals present in wash water.
The resulting coated particles can be in any form which is suitable for incorporation into liquid or powders, preferably powders, such as agglomerate, pellets, tablets, or mixtures thereof.
Suitable coating agents for both solid, including paste, and liquid mixtures are substantially water-soluble solid binder or agglomerating agents 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 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, carbonates, bicarbonates, borates, phosphates, sulfate salts like sodium and magnesium sulfate, inorganic perhydrate salts including perborate like perborate monohydrate, percarbonate, silicates, starch, cyclodextrin, and mixtures of any of the foregoing.
Suitable organic polymeric compounds suitable as coating agents include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylcellulose and hydmxyethylcellulose, 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 oxypolycarboxylate 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 cyclopentanecis,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.
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 sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on Nov. 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 WO96105358, 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 disdosed in EP-A-0164514 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].276H2O.
Typically when the amine reaction product is mixed with a carrier and further processed to form a coated particle, the amine reaction product will be present in an amount of from 1 to 75%, preferably 5 to 30%, more preferably 6 to 25% 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 carbonate, starch, cyclodextrin, sulfate salts, silicates, 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 take 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, 50 g of a mixture containing a hydrophobic perfume composition and 25 g of the amine reaction product is poured at room temperature into a Braun Mixer containing 200 g of starch. The mixing of the ingredients is carried out for about 5 minutes.
Once the coated particle is obtained, it may be useful to remove the carrier. Such removal can be made by conventional techniques. One typical of these technique is vacuum drying. By removal of the carrier, in particular with liquid carrier having a boiling point between 5 and 200xc2x0 C., the original viscosity of the amine reaction product, i.e. higher viscosity, in the coated particle is restored which as a result gives a better stability of the coated particle towards the wash liquor environment. The coated particle can then be used as is for incorporation into the finished composition.
Accordingly, there is provided a processed amine reaction product as obtainable by the process of the invention.
If desired, the coated particle may also 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, a cationic, anion or non-ionic surfactant like. Preferably, the weight ratio of such additional ingredient(s) to the coating agent is of up to 1:1.
In another preferred marketing execution, an additional coating on the coated particle can be provided, which depending on the nature of this additional coating will give improved storage stability, flowability and/or improved fabric substantivity of the coated particle. One typical example is polyvinyl alcohol.
The finished compositions aspect of the invention, including laundry compositions, hard surface cleaning compositions, personal cleaning compositions, comprises the incorporation of the hereinbefore described processed amine reaction product together with one or more laundry or cleaning ingredient in a finished composition. 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.
As mentioned hereinbefore, the incorporation of the processed amine reaction product is conveniently made depending on its end form by either by spraying when in sprayable liquid form, or dry-addition when 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.
Finished compositions incorporating the processed amine reaction product will normally contain from 0.001 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.
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.
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. Nos. 3,862,058 3,948,790, 3,954,632 and 4,062,647 and European Patents Nos. EP-A-299,575 and EP-A-313,146 all in the name of the Procter and Gamble Company.
The term smectite clays 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. Typical smectite clay compounds include the compounds having the general formula Al2(Si2O5)2(OH)2.nH2O and the compounds having the general formula Mg3(Si2O5)2(OH)2.nH2O. Smectite clays tend to adopt an expandable three layer structure.
Specific examples of suitable smectite days 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 day 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 hav 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 xe2x80x9chydrophobically activatedxe2x80x9d 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-B-0 011 340.
A preferred commercially available xe2x80x9chydrophobically activatedxe2x80x9d clay is a bentonite clay containing approximately 40% by weight of a dimethyl ditallow quatemary 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 altematively, 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.
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 Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe preferred organic polymeric clay flocculating agents for use herein.
The weight ratio of day 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 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).
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 relative 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 cogranules 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 xe2x80x9cdry-addedxe2x80x9d 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, also 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.
The composition of the invention may take a variety of physical form including liquid, gel, foam in either aqueous 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.
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 cyclodextrins, 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.
Also provided herein is a method for providing a delayed release of an active ketone or aldehyde which comprises the step of contacting the surface to be treated with 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 perfume 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 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:
To an ice cooled stirred solution of 10 g of 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde (0.07 mol) in 35 mL EtOH and molecular sieves (4 xc3x85, 20 g) 1 eq of the amine was added via an addition funnel. The reaction mixture was stirred under nitrogen atmosphere and protected from light. After 6 days the mixture was filtrated and the solvent was removed. The yield of imine formation is about 90%.
Similar results were obtained where the 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was replaced by bourgeonal, trans-2-nonenal, or trans-2-hexenal.
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-aminopropylypiperazine 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 u-Damascone was replaced by 2.4-dimethyl-3-cyclohexen-1-carboxaldehyde, vertocitral, bourgeonal, xcex4-Damascone or citronellal in these instances, Schiff-bases are formed.
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-clohexen-1-carboxaldehyde.
Still another possible route of synthesis is by using Lupasol P. The P-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
1)-Processing Method for Spray-on
Processing of the amine reaction product with the carrier is done as hereinbefore described. In particular, 20 g of amine reaction product as above synthesised is mixed with 10 to 80 g of a carrier, e.g. hydrophobic perfume composition, dipropylene glycol, diethylphthalate in an Ultra Turrax until an homogenous mixture is obtained. The temperature of mixing is about room temperature, and the speed of the mixer is sufficient to maintain such temperature substantially constant. Temperature and time will depend on the nature of the carrier but are a conventional step to skilled man. Of course, the amount of carrier relative to the amine reaction product will depends on the desired sprayability and the end viscosity of the resulting mixture. In the examples of the present invention, the viscosity was below 500 Cps, as measured on a rheometer, TA Instrument CSL2100 at a temperature of 25C with a gap setting of 500 microns.
2)-Processing Method for coating
Processing of the amine reaction product with the carrier is done as hereinbefore described. In particular, 20 g of amine reaction product as above synthesised is mixed in an Ultra Turrax containing 20 g of carrier, e.g. methanol or perfume mixture or composition for 5 minutes, the temperature of mixing being to about room temperature, and the speed of the mixer being sufficient so as to maintain such temperature substantially constant. Temperature and time will depend on the nature of the carrier but are a conventional step to skilled man.
When use of a perfume mixture is made, the composition in % by weight of a typical hydrophobic perfume mixture is as follows:
When desired, the obtained processed amine reaction product from above is subsequently coated. In particular, the resulting mixture is maintained at a temperature substantially equal to the melting point of the carrier material and poured onto the coating material and agglomerated in an electrical mixer like a Braun Mixer. Care is also taken that the temperature during the mixing does not substantially exceed the melting point of the carrier material. For example, 100 g of a mixture containing the methanol or perfume mixture and 20 g of the amine reaction product is poured at room temperature into a Braun Mixer containing 300 g of carbonate. The mixing of the ingredients is carried out for about 5 minutes. Again, temperature and time will depend on the nature of the coating agent but are conventional step to skilled man.
Once the coated particle is obtained, it may be desired to remove the methanol by vacuum distillation.
In the laundry and cleaning compositions, the abbreviated component identifications have the following meanings:

Process for producing particles of amine reaction products


A method and apparatus for stacking articles in a side-by-side stack and feeding the stacks to a discharge conveyor. Articles such as video cassette containers or CD containers, are conveyed in an upright singulated fashion by a guide arrangement. Each individual article enters a transfer location where it is supported by a transfer platform. A pusher device extends to push the article from the transfer location onto a support platform. The support platform supports the individual articles as they are assembled into a stack. After the pusher device has been retracted, a hold-back member is extended to support the outermost article of the assembled stack. Once a stack of articles has been assembled, a stack pusher assembly pushes the stack off of the support platform and onto an outfeed conveyor assembly. A back-up slide assembly supports the outermost article of the stack as the stack is assembled by the stacker mechanism.

Conveying systems are often employed to convey articles through a series of working stations. In certain conveyor systems, it is desired to form a stack of articles from a single transferred row of articles and transfer the assembled stack to packaging or other working equipment. Frequently, a variety of article sizes are conveyed in an intermingled order and the conveying system is operable to separate the articles based on the type and/or size of article before the stack is formed. A series of stacking units are often utilized and the stacking units must be capable of automatically separating and stacking the dissimilar articles and feeding the stacks onto a discharge conveyor without interference between stacks.
The present invention is directed to a method and apparatus for stacking individual articles and feeding the assembled stack to a discharge conveyor. A plurality of articles, such as video cassette containers, compact disc containers, or the like, are conveyed on an infeed conveyor in an upright singulated fashion. A stacker mechanism receives each of the individual articles on a transfer platform located at a transfer location. Upon receiving one of the articles, an article pusher assembly is activated to push the article off of the transfer platform and onto a support platform. The support platform is used to assemble the stack from the plurality of individual articles fed successively from the transfer location.
The outermost article of the stack is pushed into contact with a backstop contained within a back-up slide assembly. The backstop is connected to a single-acting back-up cylinder that is unpressurized, such that the backstop is free to move along the support platform as the stack is assembled. A friction device contained in the back-up slide assembly provides the required force to support the outermost article of the stack.
A hold-back member is positioned between the transfer location and the support platform such that after an article is added to the stack, the hold-back member is moved to an extended, retaining position, during which the hold-back member supports the innermost article of the stack. Thus, the combination of the hold-back member and the backstop supports the stack at both the inner and outer ends of the stack.
Once a complete stack of articles is assembled on the support platform, a stack pusher assembly is activated to push the stack off of the support platform and onto a discharge or outfeed conveyor assembly. Specifically, the stack pusher assembly includes a pusher plate that is attached to a drive cylinder and is movable between a retracted position and an extended position.
Once a complete stack of articles has been assembled and pushed onto the outfeed conveyor, the pusher plate of the stack pusher assembly is retracted and the backstop of the back-up slide assembly is completely extended by operation of the single-acting back-up cylinder, such that the backstop can receive the first article of a new stack.
Therefore, it is an object of the invention to provide a stacker mechanism that can receive a plurality of single articles and assemble the articles into a side-by-side stack. It is an additional object of the invention to provide a stacker mechanism that supports the stack of articles while the stack is being assembled to prevent the stack from falling apart. It is another object of the invention to provide a stacker mechanism having a hold-back member that supports the innermost article of the stack and can be retracted to permit additional articles to be added to the stack. It is a further object of the invention to provide a method of assembling a stack of articles from a supply fed in a singulated fashion.
Various other features, objects and advantages of the invention will be made apparent from the following description taken together with the drawings.

Mechanism and method for forming a stack of articles


A self-adhesive protective film, especially for painted vehicles or vehicle parts, having a single-ply or multi-ply backing layer and an adhesive layer,

The invention relates to a protective film whose great weathering stability and adhesion reliability make it especially suitable for temporarily protecting fresh automobile finishes from soiling and damage, as well as for other sensitive surfaces such as metals, plastics and glazing.
The preservation and protection of motor vehicles in the course of transportation from manufacturer to dealer has long been common practice.
The conventional method of preserving automobiles is to apply paraffin waxes in a thickness of from 5 to 20 xcexcm. However, it has been found that, especially on horizontal areas of the vehicles, such as the hood, roof and trunk lid, a thin and usually nonuniform layer of this nature does not afford adequate protection against external influences, such as the corrosive effect of bird droppings, for example.
A considerable disadvantage of sealing with paraffin wax is the need to remove the preservative using a steam jet, surfactants or solvents. Environmentally sound recovery and disposal of the residues are the cause of great complexity in terms of apparatus, and of very high costs.
A current development in the field of automotive transit protection is the use of covers which go over the entire vehicle and are shrunk on to fit by exposure to heat. Cover solutions of this kind are very costly and involve a great deal of effort in applying the cover, effecting shrinkage, and especially when climbing into the masked automobile. For that particular purpose, zip fastener openings are provided, whose necessary opening and reclosing is time-consuming. Visibility when parking is severely impaired, and there are areas of dulling on the finish as a result of enclosed dirt and unavoidable scuffing. This solution cannot become widespread.
Instead, increasing use is being made of temporarily applied self-adhesive surface protective films. These are specifically intended for the mechanical and chemical protection of fresh motor vehicle finishes, have a protective action which is much better than that of the waxes, and have the advantage over the covers of being more cost effective and significantly quicker to apply.
A key requirement of a surface protective film is its weathering stability over a period of more than six months. Accordingly, even after six months of intense sunlight exposure, such a film must be removable in one piece and must not leave any residues of adhesive composition on the finish. Moreover, it must have a sufficient initial tack, so as not to detach of itself prematurely in situations of difficult bonding geometry, but at the same time must not have too great an ultimate bond strength to the finish, so that the film can be removed without substantial force being applied and certainly without tearing.
In accordance with the prior art, therefore, film materials used are generally polyolefins or mixtures thereof which are normally blended with light stabilizers and titanium dioxide.
A diversity of systems are used as self-adhesive compositions, but are without exception hampered by weaknesses.
Self-adhesive compositions based on natural rubber possess relatively good initial adhesion and can be removed again without residue. Even on short-term exposure to UV radiation, however, these compositions are not stable to aging. Following realistic weathering exposures over a period of several months, this leads to severe greasy residues or hardened paintlike residues on the finish.
U.S. Pat. No. 5,612,136 mentions a protective film having an acrylate-based self-adhesive composition. Polyacrylate compositions are indeed highly UV-stable. If, however, uncrosslinked polyacrylate compositions are stored under alternating climatic conditions, their compatibility with paint surfaces is good only in some cases. Compatibility denotes that the paint surface shows no deformation whatsoever after the adhesive tape is removed. Moreover, these compositions exhibit an undesirable level of peel increase. Where these compositions are strongly crosslinked chemically or by radiation, they are indeed easier to remove but on the other hand cause increased incidence of permanent deformations of the paint surface which are clearly visible.
Self-adhesive compositions based on polyisobutylene (polyisobutylene homopolymer or butyl rubber) exhibit little adhesion to finishes customary in the automotive industry following storage under alternating climatic conditions. Under jerky stresses, such as on flapping in the slipstream, the adhesion is so low that the bond strength required in the art is not always present to a sufficient extent. Under the influence of moisture, in particular, the adhesion is often reduced to such an extent that the film detaches from the protected vehicles in the course of transit, resulting firstly in a loss of protection and secondly in a safety risk if it drifts onto the windshield of following vehicles. Furthermore, these adhesives are not very cohesive and therefore produce residues of composition when the film is removed, especially in the edge region after UV aging. Moreover, this self-adhesive composition is not compatible with the sealing profiles customary in automobile construction or with the plasticizers they contain: when the protective film is removed from window profiles, residues of the adhesive remain on the rubber. Adhesive articles of this kind are described in EP 0 519 278, JP 95-325285 and U.S. Pat. No. 5,601,917.
Substantially more UV-stable than polyisobutylenes are adhesives produced from hydrogenated styrene-diene block copolymers, whose use is described in JP 827 444. An important disadvantage of such block copolymers is their thermally reversible crosslinking by way of the styrene domains. If an adhesive film produced from them is removed in the summer from a vehicle which has become hot in the sun, the adhesive largely remains adhering to the finish, since the cohesion of the adhesive compositions is lower than the adhesion to the finish. Heating always leads to the shrinkage of the protective film, and so the adhesive, soft in the heat, smears onto the metal at the retreating edges of the adhesive film.
The adhesive film described in DE 195 32 220 A1, comprising ethylene-vinyl acetate (EVAc) adhesive, is significantly superior in adhesion to the systems described above. With the exception of one-component PU systems, there is no effect on the finishes to be protected. During removal after use, however, this adhesive film has a bond strength which is much too high, as a result of which it is in many cases impossible to remove the adhesive film without tearing. This increase in bond strength when the adhesive composite is stored, referred to by the skilled worker as peel increase, is caused by interactions of the adhesive, especially polar forces, with the finish. On the other hand, polar comonomers such as acrylate or vinyl acetate give rise to the desired high initial adhesion.
WO 96/37568A1 describes the use of polyhexene and/or polyoctene for a nonpolar pressure-sensitive adhesive. Because of the low cohesion, the polymers described in the examples do in fact exhibit little peel increase, but these polymers, owing to the low molecular weight of commercial polymers of this kind, likewise lead to residues, which it is attempted to avoid by adding other polymers, referred to therein as xe2x80x9ccold flow restricting agentsxe2x80x9d. For practical purposes, nevertheless, these adhesives are of inadequate cohesion, which leads to residues after weathering, especially if the adhesive tape shrinks under the effect of heat. A similar phenomenon is displayed by ethylene-propylene-diene copolymers (EPDM) as specified in DE 197 42 805. These, furthermore, exhibit very limited initial adhesion.
It is an object of the invention to provide a self-adhesive protective film, especially for fresh automobile finishes, which does not have (or not to the same extent) the above-described disadvantages of the prior art. In particular, the self-adhesive protective film should possess not only a pronounced initial bond strength but also a balanced (not too strong) ultimate bond strength, freedom from residues on removal, and finish compatibility.
This object is achieved by a self-adhesive protective film as specified in the main claim. The subclaims relate to advantageous developments of the self-adhesive protective film, particular possibilities for use, and a particularly advantageous process for preparing the surface protective film.
The invention accordingly provides a self-adhesive protective film, especially for painted vehicles or vehicle parts, having a single-ply or multi-ply backing layer and an adhesive layer comprising a mixture of synthetic rubbers,
a) the adhesive layer comprising a polar component A and an apolar component B,
b) the weight fraction of the polar component A being from 50 to 99% and comprising one or a mixture of copolymers of ethylene and vinyl acetate whose vinyl acetate content is between 40 and 80% by weight, and
c) the weight fraction of the apolar component B being from 1 to 50% and comprising one or a mixture of slightly crystalline or amorphous homopolymers or copolymers of xcex1-olefins of 2 to 12 carbon atoms, said polymers being saturated in the main chain.
In the self-adhesive protective film, especially for painted vehicles or vehicle parts, having a single-ply or multi-ply backing layer and an adhesive layer, the weight fraction of the apolar component B may be from 1 to 50% and comprise copolymers of xcex1-olefins of 2 to 12 carbon atoms and nonconjugated dienes.
The backing layer of the adhesive is a thermoplastic polyolefin film which in another advantageous embodiment is unoriented. Furthermore, it preferably comprises at least one polyolefin from the group of the polyethylenes (for example, HDPE, LDPE, MDPE, LLDPE, VLLDPE, copolymers of ethylene with polar comonomers) and/or from the group of the polypropylenes (for example, polypropylene homopolymers, polypropylene random copolymers or polypropylene block copolymers).
Preference is given to using mixtures of different suitable polyolefins in order to allow optimum adjustment of the mechanical and thermal properties and also of gloss, extrusion behavior, anchoring of the adhesive, etc.
For the backing films, a thickness of from 20 to 80 xcexcm is preferred. The softness of the backing film plays a part in connection with the deformability during the application of the protective film; the force at 10% elongation should not exceed 25 N/15 mm, preferably 16 N/15 mm, both in the lengthwise and in the transverse direction (tensile test in accordance with DIN EN ISO 527-7-5). Therefore, the backing films should be unoriented. Orientation raises the force at 10% elongation so greatly that the film is no longer assured of conformability.
In order to give the backing film the required weathering stability, it is necessary to add light stabilizers. Their function consists primarily in preventing the embrittlement of the backing film. Light stabilizers of this kind are described in Gaechter and Mxc3xcller, Taschenbuch der Kunststoff-Additive, Munich 1979, in Kirk-Othmer (3rd ed.) 23, 615-627, in Encycl. Polym. Sci. Technol. 14, 125-148 and in Ullmann (4th ed.) 8, 21; 15, 529, 676. In particular, HALS light stabilizers such as, for example, dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (CAS No. 65447-77-0), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (CAS No. 52829-07-9) or poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][[(2,2,6,6-tetramethyl-4-piperidyl)imino] hexamethylene [(2,2,6,6-tetramethyl4-piperidyl)imino]] (CAS No. 70624-18-9) are suitable for the protective film of the invention. The amount of the light stabilizer should be at least 0.15% by weight, preferably at least 0.30% by weight, based on the backing film.
The use of antioxidants for the film (for example, Irganox 1010 or trisnonylphenyl phosphite) is advantageous but not absolutely necessary. Further suitable UV absorbers, light stabilizers and aging inhibitors are set out in EP 0 763 584 A1. Accordingly, antioxidants which may be used include N,N-di-2-naphthyl-p-phenylenediamine, 2,5-di(t-amyl)hydroquinone, trimethyidihydroquinoline polymer and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-t-butyl-p-cresol, 2,2xe2x80x2-methylenebis-(4-methyl-6-t-butylphenol), 4,4xe2x80x2-butylidenebis(3-methyl-6-t-butylphenol), 4,4xe2x80x2-thiobis-(3-methyl-6-t-butylphenol), stearyl beta-(3,5-di-t-butyl4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxyphenyl)propionate]methane, 1,3,5-tri-methyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenol)butane, dilauryl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate and dimyristyl thiodipropionate, triisodecyl phosphite, diphenyl isodecyl phosphite triphenyl phosphite and trinonyl phosphite and also N-salicyloyl-Nxe2x80x2-aldehyde hydrazine, N-salicyloyl-Nxe2x80x2-acetylhydrazine, N,Nxe2x80x2-diphenyl-oxamide and N,Nxe2x80x2-di-(2-hydroxyphenyl)oxamide.
An additional improvement in the light stability of the backing film is also possible by adding titanium dioxide. Advantageous in terms of mechanical properties and the homogeneity of the whiteness are from 5 to 15% by weight additions of titanium dioxide.
The UV permeability of the protective film in the region from 290 to 360 nm is preferably less than 1%, more preferably less than 0.1%, owing to the interaction of light stabilizers and pigments.
Suitable compounds for the polar component of the adhesive composition are ethylene-vinyl acetate grades (EVAc) whose VAc fraction is between 40 and 80% by weight, preferably between 50 and 70% by weight. It is also possible to mix different EVAc grades. Compounds suitable for the apolar component are poly-xcex1-olefins such as polyisobutylene (PIB), poly-1-butene (PB), ethylenepropylene copolymers (EPM), ethylenepropylene-diene terpolymers (EPDM), the diene being nonconjugated, poly-1-hexene, poly-1-octene and other slightly crystalline or amorphous copolymers of ethylene and xcex1-olefins of 4-12 carbon atoms. The apolar polymers may also be mixed in order to provide optimum properties.
The protective films produced in this way possess, on the one hand, good adhesion to a variety of finishes common in the automotive industry, which is retained under the effect of moisture or humid conditions, so that the protective film does not detach from the vehicle even under wind exposure or under tension caused by bonding to curved surfaces. Moreover, the self-adhesive composition possesses a sufficient bond strength within the first few minutes after application, so that after just half an hour, for example, the protective film may be subjected to a severe slipstream load (up to 160 km/h). Unlike straight EVAc adhesive compositions, on the other hand, the film may be removed from the finish without tearing, without employing excessive force. Moreover, even without application of a release layer, the protective film of the invention has an unwind force which is sufficiently low for the user, despite the strong adhesive.
The bond strength of the protective film of the invention to two-component polyurethane (2K PU) finishes is generally more than 0.4 in the fresh state and less than 2.8 N/cm following storage under alternating climatic conditions (in analogy to AFERA method 4001). Even exposure of the protective film to UV light in accordance with DIN 53387 1-A-X over 1 000 hours does not cause any deficiencies in the properties of the protective film: there is no embrittlement of the film and no residues of composition on removal.
Finally, the self-adhesive protective film of the invention may be produced in a particularly advantageous manner by coextrusion.
The protective film of the invention is therefore particularly suitable for protecting the fresh finish of automobiles during assembly or transit or as processing and transit protection for freshly painted surfaces, such as primarily for the protection of sensitive paint, metal, plastic or glass surfaces. The protective film can be bonded just half an hour after the painted surfaces have passed through the oven, without any disadvantages whatsoever, despite the fact that at this point in time the finish has not yet fully cured. A further feature of the protective film of the invention is that it can be applied in a large width over the hood, roof and trunk of automobiles and that, owing to its deformability, it conforms very well to planar and even gently curved surfaces. It is therefore possible to protect the horizontal surfaces which are most at risk from soiling. However, even narrow areas such as, for example, the projection of the door below the windows, the sill region, or bumpers can easily be covered. Protection of the vertical surfaces on the vehicle is particularly appropriate during its assembly. The protective film is resistant to sunlight, moisture, heat and cold, with weathering stability of at least six months. The addition of pigments such as titanium dioxide and of light stabilizers, in particular, leads to an improvement in UV stability of the protective film. Even very high sun levels, as are encountered in Florida, for example, do not cause the protective film to fail or detach. The extremely low UV permeability of the protective film prevents the adhesive being broken down by sun exposure.
Furthermore, the strength of the protective film in comparison to preservation with wax ensures impeccable protection against soiling such as bird droppings and against damage to the vehicle as a whole by minor mechanical events. It is possible to recycle the protective film or recover energy from it, in particular since it is halogen-free.
In the text below, the invention will be illustrated on the basis of examples which are not, however, intended to restrict the invention.

Self-adhesive protective film especially for painted vehicles or vehicle parts