WO2002048309A1 - Portions de produit de lavage, de rinçage ou de nettoyage a enveloppe transparente - Google Patents
Portions de produit de lavage, de rinçage ou de nettoyage a enveloppe transparente Download PDFInfo
- Publication number
- WO2002048309A1 WO2002048309A1 PCT/EP2001/014386 EP0114386W WO0248309A1 WO 2002048309 A1 WO2002048309 A1 WO 2002048309A1 EP 0114386 W EP0114386 W EP 0114386W WO 0248309 A1 WO0248309 A1 WO 0248309A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- detergent
- water
- active
- cleaning
- soluble
- Prior art date
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- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical group C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 229960000601 octocrylene Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GKWCCSUCDFFLBP-UHFFFAOYSA-N oxirane Chemical compound C1CO1.C1CO1 GKWCCSUCDFFLBP-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- WZXKPNYMUZGZIA-RMKNXTFCSA-N propyl (e)-3-(4-methoxyphenyl)prop-2-enoate Chemical compound CCCOC(=O)\C=C\C1=CC=C(OC)C=C1 WZXKPNYMUZGZIA-RMKNXTFCSA-N 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
Definitions
- the present invention relates to detergent, detergent or cleaning agent portions containing stabilizing agents which have a completely or partially water-soluble and transparent covering.
- detergents and cleaning agents were usually given to the consumer in containers containing large volumes, such as plastic bottles. The dosing was then carried out as required (degree of contamination of the items to be washed, washed or cleaned, amount of items to be washed, washed or cleaned) or, based on experience, in each individual case using suitable devices for measuring amounts of liquid.
- Pre-metered portions of detergent, detergent or cleaning agent containing water-free alcohol ether sulfates (isopropanolammonium ether sulfates) as components of highly concentrated washing and cleaning agent systems are described in the article “U. Schoenkaes et al .; Water-free Alcohol Ether Sulfates - New high-active surfactants for superconcentrated detergent formulations ".
- Such systems are described as having excellent washing activity and are suitable for the stable incorporation of bleaches and other water-sensitive detergents, detergent and cleaning agent components.
- the detergent, cleaning or rinsing agent portions are, however, offered in opaque or completely opaque, water-soluble coatings, such as soft gelatin, or must be in opaque, i.e. H. little or no translucent outer packaging are presented. To underline the aesthetic characteristics of the agents, however, it is advantageous if the washing, cleaning or rinsing agent portions can be offered in transparent, water-soluble envelopes.
- the problem is the inconsistency of the coated detergent, cleaning or rinsing agent components in relation to light. Due to the transparency and the predetermined light permeability (range 250 to 800 nm), in particular the permeability of UV light (250 to 460 nm), the water-soluble coating materials, there are often signs of decomposition (e.g. radical decomposition of polymeric thickeners, dyes, etc.). ) or to signs of deactivation of active agent components (e.g. enzymes, bleach, etc.).
- decomposition e.g. radical decomposition of polymeric thickeners, dyes, etc.
- active agent components e.g. enzymes, bleach, etc.
- WO 00/36062 and WO 00/36067 describe transparent or transparent, liquid, enzyme-containing detergents, which are presented in clear bottles or containers made of water-insoluble polymers or glass. The enzymes are protected by antioxidants or by encapsulation.
- WO 00/36068 and WO 00/36074 disclose transparent or transparent liquid detergents which are presented in clear bottles or containers made of water-insoluble polymers or glass. The detergent dyes or the detergent enzymes are protected by fluorescent dyes or UV absorbers.
- the object of the invention was to provide washing, cleaning and rinsing agent portions which are in a transparent, completely or partially water-soluble coating.
- the components present in the portions are to be stabilized against the radiation-related decomposition and deactivation phenomena.
- the invention therefore relates to a detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble capsule-shaped envelope which completely surrounds at least one formulation of a detergent-active, detergent-active or cleaning-active material, and the portion contains at least one stabilizing agent, the water-soluble coating has a transmittance above 20% at wavelengths of 410 to 800 nm.
- the invention relates to a detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble envelope in spherical form, which completely surrounds at least one formulation of a detergent-active, detergent-active or cleaning-active material, and the portion contains at least one stabilizing agent, wherein the water-soluble coating has a transmittance above 20% at wavelengths from 410 to 800 nm.
- the invention relates to a detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble envelope in the form of a bag, which completely surrounds at least one formulation of a detergent-active, detergent-active or cleaning-active material, and at least the portion contains a stabilizing agent, the water-soluble coating having a transmittance above 20% at wavelengths of 410 to 800 nm.
- the invention also relates to a washing process, a rinsing process and a cleaning process using the detergent, detergent or cleaning agent portions described below.
- the term “detergent, detergent or cleaning agent portion” is understood to mean a sufficient amount of a detergent, detergent or cleaning agent for a washing, rinsing or cleaning process taking place in an aqueous phase.
- This can be, for example, a machine Washing, rinsing or cleaning process, such as is carried out with commercially available washing machines or dishwashers or cleaning machines, but according to the invention this term also includes a handwashing cycle (for example carried out in a hand wash basin or in a bowl) or a dishwashing cycle carried out by hand or by means of a cleaning liquor in a vessel, such as a cleaning cycle carried out in a bucket or another process of washing, rinsing or cleaning.
- the detergent, washing-up liquid or cleaning agent portions are preferred in the case of machines Washing, rinsing or cleaning processes are used.
- portion of detergent or “portion of detergent” or “portion of detergent” is understood to mean a portion of a portion of detergent, dishwashing detergent or detergent which is contained in another detergent or dishwashing detergent. or detergent portion portions separate phase in spatial connection with other detergent, dishwashing or cleaning agent portion portions of the same detergent, dishwashing or cleaning agent portion and is prepared by suitable measures so that it is separated from other detergent, dishwashing or cleaning agent portions the same detergent, detergent or cleaning agent portion can be added to the liquor and optionally dissolved or suspended in it, whereby a detergent, washing-up liquid or cleaning agent portion can contain the same ingredients as another detergent, washing-up liquid or cleaning agent -Teilpo rtion of the same detergent, dish soap or detergent portion; However, two portions of detergent, dishwashing detergent or cleaning agent preferably contain the same portion of detergent, dishwashing detergent or cleaning agent, different ingredients, in particular different detergent-active, dishwashing-active or detergent-active preparations.
- the detergent, dishwashing or cleaning agent portions contain measured amounts of at least one washing-active, washing-active or cleaning-active preparation, usually measured amounts of several washing-active, washing-active or cleaning-active preparations. It is possible that the portions contain only wash-active, rinse-active or cleaning-active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least two, wash-active, wash-active or cleaning-active preparations of different compositions are contained in the detergent, detergent or cleaning agent portions.
- the composition can differ in terms of the concentration of the individual components of the wash-active, rinse-active or cleaning-active preparation (quantitative) and / or in terms of the type of individual components of the wash-active, rinse-active or cleaning-active preparation (qualitative). It is particularly preferred that the components are adapted in terms of type and concentration to the tasks which the detergent, dishwashing or cleaning agent portions have to perform in the washing, washing or cleaning process.
- the detergent, dishwashing or cleaning agent portion according to the invention comprises a completely or partially water-soluble casing.
- the shape of the envelope is not limited to certain shapes according to the invention. Basically, all Archimedean and Platonic bodies, i.e. three-dimensional shaped bodies, can be used as forms of wrapping. Examples of the shape of the covering are capsules, cubes, spheres, egg-shaped moldings, cuboids, cones, rods or bags. Hollow bodies with one or more compartments, as described in co-pending patent application No. DE 100 33 827.5 with the title “compartment hollow body”, are also suitable as a covering for the washing-active, rinsing-active or cleaning-active materials.
- the envelopes are in the form of capsules, such as those used in pharmacy for the administration of pharmaceuticals, of spheres or sachets, the latter preferably being welded or glued on at least one side, an adhesive being the adhesive in particularly preferred embodiments of the invention is used, which is water-soluble.
- polymers which can dissolve completely or partially in the aqueous phase under the given conditions of a washing process, rinsing process or cleaning process are suitable as materials for the completely or partially water-soluble coating.
- the polymer materials can particularly preferably be the groups (optionally partially acetalized) of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates, etc.) of the belong to the materials mentioned.
- Gelatin and polyvinyl alcohols and the two materials mentioned are particularly preferred in each case in combination with starch or modified starch.
- Inorganic salts and mixtures thereof can also be used as materials for the at least partially water-soluble coating.
- Polyvinyl alcohols (PVAL for short) are polymers of the general structure
- polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. These technical processes also make PVAL accessible which contain a predetermined residual proportion of acetate groups.
- PVAL eg Mowiol ® types from Hoechst
- PVAL polyvinyl acetates with a residual acetyl group content of, for example, about 1 to 2 or 11 to 13 mol%.
- the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
- aldehydes acetalization
- ketones ketalization
- Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water.
- the reaction products made of PVAL and starch are extremely advantageous to use.
- solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
- PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
- PVP polyvinylpyrrolidone
- PVP are produced by radical polymerization of 1-vinyl pyrrolidone.
- Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
- Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
- Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
- the amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
- the use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
- detergent, detergent and cleaning agent portions are also preferred, the packaging of which consists of at least partially water-soluble film made from at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
- Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% wheel-chain amylose (MW. approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations.
- amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4-position
- the chain in the amylopectin branches after an average of 25 glucose units through 1,6-binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose.
- starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions in the context of the present invention.
- Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
- the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
- Pure cellulose has the formal gross composition (C 6 H 10 ⁇ 5) n and, viewed formally, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
- Preferred coverings made of at least partially water-soluble film contain at least one polymer with a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol.
- the water-soluble film which forms the covering preferably has a thickness of 1 to 300 ⁇ m, preferably 2 to 200 ⁇ m, particularly preferably 5 to 150 ⁇ m and in particular 10 to 100 ⁇ m.
- these water-soluble films can be produced by various manufacturing processes.
- blowing, calendering and casting processes should be mentioned here.
- the films are blown from a melt with air through a blow mandrel to form a tube.
- the raw materials plasticized by suitable additives become Forming the foils atomized.
- an aqueous polymer preparation is placed on a heatable drying roller; after the water has evaporated, cooling is optional and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal.
- Organic and / or inorganic salts are also suitable as materials for the coating of the detergent, detergent or cleaning agent portion according to the invention.
- these are salts which can be formed into a coating, for example by crystallization, pressing, compacting or other suitable processes, and which dissolve in sufficient time in water or aqueous liquor under the conditions of the washing, rinsing or cleaning process.
- salts are used which can also perform other functions in a washing, rinsing or cleaning process.
- the covering is water-soluble as a whole, ie. H. dissolves completely when used as intended for washing, rinsing or cleaning, for example machine washing, rinsing or cleaning, if the conditions provided for the detachment have been reached.
- Particularly preferred as completely water-soluble coatings are, for. B. capsules made of gelatin, advantageously made of soft gelatin, or bags made of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably balls made of soft gelatin.
- a significant advantage of this embodiment is that the sheath dissolves at least partially within a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions in the washing liquor, rinsing liquor or cleaning liquor and thus the enveloped in accordance with the requirements Content, d. H. brings the wash-active, rinse-active or cleaning-active material or several materials into the fleet.
- the water-soluble covering comprises areas which are less or not water-soluble or only water-soluble at a higher temperature and areas which are water-soluble or water-soluble at a low temperature.
- the covering does not consist of a uniform material which has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand.
- the invention is not subject to any restrictions for the formation of such systems. Enclosures can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble one.
- water-soluble areas or non-water-soluble areas or only at higher temperatures water-soluble areas of the casing are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or a content has water-insoluble salt components and / or contains a water-insoluble polymer.
- PVAL for example with saccharides, polysaccharides, such as starch
- the water-soluble covering material is transparent.
- transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%.
- a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.
- the transparent, water-soluble portions contain at least one stabilizing agent as an essential component.
- Stabilizing agents in the sense of the invention are materials that Protect detergent, detergent or detergent ingredients in their water-soluble, transparent coatings against decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
- Particularly suitable stabilizers in the sense of the invention are the antioxidants.
- the formulations can contain antioxidants.
- Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants.
- Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
- aromatic amines preferably secondary aromatic amines and substituted p-phenylenediamines
- phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites
- citric acids and citric acid derivatives such as isopropyl citrate
- compounds containing endiol groups so-called reductones, such as ascorbic acid and its derivatives such as As- corbinklamitat
- organosulfur compounds such as the esters of 3,3 'thiodipropionic acid with Ci.-is-alkanols, in particular C 10 . ⁇ 8 alkanols
- metal ion deactivators that are capable of catalyzing the auto-oxidation Me - complex ions such as copper, such as nitrilotriacetic acid and its derivatives and their mixtures.
- Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.
- UV absorbers can improve the lightfastness of the formulation components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
- substituted Benzotri- azole such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ® Fast H), 3-phenyl-substituted acrylates ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid.
- 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
- Sulfonic acid derivatives of 3-benzylidene camphor such as 4- (2 ⁇ oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
- UV-A filters -4'-meth-oxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 19712033 A1 (BASF).
- the UV-A and UV-B filters can of course also be used in mixtures.
- insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts
- suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
- Silicates (talc), barium sulfate or zinc stearate can be used as salts.
- the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
- the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
- UV absorbers can be present in the formulations in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight.
- Another preferred class of stabilizers is the fluorescent dyes. They include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic), 4,4 '-Distyrylbiphenylen, methyl umbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and Benzimidazole systems and the pyrene derivatives substituted by heterocycles.
- flavonic 4,4'-diamino-2,2'-stilbenedisulfonic acids
- 4 '-Distyrylbiphenylen methyl umbelliferone
- coumarins dihydroquinolinones
- 1, 3-diaryl pyrazolines 1, 3-diaryl pyrazolines
- naphthalimides benzoxazole, benzisoxazole, and Benzimidazole
- Fluorescent substances can be present in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.
- the aforementioned stabilizing agents are used in any mixtures.
- the stabilizing agents are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.
- wash-active preparation or “rinse-active preparation” or “cleaning-active preparation” (or “wash-active etc. material” or “wash-active etc. component”) in the context of the present invention relates to preparations, materials or components of all conceivable relevant substances with a washing, rinsing or cleaning process. These are primarily the actual detergents, rinsing agents or cleaning agents with their individual components, which are explained in more detail below.
- active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (e.g. those with cobuilder properties), graying inhibitors, dyes and the like d fragrances (perfumes), without the term being restricted to these substance groups.
- active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (e.g. those with cobuilder properties), graying inhibitors, dyes and the like d fragrances (perfumes), without the term being restricted to these substance groups.
- wash-active preparations materials, components
- rinse-active preparations materials, components
- cleaning-active preparations materials, components
- cleaning aids examples of these are optical brighteners , so-called soil repellents, i.e. polymers that counteract re-soiling of fibers or hard surfaces, as well as silver Retardants.
- Laundry treatment agents such as fabric softener or dishwashing detergent additives, such as rinse aid, are also considered according to the invention as wash-active or rinse-active preparations.
- the completely or partially water-soluble coating of the detergent, detergent or cleaning agent portions according to the invention completely surrounds a formulation, preferably a liquid-based, at least one washing-active, rinsing-active or cleaning-active material.
- liquid-based is understood to mean that the formulation of a wash-active, rinse-active or cleaning-active material or a plurality of wash-active, rinse-active or cleaning-active materials is, at least during production, a formulation based on liquid components, as is the case are explained in detail below, even if this formulation contains solid components (suspended or dispersed) in large quantities.
- Formulations of the detergent, dishwashing detergent or cleaning agent portions according to the invention completely surrounded by the envelopes can be either low-water formulations or essentially anhydrous formulations.
- Low-water formulations comprise water as an essential component in an amount of, for example, 15 15% by weight, based on the weight of all components of the formulation.
- non-aqueous or essentially water-free formulations comprise water only in small amounts, preferably in amounts less than 10% by weight, more preferably in amounts of 1 to 5% by weight, in each case based on the weight of all components of the formulation, non-aqueous or essentially water-free formulations are particularly preferred.
- the formulations contain surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants being used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, the proportion of nonionic surfactants advantageously being greater than the proportion of anionic surfactants.
- the total surfactant content of the detergent, detergent or cleaning agent portions is preferably above 25% by weight, based on the total liquid detergent.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- the preferred ethoxylated alcohols include, for example, -C 2 -C 4 alcohols with 3 EO, 4 EO or 7 EO, Cg-n alcohols with 7 EO, C 13 -C 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -i 8 ⁇ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 - alcohol with 3 EO and C 12 -i 8 alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
- block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
- mixed alkoxylated nonionic surfactants can also be used, in which the EO and PO units are not distributed in blocks, but are statistically distributed. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO 90/13533.
- Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula I, R1
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula II
- R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
- R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
- [Z 2 ] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.
- [Z 2 ] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- the content of preferred formulations of nonionic surfactants is up to 95% by weight, preferably 10 to 60% by weight and in particular 15 to 50% by weight, in each case based on the total composition.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C 9 . 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates as they are for example from C 12 - ⁇ 8 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- Alkanesulfonates which are derived from C 12 are also suitable.
- esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
- Fatty acid lycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfonated fatty acid lycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- the alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred.
- alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- the C 12 -C 6 alkyl sulfates and C 12 -C 5 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred from a washing-technical point of view.
- 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
- 21 alcohols such as 2-methyl-branched C 9 .
- Alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 -i 8 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fat Ikoholrest, which is derived from ethoxylated fatty alcohols, which in themselves are non-ionic surfactants (description see above).
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Soaps are particularly suitable as further anionic surfactants.
- Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as, for example, mono-, di- or triethanolamine, monoisopropanolamine or triisopropanolamine.
- the anionic surfactants are preferably in the form of their ammonium salts, in particular their ammonium salts with at least one long-chain alkyl radical or alkanolamine radical on ammonium nitrogen.
- the content of preferred detergent, detergent or cleaning agent portions of anionic surfactants is up to 95% by weight, preferably 10 to 60% by weight and in particular 15 to 50% by weight, in each case based on the total portion.
- the detergent, dishwashing or cleaning agent portions according to the invention irrespective of whether they contain water or low in water or essentially water-free - can contain further ingredients which further improve the technical and / or aesthetic properties of the agent improve.
- preferred detergent, detergent or cleaning agent portions contain, in addition to the surfactant (s), one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, perfumes, perfume carriers, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, transfer inhibitors optical brighteners, graying inhibitors, shrink preventatives, anticrease agents, dyes, antimicrobial active ingredients, germicides, fungicides, corrosion inhibitors, antistats, ironing aids, waterproofing and impregnating agents, swelling and Anti-slip agents and theological additives.
- surfactant s
- Suitable crystalline, layered sodium silicates have the general formula NaMSi x 0 x + ⁇ ' H 2 0, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
- Such crystalline layered silicates are described, for example, in European patent application EP-A 0 164 514.
- Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both ß- and ⁇ -sodium disilicate
- Na 2 Si 2 0 5 -yH 2 0 is preferred, ⁇ -sodium disilicate being able to be obtained, for example, by the process described in international patent application WO-A 91/08171.
- the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
- the term “amorphous” is also understood to mean “X-ray amorphous”.
- silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
- it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P.
- the zeolite P, zeolite MAP ® (commercially available from Crosfield) is especially preferred.
- zeolite X and mixtures of A, X and / or P are also suitable.
- Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
- nNa 2 0 '(1-n) K 2 0' Al 2 0 3 ⁇ (2 - 2.5) Si0 2 '(3.5 - 5.5) H 2 0 can be described.
- the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- phosphates As builders, provided that such use should not be avoided for ecological reasons.
- the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
- bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracid salts or peracids, such as persulfates or persulfuric acid.
- the urea peroxohydrate percarbamide can also be used, which can be described by the formula H 2 N-CO-NH 2 ⁇ 2 0 2 .
- the agents for cleaning hard surfaces when using the agents for cleaning hard surfaces, for example in automatic dishwashing, they can, if desired, also contain bleaching agents from the group of organic bleaching agents, although their use is in principle also possible for agents for textile washing.
- Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
- Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
- Preferred representatives are peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid, phthalimidaproacid (hexthalimide), Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassyldiperoxyacid, 4-diperoxyacid N-terephthaloyl-di (6-aminopercaproic
- bleach activators can be incorporated into the detergent portions.
- Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxo- carboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid are used. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
- Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triethyl acetic acid, triethyl acetic acid, acetic acid triethyl acetic acid , 2,5-diacetoxy-2,
- hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
- the combinations of conventional bleach activators known from German patent application DE 4443 177 can also be used.
- bleach catalysts can also be incorporated into the wash-active preparations for the portions according to the invention.
- These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
- Enzymes for use in detergent, detergent or cleaning agent portions are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned.
- the hydrolases help remove stains such as protein, fat or starchy stains and graying in laundry, for example.
- Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils.
- Oxireductases can also be used to bleach or inhibit the transfer of color.
- Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Substances. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
- Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest for the detergent, detergent or cleaning agent portions according to the invention.
- Known cutinases are examples of such lipolytically active enzymes.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
- Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
- the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
- the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.01 to 5% by weight, preferably 0.012 to about 2% by weight.
- a wide number of different salts can be used as electrolytes from the group of inorganic salts.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
- the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
- Non-aqueous solvents that can be used in the detergent, detergent or cleaning agent portions according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
- the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, polyethylene glycol, dipropylene glycol, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2- propanol, butoxy-propoxy-propanol (BPP), 3-methyl-3-me
- pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation.
- Foam inhibitors that can be used in the detergent, detergent or cleaning agent portions according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
- Suitable anti-redeposition agents which are also referred to as “soil repellents”, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ethers, and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof, particularly preferred among the compounds mentioned the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
- nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by
- Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
- water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose.
- Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
- Polyvinyl pyrrolidone can also be used.
- cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition.
- graying inhibitors based on optionally modified polyacrylates and their copolymers are also suitable.
- textile fabrics in particular made of rayon, rayon, cotton and their blends, can tend to wrinkle because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the direction of the fibers, contain synthetic anti-crease agents.
- synthetic anti-crease agents include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
- the detergent, dishwashing or cleaning agent portions according to the invention can contain antimicrobial active ingredients.
- antimicrobial active ingredients Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides etc.
- Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the portions according to the invention.
- Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
- External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These usually surface-active antistatic agents can be subdivided into nitrogen-containing (amines, quaternary ammonium compounds ⁇ amides), phosphorus (organophosphate) and sulfur-containing (alkylsulfonates, alkyl sulfates) antistats.
- External antistatic agents are described, for example, in patent applications FR 1, 156.513, GB 873 214 and GB 839 407.
- the lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.
- silicone derivatives can be used in the detergent portions according to the invention. These additionally improve the rinsing behavior of the portions according to the invention due to their foam-inhibiting properties.
- Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partly fluorinated.
- Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and then are amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
- the viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 mPas, and the silicones can be used in amounts between 0.2 and 5% by weight, based on the total agent.
- Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediamine tetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) or its derivatives or derivatives, and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
- EDTA ethylenediamine tetraacetic acid
- NTA nitrilotriacetic acid
- anionic polyelectrolytes such as polymaleates and polysulfonates.
- a preferred class of complexing agents are the phosphonates, which in preferred detergent, dishwashing or cleaning agent portions in amounts of 0.01 to 2.5% by weight, preferably 0.02 to 1% by weight and in particular 0 , 03 to 0.5 wt .-% are included.
- These preferred compounds include, in particular, organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylene phosphine acid) (ATMP), diethylene triamine penta (methylene phosphine acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
- organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylene phosphine acid) (ATMP), diethylene triamine penta (methylene phosphin
- the low-water and advantageously liquid formulation comprises a rheological additive.
- a rheological additive This can consist of one or more components.
- the rheological additives often serve as thickeners.
- Polymers originating from nature and used as rheological additives are, for example, agar agar, carrageenan, tragacanth, arabic gum, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein.
- Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
- a large group of rheological additives that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
- Rheological additives from the mentioned classes of compounds are widely available commercially and are sold for example under the trade name Acusol ® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ® -GT-282-S (alkyl polyglycol ether, Akzo), Deuterol ® polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ® thickener-0 (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® - 91 (ethylene
- this water-poor or water-free formulation preferably comprises one or more anionic surfactant (s) and / or one or more nonionic surfactant () to adjust its rheological parameters.
- e) comprehensive material e.
- the anionic surfactant (s) is / are selected from the group of the sulfonates and sulfates and their mixtures and / or the / the nonionic surfactant (s) is / are selected from the group of alkoxylated alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides and their mixtures.
- Rheological additives with a thickening effect are advantageously used in low-water or essentially water-free systems.
- These can be, for example (but not necessarily), acrylic-based polymers which, for. T. can have relatively high molecular weights in the range of> 1,000,000 g / mol. They are used in the washing-active, rinsing-active or cleaning-active formulations in amounts of 0.01 to 10% by weight, for example in amounts of 0.5 to 4% by weight.
- Suitable products are, for example, the products sold by Rohm & Haas under the name Aculos R , which are predominantly polyacrylates with different alkylation or crosslinking or hydrophobically modified nonionic polyols, or the products sold by BF Goodrich under the name Carbopol R , which are polyacrylates or copolymers of acrylic acid and alkylated (preferably C 5 - to C 10 -alkylated) acrylic acids, or the products sold by BF Goodrich under the name Pemulen R , the are high molecular acrylic copolymers of the type acrylic Iat C 10 to C 30 alkyl acrylate cross polymer.
- polyacrylate or polyurethane thickeners can also be used in water-free or essentially water-free systems which offer the possibility of adjusting the viscosity via a different mode of action (ie not associatively) in the presence of small amounts of water.
- Preferred low-water formulations contain rheological additives in amounts of 0.01 to 10% by weight, preferably 0.1 to 5% by weight and in particular 0.2 to 3% by weight.
- the liquid-based formulations show non-Newtonian flow behavior, preferably thixotropic or pseudoplastic flow behavior.
- the liquid-based formulations have a low viscosity during production, for example a viscosity in the range from 10 to 50 mPa.s, and the liquid-based formulations have a higher viscosity during storage, for example in the range of 10 to 100,000 mPa-s, preferably 100 to 20,000 mPa • s, more preferably a viscosity in the range of 200 to 10,000 mPa s.
- the viscosity can be lower than in systems in which solid components (which are visually noticeable in a turbidity) are present; the latter thickens regularly during storage ("setting") and can even become pasty.
- Detergent, dishwashing or cleaning agent portions according to the present invention which are present, for example, in capsule form, spherical shape or in the form of bags, can contain a liquid-based formulation contained in the wrappings of the detergent, dishwashing agent or cleaning agent portion of at least one detergent-active formulation , rinse-active or cleaning-active material can have clear solutions of one or more wash-active, rinse-active or cleaning-active component (s) or microemulsions.
- liquid-based formulations contain one or more solids suspended or dispersed, in particular when low-water or essentially water-free formulations are used. This is an advantage over the prior art, since water-sensitive components of wash-active, rinse-active or cleaning-active materials can be kept stable and uniformly distributed in the liquid phase and problems with a reduction in activity do not occur.
- the invention also relates to a washing method, in particular a method for machine washing in a commercially available washing machine, comprising the steps of introducing a detergent portion into the washing machine, in particular into the dispenser or the washing drum, according to the detailed description above; makes contact between the detergent portion and the washing liquor by adding water; sets the desired washing conditions; and when the desired conditions occur, the wash-active material (s) of the detergent portion is released into the wash liquor and brings it into contact with the items to be washed.
- a washing method in particular a method for machine washing in a commercially available washing machine, comprising the steps of introducing a detergent portion into the washing machine, in particular into the dispenser or the washing drum, according to the detailed description above; makes contact between the detergent portion and the washing liquor by adding water; sets the desired washing conditions; and when the desired conditions occur, the wash-active material (s) of the detergent portion is released into the wash liquor and brings it into contact with the items to be washed.
- the invention also relates to a washing method, in particular a method for machine washing in a commercially available dishwasher, comprising the steps of inserting a detergent portion into the dishwasher, in particular into the washing-up chamber or into the washing-up compartment, according to the detailed description above; makes contact between the detergent portion and the washing liquor by adding water; sets the desired rinsing conditions; and when these conditions occur, the rinsing active material (s) of the rinsing agent portion releases into the rinsing liquor and brings them into contact with the items to be rinsed.
- a washing method in particular a method for machine washing in a commercially available dishwasher, comprising the steps of inserting a detergent portion into the dishwasher, in particular into the washing-up chamber or into the washing-up compartment, according to the detailed description above; makes contact between the detergent portion and the washing liquor by adding water; sets the desired rinsing conditions; and when these conditions occur, the rinsing active material (s) of the rinsing agent portion releases into the rins
- the invention also relates to a cleaning process comprising the steps of adding a detergent portion to the cleaning liquor as detailed above; sets the desired cleaning conditions; and when these conditions occur, the cleaning-active material (s) of the detergent portion is released into the cleaning liquor and brings it into contact with the goods to be cleaned.
- the portions according to the present invention can also be used in other areas. For example, they are also conceivable as a cleaner for toilet cisterns for the continuous delivery of a cleaning agent and disinfectant to the toilet flushing water, if necessary, or as a cleaner for pipes, etc.
- such cleaners can also contain gas-releasing systems (e.g. an acid such as citric acid with a carbonate such as sodium carbonate).
- the transparency of the films was determined using a commercially available UV / Vis spectrophotometer, for example using a Milton Roy Spectronic 601.
- the permeability (T) was defined according to the Lambert-Beer law as:
- those water-soluble coatings are transparent in which a transmittance (T) above 20% is measured in the wavelength range from 410 to 800 nm, at least one wavelength.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
L'invention concerne une portion de produit de lavage, de rinçage ou de nettoyage qui comprend une enveloppe entièrement ou partiellement soluble dans l'eau se présentant sous forme de capsule, de bille ou de sachet, le matériau d'enveloppe étant transparent et les portions contenant un stabilisant. L'invention concerne en outre un procédé de lavage, de rinçage ou de nettoyage faisant appel à la portion de produit de lavage, de rinçage ou de nettoyage mentionnée ci-dessus.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002229632A AU2002229632A1 (en) | 2000-12-16 | 2001-12-07 | Washing, rinsing or cleaning agent portions with transparent shell |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10062857.5 | 2000-12-16 | ||
DE2000162857 DE10062857A1 (de) | 2000-12-16 | 2000-12-16 | Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen mit transparenter Umhüllung |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002048309A1 true WO2002048309A1 (fr) | 2002-06-20 |
Family
ID=7667492
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/014386 WO2002048309A1 (fr) | 2000-12-16 | 2001-12-07 | Portions de produit de lavage, de rinçage ou de nettoyage a enveloppe transparente |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU2002229632A1 (fr) |
DE (1) | DE10062857A1 (fr) |
WO (1) | WO2002048309A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003026982A1 (fr) * | 2001-09-20 | 2003-04-03 | Unilever N.V. | Emballage compose d'une pellicule soluble dans l'eau contenant un colorant fluorescent |
WO2004046287A3 (fr) * | 2002-11-15 | 2004-07-08 | Henkel Kgaa | Agents sous forme de portions comportant differents constituants |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10313453A1 (de) * | 2003-03-25 | 2004-10-14 | Henkel Kgaa | Portionierte Wasch- oder Reinigungsmittelzusammensetzung |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0314890A2 (fr) * | 1987-10-02 | 1989-05-10 | Ecolab Inc. | Distributeur pour un Produit comprenant une poche hydrosoluble contenant une matière fonctionnelle granulée et mèthodes de son emploi |
WO1994004656A2 (fr) * | 1992-08-20 | 1994-03-03 | Kao Corp | Produit detergent a conditionnement aliquote utilisant un film hydrosoluble |
EP0879874A2 (fr) * | 1997-05-23 | 1998-11-25 | Henkel Kommanditgesellschaft auf Aktien | Détergent encapsulé |
WO2001000781A1 (fr) * | 1999-06-25 | 2001-01-04 | Henkel Kommanditgesellschaft Auf Aktien | Emballage-portion de matiere active |
WO2002014460A2 (fr) * | 2000-08-17 | 2002-02-21 | Henkel Kommanditgesellschaft Auf Aktien | Doses d'agent de lavage, de rinçage ou de nettoyage a formulation liquide mecaniquement stables |
-
2000
- 2000-12-16 DE DE2000162857 patent/DE10062857A1/de not_active Ceased
-
2001
- 2001-12-07 WO PCT/EP2001/014386 patent/WO2002048309A1/fr not_active Application Discontinuation
- 2001-12-07 AU AU2002229632A patent/AU2002229632A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0314890A2 (fr) * | 1987-10-02 | 1989-05-10 | Ecolab Inc. | Distributeur pour un Produit comprenant une poche hydrosoluble contenant une matière fonctionnelle granulée et mèthodes de son emploi |
WO1994004656A2 (fr) * | 1992-08-20 | 1994-03-03 | Kao Corp | Produit detergent a conditionnement aliquote utilisant un film hydrosoluble |
EP0879874A2 (fr) * | 1997-05-23 | 1998-11-25 | Henkel Kommanditgesellschaft auf Aktien | Détergent encapsulé |
WO2001000781A1 (fr) * | 1999-06-25 | 2001-01-04 | Henkel Kommanditgesellschaft Auf Aktien | Emballage-portion de matiere active |
WO2002014460A2 (fr) * | 2000-08-17 | 2002-02-21 | Henkel Kommanditgesellschaft Auf Aktien | Doses d'agent de lavage, de rinçage ou de nettoyage a formulation liquide mecaniquement stables |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003026982A1 (fr) * | 2001-09-20 | 2003-04-03 | Unilever N.V. | Emballage compose d'une pellicule soluble dans l'eau contenant un colorant fluorescent |
WO2004046287A3 (fr) * | 2002-11-15 | 2004-07-08 | Henkel Kgaa | Agents sous forme de portions comportant differents constituants |
Also Published As
Publication number | Publication date |
---|---|
DE10062857A1 (de) | 2002-07-11 |
AU2002229632A1 (en) | 2002-06-24 |
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