EP0941300B1 - Shaped soap products - Google Patents
Shaped soap products Download PDFInfo
- Publication number
- EP0941300B1 EP0941300B1 EP97951961A EP97951961A EP0941300B1 EP 0941300 B1 EP0941300 B1 EP 0941300B1 EP 97951961 A EP97951961 A EP 97951961A EP 97951961 A EP97951961 A EP 97951961A EP 0941300 B1 EP0941300 B1 EP 0941300B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- soap
- fatty acids
- soap product
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000344 soap Substances 0.000 title claims abstract description 57
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 18
- 239000000194 fatty acid Substances 0.000 claims abstract description 18
- 229930195729 fatty acid Natural products 0.000 claims abstract description 18
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 239000000454 talc Substances 0.000 claims abstract description 11
- 229910052623 talc Inorganic materials 0.000 claims abstract description 11
- 235000012222 talc Nutrition 0.000 claims abstract description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 8
- 239000004571 lime Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 2
- 150000001340 alkali metals Chemical class 0.000 claims abstract 2
- 229930182470 glycoside Natural products 0.000 claims description 9
- 229940095696 soap product Drugs 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000002338 glycosides Chemical class 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 238000006384 oligomerization reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 4
- 235000021588 free fatty acids Nutrition 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 229930182478 glucoside Natural products 0.000 description 5
- 150000008131 glucosides Chemical class 0.000 description 5
- 235000012149 noodles Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- -1 alkyl glycosides Chemical class 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- AOHAPDDBNAPPIN-UHFFFAOYSA-N 3-Methoxy-4,5-methylenedioxybenzoic acid Chemical compound COC1=CC(C(O)=O)=CC2=C1OCO2 AOHAPDDBNAPPIN-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical class CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 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
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- the invention relates to shaped soap products, e.g. Bar soaps with improved smoothness and increased lime soap dispersibility due to the content of alkyl (oligo) glycosides and talc.
- the shaped soap products according to the invention also have after mechanical deformation a particularly smooth surface. When using they create a creamy, stable foam. The one formed in hard water Lime soap deposit remains dispersed in the water and does not lead to the greasy gray Coverings on the surface of sanitary objects.
- Under talc according to the invention is a hydrated magnesium silicate with the theoretical composition 3MgO ⁇ 4SiO 2 ⁇ H 2 O and Mg 3 (Si 4 O 10) ⁇ (OH) 2, which however fractions of hydrated magnesium aluminum silicate of up to 12 parts by weight % Al 2 O 3 , based on the entire product, may contain.
- the particle diameter (equivalent spherical diameter) of the talc should be in the range of 0.5 - 50 ⁇ m. In general, such talc qualities have proven themselves not more than 5% by weight of particles below 1 ⁇ m and not more than 5% by weight Contain particles larger than 50 ⁇ m. Preferably the proportion of particles is larger than 40 ⁇ m in diameter (sieve residue), at most 2% by weight.
- the middle one Particle diameter (D 50) is preferably 5-15 ⁇ m.
- the content of accompanying substances should not exceed 1.6% by weight of Fe 2 O 3 , 1% by weight of CaO and 1% by weight of unbound water (loss of drying at 105 ° C.).
- the hydrated magnesium aluminum silicate content can be up to 60% by weight, calculated as Al 2 O 3 , up to 12% by weight.
- the linear fatty acids with 12 to 22 carbon atoms for example lauric, myristic, palmitic, stearic, arachic and behenic acid, but also the unsaturated fatty acids, for example the palmitoleic, oleic, , Linole. Linolenic, arachidonic and erucic acids are used.
- Technical mixtures such as those obtainable from vegetable and animal fats and oils, are preferably used, for example coconut oil fatty acid and tallow fatty acid. Mixtures of coconut and tallow fatty acid cuts are particularly preferred, in particular a mixture of 50-80% by weight of C 16 -C 18 tallow fatty acid and 20-50% by weight of C 12 -C 14 coconut fatty acid.
- the fatty acids are in the form of their alkali soap, usually as sodium soaps used.
- the soaps can also be saponified directly from the fats and oils (Hydrolysis) with sodium hydroxide solution and separation of the glycerol.
- R ' is a primary C 12 -C 16 - Alkyl group
- the alkyl (oligo) glycosides can be derived from aldoses or ketoses with 5 or 6 carbons. Because of the easy accessibility, mainly alkyl- (oligo) -glucosides derived from glucose are produced on an industrial scale.
- the degree of oligomerization x represents an average that results from the Homolog distribution of mono-, di-, tri- and higher polyglucosides results.
- Such Products are e.g. under the trade name Plantaren®1200 from HENKEL KGaA available.
- the shaped soap products according to the invention can also contain other synthetic surfactants, for example strongly foaming skin-friendly anionic surfactants, amphoteric surfactants, betaine surfactants or nonionic surfactants.
- a soap product according to the invention is particularly preferred which additionally contains up to 15% by weight of synthetic, anionic, zwitterionic or ampholytic surfactants.
- Preferred suitable anionic surfactants are, for example, alkyl ether sulfates of the formula R 2 O- (C 2 H 4 O) n -SO 3 Na, in which R 2 is a preferably linear, primary alkyl group with 12-16 C atoms and n is an average value of 1- 10 is.
- anionic surfactants are, for example, acyl isethionates of the formula R 3 CO-OCH 2 CH 2 -SO 3 Na, in which R 3 CO is a linear acyl group with 12-18 C atoms.
- R 3 CO is a linear acyl group with 12-18 C atoms.
- the anionic surfactants mentioned are also commercially available.
- the shaped soap products according to the invention preferably also contain water in an amount of 5-15% by weight.
- the water content is due to the one hand Manufacturing process, on the other hand, it has a beneficial effect on the properties of use the soap out.
- the shaped soap products according to the invention can contain fragrances and contain further customary auxiliaries and additives in an amount of up to 5% by weight.
- Suitable excipients are e.g. Binders or plasticizers.
- the Fatty alcohols can e.g. as a by-product of the alkyl (oligo) glucosides together with these are added when using the alkyl (oligo) glucoside as a crude product contains up to 50% by weight of free fatty alcohol.
- auxiliaries are, for example, dyes, antimicrobial substances, deodorant active ingredients, pigments (TiO 2 ), optical brighteners and complexing agents.
- the production of the shaped soap products according to the invention can be carried out for soaps usual way.
- a fatty acid mixture and sodium hydroxide solution become one Basic soap with a solids content of 25 - 50 wt .-% produced and on a Solids content of 50 - 70 wt .-% concentrated.
- 60% basic soap can already the talcum, optionally also free fatty acid, an anionic surfactant and a complexing agent can be mixed in.
- the basic soap is e.g. in one Vacuum expansion dryer further dewatered at 120 ° C to 130 ° C. When expanding The soap spontaneously cools down to temperatures below 60 ° C and becomes solid. Fall in the process Soap noodles with a solids content of 73-85% by weight.
- this basic soap then turns it into a fine soap It takes place in a soap mixer in which a slurry of the alkyl (oligo) glucoside and the other auxiliaries and additives are mixed into the soap noodles.
- a soap mixer in which a slurry of the alkyl (oligo) glucoside and the other auxiliaries and additives are mixed into the soap noodles.
- the base soap noodles and the slurry of alkyl (oligo) glycoside and e.g. Fragrances, dyes, pigments and other auxiliaries in one Screw mixer intensively mixed with perforated sieves and finally over a Extruded press discharged and, if necessary, fed to a piece press, if Soap bars are to be made.
- Shaped soap products in the sense of the invention can also be used as noodles. needles Granules, extrudates, flakes and any other common for soap products Shape available.
- the talc can only be obtained from Assembly into the 73 - 85% basic soap.
- the talcum powder is dispensed using suitable dosing devices, e.g. Belt scale and Shaker with the slurry of alkyl (oligo) glycoside, fragrances and Tools supplied to the soap mixer.
- the soap products according to the invention are particularly smooth Surface, which is particularly pleasant when processed into bar soap noticeable. A lot of fine-bubble, creamy foam forms when in use. In Hard water also forms lime soap deposits, but these remain in the Solution disperses and does not form a greasy gray on hard surfaces Stains or cheesy edge, but at most as a light, finely divided veil.
- the basic soap noodles are mixed with the other components in a usual way Soap mixer (screw mixer with perforated sieve) dosed by mixing several times homogenized, discharged via an extruder, cut and cut in the usual way Pieces processed.
- Soap mixer screw mixer with perforated sieve
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
Description
Die Erfindung betrifft geformte Seifenprodukte, z.B. Stückseifen mit verbesserter Glätte und erhöhtem Kalkseifendispergiervermögen durch einen Gehalt an Alkyl-(oligo)-glycosiden und Talkum.The invention relates to shaped soap products, e.g. Bar soaps with improved smoothness and increased lime soap dispersibility due to the content of alkyl (oligo) glycosides and talc.
Es ist bekannt, daß Feinseifen auf Basis von Talg- und Kokosfettsäuren durch zahlreiche Zusatzstoffe in ihren anwendungstechnischen Eigenschaften verändert und verbessert werden können.It is known that fine soaps based on tallow and coconut fatty acids by numerous The properties of additives changed and improved can be.
So ist z.B. aus DE-PS 593 422 bekannt, daß durch Zusatz von 10 bis 15 Gew.-% Cetylmaltosid zu einer Grundseifenmischung die Waschkraft und die Kalkseifendispergierung verbessert werden. Weiterhin sind aus EP 0 463 912 A1, DE 43 31 297 A1 und DE 43 37 031 C2 Seifenstücke auf Basis von Fettsäure-Grundseifen mit einem Gehalt an Alkyl-(oligo)-glucosiden bekannt. In gängigen Handbüchern, z.B. Geoffrey Martin: The Modern Soap and Detergent Industry, Vol. 1, (1950), Kapitel VI, sind zwar anorganische Füllstoffe als Streckmittel für Seifen beschrieben, dabei wird dem Talkum jedoch eher eine nachteilige Wirkung in Stückseifen zugeschrieben.For example, from DE-PS 593 422 known that by adding 10 to 15 wt .-% Cetyl maltoside to a basic soap mix the washing power and the lime soap dispersion be improved. Furthermore, EP 0 463 912 A1, DE 43 31 297 A1 and DE 43 37 031 C2 soap bars based on fatty acid base soaps containing Alkyl (oligo) glucosides known. In common manuals, e.g. Geoffrey Martin: The Modern Soap and Detergent Industry, Vol. 1, (1950), Chapter VI, are inorganic Fillers are described as extenders for soaps, but the talc is more likely attributed an adverse effect in bar soaps.
Entgegen den aus dem Stand der Technik zu erwartenden Einbußen wurde überraschend festgestellt, daß bei Stückseifen, die bereits Alkylglycoside als Zusatz enthalten, durch einen Zusatz von Talkum eine weitere Verbesserung der physikalischen und anwendungstechnischen Eigenschaften, insbesondere des Wasch- und Kalkseifendispergiervermögens und der Seifenglätte erzielt wird.Contrary to the losses to be expected from the prior art, it was surprising found that with bar soaps that already contain alkyl glycosides as an additive an addition of talcum further improves the physical and application technology Properties, in particular of the washing and lime soap dispersing ability and the smoothness of the soap is achieved.
Gegenstand der Erfindung ist daher ein geformtes Seifenprodukt das
- 60 - 85 Gew.-%
- Fettsäuren mit 12 bis 22 C-Atomen in Form ihrer Alkaliseifen und
- 1 - 10 Gew.-%
- Alkyl-(oligo)-glycoside der Formel R1O-(G)x, in der R1 eine primäre C12-C16-Alkylgruppe und (G)x ein Oligo-Glycosidrest ist, dessen Oligomerisationsgrad x = 1 - 2 ist, sowie
- 60-85% by weight
- Fatty acids with 12 to 22 carbon atoms in the form of their alkali soaps and
- 1 - 10% by weight
- Alkyl (oligo) glycosides of the formula R 1 O- (G) x , in which R 1 is a primary C 12 -C 16 alkyl group and (G) x is an oligo-glycoside residue, the degree of oligomerization of which is x = 1 - 2 , such as
Die erfindungsgemäßen geformten Seifenprodukte besitzen darüber hinaus nach der mechanischen Verformung eine besonders glatte Oberfläche. Bei der Anwendung erzeugen sie einen cremigen, stabilen Schaum. Der in hartem Wasser gebildete Kalkseifenniederschlag bleibt im Wasser dispergiert und führt nicht zu den grau-schmierigen Belägen auf der Oberfläche von Sanitärobjekten.The shaped soap products according to the invention also have after mechanical deformation a particularly smooth surface. When using they create a creamy, stable foam. The one formed in hard water Lime soap deposit remains dispersed in the water and does not lead to the greasy gray Coverings on the surface of sanitary objects.
Unter Talkum im Sinne der Erfindung wird ein hydratisiertes Magnesiumsilikat der theoretischen Zusammensetzung 3MgO · 4SiO2 · H2O bzw. Mg3(Si4O10) · (OH)2, das jedoch Anteile an hydratisiertem Magnesiumaluminiumsilikat von bis zu 12 Gew.-% Al2O3, bezogen auf das gesamte Produkt, enthalten kann.Under talc according to the invention is a hydrated magnesium silicate with the theoretical composition 3MgO · 4SiO 2 · H 2 O and Mg 3 (Si 4 O 10) · (OH) 2, which however fractions of hydrated magnesium aluminum silicate of up to 12 parts by weight % Al 2 O 3 , based on the entire product, may contain.
Der Teilchendurchmesser (equivalent spherical diameter) des Talkums sollte im Bereich von 0,5 - 50 µm liegen. Im allgemeinen haben sich solche Talkumqualitäten bewährt, die nicht mehr als 5 Gew.-% an Teilchen unter 1 µm und nicht mehr als 5 Gew.-% an Teilchen über 50 µm Größe enthalten. Vorzugsweise ist der Anteil an Teilchen, die größer als 40 µm im Durchmesser sind (Siebrückstand), höchstens 2 Gew.-%. Der mittlere Teilchendurchmesser (D 50) liegt bevorzugt bei 5 - 15 µm.The particle diameter (equivalent spherical diameter) of the talc should be in the range of 0.5 - 50 µm. In general, such talc qualities have proven themselves not more than 5% by weight of particles below 1 µm and not more than 5% by weight Contain particles larger than 50 µm. Preferably the proportion of particles is larger than 40 µm in diameter (sieve residue), at most 2% by weight. The middle one Particle diameter (D 50) is preferably 5-15 µm.
Der Gehalt an Begleitstoffen sollte nicht mehr als 1,6 Gew.-% Fe2O3, 1 Gew.-% CaO und 1 Gew.-% an ungebundenem Wasser (Trockenverlust bei 105° C) ausmachen. Der Gehalt an hydratisiertem Magnesiumaluminiumsilikat kann bis zu 60 Gew.-%, berechnet als Al2O3, bis zu 12 Gew.-% liegen.The content of accompanying substances should not exceed 1.6% by weight of Fe 2 O 3 , 1% by weight of CaO and 1% by weight of unbound water (loss of drying at 105 ° C.). The hydrated magnesium aluminum silicate content can be up to 60% by weight, calculated as Al 2 O 3 , up to 12% by weight.
Als Fettsäuren zur Herstellung der Grundseife werden die linearen Fettsäuren mit 12 bis 22 C-Atomen, z.B. die Laurin-, Myristin-, Palmitin-, Stearin-, Arachin- und Behensäure, aber auch die ungesättigten Fettsäuren, z.B. die Palmitolein-, Öl-, Linol-. Linolen-, Arachidon- und Erucasäure verwendet. Bevorzugt werden technische Gemische, wie sie aus pflanzlichen und tierischen Fetten und Ölen erhältlich sind, eingesetzt, z.B. Kokosölfettsäure und Talgfettsäure. Besonders bevorzugt sind Gemische aus Kokos- und Talgfettsäureschnitten, insbesondere ein Gemisch aus 50 - 80 Gew.-% C16-C18-Talgfettsäure und 20 - 50 Gew.-% C12-C14-Kokosfettsäure.The linear fatty acids with 12 to 22 carbon atoms, for example lauric, myristic, palmitic, stearic, arachic and behenic acid, but also the unsaturated fatty acids, for example the palmitoleic, oleic, , Linole. Linolenic, arachidonic and erucic acids are used. Technical mixtures, such as those obtainable from vegetable and animal fats and oils, are preferably used, for example coconut oil fatty acid and tallow fatty acid. Mixtures of coconut and tallow fatty acid cuts are particularly preferred, in particular a mixture of 50-80% by weight of C 16 -C 18 tallow fatty acid and 20-50% by weight of C 12 -C 14 coconut fatty acid.
Die Fettsäuren werden in Form ihrer Alkaliseife, üblicherweise als Natriumseifen eingesetzt. Die Seifen können aber auch aus den Fetten und Ölen direkt durch Verseifung (Hydrolyse) mit Natronlauge und Abtrennen des Glycerins erzeugt werden. Bevorzugt enthalten die erfindungsgemäßen geformten Seifenprodukte einen zusätzlichen Anteil von 1 - 10 Gew.-% an freien Fettsäuren mit 12 - 22 C-Atomen. Diese können mit den Fettsäuren der Grundseife identisch sein und durch einen entsprechenden Alkali-Unterschuß bei der Verseifung in die Grundseife eingebracht werden. Bevorzugt werden die freien Fettsäuren aber nach der Verseifung und nach dem Aufkonzentrieren, vor der Trocknung, zudosiert.The fatty acids are in the form of their alkali soap, usually as sodium soaps used. The soaps can also be saponified directly from the fats and oils (Hydrolysis) with sodium hydroxide solution and separation of the glycerol. Prefers The shaped soap products according to the invention contain an additional proportion of 1 - 10% by weight of free fatty acids with 12 - 22 carbon atoms. This can be done with the Fatty acids of the basic soap should be identical and by an appropriate alkali deficit be introduced into the basic soap during saponification. To be favoured the free fatty acids after saponification and after concentrating, before Drying, added.
Alkyl-(oligo)-glycoside sind bekannte, im Handel erhältliche nichtionogene Tenside, die nach einschlägigen Verfahren der organischen Chemie zugänglich sind und der Formel R1-O(G)x entsprechen, in der R' eine primäre C12-C16-Alkylgruppe und (G)x ein Oligoglycosidrest ist, dessen Oligomerisationsgrad x = 1 bis 2 ist. Stellvertretend für das umfangreiche Schrifttum sei hier auf EP-A-0 301 298 und WO-A-90/3977 verwiesen. Die Alkyl-(oligo)-glycoside können sich von Aldosen oder Ketosen mit 5 oder 6 Kohlenstoffen ableiten. Wegen der leichten Zugänglichkeit werden im großtechnischen Maßstab hauptsächlich von Glucose abgeleitete Alkyl-(oligo)-glucoside hergestellt.Alkyl (oligo) glycosides are known, commercially available nonionic surfactants which can be obtained by relevant processes in organic chemistry and which correspond to the formula R 1 -O (G) x , in which R 'is a primary C 12 -C 16 - Alkyl group and (G) x is an oligoglycoside residue whose degree of oligomerization x = 1 to 2. As a representative of the extensive literature, reference is made here to EP-A-0 301 298 and WO-A-90/3977. The alkyl (oligo) glycosides can be derived from aldoses or ketoses with 5 or 6 carbons. Because of the easy accessibility, mainly alkyl- (oligo) -glucosides derived from glucose are produced on an industrial scale.
Der Oligomerisierungsgrad x stellt einen Mittelwert dar, der sich aus der Homologenverteilung von Mono-, Di-, Tri- und höheren Polyglucosiden ergibt. Anwendungstechnisch besonders bevorzugt sind solche Alkyl-(oligo)-glucoside, deren Oligomerisationsgrad x unter 1.7, insbesonderen zwischen 1.2 und 1.5 liegt. Solche Produkte sind z.B. unter der Handelsbezeichnung Plantaren®1200 der HENKEL KGaA erhältlich.The degree of oligomerization x represents an average that results from the Homolog distribution of mono-, di-, tri- and higher polyglucosides results. In terms of application technology, those alkyl (oligo) glucosides whose Degree of oligomerization x is below 1.7, in particular between 1.2 and 1.5. Such Products are e.g. under the trade name Plantaren®1200 from HENKEL KGaA available.
Zusätzlich zu den Alkyl-(oligo)-glycosiden können die erfindungsgemäßen geformten Seifenprodukte auch andere synthetische Tenside, z.B. stark schäumende hautfreundliche Aniontenside, Amphotenside, Betaintenside oder nichtionische Tenside enthalten. Besonders bevorzugt ist ein erfindungsgemäßes Seifenprodukt, in dem zusätzlich bis zu 15 Gew.-% synthetischer, anionischer, zwitterionischer oder ampholytischer Tenside enthalten sind. Bevorzugt geeignete anionische Tenside sind z.B. Alkylethersulfate der Formel R2O-(C2H4O)n-SO3Na, in der R2 eine bevorzugt lineare, primäre Alkylgruppe mit 12 - 16 C-Atomen und n ein Mittelwert von 1 - 10 ist. Weitere geeignete anionische Tenside sind z.B. Acylisethionate der Formel R3CO-OCH2CH2-SO3Na, in der R3CO eine lineare Acylgruppe mit 12 - 18 C-Atomen ist Auch die genannten anionischen Tenside sind handelsüblich.In addition to the alkyl (oligo) glycosides, the shaped soap products according to the invention can also contain other synthetic surfactants, for example strongly foaming skin-friendly anionic surfactants, amphoteric surfactants, betaine surfactants or nonionic surfactants. A soap product according to the invention is particularly preferred which additionally contains up to 15% by weight of synthetic, anionic, zwitterionic or ampholytic surfactants. Preferred suitable anionic surfactants are, for example, alkyl ether sulfates of the formula R 2 O- (C 2 H 4 O) n -SO 3 Na, in which R 2 is a preferably linear, primary alkyl group with 12-16 C atoms and n is an average value of 1- 10 is. Other suitable anionic surfactants are, for example, acyl isethionates of the formula R 3 CO-OCH 2 CH 2 -SO 3 Na, in which R 3 CO is a linear acyl group with 12-18 C atoms. The anionic surfactants mentioned are also commercially available.
Die erfindungsgemäßen geformten Seifenprodukte enthalten vorzugsweise darüber hinaus Wasser in einer Menge von 5 - 15 Gew.-%. Der Wassergehalt ist einerseits bedingt durch das Herstellungsverfahren, andererseits wirkt er sich günstig auf die Gebraucheigenschaften der Seife aus.The shaped soap products according to the invention preferably also contain water in an amount of 5-15% by weight. The water content is due to the one hand Manufacturing process, on the other hand, it has a beneficial effect on the properties of use the soap out.
Schließlich können die erfindungsgemäßen geformten Seifenprodukte Duftstoffe und weitere übliche Hilfs- und Zusatzstoffe in einer Menge von bis zu 5 Gew.-% enthalten. Geeignete Hilfsstoffe sind z.B. Bindemittel oder Plastifikatoren. Als solche eignen sich z.B. Glycerin, Fettsäurepartialglyceride oder Fettalkohole mit 12 - 22 C-Atomen. Die Fettalkohole können z.B. als Nebenprodukt der Alkyl-(oligo)-glucoside gemeinsam mit diesen zugesetzt werden, wenn man die Alkyl-(oligo)-glucoside als Rohprodukt mit einem Gehalt an bis zu 50 Gew.-% freiem Fettalkohol einsetzt.Finally, the shaped soap products according to the invention can contain fragrances and contain further customary auxiliaries and additives in an amount of up to 5% by weight. Suitable excipients are e.g. Binders or plasticizers. As such are suitable e.g. Glycerin, fatty acid partial glycerides or fatty alcohols with 12 - 22 C atoms. The Fatty alcohols can e.g. as a by-product of the alkyl (oligo) glucosides together with these are added when using the alkyl (oligo) glucoside as a crude product contains up to 50% by weight of free fatty alcohol.
Weitere Hilfsstoffe sind z.B. Farbstoffe, antimikrobielle Stoffe, Deodorantwirkstoffe, Pigmente (TiO2), optische Aufheller und Komplexbildner.Other auxiliaries are, for example, dyes, antimicrobial substances, deodorant active ingredients, pigments (TiO 2 ), optical brighteners and complexing agents.
Die Herstellung der erfindungsgemäßen geformten Seifenprodukte kann in der für Seifen üblichen Weise erfolgen. Dabei wird zunächst aus Fettsäureansatz und Natronlauge eine Grundseife mit einem Feststoffgehalt von 25 - 50 Gew.-% hergestellt und auf einen Feststoffgehalt von 50 - 70 Gew.-% aufkonzentriert. In diese z.B. 60 %ige Grundseife kann bereits das Talkum, gegebenenfalls auch freie Fettsäure, ein anionisches Tensid und ein Komplexbildner eingemischt werden. Danach wird die Grundseife z.B. in einem Vakuumexpansionstrockner bei 120°C bis 130°C weiter entwässert. Bei der Expansion kühlt sich die Seife spontan auf Temperaturen unter 60°C ab und wird fest. Dabei fallen Seifennudeln mit einem Feststoffgehalt von 73 - 85 Gew.-% an.The production of the shaped soap products according to the invention can be carried out for soaps usual way. First, a fatty acid mixture and sodium hydroxide solution become one Basic soap with a solids content of 25 - 50 wt .-% produced and on a Solids content of 50 - 70 wt .-% concentrated. In this e.g. 60% basic soap can already the talcum, optionally also free fatty acid, an anionic surfactant and a complexing agent can be mixed in. Then the basic soap is e.g. in one Vacuum expansion dryer further dewatered at 120 ° C to 130 ° C. When expanding The soap spontaneously cools down to temperatures below 60 ° C and becomes solid. Fall in the process Soap noodles with a solids content of 73-85% by weight.
Die Weiterverarbeitung dieser Grundseife stellt dann die Konfektionierung zur Feinseife dar. Sie erfolgt in einem Seifenmischer, in dem ein Slurry aus dem Alkyl-(oligo)-glucosid und den übrigen Hilfs- und Zusatzmitteln in die Seifennudeln eingemischt wird. Dabei werden die Grundseifennudeln und der Slurry aus Alkyl-(oligo)-glycosid und z.B. Duftstoffen, Farbstoffen, Pigmenten und anderen Hilfsmitteln in einem Schneckenmischer mit Lochsieben intensiv gemischt und schließlich über eine Strangpresse ausgetragen und gegebenenfalls einer Stückpresse zugeführt, wenn Seifenstücke hergestellt werden sollen.The processing of this basic soap then turns it into a fine soap It takes place in a soap mixer in which a slurry of the alkyl (oligo) glucoside and the other auxiliaries and additives are mixed into the soap noodles. there the base soap noodles and the slurry of alkyl (oligo) glycoside and e.g. Fragrances, dyes, pigments and other auxiliaries in one Screw mixer intensively mixed with perforated sieves and finally over a Extruded press discharged and, if necessary, fed to a piece press, if Soap bars are to be made.
Geformte Seifenprodukte im Sinne der Erfindung können aber auch als Nudeln. Nadeln, Granulate, Extrudate, Schuppen und in jeder anderen für Seifenprodukte übliche Formgebung vorliegen.Shaped soap products in the sense of the invention can also be used as noodles. needles Granules, extrudates, flakes and any other common for soap products Shape available.
Alternativ zu dem beschriebenen Verfahren kann das Talkum auch erst bei der Konfektionierung in die 73 - 85 %ige Grundseife eingearbeitet werden. In diesem Falle wird das Talkumpulver über geeignete Dosiergeräte, z.B. Bandwaage und Schütteldosierer gleichzeitig mit dem Slurry aus Alkyl-(oligo)-glycosid, Duftstoffen und Hilfsmitteln dem Seifenmischer zugeführt.As an alternative to the described method, the talc can only be obtained from Assembly into the 73 - 85% basic soap. In this case the talcum powder is dispensed using suitable dosing devices, e.g. Belt scale and Shaker with the slurry of alkyl (oligo) glycoside, fragrances and Tools supplied to the soap mixer.
Die erfindungsgemäßen Seifenprodukte zeichnen sich durch eine besonders glatte Oberfläche aus, was sich insbesondere bei Verarbeitung zu Stückseife angenehm bemerkbar macht. Bei Gebrauch bildet sich reichlich feinblasiger, cremiger Schaum. In hartem Wasser bilden sich zwar auch Kalkseifenausfällungen, diese bleiben aber in der Lösung dispergiert und schlagen sich auf harten Oberflächen nicht als schmierig-graue Flecken oder käsiger Rand, sondern allenfalls als leichter, feinteiliger Schleier nieder.The soap products according to the invention are particularly smooth Surface, which is particularly pleasant when processed into bar soap noticeable. A lot of fine-bubble, creamy foam forms when in use. In Hard water also forms lime soap deposits, but these remain in the Solution disperses and does not form a greasy gray on hard surfaces Stains or cheesy edge, but at most as a light, finely divided veil.
Die folgenden Beispiele sollen den Erfindungsgegenstand näher erläutern: The following examples are intended to explain the subject of the invention in more detail:
Die Grundseifennudeln werden mit den übrigen Komponenten in einen üblichen Seifenmischer (Schneckenmischer mit Lochsieb) dosiert, durch mehrmaliges Vermischen homogenisiert, über eine Strangpresse ausgetragen, geschnitten und in üblicher Weise zu Stücken verarbeitet.The basic soap noodles are mixed with the other components in a usual way Soap mixer (screw mixer with perforated sieve) dosed by mixing several times homogenized, discharged via an extruder, cut and cut in the usual way Pieces processed.
Claims (6)
- A shaped soap product containing
- 60 to 85% by weight
- of fatty acids containing 12 to 22 carbon atoms in the form of their alkali metal soaps and
- 1 to 10% by weight
- of alkyl (oligo)glycosides with the formula R1-O(G)x, where R1 is a primary C12-16 alkyl group and (G)x is an oligoglycoside unit with a degree of oligomerization x of 1 to 2,
- A soap product as claimed in claim 1, characterized in that the fatty acids are composed of 50 to 80% by weight C16-18 fatty acids and 20 to 50% by weight C12-14 fatty acids.
- A soap product as claimed in claim 1 or 2, characterized in that 1 to 10% by weight of free fatty acids containing 12 to 22 carbon atoms are additionally present.
- A soap product as claimed in any of claims 1 to 3, characterized in that up to 15% by weight of synthetic, anionic, zwitterionic or ampholytic surfactants are additionally present.
- A soap product as claimed in of any claims 1 to 4, characterized in that 5 to 15% by weight of water is present.
- A soap product as claimed in any of claims 1 to 5, characterized in that fragrances and other typical auxiliaries and additives are present in a quantity of up to 5% by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19649896 | 1996-12-02 | ||
| DE19649896A DE19649896A1 (en) | 1996-12-02 | 1996-12-02 | Shaped soap products |
| PCT/EP1997/006557 WO1998024872A1 (en) | 1996-12-02 | 1997-11-24 | Shaped soap products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0941300A1 EP0941300A1 (en) | 1999-09-15 |
| EP0941300B1 true EP0941300B1 (en) | 2003-05-21 |
Family
ID=7813366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97951961A Expired - Lifetime EP0941300B1 (en) | 1996-12-02 | 1997-11-24 | Shaped soap products |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6225270B1 (en) |
| EP (1) | EP0941300B1 (en) |
| CN (1) | CN1117847C (en) |
| AT (1) | ATE241002T1 (en) |
| CA (1) | CA2273969A1 (en) |
| DE (2) | DE19649896A1 (en) |
| ES (1) | ES2200210T3 (en) |
| HU (1) | HUP0000360A3 (en) |
| NO (1) | NO992631D0 (en) |
| PL (1) | PL188847B1 (en) |
| SK (1) | SK73199A3 (en) |
| WO (1) | WO1998024872A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10035211A1 (en) * | 2000-07-20 | 2002-01-31 | Beiersdorf Ag | Shaped soap product containing talc, one or more fatty acids in the form of their alkali soaps and one or more nonionic surfactants in the absence of alkyl (oligo) glycosides |
| DE10035213A1 (en) | 2000-07-20 | 2002-01-31 | Beiersdorf Ag | Shaped soap product containing talc, one or more fatty acids in the form of their alkali soaps and one or more lipid-replenishing substances in the absence of alkyl (oligo) glycosides |
| DE10035207A1 (en) * | 2000-07-20 | 2002-01-31 | Beiersdorf Ag | Shaped soap product containing talc, one or more fatty acids in the form of their alkali soaps and one or more amphoteric surfactants in the absence of alky / olig) glycosides |
| US20060019854A1 (en) * | 2004-07-21 | 2006-01-26 | Johnsondiversey. Inc. | Paper mill cleaner with taed |
| US20080125340A1 (en) * | 2005-08-19 | 2008-05-29 | The Dial Corporation | Personal cleansing composition with enhanced skin feel characteristics |
| US20080153728A1 (en) * | 2005-08-19 | 2008-06-26 | The Dial Corporation | Cleansing compositions having improved fragrance characteristics and methods for the formulation thereof |
| EP4014977A1 (en) * | 2015-11-04 | 2022-06-22 | Merck Patent GmbH | Pyrimidine compounds with btk inhibitory activity for use in treating cancer |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE593422C (en) | 1931-02-05 | 1934-02-26 | H Th Boehme A G | Use of high molecular weight synthetic glucosides as a saponin substitute, as an emulsifying, cleaning and wetting agent |
| DE3723826A1 (en) | 1987-07-18 | 1989-01-26 | Henkel Kgaa | METHOD FOR PRODUCING ALKYL GLYCOSIDES |
| AU640786B2 (en) | 1990-06-22 | 1993-09-02 | Colgate-Palmolive Company, The | Toilet soap bar composition with alkyl polyglycoside surfactant |
| US5340492A (en) * | 1990-11-26 | 1994-08-23 | The Procter & Gamble Company | Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid |
| US5262079A (en) * | 1992-03-20 | 1993-11-16 | The Procter & Gamble Company | Framed neutral pH cleansing bar |
| DE4331297A1 (en) | 1993-09-15 | 1995-03-16 | Henkel Kgaa | Bar soaps |
| DE4337031C2 (en) | 1993-10-29 | 1995-11-30 | Henkel Kgaa | Bar soaps |
| US5631215A (en) * | 1994-07-21 | 1997-05-20 | Henkel Corporation | Process for making high moisture content soap bars |
| AU6519196A (en) | 1995-07-14 | 1997-02-18 | Novartis Ag | Thiopyrans microbicides |
-
1996
- 1996-12-02 DE DE19649896A patent/DE19649896A1/en not_active Withdrawn
-
1997
- 1997-11-24 SK SK731-99A patent/SK73199A3/en unknown
- 1997-11-24 DE DE59710142T patent/DE59710142D1/en not_active Expired - Lifetime
- 1997-11-24 WO PCT/EP1997/006557 patent/WO1998024872A1/en active IP Right Grant
- 1997-11-24 ES ES97951961T patent/ES2200210T3/en not_active Expired - Lifetime
- 1997-11-24 AT AT97951961T patent/ATE241002T1/en active
- 1997-11-24 PL PL97333532A patent/PL188847B1/en unknown
- 1997-11-24 CA CA002273969A patent/CA2273969A1/en not_active Abandoned
- 1997-11-24 CN CN97180188A patent/CN1117847C/en not_active Expired - Fee Related
- 1997-11-24 HU HU0000360A patent/HUP0000360A3/en unknown
- 1997-11-24 EP EP97951961A patent/EP0941300B1/en not_active Expired - Lifetime
- 1997-11-24 US US09/319,193 patent/US6225270B1/en not_active Expired - Lifetime
-
1999
- 1999-06-01 NO NO992631A patent/NO992631D0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| HUP0000360A3 (en) | 2003-02-28 |
| CA2273969A1 (en) | 1998-06-11 |
| CN1117847C (en) | 2003-08-13 |
| DE19649896A1 (en) | 1998-06-04 |
| SK73199A3 (en) | 1999-11-08 |
| ATE241002T1 (en) | 2003-06-15 |
| WO1998024872A1 (en) | 1998-06-11 |
| CN1238804A (en) | 1999-12-15 |
| ES2200210T3 (en) | 2004-03-01 |
| NO992631L (en) | 1999-06-01 |
| HUP0000360A2 (en) | 2000-07-28 |
| NO992631D0 (en) | 1999-06-01 |
| EP0941300A1 (en) | 1999-09-15 |
| PL188847B1 (en) | 2005-05-31 |
| DE59710142D1 (en) | 2003-06-26 |
| US6225270B1 (en) | 2001-05-01 |
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