EP1740687A1 - Substances solides parfumees - Google Patents

Substances solides parfumees

Info

Publication number
EP1740687A1
EP1740687A1 EP05729069A EP05729069A EP1740687A1 EP 1740687 A1 EP1740687 A1 EP 1740687A1 EP 05729069 A EP05729069 A EP 05729069A EP 05729069 A EP05729069 A EP 05729069A EP 1740687 A1 EP1740687 A1 EP 1740687A1
Authority
EP
European Patent Office
Prior art keywords
weight
advantageously
carrier material
acid
perfume
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.)
Withdrawn
Application number
EP05729069A
Other languages
German (de)
English (en)
Inventor
Rene-Andres Artiga Gonzalez
Stefan Hammelstein
Hubert Harth
Jürgen HILSMANN
Mario Sturm
Andreas Bauer
Wolfgang Lahn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1740687A1 publication Critical patent/EP1740687A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/505Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034Fixed on a solid conventional detergent ingredient
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/10Carbonates ; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites

Definitions

  • the coating of the particles can be carried out in the ways described in the prior art.
  • the coating material preferably completely surrounds the respective particles, although an incoherent coating may also be desirable.
  • the most suitable coating materials are those which are commonly used in connection with detergents and cleaning agents.
  • the coating material contains a polyacrylate and / or a derivative thereof and / or a corresponding copolymer based on acrylic acid esters or acrylic acids and other monomers. Copolymers of acrylamide and acrylic acid and / or their derivatives are particularly advantageous for the coating material according to the invention.
  • the carrier material or the particles at least partially has a coating which comprises an at least partially water-soluble or at least partially water-dispersible component which comprises 0% by weight to 80% by weight of at least one solid polyol with preferably more than 3 hydroxyl radicals and from 20% to 100% by weight of a liquid diol or polyol in which the perfume is substantially insoluble and in which the solid polyol is substantially soluble, said liquid polyol or diol preferably from glycerin , Ethylene glycol and diglycerin or mixtures thereof and in which the solid polyol is preferably selected from glucose, sorbitol, maltose, glucamine, sucrose, polyvinyl alcohol, starch, Al- kylpolyglycosid, sorbitan fatty esters, polyhydroxy fatty acid amides, the fatty acid residues of which contain 1 to 18 carbon atoms, and mixtures thereof, a further preferred embodiment of the invention is present.
  • Another object of this invention is a method for producing a particle according to the invention comprising a) the provision of the carrier material according to the invention, preferably based on aqueous suspensions of inorganic and organic constituents, which advantageously comprise nonionic surfactant, the aqueous suspensions then being dried, then b) optionally impregnating the carrier material according to the invention with at least one nonionic surfactant, and c) loading the carrier material with perfume by mixing perfume and (impregnated) carrier material and / or by spraying perfume onto the (impregnated) carrier material, and
  • drying means any technical drying option with which water and / or other solvents can be largely removed from the aqueous suspensions so that at the end of the drying process, particles, i.e. there are particulate solids that form the desired carrier material.
  • these particles do not have to be completely solvent-free and / or water-free, for example they can still contain significant amounts of solvent and / or water, but they preferably have water components below 30% by weight, advantageously below 25% by weight, in particular below 20% by weight .-%, based in each case on the solid obtained at the end of drying.
  • the water content can also be lower, for example below 15% by weight or below 10% by weight or below 5% by weight, in each case based on the solid obtained at the end of drying.
  • heat is advantageously added to the material to be dried. Drying can preferably be carried out in cocurrent, countercurrent or crossflow.
  • convection drying the heat is transferred to the material to be dried mainly by hot gases (air or inert gas), which is preferred.
  • Channel, chamber, belt, shaft, fluidized bed and atomization dryers are used for this, which is preferred.
  • the heat is transferred via heat exchanger surfaces.
  • Contact dryers include roller, tube and cabinet dryers. Floor, plate, drum and paddle dryers work according to both principles of heat supply.
  • the aqueous suspension to be dried according to the invention contains substance (s) which, at elevated temperatures, contain carbon.
  • Release oil dioxide preferably selected from hydrogen carbonate compounds, citric acid and / or aconitic acid.
  • bicarbonate compounds sodium bicarbonate is preferred.
  • the carrier material containing the nonionic surfactant is loaded with perfume by mixing or spraying, as just described.
  • Another object of the invention is a detergent composition containing: o (A) particles according to the invention o (B) 0.01% by weight to 95% by weight, preferably 5% by weight to 85% by weight, preferably 3% by weight to 30% by weight, and more preferably 5% by weight. -% to 22% by weight of additional surfactant (s).
  • the detergent compositions can preferably be cleaning agents, (textile) care agents or detergents.
  • a detergent composition according to the invention which comprises at least one surfactant, preferably at least two from the group of alkylbenzenesulfonates, alkyl ester sulfonates, alkyl ethoxylates, alkylphenol alkoxylates, alkyl polyglucosides, alkyl sulfates, alkyl ethoxysulfate, secondary alkyl sulfates and / or mixtures thereof, these additional surfactants advantageously in amounts of 1% by weight % to 75% by weight, based on the total composition, is a preferred embodiment.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 0 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • the C 2 -C 16 alkyl sulfates and C 12 - C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred for washing technology reasons.
  • 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.
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use 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 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 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 mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants (additional 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 is linear or preferably in 2- The position may be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants (additional surfactants), in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is 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.
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 2 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • 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 (III) R 3 -OR 4 I R-CO-N- [Z] (III)
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced 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-A-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.
  • Particularly preferred cationic surfactants are the quaternary, partly antimicrobial ammonium compounds (QAV; INCI Quaternary Ammonium Compounds) according to the general formula (R I ) (R II ) (R III ) (R IV ) N + X ⁇ , in which R 1 to R lv identical or different C- 22 alkyl radicals, C 7 .
  • QAV quaternary, partly antimicrobial ammonium compounds
  • QAV are by reacting tertiary amines with alkylating agents such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced.
  • alkylating agents such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced.
  • alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions.
  • Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
  • Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS No 58390-78-6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl ⁇ ammonium bromide, CAS No.
  • QAV cocospentaethoxymethylammonium methosulfate
  • anionic surfactant-compatible and / or as little cationic surfactant as possible are used or, in a particular embodiment of the invention, no cationic surfactants with an antimicrobial effect are used.
  • the detergent compositions according to the invention can contain one or more cationic surfactants in amounts, based on the total composition, of 0 to 5% by weight, greater than 0 to 5% by weight, preferably 0.01 to Contain 3 wt .-%, in particular 0.1 to 1 wt .-%.
  • the detergent compositions according to the invention can contain one or more amphoteric surfactants in amounts, based on the overall composition, of 0 to 5% by weight, greater than 0 to 5% by weight, preferably 0.01 to Contain 3 wt .-%, in particular 0.1 to 1 wt .-%.
  • the detergent compositions can preferably also contain additional builders in addition to the builders present in the particles according to the invention. If the detergent composition thus further comprises at least 1% by weight of an additional detergent builder, there is a further preferred embodiment of the invention, it also being preferred if additional constituents customary for detergents and cleaning agents are also present.
  • ingredients customary in washing and cleaning agents in particular from the group of bleaching agents, bleach activators, enzymes, enzyme stabilizers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transmission inhibitors and corrosion inhibitors be introduced into or contained in the detergent composition.
  • Other optional ingredients preferably come from the group of oligomeric and polymeric polycarboxylates, pH regulators, fluorescent agents, anti-shrink agents, wetting agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, anti-repellants. and impregnating agents, swelling and anti-slip agents, chelating agents, fabric softeners and UV absorbers.
  • bleach activators can be incorporated as the sole constituent or as an ingredient of component b).
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable.
  • compositions can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenyl styrene type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used. In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers, in order not to dye them.
  • the detergent composition according to the invention is in the form of agglomerates and the density of the detergent composition is advantageously at least 300 g / l, advantageously 400 g / l, advantageously 500 g / l, preferably at least 600 g / l and in particular at least 650 g / l, it is also a preferred embodiment of the invention.
  • the detergent composition according to the invention further comprises a second perfume which is sprayed onto the surface of the detergent granules contained, then again there is a preferred embodiment of the invention.
  • Another preferred embodiment is a detergent composition according to the invention in the form of a piece of laundry detergent, preferably in tablet form.
  • Another object of this invention is again a method for washing textiles, comprising the step of contacting the textiles with an aqueous medium which contains an effective amount of a detergent composition according to the invention which contains features as described above.
  • Another object of this invention is the use of nonionic surfactant to increase the perfume absorption capacity of the carrier material, and preferably to stabilize the perfume in the carrier material, and advantageously to produce a fragrance-retarding effect, as described at the beginning, and to achieve a fragrance-enhancing effect.
  • zeolite A anhydrous active substance
  • carboxymethyl cellulose 78% by weight, zeolite A (anhydrous active substance), 2% by weight of carboxymethyl cellulose
  • zeolite A anhydrous active substance
  • carboxymethyl cellulose 78% by weight, zeolite A (anhydrous active substance), 2% by weight of carboxymethyl cellulose
  • zeolite A anhydrous active substance
  • carboxymethyl cellulose sodium salt 0.5% by weight of sodium hydroxide
  • sodium sulfate 2% by weight of sodium sulfate
  • remainder water, salts, impurities
  • Granules 1 amount of perfume absorbed: approx. 30% by weight
  • Granules 2 amount of perfume absorbed: approx. 30% by weight
  • granules 3 amount of perfume absorbed: approx. 30% by weight
  • Granules 4 amount of perfume absorbed: approx. 20% by weight
  • the amount of perfume absorbed is based on the perfume-free particles. To do this, weigh the particles before and after the perfume application and measure the weight gain. The increase in weight represents the maximum possible perfume absorption of the respective particles. The particles remained free-flowing and did not stick together. If the amount of the perfume absorbed is given as 30% by weight, this means, to give an illustrative example, that 100 g of particles after the perfume application have a weight of 130 g.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne des particules contenant un excipient inorganique déterminé, dans une quantité minimale déterminée, du parfum et un(des) tensioactif(s) non ionique(s), dans des quantités d'au moins 0,1 % en poids. L'invention concerne également un procédé permettant de produire de telles particules, ainsi qu'un procédé pour laver des textiles à l'aide de cette composition détergente.
EP05729069A 2004-04-23 2005-04-01 Substances solides parfumees Withdrawn EP1740687A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004020400A DE102004020400A1 (de) 2004-04-23 2004-04-23 Parfümierte Feststoffe
PCT/EP2005/003418 WO2005105972A1 (fr) 2004-04-23 2005-04-01 Substances solides parfumees

Publications (1)

Publication Number Publication Date
EP1740687A1 true EP1740687A1 (fr) 2007-01-10

Family

ID=34963288

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05729069A Withdrawn EP1740687A1 (fr) 2004-04-23 2005-04-01 Substances solides parfumees

Country Status (5)

Country Link
US (1) US7585825B2 (fr)
EP (1) EP1740687A1 (fr)
JP (1) JP2007533800A (fr)
DE (1) DE102004020400A1 (fr)
WO (1) WO2005105972A1 (fr)

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CN110295183B (zh) * 2019-07-29 2023-05-02 西南大学 一种基于CsPrx25超量表达提高柑橘对溃疡病抗性的方法
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JP2007533800A (ja) 2007-11-22
US20070111921A1 (en) 2007-05-17
DE102004020400A1 (de) 2005-11-17
WO2005105972A1 (fr) 2005-11-10

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