WO2021013412A1 - Moulded bodies containing active substances and method for the production thereof - Google Patents

Moulded bodies containing active substances and method for the production thereof Download PDF

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Publication number
WO2021013412A1
WO2021013412A1 PCT/EP2020/065010 EP2020065010W WO2021013412A1 WO 2021013412 A1 WO2021013412 A1 WO 2021013412A1 EP 2020065010 W EP2020065010 W EP 2020065010W WO 2021013412 A1 WO2021013412 A1 WO 2021013412A1
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WIPO (PCT)
Prior art keywords
weight
active substance
shaped body
group
mol
Prior art date
Application number
PCT/EP2020/065010
Other languages
German (de)
French (fr)
Inventor
Mireia SUBINYA
Peter Schmiedel
Ines Baranski
Regina Stehr
Michael Dreja
Filiz Yapici
Boray TORUN
Original Assignee
Henkel Ag & 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.)
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Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to EP20730225.8A priority Critical patent/EP4004173A1/en
Publication of WO2021013412A1 publication Critical patent/WO2021013412A1/en

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    • 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
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2096—Heterocyclic compounds
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present application describes active substance-containing moldings and a process for producing active substance-containing moldings.
  • the present application describes in particular fragrance-containing molded articles and processes for their production.
  • fragrance lozenges In order to meet the needs of consumers for long-lasting laundry scenting, special scented lozenges have been offered for some time.
  • Known fragrance lozenges are usually based on carrier polymers such as polyethylene glycol (PEG) with an average molecular weight of approximately 2000 to 12000 g / mol, into which fragrances or fragrance capsules are incorporated.
  • PEG polyethylene glycol
  • the marketing of such systems is associated with high production costs due to the use of high polymer proportions and also pollutes the environment.
  • the commercially available scented lozenges are hard, non-elastic lozenges due to their carrier material, which form or break during transport or when the packaging is shaken vigorously.
  • Scented lozenges based on PEG also often have a non-transparent, inhomogeneous appearance, which is due to the presence of undissolved, unevenly distributed solid particles. These properties contradict the consumer's aesthetic perception.
  • a solvent-based carrier system which, by means of a combination of a low molecular weight gel former with a molar mass ⁇ 2000 g / mol, preferably dibenzylidene sorbitol (DBS), with a polymeric gel former of a molar mass > 10000 g / mol, preferably polyvinyl alcohol, is thickened.
  • a low molecular weight gel former with a molar mass ⁇ 2000 g / mol, preferably dibenzylidene sorbitol (DBS)
  • DBS dibenzylidene sorbitol
  • a first subject of this application is an active substance-containing shaped body with a weight of 0.2 to 20 g, comprising
  • the active substance-containing moldings are preferably dimensionally stable.
  • “Dimensionally stable”, as used herein, refers to the property of the molded body to maintain its three-dimensional shape under the conditions customary for storage and transport, i.e. in the temperature ranges customary for storage and transport and under the action of the forces customary for storage and transport, neither to disintegrate nor to be irreversible Enter into deformations.
  • Particularly preferred moldings are translucent and / or transparent, particularly preferably transparent. If a shaped body according to the invention has a residual light output (transmission) of at least 20% in the spectral range between 380 nm and 780 nm, based on the reference measurement, it is considered transparent in the context of the invention.
  • the transparency of the moldings can be determined using various methods.
  • the nephelometric turbidity unit (nephelometric turbidity value; NTU) is often used as a measured value for transparency. It is a unit used e.g. in water treatment for turbidity measurements e.g. in liquids. It is the unit of turbidity measured with a calibrated nephelometer. High NTU values are measured for opaque compositions, whereas low values are determined for clear compositions.
  • the HACH Turbidimeter 2100Q from the Hach Company, Loveland, Colorado (USA) is used using the calibration tools StabICal Solution HACH (20 NTU), StabICal Solution HACH (100 NTU) and StabICal Solution HACH (800 NTU) , all can also be ordered from Hach Company.
  • the measurement is filled in a 10 ml measuring cuvette with a cap with the composition to be examined and the measurement is carried out at 20 ° C.
  • moldings At an NTU value (at 20 ° C.) of 60 or more, moldings have a perceptible haze that can be seen with the naked eye within the meaning of the invention. It is therefore preferred if the moldings according to the invention have an NTU value (at 20 ° C.) of at most 120, more preferably at most 110, more preferably at most 100, particularly preferably at most 80.
  • the transparency of the moldings according to the invention is determined by a transmission measurement in the visual light spectrum over a wavelength range from 380 nm to 780 nm at 20.degree.
  • a reference sample water, fully demineralized
  • the cuvette is then filled with a sample of the shaped body according to the invention and measured again.
  • the sample is filled in a liquid state at 80 ° C. and solidified in the cuvette to form a shaped body and then measured.
  • the transparent molded body according to the invention has a transmission (20 ° C.) of preferably at least 25%, more preferably at least 30%, more preferably at least 40%, in particular at least 50%, particularly preferably at least 60%.
  • the transparent molding according to the invention has a transmission (at 20 ° C.) of at least 30% (in particular of at least 40%, more preferably of at least 50%, particularly preferably of at least 60%) and an NTU value (at 20 ° C) of at most 120 (more preferably at most 1 10, more preferably at most 100, particularly preferably at most 80).
  • the weight ratio of low molecular weight gel former to polymeric gel former is 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10 .
  • the weight of an individual active substance-containing shaped body is preferably 0.2 to 10 g, more preferably 0.5 to 5 g.
  • the active substance-containing shaped bodies contain as the first essential component a) at least one low molecular weight gel former with a molar mass of up to 2000 g / mol, preferably with a molar mass of 200 g / mol to 2000 g / mol.
  • the use of gel formers with a molar mass of 200 g / mol to 1000 g / mol has proven to be particularly advantageous with regard to producibility, packability and subsequent use.
  • the proportion by weight of the low molecular weight gel former a) in the total weight of the active substance-containing shaped body is preferably from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight and in particular from 1 to 4% by weight.
  • the gel former a) has a solubility in water of less than 0.1 g / L (20 ° C.).
  • the solubility of the organic gelator compound a) is determined at 20 ° C. in double-distilled, demineralized water.
  • gel formers are preferably suitable which have a structure containing at least one hydrocarbon structural unit with 6 to 20 carbon atoms (preferably at least one carbocyclic, aromatic structural unit) and in addition an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, the at least two groups selected from -OH, -NH-, or mixtures thereof.
  • the at least one gelling agent selected from the group consisting of Benzylidenalditol compound, hydroxystearic acid, hydrogenated castor oil, Diarylamidocystin compound, N- (C8-C 24) -Hydrocarbylglyconamid, diketopiperazine compound, 2-methyl-acrylic acid 2-ureido-ethyl ester and mixtures thereof. Because of his The at least one gelling agent dibenzylidene sorbitol (DBS) is particularly more preferred for technical purposes.
  • DBS dibenzylidene sorbitol
  • Particularly preferred shaped bodies are characterized in that said shaped body contains at least one benzylidene alditol compound of the formula (GB-I) as a gel former
  • * - stands for a covalent single bond between an oxygen atom of the alditol backbone and the intended residue
  • n 0 or 1, preferably 1,
  • n 0 or 1, preferably 1,
  • both said benzylidene alditols in the L configuration or in the D configuration or a mixture of both are suitable according to the invention. Because of their natural availability, the benzylidene alditol compounds in the D configuration are preferably used according to the invention.
  • the alditol basic structure of the benzylidene alditol compound according to formula (GB-I) contained in the molded body is derived from D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L -Glucitol, L-mannitol, L-arabinitol, L-ribitol or L-xylitol.
  • Particularly preferred moldings are those which are characterized in that R 1 , R 2 , R 3 , R 4 , R 5 and R 6 according to the benzylidene alditol compound of the formula (GB-I) independently represent a hydrogen atom, methyl, ethyl, chlorine , Fluorine or methoxy, preferably a hydrogen atom.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent a hydrogen atom, methyl, ethyl, chlorine , Fluorine or methoxy, preferably a hydrogen atom.
  • n is preferably 1.
  • m preferably represents 1.
  • the molding according to the invention very particularly preferably contains at least one compound of the formula (GB-11) as the benzylidene alditol compound of the formula (GB-I)
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined in formula (I).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another represent a hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom.
  • the benzylidene alditol compound of formula (GB-I) is selected from 1, 3: 2,4-di-O-benzylidene-D-sorbitol; 1, 3: 2,4-di-0- (p-methylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (p-chlorobenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (2,4-dimethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (p-ethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (3,4-dimethylbenzylidene) -D-sorbitol or mixtures thereof.
  • Preferred moldings contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as a gel former
  • R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxyl group, a (Ci-C6) -alkyl group, a (C2-C6) -alkenyl group, a (C2-C6) -acyl group, a ( C2-C6) - acyloxy group, a (Ci-C6) -alkoxy group, an amino group, a (C2-C6) -acylamino group, a (Ci-C6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, a Aryl (Ci-C 4 ) alkyloxy group, an aryl (Ci-C3) alkyl group, a heteroaryl group, a Hetroaryl- (Ci-C3) -alkyl distr, a (Ci-C 4 ) -hydroxyalkyl distr, a (Ci
  • R 5 stands for a hydrogen atom, a linear (Ci to C6) -alkyl group, a branched (C3 to C10) -alkyl group, a (C3 to C6) -cycloalkyl group, a (C2-C6) -alkenyl group, a (C2-C6 ) Alkynyl group, a (Ci-C 4 ) -hydroxyalkyl group, a (Ci-C 4 ) -alkoxy- (Ci-C 4 ) -alkyl group, a (Ci-C 4 ) -acyloxy- (Ci- C 4 ) - alkyl group, an aryloxy (Ci-C 4 ) -alkyl group, an 0- (aryl- (Ci-C 4 ) -alkyl) oxy- (Ci-C 4 ) -alkyl group, a (Ci-C 4 ) -Alkylsulfanyl- (
  • R 3 and R 4 according to formula (GB-II) represent a hydrogen atom. It is particularly preferred according to the invention if R 2 , R 3 and R 4 according to formula (GB-II) represent a hydrogen atom. Therefore, particularly preferred moldings according to the invention contain at least one 2,5-diketopiperazine compound according to formula (GB-Ila)
  • R 1 and R 5 are as defined under formula (GB-II) (vide supra).
  • R 1 and R 5 are defined as above under formula (GB-II) (vide supra).
  • the numbers 3 and 6 positioned on the ring atoms in formula (GB-IIb) only mark positions 3 and 6 of the diketopiperazine ring, as they are generally used in the context of the invention for naming all 2,5-diketopiperazines according to the invention.
  • the 2,5-diketopiperazine compounds of the formula (GB-II) have centers of chirality at least on the carbon atoms in positions 3 and 6 of the 2,5-diketopiperazine ring.
  • the numbering of the ring positions 3 and 6 was illustrated by way of example in formula (GB-Ilb).
  • the 2,5-diketopiperazine compound of the formula (GB-II) of the compositions according to the invention is preferably the configuration isomer 3S, 6S, 3R, 6S, 3S based on the stereochemistry of the carbon atoms at the 3- and 6-position of the 2,5-diketopiperazine ring , 6R, 3R, 6R or mixtures thereof, particularly preferably 3S, 6S.
  • Preferred molded articles contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as a gel former, selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5- diketopiperazine, 3-benzyl-6- (p-hydroxybenzyl) -2,5-diketopiperazine, 3-benzyl-6-isopropyl-2,5-diketopiperazine, 3-benzyl-6- (4-aminobutyl) -2, 5-diketopiperazine, 3,6-di (benzyl) -2,5- diketopiperazine, 3,6-di (p-hydroxybenzyl) -2,5-diketopiperazine, 3,6-di (p- (benzyloxy) benzyl) - 2,5-diketopiperazine, 3-benzyl-6- (4-imidazolyl) methyl-2,5
  • the shaped bodies according to the invention may contain at least one diarylamidocystine compound of the formula (GB-III) as gel former a)
  • X + independently represent a hydrogen atom or an equivalent of a cation
  • R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a Ci-C 4 alkoxy group, a C 2 -C 4 hydroxyalkyl group, a hydroxyl group, an amino group, an N- (Ci-C 4 -alkyl) amino group, an N, N-di (Ci-C 4 -alkyl) amino group, an N- (C 2 -C 4 - hydroxyalkyl) amino group, an N, N-di ( C 2 -C 4 -hydroxyalkyl) amino group or R 1 with R 2 or R 3 with R 4 forms a 5- or 6-membered fused ring, which in turn each with at least one group from Ci-C 4 -alkyl group, Ci-C 4 -alkoxy group, C 2 -C 4 -hydroxyalkyl group, hydroxyl group, amino group, N- (Ci-C 4
  • Each of the stereocenters contained in the compound of the formula (GB-III) can, independently of one another, stand for the L or D stereoisomer. It is preferred according to the invention if the said cystine compound of the formula (GB-III) is derived from the L-stereoisomer of cysteine.
  • Said shaped bodies can contain at least one compound of the formula (GB-III) in which R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a Ci-C 4 -alkyl group, a Ci-C 4 -Alkoxy group, a C 2 -C 4 -hydroxyalkyl group, a hydroxyl group, or R 1 with R 2 or R 3 with R 4 forms a 5- or 6-membered fused ring, which in turn each with at least one group from Ci-C 4 -Alkyl group, Ci-C 4 alkoxy group, C 2 -C 4 hydroxyalkyl group, hydroxyl group can be substituted.
  • R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a Ci-C 4 -alkyl group, a Ci-C 4 -Alkoxy group, a C 2 -C 4 -hydroxy
  • N- (C8-C 24 ) -hydrocarbylglyconamide compounds suitable as gel formers a) preferably have the formula (GB-IV)
  • n 2 to 4, preferably 3 or 4, especially 4;
  • R 1 is selected from hydrogen, C1-C16 alkyl radicals, C1-C3 hydroxy or methoxyalkyl radicals, preferably C1-C3 alkyl, hydroxyalkyl or methoxyalkyl radicals, particularly preferably methyl;
  • R 2 is selected from C8-C24 alkyl, Cs-C 24 -Monoalkenylresten, Cs-C 24 -Dialkenylresten, Cs C 24 -Trialkenylresten, Cs-C 24 -hydroxyalkyl, Cs-C 24 -Hydroxyalkenylresten, C1-C3 Hydroxyalkyl radicals or methoxy-Ci-C3-alkyl radicals, preferably Cs-Cis alkyl radicals and mixtures thereof, more preferably C10, C12, C14, C16 and Cis-alkyl radicals and mixtures thereof, most preferably C12 and C14 alkyl radicals or a mixture thereof.
  • the HO-CH2- (CHOH) n -C- radical is one of one
  • Glucuronic acid in particular is to be mentioned as a preferred radical.
  • R 1 is preferably H or a short-chain alkyl radical, in particular methyl.
  • R 2 is preferably a long-chain alkyl radical, for example a Cs-Ci8 alkyl radical.
  • R 2 has the meanings given for formula (GB-IV).
  • a second essential component b) of the active substance-containing moldings is the polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol. It has proven to be particularly advantageous in relation to the production, packaging and handling of the shaped bodies to use polymeric gel formers with a molar mass of 10,000 to 40,000 g / mol.
  • the proportion by weight of polymeric forming agent b) in the total weight of active substance-containing shaped bodies is preferably from 0.01 to 15% by weight, more preferably from 0.1 to 12% by weight and in particular from 1 to 10% by weight.
  • Polymeric gel formers b) from the group of have proven to be technically advantageous
  • - Starch in particular potato starch, corn starch, wheat starch, pea starch or tapioca starch;
  • Suitable polyacrylates are homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and polysaccharides, especially heteropolysaccharides, and other customary polymer thickeners.
  • Suitable acrylic acid polymers are, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
  • a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
  • Such polyacrylic acids are available inter alia from the company. BF Goodrich under the trade names Carbopof ®.
  • acrylic acid copolymers are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, Esters (INCI Acrylates Copolymer) preferably formed with Ci- 4 alkanols, which include copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are obtainable for example from the company Rohm & Haas under the trade names Aculyn ® and Acusol ®, and from Degussa (Goldschmidt) under the trade name Tego ® polymer.
  • acrylic acid copolymers include copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are
  • (ii) crosslinked high molecular weight acrylic acid copolymers including, for example, the copolymers of Cio so-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with Cu alkanols, with an allyl ether of sucrose or pentaerythritol (INCI acrylates / C10-30 alkyl acrylate Crosspolymer) and which are obtainable, for example, by the company BF Goodrich under the trade name Carbopol ®. Suitable acrylate are also available under the trade name Sk ⁇ lan ® AT 120 and AT 120 Rheovis ® by the company BASF. If acrylic acid polymers and especially acrylic acid esters are used as polymeric thickeners, the pH is preferably more than 7, in particular at least 7.5, preferably 8 or more.
  • Preferred polyvinyl alcohols have a molecular weight of 10,000 g / mol to 150,000 g / mol, particularly preferably 10,000 g / mol to 80,000 g / mol and in particular 10,000 g / mol to 40,000 g / mol.
  • the degree of hydrolysis of preferred polyvinyl alcohols is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%
  • the weight ratio of dibenzylidene sorbitol to polyvinyl alcohol is 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10.
  • the moldings comprise an active substance c) as a third essential component. At least one active ingredient from the group of fragrances, enzymes and colorants, preferably at least one active ingredient from the group of fragrances, is preferably used as active ingredient c).
  • the proportion by weight of the active substance c), in particular the fragrance, in the total weight of the active substance-containing molding is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight and in particular 0.5 to 10% by weight. %.
  • a fragrance is a chemical substance that stimulates the sense of smell.
  • the chemical substance should be at least partially dispersible in the air, ie the fragrance should be at least slightly volatile at 25 ° C. If the fragrance is now very volatile, the odor intensity then quickly subsides again. If the volatility is lower, however, the odor impression is more lasting, ie it does not disappear as quickly.
  • the fragrance therefore has a melting point which is in the range from -100 ° C to 100 ° C, preferably from -80 ° C to 80 ° C, even more preferably from -20 ° C to 50 ° C, in particular from - 30 ° C to 20 ° C.
  • the fragrance has a boiling point which is in the range from 25 ° C. to 400 ° C., preferably from 50 ° C. to 380 ° C., more preferably from 75 ° C. to 350 ° C., in particular from 100 ° C. to 330 ° C.
  • a chemical substance should not exceed a certain molecular mass in order to function as a fragrance, since if the molecular mass is too high, the required volatility can no longer be guaranteed.
  • the fragrance has a molecular weight of 40 to 700 g / mol, more preferably 60 to 400 g / mol.
  • fragrances can also be used to mask unpleasant odors or to provide a non-odorous substance with a desired odor.
  • Individual fragrance compounds e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used as fragrances.
  • Fragrance compounds of the aldehyde type are, for example, adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropyl-phenyl) -2-methylpropanal), ethylvanillin, florhydral ( 3- (3-isopropylphenyl) butanal), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy-4-methylpentyl) - 3- cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, vanillin
  • Methylphenoxyacetaldehyde 2-methyl-3-phenyl-2-propen-1 -al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo- [2.2.1] - hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal and trans-2-hexenal.
  • Fragrance compounds of the ketone type are, for example, methyl beta-naphthyl ketone, musk indanone (1, 2, 3,5,6, 7-hexahydro-1, 1, 2,3,3-pentamethyl-4H-inden-4-one), Tonalid (6-acetyl-1, 1, 2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate, menthone, carvone, camphor, coavone (3 , 4, 5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, betalonone, gamma-methyl-ionone, fleuramone (2-heptylcyclopen-tanone), dihydrojasmone, cis-jasmone , iso-E-Super (1 -
  • Fragrance compounds of the alcohol type are, for example, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methyl-butanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenyl-pentanol, 3-octanol, 3-phenyl-propanol, 4-heptenol, 4-isopropyl-cyclohexanol, 4-tert.-butycyclohexanol, 6 , 8-dimethyl-2-nona-nol, 6-nonene-1 -ol, 9-decen-1 -ol, ⁇ -methylbenzyl alcohol, ⁇ -terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, ß-ter
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, Benzyl acetate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmacyclate.
  • DMBCA dimethylbenzylcarbinylacetate
  • the ethers include, for example, benzyl ethyl ether and ambroxan.
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • fragrances are preferably used, which together produce an appealing fragrance note.
  • a mixture of fragrances can also be referred to as perfume or perfume oil.
  • perfume oils can also contain natural fragrance mixtures, such as are available from vegetable sources.
  • the fragrances of vegetable origin include essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, citrus oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, guajun oil, gourd oil, gjajun oil, galbanum oil, gourd oil, gjajun oil , Ginger oil, iris oil, jasmine oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemon linden oil, almond blossom oil , Muscatel oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange blossom oil, orange peel oil
  • Methyl anthranilic acid methyl ester p-methylacetophenone, methylchavikol, p-methylquinoline, methyl-betanaphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muskon, beta-naphthol ethyl ether, beta-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, beta-phenylethyl alcohol, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate,
  • the active substance c in particular the fragrance substance.
  • at least part of the fragrance is used in encapsulated form (fragrance capsules), in particular in microcapsules.
  • the entire fragrance can also be used in encapsulated form.
  • the microcapsules can be water-soluble and / or water-insoluble microcapsules.
  • melamine-urea-formaldehyde microcapsules, melamine-formaldehyde microcapsules, urea-formaldehyde microcapsules or starch microcapsules can be used.
  • “Fragrance precursors” refers to compounds that only release the actual fragrance after chemical conversion / cleavage, typically through exposure to light or other environmental conditions, such as pH, temperature, etc. Such compounds are often referred to as fragrance storage substances or “pro-fragrance”.
  • the active ingredient c) is selected from the group of perfume oils and fragrance capsules.
  • the use of a combination of perfume oil and fragrance capsule is very particularly preferred.
  • the active ingredient-containing shaped bodies described in this application contain at least one further component d) as an essential component.
  • Suitable solvents are selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, propylene carbonate, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol methyl ether, diethylene glycol ether, diethylene glycol , Diethylene glycol n-butyl ether acetate, ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, ethylene glycol n-butyl ether acetate, triethylene glycol, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol ether,
  • a first group of particularly preferred active substance-containing moldings is characterized in that the solvent d) is a solvent from the group of polyalkylene glycols liquid at room temperature (20 ° C), in particular polyalkylene glycols liquid at room temperature (20 ° C), particularly preferably from the PEG group 200 and PEG 400 includes.
  • a second group of particularly preferred active substance-containing moldings is characterized in that the solvent d) is a solvent from the group of organic polyols liquid at room temperature (20 ° C.), in particular diols liquid at room temperature (20 ° C.), particularly preferably from the group 2-methyl-1,3-propanediol (MPDiol) and 3-methyl-1,3-butanediol (isopentyldiol).
  • the solvent d) is a solvent from the group of organic polyols liquid at room temperature (20 ° C.), in particular diols liquid at room temperature (20 ° C.), particularly preferably from the group 2-methyl-1,3-propanediol (MPDiol) and 3-methyl-1,3-butanediol (isopentyldiol).
  • compositions d) glycerol or triacetin or water include as solvents d) glycerol or triacetin or water.
  • solvents have proven to be technically particularly advantageous, in particular the combination of water and 3-methyl-1,3-butanediol (isopentyldiol), but in particular the combination of water, glycerol and 3-methyl-1,3-butanediol are called.
  • the proportion by weight of solvent d) in the total weight of active substance-containing shaped bodies is preferably 10 to 98% by weight, particularly preferably 40 to 97% by weight and in particular 60 to 96% by weight.
  • particularly preferred active substance-containing shaped bodies have a weight of 0.2 to 20 g and comprise, based on its total weight
  • the active substance-containing shaped bodies preferably comprise less than 10% by weight, preferably less than 8% by weight, particularly preferably less than 4% by weight and in particular less than 1% by weight of surfactant. Very particularly preferred active substance-containing moldings do not comprise any surfactant.
  • compositions for tablets containing active substances can be found in the tables below (data in% by weight based on the total weight of the tablets).
  • the active substance-containing moldings in these tables preferably comprise less than 10% by weight, more preferably less than 8% by weight, particularly preferably less than 4% by weight and in particular less than 1% by weight of surfactant. It is also preferred if the shaped bodies have a weight of 0.2 to 20 g.
  • the active substance-containing shaped body preferably has a storage modulus G 'of 10 3 Pascal to 10 8 Pascal, more preferably 10 4 Pascal to 10 6 Pascal, measured with a rotational rheometer using a cone-plate measuring system with a diameter of 40 mm and an opening angle of 2 ° a temperature of 20 ° C.
  • the rheological characterization is carried out in the context of this invention with a rotational rheometer, for example from TA-Instruments, type AR G2, from Malvern "Kinexus", using a cone-plate measuring system with a diameter of 40 mm and a 2 ° opening angle at a temperature of 20 ° C performed. These are shear stress controlled rheometers. The determination can, however, also be carried out with other instruments or measurement geometries with comparable specifications.
  • the measurement of the storage modulus (abbreviation: G mix) and the loss modulus (abbreviation: G “) (each unit: Pa) was carried out with the equipment described above in an experiment with oscillating deformation.
  • the linear viscoelastic range is first determined in a “stress sweep experiment”.
  • the shear stress amplitude is increased at a constant frequency of e.g. 1 Hz.
  • the modules G ‘and G“ are plotted in a double logarithmic plot.
  • the shear stress amplitude or the (resulting) deformation amplitude can optionally be plotted on the x-axis.
  • the kink point is expediently determined by applying tangents to the two curve sections.
  • the corresponding deformation amplitude or shear stress amplitude is usually referred to as “critical deformation” or “critical shear stress”.
  • a frequency ramp e.g. between 0.01 Hz and 10 Hz, is run at a constant deformation amplitude.
  • the deformation amplitude must be chosen so that it is in the linear range, i.e. below the critical deformation mentioned above. In the case of the compositions according to the invention, a deformation amplitude of 0.1% has proven to be suitable.
  • the modules G ‘and G“ are plotted against the frequency in a double logarithmic plot.
  • Preferred optional constituents include tablets containing active ingredients, dyes, preservatives or bitter substances.
  • they preferably comprise at least one dye.
  • the shaped bodies comprise at least one water-soluble dye, particularly preferably a water-soluble polymer dye.
  • Preferred dyes should have high storage stability and insensitivity to the other ingredients of the detergents or cleaning agents and to light and not have any pronounced substantivity towards textile fibers in order not to stain them.
  • the dye is a common dye that can be used for various detergents or cleaning agents.
  • the dye is preferably selected from Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 ( CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1, Acid Yellow 3 (CI 47005), Acid Yellow 1 1, Acid Yellow 23 (CI 19140), Acid Yellow 3, Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5: 2 (CI 42051: 2), Food Red 7 (01 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (C1 15985), Food Yellow 4 (C1 19140), Reactive Green 12, Solvent Green 7 (CI 59040).
  • Particularly preferred dyes are water-soluble acid dyes, for example Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet48, Acid Blue 80 (01 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570), Acid Green 81.
  • Food Yellow 13 Acid Yellow 3, CI 47005
  • Food Yellow 4 Acid Yellow 23, CI 19140
  • Food Red 7 Acid Red 18, CI 16255
  • Food Blue 2 Acid Blue 9, CI 42090
  • Food Blue 5 Acid Blue 3, CI 42051
  • Acid Red 249 CI 18134
  • Acid Red 52 CI 45100
  • Acid Violet 126 Acid Violet48
  • Acid Blue 80 01 61585
  • Acid Blue 182 Acid Blue 18
  • Water-soluble direct dyes for example Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) and water-soluble reactive dyes, for example Reactive Green 12, and the dyes Food Yellow 3 (CI 15985), Acid Yellow 184 are also preferably used.
  • Aqueous dispersions of the following pigment dyes Pigment Black 7 (CI 77266), Pigment Blue 15 (CI 74160), Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Green 7 are also preferably used (CI 74260), Pigment Orange 5, Pigment Red 1 12 (CI 12370), Pigment Red 1 12 (CI 12370), Pigment Red 122 (CI 73915), Pigment Red 179 (CI 71 130), Pigment Red 184 (CI 12487 ), Pigment Red 188 (CI 12467), Pigment Red 4 (CI 12085), Pigment Red 5 (CI 12490), Pigment Red 9, Pigment Violet 23 (CI 51319), Pigment Yellow 1 (CI 28 1 1680), Pigment Yellow 13 (CI 21 100), Pigment Yellow 154, Pigment Yellow 3 (CI 1 1710), Pigment Yellow 74, Pigment Yellow 83 (CI 21 108), Pigment Yellow 97.
  • pigment Yellow 1 (CI 1 1680), Pigment Yellow 3 (C1 1 1710), Pigment Red 1 12 (CI 12370), Pigment Red 5 (CI 12490), Pigment Red 181 (CI 73360), Pigment Violet 23 (CI 51319), Pigment Blue 15: 1 (CI 7 4160), Pigment Green 7 (CI 74260), Pigment Black 7 (CI 77266).
  • water-soluble polymer dyes for example Liquitint, Liquitint Blue HP, Liquitint Blue MC, Liquitint Blue 65, Liquitint Cyan 15, Liquitint Patent Blue, Liquitint Violet 129, Liquitint Royal Blue, Liquitint Experimental Yellow 8949-43, Liquitint Green HMC, Liquitint Yellow LP, Liquitint Yellow II and mixtures thereof are used.
  • the group of very particularly preferred dyes includes Acid Blue 3, Acid Yellow 23, Acid Red 33, Acid Violet 126, Liquitint Yellow LP, Liquitint Cyan 15, Liquitint Blue HP and Liquitint Blue MC.
  • the proportion by weight of the dye in the total weight of the active substance-containing shaped bodies is preferably from 0.001 to 0.5% by weight, more preferably from 0.002 to 0.2% by weight.
  • bitter substances primarily serves to avoid oral ingestion of the tablets containing active substances.
  • Preferred moldings contain at least one bitter substance in an amount of 0.0001 to 0.1% by weight, based on the total weight of the composition. Quantities from 0.0005 to 0.02% by weight are particularly preferred. According to the present invention, those bitter substances are particularly preferred which are soluble in water at 20 ° C. to the extent of at least 5 g / l. With regard to an undesirable interaction with the fragrance components also contained in the composition, in particular a change in the fragrance note perceived by the consumer, the ionic bitter substances have proven to be superior to the non-ionic ones. Ionic bitter substances consisting of organic cation (s) and organic anion (s) are consequently preferred for the composition according to the invention.
  • the at least one bitter substance is therefore an ionogenic bitter substance.
  • quaternary ammonium compounds which contain an aromatic group both in the cation and in the anion are eminently suitable.
  • the at least one bitter substance is therefore a quaternary ammonium compound.
  • a suitable quaternary ammonium compound is, for example, without restriction, benzyldiethyl ((2,6-xylylcarbamoyl) methyl) ammonium benzoate, which is commercially available, for example, under the trademarks Bitrex® and Indige-stin®. This compound is also known as Denatonium Benzoate.
  • the at least one bitter substance is benzyl diethyl ((2,6-xylylcarbamoyl) methyl) ammonium benzoate (Bitrex®). If Bitrex® is used, most amounts up to 0.002% by weight are preferred. The information is based on the active substance content.
  • This application also relates to a method for producing a molded body, comprising the steps
  • step i) the first preparation in step a) and / or
  • an active ingredient is added to the mixture of the first preparation and the second preparation in step c).
  • the first preparation in step a) has a temperature between 30.degree. C. and 180.degree. C., preferably between 60.degree. C. and 160.degree.
  • the second preparation in step b) preferably has a temperature between 30.degree. C. and 90.degree. C., in particular between 40.degree. C. and 70.degree. C., for the same technical reasons.
  • the mixture is preferably introduced into a mold in step d).
  • the shape can be a permanent mold or a “lost” shape (Mughal technique).
  • Durable casting molds are preferred. These casting molds are preferably made of metallic or polymeric materials. The use of polymeric materials for the casting mold or any coating on the casting mold is preferred.
  • the casting mold can be open or closed on one side, casting molds open on one side being preferred. If casting molds that are open on one side are used, the resulting moldings have a flat top side corresponding to the open top side if the viscosity of the casting compound is sufficiently low.
  • the geometry of the casting mold (and thus of the molded body produced by the process) is variable over a wide range. It not only influences the later product aesthetics but also the manufacturability of the molded body and its later dissolution behavior.
  • the term processability includes, for example, the solidification behavior of the molded body, its detachability from the casting mold and its transportability and storability.
  • the mixture is portioned in step d) by dripping onto a surface and then shaped on this surface.
  • it is particularly preferred to portion the mixture in step d) by dropping it onto a steel belt using a drop former with a rotating, perforated outer drum and then to shape it on this surface.
  • the mixture is preferably cooled in step d).
  • a method for cleaning a textile surface using a molded body described above is a further subject of this application.
  • Active substance-containing moldings with a weight of 0.2 to 20 g, comprising
  • Active substance-containing shaped body according to item 1 wherein the shaped body has a weight of 0.2 to 10 g, preferably 0.5 to 5 g.
  • the weight ratio of low molecular weight gel former to polymeric gel former being 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10.
  • the low molecular weight gel former having a molar mass of 200 g / mol to 2000 g / mol, preferably from 200 g / mol to 1000 g / mol.
  • Active substance-containing shaped body according to one of the preceding points, wherein the shaped body, based on its total weight, has a proportion by weight of low molecular weight component a) of 0.01 to 15% by weight, preferably 0.1 to 10% by weight and in particular 1 to 4 wt .-%.
  • the low-molecular gelling agent is a) selected from the group of Benzylidenalditol compounds, hydroxystearic acid, hydrogenated castor oil, Diarylamidocystin compound, N- (C8-C 24) - Hydrocarbylglyconamid, diketopiperazine compound, 2-methyl-acrylic acid-2-ureido-ethyl ester and mixtures thereof.
  • Active substance-containing molded body according to one of the preceding points the polymeric gel former having a molar mass of 10,000 to 40,000 g / mol.
  • Active substance-containing shaped body according to one of the preceding points wherein the shaped body, based on its total weight, has a weight fraction of polymeric forming agent b) of 0.01 to 15% by weight, preferably 0.1 to 12% by weight and in particular from 1 to 10 Has wt .-%.
  • Active substance-containing shaped body according to one of the preceding points, wherein the polymeric gel former b) is selected from the group of
  • Celluloses and cellulose derivatives especially methyl cellulose
  • Starch especially potato starch, corn starch, wheat starch, pea starch or
  • Active substance-containing shaped body according to one of the preceding points wherein the polymeric gel former b) is selected from the group of polyvinyl alcohols. Active substance-containing molded body according to one of the preceding points, the weight ratio of dibenzylidene sorbitol to polyvinyl alcohol being 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body, based on its total weight, has a weight fraction of active substance of 0.1 to 20% by weight, preferably 0.2 to 15% by weight and in particular 0.5 to 10% by weight .-% having.
  • Active substance-containing shaped body according to one of the preceding points wherein the shaped body comprises as active substance c) at least one active substance from the group of fragrances, enzymes and colorants. Active substance-containing shaped body according to one of the preceding points, wherein the active substance c) is encapsulated.
  • the solvent d) being selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, propylene carbonate, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, Diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol n-butyl ether, Diethylene glycol hexyl ether, diethylene glycol n-butyl ether acetate, ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, ethylene glycol n-butyl ether acetate, ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, ethylene glyco
  • the solvent d) is a solvent from the group of polyalkylene glycols liquid at room temperature (20 ° C), in particular the polyalkylene glycols liquid at room temperature (20 ° C), particularly preferably from the group PEG 200 and PEG 400 includes.
  • Active substance-containing molded body according to one of the preceding points wherein the solvent d) is a solvent from the group of organic polyols liquid at room temperature (20 ° C.), in particular the diols liquid at room temperature (20 ° C.), particularly preferably from the 2-methyl group -1, 3-propanediol (MPDiol) and 3-methyl-1,3-butanediol (isopentyldiol) includes.
  • Active substance-containing shaped body according to one of the preceding points, wherein d) comprises triacetin as the solvent.
  • Active substance-containing shaped body according to one of the preceding points, the shaped body having, based on its total weight, a weight fraction of solvent d) of 10 to 98% by weight, preferably 40 to 97% by weight and in particular 60 to 96% by weight .
  • Active substance-containing moldings with a weight of 0.2 to 20 g, based on its total weight
  • Active substance-containing shaped body according to one of the preceding points comprising less than 10% by weight, preferably less than 8% by weight, particularly preferably less than 4% by weight and in particular less than 1% by weight surfactant. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body does not comprise a surfactant.
  • Active substance-containing shaped body according to one of the preceding points the shaped body having a storage module G '(rotational rheometer using a cone-plate measuring system with a diameter of 40 mm and a 2 ° opening angle at a temperature of 20 ° C) of 10 3 Pascal to 10 8 Pascal, preferably 10 4 pascals to 10 6 pascals.
  • Active substance-containing shaped body according to one of the preceding points the shaped body further comprising at least one dye, preferably at least one water-soluble dye, particularly preferably a water-soluble polymer dye.
  • Active substance-containing shaped body according to one of the preceding points wherein the shaped body further comprises at least one bitter substance.
  • Active substance-containing shaped body according to one of the preceding points the shaped body being translucent and / or transparent, particularly preferably transparent.
  • Washing or cleaning agent comprising at least one active substance-containing shaped body according to one of the preceding points.
  • step i) the first preparation in step a) and / or
  • an active substance preferably a fragrance
  • the first preparation in step a) has a temperature between 30 ° C and 180 ° C, preferably between 60 ° C and 160 ° C.
  • the second preparation in step b) has a temperature between 30 ° C and 90 ° C, preferably between 40 ° C and 70 ° C.
  • the mixture is introduced into a mold in step d).
  • the mixture being portioned in step d) by dripping onto a surface and then being shaped on this surface.
  • Method according to one of the preceding points the mixture being portioned in step d) by dripping onto a steel belt by means of a drop former with a rotating, perforated outer drum and then being shaped on this surface.
  • Method according to one of the preceding points wherein the mixture is cooled in step d). Process for cleaning a textile surface using a shaped body according to one of the preceding points.

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Abstract

The invention relates to moulded bodies containing active substances with a weight of 0.2 to 20 g, comprising a) at least one low-molecular gel former with a molar mass of up to 2000 g/mol; b) at least one polymeric gel former with a molar mass of 10,000 g/mol to 200,000 g/mol; c) at least one active substance; d) at least one solvent. The invention also relates to a method for the production thereof.

Description

Aktivstoffhaltige Formkörper und Verfahren zu deren Herstellung Moldings containing active substances and processes for their production
Die vorliegende Anmeldung beschreibt aktivstoffhaltige Formkörper sowie ein Verfahren zur Herstellung aktivstoffhaltiger Formkörper. Die vorliegende Anmeldung beschreibt insbesondere duftstoffhaltige Formkörper und Verfahren zu deren Herstellung. The present application describes active substance-containing moldings and a process for producing active substance-containing moldings. The present application describes in particular fragrance-containing molded articles and processes for their production.
Die meisten kommerziell verfügbaren Wasch- und Reinigungsmittel enthalten leichtflüchtige Duftstoffe, sodass insbesondere nach der Wäsche der Duft über die Zeit schwächer wird oder ganz verschwindet. Most commercially available detergents and cleaning agents contain highly volatile fragrances, so that the fragrance becomes weaker over time or disappears completely, especially after washing.
Um dem Bedürfnis der Verbraucher nach einer langanhaltenden Wäschebeduftung zu entsprechen, werden seit geraumer Zeit spezielle Duftpastillen angeboten. Bekannte Duftpastillen basieren in der Regel auf Trägerpolymeren wie z.B. Polyethylenglykol (PEG) mit einem mittleren Molekulargewicht von ungefähr 2000 bis 12000 g/mol, in welche Duftstoffe oder Duftstoffkapseln eingearbeitet werden. Die Vermarktung derartiger Systeme geht aufgrund des Einsatzes hoher Polymeranteile mit hohen Herstellungskosten einher und belastet zudem die Umwelt. In order to meet the needs of consumers for long-lasting laundry scenting, special scented lozenges have been offered for some time. Known fragrance lozenges are usually based on carrier polymers such as polyethylene glycol (PEG) with an average molecular weight of approximately 2000 to 12000 g / mol, into which fragrances or fragrance capsules are incorporated. The marketing of such systems is associated with high production costs due to the use of high polymer proportions and also pollutes the environment.
Bei den kommerziell erhältlichen Duftpastillen handelt es sich auf Grund ihres Trägermaterials um harte, nicht-elastische Pastillen, welche beim Transport oder bei stärkerem Schütteln der Verpackung Abrieb bilden oder zerbrechen. The commercially available scented lozenges are hard, non-elastic lozenges due to their carrier material, which form or break during transport or when the packaging is shaken vigorously.
Auch weisen Duftpastillen, die auf PEG basieren, oft eine intransparente, inhomogene Erscheinung auf, die auf das Vorliegen ungelöster, ungleichmäßig verteilter Feststoffteilchen zurückzuführen ist. Diese Eigenschaften stehen im Widerspruch zum Ästhetik-Empfinden des Konsumenten. Scented lozenges based on PEG also often have a non-transparent, inhomogeneous appearance, which is due to the presence of undissolved, unevenly distributed solid particles. These properties contradict the consumer's aesthetic perception.
Aus den vorgenannten Gründen besteht ein Bedarf an Duftpastillen, die auf alternativen Rohstoffen basieren und bei der Herstellung PEG als Trägerpolymer ersetzt werden kann. For the reasons mentioned above, there is a need for scented lozenges which are based on alternative raw materials and which can be substituted for PEG as a carrier polymer during manufacture.
Überraschenderweise wurde gefunden, dass die zuvor beschriebenen technischen Aufgaben durch ein Lösungsmittel-basiertes Trägersystems gelöst werden können, welches mittels einer Kombination eines niedermolekularen Gelbildners mit einer molaren Masse < 2000 g/mol, bevorzugt Dibenzylidensorbitol (DBS), mit einem polymeren Gelbildner einer molaren Masse > 10000 g/mol, bevorzugt Polyvinylalkohol, verdickt wird. Surprisingly, it has been found that the technical problems described above can be achieved by a solvent-based carrier system which, by means of a combination of a low molecular weight gel former with a molar mass <2000 g / mol, preferably dibenzylidene sorbitol (DBS), with a polymeric gel former of a molar mass > 10000 g / mol, preferably polyvinyl alcohol, is thickened.
Ein erster Gegenstand dieser Anmeldung ist ein aktivstoffhaltiger Formkörper mit einem Gewicht von 0,2 bis 20 g, umfassend A first subject of this application is an active substance-containing shaped body with a weight of 0.2 to 20 g, comprising
a) mindestens einen niedermolekularen Gelbildner mit einer molaren Masse bis 2000 g/mol; b) mindestens einen polymeren Gelbildner mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; c) mindestens einen Aktivstoff; a) at least one low molecular weight gel former with a molar mass of up to 2000 g / mol; b) at least one polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol; c) at least one active ingredient;
d) mindestens ein Lösungsmittel. d) at least one solvent.
Die aktivstoffhaltigen Formkörper sind vorzugsweise formstabil. „Formstabil“, wie hierin verwendet, bezeichnet die Eigenschaft der Formkörper unter den für Lagerung und Transport üblichen Bedingungen ihre dreidimensionale Raumform beizubehalten, also in den für Lagerung und Transport üblichen Temperaturbereichen und unter Einwirkung der für Lagerung und Transport üblichen Kräfte weder zu desintegrieren noch irreversible Verformungen einzugehen. The active substance-containing moldings are preferably dimensionally stable. "Dimensionally stable", as used herein, refers to the property of the molded body to maintain its three-dimensional shape under the conditions customary for storage and transport, i.e. in the temperature ranges customary for storage and transport and under the action of the forces customary for storage and transport, neither to disintegrate nor to be irreversible Enter into deformations.
Besonders bevorzugte Formkörper sind transluzent und/oder transparent, besonders bevorzugt transparent. Weist ein erfindungsgemäßer Formkörper im spektralen Bereich zwischen 380 nm und 780 nm eine auf die Referenzmessung bezogene rest-Lichtleistung (Transmission) von mindestens 20 % auf, gilt er als transparent im Sinne der Erfindung. Particularly preferred moldings are translucent and / or transparent, particularly preferably transparent. If a shaped body according to the invention has a residual light output (transmission) of at least 20% in the spectral range between 380 nm and 780 nm, based on the reference measurement, it is considered transparent in the context of the invention.
Die Transparenz der Formkörper kann mit verschiedenen Methoden ermittelt werden. Die Nephelometrie Turbidity Unit (Nephelometrischer Trübungswert; NTU) wird häufig als Messwert für Transparenz herangezogen. Sie ist eine z.B. in der Wasseraufbereitung verwendete Einheit für Trübungsmessungen z.B. in Flüssigkeiten. Sie ist die Einheit einer mit einem kalibrierten Nephelometer gemessenen Trübung. Hohe NTU-Werte werden für getrübte Zusammensetzungen gemessen, wogegen niedrige Werte für klare Zusammensetzungen bestimmt werden. The transparency of the moldings can be determined using various methods. The nephelometric turbidity unit (nephelometric turbidity value; NTU) is often used as a measured value for transparency. It is a unit used e.g. in water treatment for turbidity measurements e.g. in liquids. It is the unit of turbidity measured with a calibrated nephelometer. High NTU values are measured for opaque compositions, whereas low values are determined for clear compositions.
Der Einsatz des Turbidimeters vom Typ HACH Turbidimeter 2100Q der Fa. Hach Company, Loveland, Colorado (USA) erfolgt dabei unter Verwendung der Kalibriersusbstanzen StabICal Solution HACH (20 NTU), StabICal Solution HACH (100 NTU) und StabICal Solution HACH (800 NTU), alle können ebenfalls von der Firma Hach Company bestellt werden. Die Messung wird in einer 10 ml Messküvette mit Kappe mit der zu untersuchenden Zusammensetzung befüllt und die Messung bei 20 °C durchgeführt. The HACH Turbidimeter 2100Q from the Hach Company, Loveland, Colorado (USA) is used using the calibration tools StabICal Solution HACH (20 NTU), StabICal Solution HACH (100 NTU) and StabICal Solution HACH (800 NTU) , all can also be ordered from Hach Company. The measurement is filled in a 10 ml measuring cuvette with a cap with the composition to be examined and the measurement is carried out at 20 ° C.
Bei einem NTU-Wert (bei 20°C) von 60 oder mehr weisen Formkörper mit dem bloßen Auge erkennbar im Sinne der Erfindung eine wahrnehmbare Trübung auf. Daher ist es bevorzugt, wenn die erfindungsgemäßen Formkörper einen NTU-Wert (bei 20°C) von höchstens 120, bevorzugter höchstens 1 10, bevorzugter höchstens 100, besonders bevorzugt von höchstens 80, aufweisen. At an NTU value (at 20 ° C.) of 60 or more, moldings have a perceptible haze that can be seen with the naked eye within the meaning of the invention. It is therefore preferred if the moldings according to the invention have an NTU value (at 20 ° C.) of at most 120, more preferably at most 110, more preferably at most 100, particularly preferably at most 80.
Im Rahmen der vorliegenden Erfindung wird die Transparenz der erfindungsgemäßen Formkörper durch eine Transmissionsmessung im visuellen Lichtspektrum über einen Wellenlängenbereich von 380 nm bis 780 nm bei 20°C bestimmt. Dazu wird zunächst eine Referenzprobe (Wasser, vollentsalzt) in einem Photometer (Fa. Specord S 600 von AnalytikJena) mit einer im zu untersuchendem Spektrum transparenten Küvette (Schichtdicke 10 mm) vermessen. Anschließend wird die Küvette mit einer Probe des erfindungsgemäßen Formkörpers befüllt und abermals vermessen. Dabei wird im Rahmen der Probenherstellung die Probe in flüssigem Zustand bei 80°C eingefüllt und in der Küvette zum Formkörper verfestigt und dann vermessen. Es ist bevorzugt, wenn der erfindungsgemäße transparente Formkörper eine Transmission (20°C) von bevorzugter mindestens 25 %, bevorzugter mindestens 30%, bevorzugter mindestens 40 %, insbesondere von mindestens 50 %, besonders bevorzugt von mindestens 60 %, aufweist. In the context of the present invention, the transparency of the moldings according to the invention is determined by a transmission measurement in the visual light spectrum over a wavelength range from 380 nm to 780 nm at 20.degree. For this purpose, a reference sample (water, fully demineralized) is first measured in a photometer (Specord S 600 from AnalytikJena) with a cuvette (layer thickness 10 mm) that is transparent in the spectrum to be examined. The cuvette is then filled with a sample of the shaped body according to the invention and measured again. In the course of sample production, the sample is filled in a liquid state at 80 ° C. and solidified in the cuvette to form a shaped body and then measured. It is preferred if the transparent molded body according to the invention has a transmission (20 ° C.) of preferably at least 25%, more preferably at least 30%, more preferably at least 40%, in particular at least 50%, particularly preferably at least 60%.
Es ist ganz besonders bevorzugt, wenn der erfindungsgemäße transparente Formkörper eine Transmission (bei 20°C) von mindestens 30 % (insbesondere von mindestens 40 % bevorzugter von mindestens 50 %, besonders bevorzugt von mindestens 60 %) und einen NTU-Wert (bei 20°C) von höchstens 120 (bevorzugter höchstens 1 10, bevorzugter höchstens 100, besonders bevorzugt von höchstens 80) aufweist. It is very particularly preferred if the transparent molding according to the invention has a transmission (at 20 ° C.) of at least 30% (in particular of at least 40%, more preferably of at least 50%, particularly preferably of at least 60%) and an NTU value (at 20 ° C) of at most 120 (more preferably at most 1 10, more preferably at most 100, particularly preferably at most 80).
Für die Herstellbarkeit und Gebrauchseigenschaften der aktivstoffhaltigen Formkörper hat es sich als vorteilhaft erwiesen, wenn das Gewichtsverhältnis von niedermolekularem Gelbildner zu polymeren Gelbildner 10:1 bis 1 :20, vorzugsweise 8:1 bis 1 :15 und insbesondere 6:1 bis 1 :10 beträgt. For the producibility and performance properties of the active substance-containing moldings, it has proven to be advantageous if the weight ratio of low molecular weight gel former to polymeric gel former is 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10 .
Das Gewicht eines einzelnen aktivstoffhaltigen Formkörpers beträgt vorzugsweise 0,2 bis 10 g, bevorzugt 0,5 bis 5 g. The weight of an individual active substance-containing shaped body is preferably 0.2 to 10 g, more preferably 0.5 to 5 g.
Die aktivstoffhaltigen Formkörper enthalten als ersten wesentlichen Bestandteil a) mindestens einen niedermolekularen Gelbildner mit einer molaren Masse bis 2000 g/mol, vorzugsweise mit einer molaren Masse von 200 g/mol bis 2000 g/mol. Als in Bezug die Herstellbarkeit, Konfektionierbarkeit und den späteren Einsatz besonders vorteilhaft hat sich der Einsatz von Gelbildnern mit einer molaren Masse von 200 g/mol bis 1000 g/mol erwiesen. The active substance-containing shaped bodies contain as the first essential component a) at least one low molecular weight gel former with a molar mass of up to 2000 g / mol, preferably with a molar mass of 200 g / mol to 2000 g / mol. The use of gel formers with a molar mass of 200 g / mol to 1000 g / mol has proven to be particularly advantageous with regard to producibility, packability and subsequent use.
Der Gewichtsanteil des niedermolekularen Gelbildners a) am Gesamtgewicht des aktivstoffhaltigen Formkörpers beträgt vorzugsweise von 0,01 bis 15 Gew.-%, vorzugsweise von 0,1 bis 10 Gew.-% und insbesondere von 1 bis 4 Gew.-%. The proportion by weight of the low molecular weight gel former a) in the total weight of the active substance-containing shaped body is preferably from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight and in particular from 1 to 4% by weight.
In einer bevorzugten Ausführungsform weist der Gelbildner a) eine Löslichkeit in Wasser von weniger als 0,1 g/L (20°C) auf. Die Löslichkeit der organischen Gelatorverbindung a) wird bei 20°C in bidestilliertem, entmineralisiertem Wasser bestimmt. In a preferred embodiment, the gel former a) has a solubility in water of less than 0.1 g / L (20 ° C.). The solubility of the organic gelator compound a) is determined at 20 ° C. in double-distilled, demineralized water.
Weiterhin sind Gelbildner bevorzugt geeignet, die eine Struktur, enthaltend mindestens eine Kohlenwasserstoff-Struktureinheit mit 6 bis 20 Kohlenstoffatomen (bevorzugt mindestens eine carbozyklische, aromatische Struktureinheit) und zusätzlich eine an vorgenannte Kohlenwasserstoff- Einheit kovalent gebundene organische Struktureinheit, die mindestens zwei Gruppen, ausgewählt aus -OH, -NH-, oder Mischungen daraus, aufweisen. Furthermore, gel formers are preferably suitable which have a structure containing at least one hydrocarbon structural unit with 6 to 20 carbon atoms (preferably at least one carbocyclic, aromatic structural unit) and in addition an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, the at least two groups selected from -OH, -NH-, or mixtures thereof.
In einer besonders bevorzugten Ausführungsform wird der mindestens eine Gelbildner ausgewählt aus der Gruppe bestehend aus Benzylidenalditol-Verbindung, Hydroxystearinsäure, hydrogeniertem Castoröl, Diarylamidocystin-Verbindung, N-(C8-C24)-Hydrocarbylglyconamid, Diketopiperazin- Verbindung, 2-Methyl-acrylsäure-2-ureido-ethylester und Mischungen davon. Aufgrund seiner technischen Wirkung besonders stärker bevorzugt ist der mindestens eine Gelbildner Dibenzylidensorbitol (DBS). In a particularly preferred embodiment, the at least one gelling agent selected from the group consisting of Benzylidenalditol compound, hydroxystearic acid, hydrogenated castor oil, Diarylamidocystin compound, N- (C8-C 24) -Hydrocarbylglyconamid, diketopiperazine compound, 2-methyl-acrylic acid 2-ureido-ethyl ester and mixtures thereof. Because of his The at least one gelling agent dibenzylidene sorbitol (DBS) is particularly more preferred for technical purposes.
Besonders bevorzugte Formkörper sind dadurch gekennzeichnet, dass besagter Formkörper mindestens eine Benzylidenalditol-Verbindung der Formel (GB-I) als Gelbildner enthält Particularly preferred shaped bodies are characterized in that said shaped body contains at least one benzylidene alditol compound of the formula (GB-I) as a gel former
Figure imgf000005_0001
Figure imgf000005_0001
*- für eine kovalente Einfachbindung zwischen einem Sauerstoffatom des Alditol-Grundgerüsts und dem vorgesehenen Rest steht, * - stands for a covalent single bond between an oxygen atom of the alditol backbone and the intended residue,
n für 0 oder 1 , bevorzugt für 1 , steht, n is 0 or 1, preferably 1,
m für 0 oder 1 , bevorzugt für 1 , steht, m is 0 or 1, preferably 1,
R1 , R2 und R3 unabhängig voneinander steht für ein Wasserstoffatom, ein Halogenatom, eine C1-C4- Alkylgruppe, eine Cyanogruppe, eine Nitrogruppe, eine Aminogruppe, eine Carboxylgruppe, eine Hydroxygruppe, eine Gruppe -C(=0)-NH-NH2, eine Gruppe -NH-C(=0)-(C2-C4-Alkyl), eine C1-C4- Alkoxygruppe, eine Ci-C4-Alkoxy-C2-C4-alkylgruppe, zwei der Reste gemeinsam mit dem Restmolekül einen 5- oder 6-gliedrigen Ring bilden, R 1 , R 2 and R 3 independently of one another represent a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a group -C (= 0) -NH -NH 2 , a group -NH-C (= 0) - (C 2 -C 4 -alkyl), a C1-C4-alkoxy group, a Ci-C 4 -alkoxy-C 2 -C 4 -alkyl group, two of the Residues form a 5- or 6-membered ring together with the residual molecule,
R4, R5 und R6 unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine C1- C4-Alkylgruppe, eine Cyanogruppe, eine Nitrogruppe, eine Aminogruppe, eine Carboxylgruppe, eine Hydroxygruppe, eine Gruppe -C(=0)-NH-NH2, eine Gruppe -NH-C(=0)-(C2-C4-Alkyl), eine C1-C4- Alkoxygruppe, eine Ci-C4-Alkoxy-C2-C4-alkylgruppe, zwei der Reste gemeinsam mit dem Restmolekül einen 5- oder 6-gliedrigen Ring bilden. R 4 , R 5 and R 6 independently stand for a hydrogen atom, a halogen atom, a C1- C 4 alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a group -C (= 0) - NH-NH 2 , a group -NH-C (= 0) - (C 2 -C 4 -alkyl), a C1-C4- alkoxy group, a Ci-C 4 -alkoxy-C 2 -C 4 -alkyl group, two of the residues together with the remainder of the molecule form a 5- or 6-membered ring.
Aufgrund der Stereochemie der Alditole sei erwähnt, dass sich erfindungsgemäße sowohl besagte Benzylidenalditole in der L-Konfiguration oder in der D-Konfiguration oder ein Gemisch aus beiden eignen. Aufgrund der natürlichen Verfügbarkeit werden erfindungsgemäß bevorzugt die Benzylidenalditol-Verbindungen in der D-Konfiguration eingesetzt. Es hat sich als bevorzugt herausgestellt, wenn sich das Alditol-Grundgerüst der in dem Formkörper enthaltenen Benzylidenalditol-Verbindung gemäß Formel (GB-I) von D-Glucitol, D-Mannitol, D-Arabinitol, D-Ribitol, D-Xylitol, L-Glucitol, L-Mannitol, L-Arabinitol, L-Ribitol oder L-Xylitol ableitet. Besonders bevorzugt sind solche Formkörper, die sich dadurch kennzeichnen, dass R1 , R2, R3, R4, R5 und R6 gemäß Benzylidenalditol-Verbindung der Formel (GB-I) unabhängig voneinander ein Wasserstoffatom, Methyl, Ethyl, Chlor, Fluor oder Methoxy, bevorzugt ein Wasserstoffatom, bedeuten. n gemäß Benzylidenalditol-Verbindung der Formel (GB-I) steht bevorzugt für 1 . m gemäß Benzylidenalditol-Verbindung Formel (GB-I) steht bevorzugt für 1 . On the basis of the stereochemistry of the alditols, it should be mentioned that both said benzylidene alditols in the L configuration or in the D configuration or a mixture of both are suitable according to the invention. Because of their natural availability, the benzylidene alditol compounds in the D configuration are preferably used according to the invention. It has been found to be preferred if the alditol basic structure of the benzylidene alditol compound according to formula (GB-I) contained in the molded body is derived from D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L -Glucitol, L-mannitol, L-arabinitol, L-ribitol or L-xylitol. Particularly preferred moldings are those which are characterized in that R 1 , R 2 , R 3 , R 4 , R 5 and R 6 according to the benzylidene alditol compound of the formula (GB-I) independently represent a hydrogen atom, methyl, ethyl, chlorine , Fluorine or methoxy, preferably a hydrogen atom. According to the benzylidene alditol compound of the formula (GB-I), n is preferably 1. According to the benzylidene alditol compound formula (GB-I), m preferably represents 1.
Ganz besonders bevorzugt enthält der erfindungsgemäße Formkörper als Benzylidenalditol- Verbindung der Formel (GB-I) mindestens eine Verbindung der Formel (GB-11) The molding according to the invention very particularly preferably contains at least one compound of the formula (GB-11) as the benzylidene alditol compound of the formula (GB-I)
Figure imgf000006_0001
Figure imgf000006_0001
worin R1 , R2, R3, R4, R5 und R6 wie in Formel (I) definiert sind. Am bevorzugtesten stehen gemäß Formel (GB-11) R1 , R2, R3, R4, R5 und R6 unabhängig voneinander für ein Wasserstoffatom, Methyl, Ethyl, Chlor, Fluor oder Methoxy, bevorzugt für ein Wasserstoffatom. wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined in formula (I). Most preferably, according to formula (GB-11), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another represent a hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom.
Am bevorzugtesten wird die Benzylidenalditol-Verbindung der Formel (GB-I) ausgewählt aus 1 , 3:2,4- Di-O-benzyliden-D-sorbitol; 1 ,3:2,4-Di-0-(p-methylbenzyliden)-D-sorbitol; 1 ,3:2,4-Di-0-(p- chlorobenzyliden)-D-sorbitol; 1 ,3:2,4-Di-0-(2,4-dimethylbenzyliden)-D-sorbitol; 1 ,3:2,4-Di-0-(p- ethylbenzyliden)-D-sorbitol; 1 ,3:2,4-Di-0-(3,4-dimethylbenzyliden)-D-sorbitol oder Mischungen daraus. Most preferably the benzylidene alditol compound of formula (GB-I) is selected from 1, 3: 2,4-di-O-benzylidene-D-sorbitol; 1, 3: 2,4-di-0- (p-methylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (p-chlorobenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (2,4-dimethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (p-ethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (3,4-dimethylbenzylidene) -D-sorbitol or mixtures thereof.
Bevorzugte Formkörper enthalten als Gelbildner mindestens eine 2,5-Diketopiperazin-Verbindung der Formel (GB-II) Preferred moldings contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as a gel former
Figure imgf000006_0002
Figure imgf000006_0002
worin wherein
R1 , R2, R3 und R4 stehen unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (Ci-C6)-Alkylgruppe, eine (C2-C6)-Alkenylgruppe, eine (C2-C6)-Acylgruppe, eine (C2-C6)- Acyloxygruppe, eine (Ci-C6)-Alkoxygruppe, eine Aminogruppe, eine (C2-C6)-Acylaminogruppe, eine (Ci-C6)-Alkylaminocarbonylgruppe, eine Arylgruppe, eine Aroylgruppe, eine Aroyloxygruppe, eine Aryloxygruppe, eine Aryl-(Ci-C4)-alkyloxygruppe, eine Aryl-(Ci-C3)-alkylgruppe, eine Heteroarylgruppe, eine Hetroaryl-(Ci-C3)-alkylgruppe, eine (Ci-C4)-Hydroxyalkylgruppe, eine (Ci-C4)-Aminoalkylgruppe, eine Carboxy-(Ci-C3)-alkylgruppe, wobei mindestens zwei der Reste R1 bis R4 gemeinsam mit dem Restmolekül einen 5 oder 6-gliedrigen Ring bilden können, R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxyl group, a (Ci-C6) -alkyl group, a (C2-C6) -alkenyl group, a (C2-C6) -acyl group, a ( C2-C6) - acyloxy group, a (Ci-C6) -alkoxy group, an amino group, a (C2-C6) -acylamino group, a (Ci-C6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, a Aryl (Ci-C 4 ) alkyloxy group, an aryl (Ci-C3) alkyl group, a heteroaryl group, a Hetroaryl- (Ci-C3) -alkylgruppe, a (Ci-C 4 ) -hydroxyalkylgruppe, a (Ci-C 4 ) -aminoalkylgruppe, a carboxy- (Ci-C3) -alkylgruppe, whereby at least two of the remainders R 1 to R 4 together with the remaining molecule can form a 5 or 6-membered ring,
R5 steht für ein Wasserstoffatom, eine lineare (Ci bis C6)-Alkylgruppe, eine verzweigte (C3 bis C10)- Alkylgruppe, eine (C3 bis C6)-Cycloalkylgruppe, eine (C2-C6)-Alkenylgruppe, eine (C2-C6)-Alkinylgruppe, eine (Ci-C4)-Hydroxyalkylgruppe, eine (Ci-C4)-Alkoxy-(Ci-C4)-alkylgruppe, eine (Ci-C4)-Acyloxy-(Ci- C4)-alkylgruppe, eine Aryloxy-(Ci-C4)-alkylgruppe, eine 0-(Aryl-(Ci-C4)-alkyl)oxy-(Ci-C4)-alkylgruppe, eine (Ci-C4)-Alkylsulfanyl-(Ci-C4)-alkylgruppe, eine Arylgruppe, eine Aryl-(Ci-C3)-alkylgruppe, eine Heteroarylgruppe, eine Hetroaryl-(Ci-C3)-alkylgruppe, eine (Ci-C4)-Hydroxyalkylgruppe, eine (C1-C4)- Aminoalkylgruppe, eine N-(Ci-C4)-Alkylamino-(Ci-C4)-alkylgruppe, eine N,N-(Ci-C4)-Dialkylamino-(Ci- C4)-alkylgruppe, eine N-(C2-C8)-Acylamino-(Ci-C4)-alkylgruppe, eine N-(C2-C8)-Acyl-N-(Ci-C4)- alkylamino-(Ci-C4)-alkylgruppe, eine N-(C2-C8)-Aroyl-N-(Ci-C4)-alkylamino-(Ci-C4)-alkylgruppe, eine N,N-(C2-C8)-Diacylamino-(Ci-C4)-alkylgruppe, eine N-(Aryl-(Ci-C4)-alkyl)amino-(Ci-C4)-alkylgruppe, eine N,N-Di(aryl-(Ci-C4)-alkyl)amino-(Ci-C4)-alkylgruppe, eine (Ci-C4)-Carboxyalkylgruppe, eine (C1- C4)-Alkoxycarbonyl-(Ci-C3)-alkylgruppe, eine (Ci-C4)-Acyloxy-(Ci-C3)-alkylgruppe, eine Guanidino-(Ci- C3)-alkylgruppe, eine Aminocarbonyl-(Ci-C4)-alkylgruppe, eine N-(Ci-C4)-Alkylaminocarbonyl-(Ci-C4)- alkylgruppe, eine N,N-Di((Ci-C4)-Alkyl)aminocarbonyl-(Ci-C4)-alkylgruppe, eine N-(C2-Cs)- Acylaminocarbonyl-(Ci-C4)-alkylgruppe, eine N,N-(C2-C8)-Diacylaminocarbonyl-(Ci-C4)-alkylgruppe, eine N-(C2-C8)-Acyl-N-(Ci-C4)-alkylaminocarbonyl-(Ci-C4)-alkylgruppe, eine N-(Aryl-(Ci-C4)- alkyl)aminocarbonyl-(Ci-C4)-alkylgruppe, eine N-(Aryl-(Ci-C4)-alkyl)-N-(Ci-C6)-alkylaminocarbonyl-(Ci- C4)-alkylgruppe oder eine N,N-Di(aryl-(Ci-C4)-alkyl)aminocarbonyl-(Ci-C4)-alkylgruppe. R 5 stands for a hydrogen atom, a linear (Ci to C6) -alkyl group, a branched (C3 to C10) -alkyl group, a (C3 to C6) -cycloalkyl group, a (C2-C6) -alkenyl group, a (C2-C6 ) Alkynyl group, a (Ci-C 4 ) -hydroxyalkyl group, a (Ci-C 4 ) -alkoxy- (Ci-C 4 ) -alkyl group, a (Ci-C 4 ) -acyloxy- (Ci- C 4 ) - alkyl group, an aryloxy (Ci-C 4 ) -alkyl group, an 0- (aryl- (Ci-C 4 ) -alkyl) oxy- (Ci-C 4 ) -alkyl group, a (Ci-C 4 ) -Alkylsulfanyl- (Ci-C 4 ) -alkyl group, an aryl group, an aryl (Ci-C3) -alkyl group, a heteroaryl group, a heteroaryl- (Ci-C3) -alkyl group, a (Ci-C 4 ) -hydroxyalkyl group, a (C1 -C4) - aminoalkyl group, an N- (Ci-C 4 ) -alkylamino- (Ci-C 4 ) -alkyl group, an N, N- (Ci-C 4 ) -dialkylamino- (Ci- C4) -alkyl group, a N- (C2-C8) acylamino (Ci-C4) alkyl group, a N- (C2-C8) acyl-N- (Ci-C4) - alkylamino (Ci-C 4) alkyl group, a N - (C 2 -C8) -Aroyl-N- (Ci-C 4 ) -alkylamino- (Ci-C 4 ) -alkyl group, an N, N- (C 2 -C8) -diacylamino- (Ci-C 4 ) -alkyl group, an N- (A ryl- (Ci-C 4 ) -alkyl) amino- (Ci-C 4 ) -alkyl group, an N, N-di (aryl- (Ci-C 4 ) -alkyl) amino- (Ci-C 4 ) -alkyl group , a (Ci-C 4 ) -carboxyalkyl group, a (C1-C 4 ) -alkoxycarbonyl- (Ci-C3) -alkyl group, a (Ci-C 4 ) -acyloxy- (Ci-C3) -alkyl group, a guanidino (Ci- C3) alkyl group, an aminocarbonyl (Ci-C4) alkyl group, a N- (Ci-C4) alkylaminocarbonyl (Ci-C4) - alkyl group, a N, N-di ((Ci-C 4 ) -Alkyl) aminocarbonyl- (Ci-C 4 ) -alkyl group, an N- (C2-Cs) - acylaminocarbonyl- (Ci-C 4 ) -alkyl group, an N, N- (C 2 -C8) -diacylaminocarbonyl- ( Ci-C 4 ) -alkyl group, an N- (C 2 -C8) -acyl-N- (Ci-C 4 ) -alkylaminocarbonyl- (Ci-C 4 ) -alkyl group, an N- (aryl- (Ci-C 4 ) - alkyl) aminocarbonyl- (Ci-C 4 ) -alkyl group, an N- (aryl- (Ci-C 4 ) -alkyl) -N- (Ci-C6) -alkylaminocarbonyl- (Ci-C 4 ) -alkyl group or an N, N-di (aryl- (Ci-C 4 ) -alkyl) aminocarbonyl- (Ci-C 4 ) -alkyl group.
Es ist erfindungsgemäß bevorzugt, wenn R3 und R4 gemäß Formel (GB-II) für ein Wasserstoffatom stehen. Es ist erfindungsgemäß besonders bevorzugt, wenn R2, R3 und R4 gemäß Formel (GB-II) für ein Wasserstoffatom stehen. Daher enthalten ganz besonders bevorzugte erfindungsgemäße Formkörper mindestens eine 2,5-Diketopiperazin-Verbindung gemäß Formel (GB-Ila) It is preferred according to the invention if R 3 and R 4 according to formula (GB-II) represent a hydrogen atom. It is particularly preferred according to the invention if R 2 , R 3 and R 4 according to formula (GB-II) represent a hydrogen atom. Therefore, particularly preferred moldings according to the invention contain at least one 2,5-diketopiperazine compound according to formula (GB-Ila)
Figure imgf000007_0001
Figure imgf000007_0001
worin R1 und R5 wie unter Formel (GB-II) (vide supra) definiert sind. wherein R 1 and R 5 are as defined under formula (GB-II) (vide supra).
Es hat sich als bevorzugt herausgestellt, wenn der Rest R1 gemäß Formel (GB-II) und gemäß Formel (GB-Ila) in para-Position des Phenylringes bindet. Daher sind im Sinne der vorliegenden Erfindung solche erfindungsgemäßen Formkörper bevorzugt, die mindestens eine 2,5-Diketopiperazin- Verbindung gemäß Formel (GB-Ilb) enthalten,
Figure imgf000008_0001
It has been found to be preferred if the radical R 1 according to formula (GB-II) and according to formula (GB-Ila) binds in the para position of the phenyl ring. For the purposes of the present invention, therefore, those moldings according to the invention are preferred which contain at least one 2,5-diketopiperazine compound of the formula (GB-IIb),
Figure imgf000008_0001
worin R1 und R5 wie zuvor unter Formel (GB-II) (vide supra) definiert sind. Die an den Ringatomen in Formel (GB-Ilb) positionierten Ziffern 3 und 6 markieren zur Veranschaulichung lediglich die Positionen 3 und 6 des Diketopiperazinringes, wie sie generell im Rahmen der Erfindung für die Namensgebung aller erfindungsgemäßen 2,5-Diketopiperazine genutzt werden. wherein R 1 and R 5 are defined as above under formula (GB-II) (vide supra). The numbers 3 and 6 positioned on the ring atoms in formula (GB-IIb) only mark positions 3 and 6 of the diketopiperazine ring, as they are generally used in the context of the invention for naming all 2,5-diketopiperazines according to the invention.
Die 2,5-Diketopiperazinverbindungen der Formel (GB-II) weisen zumindest an den Kohlenstoffatomen der Positionen 3 und 6 des 2,5-Diketopiperazinringes Chiralitätszentren auf. Die Nummerierung der Ringpositionen 3 und 6 wurde exemplarisch in Formel (GB-Ilb) illustriert. Die 2,5-Diketopiperazin- Verbindung der Formel (GB-II) der erfindungsgemäßen Zusammensetzungen ist bevorzugt bezogen auf die Stereochemie der Kohlenstoffatome an 3- und 6-Position des 2,5-Diketopiperazinringes das Konfigurationsisomere 3S,6S , 3R,6S , 3S,6R , 3R,6R oder Mischungen daraus, besonders bevorzugt 3S,6S. The 2,5-diketopiperazine compounds of the formula (GB-II) have centers of chirality at least on the carbon atoms in positions 3 and 6 of the 2,5-diketopiperazine ring. The numbering of the ring positions 3 and 6 was illustrated by way of example in formula (GB-Ilb). The 2,5-diketopiperazine compound of the formula (GB-II) of the compositions according to the invention is preferably the configuration isomer 3S, 6S, 3R, 6S, 3S based on the stereochemistry of the carbon atoms at the 3- and 6-position of the 2,5-diketopiperazine ring , 6R, 3R, 6R or mixtures thereof, particularly preferably 3S, 6S.
Bevorzugte Durftformkörper enthalten mindestens eine 2,5-Diketopiperazin-Verbindung der Formel (GB-II) als Gelbildner, ausgewählt aus 3-Benzyl-6-carboxyethyl-2,5-diketopiperazin, 3-Benzyl-6- carboxymethyl-2,5-diketopiperazin, 3-Benzyl-6-(p-hydroxybenzyl)-2,5-diketopiperazin, 3-Benzyl-6-iso- propyl-2,5-diketopiperazin, 3-Benzyl-6-(4-aminobutyl)-2,5-diketopiperazin, 3,6-Di(benzyl)-2,5- diketopiperazin, 3,6-Di(p-hydroxybenzyl)-2,5-diketopiperazin, 3,6-Di(p-(Benzyloxy)benzyl)-2,5- diketopiperazin, 3-Benzyl-6-(4-imidazolyl)methyl-2,5-diketopiperazin, 3-Benzyl-6-methyl-2,5- diketopiperazin, 3-Benzyl-6-(2-(benzyloxycarbonyl)ethyl)-2,5-diketopiperazin oder Mischungen daraus. Dabei sind wiederum Verbindungen mit den vorgenannten Konfigurationsisomeren bevorzugt zur Auswahl geeignet. Preferred molded articles contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as a gel former, selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5- diketopiperazine, 3-benzyl-6- (p-hydroxybenzyl) -2,5-diketopiperazine, 3-benzyl-6-isopropyl-2,5-diketopiperazine, 3-benzyl-6- (4-aminobutyl) -2, 5-diketopiperazine, 3,6-di (benzyl) -2,5- diketopiperazine, 3,6-di (p-hydroxybenzyl) -2,5-diketopiperazine, 3,6-di (p- (benzyloxy) benzyl) - 2,5-diketopiperazine, 3-benzyl-6- (4-imidazolyl) methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl-6- [2- (benzyloxycarbonyl ) ethyl) -2,5-diketopiperazine or mixtures thereof. In turn, compounds with the aforementioned configurational isomers are preferably suitable for selection.
Es ist ebenso möglich, dass die erfindungsgemäßen Formkörper als Gelbildner a) mindestens eine Diarylamidocystin-Verbindung der Formel (GB-Ill) enthalten It is also possible for the shaped bodies according to the invention to contain at least one diarylamidocystine compound of the formula (GB-III) as gel former a)
Figure imgf000008_0002
Figure imgf000008_0002
worin X+ unabhängig voneinander für Wasserstoffatom oder ein äquivalent eines Kations steht,wherein X + independently represent a hydrogen atom or an equivalent of a cation,
R1 , R2, R3 und R4 unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C1-C4- Alkylgruppe, eine Ci-C4-Alkoxygruppe, eine C2-C4-Hydroxyalkylgruppe, eine Hydroxylgruppe, eine Aminogruppe, eine N-(Ci-C4-Alkyl)aminogruppe, eine N,N-Di(Ci-C4-Alkyl)aminogruppe, eine N-(C2-C4- hydroxyalkyl)aminogruppe, eine N,N-Di(C2-C4-hydroxyalkyl)aminogruppe oder R1 mit R2 oder R3 mit R4 einen 5- oder 6-gliedrigen annelierten Ring bildet, der wiederum jeweils mit mindestens einer Gruppe aus Ci-C4-Alkylgruppe, Ci-C4-Alkoxygruppe, C2-C4-Hydroxyalkylgruppe, Hydroxylgruppe, Aminogruppe, N-(Ci-C4-Alkyl)aminogruppe, N,N-Di(Ci-C4-Alkyl)aminogruppe, N-(C2-C4- hydroxyalkyl)aminogruppe, N,N-Di(C2-C4-hydroxyalkyl)aminogruppe substituiert sein kann. R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a Ci-C 4 alkoxy group, a C 2 -C 4 hydroxyalkyl group, a hydroxyl group, an amino group, an N- (Ci-C 4 -alkyl) amino group, an N, N-di (Ci-C 4 -alkyl) amino group, an N- (C 2 -C 4 - hydroxyalkyl) amino group, an N, N-di ( C 2 -C 4 -hydroxyalkyl) amino group or R 1 with R 2 or R 3 with R 4 forms a 5- or 6-membered fused ring, which in turn each with at least one group from Ci-C 4 -alkyl group, Ci-C 4 -alkoxy group, C 2 -C 4 -hydroxyalkyl group, hydroxyl group, amino group, N- (Ci-C 4 -alkyl) amino group, N, N-di (Ci-C 4 -alkyl) amino group, N- (C 2 -C 4 -hydroxyalkyl) amino group, N, N-di (C 2 -C 4 -hydroxyalkyl) amino group can be substituted.
Jedes der in der Verbindung der Formel (GB-Ill) enthaltenen Stereozentren kann unabhängig voneinander für das L- oder D-Stereoisomer stehen. Es ist erfindungsgemäß bevorzugt, wenn sich die besagte Cystinverbindung der Formel (GB-Ill) vom L-Stereoisomer des Cysteins ableitet. Each of the stereocenters contained in the compound of the formula (GB-III) can, independently of one another, stand for the L or D stereoisomer. It is preferred according to the invention if the said cystine compound of the formula (GB-III) is derived from the L-stereoisomer of cysteine.
Besagte Formkörper können mindestens eine Verbindung der Formel (GB-Ill) enthalten, in der R1 , R2, R3 und R4 unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine Ci-C4-Alkylgruppe, eine Ci-C4-Alkoxygruppe, eine C2-C4-Hydroxyalkylgruppe, eine Hydroxylgruppe, oder R1 mit R2 oder R3 mit R4 einen 5- oder 6-gliedrigen annelierten Ring bildet, der wiederum jeweils mit mindestens einer Gruppe aus Ci-C4-Alkylgruppe, Ci-C4-Alkoxygruppe, C2-C4-Hydroxyalkylgruppe, Hydroxylgruppe substituiert sein kann, stehen. Es sind insbesondere solche Formkörper besonders geeignet, die als Diarylamidocystin-Verbindung der Formel (GB-Ill) N,N‘-Dibenzoylcystin (R1 = R2 = R3 = R4 = Wasserstoffatom; X+ = unabhängig voneinander für Wasserstoffatom oder ein äquivalent eines Kations), insbesondere N,N‘-Dibenzoyl-L-cystin, enthalten. Said shaped bodies can contain at least one compound of the formula (GB-III) in which R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a Ci-C 4 -alkyl group, a Ci-C 4 -Alkoxy group, a C 2 -C 4 -hydroxyalkyl group, a hydroxyl group, or R 1 with R 2 or R 3 with R 4 forms a 5- or 6-membered fused ring, which in turn each with at least one group from Ci-C 4 -Alkyl group, Ci-C 4 alkoxy group, C 2 -C 4 hydroxyalkyl group, hydroxyl group can be substituted. In particular, those moldings are particularly suitable which are used as the diarylamidocystine compound of the formula (GB-III) N, N'-dibenzoylcystine (R 1 = R 2 = R 3 = R 4 = hydrogen atom; X + = independently of one another for hydrogen atom or a equivalent of a cation), in particular N, N'-dibenzoyl-L-cystine.
Die als Gelbildner a) geeigneten N-(C8-C24)-Hydrocarbylglyconamid-Verbindungen weisen bevorzugt die Formel (GB-IV) auf
Figure imgf000009_0001
The N- (C8-C 24 ) -hydrocarbylglyconamide compounds suitable as gel formers a) preferably have the formula (GB-IV)
Figure imgf000009_0001
wobei in which
n 2 bis 4, vorzugsweise 3 oder 4, insbesondere 4, ist; n is 2 to 4, preferably 3 or 4, especially 4;
R1 ausgewählt wird aus Wasserstoff, C1-C16 Alkylresten, C1-C3 Hydroxy- oder Methoxyalkylresten, vorzugsweise C1-C3 Alkyl-, Hydroxyalkyl- oder Methoxyalkylresten, besonders bevorzugt Methyl;R 1 is selected from hydrogen, C1-C16 alkyl radicals, C1-C3 hydroxy or methoxyalkyl radicals, preferably C1-C3 alkyl, hydroxyalkyl or methoxyalkyl radicals, particularly preferably methyl;
R2 ausgewählt wird aus C8-C24-Alkylresten, Cs-C24-Monoalkenylresten, Cs-C24-Dialkenylresten, Cs- C24-Trialkenylresten, Cs-C24-Hydroxyalkylresten, Cs-C24-Hydroxyalkenylresten, C1-C3 Hydroxyalkylresten oder Methoxy-Ci-C3-alkylresten, vorzugsweise Cs-Cis Alkylresten und Mischungen davon, noch bevorzugter es, C10, C12, C14, C16 und Cis-Alkylresten und Mischungen davon, am meisten bevorzugt C12 und C14 Alkylresten oder einer Mischung davon. ln besonders bevorzugten Ausführungsformen ist der Rest HO-CH2-(CHOH)n-C- ein von einer R 2 is selected from C8-C24 alkyl, Cs-C 24 -Monoalkenylresten, Cs-C 24 -Dialkenylresten, Cs C 24 -Trialkenylresten, Cs-C 24 -hydroxyalkyl, Cs-C 24 -Hydroxyalkenylresten, C1-C3 Hydroxyalkyl radicals or methoxy-Ci-C3-alkyl radicals, preferably Cs-Cis alkyl radicals and mixtures thereof, more preferably C10, C12, C14, C16 and Cis-alkyl radicals and mixtures thereof, most preferably C12 and C14 alkyl radicals or a mixture thereof. In particularly preferred embodiments, the HO-CH2- (CHOH) n -C- radical is one of one
II II
O Glycuronsäure, insbesondere der Glycuronsäure einer Hexose (n=4), abgeleiteter Rest. Hierbei ist insbesondere Glucuronsäure als bevorzugter Rest zu nennen. R1 ist vorzugsweise H oder ein kurzkettiger Alkylrest, insbesondere Methyl. R2 ist vorzugsweise ein langkettiger Alkylrest, beispielsweise eine Cs-Ci8 Alkylrest. O Glycuronic acid, in particular the glycuronic acid of a hexose (n = 4), derived radical. Glucuronic acid in particular is to be mentioned as a preferred radical. R 1 is preferably H or a short-chain alkyl radical, in particular methyl. R 2 is preferably a long-chain alkyl radical, for example a Cs-Ci8 alkyl radical.
Ganz besonders bevorzugt sind daher Verbindungen der Formel (GB-IV1)
Figure imgf000010_0001
Compounds of the formula (GB-IV1) are therefore very particularly preferred
Figure imgf000010_0001
wobei R2 die für Formel (GB-IV) angegebenen Bedeutungen hat. where R 2 has the meanings given for formula (GB-IV).
Ein zweiter wesentlicher Bestandteil b) der aktivstoffhaltigen Formkörper ist der polymere Gelbildner mit einer molaren Masse von 10000 g/mol bis 200000 g/mol. Als besonders vorteilhaft in Bezug auf die Herstellung, Konfektionierung und Handhabung der Formkörper hat es sich erwiesen, polymere Gelbildner einer molaren Masse von 10000 bis 40000 g/mol einzusetzen. A second essential component b) of the active substance-containing moldings is the polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol. It has proven to be particularly advantageous in relation to the production, packaging and handling of the shaped bodies to use polymeric gel formers with a molar mass of 10,000 to 40,000 g / mol.
Der Gewichtsanteil polymeren Gebildners b) am Gesamtgewicht aktivstoffhaltiger Formkörper beträgt vorzugsweise von 0,01 bis 15 Gew.-%, bevorzugt von 0,1 bis 12 Gew.-% und insbesondere von 1 bis 10 Gew.-%. The proportion by weight of polymeric forming agent b) in the total weight of active substance-containing shaped bodies is preferably from 0.01 to 15% by weight, more preferably from 0.1 to 12% by weight and in particular from 1 to 10% by weight.
Als technisch vorteilhaft haben sich polymere Gelbildner b) aus der Gruppe der Polymeric gel formers b) from the group of have proven to be technically advantageous
- Cellulosen und Cellulosederivate, insbesondere der Methylcellulose, Hydroxypropylmethylcellulose und der Hydroxypropylcellulose; - Celluloses and cellulose derivatives, in particular methyl cellulose, hydroxypropylmethyl cellulose and hydroxypropyl cellulose;
- Stärke, insbesondere der Kartoffelstärke, Maisstärke, Weizenstärke, Erbsenstärke oder Tapiokastärke; - Starch, in particular potato starch, corn starch, wheat starch, pea starch or tapioca starch;
- Polyacrylate; - polyacrylates;
- Polyvinylpyrrolidone; - polyvinylpyrrolidones;
- Polyvinylalkohole - polyvinyl alcohols
erwiesen. Besonders vorteilhaft ist der Einsatz von Polyvinylalkoholen. proven. The use of polyvinyl alcohols is particularly advantageous.
Als Polyacrylate eignen sich Homo- und Copolymerisate der Acrylsäure, insbesondere Acrylsäure- Copolymere wie Acrylsäure-Methacrylsäure-Copolymere, und Polysaccharide, insbesondere Heteropolysaccharide, sowie andere übliche polymere Verdicker. Suitable polyacrylates are homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and polysaccharides, especially heteropolysaccharides, and other customary polymer thickeners.
Geeignete Acrylsäure-Polymere sind beispielsweise hochmolekulare mit einem Polyalkenylpolyether, insbesondere einem Allylether von Saccharose, Pentaerythrit oder Propylen, vernetzte Homopolymere der Acrylsäure (INCI Carbomer), die auch als Carboxyvinylpolymere bezeichnet werden. Solche Polyacrylsäuren sind unter anderem von der Fa. BFGoodrich unter dem Handelsnamen Carbopof® erhältlich. Suitable acrylic acid polymers are, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are available inter alia from the company. BF Goodrich under the trade names Carbopof ®.
Besonders geeignete Polymere sind aber folgende Acrylsäure-Copolymere: (i) Copolymere von zwei oder mehr Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit Ci-4-Alkanolen gebildeten, Ester (INCI Acrylates Copolymer), zu denen etwa die Copolymere von Methacrylsäure, Butylacrylat und Methylmethacrylat (CAS 25035-69-2) oder von Butylacrylat und Methylmethacrylat (CAS 25852-37-3) gehören und die beispielsweise von der Fa. Rohm & Haas unter den Handelsnamen Aculyn® und Acusol® sowie von der Firma Degussa (Goldschmidt) unter dem Handelsnamen Tego® Polymer erhältlich sind; (ii) vernetzte hochmolekulare Acrylsäurecopolymere, zu denen etwa die mit einem Allylether der Saccharose oder des Pentaerythrits vernetzten Copolymere von Cio so-Alkylacrylaten mit einem oder mehreren Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit Cu-Alkanolen gebildeten, Ester (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) gehören und die beispielsweise von der Firma BFGoodrich unter dem Handelsnamen Carbopol® erhältlich sind. Geeignete Acrylsäureester sind ebenfalls unter dem Handelsnamen Skalan® AT 120 und Rheovis® AT 120 von der Firma BASF erhältlich. Werden Acrylsäurepolymere und insbesondere Acrylsäureester als polymere Verdicker eingesetzt, so beträgt der pH-Wert vorzugsweise mehr als 7, insbesondere wenigstens 7,5, bevorzugt 8 oder mehr. Particularly suitable polymers, however, are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, Esters (INCI Acrylates Copolymer) preferably formed with Ci- 4 alkanols, which include copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are obtainable for example from the company Rohm & Haas under the trade names Aculyn ® and Acusol ®, and from Degussa (Goldschmidt) under the trade name Tego ® polymer. (ii) crosslinked high molecular weight acrylic acid copolymers, including, for example, the copolymers of Cio so-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with Cu alkanols, with an allyl ether of sucrose or pentaerythritol (INCI acrylates / C10-30 alkyl acrylate Crosspolymer) and which are obtainable, for example, by the company BF Goodrich under the trade name Carbopol ®. Suitable acrylate are also available under the trade name Skålan ® AT 120 and AT 120 Rheovis ® by the company BASF. If acrylic acid polymers and especially acrylic acid esters are used as polymeric thickeners, the pH is preferably more than 7, in particular at least 7.5, preferably 8 or more.
Bevorzugte Polyvinylalkohole weisen ein Molekulargewicht von 10000 g/mol bis 150000 g/mol, besonders bevorzugt von 10000 g/mol bis 80000 g/mol und insbesondere von 10000 g/mol bis 40000 g/mol auf. Der Hydrolysegrad bevorzugter Polyvinylalkohole beträgt 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% Preferred polyvinyl alcohols have a molecular weight of 10,000 g / mol to 150,000 g / mol, particularly preferably 10,000 g / mol to 80,000 g / mol and in particular 10,000 g / mol to 40,000 g / mol. The degree of hydrolysis of preferred polyvinyl alcohols is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%
Aufgrund der Vorteile bei ihrer Herstellung und ihrem Gebrauch sind solche aktivstoffhaltigen Formkörper bevorzugt, bei denen das Gewichtsverhältnis von Dibenzylidensorbitol zu Polyvinylalkohol 10:1 bis 1 :20, vorzugsweise 8:1 bis 1 :15 und insbesondere 6:1 bis 1 :10 beträgt. Due to the advantages in their production and use, those active substance-containing moldings are preferred in which the weight ratio of dibenzylidene sorbitol to polyvinyl alcohol is 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10.
Als dritten wesentlichen Bestandteil umfassen die Formkörper einen Aktivstoff c). Als Aktivstoff c) wird vorzugsweise mindestens einen Aktivstoff aus der Gruppe der Duftstoffe, der Enzyme und der Färbemittel, vorzugsweise mindestens ein Aktivstoff aus der Gruppe der Duftstoffe eingesetzt. The moldings comprise an active substance c) as a third essential component. At least one active ingredient from the group of fragrances, enzymes and colorants, preferably at least one active ingredient from the group of fragrances, is preferably used as active ingredient c).
Der Gewichtsanteil des Aktivstoffs c), insbesondere des Duftstoffs, am Gesamtgewicht des aktivstoffhaltigen Formkörpers beträgt vorzugsweise 0,1 bis 20 Gew.-%, vorzugweise von 0,2 bis 15 Gew.-% und insbesondere von 0,5 bis 10 Gew.-%. The proportion by weight of the active substance c), in particular the fragrance, in the total weight of the active substance-containing molding is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight and in particular 0.5 to 10% by weight. %.
Bei einem Duftstoff handelt es sich um eine den Geruchsinn anregende, chemische Substanz. Um den Geruchssinn anregen zu können, sollte die chemische Substanz zumindest teilweise in der Luft verteilbar sein, d.h. der Duftstoff sollte bei 25°C zumindest in geringem Maße flüchtig sein. Ist der Duftstoff nun sehr flüchtig, klingt die Geruchsintensität dann schnell wieder ab. Bei einer geringeren Flüchtigkeit ist der Gerucheindruck jedoch nachhaltiger, d.h. er verschwindet nicht so schnell. In einer Ausführungsform weist der Duftstoff daher einen Schmelzpunkt auf, der im Bereich von -100°C bis 100°C, bevorzugt von -80°C bis 80°C, noch bevorzugter von -20°C bis 50°C, insbesondere von -30°C bis 20°C liegt. In einer weiteren Ausführungsform weist der Duftstoff einen Siedepunkt auf, der im Bereich von 25°C bis 400°C, bevorzugt von 50°C bis 380°C, mehr bevorzugt von 75°C bis 350°C, insbesondere von 100°C bis 330°C liegt. Insgesamt sollte eine chemische Substanz eine bestimmte Molekülmasse nicht überschreiten, um als Duftstoff zu fungieren, da bei zu hoher Molekülmasse die erforderliche Flüchtigkeit nicht mehr gewährleitstet werden kann. In einer Ausführungsform weist der Duftstoff eine Molekülmasse von 40 bis 700 g/mol, noch bevorzugter von 60 bis 400 g/mol auf. A fragrance is a chemical substance that stimulates the sense of smell. In order to be able to stimulate the sense of smell, the chemical substance should be at least partially dispersible in the air, ie the fragrance should be at least slightly volatile at 25 ° C. If the fragrance is now very volatile, the odor intensity then quickly subsides again. If the volatility is lower, however, the odor impression is more lasting, ie it does not disappear as quickly. In one embodiment, the fragrance therefore has a melting point which is in the range from -100 ° C to 100 ° C, preferably from -80 ° C to 80 ° C, even more preferably from -20 ° C to 50 ° C, in particular from - 30 ° C to 20 ° C. In a further embodiment, the fragrance has a boiling point which is in the range from 25 ° C. to 400 ° C., preferably from 50 ° C. to 380 ° C., more preferably from 75 ° C. to 350 ° C., in particular from 100 ° C. to 330 ° C. Overall, a chemical substance should not exceed a certain molecular mass in order to function as a fragrance, since if the molecular mass is too high, the required volatility can no longer be guaranteed. In one embodiment, the fragrance has a molecular weight of 40 to 700 g / mol, more preferably 60 to 400 g / mol.
Der Geruch eines Duftstoffes wird von den meisten Menschen als angenehm empfunden und entspricht häufig dem Geruch nach beispielsweise Blüten, Früchten, Gewürzen, Rinde, Harz, Blättern, Gräsern, Moosen und Wurzeln. So können Duftstoffe auch dazu verwendet werden, um unangenehme Gerüche zu überlagern oder aber auch um einen nicht riechenden Stoff mit einem gewünschten Geruch zu versehen. Als Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Most people find the smell of a fragrance pleasant and often corresponds to the smell of, for example, flowers, fruits, spices, bark, resin, leaves, grasses, mosses and roots. For example, fragrances can also be used to mask unpleasant odors or to provide a non-odorous substance with a desired odor. Individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used as fragrances.
Duftstoffverbindungen vom Typ der Aldehyde sind beispielsweise Adoxal (2,6,10-Trimethyl-9- undecenal), Anisaldehyd (4-Methoxybenzaldehyd), Cymal (3-(4-lsopropyl-phenyl)-2-methylpropanal), Ethylvanillin, Florhydral (3-(3-isopropylphenyl)butanal), Helional (3-(3,4-Methylendioxyphenyl)-2- methylpropanal), Heliotropin, Hydroxycitronellal, Lauraldehyd, Lyral (3- und 4-(4-Hydroxy-4- methylpentyl)-3- cyclohexen-1 -carboxaldehyd), Methylnonylacetaldehyd, Lilial (3-(4-tert-Butylphenyl)-2- methylpropanal), Phenylacetaldehyd, Undecylenaldehyd, Vanillin, 2,6,10-Trimethyl-9-undecenal, 3- Dodecen-1 -al, alpha-n-Amylzimtaldehyd, Melonal (2,6-Dimethyl-5-heptenal), 2,4-Di-methyl-3- cyclohexen-1 -carboxaldehyd (Triplal), 4-Methoxybenzaldehyd, Benzaldehyd, 3-(4-tert- Butylphenyl)- propanal, 2-Methyl-3-(para-methoxyphenyl)propanal, 2-Methyl-4-(2,6,6-timethyl-2(1)-cyclohexen-1 - yl)butanal, 3-Phenyl-2-propenal, cis-/trans-3,7-Dimethyl-2,6-octadien-1 -al, 3,7-Dimethyl-6-octen-1 -al, [(3,7-Dimethyl-6-octenyl)oxy]acetaldehyd, 4-lsopropylbenzylaldehyd, 1 ,2,3,4,5,6,7,8-Octahydro-8,8- dimethyl-2-naphthaldehyd, 2, 4-Dimethyl-3-cyclohexen-1 -carboxaldehyd, 2-Methyl-3-Fragrance compounds of the aldehyde type are, for example, adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropyl-phenyl) -2-methylpropanal), ethylvanillin, florhydral ( 3- (3-isopropylphenyl) butanal), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy-4-methylpentyl) - 3- cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3- dodecen 1 -al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (triplal), 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) propanal, 2-methyl-3- (para-methoxyphenyl) propanal, 2-methyl-4- (2,6,6-timethyl-2 (1) -cyclohexen-1-yl) butanal , 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadien-1 -al, 3,7-dimethyl-6-octen-1 -al, [(3,7- Dimethyl-6-octenyl ) oxy] acetaldehyde, 4-isopropylbenzylaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde , 2-methyl-3-
(isopropylphenyl)propanal, 1 -Decanal, 2,6-Dimethyl-5-heptenal, 4-(Tricyclo[5.2.1 0(2,6)]-decyliden-8)- butanal, Octahydro-4,7-methan-1 H-indencarboxaldehyd, 3-Ethoxy-4-hydroxybenzaldehyd, para-Ethyl- alpha.alpha-dimethylhydrozimtaldehyd, alpha-Methyl-3,4-(methylendioxy)-hydrozimtaldehyd, 3,4- Methylendioxybenzaldehyd, alpha-n-Hexylzimtaldehyd, m-Cymen-7-carboxaldehyd, alpha- Methylphenylacetaldehyd, 7-Hydroxy-3,7-dimethyloctanal, Undecenal, 2,4,6-Trimethyl-3-cyclohexen-1 - carboxaldehyd, 4-(3)(4-Methyl-3-pentenyl)-3-cyclohexencarboxaldehyd, 1 -Dodecanal, 2,4- Dimethylcyclohexen-3-carboxaldehyd, 4-(4-Hydroxy-4-methylpentyl)-3-cylohexen-1 -carboxaldehyd, 7- Methoxy-3,7-dimethyloctan-1 -al, 2-Methyl- undecanal, 2-Methyldecanal, 1 -Nonanal, 1 -Octanal, 2,6,10- T rimethyl-5,9-undecadienal, 2-Methyl-3-(4-tert-butyl)propanal, Dihydrozimtaldehyd , 1 -Methyl-4-(4- methyl-3-pentenyl)-3-cyclohexen-1 -carboxaldehyd, 5- oder 6-Methoxyhexahydro-4,7-methanindan-1 - oder -2-carboxaldehyd, 3,7-Dimethyloctan-1 -al, 1 -Undecanal, 10-Undecen-1 -al, 4-Hydroxy-3- methoxybenzaldehyd, 1 -Methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyd, 7-Hydroxy-3J- dimethyl-octanal, trans-4-Decenal, 2,6-Nonadienal, para-Tolylacetaldehyd, 4- Methylphenylacetaldehyd, 2-Methyl-4-(2, 6, 6-trimethyl-1 -cyclohexen-1 -yl)-2-butenal, ortho-(isopropylphenyl) propanal, 1-decanal, 2,6-dimethyl-5-heptenal, 4- (tricyclo [5.2.1 0 (2,6)] - decylidene-8) - butanal, octahydro-4,7-methane 1 H-indene carboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha.alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m -Cymen-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4-methyl-3 -pentenyl) -3-cyclohexenecarboxaldehyde, 1 -dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexen-1-carboxaldehyde, 7-methoxy-3,7- dimethyloctan-1 -al, 2-methyl-undecanal, 2-methyl-decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3- (4-tert- butyl) propanal, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde, 5- or 6-methoxyhexahydro-4,7-methanindane-1 - or -2-carboxaldehyde , 3,7-dimethy 1-octane-1-al, 1-undecanal, 10-undecene-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexenecarboxaldehyde, 7-hydroxy-3J-dimethyl- octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4- (2, 6, 6-trimethyl-1-cyclohexen-1 -yl) -2-butenal, ortho-
Methoxyzimtaldehyd, 3,5,6-Trimethyl-3-cyclohexen- carboxaldehyd, 3J-Dimethyl-2-methylen-6-octenal, Phenoxyacetaldehyd, 5,9-Dimethyl-4,8- decadienal, Päonienaldehyd (6,10-Dimethyl-3-oxa-5,9- undecadien-1 -al), Hexahydro-4,7-methanindan-1 -carboxaldehyd, 2-Methyloctanal, alpha-Methyl-4-(1 - methylethyl)benzolacetaldehyd, 6,6-Dimethyl-2-norpinen-2-propionaldehyd, para-Methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexene-carboxaldehyde, 3J-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl- 3-oxa-5.9- undecadien-1 -al), hexahydro-4,7-methanindan-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4- (1-methylethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2-propionaldehyde, para
Methylphenoxyacetaldehyd, 2-Methyl-3-phenyl-2-propen-1 -al, 3,5,5-Trimethylhexanal, Hexahydro-8,8- dimethyl-2-naphthaldehyd, 3-Propyl-bicyclo-[2.2.1 ]-hept-5-en-2-carbaldehyd, 9-Decenal, 3-Methyl-5- phenyl-1 -pentanal, Methylnonylacetaldehyd, Hexanal und trans-2-Hexenal. Methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1 -al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo- [2.2.1] - hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal and trans-2-hexenal.
Duftstoffverbindungen vom Typ der Ketone sind beispielsweise Methyl-beta-naphthylketon, Moschusindanon (1 ,2, 3,5,6, 7-Hexahydro-1 ,1 ,2,3,3- pentamethyl-4H-inden-4-on), Tonalid (6-Acetyl- 1 ,1 ,2,4,4,7-hexamethyltetralin), alpha-Damascon, beta-Damascon, delta-Damascon, iso-Damascon, Damascenon, Methyldihydrojasmonat, Menthon, Carvon, Kampfer, Koavon (3, 4, 5,6,6- Pentamethylhept-3-en-2-on), Fenchon, alpha-lonon, beta- lonon, gamma-Methyl-lonon, Fleuramon (2- heptylcyclopen-tanon), Dihydrojasmon, cis-Jasmon, iso-E-Super (1 -(1 ,2, 3,4,5, 6J,8-octahydro-2, 3,8,8- tetramethyl-2-naphthalenyl)-ethan-1 -on (und Isomere)), Methylcedrenylketon, Acetophenon, Methylacetophenon, para-Methoxyacetophenon, Methyl-beta-naphtylketon, Benzylaceton, Benzophenon, para-Hydroxyphenylbutanon, Sellerie- Keton(3-methyl-5-propyl-2-cyclohexenon), 6- lsopropyldecahydro-2-naphton, Dimethyloctenon, Frescomenthe (2-butan-2-yl-cyclohexan-1 -on), 4-(1 - Ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanon, Methylheptenon, 2-(2-(4-Methyl-3-cyclohexen-1 - yl)propyl)cyclopentanon, 1 -(p-Menthen-6(2)yl)-1 -propanon, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanon, 2-Acetyl-3,3-dimethylnorbornan, 6,7- Dihydro-1 ,1 ,2,3,3-pentamethyl-4(5H)-indanon, 4-Damascol, Dulcinyl(4-(1 ,3-benzodioxol-5-yl) butan-2-on), Hexalon (1 -(2,6,6-trimethyl-2-cyclohexene-1 -yl)-1 ,6- heptadien-3-on), lsocyclemonE(2-acetonaphthon-1 ,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), Methylnonylketon, Methylcyclocitron, Methyllavendelketon, Orivon (4-tert-Amyl-cyclohexanon), 4-tert- Butylcyclohexanon, Delphon (2-pentyl-cyclopentanon), Muscon (CAS 541 -91 -3), Neobutenon (1 -(5,5- dimethyl-1 - cyclohexenyl)pent-4-en-1 -on), Plicaton (CAS 41724-19-0), Velouton (2,2,5-Trimethyl-5- pentylcyclopentan-1 -on),2,4,4,7-Tetramethyl-oct-6-en-3-on und Tetrameran (6,10- Dimethylundecen-2- on). Fragrance compounds of the ketone type are, for example, methyl beta-naphthyl ketone, musk indanone (1, 2, 3,5,6, 7-hexahydro-1, 1, 2,3,3-pentamethyl-4H-inden-4-one), Tonalid (6-acetyl-1, 1, 2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate, menthone, carvone, camphor, coavone (3 , 4, 5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, betalonone, gamma-methyl-ionone, fleuramone (2-heptylcyclopen-tanone), dihydrojasmone, cis-jasmone , iso-E-Super (1 - (1, 2, 3,4,5, 6J, 8-octahydro-2, 3,8,8-tetramethyl-2-naphthalenyl) -ethan-1-one (and isomers) ), Methyl cedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl-beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldecahydro- , Dimethyloctenone, Frescomenthe (2-butan-2-yl-cyclohexan-1-one), 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2 - (2- (4-methyl-3-cyclohexen-1 - yl) propyl) cyclopentanone, 1 - (p-menthen-6 (2) yl) -1-propanone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1, 1, 2,3,3-pentamethyl-4 (5H) -indanone, 4-damascol, dulcinyl (4- (1 , 3-benzodioxol-5-yl) butan-2-one), hexalone (1 - (2,6,6-trimethyl-2-cyclohexene-1-yl) -1,6-heptadien-3-one), isocyclemonE (2-acetonaphthon-1, 2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methyl nonyl ketone, methylcyclocitron, methyl lavender ketone, orivon (4-tert-amyl-cyclohexanone) , 4-tert-butylcyclohexanone, Delphon (2-pentyl-cyclopentanone), Muscon (CAS 541-91-3), neobutenone (1 - (5,5-dimethyl-1-cyclohexenyl) pent-4-en-1 -one ), Plicaton (CAS 41724-19-0), Velouton (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one and tetrameran (6,10-dimethylundecen-2-one).
Duftstoffverbindungen vom Typ der Alkohole sind beispielsweise 10-Undecen-1 -ol, 2,6-Dimethylheptan- 2-ol, 2-Methyl-butanol, 2-Methylpentanol, 2- Phenoxyethanol, 2-Phenylpropanol, 2-tert.- Butycyclohexanol, 3,5,5-Trimethylcyclohexanol, 3-Hexanol, 3-Methyl-5-phenyl-pentanol, 3-Octanol, 3- Phenyl-propanol, 4-Heptenol, 4-lsopropyl- cyclohexanol, 4-tert.-Butycyclohexanol, 6,8-Dimethyl-2- nona-nol, 6-Nonen-1 -ol, 9-Decen-1 -ol, a-Methylbenzylalkohol, a-Terpineol, Amylsalicylat, Benzylalkohol, Benzylsalicylat, ß-Terpineol, Butylsalicylat, Citronellol, Cyclohexylsalicylat, Decanol, Di- hydromyrcenol, Dimethylbenzylcarbinol, Dimethylheptanol, Dimethyloctanol, Ethylsalicylat, Ethylvanilin, Eugenol, Farnesol, Geraniol, Heptanol, Hexylsalicylat, Isoborneol, Isoeugenol, Isopulegol, Linalool, Menthol, Myrtenol, n-Hexanol, Nerol, Nonanol, Octanol, p-Menthan-7-ol, Phenylethylalkohol, Phenol, Phenylsalicylat, Tetrahydrogeraniol, Tetrahydrolinalool, Thymol, trans-2-cis-6-Nonadicnol, trans-2- Nonen-1 -ol, trans-2-Octenol, Undecanol, Vanillin, Champiniol, Hexenol und Zimtalkohol. Fragrance compounds of the alcohol type are, for example, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methyl-butanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenyl-pentanol, 3-octanol, 3-phenyl-propanol, 4-heptenol, 4-isopropyl-cyclohexanol, 4-tert.-butycyclohexanol, 6 , 8-dimethyl-2-nona-nol, 6-nonene-1 -ol, 9-decen-1 -ol, α-methylbenzyl alcohol, α-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, ß-terpineol, butyl salicylate, citronellol, cyclohexyl salicyl , decanol, dihydromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethyl salicylate, ethylvanillin, eugenol, farnesol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, p -Menthan-7-ol, phenylethyl alcohol, phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-cis-6-nonadicnol, trans-2-nonene-1 -o l, trans-2-octenol, undecanol, vanillin, champiniol, hexenol and cinnamon alcohol.
Duftstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert- Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat (DMBCA), Phenylethylacetat, Benzylacetat, Ethylmethylphenyl- glycinat, Allylcyclohexylpropionat, Styrallylpropionat, Benzylsalicylat, Cyclohexylsalicylat, Floramat, Melusat und Jasmacyclat. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, Benzyl acetate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmacyclate.
Zu den Ethern zählen beispielsweise Benzylethylether und Ambroxan. Zu den Kohlenwasserstoffen gehören hauptsächlich Terpene wie Limonen und Pinen. The ethers include, for example, benzyl ethyl ether and ambroxan. The hydrocarbons mainly include terpenes such as limonene and pinene.
Bevorzugt werden Mischungen verschiedener Duftstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Ein derartiges Gemisch an Duftstoffen kann auch als Parfüm oder Parfümöl bezeichnet werden. Solche Parfümöle können auch natürliche Duftstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind. Mixtures of different fragrances are preferably used, which together produce an appealing fragrance note. Such a mixture of fragrances can also be referred to as perfume or perfume oil. Such perfume oils can also contain natural fragrance mixtures, such as are available from vegetable sources.
Zu den Duftstoffen pflanzlichen Ursprungs zählen ätherische Öle wie Angelikawurzelöl, Anisöl, Arnikablütenöl, Basilikumöl, Bayöl, Champacablütenöl, Citrusöl, Edeltannenöl, Edeltannenzapfenöl, Elemiöl, Eukalyptusöl, Fenchelöl, Fichtennadelöl, Galbanumöl, Geraniumöl, Gingergrasöl, Guajakholzöl, Gurjunbalsamöl, Helichrysumöl, Ho-Öl, Ingweröl, Irisöl, jasminöl, Kajeputöl, Kalmusöl, Kamillenöl, Kampferöl, Kanagaöl, Kardamomenöl, Kassiaöl, Kiefernnadelöl, Kopaivabalsamöl, Korianderöl, Krauseminzeöl, Kümmelöl, Kuminöl, Labdanumöl, Lavendelöl, Lemongrasöl, Lindenblütenöl, Limettenöl, Mandarinenöl, Melissenöl, Minzöl, Moschuskörneröl, Muskatelleröl, Myrrhenöl, Nelkenöl, Neroliöl, Niaouliöl, Olibanumöl, Orangenblütenöl, Orangenschalenöl, Origanumöl, Palmarosaöl, Patschuliöl, Perubalsamöl, Petitgrainöl, Pfefferöl, Pfefferminzöl, Pimentöl, Pine-Öl, Rosenöl, Rosmarinöl, Salbeiöl, Sandelholzöl, Sellerieöl, Spiköl, Sternanisöl, Terpentinöl, Thujaöl, Thymianöl, Verbenaöl, Vetiveröl, Wacholderbeeröl, Wermutöl, Wintergrünöl, Ylang-Ylang-Öl, Ysop-Öl, Zimtöl, Zimtblätteröl, Zitronellöl, Zitronenöl sowie Zypressenöl sowie Ambrettolid, Ambroxan, alpha- Amylzimtaldehyd, Anethol, Anisaldehyd, Anisalkohol, Anisol, Anthranilsäuremethylester, Acetophenon, Benzylaceton, Benzaldehyd, Benzoesäureethylester, Benzophenon, Benzylalkohol, Benzylacetat, Benzylbenzoat, Benzylformiat, Benzylvalerianat, Borneol, Bornylacetat, Boisambrene forte, alpha- Bromstyrol, n-Decylaldehyd, n-Dodecylaldehyd, Eugenol, Eugenolmethylether, Eukalyptol, Farnesol, Fenchon, Fenchylacetat, Geranylacetat, Geranylformiat, Heliotropin, Heptincarbonsäuremethylester, Heptaldehyd, Hydrochinon-Dimethylether, Hydroxyzimtaldehyd, Hydroxyzimtalkohol, Indol, Iran, Isoeugenol, Isoeugenolmethylether, Isosafrol, Jasmon, Kampfer, Karvakrol, Karvon, p- Kresolmethylether, Cumarin, p-Methoxyacetophenon, Methyl-n-amylketon,The fragrances of vegetable origin include essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, citrus oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, guajun oil, gourd oil, gjajun oil, galbanum oil, gourd oil, gjajun oil , Ginger oil, iris oil, jasmine oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemon linden oil, almond blossom oil , Muscatel oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange blossom oil, orange peel oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, celery oil, sage oil, starch oil, rosemary oil, sandstone oil, rosemary oil , Turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper oil, W ermut oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil as well as ambrettolide, ambroxan, alpha-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, benzyl acetophenone, methyl ester, benzyl acetophenone Benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, boisambrene forte, alpha-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptyl acetate, geranium acid ethyl acetate, geranium acid ethyl acetate, geranium acetyl acetate, fenchone, fencheptanyol , Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamic alcohol, indole, Iran, isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone,
Methylanthranilsäuremethylester, p-Methylacetophenon, Methylchavikol, p-Methylchinolin, Methyl-beta- naphthylketon, Methyl-n-nonylacetaldehyd, Methyl-n-nonylketon, Muskon, beta-Naphtholethylether, beta-Naphthol-methylether, Nerol, n-Nonylaldehyd, Nonylalkohol, n-Octylaldehyd, p-Oxy-Acetophenon, Pentadekanolid, beta-Phenylethylalkohol, Phenylessigsäure, Pulegon, Safrol, Salicylsäureisoamylester, Salicylsäuremethylester, Salicylsäurehexylester,Methyl anthranilic acid methyl ester, p-methylacetophenone, methylchavikol, p-methylquinoline, methyl-betanaphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muskon, beta-naphthol ethyl ether, beta-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, beta-phenylethyl alcohol, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate,
Salicylsäurecyclohexylester, Santalol, Sandelice, Skatol, Terpineol, Thymen, Thymol, Troenan, gamma- Undelacton, Vanillin, Veratrumaldehyd, Zimtaldehyd, Zimtalkohol, Zimtsäure, Zimtsäureethylester, Zimtsäurebenzylester, Diphenyloxid, Limonen, Linalool, Linalylacetat und - Propionat, Melusat, Menthol, Menthon, Methyl-n-heptenon, Pinen, Phenylacetaldehyd, Terpinylacetat, Citral, Citronellal, sowie Mischungen daraus. Für die Verlängerung der Aktivstoffwirkung, insbesondere der verlängerten Duftwirkung hat es sich als vorteilhaft erwiesen, den Aktivstoff c), insbesondere den Duftstoff zu verkapseln. In einer entsprechenden Ausführungsform wird zumindest ein Teil des Duftstoffs in verkapselter Form (Duftstoffkapseln), insbesondere in Mikrokapseln, eingesetzt. Es kann aber auch der gesamte Duftstoff in verkapselter Form eingesetzt werden. Bei den Mikrokapseln kann es sich um wasserlösliche und/oder wasserunlösliche Mikrokapseln handeln. Es können beispielsweise Melamin-Harnstoff-Formaldehyd- Mikrokapseln, Melamin-Formaldehyd-Mikrokapseln, Harnstoff-Formaldehyd-Mikrokapseln oder Stärke- Mikrokapseln eingesetzt werden. „Duftstoffvorläufer“ bezieht sich auf Verbindungen, die erst nach chemischer Umwandlung/Spaltung, typischerweise durch Einwirkung von Licht oder anderen Umgebungsbedingungen, wie pH-Wert, Temperatur, etc., den eigentlichen Duftstoff freisetzen. Derartige Verbindungen werden häufig auch als Duftspeicherstoffe oder„Pro-Fragrance“ bezeichnet. Salicylic acid cyclohexyl ester, santalol, sandelice, skatol, terpineol, thymen, thymol, troenan, gamma- undelactone, vanillin, veratrumaldehyde, cinnamaldehyde, cinnamic alcohol, cinnamic acid, ethyl cinnamate, methyl cinnamate, methyl cinnamate, lenthic acid benzyl ester, limonate, benzyl acetate, lime methyl acetate, benzyl esters, benzyl esters, benzyl esters, benzyl esters, benzyl esters, benzyl esters, lime acetyl acetate, benzyl esters , Methyl-n-heptenone, pinene, phenylacetaldehyde, terpinylacetate, citral, citronellal, and mixtures thereof. For the extension of the active substance effect, in particular the extended fragrance effect, it has proven advantageous to encapsulate the active substance c), in particular the fragrance substance. In a corresponding embodiment, at least part of the fragrance is used in encapsulated form (fragrance capsules), in particular in microcapsules. However, the entire fragrance can also be used in encapsulated form. The microcapsules can be water-soluble and / or water-insoluble microcapsules. For example, melamine-urea-formaldehyde microcapsules, melamine-formaldehyde microcapsules, urea-formaldehyde microcapsules or starch microcapsules can be used. “Fragrance precursors” refers to compounds that only release the actual fragrance after chemical conversion / cleavage, typically through exposure to light or other environmental conditions, such as pH, temperature, etc. Such compounds are often referred to as fragrance storage substances or “pro-fragrance”.
Für die spätere Wirkung der Formkörper hat es sich als vorteilhaft erwiesen, wenn der Aktivstoff c) ausgewählt ist aus der Gruppe der Parfümöle und Duftstoffkapseln. Ganz besonders bevorzugt ist der Einsatz einer Kombination aus Parfümöl und Duftstoffkapsel. For the subsequent effect of the shaped bodies, it has proven to be advantageous if the active ingredient c) is selected from the group of perfume oils and fragrance capsules. The use of a combination of perfume oil and fragrance capsule is very particularly preferred.
Anders als in herkömmlichen Aktivstoffpastillen, welche zu einem wesentlichen Teil auf polymeren Trägermaterialien beruhen, enthalten die in dieser Anmeldung beschriebenen aktivstoffhaltigen Formkörper als wesentlichen weiteren Bestandteil mindestens ein Lösungsmittel d). In contrast to conventional active ingredient lozenges, which are based to a substantial extent on polymeric carrier materials, the active ingredient-containing shaped bodies described in this application contain at least one further component d) as an essential component.
Geeignete Lösungsmittel sind ausgewählt aus der Gruppe Ethanol, n-Propanol, i-Propanol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin, Proplyencarbonat, Diglykol, Propyldiglycol, Butyldiglykol, Hexylenglycol, Diethylenglykolethylether, Diethylenglykolmethylether, Diethylenglykol-n- butylether, Diethylenglykolhexylether, Diethylenglykol-n-butyletheracetat, Ethylenglykolpropylether, Ethylenglykol-n-butylether, Ethylenglykolhexylether, Ethylenglykol-n-butyletheracetat, T riethylenglycol, T riethylenglykolmethylether, T riethyleng lykolethylether, T riethylenglykol-n-butylether,Suitable solvents are selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, propylene carbonate, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol methyl ether, diethylene glycol ether, diethylene glycol , Diethylene glycol n-butyl ether acetate, ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, ethylene glycol n-butyl ether acetate, triethylene glycol, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol ether,
Ethylenglykolphenylether, Propylenglykolmethylether, Dipropylenglykolmethylether,Ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether,
Tripropylenglycolmethylether, Propylenglycolmethyletheracetat, Dipropylenglykol-methyletheracetat, propylenglykol-n-propylether, Dipropylenglykol-n-propylether, Propylenglycol-n-butylether,Tripropylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether,
Dipropylenglycol-n-butylether, Tripropylenglykol-n-butylether, Propylenglykolphenylether,Dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether,
Propylenglykoldiacetat, Dipropylenglykoldimethylether, Methoxytriglykol, Ethoxytriglykol, Butoxytriglykol, Glycerincarbonat, Propylencarbonat, 1 -Butoxyethoxy-2-propanol, 3-Methyl-3- methoxybutanol, Propylen-glykol-t-butylether, Di-n-octylether, vorzugsweise aus der Gruppe Glycerin, Propylenglycol, Ethanol, Isoporpanol, Methylpropanoldiol, Triethylenglycol, Propylencarbonat, Glycerincarbonat, 3-Methyl-3-methoxybutanol und 2-Methylpropan-1 ,3-diol. Propylene glycol diacetate, dipropylene glycol dimethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, glycerine carbonate, propylene carbonate, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether, preferably from Propylene glycol, ethanol, isoporpanol, methyl propanol diol, triethylene glycol, propylene carbonate, glycerine carbonate, 3-methyl-3-methoxybutanol and 2-methylpropane-1,3-diol.
Es wurde festgestellt, dass die Herstellbarkeit, Konfektionierung und Handhabung der aktivstoffhaltigen Formkörper außer durch die weiter oben beschriebenen bevorzugten Gelbildner a) und b) weiterhin auch durch die Auswahl spezifischer Lösungsmittel d) in vorteilhafter Weise beeinflusst werden können. Eine erste Gruppe besonders bevorzugter aktivstoffhaltiger Formkörper sind dadurch gekennzeichnet, dass das Lösungsmittel d) ein Lösungsmittel aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglycole, insbesondere der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, besonders bevorzugt aus der Gruppe PEG 200 und PEG 400 umfasst. It was found that the producibility, packaging and handling of the active substance-containing shaped bodies can be influenced in an advantageous manner not only by the preferred gel formers a) and b) described above, but also by the selection of specific solvents d). A first group of particularly preferred active substance-containing moldings is characterized in that the solvent d) is a solvent from the group of polyalkylene glycols liquid at room temperature (20 ° C), in particular polyalkylene glycols liquid at room temperature (20 ° C), particularly preferably from the PEG group 200 and PEG 400 includes.
Eine zweite Gruppe besonders bevorzugter aktivstoffhaltiger Formkörper sind dadurch gekennzeichnet, dass das Lösungsmittel d) ein Lösungsmittel aus der Gruppe der bei Raumtemperatur (20°C) flüssigen organischen Polyole, insbesondere der bei Raumtemperatur (20°C) flüssigen Diole, besonders bevorzugt aus der Gruppe 2-Methyl-1 ,3-Propandiol (MPDiol) und 3-Methyl-1 ,3-Butandiol (Isopentyldiol) umfasst. A second group of particularly preferred active substance-containing moldings is characterized in that the solvent d) is a solvent from the group of organic polyols liquid at room temperature (20 ° C.), in particular diols liquid at room temperature (20 ° C.), particularly preferably from the group 2-methyl-1,3-propanediol (MPDiol) and 3-methyl-1,3-butanediol (isopentyldiol).
Weitere Gruppen besonders bevorzugter aktivstoffhaltiger Formkörper umfassen als Lösungsmittel d) Glycerin oder Triacetin oder Wasser. Further groups of particularly preferred active substance-containing molded bodies include as solvents d) glycerol or triacetin or water.
Als technisch besonders vorteilhaft haben sich Mischungen von Lösungsmitteln erwiesen, wobei insbesondere die Kombination von Wasser und 3-Methyl-1 ,3-Butandiol (Isopentyldiol), insbesondere jedoch die Kombination von Wasser, Glycerin und 3-Methyl-1 ,3-Butandiol zu nennen sind. Mixtures of solvents have proven to be technically particularly advantageous, in particular the combination of water and 3-methyl-1,3-butanediol (isopentyldiol), but in particular the combination of water, glycerol and 3-methyl-1,3-butanediol are called.
Der Gewichtsanteil an Lösungsmittel d) am Gesamtgewicht aktivstoffhaltiger Formkörper beträgt bevorzugt 10 bis 98 Gew.-%, besonders bevorzugt 40 bis 97 Gew.-% und insbesondere 60 bis 96 Gew.- %. The proportion by weight of solvent d) in the total weight of active substance-containing shaped bodies is preferably 10 to 98% by weight, particularly preferably 40 to 97% by weight and in particular 60 to 96% by weight.
Zusammenfassend weisen besonders bevorzugte aktivstoffhaltige Formkörper ein Gewicht von 0,2 bis 20 g und umfassen, bezogen auf sein Gesamtgewicht In summary, particularly preferred active substance-containing shaped bodies have a weight of 0.2 to 20 g and comprise, based on its total weight
a) 0,1 bis 10 Gew.-% Dibenzylidensorbitol; a) 0.1 to 10% by weight of dibenzylidene sorbitol;
b) 0,1 bis 12 Gew.-% Polyvinylalkohol mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; b) 0.1 to 12% by weight of polyvinyl alcohol with a molar mass of 10,000 g / mol to 200,000 g / mol;
c) 0,1 bis 20 Gew.-% vorzugsweise verkapselten Duftstoff; c) 0.1 to 20% by weight, preferably encapsulated fragrance;
d) 10 bis 96 Gew.-% Lösungsmittel. d) 10 to 96% by weight of solvent.
Die aktivstoffhaltigen Formkörper umfassen vorzugsweise weniger als 10 Gew.-%, bevorzugt weniger als 8 Gew.-%, besonders bevorzugt weniger als 4 Gew.-% und insbesondere weniger als 1 Gew.-% Tensid. Ganz besonders bevorzugte aktivstoffhaltige Formkörper umfassen kein Tensid. The active substance-containing shaped bodies preferably comprise less than 10% by weight, preferably less than 8% by weight, particularly preferably less than 4% by weight and in particular less than 1% by weight of surfactant. Very particularly preferred active substance-containing moldings do not comprise any surfactant.
Weitere besonders bevorzugte Formulierungen für aktivstoffhaltige Formkörper sind den nachfolgenden Tabellen zu entnehmen (Angabe in Gew.-% bezogen auf das Gesamtgewicht der Formkörper). Die aktivstoffhaltigen Formkörper dieser Tabellen umfassen vorzugsweise weniger als 10 Gew.-%, bevorzugt weniger als 8 Gew.-%, besonders bevorzugt weniger als 4 Gew.-% und insbesondere weniger als 1 Gew.-% Tensid. Weiterhin ist es bevorzugt wenn die Formkörper ein Gewicht von 0,2 bis 20 g aufweisen. Further particularly preferred formulations for tablets containing active substances can be found in the tables below (data in% by weight based on the total weight of the tablets). The active substance-containing moldings in these tables preferably comprise less than 10% by weight, more preferably less than 8% by weight, particularly preferably less than 4% by weight and in particular less than 1% by weight of surfactant. It is also preferred if the shaped bodies have a weight of 0.2 to 20 g.
Figure imgf000017_0001
Figure imgf000017_0001
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Figure imgf000017_0003
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* aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, der bei Raumtemperatur (20°C) flüssigen Diole, Gylcerin, Triacetin und Wasser * from the group of polyalkylene glycols liquid at room temperature (20 ° C), diols liquid at room temperature (20 ° C), glycerine, triacetin and water
Figure imgf000017_0004
Figure imgf000017_0004
* aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, der bei Raumtemperatur (20°C) flüssigen Diole, Gylcerin, Triacetin und Wasser
Figure imgf000018_0001
* from the group of polyalkylene glycols liquid at room temperature (20 ° C), diols liquid at room temperature (20 ° C), glycerine, triacetin and water
Figure imgf000018_0001
Figure imgf000018_0002
Figure imgf000018_0002
Figure imgf000018_0003
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* aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, der bei Raumtemperatur (20°C) flüssigen Diole, Gylcerin, Triacetin und Wasser * from the group of polyalkylene glycols liquid at room temperature (20 ° C), diols liquid at room temperature (20 ° C), glycerine, triacetin and water
Figure imgf000018_0004
Figure imgf000018_0004
* aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, der bei Raumtemperatur (20°C) flüssigen Diole, Gylcerin, Triacetin und Wasser * from the group of polyalkylene glycols liquid at room temperature (20 ° C), diols liquid at room temperature (20 ° C), glycerine, triacetin and water
Figure imgf000018_0005
Figure imgf000019_0001
Figure imgf000018_0005
Figure imgf000019_0001
Figure imgf000019_0002
Figure imgf000019_0002
* aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, der bei Raumtemperatur (20°C) flüssigen Diole, Gylcerin, Triacetin und Wasser * from the group of polyalkylene glycols liquid at room temperature (20 ° C), diols liquid at room temperature (20 ° C), glycerine, triacetin and water
Figure imgf000019_0003
Figure imgf000019_0003
* aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, der bei Raumtemperatur (20°C) flüssigen Diole, Gylcerin, Triacetin und Wasser * from the group of polyalkylene glycols liquid at room temperature (20 ° C), diols liquid at room temperature (20 ° C), glycerine, triacetin and water
Figure imgf000019_0004
Figure imgf000019_0004
Figure imgf000019_0005
Figure imgf000020_0001
Figure imgf000019_0005
Figure imgf000020_0001
* aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, der bei Raumtemperatur (20°C) flüssigen Diole, Gylcerin, Triacetin und Wasser * from the group of polyalkylene glycols liquid at room temperature (20 ° C), diols liquid at room temperature (20 ° C), glycerine, triacetin and water
Figure imgf000020_0002
Figure imgf000020_0002
* aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, der bei Raumtemperatur (20°C) flüssigen Diole, Gylcerin, Triacetin und Wasser * from the group of polyalkylene glycols liquid at room temperature (20 ° C), diols liquid at room temperature (20 ° C), glycerine, triacetin and water
Figure imgf000020_0003
Figure imgf000020_0003
Figure imgf000020_0004
Figure imgf000020_0004
Figure imgf000020_0005
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Figure imgf000020_0006
Figure imgf000021_0001
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Figure imgf000021_0001
Der aktivstoffhaltige Formkörper weist bevorzugt ein Speichermodul G‘ mit 103 Pascal bis 108 Pascal, stärker bevorzugt mit 104 Pascal bis 106 Pascal, gemessen mit einem Rotationsrheometer unter Verwendung eines Kegel-Platte-Messystems mit 40 mm Durchmesser und 2° Öffnungswinkel bei einer Temperatur von 20°C, auf. The active substance-containing shaped body preferably has a storage modulus G 'of 10 3 Pascal to 10 8 Pascal, more preferably 10 4 Pascal to 10 6 Pascal, measured with a rotational rheometer using a cone-plate measuring system with a diameter of 40 mm and an opening angle of 2 ° a temperature of 20 ° C.
Die rheologische Charakterisierung wird im Rahmen dieser Erfindung mit einem Rotationsrheometer, beispielsweise Firma TA-Instruments, Typ AR G2, Firma Malvern„Kinexus“, unter Verwendung eines Kegel-Platte-Messystems mit 40 mm Durchmesser und 2° Öffnungswinkel bei einer Temperatur von 20°C durchgeführt. Hierbei handelt es sich um schubspannungskontrollierte Rheometer. Die Bestimmung kann jedoch auch mit anderen Instrumenten oder Messgeometrien vergleichbarer Spezifikationen durchgeführt werden. The rheological characterization is carried out in the context of this invention with a rotational rheometer, for example from TA-Instruments, type AR G2, from Malvern "Kinexus", using a cone-plate measuring system with a diameter of 40 mm and a 2 ° opening angle at a temperature of 20 ° C performed. These are shear stress controlled rheometers. The determination can, however, also be carried out with other instruments or measurement geometries with comparable specifications.
Die Messung des Speichermoduls (Abkürzung: G‘) und des Verlustmoduls (Abkürzung: G“) (jeweils Einheit: Pa) erfolgte mit oben beschriebener Geräteausstattung in einem Experiment mit oszillierender Deformation. Dazu wird zunächst in einem „Stress-Sweep-Experiment“ der linear viskoelastische Bereich bestimmt. Hierbei wird bei einer konstanten Frequenz von z.B. 1 Hz die Schubspannungsamplitude gesteigert. Die Module G‘ und G“ werden in einem doppeltlogarithmischen Plot aufgetragen. Auf der x-Achse kann wahlweise die Schubspannungsamplitude oder die (daraus resultierende) Deformationsamplitude aufgetragen werden. Der Speichermodul G‘ ist dabei unterhalb einer gewissen Schubspannungsamplitude bzw. Deformationsamplitude konstant, oberhalb davon bricht er zusammen. Der Knickpunkt wird zweckmäßig durch Anlegen von Tangenten an die beiden Kurve nabschnitte bestimmt. Die entsprechende Deformationsamplitude bzw. Schubspannungsamplitude wird üblicherweise als „kritische Deformation“ bzw. „kritische Schubspannung“ bezeichnet. The measurement of the storage modulus (abbreviation: G Verlust) and the loss modulus (abbreviation: G “) (each unit: Pa) was carried out with the equipment described above in an experiment with oscillating deformation. For this purpose, the linear viscoelastic range is first determined in a “stress sweep experiment”. The shear stress amplitude is increased at a constant frequency of e.g. 1 Hz. The modules G ‘and G“ are plotted in a double logarithmic plot. The shear stress amplitude or the (resulting) deformation amplitude can optionally be plotted on the x-axis. The storage modulus G ‘is constant below a certain shear stress amplitude or deformation amplitude, above which it collapses. The kink point is expediently determined by applying tangents to the two curve sections. The corresponding deformation amplitude or shear stress amplitude is usually referred to as “critical deformation” or “critical shear stress”.
Zur Bestimmung der Frequenzabhängigkeit der Module wird eine Frequenzrampe, z.B. zwischen 0,01 Hz und 10 Hz bei einer konstanten Deformationsamplitude gefahren. Die Deformationsamplitude muss dabei so gewählt werden, dass sie im linearen Bereich liegt, d.h. unterhalb der o.g. kritischen Deformation liegt. Im Fall der erfindungsgemäßen Zusammensetzungen hat sich eine Deformationsamplitude von 0,1 % als geeignet erwiesen. Die Module G‘ und G“ werden in einem doppellogarithmischen Plot gegen die Frequenz aufgetragen. To determine the frequency dependence of the modules, a frequency ramp, e.g. between 0.01 Hz and 10 Hz, is run at a constant deformation amplitude. The deformation amplitude must be chosen so that it is in the linear range, i.e. below the critical deformation mentioned above. In the case of the compositions according to the invention, a deformation amplitude of 0.1% has proven to be suitable. The modules G ‘and G“ are plotted against the frequency in a double logarithmic plot.
Als bevorzugte optionale Bestandteile umfassen aktivstoffhaltige Formkörper Farbstoffe, Konservierungsmittel oder Bitterstoffe. Um den ästhetischen Eindruck der aktivstoffhaltigen Formkörper zu verbessern umfassen diese vorzugsweise mindestens einen Farbstoff. Bevorzugt ist es dabei, dass die Formkörper mindestens einen wasserlöslichen Farbstoff, besonders bevorzugt einen wasserlöslichen Polymerfarbstoff umfassen. Preferred optional constituents include tablets containing active ingredients, dyes, preservatives or bitter substances. In order to improve the aesthetic impression of the active substance-containing shaped bodies, they preferably comprise at least one dye. It is preferred that the shaped bodies comprise at least one water-soluble dye, particularly preferably a water-soluble polymer dye.
Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, sollten eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Wasch- oder Reinigungsmittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber Textilfasern aufweisen, um diese nicht anzufärben. Preferred dyes, the choice of which does not present any difficulty to the person skilled in the art, should have high storage stability and insensitivity to the other ingredients of the detergents or cleaning agents and to light and not have any pronounced substantivity towards textile fibers in order not to stain them.
Der Farbstoff ist ein üblicher Farbstoff, der für unterschiedliche Wasch- oder Reinigungsmittel eingesetzt werden kann. Vorzugsweise ist der Farbstoff ausgewählt aus Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51 , Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1 , Acid Yellow 3 (CI 47005), Acid Yellow 1 1 , Acid Yellow 23 (CI 19140), Acid Yellow 3, Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5:2 (CI 42051 :2), Food Red 7(01 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (C1 15985), Food Yellow 4 (C1 19140), Reactive Green 12, Solvent Green 7 (CI 59040). The dye is a common dye that can be used for various detergents or cleaning agents. The dye is preferably selected from Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 ( CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1, Acid Yellow 3 (CI 47005), Acid Yellow 1 1, Acid Yellow 23 (CI 19140), Acid Yellow 3, Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5: 2 (CI 42051: 2), Food Red 7 (01 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (C1 15985), Food Yellow 4 (C1 19140), Reactive Green 12, Solvent Green 7 (CI 59040).
Besonders bevorzugte Farbstoffe sind wasserlösliche Säurefarbstoffe, beispielsweise Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet48, Acid Blue 80(01 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570), Acid Green 81 . Particularly preferred dyes are water-soluble acid dyes, for example Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet48, Acid Blue 80 (01 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570), Acid Green 81.
Ebenso bevorzugt eingesetzt werden auch wasserlösliche Direktfarbstoffe, beispielsweise Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) und wasserlösliche Reaktiv-Farbstoffe, beispielsweise Reactive Green 12, sowie die Farbstoffe Food Yellow 3 (CI 15985), Acid Yellow 184. Water-soluble direct dyes, for example Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) and water-soluble reactive dyes, for example Reactive Green 12, and the dyes Food Yellow 3 (CI 15985), Acid Yellow 184 are also preferably used.
Ebenso bevorzugt eingesetzt werden wässrige Dispersionen folgender Pigment-Farbstoffe, Pigment Black 7 (CI 77266), Pigment Blue 15 (CI 74160), Pigment Blue 15:1 (CI 74160), Pigment Blue 15:3 (CI 74160), Pigment Green 7 (CI 74260), Pigment Orange 5, Pigment Red 1 12 (CI 12370), Pigment Red 1 12 (CI 12370), Pigment Red 122 (CI 73915), Pigment Red 179 (CI 71 130), Pigment Red 184 (CI 12487), Pigment Red 188 (CI 12467), Pigment Red 4 (CI 12085), Pigment Red 5 (CI 12490), Pigment Red 9, Pigment Violet 23 (CI 51319), Pigment Yellow 1 (CI 28 1 1680), Pigment Yellow 13 (CI 21 100), Pigment Yellow 154, Pigment Yellow 3 (CI 1 1710), Pigment Yellow 74, Pigment Yellow 83 (CI 21 108), Pigment Yellow 97. In bevorzugten Ausführungsformen werden folgende Pigmentfarbstoffe in Form von Dispersionen eingesetzt: Pigment Yellow 1 (CI 1 1680), Pigment Yellow 3 (C1 1 1710), Pigment Red 1 12 (CI 12370), Pigment Red 5 (CI 12490), Pigment Red 181 (CI 73360), Pigment Violet 23 (CI 51319), Pigment Blue 15:1 (CI 74160), Pigment Green 7 (CI 74260), Pigment Black 7 (CI 77266). In ebenfalls bevorzugten Ausführungsformen werden wasserlösliche Polymerfarbstoffe, beispielsweise Liquitint, Liquitint Blue HP, Liquitint Blue MC, Liquitint Blue 65, Liquitint Cyan 15, Liquitint Patent Blue.Liquitint Violet 129, Liquitint Royal Blue, Liquitint Experimental Yellow 8949- 43, Liquitint Green HMC, Liquitint Yellow LP, Liquitint Yellow II und Mischungen daraus eingesetzt. Aqueous dispersions of the following pigment dyes, Pigment Black 7 (CI 77266), Pigment Blue 15 (CI 74160), Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Green 7 are also preferably used (CI 74260), Pigment Orange 5, Pigment Red 1 12 (CI 12370), Pigment Red 1 12 (CI 12370), Pigment Red 122 (CI 73915), Pigment Red 179 (CI 71 130), Pigment Red 184 (CI 12487 ), Pigment Red 188 (CI 12467), Pigment Red 4 (CI 12085), Pigment Red 5 (CI 12490), Pigment Red 9, Pigment Violet 23 (CI 51319), Pigment Yellow 1 (CI 28 1 1680), Pigment Yellow 13 (CI 21 100), Pigment Yellow 154, Pigment Yellow 3 (CI 1 1710), Pigment Yellow 74, Pigment Yellow 83 (CI 21 108), Pigment Yellow 97. In preferred embodiments, the following pigment dyes are used in the form of dispersions: pigment Yellow 1 (CI 1 1680), Pigment Yellow 3 (C1 1 1710), Pigment Red 1 12 (CI 12370), Pigment Red 5 (CI 12490), Pigment Red 181 (CI 73360), Pigment Violet 23 (CI 51319), Pigment Blue 15: 1 (CI 7 4160), Pigment Green 7 (CI 74260), Pigment Black 7 (CI 77266). In also preferred embodiments, water-soluble polymer dyes, for example Liquitint, Liquitint Blue HP, Liquitint Blue MC, Liquitint Blue 65, Liquitint Cyan 15, Liquitint Patent Blue, Liquitint Violet 129, Liquitint Royal Blue, Liquitint Experimental Yellow 8949-43, Liquitint Green HMC, Liquitint Yellow LP, Liquitint Yellow II and mixtures thereof are used.
Zur Gruppe der ganz besonders bevorzugten Farbstoffe zählen Acid Blue 3, Acid Yellow 23, Acid Red 33, Acid Violet 126, Liquitint Yellow LP, Liquitint Cyan 15, Liquitint Blue HP und Liquitint Blue MC. The group of very particularly preferred dyes includes Acid Blue 3, Acid Yellow 23, Acid Red 33, Acid Violet 126, Liquitint Yellow LP, Liquitint Cyan 15, Liquitint Blue HP and Liquitint Blue MC.
Der Gewichtsanteil des Farbstoffs am Gesamtgewicht der aktivstoffhaltigen Formkörper beträgt vorzugsweise 0,001 bis 0,5 Gew.-%, bevorzugt 0,002 bis 0,2 Gew.-%. The proportion by weight of the dye in the total weight of the active substance-containing shaped bodies is preferably from 0.001 to 0.5% by weight, more preferably from 0.002 to 0.2% by weight.
Der Zusatz von Bitterstoffen dient in erster Linie der Vermeidung einer oralen Aufnahme der aktivstoffhaltigen Formkörper. The addition of bitter substances primarily serves to avoid oral ingestion of the tablets containing active substances.
Bevorzugte Formkörper enthalten mindestens einen Bitterstoff in einer Menge von 0,0001 bis 0,1 Gew.- %, bezogen auf das Gesamtgewicht der Zusammensetzung. Besonders bevorzugt sind Mengen von 0,0005 bis 0,02 Gew.-%. Gemäß der vorliegenden Erfindung sind insbesondere solche Bitterstoffe bevorzugt, die in Wasser bei 20 °C zu mindestens 5 g/l löslich sind. Hinsichtlich einer unerwünschten Wechselwirkung mit den ebenfalls in der Zusammensetzung enthaltenen Duft-Komponenten, insbesondere einer Veränderung der vom Verbraucher wahrgenommenen Duftnote, haben die ionogenen Bitterstoffe sich den nichtionogenen als überlegen erwiesen. Ionogene Bitterstoffe, bestehend aus organischem(n) Kation(en) und organischem(n) Anion(en), sind folglich für die erfindungsgemäße Zusammensetzung bevorzugt. Preferred moldings contain at least one bitter substance in an amount of 0.0001 to 0.1% by weight, based on the total weight of the composition. Quantities from 0.0005 to 0.02% by weight are particularly preferred. According to the present invention, those bitter substances are particularly preferred which are soluble in water at 20 ° C. to the extent of at least 5 g / l. With regard to an undesirable interaction with the fragrance components also contained in the composition, in particular a change in the fragrance note perceived by the consumer, the ionic bitter substances have proven to be superior to the non-ionic ones. Ionic bitter substances consisting of organic cation (s) and organic anion (s) are consequently preferred for the composition according to the invention.
In verschiedenen Ausführungsformen handelt es sich bei dem mindestens einen Bitterstoff daher um einen ionogenen Bitterstoff. In various embodiments, the at least one bitter substance is therefore an ionogenic bitter substance.
Im Kontext der vorliegenden Erfindung hervorragend geeignet sind quartäre Ammoniumverbindungen, die sowohl im Kation als auch im Anion eine aromatische Gruppe enthalten. In verschiedenen Ausführungsformen handelt es sich bei dem mindestens einen Bitterstoff daher um eine quartäre Ammoniumverbindungen. In the context of the present invention, quaternary ammonium compounds which contain an aromatic group both in the cation and in the anion are eminently suitable. In various embodiments, the at least one bitter substance is therefore a quaternary ammonium compound.
Eine geeignete quartäre Ammoniumverbindung ist, beispielsweise, ohne Einschränkung, das kommerziell z.B. unter den Warenzeichen Bitrex® und Indige-stin® erhältliche Benzyldiethyl((2,6- xylylcarbamoyl)methyl)ammoniumbenzoat. Diese Verbindung ist auch unter der Bezeichnung Denatonium Benzoate bekannt. In verschiedenen Ausführungsformen handelt es sich bei dem mindestens einen Bitterstoff um Benzyldiethyl((2,6-xylylcarbamoyl)methyl)ammoniumbenzoat (Bitrex®). Falls Bitrex® eingesetzt wird, sind am meisten Mengen bis 0,002 Gew.-% bevorzugt. Dabei sind die Angaben jeweils auf den Aktivstoffgehalt bezogen. Ein weiterer Gegenstand dieser Anmeldung ist ein Verfahren zur Herstellung eines Formkörpers, umfassend die Schritte A suitable quaternary ammonium compound is, for example, without restriction, benzyldiethyl ((2,6-xylylcarbamoyl) methyl) ammonium benzoate, which is commercially available, for example, under the trademarks Bitrex® and Indige-stin®. This compound is also known as Denatonium Benzoate. In various embodiments, the at least one bitter substance is benzyl diethyl ((2,6-xylylcarbamoyl) methyl) ammonium benzoate (Bitrex®). If Bitrex® is used, most amounts up to 0.002% by weight are preferred. The information is based on the active substance content. This application also relates to a method for producing a molded body, comprising the steps
a) Bereitstellung einer ersten Zubereitung aus mindestens einem wasserlöslichen organischen Lösungsmittel sowie mindestens einem niedermolekularen Gelbildner mit einer molaren Masse bis 2000 g/mol; a) providing a first preparation of at least one water-soluble organic solvent and at least one low molecular weight gel former with a molar mass of up to 2000 g / mol;
b) Bereitstellung einer zweiten Zubereitung aus Wasser und/oder mindestens einem wasserlöslichen organischen Lösungsmittel sowie mindestens einem polymeren Gelbildner mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; b) providing a second preparation of water and / or at least one water-soluble organic solvent and at least one polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol;
c) Vermischung der ersten Zubereitung und der zweiten Zubereitung; c) mixing the first preparation and the second preparation;
d) Ausbildung formstabiler, duftstoffhaltiger Formkörper d) Formation of dimensionally stable, fragrance-containing molded bodies
wobei in which
i) der ersten Zubereitung in Schritt a) und/oder i) the first preparation in step a) and / or
ii) der zweiten Zubereitung in Schritt b) und/oder ii) the second preparation in step b) and / or
iii) dem Gemisch der ersten Zubereitung und der zweiten Zubereitung in Schritt c) ein Aktivstoff beigefügt wird. iii) an active ingredient is added to the mixture of the first preparation and the second preparation in step c).
Zur Beschleunigung und Vereinfachung der Verfahrensführung ist es bevorzugt, dass die erste Zubereitung in Schritt a) eine Temperatur zwischen 30°C und 180°C, vorzugsweise zwischen 60°C und 160°C aufweist. Alternativ oder in Kombination mit dieser Temperaturführung weist die zweite Zubereitung in Schritt b) aus den gleichen technischen Gründen vorzugsweise eine Temperatur zwischen 30°C und 90°C, insbesondere zwischen 40°C und 70°C auf. To accelerate and simplify the process, it is preferred that the first preparation in step a) has a temperature between 30.degree. C. and 180.degree. C., preferably between 60.degree. C. and 160.degree. Alternatively or in combination with this temperature control, the second preparation in step b) preferably has a temperature between 30.degree. C. and 90.degree. C., in particular between 40.degree. C. and 70.degree. C., for the same technical reasons.
Um eine räumlich kontrollierte Ausformung der Formkörper zu gewährleisten, wird das Gemisch in Schritt d) vorzugsweise in eine Form eingeleitet. Bei der Form kann es sich um eine beständige Gießform oder eine„verlorene“ Form (Mogultechnik) handeln. Bevorzugt sind beständige Gießformen. Diese Gießformen sind vorzugsweise aus metallischen oder polymeren Werkstoffen gefertigt. Bevorzugt ist der Einsatz polymerer Werkstoffe für die Gießform bzw. eine etwaige Beschichtung der Gießform. In order to ensure spatially controlled shaping of the shaped bodies, the mixture is preferably introduced into a mold in step d). The shape can be a permanent mold or a “lost” shape (Mughal technique). Durable casting molds are preferred. These casting molds are preferably made of metallic or polymeric materials. The use of polymeric materials for the casting mold or any coating on the casting mold is preferred.
Die Gießform kann einseitig offen oder geschlossen sein, wobei einseitig offene Gießformen bevorzugt sind. Werden einseitig offene Gießformen eingesetzt, weisen die resultierenden Formkörper bei ausreichend niedriger Viskosität der Gießmasse eine der offenen Oberseite entsprechende flache Oberseite auf. The casting mold can be open or closed on one side, casting molds open on one side being preferred. If casting molds that are open on one side are used, the resulting moldings have a flat top side corresponding to the open top side if the viscosity of the casting compound is sufficiently low.
Die Geometrie der Gießform (und damit des durch das Verfahren hergestellten Formköpers) ist in weiten Bereichen variabel. Sie beeinflusst nicht allein die spätere Produktästhetik sondern darüber hinaus auch die Herstellbarkeit des Formkörpers und dessen späteres Auflösungsverhalten. Unter dem Begriff der Prozessierbarkeit wird beispielsweise das Erstarrungsverhalten des Formkörpers, dessen Herauslösbarkeit aus der Gießform sowie seine Transport- und Lagerfähigkeit erfasst. In einer alternativen Verfahrensvariante wird das Gemisch in Schritt d) durch Vertropfen auf eine Oberfläche portioniert und nachfolgend auf dieser Oberfläche ausgeformt. Im Rahmen dieser Verfahrensvariante ist es besonders bevorzugt, das Gemisch in Schritt d) durch Vertropfen auf ein Stahlband mittels eines Tropfenformers mit rotierender, gelochter Außentrommel zu portionieren und nachfolgend auf dieser Oberfläche auszuformen. The geometry of the casting mold (and thus of the molded body produced by the process) is variable over a wide range. It not only influences the later product aesthetics but also the manufacturability of the molded body and its later dissolution behavior. The term processability includes, for example, the solidification behavior of the molded body, its detachability from the casting mold and its transportability and storability. In an alternative variant of the method, the mixture is portioned in step d) by dripping onto a surface and then shaped on this surface. In the context of this variant of the method, it is particularly preferred to portion the mixture in step d) by dropping it onto a steel belt using a drop former with a rotating, perforated outer drum and then to shape it on this surface.
Zur Beschleunigung der Ausformung wird das Gemisch in Schritt d) vorzugsweise gekühlt. In order to accelerate the shaping, the mixture is preferably cooled in step d).
Ein Verfahren zur Reinigung einer textilen Oberfläche unter Einsatz eines zuvor beschriebenen Formkörpers ist ein weiterer Gegenstand dieser Anmeldung. A method for cleaning a textile surface using a molded body described above is a further subject of this application.
Im Rahmen dieser Anmeldung werden unter anderem die folgenden Mittel und Verfahren bereitgestellt: As part of this registration, the following means and methods are provided, among others:
1. Aktivstoffhaltiger Formkörper mit einem Gewicht von 0,2 bis 20 g, umfassend 1. Active substance-containing moldings with a weight of 0.2 to 20 g, comprising
a) mindestens einen niedermolekularen Gelbildner mit einer molaren Masse bis 2000 g/mol; b) mindestens einen polymeren Gelbildner mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; a) at least one low molecular weight gel former with a molar mass of up to 2000 g / mol; b) at least one polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol;
c) mindestens einen Aktivstoff; c) at least one active ingredient;
d) mindestens ein Lösungsmittel. d) at least one solvent.
2. Aktivstoffhaltiger Formkörper nach Punkt 1 , wobei der Formkörper ein Gewicht von 0,2 bis 10 g, vorzugsweise von 0,5 bis 5 g aufweist. 2. Active substance-containing shaped body according to item 1, wherein the shaped body has a weight of 0.2 to 10 g, preferably 0.5 to 5 g.
3. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei das Gewichtsverhältnis von niedermolekularem Gelbildner zu polymeren Gelbildner 10:1 bis 1 :20, vorzugsweise 8:1 bis 1 :15 und insbesondere 6:1 bis 1 :10 beträgt. 3. Active substance-containing molded body according to one of the preceding points, the weight ratio of low molecular weight gel former to polymeric gel former being 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10.
4. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der niedermolekulare Gelbildner eine molare Masse von 200 g/mol bis 2000 g/mol, bevorzugt von 200 g/mol bis 1000 g/mol aufweist. 4. Active substance-containing molded body according to one of the preceding points, the low molecular weight gel former having a molar mass of 200 g / mol to 2000 g / mol, preferably from 200 g / mol to 1000 g / mol.
5. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper bezogen auf sein Gesamtgewicht einen Gewichtsanteil an niedermolekularem Gebildner a) von 0,01 bis 15 Gew.- %, vorzugsweise von 0,1 bis 10 Gew.-% und insbesondere von 1 bis 4 Gew.-% aufweist. 5. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body, based on its total weight, has a proportion by weight of low molecular weight component a) of 0.01 to 15% by weight, preferably 0.1 to 10% by weight and in particular 1 to 4 wt .-%.
6. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der niedermolekulare Gelbildner a) ausgewählt ist aus der Gruppe der Benzylidenalditol-Verbindungen, Hydroxystearinsäure, hydrogeniertem Castoröl, Diarylamidocystin-Verbindung, N-(C8-C24)- Hydrocarbylglyconamid, Diketopiperazin-Verbindung, 2-Methyl-acrylsäure-2-ureido-ethylester und Mischungen davon. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei als niedermolekularer Gelbildner Dibenzylidensorbitol eingesetzt wird. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der polymere Gelbildner eine molare Masse von 10000 bis 40000 g/mol aufweist. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper bezogen auf sein Gesamtgewicht einen Gewichtsanteil an polymerem Gebildner b) von 0,01 bis 15 Gew.-%, vorzugsweise von 0,1 bis 12 Gew.-% und insbesondere von 1 bis 10 Gew.-% aufweist. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der polymere Gelbildner b) ausgewählt ist aus der Gruppe der 6. Aktivstoffhaltiger molding according to one of the preceding points, wherein the low-molecular gelling agent is a) selected from the group of Benzylidenalditol compounds, hydroxystearic acid, hydrogenated castor oil, Diarylamidocystin compound, N- (C8-C 24) - Hydrocarbylglyconamid, diketopiperazine compound, 2-methyl-acrylic acid-2-ureido-ethyl ester and mixtures thereof. Active substance-containing shaped body according to one of the preceding points, wherein dibenzylidene sorbitol is used as the low molecular weight gel former. Active substance-containing molded body according to one of the preceding points, the polymeric gel former having a molar mass of 10,000 to 40,000 g / mol. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body, based on its total weight, has a weight fraction of polymeric forming agent b) of 0.01 to 15% by weight, preferably 0.1 to 12% by weight and in particular from 1 to 10 Has wt .-%. Active substance-containing shaped body according to one of the preceding points, wherein the polymeric gel former b) is selected from the group of
Cellulosen und Cellulosederivate, insbesondere der Methylcellulose, Celluloses and cellulose derivatives, especially methyl cellulose,
Hydroxypropylmethylcellulose und der Hydroxypropylcellulose; Hydroxypropyl methyl cellulose and the hydroxypropyl cellulose;
Stärke, insbesondere der Kartoffelstärke, Maisstärke, Weizenstärke, Erbsenstärke oder Starch, especially potato starch, corn starch, wheat starch, pea starch or
Tapiokastärke; Tapioca starch;
Polyacrylate; Polyacrylates;
Polyvinylpyrrolidone; Polyvinyl pyrrolidones;
Polyvinylalkohole. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der polymere Gelbildner b) ausgewählt ist aus der Gruppe der Polyvinylalkohole. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei das Gewichtsverhältnis von Dibenzylidensorbitol zu Polyvinylalkohol 10:1 bis 1 :20, vorzugsweise 8:1 bis 1 :15 und insbesondere 6:1 bis 1 :10 beträgt. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper bezogen auf sein Gesamtgewicht einen Gewichtsanteil an Aktivstoff von 0,1 bis 20 Gew.-%, vorzugweise von 0,2 bis 15 Gew.-% und insbesondere von 0,5 bis 10 Gew.-% aufweist. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper als Aktivstoff c) mindestens einen Aktivstoff aus der Gruppe der Duftstoffe, der Enzyme und der Färbemittel umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Aktivstoff c) verkapselt ist. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei das Lösungsmittel d) ausgewählt ist aus der Gruppe Ethanol, n-Propanol, i-Propanol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin, Proplyencarbonat, Diglykol, Propyldiglycol, Butyldiglykol, Hexylenglycol, Diethylenglykolethylether, Diethylenglykolmethylether, Diethylenglykol-n-butylether, Diethylenglykolhexylether, Diethylenglykol-n-butyletheracetat, Ethylenglykolpropylether, Ethylenglykol-n-butylether, Ethylenglykolhexylether, Ethylenglykol-n-butyletheracetat,Polyvinyl alcohols. Active substance-containing shaped body according to one of the preceding points, wherein the polymeric gel former b) is selected from the group of polyvinyl alcohols. Active substance-containing molded body according to one of the preceding points, the weight ratio of dibenzylidene sorbitol to polyvinyl alcohol being 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body, based on its total weight, has a weight fraction of active substance of 0.1 to 20% by weight, preferably 0.2 to 15% by weight and in particular 0.5 to 10% by weight .-% having. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body comprises as active substance c) at least one active substance from the group of fragrances, enzymes and colorants. Active substance-containing shaped body according to one of the preceding points, wherein the active substance c) is encapsulated. Active substance-containing molded body according to one of the preceding points, the solvent d) being selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, propylene carbonate, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, Diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol n-butyl ether, Diethylene glycol hexyl ether, diethylene glycol n-butyl ether acetate, ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, ethylene glycol n-butyl ether acetate,
Triethylenglycol, Triethylenglykolmethylether, Triethylenglykolethylether, Triethylenglykol-n- butylether, Ethylenglykolphenylether, Propylenglykolmethylether, Dipropylenglykolmethylether, Tripropylenglycolmethylether, Propylenglycolmethyletheracetat, Dipropylenglykol- methyletheracetat, propylenglykol-n-propylether, Dipropylenglykol-n-propylether, Propylenglycol-n- butylether, Dipropylenglycol-n-butylether, Tripropylenglykol-n-butylether,Triethylene glycol, Triethylenglykolmethylether, Triethylenglykolethylether, triethylene glycol-n-butyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether acetate, propylene glycol-n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, Tripropylene glycol n-butyl ether,
Propylenglykolphenylether, Propylenglykoldiacetat, Dipropylenglykoldimethylether,Propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol dimethyl ether,
Methoxytriglykol, Ethoxytriglykol, Butoxytriglykol, Glycerincarbonat, Propylencarbonat, 1 - Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glykol-t-butylether, Di-n-octylether, vorzugsweise aus der Gruppe Glycerin, Propylenglycol, Ethanol, Isoporpanol, Methylpropanoldiol, Triethylenglycol, Propylencarbonat, Glycerin carbonat, 3-Methyl-3-methoxybutanol und 2- Methylpropan-1 ,3-diol. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei das Lösungsmittel d) ein Lösungsmittel aus der Gruppe der bei Raumtemperatur (20°C) flüssigen Polyalkylenglycole, insbesondere der bei Raumtemperatur (20°C) flüssigen Polyalkylenglcole, besonders bevorzugt aus der Gruppe PEG 200 und PEG 400 umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei das Lösungsmittel d) ein Lösungsmittel aus der Gruppe der bei Raumtemperatur (20°C) flüssigen organischen Polyole, insbesondere der bei Raumtemperatur (20°C) flüssigen Diole, besonders bevorzugt aus der Gruppe 2-Methyl-1 ,3-Propandiol (MPDiol) und 3-Methyl-1 ,3-Butandiol (Isopentyldiol) umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei als Lösungsmittel d) Glycerin umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei als Lösungsmittel d) Triacetin umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei als Lösungsmittel d) Wasser umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei das Lösungsmittel d) Wasser und 3-Methyl-1 ,3-Butandiol (Isopentyldiol), bevorzugt Wasser, Glycerin und 3-Methyl-1 ,3- Butandiol umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper bezogen auf sein Gesamtgewicht einen Gewichtsanteil an Lösungsmittel d) von 10 bis 98 Gew.-%, vorzugsweise von 40 bis 97 Gew.-% und insbesondere von 60 bis 96 Gew.-% aufweist. Aktivstoffhaltiger Formkörper mit einem Gewicht von 0,2 bis 20 g, umfassend, bezogen auf sein Gesamtgewicht Methoxytriglycol, ethoxytriglycol, butoxytriglycol, glycerine carbonate, propylene carbonate, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether, preferably from the group glycerine, propylene glycol, ethanol, Isoporpanol, methylpropanoldiol, triethylene glycol, propylene carbonate, glycerol carbonate, 3-methyl-3-methoxybutanol and 2-methylpropane-1,3-diol. Active substance-containing molded body according to one of the preceding points, wherein the solvent d) is a solvent from the group of polyalkylene glycols liquid at room temperature (20 ° C), in particular the polyalkylene glycols liquid at room temperature (20 ° C), particularly preferably from the group PEG 200 and PEG 400 includes. Active substance-containing molded body according to one of the preceding points, wherein the solvent d) is a solvent from the group of organic polyols liquid at room temperature (20 ° C.), in particular the diols liquid at room temperature (20 ° C.), particularly preferably from the 2-methyl group -1, 3-propanediol (MPDiol) and 3-methyl-1,3-butanediol (isopentyldiol) includes. Active substance-containing shaped body according to one of the preceding points, wherein d) comprises glycerol as the solvent. Active substance-containing shaped body according to one of the preceding points, wherein d) comprises triacetin as the solvent. Active substance-containing shaped body according to one of the preceding points, wherein d) comprises water as the solvent. Active substance-containing shaped body according to one of the preceding points, wherein the solvent d) comprises water and 3-methyl-1,3-butanediol (isopentyldiol), preferably water, glycerol and 3-methyl-1,3-butanediol. Active substance-containing shaped body according to one of the preceding points, the shaped body having, based on its total weight, a weight fraction of solvent d) of 10 to 98% by weight, preferably 40 to 97% by weight and in particular 60 to 96% by weight . Active substance-containing moldings with a weight of 0.2 to 20 g, based on its total weight
a) 0,1 bis 10 Gew.-% Dibenzylidensorbitol; a) 0.1 to 10% by weight of dibenzylidene sorbitol;
b) 0,1 bis 12 Gew.-% Polyvinylalkohol mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; c) 0,1 bis 20 Gew.-% vorzugsweise verkapselten Duftstoff; b) 0.1 to 12% by weight of polyvinyl alcohol with a molar mass of 10,000 g / mol to 200,000 g / mol; c) 0.1 to 20% by weight, preferably encapsulated fragrance;
d) 10 bis 96 Gew. -% Lösungsmittel. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper weniger als 10 Gew.-%, vorzugsweise weniger als 8 Gew.-%, besonders bevorzugt weniger als 4 Gew.-% und insbesondere weniger als 1 Gew.-% Tensid umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper kein Tensid umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper ein Speichermodul G‘ (Rotationsrheometer unter Verwendung eines Kegel-Platte-Messystems mit 40 mm Durchmesser und 2° Öffnungswinkel bei einer Temperatur von 20°C ) von 103 Pascal bis 108 Pascal, bevorzugt 104 Pascal bis 106 Pascal, aufweist. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper weiterhin mindestens einen Farbstoff, vorzugsweise mindestens einen wasserlöslichen Farbstoff, besonders bevorzugt einen wasserlöslichen Polymerfarbstoff umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper weiterhin mindestens ein Konservierungsmittel umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper weiterhin mindestens einen Bitterstoff umfasst. Aktivstoffhaltiger Formkörper nach einem der vorherigen Punkte, wobei der Formkörper transluzent und/oder transparent, besonders bevorzugt transparent ist. Wasch- oder Reinigungsmittel, umfassend mindestens einen aktivstoffhaltigen Formkörper nach einem der vorherigen Punkte. Verwendung aktivstoffhaltiger Formköper oder von Wasch- oder Reinigungsmittel nach einem der vorherigen Punkte zur Beduftung von Oberflächen, vorzugsweise textilen Oberflächen. Verfahren zur Herstellung eines Formkörpers, umfassend die Schritte d) 10 to 96% by weight of solvent. Active substance-containing shaped body according to one of the preceding points, the shaped body comprising less than 10% by weight, preferably less than 8% by weight, particularly preferably less than 4% by weight and in particular less than 1% by weight surfactant. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body does not comprise a surfactant. Active substance-containing shaped body according to one of the preceding points, the shaped body having a storage module G '(rotational rheometer using a cone-plate measuring system with a diameter of 40 mm and a 2 ° opening angle at a temperature of 20 ° C) of 10 3 Pascal to 10 8 Pascal, preferably 10 4 pascals to 10 6 pascals. Active substance-containing shaped body according to one of the preceding points, the shaped body further comprising at least one dye, preferably at least one water-soluble dye, particularly preferably a water-soluble polymer dye. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body further comprises at least one preservative. Active substance-containing shaped body according to one of the preceding points, wherein the shaped body further comprises at least one bitter substance. Active substance-containing shaped body according to one of the preceding points, the shaped body being translucent and / or transparent, particularly preferably transparent. Washing or cleaning agent, comprising at least one active substance-containing shaped body according to one of the preceding points. Use of moldings containing active substances or of washing or cleaning agents according to one of the preceding points for scenting surfaces, preferably textile surfaces. A method for producing a shaped body, comprising the steps
a) Bereitstellung einer ersten Zubereitung aus mindestens einem wasserlöslichen organischen Lösungsmittel sowie mindestens einem niedermolekularen Gelbildner mit einer molaren Masse bis 2000 g/mol; b) Bereitstellung einer zweiten Zubereitung aus Wasser und/oder mindestens einem wasserlöslichen organischen Lösungsmittel sowie mindestens einem polymeren Gelbildner mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; a) providing a first preparation of at least one water-soluble organic solvent and at least one low molecular weight gel former with a molar mass of up to 2000 g / mol; b) providing a second preparation of water and / or at least one water-soluble organic solvent and at least one polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol;
c) Vermischung der ersten Zubereitung und der zweiten Zubereitung; c) mixing the first preparation and the second preparation;
d) Ausbildung formstabiler Formkörper d) Forming dimensionally stable molded bodies
wobei in which
i) der ersten Zubereitung in Schritt a) und/oder i) the first preparation in step a) and / or
ii) der zweiten Zubereitung in Schritt b) und/oder ii) the second preparation in step b) and / or
iii) dem Gemisch der ersten Zubereitung und der zweiten Zubereitung in Schritt c) ein Aktivstoff, vorzugsweise ein Duftstoff beigefügt wird. Verfahren nach Punkt 34, wobei die erste Zubereitung in Schritt a) eine Temperatur zwischen 30°C und 180°C, vorzugsweise zwischen 60°C und 160°C aufweist. Verfahren nach einem der vorherigen Punkte, wobei die zweite Zubereitung in Schritt b) eine Temperatur zwischen 30°C und 90°C, vorzugsweise zwischen 40°C und 70°C aufweist. Verfahren nach einem der vorherigen Punkte, wobei das Gemisch in Schritt d) in eine Form eingeleitet wird. Verfahren nach einem der vorherigen Punkte, wobei das Gemisch in Schritt d) durch Vertropfen auf eine Oberfläche portioniert und nachfolgend auf dieser Oberfläche ausgeformt wird. Verfahren nach einem der vorherigen Punkte, wobei das Gemisch in Schritt d) durch Vertropfen auf ein Stahlband mittels eines Tropfenformers mit rotierender, gelochter Außentrommel portioniert und nachfolgend auf dieser Oberfläche ausgeformt wird. Verfahren nach einem der vorherigen Punkte, wobei das Gemisch in Schritt d) gekühlt wird. Verfahren zur Reinigung einer textilen Oberfläche unter Einsatz eines Formkörpers nach einem der vorherigen Punkte. iii) an active substance, preferably a fragrance, is added to the mixture of the first preparation and the second preparation in step c). Method according to point 34, wherein the first preparation in step a) has a temperature between 30 ° C and 180 ° C, preferably between 60 ° C and 160 ° C. Method according to one of the preceding points, wherein the second preparation in step b) has a temperature between 30 ° C and 90 ° C, preferably between 40 ° C and 70 ° C. Method according to one of the preceding points, wherein the mixture is introduced into a mold in step d). Method according to one of the preceding points, the mixture being portioned in step d) by dripping onto a surface and then being shaped on this surface. Method according to one of the preceding points, the mixture being portioned in step d) by dripping onto a steel belt by means of a drop former with a rotating, perforated outer drum and then being shaped on this surface. Method according to one of the preceding points, wherein the mixture is cooled in step d). Process for cleaning a textile surface using a shaped body according to one of the preceding points.

Claims

Patentansprüche Claims
1. Aktivstoffhaltiger Formkörper mit einem Gewicht von 0,2 bis 20 g, umfassend 1. Active substance-containing moldings with a weight of 0.2 to 20 g, comprising
a) mindestens einen niedermolekularen Gelbildner mit einer molaren Masse bis 2000 g/mol; b) mindestens einen polymeren Gelbildner mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; a) at least one low molecular weight gel former with a molar mass of up to 2000 g / mol; b) at least one polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol;
c) mindestens einen Aktivstoff; c) at least one active ingredient;
d) mindestens ein Lösungsmittel. d) at least one solvent.
2. Aktivstoffhaltiger Formkörper nach Anspruch 1 , wobei der Formkörper bezogen auf sein Gesamtgewicht einen Gewichtsanteil an niedermolekularem Gebildner a) von 0,01 bis 15 Gew.-%, vorzugsweise von 0,1 bis 10 Gew.-% und insbesondere von 1 bis 4 Gew.-% aufweist. 2. Active substance-containing shaped body according to claim 1, wherein the shaped body, based on its total weight, has a proportion by weight of low molecular weight forming agent a) of 0.01 to 15% by weight, preferably 0.1 to 10% by weight and in particular 1 to 4 Has wt .-%.
3. Aktivstoffhaltiger Formkörper nach einem der vorherigen Ansprüche, wobei der niedermolekulare Gelbildner a) ausgewählt ist aus der Gruppe der Benzylidenalditol-Verbindungen, Hydroxystearinsäure, hydrogeniertem Castoröl, Diarylamidocystin-Verbindung, N-(C8-C24)- Hydrocarbylglyconamid, Diketopiperazin-Verbindung, 2-Methyl-acrylsäure-2-ureido-ethylester und Mischungen davon. 3. Active substance-containing molded body according to one of the preceding claims, wherein the low molecular weight gel former a) is selected from the group of benzylidene alditol compounds, hydroxystearic acid, hydrogenated castor oil, diarylamidocystine compound, N- (C8-C 24 ) - hydrocarbylglyconamide, diketopiperazine compound, 2-methyl-acrylic acid-2-ureido-ethyl ester and mixtures thereof.
4. Aktivstoffhaltiger Formkörper nach einem der vorherigen Ansprüche, wobei der Formkörper bezogen auf sein Gesamtgewicht einen Gewichtsanteil an polymerem Gebildner b) von 0,01 bis 15 Gew.-%, vorzugsweise von 0,1 bis 12 Gew.-% und insbesondere von 1 bis 10 Gew.-% aufweist. 4. Active substance-containing shaped body according to one of the preceding claims, wherein the shaped body, based on its total weight, has a weight fraction of polymeric forming agent b) of 0.01 to 15% by weight, preferably 0.1 to 12% by weight and in particular 1 to 10 wt .-%.
5. Aktivstoffhaltiger Formkörper nach einem der vorherigen Ansprüche, wobei der polymere Gelbildner b) ausgewählt ist aus der Gruppe der 5. Active substance-containing shaped body according to one of the preceding claims, wherein the polymeric gel former b) is selected from the group of
Cellulosen und Cellulosederivate, insbesondere der Methylcellulose, Celluloses and cellulose derivatives, especially methyl cellulose,
Hydroxypropylmethylcellulose und der Hydroxypropylcellulose; Hydroxypropyl methyl cellulose and the hydroxypropyl cellulose;
Stärke, insbesondere der Kartoffelstärke, Maisstärke, Weizenstärke, Erbsenstärke oder Starch, especially potato starch, corn starch, wheat starch, pea starch or
Tapiokastärke; Tapioca starch;
Polyacrylate; Polyacrylates;
Polyvinylpyrrolidone; Polyvinyl pyrrolidones;
Polyvinylalkohole. Polyvinyl alcohols.
6. Aktivstoffhaltiger Formkörper nach einem der vorherigen Ansprüche, wobei der Formkörper bezogen auf sein Gesamtgewicht einen Gewichtsanteil an Aktivstoff von 0,1 bis 20 Gew.-%, vorzugweise von 0,2 bis 15 Gew.-% und insbesondere von 0,5 bis 10 Gew.-% aufweist. 6. Active substance-containing shaped body according to one of the preceding claims, wherein the shaped body, based on its total weight, has a weight fraction of active substance of 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.5 to 10% by weight.
7. Aktivstoffhaltiger Formkörper nach einem der vorherigen Ansprüche, wobei der Formkörper als Aktivstoff c) mindestens einen Aktivstoff aus der Gruppe der Duftstoffe, der Enzyme und der Färbemittel, vorzugsweise aus der Gruppe der Duftstoffe umfasst. 7. Active substance-containing shaped body according to one of the preceding claims, wherein the shaped body comprises as active substance c) at least one active substance from the group of fragrances, enzymes and colorants, preferably from the group of fragrances.
8. Aktivstoffhaltiger Formkörper nach einem der vorherigen Ansprüche, wobei der Formkörper bezogen auf sein Gesamtgewicht einen Gewichtsanteil an Lösungsmittel d) von 10 bis 98 Gew.-%, vorzugsweise von 40 bis 97 Gew.-% und insbesondere von 60 bis 96 Gew.-% aufweist. 8. Active substance-containing shaped body according to one of the preceding claims, wherein the shaped body, based on its total weight, has a weight fraction of solvent d) of 10 to 98% by weight, preferably from 40 to 97% by weight and in particular from 60 to 96% by weight % having.
9. Aktivstoffhaltiger Formkörper mit einem Gewicht von 0,2 bis 20 g, umfassend, bezogen auf sein Gesamtgewicht 9. Active substance-containing molded body with a weight of 0.2 to 20 g, comprising, based on its total weight
a) 0,1 bis 10 Gew.-% Dibenzylidensorbitol; a) 0.1 to 10% by weight of dibenzylidene sorbitol;
b) 0,1 bis 12 Gew.-% Polyvinylalkohol mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; b) 0.1 to 12% by weight of polyvinyl alcohol with a molar mass of 10,000 g / mol to 200,000 g / mol;
c) 0,1 bis 20 Gew.-% vorzugsweise verkapselten Duftstoff; c) 0.1 to 20% by weight, preferably encapsulated fragrance;
d) 10 bis 96 Gew.-% Lösungsmittel. d) 10 to 96% by weight of solvent.
10 Verfahren zur Herstellung eines Formkörpers nach einem der vorherigen Ansprüche, umfassend die Schritte 10. A method for producing a molded body according to any one of the preceding claims, comprising the steps
a) Bereitstellung einer ersten Zubereitung aus mindestens einem wasserlöslichen organischen Lösungsmittel sowie mindestens einem niedermolekularen Gelbildner mit einer molaren Masse bis 2000 g/mol; a) providing a first preparation of at least one water-soluble organic solvent and at least one low molecular weight gel former with a molar mass of up to 2000 g / mol;
b) Bereitstellung einer zweiten Zubereitung aus Wasser und/oder mindestens einem wasserlöslichen organischen Lösungsmittel sowie mindestens einem polymeren Gelbildner mit einer molaren Masse von 10000 g/mol bis 200000 g/mol; b) providing a second preparation of water and / or at least one water-soluble organic solvent and at least one polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol;
c) Vermischung der ersten Zubereitung und der zweiten Zubereitung; c) mixing the first preparation and the second preparation;
d) Ausbildung formstabiler Formkörper d) Forming dimensionally stable molded bodies
wobei in which
i) der ersten Zubereitung in Schritt a) und/oder i) the first preparation in step a) and / or
ii) der zweiten Zubereitung in Schritt b) und/oder ii) the second preparation in step b) and / or
iii) dem Gemisch der ersten Zubereitung und der zweiten Zubereitung in Schritt c) ein Aktivstoff, vorzugsweise ein Duftstoff beigefügt wird. iii) an active substance, preferably a fragrance, is added to the mixture of the first preparation and the second preparation in step c).
PCT/EP2020/065010 2019-07-23 2020-05-29 Moulded bodies containing active substances and method for the production thereof WO2021013412A1 (en)

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