EP2245131B2 - Low-concentration liquid detergents or cleaners containing perfume - Google Patents
Low-concentration liquid detergents or cleaners containing perfume Download PDFInfo
- Publication number
- EP2245131B2 EP2245131B2 EP09714574.2A EP09714574A EP2245131B2 EP 2245131 B2 EP2245131 B2 EP 2245131B2 EP 09714574 A EP09714574 A EP 09714574A EP 2245131 B2 EP2245131 B2 EP 2245131B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- detergent
- perfume oil
- perfume
- surfactants
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000002304 perfume Substances 0.000 title claims description 62
- 239000007788 liquid Substances 0.000 title claims description 22
- 239000003599 detergent Substances 0.000 title description 93
- 239000000203 mixture Substances 0.000 claims description 52
- 239000002736 nonionic surfactant Substances 0.000 claims description 51
- 239000003945 anionic surfactant Substances 0.000 claims description 46
- 239000004094 surface-active agent Substances 0.000 claims description 30
- 239000003205 fragrance Substances 0.000 claims description 23
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 239000000344 soap Substances 0.000 claims description 11
- 239000004753 textile Substances 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 description 38
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- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 17
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
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- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 3
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
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- 239000002689 soil Substances 0.000 description 3
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
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- LFSYLMRHJKGLDV-UHFFFAOYSA-N tetradecanolide Natural products O=C1CCCCCCCCCCCCCO1 LFSYLMRHJKGLDV-UHFFFAOYSA-N 0.000 description 1
- OHOTVSOGTVKXEL-WJXVXWFNSA-K trisodium;(2s)-2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)[C@H](C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-WJXVXWFNSA-K 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
Definitions
- the invention relates to a liquid detergent containing a surfactant mixture of anionic and nonionic surfactants and a perfume.
- the invention also relates to the use of the detergent and to a process for its preparation.
- WO01 / 00776 discloses a liquid detergent containing perfume oil and a surfactant system of nonionic and anionic surfactants wherein the ratio of nonionic to anionic surfactants is at least 0.75: 1 and the ratio of nonionic surfactants to perfume oil is between 5: 1 and 30: 1.
- the examples of D1 include alkanesulfonates and soap as the anionic surfactant.
- a liquid detergent containing a perfume oil and 5 to 18 wt .-% of a surfactant mixture of nonionic and anionic surfactants, said anionic surfactant containing an alkylbenzenesulfonate and a soap and wherein the amount of alkylbenzenesulfonate more than 3.2 wt %, the amount of perfume oil 0.4 to 1.5 wt .-%, the ratio of nonionic surfactants to anionic surfactants at least 0.75: 1 and the ratio of nonionic surfactants to the perfume oil between 5: 1 and 30 : 1 is.
- the ratio of the nonionic surfactants to the perfume oil is between 5: 1 and 15: 1, and more preferably between 5: 1 and 10: 1.
- liquid detergents preferably contain a surfactant mixture of nonionic and anionic surfactants.
- nonionic surfactants are particularly effective for fatty soils.
- Anionic surfactants are used because of their good water solubility and their high washing power at low temperatures. It has now surprisingly been found that high levels of perfume oil can be incorporated into a storage-stable, low-concentration, liquid detergent if the nonionic surfactants at least 75% of the amount by weight of anionic surfactants, ie at least in the ratio 0.75: 1, are present , The resulting detergent is storage stable under various climatic conditions and especially at low storage temperatures.
- the amount of the surfactant mixture is 8 to 15% by weight, based in each case on the total amount of detergent.
- the ratio of nonionic surfactants to anionic surfactants is between 0.75: 1 and 5: 1, preferably between 0.75: 1 and 3: 1.
- the anionic surfactants give a liquid detergent according to the invention containing a surfactant mixture of nonionic and anionic surfactants, a good cleaning performance on fatty soils.
- the anionic surfactant contains an alkylbenzenesulfonate and a soap, and the amount of alkylbenzenesulfonate is more than 3.2% by weight.
- Alkylbenzenesulfonates are preferably used in the detergents according to the invention because of their detergency.
- the detergent preferably contains more than 3.2% by weight of these anionic surfactants in order to achieve a sufficiently good cleaning performance, in particular on greasy stains of the liquid detergent.
- the detergent contains 2 to 12 wt .-% and preferably 3 to 10 wt .-% of a polyol, each based on the total amount of detergent, which consists of the group consisting of glycerol, 1,2-propanediol, 1 , 3-propanediol, ethylene glycol, diethylene glycol, dipropylene glycol and mixtures thereof.
- the agent contains glycerin.
- detergents containing certain amounts of polyol are more stable than detergents with other non-polyol-containing solvents.
- the chemical stability of the ingredients, in particular the enzymes is increased.
- the amount of perfume oil is 0.7 to 1.3% by weight based on the total amount of the detergent.
- the perfume oil contains at least 15% by weight of fragrances having a boiling point above 250 ° C. and a log P value of ⁇ 3.0.
- perfume oils may also be referred to as "hydrophobic perfume oils" and, in particular, have a better scent effect on textiles in terms of appeal, intensity and durability of the scent impression on textiles.
- the invention relates to the use of the detergent according to the invention for washing and / or cleaning of textile fabrics.
- the invention relates to a process for the preparation of a liquid detergent containing a perfume oil and a surfactant mixture of nonionic and anionic surfactants, wherein the agent, the nonionic surfactants at least in the ratio of 0.75: 1 to the anionic surfactants and in the ratio between 5 : 1 and 30: 1 are added to the perfume oil.
- the invention also relates to the use of a surfactant mixture of nonionic and anionic surfactants, wherein the ratio of the nonionic surfactants to the anionic surfactants is at least 0.75: 1, in an amount up to 25% by weight for improving the storage stability of a liquid detergent which comprises a perfume oil, when stored in certain temperature ranges, with the proviso that the ratio of the nonionic surfactants to the perfume oil is between 5: 1 and 30: 1.
- the stabilization occurs in particular when stored in a temperature range of 0 ° C to 10 ° C, when stored in a temperature range of 10 ° C to 25 ° C when stored in a temperature range of 25 ° C and 40 ° C.
- liquid detergents with high perfume contents can be obtained, which are storage-stable under the most diverse climatic conditions.
- the storage stability of the liquid detergent in a temperature range of 0 ° C to 10 ° C is improved.
- the detergent contains 5 to 18 wt .-% of a surfactant mixture of anionic and nonionic surfactants.
- nonionic surfactants are preferably alkoxylated, advantageously ethoxylated; in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture , as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
- block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
- a mixture of a branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol such as a mixture of a C 16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
- nonionic surfactants which can also be employed are alkylglucosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol representing a glycoside unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
- Alkyl glucosides are known, mild surfactants.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- Other suitable surfactants are polyhydroxy fatty acid amides.
- a linear, ethoxylated compound having 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol.
- the content of nonionic surfactants is in the detergent preferably 2 to 12.5 wt .-%, preferably 4 to 10 wt .-% and in particular 5 to 8 wt .-%, each based on the total detergent.
- the surfactant mixture of the detergent also necessarily contains an anionic surfactant.
- the anionic surfactant contains an alkyl benzene sulfonate and a soap.
- Soaps are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
- the anionic surfactants including the soaps may be in the form of their sodium, potassium or magnesium salts.
- the anionic surfactants are in the form of their sodium salts.
- Another preferred counterion for anionic surfactants is choline.
- Alkylbenzenesulfonates preferably used in the invention are particularly preferably C9-13-alkylbenzenesulfonates.
- the detergent according to the invention contains more than 3.2 wt .-%, based on the total agent, of alkylbenzenesulfonates.
- the content of a detergent to anionic surfactants may be up to 14 wt .-%, based on the total detergent. However, the content of a detergent to anionic surfactants is preferably below 10 wt .-%, based on the total agent.
- the detergent contains a perfume oil.
- the perfume oil is present in an amount of from 0.4 to 1.5% by weight and preferably from 0.7 to 1.3% by weight.
- the ratio of the perfume oil to the nonionic surfactants is between 1: 5 and 1: 30, preferably 1: 5 and 1:15 and more preferably between 1: 5 and 1:10.
- perfume oils individual fragrance compounds, for example, the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
- perfume oils may also contain natural fragrance mixtures as are available from plant sources.
- the perfume oil contains at least 15% by weight of fragrances having a boiling point above 250 ° C. and a logP value of ⁇ 3.0. It has been found that inventive low-concentration detergents containing perfume oils with such a minimum amount of fragrances having a boiling point above 250 ° C and a logP value of ⁇ 3.0, have particularly advantageous fragrance properties. For example, an even longer lasting fragrance impression on the laundry can be achieved. Likewise, the Aufzieh the fragrances in the dryer can be further improved on the laundry, so that the laundry smells even longer and more intense.
- the octanol / water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. Since the distribution coefficients of the perfume ingredients often have high values, for example 1000 or higher, they more appropriately become base in terms of their logarithm 10, one speaks of the so-called log P value.
- Preferred fragrances of this invention have a logP of ⁇ 3.0 or higher, for example, ⁇ 3.1, preferably ⁇ 3.2, and especially ⁇ 3.3.
- the logP value of numerous fragrances is documented; For example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc., (Daylight CIS), Irvine, California, contains numerous logP values, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP” program, which is also available from Daylight CIS. This program also lists the experimental logP values if they are available in the Pomona92 database.
- the "calculated logP" (ClogP value) is determined by the fragment approximation according to Harsch and Leo (see Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Harsch, PG Sammens, JB Taylor and CA Ransden, Eds., P.
- the fragment approximation is based on the chemical structure of each of the perfume ingredients, taking into account the numbers and types of atoms, the atomic bonding ability, and the chemical bond.
- the ClogP values which are the most reliable and widely used estimates for this physicochemical property, are preferably used in the present invention instead of the experimental logP values in selecting the perfume ingredients useful in the present invention.
- boiling point values can be obtained, for example, from various known chemical manuals and databases. If a boiling point is given only at a different pressure, usually a pressure lower than the normal pressure of 760 mm Hg, the boiling point at normal pressure can be determined approximately with the help of boiling point pressure nomographs such as those in " The Chemist's Companion, AJ Gordon and RA Ford, John Wiley & Sons Publishers, 1972, pp. 30-36 , specified, estimated. Where applicable, the boiling point values can also be calculated by computer programs based on the molecular structure data such as those described in " Computer-assisted Prediction of Normal Boiling Points of Pyrans and Pynoles ", DT Starton et al., J. Chem. Inf. Comput.
- odoriferous substances which fulfill the criteria boiling point> 250 ° C and ClogP ⁇ 3 are listed by way of example in Table 1.
- Table 1 Examples of fragrances Perfume ingredients with a boiling point> 250 ° C and a ClogP ⁇ 3.0 Approximate boiling point (° C) ClogP Allylcylclohexanpropionat 267 3,935 ambrettolide 300 6.261 amyl benzoate 262 3,417 Amylcinnamat 310 3,771 amyl cinnamic aldehyde 285 4,324 Amylzimtaldehyddimethylacetal 300 4,033 iso-amyl salicylate 277 4,601 aurantiol 450 4,216 benzophenone 306 3,120 benzyl 300 4,383 para-tert-butylcyclohexyl acetate > 250 4,019 iso-butylquinoline 252 4,193 beta-caryophyllene 256 6,333
- fragrances which are preferred for use in this invention.
- the perfume oils of the inventive detergents preferably contain at least 3 different fragrances, more preferably at least 4 different fragrances, and even more preferably at least 5 different fragrances.
- the detergent may contain other ingredients that further improve the performance and / or aesthetic properties of the detergent.
- the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, Silicone oils, anti redeposition agents, graying inhibitors, anti-shrinkage agents, wrinkle inhibitors, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.
- Suitable builders which may be present in the detergent are, for example, silicates, aluminum silicates (in particular zeolites), phosphates or carbonates.
- Organic builders which may be present in the detergent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
- the acids themselves can also be used.
- the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents.
- citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
- polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- biodegradable polymers of more than two different monomer units for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
- Citric acid or its salts, are preferably used as soluble, organic builders in the liquid detergents.
- the liquid detergent may also contain an enzyme or a mixture of enzymes.
- an enzyme or a mixture of enzymes.
- Particularly suitable are those from the classes of hydrolases such as proteases, (poly) esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, ⁇ -glucanases, oxidases, peroxidases, mannanases, perhydrolases, Oxireductases and / or laccases.
- Proteases amylases, lipases, cellulases, mannanases, laccases, tannanases and esterases / polyesterases and mixtures of two or more of these enzymes are preferably used in the context of the present invention.
- the amount of enzyme or of the enzymes is based on the total agent 0.01 to 10 wt .-%, preferably 0.12 to about 3 wt .-%.
- the enzymes are preferably used as enzyme liquid formulation (s).
- the detergents according to the invention may contain stabilizing agents, such as boric acid or borates, boric acid derivatives or amino alcohols.
- electrolytes from the group of inorganic salts a wide number of different salts can be used.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates.
- the proportion of electrolytes in the detergent is usually 0.1 to 5 wt .-%.
- Non-aqueous solvents that can be used in the detergent come from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range.
- Solvents can be used which consist of ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl
- the detergent contains certain amounts of a polyol as a nonaqueous solvent. It is preferable that the detergent contains 2 to 10% by weight of a polyol.
- the polyol may include glycerol, 1,2-propanediol, 1,3-propanediol, ethylene glycol, diethylene glycol and / or dipropylene glycol. Most preferably, the detergent contains glycerol.
- pH adjusters In order to bring the pH of the detergent into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited.
- the pH of the detergent is preferably between 4 and 10, preferably between 6.5 and 9, and most preferably between 7 and 8.8.
- the liquid detergents preferably have viscosities in the range from 200 to 5000 mPas, with values between 300 and 2000 mPas and in particular 400 and 1000 mPas being particularly preferred.
- the viscosity was determined using a Brookfield LVT-II viscometer at 20 rpm and 20 ° C., spindle 3.
- dyes can be dyed with suitable dyes.
- Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents or cleaning agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
- Suitable foam inhibitors which can be used in the detergents are, for example, soaps, paraffins or silicone compounds, in particular silicone oils, which are optionally present as emulsions.
- Suitable soil-release polymers which are also referred to as "anti redeposition agents" are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
- Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.
- Optical brighteners can be added to the detergents to eliminate graying and yellowing of the treated fabrics.
- Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.
- the optical brighteners are usually used in amounts of between 0% and 0.3% by weight, based on the finished detergent.
- Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
- Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof are preferably used in amounts of from 0.1 to 5% by weight, based on the total amount of detergent.
- the detergent may contain a dye transfer inhibitor.
- the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole.
- Suitable color transfer inhibiting polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, and mixtures thereof.
- PVP polyvinylpyrrolidone
- PVI polyvinylimidazole
- copolymers of vinylpyrrolidone and vinylimidazole PVP / PVI
- color transfer inhibitor PVP
- Polyvinylpyrrolidones (PVP) are for example commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53.
- PVP / PVI copolymers are commercially available, for example, from BASF under the name Sokalan® HP 56.
- the amount of dye transfer inhibitor based on the total amount of the detergent is preferably from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight, and more preferably from 0.1 to 0.5% by weight.
- enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water as a color transfer inhibitor.
- a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, wherein additionally the above-mentioned polymeric dye transfer inhibitors can be used.
- the detergents according to the invention may contain preservatives, it being preferred to use only those which have no or only a slight skin-sensitizing potential.
- preservatives examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, formic acid and its salts, 3-iodo-2-propynyl butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof.
- Further suitable preservatives are isothiazolones, mixtures of isothiazolones and mixtures of isothiazolones with other compounds, for example tetramethylolglycoluril.
- Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), methylglycinediacetic acid trisodium salt (MGDA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
- EDTA ethylenediaminetetraacetic acid
- NTA nitrilotriacetic acid
- MGDA methylglycinediacetic acid trisodium salt
- anionic polyelectrolytes such as polymaleates and polysulfonates.
- a preferred class of complexing agents are the phosphonates present in the detergent in amounts of from 0.01% to 2.5%, preferably from 0.02% to 2%, and more preferably from 0.03 to 1.5% by weight. -% are included.
- These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.
- HEDP 1-hydroxyethane-1,1-diphosphonic acid
- ATMP aminotri (methylenephosphonic acid)
- DTPMP or DETPMP diethylenetriamine penta
- 2-phosphonobutane-1,2 2-phosphonobutane-1,2 , 4-tricarboxylic acid
- the detergents according to the invention can be used for washing textile fabrics.
- the detergent is produced by means of customary and known methods and processes.
- the ingredients of the detergents can be easily mixed in stirred tanks, with water, the acidic components, if present, such as the alkylbenzenesulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc., and the nonionic surfactants are conveniently presented.
- the nonaqueous solvents, if present, are preferably also added at this time, but the addition may be made at a later time.
- the fatty acid is added and the saponification of the fatty acid moiety is carried out at 50 to 60 ° C.
- the further ingredients are preferably added in portions.
- the amount of active ingredient added to nonionic surfactants is at least equal to the added amount of active anionic surfactants and that the amount of perfume oil added, between 0.5 and 1.5 wt .-%, based on the total amount of detergent , lies.
- Table 2 shows the compositions of three comparative formulations V1 and V2 and the compositions of three detergents E1-E4 according to the invention (all amounts are in% by weight of active ingredient based on the composition): Table 2: Composition of detergents V1 and V2 and E1 to E4 (in% by weight) V1 V2 E1 E2 E3 E4 C 12-13 fatty alcohol with 7 EO 5.2 5.5 6.4 6.4 6.8 7.2 Linear C 10 -C 13 -alkylbenzenesulfonate (Na salt) 6.85 6.42 6.42 5.35 4.82 4.28 C 12-18 fatty acid (Na salt) 1.98 1.98 1.98 1.98 1.98 1.98 Citric acid (Na salt) 1 1 1 1 1 1 1 1 1 phosphonic 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Boric acid (Na salt) 1 1 1 1 1 1 1 Polyacrylate thickener 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Optical brighten
- the storage of the detergent according to the invention was carried out at the indicated temperatures, wherein the temperatures each fluctuated within a defined cycle within the specified temperature range.
- the evaluation was done either at room temperature or at the lowest temperature of a temperature range.
- Table 4 shows the compositions of two comparative formulations V3 and V4 as well as two formulations E5 and E6 according to the invention (all amounts are given in% by weight of active ingredient based on the composition): Table 4: Composition of detergents V3 and V4 and E5 and E6 (in% by weight) V3 V4 E5 E6 C 12-18 fatty alcohol with 7 EO 5.2 5.2 6.4 6.4 Lin.
- Table 6 shows the compositions of three formulations E7 to E9 according to the invention (all amounts are given in% by weight of active ingredient based on the composition): Table 6: Composition of detergents E7 to E9 (in% by weight) E7 E8 E9 C 12-18 fatty alcohol with 7 EO 6.4 6.4 6.4 Lin.
- perfume oils A to C used in the context of this invention each contain at least 15% by weight of fragrances having a boiling point above 250 ° C. and a logP value or ClogP value of ⁇ 3.0.
- the content of these fragrances in the respective perfume oils A to C increases in the following order: perfume oil A ⁇ perfume oil B ⁇ perfume oil C.
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- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Description
Die Erfindung betrifft ein flüssiges Waschmittel, enthaltend eine Tensidmischung aus anionischen und nichtionischen Tensiden und ein Parfüm. Die Erfindung betrifft auch die Verwendung des Waschmittels sowie ein Verfahren zu seiner Herstellung.The invention relates to a liquid detergent containing a surfactant mixture of anionic and nonionic surfactants and a perfume. The invention also relates to the use of the detergent and to a process for its preparation.
Bei der Zielsetzung kostengünstigere, flüssige Waschmittel bei gleicher oder gar verbesserter Leistung herzustellen, wird insbesondere versucht, die Tensidmenge zu reduzieren und/oder die Tensidart zu variieren.In the objective of producing more cost-effective, liquid detergents with the same or even improved performance, it is particularly attempted to reduce the amount of surfactant and / or to vary the type of surfactant.
Jedoch hat sich gezeigt, dass sich bei flüssigen Wasch- oder Reinigungsmitteln mit geringem Tensidgehalt, dass heißt einem Tensidgehalt von maximal 25 Gew.-%, die Einarbeitung höherer Parfümmengen, dass heißt Mengen ab 0,4 Gew.-%, schwierig gestaltet. So treten Probleme bezüglich der Lagerstabilität auf, die sich insbesondere bei der Lagerung bei niedrigen Temperaturen, dass heißt Temperaturen zwischen 0 und 10 °C, zeigen. Vermutlich reicht die geringe Tensidmenge nicht mehr aus, um insbesondere die hydrophoben Bestandteile des Parfümöls stabil zu dispergieren.However, it has been shown that with liquid detergents or cleaners with a low surfactant content, that is to say a surfactant content of not more than 25% by weight, the incorporation of higher perfume quantities, ie amounts from 0.4% by weight, is difficult. Thus, problems arise with respect to the storage stability, which in particular during storage at low temperatures, ie temperatures between 0 and 10 ° C show. Presumably, the small amount of surfactant is no longer sufficient to stably disperse in particular the hydrophobic constituents of the perfume oil.
Es ist eine Aufgabe der Erfindung ein niedrigkonzentriertes, Parfümöl-haltiges, flüssiges Waschmittel bereitzustellen, welches unter den verschiedensten klimatischen Bedingungen lagerstabil ist und keiner Phasentrennung unterliegt.It is an object of the invention to provide a low-concentration, perfume-containing, liquid detergent which is storage-stable under a wide variety of climatic conditions and does not undergo phase separation.
Diese Aufgabe wird gelöst durch ein flüssiges Waschmittel, enthaltend ein Parfümöl und 5 bis 18 Gew.-% einer Tensidmischung aus nichtionischen und anionischen Tensiden, wobei das anionische Tensid ein Alkylbenzolsulfonat und eine Seife enthält und wobei die Menge an Alkylbenzolsulfonat mehr als 3,2 Gew.-%, die Menge an Parfümöl 0,4 bis 1,5 Gew.-%, das Verhältnis der nichtionischen Tenside zu den anionischen Tensiden mindestens 0,75 : 1 sowie das Verhältnis der nichtionischen Tenside zu dem Parfümöl zwischen 5 : 1 und 30 : 1 beträgt.This object is achieved by a liquid detergent containing a perfume oil and 5 to 18 wt .-% of a surfactant mixture of nonionic and anionic surfactants, said anionic surfactant containing an alkylbenzenesulfonate and a soap and wherein the amount of alkylbenzenesulfonate more than 3.2 wt %, the amount of perfume oil 0.4 to 1.5 wt .-%, the ratio of nonionic surfactants to anionic surfactants at least 0.75: 1 and the ratio of nonionic surfactants to the perfume oil between 5: 1 and 30 : 1 is.
Dabei ist es vorteilhaft, wenn das Verhältnis der nichtionischen Tenside zu dem Parfümöl zwischen 5 : 1 und 15 : 1 und mehr bevorzugt zwischen 5 : 1 und 10 : 1 beträgt.It is advantageous if the ratio of the nonionic surfactants to the perfume oil is between 5: 1 and 15: 1, and more preferably between 5: 1 and 10: 1.
Aus anwendungstechnischer Sicht enthalten flüssige Waschmittel vorzugsweise eine Tensidmischung aus nichtionischen und anionischen Tensiden. So sind nichtionische Tenside insbesondere bei Fett-haltigen Verschmutzungen wirksam. Anionische Tenside werden aufgrund ihrer guten Wasserlöslichkeit und ihres hohen Waschvermögens bei niedrigen Temperaturen eingesetzt. Es hat sich nun überraschend gezeigt, dass in ein lagerstabiles, niedrigkonzentriertes, flüssiges Waschmittel hohe Gehalte an Parfümöl eingearbeitet werden können, wenn die nichtionischen Tenside mindestens zu 75 % der Gewichtsmenge an anionischen Tensiden, also mindestens im Verhältnis 0,75 : 1, vorhanden sind. Das erhaltene Waschmittel ist bei verschiedenen klimatischen Bedingungen und insbesondere bei niedrigen Lagertemperaturen lagerstabil.From an application point of view, liquid detergents preferably contain a surfactant mixture of nonionic and anionic surfactants. Thus, nonionic surfactants are particularly effective for fatty soils. Anionic surfactants are used because of their good water solubility and their high washing power at low temperatures. It has now surprisingly been found that high levels of perfume oil can be incorporated into a storage-stable, low-concentration, liquid detergent if the nonionic surfactants at least 75% of the amount by weight of anionic surfactants, ie at least in the ratio 0.75: 1, are present , The resulting detergent is storage stable under various climatic conditions and especially at low storage temperatures.
Es ist bevorzugt, dass die Menge an der Tensidmischung 8 bis 15 Gew.-%, jeweils bezogen auf die Gesamtmenge an Waschmittel, beträgt.It is preferred that the amount of the surfactant mixture is 8 to 15% by weight, based in each case on the total amount of detergent.
Aus Kostengründen und auch aus ökologischer Sicht ist es vorteilhaft, die Gesamtmenge an Tensiden so gering wie möglich zu halten.For cost reasons and also from an ecological point of view, it is advantageous to keep the total amount of surfactants as low as possible.
Weiterhin ist es bevorzugt, dass das Verhältnis der nichtionischen Tenside zu den anionischen Tensiden zwischen 0,75 : 1 und 5 : 1, vorzugsweise zwischen 0,75 : 1 und 3 : 1 beträgt.Furthermore, it is preferred that the ratio of nonionic surfactants to anionic surfactants is between 0.75: 1 and 5: 1, preferably between 0.75: 1 and 3: 1.
Es hat sich gezeigt, dass bei diesem Verhältnis der nichtionischen Tenside zu den anionischen Tensiden eine optimale Stabilisierung des Parfümöls bei guter Waschleistung erfolgt.It has been found that with this ratio of the nonionic surfactants to the anionic surfactants optimum stabilization of the perfume oil takes place with good washing performance.
Die anionischen Tenside verleihen einem erfindungsgemäßen flüssigen Waschmittel, enthaltend eine Tensidmischung aus nichtionischen und anionischen Tensiden, eine gute Reinigungsleistung an Fetthaltigen Verschmutzungen.The anionic surfactants give a liquid detergent according to the invention containing a surfactant mixture of nonionic and anionic surfactants, a good cleaning performance on fatty soils.
Das anionische Tensid enthält ein Alkylbenzolsulfonat und eine Seife, und die Menge an Alkylbenzolsulfonat beträgt mehr als 3,2 Gew.-%.The anionic surfactant contains an alkylbenzenesulfonate and a soap, and the amount of alkylbenzenesulfonate is more than 3.2% by weight.
Alkylbenzolsulfonate werden aufgrund ihres Waschvermögens bevorzugt in den erfindungsgemäßen Waschmitteln eingesetzt. Allerdings hat sich gezeigt, dass das Waschmittel bevorzugt mehr als 3,2 Gew.-% an diesen anionischen Tensiden enthält, um eine ausreichend gute Reinigungsleistung, insbesondere an Fett-haltigen Verfleckungen des flüssigen Waschmittels zu erzielen.Alkylbenzenesulfonates are preferably used in the detergents according to the invention because of their detergency. However, it has been found that the detergent preferably contains more than 3.2% by weight of these anionic surfactants in order to achieve a sufficiently good cleaning performance, in particular on greasy stains of the liquid detergent.
In einer besonders bevorzugten Ausführungsform enthält das Waschmittel 2 bis 12 Gew.-% und vorzugsweise 3 bis 10 Gew.-% eines Polyols, jeweils bezogen auf die Gesamtmenge an Waschmittel, welches aus der Gruppe bestehend aus Glycerin, 1,2-Propandiol, 1,3-Propandiol, Ethylenglycol, Diethylenglycol, Dipropylenglycol und Mischungen daraus ausgewählt ist. In einer ganz besonders bevorzugten Ausführungsform enthält das Mittel Glycerin.In a particularly preferred embodiment, the detergent contains 2 to 12 wt .-% and preferably 3 to 10 wt .-% of a polyol, each based on the total amount of detergent, which consists of the group consisting of glycerol, 1,2-propanediol, 1 , 3-propanediol, ethylene glycol, diethylene glycol, dipropylene glycol and mixtures thereof. In a most preferred embodiment, the agent contains glycerin.
Überraschenderweise hat sich gezeigt, dass Waschmittel, die bestimmte Mengen an Polyol enthalten stabiler sind als Waschmittel mit anderen, nicht Polyol-haltigen Lösungsmitteln. Dabei wird neben der Lagerstabilität, insbesondere bei niedrigen Lagertemperaturen, auch die chemische Stabilität der Inhaltsstoffe, insbesondere der Enzyme, erhöht.Surprisingly, it has been found that detergents containing certain amounts of polyol are more stable than detergents with other non-polyol-containing solvents. In addition to the storage stability, especially at low storage temperatures, the chemical stability of the ingredients, in particular the enzymes, is increased.
Ferner ist es bevorzugt, dass die Menge an Parfümöl 0,7 bis 1,3 Gew.-%, bezogen auf die Gesamtmenge an Waschmittel, beträgt.Further, it is preferable that the amount of perfume oil is 0.7 to 1.3% by weight based on the total amount of the detergent.
Da viele Verbraucher ein Waschmittels aufgrund seines Duftes, aber insbesondere aufgrund des Duftes, welches es damit gewaschenen Textilien vermittelt, kaufen, ist es wünschenswert möglichst hohe Mengen an Parfümöl in das niedrigkonzentrierte, flüssige Waschmittel einzubringen. Allerdings werden zu hohe Parfümölmengen auch vom Verwender negativ als "Überparfümierung" empfunden, so dass sich der Bereich von 0,4 bis 1,5 Gew.-% und insbesondere von 0,7 bis 1,3 Gew.-%, bezogen auf die Gesamtmenge an Waschmittel, als optimaler Bereich herausgestellt hat.Since many consumers buy a detergent due to its fragrance, but especially because of the fragrance which it so washed textiles, buy, it is desirable to introduce as high amounts of perfume oil in the low-concentrated, liquid detergent. However, excessive amounts of perfume oil are also negatively perceived by the user as "over-perfuming", so that the range of 0.4 to 1.5 wt .-% and in particular from 0.7 to 1.3 wt .-%, based on the Total amount of detergent, as exposed to optimal area.
Es ist weiterhin bevorzugt, dass das Parfümöl mindestens 15 Gew.-% an Riechstoffen mit einem Siedepunkt über 250 °C und einem logP-Wert von ≥ 3,0 enthält.It is further preferred that the perfume oil contains at least 15% by weight of fragrances having a boiling point above 250 ° C. and a log P value of ≥ 3.0.
Derartige Parfümöle können auch als "hydrophobe Parfümöle" bezeichnet werden und weisen auf Textilien insbesondere eine bessere Duftwirkung im Hinblick auf Gefallen, Intensität und Dauerhaftigkeit des Dufteindruckes auf.Such perfume oils may also be referred to as "hydrophobic perfume oils" and, in particular, have a better scent effect on textiles in terms of appeal, intensity and durability of the scent impression on textiles.
Ferner betrifft die Erfindung die Verwendung des erfindungsgemäßen Waschmittels zum Waschen und/oder Reinigen von textilen Flächengebilden.Furthermore, the invention relates to the use of the detergent according to the invention for washing and / or cleaning of textile fabrics.
In einem weiteren Aspekt betrifft die Erfindung ein Verfahren zur Herstellung eines flüssigen Waschmittels, enthaltend ein Parfümöl und eine Tensidmischung aus nichtionischen und anionischen Tensiden, wobei dem Mittel die nichtionischen Tenside mindestens im Verhältnis 0,75 : 1 zu den anionischen Tensiden sowie im Verhältnis zwischen 5 : 1 und 30 : 1 zu dem Parfümöl zugesetzt werden.In a further aspect, the invention relates to a process for the preparation of a liquid detergent containing a perfume oil and a surfactant mixture of nonionic and anionic surfactants, wherein the agent, the nonionic surfactants at least in the ratio of 0.75: 1 to the anionic surfactants and in the ratio between 5 : 1 and 30: 1 are added to the perfume oil.
Die Erfindung betrifft auch die Verwendung einer Tensidmischung aus nichtionischen und anionischen Tensiden, wobei das Verhältnis der nichtionischen Tenside zu den anionischen Tensiden mindestens 0,75 : 1 beträgt, in einer Menge bis zu 25 Gew.-% zur Verbesserung der Lagerstabilität von einem flüssigen Waschmittel, welches ein Parfümöl umfasst, bei der Lagerung in bestimmten Temperaturbereichen, mit der Maßgabe, dass das Verhältnis der nichtionischen Tenside zu dem Parfümöl zwischen 5 : 1 und 30 : 1 beträgt. Die Stabilisierung tritt insbesondere bei Lagerung in einem Temperaturbereich von 0 °C bis 10 °C, bei Lagerung in einem Temperaturbereich von 10 °C bis 25 °C bei Lagerung in einem Temperaturbereich von 25 °C und 40 °C auf.The invention also relates to the use of a surfactant mixture of nonionic and anionic surfactants, wherein the ratio of the nonionic surfactants to the anionic surfactants is at least 0.75: 1, in an amount up to 25% by weight for improving the storage stability of a liquid detergent which comprises a perfume oil, when stored in certain temperature ranges, with the proviso that the ratio of the nonionic surfactants to the perfume oil is between 5: 1 and 30: 1. The stabilization occurs in particular when stored in a temperature range of 0 ° C to 10 ° C, when stored in a temperature range of 10 ° C to 25 ° C when stored in a temperature range of 25 ° C and 40 ° C.
Durch die Verwendung der erfindungsgemäßen Tensidmischung können flüssige Waschmittel mit hohen Parfümgehalten erhalten werden, welche unter den verschiedensten klimatischen Bedingungen lagerstabil sind. Insbesondere wird die Lagerstabilität der flüssigen Waschmittel in einem Temperaturbereich von 0 °C bis 10 °C verbessert.By using the surfactant mixture according to the invention, liquid detergents with high perfume contents can be obtained, which are storage-stable under the most diverse climatic conditions. In particular, the storage stability of the liquid detergent in a temperature range of 0 ° C to 10 ° C is improved.
Im Folgenden soll die Erfindung, unter anderem anhand von Beispielen, detaillierter beschrieben werden.In the following, the invention will be described in more detail, inter alia, by way of examples.
Das Waschmittel enthält 5 bis 18 Gew.-% einer Tensidmischung aus anionischen und nichtionischen Tensiden.The detergent contains 5 to 18 wt .-% of a surfactant mixture of anionic and nonionic surfactants.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte; insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispiel aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO, 4 EO oder 7 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch nichtionische Tenside, die EO- und PO-Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar. Hierbei können Blockcopolymere mit EO-PO-Blockeinheiten bzw. PO-EO-Blockeinheiten eingesetzt werden, aber auch EO-PO-EO-Copolymere bzw. PO-EO-PO-Copolymere. Selbstverständlich sind auch gemischt alkoxylierte Niotenside einsetzbar, in denen EO- und PO-Einheiten nicht blockweise, sondern statistisch verteilt sind. Solche Produkte sind durch gleichzeitige Einwirkung von Ethylen- und Propylenoxid auf Fettalkohole erhältlich.As nonionic surfactants are preferably alkoxylated, advantageously ethoxylated; in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture , as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
Geeignet ist ferner auch eine Mischung aus einem verzweigten ethoxylierten Fettalkohol und einem unverzweigten ethoxylierten Fettalkohol, wie beispielsweise eine Mischung aus einem C16-18-Fettalkohol mit 7 EO und 2-Propylheptanol mit 7 EO.Also suitable is also a mixture of a branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C 16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
Außerdem können als weitere nichtionische Tenside auch Alkylglucoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten, aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glycosideinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Alkylglucoside sind bekannte, milde Tenside.In addition, other nonionic surfactants which can also be employed are alkylglucosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol representing a glycoside unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4. Alkyl glucosides are known, mild surfactants.
Eine weitere Klasse nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester.Another class of nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Weitere geeignete Tenside sind Polyhydroxyfettsäureamide.Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. Other suitable surfactants are polyhydroxy fatty acid amides.
Aus leistungstechnischer Sicht und im Hinblick auf die biologische Abbaubarkeit wird besonders bevorzugt ein linearer, ethoxylierte mit 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt.From a performance point of view and with regard to biodegradability, it is particularly preferable to use a linear, ethoxylated compound having 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol.
Der Gehalt an nichtionischen Tensiden beträgt in dem Waschmittel bevorzugt 2 bis 12,5 Gew.-%, vorzugsweise 4 bis 10 Gew.-% und insbesondere 5 bis 8 Gew.-%, jeweils bezogen auf das gesamte Waschmittel.The content of nonionic surfactants is in the detergent preferably 2 to 12.5 wt .-%, preferably 4 to 10 wt .-% and in particular 5 to 8 wt .-%, each based on the total detergent.
Neben dem/den nichtionischen Tensid(en) enthält die Tensidmischung des Waschmittels zwingend auch ein anionisches Tensid. Das anionische Tensid enthält ein Alkylbenzolsulfonat und eine Seife.In addition to the nonionic surfactant (s), the surfactant mixture of the detergent also necessarily contains an anionic surfactant. The anionic surfactant contains an alkyl benzene sulfonate and a soap.
Seifen sind gesättigte und ungesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern-, Olivenöl- oder Talgfettsäuren, abgeleitete Seifengemische.Soaps are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium- oder Magnesiumsalze vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natriumsalze vor. Ein weiteres bevorzugtes Gegenion für anionische Tenside ist Cholin.The anionic surfactants including the soaps may be in the form of their sodium, potassium or magnesium salts. Preferably, the anionic surfactants are in the form of their sodium salts. Another preferred counterion for anionic surfactants is choline.
In der Erfindung bevorzugt einsetzbare Alkylbenzolsulfonate sind insbesondere bevorzugt C9-13-Alkylbenzolsulfonate.Alkylbenzenesulfonates preferably used in the invention are particularly preferably C9-13-alkylbenzenesulfonates.
Zur Gewährleistung einer guten Waschleistung an einer Vielzahl an Verfleckungen, enthält das erfindungsgemäße Waschmittel mehr als 3,2 Gew.-%, bezogen auf das gesamte Mittel, an Alkylbenzolsulfonaten.To ensure a good washing performance on a variety of stains, the detergent according to the invention contains more than 3.2 wt .-%, based on the total agent, of alkylbenzenesulfonates.
Der Gehalt eines Waschmittels an anionischen Tensiden kann bis zu 14 Gew.-%, bezogen auf das gesamte Waschmittel, betragen. Der Gehalt eines Waschmittels an anionischen Tensiden liegt aber vorzugsweise unter 10 Gew.-%, bezogen auf das gesamte Mittel.The content of a detergent to anionic surfactants may be up to 14 wt .-%, based on the total detergent. However, the content of a detergent to anionic surfactants is preferably below 10 wt .-%, based on the total agent.
Neben der Tensidmischung enthält das Waschmittel ein Parfümöl. Das Parfümöl ist in einer Menge von 0,4 bis 1,5 Gew.-% und vorzugsweise von 0,7 bis 1,3 Gew.-% vorhanden.In addition to the surfactant mixture, the detergent contains a perfume oil. The perfume oil is present in an amount of from 0.4 to 1.5% by weight and preferably from 0.7 to 1.3% by weight.
Außerdem beträgt das Verhältnis des Parfümöls zu den der nichtionischen Tenside zwischen 1 : 5 und 1 : 30, vorzugsweise 1 : 5 und 1 : 15 und mehr bevorzugt zwischen 1 : 5 und 1 : 10.In addition, the ratio of the perfume oil to the nonionic surfactants is between 1: 5 and 1: 30, preferably 1: 5 and 1:15 and more preferably between 1: 5 and 1:10.
Ein Fachmann auf dem Gebiet der Waschmittel ist in der Lage, in den angegebenen Bereichen für das Verhältnis der nichtionischen Tenside zu anionischen Tenside, das Verhältnis der nichtionischen Tenside zu dem Parfümöl sowie dem Gesamttensidgehalt die erfindungsgemäßen Kombinationen zu erkennen bzw. die einzelnen Inhaltsstoffe (nichtionisches Tensid, anionisches Tensid und Parfümöl) erfindungsgemäß zu kombinieren, um zum Gegenstand der Erfindung, niedrigkonzentrierte Waschmittel mit relativ hohem Parfümgehalt, welche bei den verschiedensten Lagerbedingungen stabil sind, zu gelangen. Der Begriff "relativ" bezieht in diesem Zusammenhang nicht auf die absolute Menge an Parfüm, die im gesamten Waschmittel vorhanden ist, sondern die Menge an Parfüm, die (relativ) im Verhältnis zur Gesamttensidmenge vorhanden ist.One skilled in the detergent art is able to recognize in the ranges indicated for the ratio of nonionic surfactants to anionic surfactants, the ratio of nonionic surfactants to the perfume oil and the total surfactant content combinations of the invention or the individual ingredients (nonionic surfactant , anionic surfactant and perfume oil) according to the invention in order to obtain the object of the invention, low-concentrated detergents with a relatively high perfume content, which are stable under various storage conditions. The term "relative" in this context does not refer to the absolute amount of perfume that is present throughout the detergent, but the amount of perfume that is present (relative) relative to the total amount of surfactant.
Als Parfümöle können einzelne Riechstoffverbindungen, zum Beispiel die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind.As perfume oils, individual fragrance compounds, for example, the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from plant sources.
In einer bevorzugten Ausführungsform enthält das Parfümöl zu mindestens 15 Gew.-% Riechstoffe mit einem Siedepunkt über 250°C und einem logP-Wert von ≥ 3,0. Es hat sich gezeigt, dass erfindungsgemäße niedrigkonzentrierte Waschmittel, welche Parfümöle mit einer solchen Mindestmenge an Riechstoffen mit einem Siedepunkt über 250°C und einem logP-Wert von ≥ 3,0 enthalten, besonders vorteilhafte Dufteigenschaften aufweisen. Beispielsweise kann ein noch länger anhaltender Dufteindruck auf der Wäsche erzielt werden. Ebenso kann das Aufziehverhalten der Riechstoffe im Trockner auf die Wäsche noch weiter verbessert werden, so dass die Wäsche noch länger und noch intensiver riecht.In a preferred embodiment, the perfume oil contains at least 15% by weight of fragrances having a boiling point above 250 ° C. and a logP value of ≥ 3.0. It has been found that inventive low-concentration detergents containing perfume oils with such a minimum amount of fragrances having a boiling point above 250 ° C and a logP value of ≥ 3.0, have particularly advantageous fragrance properties. For example, an even longer lasting fragrance impression on the laundry can be achieved. Likewise, the Aufziehverhalten the fragrances in the dryer can be further improved on the laundry, so that the laundry smells even longer and more intense.
Der Octanol/Wasser-Verteilungskoeffizient eines Duftstoff-Bestandteils ist das Verhältnis zwischen seiner Gleichgewichtskonzentration in Octanol und in Wasser. Da die Verteilungskoeffizienten der Duftstoffbestandteile oft hohe Werte haben, zum Beispiel 1000 oder höher, werden sie zweckmäßiger in der Form ihres Logarithmus zur Basis 10 angegeben, man spricht dann vom so genannten log-P-Wert. Bevorzugte Riechstoffe dieser Erfindung weisen einen logP von ≥ 3,0 oder höher auf, zum Beispiel von ≥ 3,1, vorzugsweise ≥ 3,2 und insbesondere ≥ 3,3.The octanol / water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. Since the distribution coefficients of the perfume ingredients often have high values, for example 1000 or higher, they more appropriately become base in terms of their logarithm 10, one speaks of the so-called log P value. Preferred fragrances of this invention have a logP of ≥ 3.0 or higher, for example, ≥ 3.1, preferably ≥ 3.2, and especially ≥ 3.3.
Der logP-Wert zahlreicher Riechstoffe ist dokumentiert; zum Beispiel enthält die Pomona92-Datenbank, verfügbar von Daylight Chemical Information Systems, Inc., (Daylight CIS), Irvine, Kalifornien, zahlreiche logP-Werte, zusammen mit Zitaten zur Originalliteratur. Jedoch werden die logP-Werte am zweckmäßigsten durch das "CLOGP"-Programm, das auch von Daylight CIS verfügbar ist, berechnet. Dieses Programm führt auch die experimentellen logP-Werte auf, wenn sie in der Pomona92-Datenbank verfügbar sind. Der "errechnete logP" (ClogP-Wert) wird durch die Fragmentannäherung nach Harsch und Leo (siehe
Die Siedepunkte zahlreicher Riechstoffe sind zum Beispiel in "
Andere Siedepunktwerte können zum Beispiel von verschiedenen, bekannten Chemiehandbüchern und Datenbanken erhalten werden. Wenn ein Siedepunkt nur bei einem unterschiedlichen Druck angegeben ist, in der Regel einem niedrigeren Druck als dem Normaldruck von 760 mm Hg, kann der Siedepunkt bei Normaldruck ungefähr mit Hilfe der Siedepunkt-Druck-Nomographen, wie die in "
Im Folgenden werden in Tabelle 1 einige Riechstoffe beispielhaft aufgeführt, welche die Kriterien Siedepunkt > 250°C und ClogP ≥ 3 erfüllen.
Diese Tabelle gibt eine hinreichende Anzahl nicht einschränkender Beispiele für Riechstoffe, welche im Rahmen dieser Erfindung bevorzugt einsetzbar sind. Die Parfümöle der erfindungsgemäßen Waschmittel enthalten vorzugsweise mindestens 3 unterschiedliche Riechstoffe, stärker bevorzugt mindestens 4 unterschiedliche Riechstoffe, und noch weiter bevorzugt mindestens 5 unterschiedliche Riechstoffe.This table gives a sufficient number of nonlimiting examples of fragrances which are preferred for use in this invention. The perfume oils of the inventive detergents preferably contain at least 3 different fragrances, more preferably at least 4 different fragrances, and even more preferably at least 5 different fragrances.
Zusätzlich zu den Tensiden und dem Parfümöl kann das Waschmittel weitere Inhaltsstoffe enthalten, die die anwendungstechnischen und/oder ästhetischen Eigenschaften des Waschmittels weiter verbessern. Im Rahmen der vorliegenden Erfindung enthält das Wasch- oder Reinigungsmittel vorzugsweise zusätzlich einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Bleichmittel, Bleichkatalysatoren, Bleichaktivatoren, Enzyme, Elektrolyte, nichtwässrigen Lösungsmittel, pH-Stellmittel, Parfümträger, Fluoreszenzmittel, Farbstoffe, Hydrotope, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell- und Schiebefestmittel, weichmachenden Komponenten sowie UV-Absorber.In addition to the surfactants and the perfume oil, the detergent may contain other ingredients that further improve the performance and / or aesthetic properties of the detergent. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, Silicone oils, anti redeposition agents, graying inhibitors, anti-shrinkage agents, wrinkle inhibitors, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.
Als Gerüststoffe, die in dem Waschmittel enthalten sein können, sind beispielsweise Silikate, Aluminiumsilikate (insbesondere Zeolithe), Phosphate oder Carbonate zu nennen.Suitable builders which may be present in the detergent are, for example, silicates, aluminum silicates (in particular zeolites), phosphates or carbonates.
Aus Gründen der Ästhetik werden allerdings bevorzugt lösliche, organische Gerüststoffe in den flüssigen Waschmitteln eingesetzt.For reasons of aesthetics, however, preference is given to using soluble, organic builders in the liquid detergents.
Organische Gerüststoffe, welche in dem Waschmittel vorhanden sein können, sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), Methylglycindiessigsäure (MGDA) und deren Abkömmlinge sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen.Organic builders which may be present in the detergent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Werts von Waschmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
Als Gerüststoffe sind weiter polymere Polycarboxylate geeignet. Dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure.As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid.
Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten.Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zuckerderivate enthalten.Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
Citronensäure, beziehungsweise deren Salze, werden bevorzugt als lösliche, organische Gerüststoffe in den flüssigen Waschmitteln eingesetzt.Citric acid, or its salts, are preferably used as soluble, organic builders in the liquid detergents.
Das flüssige Waschmittel kann auch ein Enzym oder eine Mischung aus Enzymen enthalten. Geeignet sind insbesondere solche aus der Klassen der Hydrolasen wie der Proteasen, (Poly)-Esterasen, Lipasen bzw. lipolytisch wirkende Enzyme, Amylasen, Cellulasen bzw. andere Glykosylhydrolasen, Hemicellulase, Cutinasen, β-Glucanasen, Oxidasen, Peroxidasen, Mannanasen, Perhydrolasen, Oxireduktasen und/oder Laccasen. Im Rahmen der vorliegenden Erfindung werden bevorzugt Proteasen, Amylasen, Lipasen, Cellulasen, Mannanasen, Laccasen, Tannanasen und Esterasen/Polyesterasen sowie Mischungen aus zwei oder mehr dieser Enzyme eingesetzt.The liquid detergent may also contain an enzyme or a mixture of enzymes. Particularly suitable are those from the classes of hydrolases such as proteases, (poly) esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, β-glucanases, oxidases, peroxidases, mannanases, perhydrolases, Oxireductases and / or laccases. Proteases, amylases, lipases, cellulases, mannanases, laccases, tannanases and esterases / polyesterases and mixtures of two or more of these enzymes are preferably used in the context of the present invention.
Die Menge an Enzym bzw. an den Enzymen beträgt bezogen auf das gesamte Mittel 0,01 bis 10 Gew.-%, vorzugsweise 0,12 bis etwa 3 Gew.-%. Die Enzyme werden bevorzugt als Enzymflüssiformulierung(en) eingesetzt.The amount of enzyme or of the enzymes is based on the total agent 0.01 to 10 wt .-%, preferably 0.12 to about 3 wt .-%. The enzymes are preferably used as enzyme liquid formulation (s).
Zur Stabilisierung der Enzyme können die erfindungsgemäßen Waschmittel Stabilisierungsmittel wie Borsäure bzw. Borate, Borsäure-Derivate oder Aminoalkohole enthalten.To stabilize the enzymes, the detergents according to the invention may contain stabilizing agents, such as boric acid or borates, boric acid derivatives or amino alcohols.
Als Elektrolyte aus der Gruppe der anorganischen Salze kann eine breite Anzahl der verschiedensten Salze eingesetzt werden. Bevorzugte Kationen sind die Alkali- und Erdalkalimetalle, bevorzugte Anionen sind die Halogenide und Sulfate. Der Anteil an Elektrolyten in dem Waschmittel beträgt üblicherweise 0,1 bis 5 Gew.-%.As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. The proportion of electrolytes in the detergent is usually 0.1 to 5 wt .-%.
Nichtwässrige Lösungsmittel, die dem Waschmittel eingesetzt werden können, stammen beispielsweise aus der Gruppe der ein- oder mehrwertigen Alkohole, Alkanolamine oder Glycolether, sofern sie im angegebenen Konzentrationsbereich mit Wasser mischbar sind. Es können Lösungsmittel eingesetzt werden, die aus Ethanol, n- oder i-Propanol, Butanolen, Glycol, Propan- oder Butandiol, Glycerin, Diglycol, Propyl- oder Butyldiglycol, Hexylenglycol, Ethylenglycolmethylether, Ethylenglycolethylether, Ethylenglycolpropylether, Ethylenglycolmono-n-butylether, Diethylenglycolmethylether, Diethylenglycolethylether, Propylenglycolmethyl-, -ethyl- oder - propylether, Dipropylenglycolmonomethyl- oder -ethylether, Di-isopropylenglycolmonomethyl- oder - ethylether, Methoxy-, Ethoxy- oder Butoxytriglycol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glycol-t-butylether, Di-n-octylether sowie Mischungen dieser Lösungsmittel ausgewählt sind. Nichtwässrige Lösungsmittel können in dem Waschmittel in Mengen zwischen 0,5 und 25 Gew.-%, bevorzugt aber unter 20 Gew.-% und insbesondere unterhalb von 15 Gew.-% eingesetzt werden.Non-aqueous solvents that can be used in the detergent, for example, come from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. Solvents can be used which consist of ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol , Propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents are selected. Non-aqueous solvents can be used in the detergent in amounts between 0.5 and 25 wt .-%, but preferably below 20 wt .-% and in particular below 15 wt .-%.
Es ist allerdings bevorzugt, dass das Waschmittel bestimmte Mengen an einem Polyol als nicht-wässriges Lösungsmittel enthält. Es ist bevorzugt, dass das Waschmittel 2 bis 10 Gew.-% eines Polyols enthält. Das Polyol kann Glycerin, 1,2-Propandiol, 1,3-Propandiol, Ethylenglycol, Diethylenglycol und/oder Dipropylenglycol umfassen. Insbesondere bevorzugt enthält das Waschmittel Glycerin.However, it is preferred that the detergent contains certain amounts of a polyol as a nonaqueous solvent. It is preferable that the detergent contains 2 to 10% by weight of a polyol. The polyol may include glycerol, 1,2-propanediol, 1,3-propanediol, ethylene glycol, diethylene glycol and / or dipropylene glycol. Most preferably, the detergent contains glycerol.
Um den pH-Wert des Waschmittels in den gewünschten Bereich zu bringen, kann der Einsatz von pH-Stellmitteln angezeigt sein. Einsetzbar sind hier sämtliche bekannten Säuren bzw. Laugen, sofern sich ihr Einsatz nicht aus anwendungstechnischen oder ökologischen Gründen bzw. aus Gründen des Verbraucherschutzes verbietet. Der pH-Wert des Waschmittels liegt bevorzugt zwischen 4 und 10, bevorzugt zwischen 6,5 und 9 und am meisten bevorzugt zwischen 7 und 8,8.In order to bring the pH of the detergent into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. The pH of the detergent is preferably between 4 and 10, preferably between 6.5 and 9, and most preferably between 7 and 8.8.
Die flüssigen Waschmittel weisen bevorzugt Viskositäten im Bereich von 200 bis 5000 mPas auf, wobei Werte zwischen 300 und 2000 mPas und insbesondere 400 und 1000 mPas besonders bevorzugt sind. Die Bestimmung der Viskosität erfolgte mit einem Brookfield-Viskosimeter LVT-II bei 20 U/min und 20°C, Spindel 3.The liquid detergents preferably have viscosities in the range from 200 to 5000 mPas, with values between 300 and 2000 mPas and in particular 400 and 1000 mPas being particularly preferred. The viscosity was determined using a Brookfield LVT-II viscometer at 20 rpm and 20 ° C., spindle 3.
Um den ästhetischen Eindruck des Waschmittels zu verbessern, können sie mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Wasch- oder Reinigungsmittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber Textilfasern, um diese nicht anzufärben.To improve the aesthetic impression of the detergent, they can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents or cleaning agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
Als Schauminhibitoren, die in den Waschmitteln eingesetzt werden können, kommen beispielsweise Seifen, Paraffine oder Silikonverbindungen, insbesondere Silikonöle, in Betracht, die gegebenenfalls als Emulsionen vorliegen.Suitable foam inhibitors which can be used in the detergents are, for example, soaps, paraffins or silicone compounds, in particular silicone oils, which are optionally present as emulsions.
Geeignete Soil-Release-Polymere, die auch als "Antiredepositionsmittel" bezeichnet werden, sind beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxypropylcellulose sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylen- und/oder Polypropylenglykolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen. Geeignete Derivate umfassen die sulfonierten Derivate der Phthalsäure- und Terephthalsäure-Polymere.Suitable soil-release polymers, which are also referred to as "anti redeposition agents", are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.
Optische Aufheller (so genannte "Weißtöner") können den Waschmitteln zugesetzt werden, um Vergrauungen und Vergilbungen der behandelten textilen Flächengebilde zu beseitigen. Geeignete Verbindungen stammen beispielsweise aus den Substanzklassen der 4,4'-Diamino-2,2'-stilbendisulfonsäuren (Flavonsäuren), 4,4'-Distyryl-biphenylen, Methylumbelliferone, Cumarine, Dihydrochinolinone, 1,3-Diarylpyrazoline, Naphthalsäureimide, Benzoxazol-, Benzisoxazol- und Benzimidazol-Systeme sowie der durch Heterocyclen substituierten Pyrenderivate. Die optischen Aufheller werden üblicherweise in Mengen zwischen 0% und 0,3 Gew.-%, bezogen auf das fertige Waschmittel, eingesetzt.Optical brighteners (so-called "whiteners") can be added to the detergents to eliminate graying and yellowing of the treated fabrics. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. The optical brighteners are usually used in amounts of between 0% and 0.3% by weight, based on the finished detergent.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Wiederaufziehen des Schmutzes zu verhindern. Bevorzugt werden dazu Celluloseether wie Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Gesamtmenge an Waschmittel, eingesetzt.Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof are preferably used in amounts of from 0.1 to 5% by weight, based on the total amount of detergent.
Um während des Waschens von gefärbten Textilien die Farbstoffablösung und/oder die Farbstoffübertragung auf andere Textilien wirksam zu unterdrücken, kann das Waschmittel einen Farbübertragungsinhibitor enthalten. Es ist bevorzugt, dass der Farbübertragungsinhibitor ein Polymer oder Copolymer von cyclischen Aminen wie beispielsweise Vinylpyrrolidon und/oder Vinylimidazol ist. Als Farbübertragungsinhibitor geeignete Polymere umfassen Polyvinylpyrrolidon (PVP), Polyvinylimidazol (PVI), Copolymere von Vinylpyrrolidon und Vinylimidazol (PVP/PVI), Polyvinylpyridin-N-oxid, Poly-N-carboxymethyl-4-vinylpyridiumchlorid sowie Mischungen daraus. Besonders bevorzugt werden Polyvinylpyrrolidon (PVP), Polyvinylimidazol (PVI) oder Copolymere von Vinylpyrrolidon und Vinylimidazol (PVP/PVI) als Farbübertragungsinhibitor eingesetzt. Polyvinylpyrrolidone (PVP) sind beispielsweise kommerziell von ISP Chemicals als PVP K 15, PVP K 30, PVP K 60 oder PVP K 90 oder von der BASF als Sokalan® HP 50 oder Sokalan® HP 53 erhältlich. PVP/PVI-Copolymere sind beispielsweise kommerziell von der BASF unter der Bezeichnung Sokalan® HP 56 erhältlich.In order to effectively suppress dye release and / or dye transfer to other fabrics during washing of dyed fabrics, the detergent may contain a dye transfer inhibitor. It is preferred that the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. Suitable color transfer inhibiting polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, and mixtures thereof. Particular preference is given to using polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as color transfer inhibitor. Polyvinylpyrrolidones (PVP) are for example commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53. PVP / PVI copolymers are commercially available, for example, from BASF under the name Sokalan® HP 56.
Die Menge an Farbübertragungsinhibitor bezogen auf die Gesamtmenge des Waschmittels liegt bevorzugt von 0,01 bis 2 Gew.-%, vorzugsweise von 0,05 bis 1 Gew.-% und mehr bevorzugt von 0,1 bis 0,5 Gew.-%.The amount of dye transfer inhibitor based on the total amount of the detergent is preferably from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight, and more preferably from 0.1 to 0.5% by weight.
Alternativ können aber auch enzymatische Systeme, umfassend eine Peroxidase und Wasserstoffperoxid beziehungsweise eine in Wasser Wasserstoffperoxid-liefernde Substanz als Farbübertragungsinhibitor eingesetzt werden. Der Zusatz einer Mediatorverbindung für die Peroxidase, zum Beispiel eines Acetosyringons, eines Phenolderivats oder eines Phenotiazins oder Phenoxazins, ist in diesem Fall bevorzugt, wobei auch zusätzlich die oben genannten polymeren Farbübertragungsinhibitoren eingesetzt werden können.Alternatively, however, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water as a color transfer inhibitor. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, wherein additionally the above-mentioned polymeric dye transfer inhibitors can be used.
Die erfindungsgemäßen Waschmittel können Konservierungsmittel enthalten, wobei vorzugsweise nur solche eingesetzt werden, die kein oder nur ein geringes hautsensibilisierendes Potential besitzen. Beispiele sind Sorbinsäure und seine Salze, Benzoesäure und seine Salze, Salicylsäure und seine Salze, Phenoxyethanol, Ameisensäure und seine Salze, 3-Iodo-2-propynylbutylcarbamat, Natrium N-(hydroxymethyl)glycinat, Biphenyl-2-ol sowie Mischungen davon. Weitere geeignete Konservierungsmittel stellen Isothiazolone, Mischungen von Isothiazolonen und Mischungen von Isothiazolonen mit anderen Verbindungen, beispielsweise Tetramethylolglycoluril, dar.The detergents according to the invention may contain preservatives, it being preferred to use only those which have no or only a slight skin-sensitizing potential. Examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, formic acid and its salts, 3-iodo-2-propynyl butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof. Further suitable preservatives are isothiazolones, mixtures of isothiazolones and mixtures of isothiazolones with other compounds, for example tetramethylolglycoluril.
Um die durch Schwermetalle katalysierte Zersetzung bestimmter Waschmittel-Inhaltsstoffe zu vermeiden, können Stoffe eingesetzt werden, die Schwermetalle komplexieren. Geeignete Schwermetallkomplexbildner sind beispielsweise die Alkalisalze der Ethylendiamintetraessigsäure (EDTA) oder der Nitrilotriessigsäure (NTA), Methylglycindiessigsäure-Trinatriumsalz (MGDA) sowie Alkalimetallsalze von anionischen Polyelektrolyten wie Polymaleaten und Polysulfonaten.In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, substances that complex heavy metals can be used. Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), methylglycinediacetic acid trisodium salt (MGDA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
Eine bevorzugte Klasse von Komplexbildnern sind die Phosphonate, die in dem Waschmittel in Mengen von 0,01 bis 2,5 Gew.-%, vorzugsweise 0,02 bis 2 Gew.-% und insbesondere von 0,03 bis 1,5 Gew.-% enthalten sind. Zu diesen bevorzugten Verbindungen zählen insbesondere Organophosphonate wie beispielsweise 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), Aminotri(methylenphosphonsäure) (ATMP), Diethylentriamin-penta(methylenphosphonsäure) (DTPMP bzw. DETPMP) sowie 2-Phosphonobutan-1,2,4-tricarbonsäure (PBS-AM), die zumeist in Form ihrer Ammonium- oder Alkalimetallsalze eingesetzt werden. Alternative Komplexbildner, die in dem Waschmittel eingesetzt werden können sind Iminodisuccinate (IDS) oder Ethylendiamin-N,N'-disuccinat (EDDS).A preferred class of complexing agents are the phosphonates present in the detergent in amounts of from 0.01% to 2.5%, preferably from 0.02% to 2%, and more preferably from 0.03 to 1.5% by weight. -% are included. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts. Alternative chelating agents that can be used in the detergent are iminodisuccinate (IDS) or ethylenediamine-N, N'-disuccinate (EDDS).
Die erfindungsgemäßen Waschmittel können zum Waschen von textilen Flächengebilden verwendet werden.The detergents according to the invention can be used for washing textile fabrics.
Die Herstellung des Waschmittels erfolgt mittels üblicher und bekannter Methoden und Verfahren. So können beispielsweise die Bestandteile der Waschmittel einfach in Rührkesseln vermischt werden, wobei Wasser, die sauren Komponenten, falls jeweils vorhanden, wie beispielsweise die Alkylbenzolsulfonate, Citronensäure, Borsäure, Phosphonsäure, die Fettalkoholethersulfate, usw., und die nichtionischen Tenside zweckmäßigerweise vorgelegt werden. Die nicht-wässrigen Lösungsmittel, falls vorhanden, werden vorzugsweise auch zu diesem Zeitpunkt zugegeben, die Zugabe kann aber auch zu einem späteren Zeitpunkt erfolgen. Anschließend wird, falls vorhanden, die Fettsäure zugegeben und es erfolgt die Verseifung des Fettsäureanteils bei 50 bis 60 °C. Dann werden die weiteren Bestandteile vorzugsweise portionsweise, hinzugefügt. Entscheidend ist allerdings, dass die zugesetzte Aktivstoffmenge an nichtionischen Tensiden mindestens gleich der zugesetzten Aktivstoffmenge der anionischen Tenside ist und dass die Menge an Parfümöl, die zugesetzt wird, zwischen 0,5 und 1,5 Gew.-%, bezogen auf die Gesamtmenge an Waschmittel, liegt.The detergent is produced by means of customary and known methods and processes. Thus, for example, the ingredients of the detergents can be easily mixed in stirred tanks, with water, the acidic components, if present, such as the alkylbenzenesulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc., and the nonionic surfactants are conveniently presented. The nonaqueous solvents, if present, are preferably also added at this time, but the addition may be made at a later time. Subsequently, if present, the fatty acid is added and the saponification of the fatty acid moiety is carried out at 50 to 60 ° C. Then the further ingredients are preferably added in portions. It is crucial, however, that the amount of active ingredient added to nonionic surfactants is at least equal to the added amount of active anionic surfactants and that the amount of perfume oil added, between 0.5 and 1.5 wt .-%, based on the total amount of detergent , lies.
In der folgenden Tabelle 2 sind die Zusammensetzungen von drei Vergleichsrezepturen V1 und V2 sowie die Zusammensetzungen von drei erfindungsgemäßen Waschmittels E1 - E4 gezeigt (alle Mengen sind in Gew.-% Aktivstoff, bezogen auf das Mittel, angegeben):
Die erhaltenen Waschmittel V1 - V2 und E1 - E4 wurden Lagertests, die unterschiedliche klimatische Bedingungen simulieren, unterworfen.
Die Lagerung der erfindungsgemäßen Waschmittel erfolgte bei den angegebenen Temperaturen, wobei die Temperaturen jeweils in einem definierten Zyklus innerhalb des angegebenen Temperaturbereichs schwankten. Die Beurteilung erfolgte entweder bei Raumtemperatur oder bei der untersten Temperatur eines Temperaturbereichs.The storage of the detergent according to the invention was carried out at the indicated temperatures, wherein the temperatures each fluctuated within a defined cycle within the specified temperature range. The evaluation was done either at room temperature or at the lowest temperature of a temperature range.
Aus den Stabilitätstests wird deutlich, dass bei Einstellung des erfindungsgemäßen Verhältnisses von nichtionischen Tensiden zu anionischen Tensiden von mindestens 0,75 : 1 niedrigkonzentrierte (der Gesamttensidgehalt beträgt zwischen 13,87 Gew.-% in Beispiel E1 und13,46 Gew.-% in Beispiel E4) Waschmitteln erhalten werden, die bei den verschiedensten klimatischen Bedingungen stabil sind. Zusätzlich wird deutlich, dass die erfindungsgemäßen Waschmittel in der Lage sind, das Parfümöl bei einem geringeren Gesamttensidgehalt lagerstabil und homogen zu dispergieren.From the stability tests it is clear that when the ratio according to the invention of nonionic surfactants to anionic surfactants of at least 0.75: 1 is adjusted to low (the total surfactant content is between 13.87% by weight in Example E1 and 13.46% by weight in Example E4) detergents are obtained which are stable under a wide variety of climatic conditions. In addition, it is clear that the detergents according to the invention are able to disperse the perfume oil at a lower total surfactant storage stability and homogeneous.
In der folgenden Tabelle 4 sind die Zusammensetzungen von zwei Vergleichsrezepturen V3 und V4 sowie zwei erfindungsgemäße Rezepturen E5 und E6 gezeigt (alle Mengen sind in Gew.-% Aktivstoff, bezogen auf das Mittel, angegeben):
Aus den Stabilitätstests wird deutlich, dass bei Einstellung des erfindungsgemäßen Verhältnisses von nichtionischen Tensiden zu anionischen Tensiden von mindestens 0,75 : 1 niedrigkonzentrierte (der Gesamttensidgehalt beträgt 13,73 Gew.-% in den Beispielen E5 und E6) Waschmitteln mit hohen Parfümölgehalten erhalten werden, die bei den verschiedensten klimatischen Bedingungen lagerstabil sind.From the stability tests it is clear that when the ratio of nonionic surfactants according to the invention to anionic surfactants of at least 0.75: 1 low concentrated (the total surfactant content is 13.73 wt .-% in Examples E5 and E6) detergents are obtained with high perfume oil which are storage stable under a wide variety of climatic conditions.
In der folgenden Tabelle 6 sind die Zusammensetzungen von drei erfindungsgemäßen Rezepturen E7 bis E9 gezeigt (alle Mengen sind in Gew.-% Aktivstoff, bezogen auf das Mittel, angegeben):
Alle drei Zusammensetzungen waren bei den oben angegebenen sechs verschiedenen Lager- und Bestimmungsbedingungen 8 Wochen lang ohne Befund ("OK").All three compositions were undetectable for 8 weeks at the six different storage and assay conditions given above ("OK").
Die im Rahmen dieser Erfindung eingesetzten Parfümöle A bis C enthalten jeweils mindestens 15 Gew.-% Riechstoffe mit einem Siedepunkt über 250 °C und einem logP-Wert bzw. ClogP-Wert von ≥ 3,0. Der Gehalt an diesen Riechstoffen in den jeweiligen Parfümölen A bis C steigt in der folgenden Reihenfolge an: Parfümöl A < Parfümöl B < Parfümöl C.The perfume oils A to C used in the context of this invention each contain at least 15% by weight of fragrances having a boiling point above 250 ° C. and a logP value or ClogP value of ≥ 3.0. The content of these fragrances in the respective perfume oils A to C increases in the following order: perfume oil A <perfume oil B <perfume oil C.
Bei Waschversuchen mit Waschmitteln, enthaltend eine Tensidmischung aus nichtionischen und anionischen Tensiden, wobei das Verhältnis der nichtionischen Tenside zu den anionischen Tensiden mindestens 0,75 : 1 beträgt, hat sich gezeigt, dass es vorteilhaft ist, wenn die Waschmittel mehr als 3,2 Gew.-% eines Alkylbenzolsulfonats enthält.
Alle drei Zusammensetzungen waren bei den oben angegebenen sechs verschiedenen Lager- und Bestimmungsbedingungen 8 Wochen lang ohne Befund ("OK").All three compositions were undetectable for 8 weeks at the six different storage and assay conditions given above ("OK").
Jedoch zeigte das Waschmittel V12 eine schlechtere Reinigungsleistung an Fett-haltigen Verfleckungen:
Claims (8)
- A liquid washing agent containing a perfume oil and from 5 to 18 wt.% of a surfactant mixture consisting of non-ionic and anionic surfactants, wherein the anionic surfactant contains an alkylbenzene sulfonate and a soap, and wherein the amount of alkylbenzene sulfonate is more than 3.2 wt.%, the amount of perfume oil is from 0.4 to 1.5 wt.%, the ratio of the non-ionic surfactants to the anionic surfactants is at least 0.75:1 and the ratio of the non-ionic surfactants to the perfume oil is between 5:1 and 30:1.
- The washing agent according to claim 1, characterized in that the ratio of the non-ionic surfactants to the perfume oil is between 5:1 and 15:1 and more preferably between 5:1 and 10:1.
- The washing agent according to claim 1 or claim 2, characterized in that the amount of the surfactant mixture is from 8 to 15 wt.%.
- The washing agent according to one of claims 1 to 3, characterized in that the ratio of the non-ionic surfactants to the anionic surfactants is between 0.75:1 and 5:1, preferably between 0.75:1 and 3:1.
- The washing agent according to one of claims 1 to 4, characterized in that the amount of perfume oil is from 0.7 to 1.3 wt.%.
- The washing agent according to one of claims 1 to 5, characterized in that the perfume oil contains at least 15 wt.% of odorants having a boiling point of above 250 °C and a logP value of ≥ 3.0.
- The use of the washing agent according to one of claims 1 to 6 for the washing of textile fabrics.
- A method for producing a liquid washing agent containing a perfume oil and from 5 to 18 wt.% of a surfactant mixture consisting of non-ionic and anionic surfactants, wherein the anionic surfactant contains an alkylbenzene sulfonate and a soap, the amount of alkylbenzene sulfonate is more than 3.2 wt.% and the amount of perfume oil is from 0.4 to 1.5 wt.%, and wherein the non-ionic surfactants are added to the agent at least in a ratio to the anionic surfactants of 0.75:1 and in a ratio to the perfume oil of between 5:1 and 30:1.
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PL09714574T PL2245131T5 (en) | 2008-02-29 | 2009-01-15 | Low-concentration liquid detergents or cleaners containing perfume |
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DE102008012061A DE102008012061A1 (en) | 2008-02-29 | 2008-02-29 | Low Concentrated Liquid Detergent or Detergent with Perfume |
PCT/EP2009/050419 WO2009106378A1 (en) | 2008-02-29 | 2009-01-15 | Low-concentration liquid detergents or cleaners containing perfume |
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EP2245131A1 EP2245131A1 (en) | 2010-11-03 |
EP2245131B1 EP2245131B1 (en) | 2016-07-06 |
EP2245131B2 true EP2245131B2 (en) | 2019-07-10 |
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EP09714574.2A Active EP2245131B2 (en) | 2008-02-29 | 2009-01-15 | Low-concentration liquid detergents or cleaners containing perfume |
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US (1) | US20100317561A1 (en) |
EP (1) | EP2245131B2 (en) |
DE (1) | DE102008012061A1 (en) |
ES (1) | ES2592688T5 (en) |
PL (1) | PL2245131T5 (en) |
WO (1) | WO2009106378A1 (en) |
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DE102008012061A1 (en) | 2008-02-29 | 2009-09-03 | Henkel Ag & Co. Kgaa | Low Concentrated Liquid Detergent or Detergent with Perfume |
DE102013226426A1 (en) * | 2013-12-18 | 2015-06-18 | Henkel Ag & Co. Kgaa | Preservative system for detergents |
WO2017010971A1 (en) * | 2015-07-10 | 2017-01-19 | Colgate-Palmolive Company | Cleaning compositions and methods for enhancing fragrance performance |
DE102016206647A1 (en) * | 2016-04-20 | 2017-10-26 | Henkel Ag & Co. Kgaa | liquid detergent |
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Also Published As
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ES2592688T3 (en) | 2016-12-01 |
ES2592688T5 (en) | 2020-02-21 |
PL2245131T3 (en) | 2017-01-31 |
PL2245131T5 (en) | 2019-10-31 |
DE102008012061A1 (en) | 2009-09-03 |
US20100317561A1 (en) | 2010-12-16 |
WO2009106378A1 (en) | 2009-09-03 |
EP2245131A1 (en) | 2010-11-03 |
EP2245131B1 (en) | 2016-07-06 |
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