EP1713896A1 - Mikroemulsionen - Google Patents
MikroemulsionenInfo
- Publication number
- EP1713896A1 EP1713896A1 EP05701327A EP05701327A EP1713896A1 EP 1713896 A1 EP1713896 A1 EP 1713896A1 EP 05701327 A EP05701327 A EP 05701327A EP 05701327 A EP05701327 A EP 05701327A EP 1713896 A1 EP1713896 A1 EP 1713896A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- microemulsion
- advantageously
- acid
- use according
- less
- 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.)
- Granted
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
- C11D17/0021—Aqueous microemulsions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
Definitions
- European Patent EP 0 789 070 B1 discloses the use of a fabric softening composition containing an skin benefit substance for delivering this substance to the skin and providing sensory and / or cosmetic benefits to the skin when combined with the composition fabrics treated with the skin in contact with the fabric softening composition of 4 to 32 weight percent of a water-insoluble fabric softening quaternary ammonium compound having two C 12 - 28 includes alkyl or alkenyl groups attached to the N atom via one or more Esteritatien, ,
- the use of a fabric softening composition containing a substance conferring an advantage on the skin for delivering this substance to the skin and for conferring sensory and / or cosmetic benefits to the skin when textiles treated with the composition come into contact with the skin wherein the skin benefit agent is a silicone is disclosed in the same document.
- DE 37 16 526 C2 discloses a stable oil-in-water microemulsion, which consists of 1 to 10 wt .-% of water-soluble anionic surfactant or 2 to 20 wt .-% of a mixture of water-soluble anionic and water-soluble nonionic surfactant, and from From 2 to 10% by weight of a cosurfactant selected from the group of polypropylene glycol ethers, monoalkyl ethers and certain esters of ethylene glycol or propylene glycol, aliphatic mono- and dicarboxylic acids having from 3 to 6 carbon atoms in the molecule, C 9 to C 15 alkyl ether polyethenoxycarboxylic acids, and Mono-, di- and triethyl phosphate, further from 0.4 to 10 wt .-% of water-insoluble, 0 to 80 wt .-% terpene-containing, fragrant perfume, and consists of water, optionally with inorganic or organic salt of a
- concentrated oil-in-water microemulsions comprising from 10 to 35% by weight of water-soluble anionic surfactant or from 18 to 65% by weight of a mixture of water-soluble anionic and water-soluble nonionic surfactant, and from 2 to 30 %
- a cosurfactant selected from the group of polypropylene glycol ethers, monoalkyl ethers and certain esters of ethylene glycol or propylene glycol, aliphatic mono- and dicarboxylic acids having 3 to 6 carbon atoms in the molecule, C 9 to C 15 alkyl ether polyethenoxycarboxylic acids, and mono-, Di- and triethyl phosphate, further from 10 to 50 wt .-% of water-insoluble, 0 to 80 wt .-% terpene-containing, fragrant perfume, and consist of water, wherein optionally inorganic or organic salt of a polyvalent metal, but no builder or Solubilizing agent is present
- the subject of the present invention is the use of a microemulsion for textile treatment in an automatic washing machine.
- This item has several advantages.
- a very important advantage is that the alternative possibility of textile treatment offered to the consumer with the object of the invention is easily carried out in an automatic washing machine, since the use of the microemulsion is characterized, inter alia, by the fact that the microemulsion excels very well from the dispensing chamber commercially available automatic washing machine can be flushed into the laundry room.
- the dispersibility of the microemulsion is very good even in cold water.
- Another advantage of the invention is that the use of the microemulsion according to the invention has a dual benefit for the consumer.
- emulsifiers are considered to be lipophilic essentially when they are advantageously predominantly soluble or miscible with C 1 -C 20 -triglycerides. Lipophilicity can result, for example, when the emulsifiers have, for example, hydrocarbon radicals having 6 to 22 carbon atoms or contain aryl radicals, for example, to give illustrative but non-limiting examples. Lipophilic emulsifiers are essentially of a slightly polar, rather non-polar character. Lipophilic emulsifiers for the purposes of this invention are lipophilic cationic emulsifiers.
- the terms skin care, skin protection and skin healing are to be distinguished.
- the skin care essentially achieves a cosmetic benefit in terms of sensory needs z. Softness or gloss of the skin under normal conditions.
- the good flushability of the microemulsion within the context of the use according to the invention is a significant advantage of the subject of the invention.
- the flushability of the microemulsion and its dispersibility even in cold water are especially good, if certain maximum values for the droplet size are not exceeded and certain minimum values are not exceeded.
- such microemulsions are also particularly stable.
- an important advantage of the subject invention is that, as a result of the use according to the invention, a textile treated with a corresponding microemulsion is beneficial to the health of the skin. It is therefore advantageous if the microemulsions to be used according to the invention have further ingredients which are beneficial for the well-being of the skin.
- the moisturizing factors mentioned are advantageous because they can help to regulate the moisture content of the skin. It is known that textiles, which generally have a certain absorbency, may also lose moisture on contact of the textile with the skin of the latter. The skin can thus be protected by the mere Before lying directly on the body or coming into contact with it, moisture is removed. The presence of moisturizing factors in the microemulsion can now advantageously lead to at least compensate for this loss, if not to overcompensate it.
- the complexing agents are preferably present in certain proportions.
- Microemulsions the complexing agent in amounts of at least 1, 5 wt .-%, advantageously of at least 2.5 wt .-%, more preferably in amounts of at least 4 wt .-%, more preferably in amounts of at least 6 %
- By weight in particular in amounts of at least 7.5% by weight, preferably having an upper limit of 25% by weight, advantageously 20% by weight, more preferably 17% by weight.
- 15 wt .-%, in particular 12 wt .-% is not exceeded are particularly advantageous and accordingly within the scope of the invention the use of these particularly advantageous microemulsions represents a particularly preferred embodiment of the invention.
- Microemulsions in which at least citrate (s) and / or at least citric acid are present, preferably exclusively citrate (s) and / or citric acid, wherein the citrate (s) and / or citric acid are preferably used in amounts of from 1% to 16% by weight .-% are included as a complexing agent, are particularly advantageous and accordingly, the use of these particularly advantageous microemulsions represents a particularly preferred embodiment of the invention.
- the microemulsion to be used according to the invention not only has an emulsifier. It is of great benefit for the stability and the flushability of the microemulsions, if in addition to at least one cationic also a nonionic, preferably nonionic hydrophilic emulsifier is present.
- ethoxylated fatty acid alkanolamides are preferably the ethoxylated KokosfettTexremonoethanolamide, especially Kokosfett Textremonoethanolamide plus 4 ethylene oxide units, which corresponds for example to the commercial product Eumulgin® C4 (available from Cognis Germany GmbH).
- Eumulgin® C4 available from Cognis Germany GmbH.
- R is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
- R 1 is H, OH or in particular O (CO) R 4
- R 2 is independent of R 1 is H, OH or O (CO) R 5
- R 4 and R 5 are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
- a, b and c may respectively independently has the value 1, 2 or 3 have
- X ⁇ is a suitable anion, preferably a halide, methosulfate, methophosphate or phosphate ion and mixtures of these to be, and / or is of the formula (II):
- R 6, R 7 and R 8 independently represents a C- ⁇ - alkyl, alkenyl or hydroxyalkyl group
- R 9 and R 10 are each independently a C 1 _ 28 alkyl group selected 8 with 0, 2 or represents 3 double bonds and u is a number between 0 and 5
- X ⁇ is a suitable anion, preferably a halide, methosulfate, methophosphate or phosphate ion and mixtures of these be of the invention are very advantageous in the frame, and accordingly provides the use of these very advantageous microemulsions is a particularly preferred embodiment of the invention.
- the content of cationic emulsifier, preferably lipophilic cationic emulsifier can be adjusted advantageously.
- microemulsions to be used according to the invention are very advantageous with regard to flushability, stability, and also with regard to skin health, if certain quantitative ranges are adhered to.
- a microemulsion comprising at least 0.05% by weight, preferably at least 0.1% by weight, advantageously at least 0.15% by weight, in particular at least 0.2% by weight, but not more than 10% by weight. -%, preferably not more than 3 wt .-%, advantageously not more than 2.5 wt .-%, very advantageously not more than 2.0 wt .-%, more preferably not more than 1, 5 Wt .-%, in an extremely advantageous manner not more than 1, 0 wt .-%, in particular not more than 0.75 wt .-%, most advantageously not more than 0.5 wt .-% of hydrophilic and / or contains lipophilic thickening agents, is classified as very advantageous in this sense, so that the use of these very advantageous microemulsions represents a particularly preferred embodiment of the invention.
- the microemulsions therefore contain fatty acid (s), preferably in amounts of up to 10% by weight, in a further advantageous manner in amounts of up to 5% by weight, in particular in amounts of from 2 to 4% by weight.
- fatty acid s
- Particularly suitable here are C12-C16 fatty acids, in particular myristic acid.
- the microemulsions to be used according to the invention preferably contain water in which the oil phase is preferably distributed.
- the water content can be adjusted advantageously.
- the oils they contain not only serve to soften the fabric, but also serve to provide the skin with benefits through the textile acting as a temporary host. This benefit is very advantageous just when the oils have certain properties.
- Microemulsions containing at least one oil with skin-protecting and / or skin-care and / or skin-healing properties are particularly advantageous in this context, accordingly, the use of these particularly advantageous microemulsions is a particularly preferred embodiment of the invention.
- the classical antiseptic includes antimicrobial measures at the point of origin or at the portal of entry of a possible infection or at the site of infection on the body surface.
- antimicrobial measures at the point of origin or at the portal of entry of a possible infection or at the site of infection on the body surface.
- such strong effectiveness is not sought in the context of the invention, as it would undoubtedly lead to the elimination of harmful germs o. ⁇ ., But it would also affect the natural skin flora of humans.
- This antiseptic oil is preferably an essential oil, which is especially selected from the group of Angelica fine - Angelica archangelica, anise - Pimpinella anisum, Benzoin siam - Styrax tokinensis, Cabreuva - Myrocarpus fastigiatus, Cajéput - Melaleuca leucadendron, Cistus - Cistrus ladaniferus, Copaiba balm - Copaifera reticulata, Costus root - Saussurea discolor, Edeltann needle - Abies alba, Elemi - Canaryum luzonicum, Fennel - Foeniculum dulce Spruce Needle - Picea abies, Geranium - Pelargonium - graveolens, Ho leaves - Cinnamonum camphora, Immortelle (Strawflower) Helichrysum ang., Ginger - Zingiber off., St.
- an essential oil which is especially selected from the group of
- Another advantage of the aforementioned essential oils lies in their particular multi-functionality, which, in addition to the described mild antiseptic activity, results from a multitude of other desirable organoleptic properties attributable to these oils.
- These oils are in most cases given an expectorant effect because they exert on the mucous membranes of the respiratory organs a mild, positive stimulus. Furthermore, a desirable feeling of warmth can be established. Deodorizing, analgesic, circulation-promoting, calming effects could be observed in connection with the use according to the invention of these designated oils by the applicant and be recognized as particularly advantageous.
- the organoleptic properties of these oils are usually not influenced by the main components, but by the secondary or trace constituents, which can often go into the hundreds and sometimes interact synergistically.
- Another advantage associated with the oils mentioned is their harmonious fragrance and scent, which in many cases leads to positive feelings in humans. i 20
- a microemulsion in which at least one of the oils contained has a minimum content of ⁇ -linolenic acid of 0.1 wt .-%, based on the oil in question is particularly advantageous for the invention and in particular is at least one of the oils, preferably at least two of Oils selected from hemp oil, borage oil, evening primrose oil, blackcurrant seed oil, echium oil, trichodesma oil and / or black cumin oil. Accordingly, the use of these particularly advantageous microemulsions is a particularly preferred embodiment of the invention.
- a particularly preferred oil in the context of this invention is z. B. the hemp oil.
- Hemp oil which contains a high proportion of essential fatty acids, and also contains up to 6% by weight of valuable ⁇ -linolenic acid (GLA), also has anti-inflammatory, slightly analgesic, healing, nourishing, improving skin structure, preventing signs of aging. It improves tissue regeneration processes and has a high regenerative effect on injured tissue. In addition, it may increase the care properties or other properties of other oils in particular of all oils explicitly mentioned here.
- the skin surface is only weakly acidic (pH 5.5 - 6.5), just there is a reduced defenses against germs or bacteria, so that it is particularly advantageous in the context of the invention, if the pH of the fabric treatment agent is not greater than pH 5.5 measured at a temperature of 20 ° C on a 1% aqueous solution of the fabric treatment agent.
- the advantage of the textile treatment agent having a pH as described above is that textiles treated therewith are able to assist the skin's self-regulating powers in terms of its alkali neutralizing ability, in that the textile contacting skin such as e.g. , As a Abtrockentuch or underwear, has a skin-optimal pH. _
- the textile treatment agent or the laundry treated with it supports the natural skin flora of humans.
- the agents to be used according to the invention are dye-free, although colorant-containing agents, such as are commercially available, can lead to slightly irritated skin only in extremely rare exceptional cases, if appropriate, for particularly sensitive people. Therefore, in order to further reduce the hypothetical potential for incompatibility from this side, it is therefore advantageous to minimize the dye content in the compositions to be used according to the invention, at best up to dye-free purity. If dyes are desired, for example, for optical reasons, the usual colorants are used.
- the colorant content is preferably below 0.002% by weight of the composition, in particular it is 0% by weight.
- microemulsion is free of dye, then it is an advantageous microemulsion, accordingly, the use of these advantageous microemulsions is a particularly preferred embodiment of the invention.
- microemulsions containing only natural flavors, but preferably no additional fragrances or other perfume oils are of great advantage, so that the use of such microemulsions represents a particularly preferred embodiment of the invention.
- fragrances or perfume oils which are not skin-healing, skin-care and / or skin-protecting active substances in the sense of the invention and natural aromas, if only very small groups of people with extremely sensitive skin and predisposition, are in very good Rarely, minor, subjectively perceived intolerance reactions which would counteract the present invention.
- the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z.
- the alcohols include anethole, citronellol, genolene, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene.
- Perfume oils may also contain natural fragrance mixtures obtainable from vegetable sources, for example pine oil, muscatel, clove oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, galbanum oil and labdanum oil and orange blossom oil, orange peel oil.
- microemulsion contains an ironing facilitator and / or wrinkle reducing agent
- an ironing facilitator and / or wrinkle reducing agent such a microemulsion is considered to be advantageous, and likewise, therefore, the use of these microemulsions is a particularly preferred embodiment of the invention.
- the advantage of this embodiment is that can be reduced by the Bügelerburgêts- and crease reduction effect, the ironing time, so that the valuable ingredients of the textile treatment agent according to the invention are not exposed to excessive thermal stress by ironing, and thus retain their full effectiveness.
- microemulsions may advantageously contain a deodorizing agent, so that the use of such microemulsion is a particularly preferred embodiment of the invention.
- oils especially essential oils, as such also have a deodorizing effect.
- the particular advantage of adding one or more deodorizing agents to the fabric treatment composition of the present invention is that these ingredients, together with the said oils, provide a particularly enhanced, because of synergistic, effect on deodorizing activity. The effect is only in one facet of the covering of evil-smelling or unpleasant odors.
- an additional rather effect based on the synergistic interaction of the active substances according to the invention with the added deodorizing agent and the self-regulatory forces, so that not only the symptom, the malodor, but the moment triggering this odor is eliminated.
- bacteria that are located on the skin or in hair or pubic hair in varying numbers. These bacteria can proteins and fats, z. B. from body sweat, decompose into malodorous sulfur compounds. These bacteria are effectively counteracted by the synergistic interaction of these factors. At the same time, the self-regulating powers of the skin are stimulated and trained.
- the tea tree oil is of great advantage for the subject invention because it combines germicidal, antiseptic, fungicidal, antiviral, wound-healing, anti-inflammatory, scarring-promoting effects in itself.
- the microemulsion contains at least 0.03% by weight, advantageously 0.04 to 4% by weight, preferably 0.1 to 1.5% by weight, in particular 0.05 to 1% by weight of natural antioxidants, in particular selected from terpene-containing antioxidants, vitamin E, vitamin C, vitamin A, selenium and / or their derivatives or mixtures thereof, this is considered to be advantageous in the context of this invention, so that it is therefore also when using sol-cher microemulsions um a particularly preferred embodiment of the invention is.
- the addition of the antioxidant contributes very well to the product stability. The Applicant has found that this also relates to the stability of the oil which is on the fibers of the treated textile after the textile treatment.
- the secreted sweat does not cause a fetus, which is very beneficial.
- This freedom from fetid smells affects both the textile and the skin. Fetid odors are thus counteracted without suppressing the sweating itself.
- the vitamin E is contained in amounts of less than 1, 5 wt .-%.
- the buffer system acids in particular selected from formic acid citric acid, acetic acid, sulfonic acid - thereby advantageously sulfamic acid - and / or derivatives thereof or mixtures thereof.
- the buffer system contains at least one salt of the acid (s) contained in the buffer system, preferably sodium citrate, this is likewise preferred.
- the buffer system contains polyacrylates, polymethacrylates and / or copolymers of acrylic acid and maleic acid, preferably having a molecular weight of 2,000 to 10,000.
- lactic acid and / or salts thereof are present in the microemulsion, preferably in amounts of less than 5% by weight, advantageously less than 3% by weight, in particular less than 2% by weight, this is advantageous because lactic acid and / or its salts skin functionally effective.
- Lactic acid is an important and moisture-binding component of an intact epidermis. Supplied from the outside, lactic acid can even improve the water-binding capacity of the skin.
- the skin-smoothing properties of lactic acid also have a positive influence on our skin texture. Since lactic acid supports the detachment of dander (keratolysis) it ensures a smooth, even skin. This property is especially important for the care of dry, flaky skin. Accordingly, the use of such microemulsions is a particularly preferred embodiment of the invention.
- the microemulsions further contain preservatives which are preferably added at low concentrations, advantageously below 0.5% by weight, to retard microbial spoilage.
- preservatives which are preferably added at low concentrations, advantageously below 0.5% by weight, to retard microbial spoilage.
- salicylic acid, benzoic acid, malic acid, lactic acid, propionic acid, acetic acid, fumaric acid and / or sorbic acid and / or their derivatives and / or salts can serve as preservatives.
- salicylic acid, sorbic acid, its derivatives and / or salts are suitable.
- the viscosity of the microemulsions can be determined by standard methods (for example Brookfield viscometer LVT-II at DV II at 22 ° C, 20 rpm, spindle 3) are measured and is advantageously in a range of 5 to 5000 mPas.
- the microemulsions according to the invention not only have good stability, but also good dispersibility in water.
- a post-treatment agent e.g., fabric softener
- high viscosity values of the post-treatment agent are detrimental to the dispensing performance.
- a viscosity value of the post-treatment agent of preferably 300 mPAs should not be exceeded. This is due to the fact that when rinsing in rinsing agents, such.
- Fabric softener e.g., softener
- the rinse aid which should come to the laundry at the end of the washing, is liquid and would therefore run into the machine immediately at the beginning.
- a microemulsion having a density in the range from 0.900 to 1.050 g / cm 3 , preferably from 0.950 to 1.030 g / cm 3 and in particular from 0.980 to 1, 015 g / cm 3 at 22 ° C can be considered very beneficial.
- the use of such microemulsions is a particularly preferred embodiment of the invention.
- a microemulsion containing a silicone advantageously a substantially linear DKC ⁇ alkylpolysiloxane or (C 1. 5 ) alkylarylpoly- siloxane, in very advantageously polydimethylsiloxane, wherein the silicone is preferably in amounts up to 10 wt .-%, in particular in amounts of 0.1 to 5 wt .-% is contained in the microemulsion, is to be regarded as advantageous against this background, and accordingly, the use of such advantageous microemulsions is a particularly preferred embodiment of the invention.
- the microemulsions further contain proteins (derivatives) such as soya proteins, wheat proteins, potato proteins, pea proteins, rice proteins, silk proteins, keratin, actin, elastin, albumins, globulins, (milk) casein or their derivatives, and / or protein hydrolysates, such as collagen.
- proteins derivatives
- soya proteins wheat proteins, potato proteins, pea proteins, rice proteins, silk proteins, keratin, actin, elastin, albumins, globulins, (milk) casein or their derivatives
- proteins derivatives
- proteins such as soya proteins, wheat proteins, potato proteins, pea proteins, rice proteins, silk proteins, keratin, actin, elastin, albumins, globulins, (milk) casein or their derivatives
- protein hydrolysates such as collagen.
- protein (derivative) s and / or protein hydrolyzates are present in a total amount of preferably 0.1 to 25% by weight, advantageously 1 to 20% by weight, more preferably 1.5 to 15% by weight .-%, more preferably 2 to 10 wt .-%, in particular in a total amount to 5 wt .-%, based on the total microemulsion included.
- the microemulsions further contain tea extracts, in particular tea extract from green tea, in a total amount of preferably 0.01 to 10 wt .-%, advantageously 0.05 to 5 wt .-%, in particular 0.1 to 3 wt .-%, based on the total microemulsion.
- the microemulsions to be used according to the invention comprise one or more of all the active substances disclosed in EP 0 789 070 A1, ie active substances from the groups of waxes, the hydrophobic plant extracts, certain hydrocarbons, higher fatty acids and esters, more essential Oils, lipids, vitamins, sunscreens, phospholipids, derivatives of alpha-hydroxy acids and / or mixtures of the above components in the extent mentioned and there beyond, wherein preferably contain less than 4 wt .-% of quaternary ammonium compounds or other relevant fabric softening compounds are.
- the substantial absence of relevant fabric softening compounds in the just mentioned context is advantageous if a possible reduction of the fiber suction capacity is to be excluded.
- the agents in particular liquid detergents, but can advantageously also have higher viscosities.
- the viscosity of the microemulsions may advantageously be in a range of from 5 to preferably 5000 mPas, with stable and readily water-dispersible microemulsions.
- Such an agent is advantageous for many reasons. It is particularly advantageous that a very good flushability from the dispensing compartment of a washing machine of the agent is made possible by the dosage form of the microemulsion and the specific droplet size. In this case, a good stability of the emulsion is ensured. In addition, the good dispersibility of the agent already comes in cold water. Also particularly advantageous is the high ecological compatibility of the agent, which, among other things, stems from the fact that preferably an upper limit of 5% by weight of cationic surfactant is not exceeded. Cationic surfactants commonly used are quaternary ammonium compounds. Such ammonium compounds, like all N-containing compounds, even though they can now be biologically degraded better, still represent an environmentally damaging factor.
- the composition according to the invention makes it possible to achieve a good softness performance which makes it possible to reduce the cationic surfactant content to less than 5% by weight.
- the softness performance is still good. It is even comparable to that of conventional fabric softeners, which usually have quite high levels of cationic surfactant, for example, 15-20 wt .-% cationic surfactant.
- the cationic surfactant can simultaneously serve as a cationic, preferably lipophilic emulsifier or co-emulsifier.
- the agents contain as antioxidants only natural antioxidants, in particular selected from terpene-containing antioxidants, vitamin E, vitamin C, vitamin A and / or selenium and / or derivatives thereof, vitamin E being the most preferred.
- natural antioxidants in particular selected from terpene-containing antioxidants, vitamin E, vitamin C, vitamin A and / or selenium and / or derivatives thereof, vitamin E being the most preferred.
- the compositions comprise cationic polymer, preferably in the form of polymeric quaternary ammonium compounds, in particular selected from copolymers of quaternized vinylimidazole and vinylpyrrolidone, copolymers of vinylcaprolactam, vinylpyrrolidone and quaternized vinylimidazole and / or quaternized copolymers from vinyl pyrrolidone and dimethylaminoethyl methacrylates.
- cationic polymer preferably in the form of polymeric quaternary ammonium compounds, in particular selected from copolymers of quaternized vinylimidazole and vinylpyrrolidone, copolymers of vinylcaprolactam, vinylpyrrolidone and quaternized vinylimidazole and / or quaternized copolymers from vinyl pyrrolidone and dimethylaminoethyl methacrylates.
- a preferred embodiment is also present when the buffer system contains acid, preferably selected from formic acid citric acid, acetic acid, sulfonic acid - advantageously sulfamic acid - and / or derivatives thereof or mixtures thereof.
- acid preferably selected from formic acid citric acid, acetic acid, sulfonic acid - advantageously sulfamic acid - and / or derivatives thereof or mixtures thereof.
- the buffer system contains at least one salt of the acid (s) contained in the buffer system, preferably sodium citrate, then a preferred embodiment is also present.
- An inventive composition in which a total amount of cationic surfactant of 4 wt .-%, preferably of 3 wt .-%, advantageously of 2.5 wt .-%, in particular of 2 wt .-% is not exceeded, therefore, a preferred embodiment of the invention.
- the fatty acids can stabilize the agent even further and, in addition, raise the oils Support the textile, so that almost all the oil contained can be applied to the textile.
- An inventive agent containing moisturizing factors such as. As glycerol or polyaspartic acid, represents a preferred embodiment of the invention. As already described above, these substances, which have already been described above, support the skin balance and prevent drying of the skin. Here too Reference is made in particular to the statements made above and referred to.
- a very preferred textile treatment agent comprises in addition to the components a) antioxidant, b) lipophilic emulsifier, c) hydrophilic emulsifier and d) oils also e) fatty acid (s) and f) an acid buffer which contains the agent and also the textile treatment bath a pH range of advantageously from 2 to 6.5, preferably from 3 to 5.5 buffers, and optionally g) moisturizing factor (s) and optionally other components which have been listed in the course of this description, such as volatile oil.
- the agents further contain protein (s) e, e.g. Soy proteins, wheat proteins, potato proteins, pea proteins, rice proteins, silk proteins, keratin, actin, elastin, albumins, globulins, (milk) casein or their derivatives, and / or protein hydrolysates, e.g. Collages.
- protein e.g. Soy proteins, wheat proteins, potato proteins, pea proteins, rice proteins, silk proteins, keratin, actin, elastin, albumins, globulins, (milk) casein or their derivatives, and / or protein hydrolysates, e.g. Collages.
- the microemulsions further contain tea extracts, in particular tea extract from green tea, in a total amount of preferably 0.01 to 10 wt .-%, advantageously 0.05 to 5 wt .-%, in particular 0.1 to 3 wt .-%, based on the total microemulsion.
- Preferred embodiments of the invention are the use of an agent according to the invention as a liquid detergent and in the use as a post-treatment agent, in particular as a fabric softener or rinse aid.
- the liquid detergent according to the invention may contain, in addition to the previously described components of the textile treatment agent or the microemulsion, all such components which are expedient and / or customary for a liquid detergent. These components are well known to those skilled in the art. If necessary, he can also take you from relevant reviews, z. BE Smulders, "Laundry Detergents", Wiley-VCH, 2nd edition, 2001.
- the aftertreatment agent according to the invention in particular as a fabric softener or rinse aid, all such components that are expedient and / or usual for such an agent.
- Liquid detergents advantageously contain surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
- the total surfactant content of the liquid detergent is preferably below 40% by weight and more preferably below 35% by weight, based on the total liquid detergent.
- the nonionic surfactants used in the liquid detergents are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably 2- Position may be methyl branched or 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.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of these are 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.
- nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose 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.
- Another class of preferred nonionic surfactants which can be used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or preferably prepared according to the method described in international patent application WO-A-90/13533.
- 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.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
- surfactants are polyhydroxy fatty acid amides of the formula (III)
- RCO is an aliphatic acyl radical having 6 to 22 carbon atoms
- R ' is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
- [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (3),
- Suitable ingredients of liquid detergents are also anionic surfactants.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- surfactants of the sulfonate type preferably come C 8 - 13 -Alkylbenzolsulfonate, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, as they are for example from C ⁇ 2 -i 8 ⁇ monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
- Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid half esters of the C 2 -C 8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myrilecyl, cetyl or stearyl alcohol or the C 10 -C 20 Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 2 -C 5 alkyl sulfates and C 14 -C ⁇ 5 alkyl sulfates are preferred.
- 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
- 21 -alcohols such as 2-methyl-branched C 9 - ⁇ alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 2 - ⁇ 8 -fatty alcohols having 1 to 4 EO, are suitable. Due to their high foaming behavior, they are preferably used only in relatively small amounts, for example in amounts of from 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 . 18- fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
- sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with narrow homologue distribution are again particularly preferred.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Suitable anionic surfactants may also be soaps.
- Suitable 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 content of preferred liquid detergents to anionic surfactants is advantageously from 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, each based on the total agent. It is particularly preferred for the amount of fatty acid soap to be at least 2% by weight and more preferably at least 4% by weight and especially preferably at least 6% by weight.
- preferred agents may additionally comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, hydrotope, foam inhibitors , Silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries; Phobic and impregnating, swelling and anti-slumping agents and UV absorbers included.
- Suitable crystalline layered sodium silicates have the general formula NaMSi ⁇ O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
- Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514.
- Preferred crisis Shelf silicates of the formula given are those in which M is sodium and x is the
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 -yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- the term "amorphous” is also understood to mean "X-ray amorphous”.
- the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred.
- zeolite can be used as a spray-dried powder or else as an undried, stabilized suspension which is still moist from its production.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C ⁇ 4 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and lainklare H 2 0 2 -yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, Diperaze-, Phthaloiminopertica or diperdodecanedioic acid.
- bleach activators can be incorporated into the detergents.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2, 5-diacetoxy-2,5-dihydrofuran.
- TAED tetraacety
- bleach catalysts can also be incorporated into the liquid detergents. These substances are to bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru - or Mo-salene complexes or -carbonylkomplexe. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
- Suitable enzymes are, in particular, those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
- hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
- subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
- enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
- lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
- the enzymes may be adsorbed to carriers to protect against premature degradation.
- the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2.5 wt .-%.
- 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 use of NaCl or MgCl 2 in the agents is preferred.
- the proportion of electrolytes in the agents is usually 0.5 to 5 wt .-%.
- Non-aqueous solvents that can be used in the liquid detergents, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible in the specified concentration range with water.
- the solvents are preferably selected from 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, diisopropylene glycol monomethyl or eth
- Suitable foam inhibitors which can be used in the liquid detergents are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
- Suitable antiredeposition agents which are also referred to as "soil repellents" are, for example, nonionic cellulose ethers, such as methylcellulose and methylhydroxypropylcellulose, with a methoxy group content of 15 to 30% by weight and of hydroxylpropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
- Optical brighteners can be added to the liquid detergents to eliminate graying and yellowing of the treated fabrics, which draw on the fiber and cause lightening and fake bleaching by converting invisible ultraviolet radiation into visible longer wavelength light wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and produces the yellow shade of the grayed or yellowed laundry pure white.
- Suitable compounds originate for example from the substance classes of 4,4'-diamino-2,2'- stilbene disulphonic acids (flavone acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems, and the heterocyclic substituted pyrene derivatives.
- the optical brighteners are usually used in amounts of between 0.03 and 0.3 wt .-%, based on the finished composition.
- 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.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
- cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions, used.
- the compositions may contain synthetic crease inhibitors.
- the liquid detergents may contain antimicrobial agents.
- antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc.
- Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, with the compounds according to the invention also being able to dispense entirely with these compounds in particular.
- compositions may contain further antioxidants. Belong to this class of compounds For example, substituted phenols, hydroquinones, catechols and aromatic amines and organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
- Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
- External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
- External antistatics are described, for example, in patent applications FR 1, 156,513, GB 873,214 and GB 839,407.
- the lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed herein are useful as antistatics for textile fabrics or as an additive to laundry detergents, with a softening effect being additionally achieved.
- silicone derivatives can be used in the liquid detergents. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties.
- Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are fully or partially fluorinated.
- Preferred silicones are polydimethylsiloxanes which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
- the viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C., wherein the silicones can be used in amounts of between 0.2 and 5% by weight, based on the total agent.
- the liquid detergents may also contain UV absorbers that wick onto the treated fabrics and improve the lightfastness of the fibers.
- Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position.
- substituted benzotriazoles in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid.
- 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) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
- EDTA ethylenediaminetetraacetic acid
- NTA nitrilotriacetic acid
- anionic polyelectrolytes such as polymaleates and polysulfonates.
- a preferred class of complexing agents are the phosphonates, which in preferred liquid detergents in amounts of 0.01 to 2.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1, 5 wt .-% 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 mostly used in the form of their ammonium or alkali metal salts.
- 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-tric
- composition according to the invention may contain dispersed particles whose diameter along their greatest spatial extent is from 0.01 to 10 000 ⁇ m.
- particles may be microcapsules as well as granules, compounds and fragrance beads, with microcapsules being preferred.
- microcapsule is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the preparation of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization.
- the microscopic capsules can be dried like powder.
- multinuclear aggregates also called microspheres, are known, which contain two or more cores distributed in the continuous shell material.
- Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath.
- Semi-synthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters.
- Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
- the agents contain preservatives, which are preferably added at low concentrations, advantageously below 0.5% by weight, in order to delay microbial spoilage.
- preservatives which are preferably added at low concentrations, advantageously below 0.5% by weight, in order to delay microbial spoilage.
- salicylic acid, benzoic acid, malic acid, lactic acid, propionic acid, acetic acid, fumaric acid and / or sorbic acid and / or their derivatives and / or salts may serve as preservatives.
- salicylic acid, sorbic acid, its derivatives and / or salts are suitable.
- the microcapsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial extent, depending on the components contained in their interior and the application between 0.01 microns (not visually recognizable as a capsule) and 10,000 microns. Preference is given to visible microcapsules having a diameter in the range from 100 ⁇ m to 7000 ⁇ m, in particular from 400 ⁇ m to 5000 ⁇ m.
- the microcapsules are accessible by methods known in the art, with coacervation and interfacial polymerization being the most important.
- microcapsules all surfactant-stable microcapsules available on the market can be used, for example the commercial products (in each case the shell material is indicated in parentheses) Hallcrest Microcapsules (gelatin, gum arabic), Coletica thalaspheres (marine collagen), Lipotec millicapsules (alginic acid, agar-agar), induchem unispheres (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), softspheres (modified agar agar) and Kuhs Probiol Na- nopses (phospholipids).
- Hallcrest Microcapsules gelatin, gum arabic
- Coletica thalaspheres marine collagen
- Lipotec millicapsules alginic acid, agar-agar
- induchem unispheres lacto
- particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckies”.
- a preferred matrix-forming material is alginate.
- an aqueous alginate solution which also contains the active ingredient to be enclosed or the active ingredients to be enclosed, is dripped off and then cured in a precipitation bath containing Ca 2+ ions or Al 3+ ions.
- the alginate-based speckles are subsequently washed with water and then washed in an aqueous solution with a complexing agent to free Ca 2+ ions or free Al 3+ ions, which undesirable interactions with ingredients of the liquid detergent , eg the fatty acid soaps, can be washed out. Subsequently, the alginate-based speckles are washed again with water to remove excess complexing agent.
- the particles can be stably dispersed in the aqueous liquid detergent.
- Stable means that the compositions are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably at least 6 weeks, without the medium creaming or sedimenting.
- the release of the active ingredients from the microcapsules or speckles is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.
- the liquid detergents contain identical or different particles in amounts of 0.01 to 10 wt .-%, in particular 0.2 to 8 wt .-% and most preferably 0.5 to 5 wt .-%.
- composition according to the invention consisting of
- Panel 5 The content of the resulting C18: 2 fatty acid methyl ester is 325% greater than that resulting from wearing the "untreated fabric” when wearing the "treated fabric".
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Abstract
Description
Claims
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| Application Number | Priority Date | Filing Date | Title |
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| PL05701327T PL1713896T3 (pl) | 2004-02-14 | 2005-02-03 | Mikroemulsje |
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| DE102004007312A DE102004007312A1 (de) | 2004-02-14 | 2004-02-14 | Mikroemulsionen |
| PCT/EP2005/001061 WO2005078061A1 (de) | 2004-02-14 | 2005-02-03 | Mikroemulsionen |
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| EP1713896A1 true EP1713896A1 (de) | 2006-10-25 |
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| US (1) | US20070197418A1 (de) |
| EP (1) | EP1713896B2 (de) |
| JP (1) | JP2007524743A (de) |
| AT (1) | ATE431845T1 (de) |
| DE (2) | DE102004007312A1 (de) |
| ES (1) | ES2326176T3 (de) |
| PL (1) | PL1713896T3 (de) |
| WO (1) | WO2005078061A1 (de) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITTO20050787A1 (it) * | 2005-11-09 | 2007-05-10 | Sagitta S R L | Composizione ammorbidente |
| US8178483B2 (en) * | 2007-03-30 | 2012-05-15 | Colgate-Palmolive Company | Polymeric encapsulates having a quaternary ammonium salt and methods for producing the same |
| US20110052738A1 (en) * | 2008-01-17 | 2011-03-03 | Gary Dean Bennett | Topical pain formulation |
| BRPI0915228B1 (pt) * | 2008-06-16 | 2018-07-10 | Firmenich Sa | Processo de preparo de microcápsulas de poliureia |
| US9309378B2 (en) * | 2009-06-19 | 2016-04-12 | Exacto, Inc. | Emulsion compositions comprising polyacrylamide copolymer and ethylene oxide—propylene oxide copolymer |
| US9428630B2 (en) | 2009-06-19 | 2016-08-30 | Exacto, Inc. | Water-in-oil polyacrylamide-based microemulsions and related methods |
| US9307758B2 (en) | 2009-06-19 | 2016-04-12 | Exacto, Inc. | Polyacrylamide based agricultural compositions |
| JP5719113B2 (ja) * | 2010-02-19 | 2015-05-13 | 稲畑香料株式会社 | 消臭剤及びそれを用いた消臭剤組成物 |
| US8883709B2 (en) * | 2010-03-19 | 2014-11-11 | S.C. Johnson & Son, Inc. | Laundry pretreatment compositions containing fatty alcohols |
| GB2498996B (en) * | 2012-02-02 | 2017-12-27 | Henkel Ltd | Lime scale remover |
| DE102014214463B4 (de) * | 2014-07-24 | 2024-09-19 | Beiersdorf Aktiengesellschaft | Deodorantzubereitungen umfassend Polyquaternium Polymere |
| JP6120888B2 (ja) * | 2015-01-27 | 2017-04-26 | ロイヤルネットワーク株式会社 | 非水系洗浄剤組成物 |
| US11260018B2 (en) | 2015-09-17 | 2022-03-01 | Jrx Biotechnology, Inc. | Approaches for improving skin hydration and moisturization |
| CN105238578B (zh) * | 2015-10-30 | 2017-12-15 | 深圳市新纶科技股份有限公司 | 一种微乳液型清洗剂及其制备方法 |
| CN106665700B (zh) * | 2016-12-07 | 2022-07-26 | 张树清 | 一种植物源类消毒组合物、消毒剂及其制备方法 |
| AU2020235128B2 (en) | 2019-03-14 | 2025-07-03 | Exacto, Inc. | Transparent or semitransparent inverse microlatices of polyacrylamide as oil emulsion drift reducing agent |
| EP3969555A1 (de) | 2019-06-21 | 2022-03-23 | Ecolab USA, Inc. | Feste nichtionische tensidzusammensetzungen |
| DE102020007520A1 (de) | 2020-12-09 | 2022-06-09 | Ovidiu Dicoi | Modifizierte strukturierte, fließfähige Wasch- und Reinigungsmittel |
| US20250171712A1 (en) * | 2022-02-25 | 2025-05-29 | Basf Se | Macaúba oil for the production of oleochemicals |
| EP4234535A1 (de) * | 2022-02-25 | 2023-08-30 | Basf Se | Macaúba-öl für die produktion von oleochemikalien |
| EP4234534A1 (de) * | 2022-02-25 | 2023-08-30 | Basf Se | Macauba-öl zur herstellung von oleochemischen produkten |
| EP4234665A1 (de) * | 2022-02-25 | 2023-08-30 | Basf Se | Macaúba-öl für die produktion von oleochemikalien |
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| US4559169A (en) * | 1984-08-17 | 1985-12-17 | The Procter & Gamble Company | Stable liquid detergents containing anionic surfactant and monosulfonated brightener |
| US5075026A (en) * | 1986-05-21 | 1991-12-24 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition |
| US5441541A (en) * | 1989-07-19 | 1995-08-15 | Colgate Polmolive Co. | Anionic/cationic surfactant mixtures |
| US5599473A (en) * | 1994-08-04 | 1997-02-04 | Colgate-Palmolive Company | Nitrogen-free rinse cycle fabric softeners based on microemulsions |
| US5656585A (en) † | 1994-12-21 | 1997-08-12 | Colgate-Palmolive Company | Clear, concentrated liquid fabric softener compositions |
| GB9602608D0 (en) * | 1996-02-09 | 1996-04-10 | Unilever Plc | Fabric softening composition |
| US7534304B2 (en) * | 1997-04-29 | 2009-05-19 | Whirlpool Corporation | Non-aqueous washing machine and methods |
| US5929009A (en) * | 1998-12-11 | 1999-07-27 | Colgate Palmolive Co. | Liquid detergent composition containing amine oxide |
| GB9910101D0 (en) * | 1999-04-30 | 1999-06-30 | Unilever Plc | Concentrated perfume compositions and manufacture of a fabric softening composition therefrom |
| GB9915964D0 (en) * | 1999-07-07 | 1999-09-08 | Unilever Plc | Fabric conditioning composition |
| GB0014891D0 (en) * | 2000-06-16 | 2000-08-09 | Unilever Plc | Fabric softening compositions |
| GB0021766D0 (en) * | 2000-09-05 | 2000-10-18 | Unilever Plc | Fabric conditioning compositions |
| GB0130556D0 (en) * | 2001-12-20 | 2002-02-06 | Unilever Plc | Fabric conditioning compositions |
| BR0316842A (pt) * | 2002-12-03 | 2005-10-18 | Unilever Nv | Composição de tratamento na lavagem de roupas, método para a deposição de um silicone sobre um substrato, processo para a lavagem de tecidos à máquina ou à mão, e, uso de uma composição de tratamento na lavagem de roupas |
-
2004
- 2004-02-14 DE DE102004007312A patent/DE102004007312A1/de not_active Withdrawn
-
2005
- 2005-02-03 US US10/589,455 patent/US20070197418A1/en not_active Abandoned
- 2005-02-03 ES ES05701327T patent/ES2326176T3/es not_active Expired - Lifetime
- 2005-02-03 JP JP2006552510A patent/JP2007524743A/ja active Pending
- 2005-02-03 WO PCT/EP2005/001061 patent/WO2005078061A1/de not_active Ceased
- 2005-02-03 DE DE502005007315T patent/DE502005007315D1/de not_active Expired - Lifetime
- 2005-02-03 PL PL05701327T patent/PL1713896T3/pl unknown
- 2005-02-03 AT AT05701327T patent/ATE431845T1/de not_active IP Right Cessation
- 2005-02-03 EP EP05701327.8A patent/EP1713896B2/de not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2005078061A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE431845T1 (de) | 2009-06-15 |
| JP2007524743A (ja) | 2007-08-30 |
| PL1713896T3 (pl) | 2009-10-30 |
| EP1713896B2 (de) | 2021-11-24 |
| EP1713896B1 (de) | 2009-05-20 |
| DE502005007315D1 (de) | 2009-07-02 |
| WO2005078061A1 (de) | 2005-08-25 |
| US20070197418A1 (en) | 2007-08-23 |
| ES2326176T3 (es) | 2009-10-02 |
| DE102004007312A1 (de) | 2005-09-01 |
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