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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic 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
  • C11D1/66—Non-ionic compounds
  • C11D1/835—Mixtures of non-ionic with cationic 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/044—Solid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
• • 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
  • C11D1/04—Carboxylic acids or salts thereof
  • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/42—Amino alcohols or amino ethers
  • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the present invention relates to a washing additive which can be added to washing liquors to increase the washing effect.
• the addition of the additive according to the invention improves the removal of bleachable soiling and of grease / oil and pigment soiling from the textiles to be washed.
• the washing liquor When washing textiles, the washing liquor is generally heated to a temperature which is higher than room temperature. This measure significantly increases the washing performance of the detergents used. The heating of the washing liquor and the textiles is associated with an increased energy expenditure during washing.
• some textiles, in particular textiles made of wool or synthetic fibers cannot be washed at elevated temperature for various reasons, attempts have repeatedly been made to achieve good washing results when washing at low temperatures. At low washing temperatures, however, the effect of the per compounds frequently used to remove bleachable stains is in some cases considerably reduced or even weakened to such an extent that such stains are no longer removed.
• bleach activators are added to detergents to increase the bleaching effect, which intensify the bleaching effect of the per compounds and allow the effect to be used even at lower washing temperatures.
• the simultaneous presence of per compounds and bleach activators in detergents reduces their storage stability, especially if the materials cannot be protected from moisture during storage. Attempts to improve the stability have generally led to a considerable reduction in the bleaching action of the detergents. It has therefore already been proposed to store the bleach activator separately from the detergent containing the per-compound and to add at least part of the activator only immediately before use of the wash liquor
• DE-OS 27 44 642 describes a detergent additive which contains an organic bleach activator in water-releasable combination with a non-particulate substrate.
• the detergent additive of DE-OS 27 44 642 can also contain other additives, such as. B. foam modifiers, chelating agents, soil suspending agents, optical brighteners, bactericides, anti-opacifiers, enzymes, fabric softeners, fragrances.
• a further improvement in the washing performance of laundry detergents based on anionic surfactants and inorganic persalts is made possible by an additive which, according to the teaching of DE-OS 28 57 153, has, in addition to a bleach activator, further laundry detergent components, namely a combination of an alkoxylated nonionic surfactant and a cationic surfactant with one Contains 8 to 20 carbon atoms and otherwise short residues with 1 to 4 carbon atoms releasable on a substrate.
• a similar proposal to use detergent ingredients e.g. B. a surfactant to apply to a substrate in dispensable form is known from DE-OS 28 12 663.
• a foam made of water-insoluble polyurethane foam is described as the substrate, which contains the active ingredients to be released in its pores.
• a pore-free, water-insoluble substrate that is used as a depot for active ingredients, e.g. B. detergents or detergents is the subject of German Offenlegungsschriften 23 47 299 and 31 03 499.
• the substrates described there are water-containing or water-free foils made of polyurethane gel.
• a disadvantage of the additives mentioned is that after washing, the water-insoluble substrate must be sorted out of the washed textiles.
• the active substances are generally only partially released from the substrate. It has therefore been proposed to use detergent combinations which improve washing power in bags made of water-soluble film (German patent application No.
• the aim of the present invention is to provide a washing additive for increasing the washing performance of textile detergents with a content of detergent-enhancing active substances which does not require a substrate which has to be sorted out of the washed textiles after washing.
• the washing additive according to the invention comprises a mixture of detergent constituents and optionally auxiliaries which are releasably embedded in organic, flexible, film-forming, water-soluble polymers.
• the mixture contains at least two of the following active ingredients: a) at least one nonionic surfactant, optionally together with an anti-gel agent for the nonionic surfactant, b) at least one activator for per compounds, c) at least one nitrogen-containing compound from the quaternary ammonium compounds with a long-chain alkyl or Alkenyl radical with 10 to 20 carbon atoms and otherwise alkyl radicals with 1 to 4 carbon atoms, addition products of 1 to 6 mol of ethylene oxide with 1 mol of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, compounds of the formula R-NH-CH 2 -CH 2 -COONa, in which R denotes an alkyl or alkenyl radical having 10 to 18 carbon atoms,
• Suitable nonionic surfactants are, in particular annealing - products of ethylene oxide with fatty or oxo alcohols particularly suitable which 12 to 18, preferably having 14 to 15 carbon atoms. The best effects are achieved with oxo alcohol ethoxylates which contain 3 to 10, preferably 6 to 8 and in particular about 7 moles of ethylene oxide per mole of alcohol.
• the content of nonionic surfactants in the washing additive according to the invention primarily promotes the removal of greasy or oily soiling during washing. In many cases it is advisable to add foam regulators; in most cases, the development of foam must be dampened.
• Suitable foam suppressants are, for example, the silicone oils known as foam inhibitors.
• N-acyl and I-acyl compounds are suitable as activators for per compounds.
• Acetyl compounds have proven particularly useful. Examples include tetraacetylglycoluril or pentaacetylglucose or in particular tetraacetylethylenediamine.
• the bleach activators mentioned lead to improved removal of bleachable textile soiling.
• Suitable nitrogen-containing compounds are, for example, quaternary ammonium compounds with a long-chain alkyl or alkenyl radical with 10 to 20, preferably alkyl groups with 10 to 16 and in particular about 14 carbon atoms.
• the suitable quaternary ammonium compounds contain 3 identical or different alkyl groups with 1 to 4 carbon atoms. In particular, these short alkyl groups are methyl groups.
• a particularly suitable and therefore preferred quaternary ammonium compound is tetradecyltrimethylammonium bromide. All or part of the quaternary ammonium compound can be replaced by the above-mentioned fatty amine ethoxylate.
• a particularly suitable fatty amine ethoxylate is the adduct of 2 moles of ethylene oxide with primary coconut alkyl amine; this product is therefore also preferred.
• a compound of the formula R-NH-OH 2 -CH 2 -COONa can also be used.
• a compound in which R is a cocoalkyl radical is preferred.
• the washing additive for complexing any interfering heavy metal ions can contain small amounts of chelating agents.
• the washing additive according to the invention optionally contains an anti-gel agent for the nonionic surfactant.
• an anti-gelling agent must be able to prevent the known gelling of the nonionic surfactant upon contact with water.
• Suitable antigelling agents are preferably polyhydric alcohols having 2 to 4 carbon atoms, which are intimately mixed with the nonionic surfactant.
• the antigelling effect of the polyhydric alcohol can be enhanced if instead of the polyhydric alcohol alone a mixture of a polyhydric alcohol and condensation products of C 10 to C 20 fatty alcohols with 1 to 4 moles of ethylene oxide per mole of fatty alcohol is used.
• Polyhydric alcohols which can be used as antigelling agents are, for example, 1,2-propylene glycol, ethylene glycol or glycerol or mixtures of the alcohols mentioned.
• An example of a particularly suitable fatty alcohol ethoxylate which can be used in a mixture with the polyhydric alcohol to enhance the anti-gelling effect is tallow alcohol ethoxylate with 2 moles of ethylene oxide; but also C12 with 3 moles of ethylene oxide, which contains approximately 70% C 12 -fatty alcohol ethoxylate to C14 fatty alcohols t hox y la t, is suitable as an anti-gelling agent.
• a good anti-gelling effect is obtained if the weight ratio of nonionic surfactant to polyhydric alcohol is in the range from about 1: 1 to 1: 2. If, on the other hand, a mixture of polyhydric alcohol and fatty alcohol ethoxylate is used, very good results are obtained if the weight ratio of nonionic surfactant to polyhydric alcohol to fatty alcohol ethoxylate in the range from (7 to 12) to (5 to 16) to (0.5 to 4 ) lies.
• the antigelling effect of the antigelling agent can be increased further if, in addition to the antigelling agents described so far, it is easily dissolved in water.
• the active ingredient mixture can additionally contain adducts of 15 to 25 moles of ethylene oxide with 1 mole of fatty alcohol as auxiliaries.
• Polyvinyl alcohol which is readily soluble in cold water and has a degree of saponification of between 70 and 90%, preferably between 78 and 88%, is suitable as the material in which the active compounds are embedded according to the invention; Particularly good results are obtained with polyvinyl alcohol which, in addition to this degree of saponification, is also characterized by a degree of polymerization from 225 to 2250, in particular from 500 to 1000. This corresponds to a molecular weight of approximately 10,000 to 100,000, in particular approximately 10,000 to 50,000. With such a polyvinyl alcohol, the rapid addition of the washing additive according to the invention is ensured during the washing cycle in automatic washing machines even when the washing is carried out with relatively little Wash liquor is washed.
• water-soluble film-forming polymers other than polyvinyl alcohol are also suitable as carriers for the washing-power-increasing active ingredient combination. What is decisive for their suitability is that the films produced from them dissolve completely in cold water and in cold wash liquors under the conditions of washing in automatic washing machines within a maximum of 15 minutes. In many cases, a mixture of several different water-soluble polymers is more soluble than each of the polymers forming the mixture per se.
• plasticizers to the preferred polyvinyl alcohol.
• Polyhydric alcohols preferably glycerol and / or polyethylene glycol, are suitable as such. If the foils are to be elastic and surface rough after drying, which means that they are easily carried away by the laundry items when they are circulated in the washing machine, they are used up to 15% by weight, based on the amount of polyvinyl alcohol, methyl cellulose and / or Cellulose fibers too.
• a particularly effective and therefore preferred washing additive according to the invention contains a combination of at least one nonionic surfactant together with an anti-gel agent, at least one activator for per compounds, at least one nitrogen-containing compound from the quaternary ammonium compounds with a long-chain alkyl or alkenyl radical with 10 to 20 carbon atoms and the rest Alkyl radicals with 1 to 4 carbon atoms, adducts of 1 to 6 moles of ethylene oxide with 1 mole of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, compounds of the formula R-NH-GH 2 -CH 2 -COONa in which R is an alkyl or alkenyl radical having 10 to 18 carbon atoms, in particular having 14 carbon atoms, comprising a group and a water-soluble salt of an alkane polyphosphonic acid.
• a method for producing the washing additive according to the invention is a further subject of the present invention.
• This process is characterized in that the active ingredients and auxiliaries, ie the nonionic surfactant, the activator for the per-compound, the nitrogen-containing compound, the anti-gel agent, in what This readily soluble sodium salt or sugar, adducts of 15 to 25 moles of ethylene oxide with 1 mole of fatty alcohol, the water-soluble salt of an alkane polyphosphonic acid and optionally water at elevated temperature, preferably at 40 to 60 ° C, with a water-soluble, film-forming polymer, to which one may add
• auxiliaries ie optionally adding the polyhydric alcohol and optionally methyl cellulose and / or cellulose fibers, are mixed, a weight ratio of (active ingredients + auxiliaries) to (polymers) from 1:10 to 5: 1, preferably from 1.5: 1 to 3 , 0: 1 sets.
• This water-containing mixture of all components of the washing additive forms a highly viscous, sticky mass; it is shaped into films which are so thick that, after drying at 60 to 80 ° C., they have a residual water content of 2 to 10% by weight, based on the water-free film containing the active substance and auxiliary, if necessary after being rolled out, Are 4 to 1.5 mm thick. On the one hand, this thickness ensures adequate mechanical stability, on the other hand, sufficient security of dissolution when using the washing additive in the washing machine.
• the shaping into foils takes place under water evaporation, for example on a preheated roller mill. After the residual water content has been reached and the rolls have cooled to about 35 to 40 ° C., the elastic film can be removed and, if necessary, rolled out to the thickness mentioned.
• the film can also be formed by extrusion from a nozzle with subsequent calendering and drying.
• washing additives are obtained, for example, by applying the active ingredient combination to a film of water-soluble polymers and covering the active ingredients with a further water-soluble film in such a way that the active compound combination is firmly anchored between the films and is only released when the film is dissolved.
• the two foils are glued or welded to one another at the edges or flat.
• Mixture C was placed on a roller mill heated to 70 ° C., the roller gap of which was set to 0.7 mm. After 3 minutes of treatment on the roller mill, the residual water content was 6% by weight.
• the roller mill was cooled to 40 ° C. and a 0.7 mm thick film was pulled off the roller. The film was cut into pieces measuring 25 x 16 cm.
• polyvinyl alcohol granules (molecular weight approx. 15,000, degree of saponification 83%) and 515 g of an internally plasticized polyvinyl alcohol granulate were suspended in 1,195 g of deionized, cold water and 375 g of glycerol in a heatable stirred vessel and by heating the mixture to 80 ° C solved.
• the mass produced in this way had a viscosity of 9,650 mPa.s (Brookfield viscometer, 60 C).
• the mixture was placed on a roller mill preheated to 70 ° C., on which the water was evaporated to a residual content of 7% by weight.
• a film was formed within 3 minutes, the thickness of which was set to 0.8 mm over the nip. After the roller mill had been cooled to 40 ° C., the film was pulled off and cut into pieces measuring 24 ⁇ 15 cm, which contained the amount of active compound sufficient to improve the washing effect.
• the films produced in this way dissolved completely in a Miele household washing machine with a 30 ° C wash program within 15 minutes.
• the soiled laundry washed with it was, despite the 2/3 nominal dosage of a single detergent, significantly cleaner than without the addition of the washing power amplifier according to the invention.
• an active substance film according to the invention was produced by suspending the polyvinyl alcohol granules in 500 ml of water and introducing heat during the dissolving process by introducing direct steam.
• a 40% by weight aqueous glycerol-containing polyvinyl alcohol solution was prepared by condensation of the steam and was mixed with the other active ingredients and auxiliaries as in Example 2.
• a compound of active substance produced according to the recipe described in Example 2 was knife-coated onto a metal plate with a hand knife to form a 0.9 mm thick film. This film was dried in a forced-air drying cabinet at 80 C for 60 minutes. A film was formed which corresponded to the rolled-out film of Example 2 in its dissolving and washing-enhancing properties.
• Example 2 200 kg of an active ingredient composition were prepared which contained 23% water. This was concentrated using a thin-film evaporator (type Filmtruder HS, Luwa company) at 50 mbar and 1 bar steam heating to a residual water content of 6% by weight. The cut-resistant mass obtained in this way was extruded at 70 ° C. through a slot die into a rolling mill (roller head system, from Berstorff) and processed into a 0.9 mm thick film which has the performance properties described in Example 2.
• a thin-film evaporator type Filmtruder HS, Luwa company
• the cut-resistant mass obtained in this way was extruded at 70 ° C. through a slot die into a rolling mill (roller head system, from Berstorff) and processed into a 0.9 mm thick film which has the performance properties described in Example 2.
• Example 2 an active substance film was produced which contained 35 g of urea instead of sodium chloride.
• the film had the same elastic and application properties as that described in Example 2.

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• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

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Cited By (7)

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• 1984
  • 1984-06-14 DE DE19843422055 patent/DE3422055A1/de not_active Withdrawn
• 1985
  • 1985-06-07 EP EP85107057A patent/EP0164703B1/fr not_active Expired - Lifetime
  • 1985-06-07 DE DE8585107057T patent/DE3575440D1/de not_active Expired - Fee Related
  • 1985-06-12 JP JP60129081A patent/JPS6112796A/ja active Pending
  • 1985-06-13 ES ES544107A patent/ES8604299A1/es not_active Expired
  • 1985-06-13 CA CA000483943A patent/CA1242949A/fr not_active Expired

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