EP2029716B1 - Feste, textil-pflegende zusammensetzung auf seifenbasis - Google Patents

Feste, textil-pflegende zusammensetzung auf seifenbasis Download PDF

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Publication number
EP2029716B1
EP2029716B1 EP07726684.9A EP07726684A EP2029716B1 EP 2029716 B1 EP2029716 B1 EP 2029716B1 EP 07726684 A EP07726684 A EP 07726684A EP 2029716 B1 EP2029716 B1 EP 2029716B1
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EP
European Patent Office
Prior art keywords
textile
care composition
solid
fatty acids
care
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.)
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Application number
EP07726684.9A
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German (de)
English (en)
French (fr)
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EP2029716A1 (de
Inventor
Konstanze Mayer
Karl-Heinz Scheffler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL07726684T priority Critical patent/PL2029716T3/pl
Publication of EP2029716A1 publication Critical patent/EP2029716A1/de
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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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/44—Perfumes; Colouring materials; Brightening agents ; Bleaching agents
    • C11D9/442—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/36—Organic compounds, e.g. vitamins containing silicon

Definitions

  • the invention relates to a solid, textile-care composition and its use and preparation, Furthermore, the invention relates to a washing or cleaning agent containing the solid, textile-care composition.
  • cationic fabric softening compounds include, for example, methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium compounds, methyl N- ⁇ 2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium compounds or N , N-dimethyl-N, N-di (talgacyloxyethyl) ammonium compounds.
  • US 3,915,882 A describes a detergent comprising smectite clay coated soap particles and a quaternary ammonium compound having anti-static properties.
  • the soap particles also contain a compound having dispersing properties.
  • the French patent application FR 2 725 456 A1 describes a granular composition comprising a matrix of soap in which liquid surfactants or fluid silicones are dispersed.
  • the matrix may contain other additives that are bases for providing alkalinity.
  • Cosmetic soap bars are described from fatty acids and synthetic surfactants.
  • the soap bars may contain other adjuvants such as paraffins, fatty alcohols or glycerides.
  • a solid textile-care composition comprising a matrix of soap and distributed therein a textile-care compound and a perfume, wherein the soap matrix further additives selected from the group consisting of propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, 1 , 3-Butylene glycol, 2,3-butylene glycol, sorbitol, glycerol, mannitol, glucose, sucrose, galactose, fructose, lactose, dextrose and mixtures thereof
  • Such a fabric care composition can be used in the main wash of an automatic washing or cleaning process.
  • the textile-care composition can be added, for example, together with the detergent or cleaning agent in the drum or the dispenser of a washing machine. This has the advantage that no additional rinse is necessary and no unsightly deposits occur in the dispenser. Furthermore, this solid composition is easier and better to handle than liquid compositions, since no drops remain on the edge of the bottle, which lead to subsequent storage of the bottle to edges on the ground or to unsightly deposits in the region of the closure. The same applies in the event that some of the composition is accidentally spilled during dosing. Since soaps also have a water-softening effect, limescale deposits on the laundry are additionally prevented
  • the textile-care compound and the perfume are already transported directly to the laundry at the beginning of the washing process and so can develop their full potential.
  • the fabric conditioning compound is comprised of fabric softening compounds, bleaches, bleach activators, enzymes, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, color transfer inhibitors, antimicrobials, germicides, fungicides, antioxidants, antistatic agents, ironing aides, Phobies and impregnating agents, swelling and slipping agents, UV absorbers and mixtures thereof is selected.
  • the fabric care compound is a fabric softening compound. It is most preferred that the fabric softening compound is selected from polysiloxanes, fabric softening clays, cationic polymers and mixtures thereof.
  • the use of polysiloxanes and / or cationic polymers as a fabric softening compound in the fabric care composition is advantageous because they not only exhibit a softening effect but also enhance the perfume impression on the linen.
  • the use of softening clays as a fabric softening compound in the fabric-care composition is advantageous because they additionally have a water-softening effect and thus lime deposits on the laundry are prevented.
  • the fabric care composition contains a combination of at least two textile care, especially at least two fabric softening compounds.
  • the soap contains sodium salts of fatty acids selected from the group consisting of palm oil fatty acids, palm kernel oil fatty acids, coconut fatty acids, peanut fatty acids, tallow fatty acids, stearic acids, oleic acid, soybean fatty acids, olive oil fatty acids, and mixtures.
  • soaps are firm and can thus function particularly well as a matrix for the solid textile-care compositions.
  • Textile-care compositions with such a soap matrix dissolve particularly well and quickly. Due to the good dissolving behavior, the textile-care compound and the perfume are quickly and evenly distributed in the wash liquor and can thus optimally achieve their effect. Furthermore, the additives increase the transparency of the textile-care composition.
  • the amount of the perfume is 0.1 to 20% by weight, preferably 1 to 10% by weight, and particularly preferably 2 to 7% by weight.
  • the matrix of the solid, fabric care composition contains from 50% to 98% by weight, preferably from 90% to 97% by weight, of soap.
  • the solid textile care composition is in particulate form. It is particularly preferred that the solid textile-care composition particle sizes in the range of 0.6 to 30 mm, in particular 0.8 to 7 mm and particularly preferably 1 to 3 mm, textile-care composition having these particle sizes are particularly dosing well and exactly.
  • the invention also relates to the use of a solid textile-care composition according to the invention for conditioning textile fabrics.
  • the invention further relates to a process for the preparation of a solid, textile-care composition
  • a process for the preparation of a solid, textile-care composition comprising a matrix of soap and further additives selected from the group consisting of propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, Sorbitol, glycerin, mannitol, glucose, sucrose, galactose, fructose, lactose, dextrose, and mixtures thereof, as well as a fabric conditioning compound and a perfume, in which the ingredients are mixed and the resultant mixture is then extruded through a rhombic orifice plate.
  • the invention relates to a washing or cleaning agent comprising a solid, textile-care composition according to the invention.
  • the consumer By introducing the textile-care composition according to the invention into a washing or cleaning agent, the consumer is provided with a textile-care washing or cleaning agent ("2in1" washing or cleaning agent) and he does not need two agents (washing or cleaning agent and Textile-care composition) to dose.
  • a textile-softening composition is introduced into a washing or cleaning agent, the consumer is then provided with a fabric-softening washing or cleaning agent ("2in1" washing or cleaning agent) and does not need two detergents or cleaners Fabric softener) and no separate rinse.
  • the fabric care composition contains a matrix of soap as well as a fabric care compound, perfume and other additives distributed therein.
  • the matrix of soap contains as its main ingredient the sodium salts of fatty acids selected from the group consisting of palm oil fatty acids, palm kernel oil fatty acids, coconut fatty acids, peanut fatty acids, tallow fatty acids, stearic acid, oleic acid, soybean fatty acids, olive oil fatty acids and mixtures thereof.
  • the matrix of the solid, textile-care composition contains preferably 50 to 98% by weight, particularly preferably 90 to 97% by weight, of soap.
  • the matrix may additionally contain potassium and / or ammonium salts of fatty acids.
  • the proportion of these fatty acid soaps should be as low as possible.
  • the matrix of soap contains further additives selected from the group consisting of propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, sorbitol, glycerol, mannitol, glucose, sucrose, galactose, fructose, lactose, Dextrose and mixtures thereof are selected.
  • additives increase the transparency of the textile-care composition.
  • the amount of these additives is preferably between 0.1 and 25 wt .-% and particularly preferably between 5 and 15 wt .-%.
  • a textile care compound is understood to mean any compound which gives textile fabrics treated therewith a beneficial effect, such as, for example, a textile softening effect, crease resistance or the harmful or negative effects which result during cleaning and / or conditioning and / or or wearing, such as fading, graying, etc., reduced.
  • the fabric care composition may include, for example, a fabric softening compound, bleaches, bleach activators, enzymes, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial Active ingredients, germicides, fungicides, antioxidants, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, UV absorbers and mixtures thereof.
  • a fabric softening compound for example, a fabric softening compound, bleaches, bleach activators, enzymes, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial Active ingredients, germicides, fungicides, antioxidants, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, UV absorbers and mixtures thereof.
  • these fabric-care compounds can be found in the description of
  • the fabric conditioning compound is preferably a fabric softening compound and is, for example, a polysiloxane, a textif softening clay, a cationic polymer, or a blend of at least two of these fabric softening compounds. Accordingly, the fabric care composition is preferably a fabric softening composition.
  • Polydimethylpolysiloxanes are known as efficient textile softening compounds.
  • Suitable polydimethysiloxanes include DC-200 (ex Dow Corning), Baysilone® M 50, Baysilone® M 100, Baysilone® M 350, Baysilone® M 500, Baysilone® M 1000, Baysilone® M 1500, Baysilone® M 2000 or Baysilone® M 5000 (all ex GE Bayer Silicones).
  • the polysiloxane contains the structural units a) and b).
  • a particularly preferred polysiloxane has the following structure: (CH 3 ) 3 Si [O-Si (CH 3 ) 2 ] n - [O-Si (CH 3 ) ⁇ (CH 2 ) 3 -NH- (CH 2 ) 2 -NH 2 ⁇ ] x -OSi ( CH 3 ) 3 where the sum n + x is a number between 2 and 10,000
  • Suitable polysiloxanes having the structural units a) and b) are for example commercially available under the trade names DC2-8663, DC2-8035, DC2-8203, DC05-7022 or DC2-8566 (all ex Dow Corning). According to the invention are also suitable for example the products commercially available Dow Corning ® 7224, Dow Corning ® 929 Cationic Emulsion or Formasil 410 (GE Silicones).
  • a suitable fabric softening clay is, for example, a smectite clay.
  • Preferred smectite clays are beidellite clays, hectorite clays, laponite clays, montmorillonite clays, nontronite clays, saponite clays, sauconite clays, and mixtures thereof.
  • Montmorillonite clays are the preferred softening clays.
  • Bentonites contain mainly montmorillonites and can serve as a preferred source of fabric softening clay.
  • Suitable bentonites are sold, for example, under the names Laundrosil® by Süd-Chemie or under the name Detercal by Laviosa.
  • the fabric care composition contains a fabric softening compound and one or more other fabric care compounds.
  • the amount of fabric care compound in the fabric care composition is from 0.1 to 10 weight percent, and preferably from 1 to 6 weight percent.
  • perfume oils or fragrances individual perfume 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 amount of perfume in the textile-care composition amounts to preferably between 0.1 and 20 wt .-%, particularly preferably between 1 and 10 wt .-% and most preferably between 2 and 7 wt .-%.
  • the textile-care composition according to the invention may optionally contain further ingredients.
  • dyes In order to improve the aesthetic impression of the textile-care composition, 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.
  • the fabric care composition may contain a filler such as silica.
  • the amount of filler may be between 0.1 and 10 wt .-% and is preferably 1 to 5 wt .-%.
  • the textile-care composition may also contain a pearlescent mortar to increase the gloss.
  • suitable pearlescing agents are ethylene glycol mono- and distearate (for example Cutina AGS from Cognis) and PEG-3-distearate.
  • the matrix may be added as a further ingredient, a chelating agent, in an amount of 0.01 to 0.03 wt .-%.
  • Suitable chelating agents include ethylenediamine tetraacetic acid (EDTA) or (1-hydroxyethylidene) diphosphonic acid (HEDP).
  • the fabric care composition may contain a skin care compound.
  • a skin-care compound is understood to mean a compound or a mixture of compounds which, upon contact of a textile with the solid, textile and / or skin-care composition, draw on the textile and, on contact of the textile with skin, confer an advantage on the skin compared with a textile which has not been treated with the textile and / or skin care composition according to the invention.
  • This benefit may include, for example, the transfer of the skin care compound from the textile to the skin, less water transfer from the skin to the textile, or less friction on the skin surface through the textile.
  • the textile-care composition has particle sizes in the range of 0.6 to 30 mm, in particular 0.8 to 7 mm and particularly preferably 1 to 3 mm. It is further preferred that the textile care composition is an extrudate.
  • the soap (s), the textile-care compound, the perfume and, if appropriate, further ingredients are mixed, and the resulting mixture is then extruded through a rhombic perforated plate.
  • the textile-care composition of the invention is particularly suitable for conditioning textile fabrics and is used together with a conventional washing or Detergent in the (main) wash of a conventional washing and cleaning process brought into contact with the fabrics.
  • the fabric care composition can be incorporated into a detergent or cleanser.
  • a solid detergent or cleaning agent with 0.1 to 20 wt .-%, preferably 1 to 10 wt .-%, of the textile-care composition according to the invention is mixed.
  • the detergents or cleaners according to the invention contain, in addition to the textile-care composition, surfactant (s), it being possible to use anionic, nonionic, zwitterionic and / or ampholytic surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
  • the total surfactant content of a detergent is preferably below 40% by weight and more preferably below 35% by weight, based on the total detergent.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, 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 ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO, 7 EO or 4 EO, C9-11 alcohol containing 7 EO, C 13-15 alcohols containing 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 12-16 -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 which contain 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.
  • mixed alkoxylated nonionic surfactants can be used in which EO and PO units are not blockwise, but are statistically distributed. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • 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.
  • Alkyl glycosides 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.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (VII) in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [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 (VIII) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the content of nonionic surfactants in the detergents or cleaners is preferably 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15 wt .-%, each based on the total detergent or cleaning agent.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-16 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide
  • alkanesulfonates which are obtained from C 12-18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • fatty acid glycerol esters are the mono-. To understand di- and triesters and their mixtures as they 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 monoesters of C 12 -C 16 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, 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 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN M are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7-21 -alkahoxyls ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12-16 Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents 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 acid esters and the 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 6-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic tesides.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog 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.
  • Particularly preferred anionic surfactants are 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 anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of preferred detergents or cleaning agents to anionic surfactants is 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, each based on the total washing or cleaning agent.
  • the detergents or cleaning agents may contain further ingredients which further improve the performance and / or aesthetic properties of the washing or cleaning agent s.
  • preferred washing or cleaning agents additionally contain one or more substances from the group of builders, bleaches, bleach activators, enzymes, perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents , 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, neutral filler salts and UV absorbers.
  • Suitable builders which may be present in the detergents or cleaners are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x 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.
  • Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. In particular, both .beta.- and ⁇ -sodium Na 2 Si 2 O 5 ⁇ yH 2 O preferred.
  • 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. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • 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 14 -fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols, suitable zeolites have an average particle size of less than 10 microns (volume distribution;
  • Coulter Counter and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Organic builders that may be present in the detergent or cleaning agent include polycarboxylate polymers such as polyacrylates and acrylic acid / maleic acid copolymers, polyaspartates and monomeric polycarboxylates such as citrates, gluconates, succinates or malonates, which are preferably used as the sodium salts.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the detergents or cleaners.
  • 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-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 be incorporated into the detergents or cleaning agents.
  • bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes.
  • 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.
  • the washing or cleaning agent may contain enzymes in encapsulated form and / or directly in the washing or cleaning agent.
  • Suitable enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, ⁇ -glucanases, oxidases, peroxidases, perhydrolases, mannanases and / or laccases and mixtures of said enzymes in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • 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.
  • Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens.
  • 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.
  • ⁇ -amylases In particular, ⁇ -amylases, iso-amylases, pullulanases and pectinases pay particular attention to the suitable amylases.
  • Cellulases used are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof. Since different types of cellulases differ in their CMCase and avicelase activities, targeted mixtures of the cellulases can set the desired activities become.
  • the enzymes may be adsorbed to carriers to protect against premature degradation.
  • the proportion of enzymes or enzyme granules directly in the washing or cleaning agent may for example be about 0.01 to 5 wt .-%, preferably 0.12 to about 2.5 wt .-% amount.
  • washing or cleaning agent contains no enzymes.
  • the washing or cleaning agent optionally contains one or more perfumes in an amount of usually up to 10 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1 to 3 wt .-%.
  • the amount of perfume used is also dependent on the type of detergent or cleaning agent. However, it is particularly preferred that the perfume is introduced into the washing or cleaning agent via the textile softening composition. However, it is also possible for the washing or cleaning agent to contain perfume which is not introduced into the washing or cleaning agent above the textile softening composition.
  • the detergents or cleaners may (optionally only partially) be colored 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 or cleaners are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable soil release polymers also referred to as "anti-redeposition agents” include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxy group content of 15 to 30% by weight and hydroxypropyl groups of 1 to 15% by weight, respectively based on the nonionic cellulose ether 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 thereof.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxy group content of 15 to 30% by weight and hydroxypropyl groups of 1 to 15% by weight, respectively based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic
  • Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Another class of suitable soil-release polymers, in particular for cotton-containing textiles, are modified, for example alkoxylated and / or quaternized and / or oxidized, polyamines.
  • the polyamines are, for example, polyalkyleneamines, such as polyethyleneamines, or polyalkylenimines, such as polyethylenimines, Preferred examples of this class of soil release polymers are ethoxylated polyethylenimines and ethoxylated polyethyleneamines.
  • Optical brighteners can be added to the detergents or cleaners to eliminate graying and yellowing of the treated textile fabrics. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure with the yellowness of the grayed or yellowed wash White results.
  • Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisultonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.
  • the optical brighteners are usually used in amounts of from 0 to 0.3% by weight, based on the finished detergent or cleaning agent.
  • Graying inhibitors have the task of keeping suspended from the fiber debris suspended in the fleet and so prevent the Nederaufutz the dirt.
  • 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 washing or cleaning agents.
  • the washing or cleaning agent may contain a dye transfer inhibitor.
  • the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as Vinylpyrrolidone and / or vinylimidazole is.
  • 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.
  • polyvinylpyrrolidone PVP
  • polyvinylimidazole PVI
  • copolymers of vinylpyrrolidone and vinylimidazole PVP / PVI
  • the polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are 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 available.
  • the copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000.
  • a PVP / PVI copolymer for example from BASF under the name Sokalan® HP 56th
  • 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, whereby the abovementioned polymeric color transfer inhibitors may additionally be used.
  • the detergents or cleaning agents may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • washing or cleaning agents 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 phenol mercuriacetate, it also being possible entirely to dispense with these compounds in the detergents or cleaners according to the invention.
  • the detergents or cleaners according to the invention may contain preservatives, it being preferred to use only those which have no or only a low skin-sensitizing potential.
  • preservatives examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, 3-iodo-2-propynyl butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof.
  • a suitable preservative is the solvent mixture, aqueous combination of diazolidinyl urea, sodium benzoate and potassium sorbate (available as Euxyl® K 500 ex Schuelke & Mayr), which can be used in a pH range up to 7.
  • the detergents or cleaners may contain antioxidants.
  • Class of compounds include, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.
  • Antistatic agents increase the surface conductivity and thus enable an improved outflow 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.
  • Lauryl (or, stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textile fabrics or as an additive to laundry detergents or cleaners, wherein additionally a softening effect is achieved.
  • silicone derivatives can be used in the detergents or cleaners. These additionally improve the rinsing out of the washing or cleaning agents by their foam-inhibiting
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely 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 detergent or cleaning agent.
  • the detergents or cleaners may also contain UV absorbers which are applied to the treated fabrics and improve the light fastness of the fibers.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • 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 detergents or cleaners 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 used mostly 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-phosphonobutan
  • neutral fillers such as sodium sulfate or sodium bicarbonate may be included in the solid detergent or cleaner.
  • washing or cleaning agents according to the invention can be used in particular for cleaning and conditioning textile fabrics.
  • the washing or cleaning agent without the textile-care compound is first prepared by known processes, which may include, for example, topping steps, mixing steps, densification steps, shaping steps and / or the subsequent addition of heat-sensitive ingredients ("post-addition") , produced. Subsequently, the resulting product is mixed with a solid, textile-care composition according to the invention.
  • the mixing step may be followed by further compaction and / or shaping steps.
  • Table 1 shows textile care compositions E2 to E5 according to the invention.
  • Table 1 E1 * E2 E3 E4 E5 Palm oil fatty acid soaps 96.99 88.99 81.99 80,99 88.99 glycerin - 7 8th 7 7 sorbitol - 1 1 1 1 1 bentonite - - 5 - - silica - - 2 - - Perfume 2 2 2 5 2 polydimethylsiloxane 1 1 - 6 - Polyquaternium-7 - - - - 1 dye 0.01 0.01 0.01 0.01 0.01 * not according to the invention
  • the textile-care compositions according to the invention exhibited a softening effect in comparison with water (the fabrics treated with water or textile-care composition were tapped after treatment and hanging drying from a panel consisting of 5 persons).
  • the fabric care compositions of the present invention are capable of reducing the hardness of water.
  • the hardness of tap water was determined by means of analysis sticks "total hardness test" (Merck) according to the manufacturer's instructions.
  • the tap water was then added to the solid textile care composition E2 according to the invention in a concentration as specified in the manufacturer's instructions, and the hardness of the water was determined.
  • the water hardness was reduced from 16 ° dH to 3 ° dH.
  • a solid, unscented washing or cleaning agent was mixed with 10% by weight (based on the total amount of finished washing or cleaning agent) of the textile-care composition E2 .
  • the washing or cleaning agent according to the invention showed good cleaning and conditioning properties.

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  • Chemical & Material Sciences (AREA)
  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP07726684.9A 2006-04-06 2007-03-07 Feste, textil-pflegende zusammensetzung auf seifenbasis Active EP2029716B1 (de)

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PL07726684T PL2029716T3 (pl) 2006-04-06 2007-03-07 Stała kompozycja do pielęgnacji tkanin oparta na mydle

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PCT/EP2007/052126 WO2007115870A1 (de) 2006-04-06 2007-03-07 Feste, textil-pflegende zusammensetzung auf seifenbasis

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DE102006016578A1 (de) * 2006-04-06 2007-10-11 Henkel Kgaa Feste, Textil-weichmachende Zusammensetzung mit einem wasserlöslichen Polymer
TR201007716A2 (tr) * 2010-09-21 2010-12-21 Dalan Ki̇mya Endüstri̇ Anoni̇m Şi̇rketi̇ Performans arttırıcı parçacıklar
US20130065812A1 (en) * 2011-09-14 2013-03-14 Ecolab Usa Inc. Water-dilutable solid concentrate
JP6224474B2 (ja) * 2014-02-05 2017-11-01 川研ファインケミカル株式会社 固形石鹸組成物
WO2018033571A1 (en) * 2016-08-17 2018-02-22 Zobele Holding S.P.A. Water soluble pellet and method for manufacturing said water soluble pellet
US11441106B2 (en) 2017-06-27 2022-09-13 Henkel Ag & Co. Kgaa Particulate fragrance enhancers

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US3226329A (en) * 1961-09-14 1965-12-28 Procter & Gamble Germicidal cleansing composition
US3915882A (en) * 1972-11-10 1975-10-28 Procter & Gamble Soap compositions
US5206019A (en) * 1989-05-30 1993-04-27 Moleculon, Inc. Soap compositions containing liquid-loaded powders
FR2725456B1 (fr) * 1994-10-07 1996-12-27 Rhone Poulenc Chimie Composition solide, granulaire, comprenant un ingredient liquide emprisonne dans une matrice solide, procede de preparation et utilisation dans une composition detergente en poudre
DE19620792A1 (de) * 1996-05-23 1997-11-27 Zschimmer & Schwarz Gmbh & Co Herstellung und Verwendung gut verarbeitbarer Komponenten für halbsynthetische Toiletteseifen
US6403543B1 (en) * 2000-05-16 2002-06-11 Original Bradford Soap Works, Inc. Soap with suspended articles
US20060234902A1 (en) 2005-04-19 2006-10-19 Unilever Home & Personal Care Usa Fabric care article and method

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US7989412B2 (en) 2011-08-02
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EP2029716A1 (de) 2009-03-04
ES2596002T3 (es) 2017-01-04
WO2007115870A1 (de) 2007-10-18
DE102006016586A1 (de) 2007-10-11

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