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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • 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
  • C11D3/3942—Inorganic per-compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3945—Organic per-compounds

Definitions

• the invention relates to a phosphate-free detergent based on zeolite and alkali silicate and a process for its production.
• zeolite in particular zeolite NaA, and in particular mixtures of zeolite with alkali silicates and alkali carbonates and polymeric polycarboxylates have been used as phosphate substitutes in washing and cleaning agents and to reduce incrustations.
• complexing agents such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and phosphonic acids.
• NTA nitrilotriacetic acid
• EDTA ethylenediaminetetraacetic acid
• the mostly selectively acting complexing agents have the task of eliminating heavy metal ions, which, even in traces, can have a very negative effect on the washing process, in particular on the bleaching process (Ullmann, 1987, Vol. 8, pp. 351 to 354).
• European patent application 291 869 (Henkel) describes phosphate-free builders combinations of zeolite and aminoalkane polyphosphonate and / or polymeric polycarboxylate and 1-hydroxyethane-1,1-diphosphonate (HEDP), certain weight ratios of the last three components being synergistic with regard to preventing the formation of fiber incrustations demonstrate.
• Crystalline, layered sodium silicates have also been described as substitutes or partial substitutes for phosphates and zeolites.
• European patent application 164 514 discloses a phosphate-free builder combination which mainly contains crystalline phyllosilicates of the formula (I) NaMSi x O 2 + 1 .yH2O, where M is sodium or hydrogen means 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.
• These layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.
• German patent application 24 12 837 (Henkel), which, in combination with zeolite, contains various complexing agents such as polymeric polycarboxylates and phosphonates as well as alkaline framework substances, such as carbonates and silicates, which are not capable of complex formation.
• "microcrystalline" zeolites are preferably used, which are at least 80% by weight of particles having a size between 10 and 0.01 ⁇ m and in particular between 8 and 0.1 ⁇ m.
• washing and cleaning agents which contain 0.5 to 3 wt .-% alkali silicate (calculated as a solid). These agents are prepared either by a conventional mixing process in which the solid silicates or a corresponding amount of a water glass solution are mixed together with the other main components, or by a spray drying process in which the slurry contains both zeolite and the corresponding amount of alkali silicate.
• the alkali silicates serve as corrosion inhibitors.
• a detergent is known from German patent application 26 56 009 (Colgate) which contains 12 to 25% by weight of zeolite, in particular of type 4A, 5 to 20% by weight of a sodium silicate with the composition Na 2 O: SiO 2 of 1: 1 to 1 : 3.2, in particular from 1: 2.0 to 1: 2.6, and contains a peroxy bleach.
• undesired deposits of the water-insoluble zeolite particles on the laundry are to be prevented by 0.3 to 3% by weight of a polymer from the group carboxymethyl cellulose, lower alkyl cellulose, hydroxy-lower alkyl-lower alkyl cellulose, polyvinyl alcohol, polyvinyl acetate and Polyvinyl pyrrolidone can be used.
• the zeolite has an average particle diameter of 0.5 to 12 ⁇ m, preferably 5 to 9 ⁇ m.
• European patent application 10 247 describes a detergent which contains surfactants in conventional amounts, zeolite, alkali silicate and optionally a peroxy bleach.
• zeolite zeolite
• alkali silicate alkali silicate
• peroxy bleach zeolite
• water-soluble organic complexing agents from the group of substituted alkanedi- and alkanetri-phosphonic acids, which are present in the form of their alkali and / or alkaline earth salts
• a detergent is obtained which not only has a good primary washing action, but also the formation of fiber incrustations reduced.
• the addition of these phosphonates results in increased bleaching stability despite the absence of conventional stabilizers such as magnesium silicate and aminopolycarboxylate.
• the agent contains 20 to 65 wt .-% of a finely divided zeolite, as described in German patent application DE 24 12 837, and 1 to 7 wt .-% solid, powdered sodium silicate of the molar composition Na2O: SiO2 from 1: 2 to 1: 2.2.
• the composition consists of a mixture of at least 2 powder constituents, the first of which is obtained by spray drying an aqueous slurry containing the zeolite, surfactants and optionally the water-soluble organic complex-forming framework substances, and the second powder constituent from the sodium silicate powder and optionally from the water-soluble phosphonates and other detergent additives that are sensitive to hydrolysis and / or temperature.
• European patent application 240 356 discloses detergents which, in addition to zeolite and water-soluble sodium silicates, as described in European patent application 10 247, contain polymeric polycarboxylates and their derivatives, for example polyacrylates and salts of acrylic acid-maleic acid copolymers. These polymeric polycarboxylates are spray dried together with the zeolite during the production of the detergent.
• builder combinations for detergents which contain crystalline phyllosilicates and optionally phosphates and polycarboxylates such as citrates, glykonates, NTA and / or iminodiacetates, but no zeolite.
• the agents which contain 10 to 50% by weight of crystalline layered silicate, are characterized by a storage-stabilized bleaching system.
• European patent application 405 122 (Hoechst) specifies a builder combination for textile detergents, the builder combination consisting of a mixture of zeolite and crystalline sodium phyllosilicate in a ratio of 4: 1 to 1: 4.
• the incrustation of the fabric can be reduced.
• the object of the invention was to further develop the field of phosphate-free builders combinations for use in textile detergents with the aim of reducing the proportion of organic synthetic compounds.
• detergents which contain a special combination of finely divided zeolite with a relatively narrow particle size spectrum and alkali silicate as builders meet the high demands placed on modern detergents.
• the invention relates to a detergent which contains surfactants, zeolite, alkali silicate and optionally a peroxy bleach and which is characterized in that it comprises 30 to 65% by weight of a finely divided, hydrated zeolite with an average particle size of 1 to 5 ⁇ m, 1 to 15 wt .-% of a solid alkali silicate of the molar composition M2O: Si2O from 1: 2.0 to 1: 3.0, wherein M is sodium and / or potassium, with the proviso that the agent is free of water-soluble organic Complexing agents from the group of substituted phosphonates, free of polymeric polycarboxylates and essentially free of alkali carbonates.
• the finely divided, hydrated zeolite generally has a water content of 17 to 25% by weight.
• the quantities for zeolite relate to the anhydrous active substance.
• Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%.
• Preferred zeolites have an average particle size between 1.8 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m (measurement method: Fraunhofer diffraction; mean volume distribution).
• the content of the agents in finely divided, in particular crystalline, hydrated zeolite is preferably 30 to 55 wt .-% and in particular 32 to 54 wt .-%, based on anhydrous active substance.
• the solid alkali silicates can be amorphous or crystalline, as powder or as granules, for example as roller-compacted chip granules, or as a spray-dried compound.
• Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
• Such amorphous alkali metal silicates are commercially available, for example, under the name Portil (R) (Henkel).
• crystalline sheet silicates of the formula (I) NaMSi x O 2 + 1 .yH2O are preferably used, in which M represents sodium, x assumes the values 2 or 3 and y is a number from 0 to 20. Both ⁇ - and ⁇ -sodium disilicates Na2Si2O5 are particularly preferred.
• the content of alkali silicates in the compositions is preferably 2 to 10% by weight and in particular 3 to 10% by weight, based on the anhydrous substance.
• the amorphous sodium silicate content of the agents is 3.5 to 8% by weight, based on the anhydrous substance.
• the weight ratio of zeolite: amorphous silicate, based in each case on anhydrous substance is preferably 4: 1 to 10: 1.
• the crystalline layered silicates are preferably used in amounts of 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, based in each case on the anhydrous substance, being at least 5: 1.
• the weight ratio of amorphous alkali silicate: crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
• the agents do not contain any water-soluble organic complexing agents from the group of the phosphonates, so that the agents have a calculated phosphorus content of 0%.
• Polymeric polycarboxylates for example polyacrylates, polymethacrylates, polymaleates or copolymers of acrylic acid with maleic acid or maleic anhydride, which are usually used in combination with zeolite, are also not present in the product according to the invention, since they do not improve its primary and secondary washability.
• the agents are also essentially free of alkali carbonates, which means that they contain no more than about 5% by weight, preferably no more than 4% by weight and particularly advantageously no more than 3% by weight of alkali carbonates, in particular of sodium carbonate.
• alkali carbonate content in the range mentioned also contributes to increased incrustation.
• alkali carbonate may only be added in the amounts in which it does not contribute to increased incrustation.
• Preferred detergents contain peroxy bleach and in particular peroxy bleach in combination with bleach activators.
• bleaching agents which supply H2O2 in water
• sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
• Other bleaches that can be used are, for example, peroxycarbonate or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
• Suitable bleach activators for these peroxy bleaches are, for example, the N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines such as N, N, N'N'-tetraacetylethylenediamine.
• the content of peroxy bleaching agent in the agents is preferably 12 to 30% by weight, in particular in combination with 1 to 10% by weight, preferably 2 to 8% by weight, of a bleach activator.
• the detergents according to the invention are not only distinguished by a reduced formation of fiber incrustations compared to agents of the prior art which usually contain polymeric polycarboxylates and / or alkali metal carbonates in larger amounts. Surprisingly, they also have an improved bleaching action or an improved stabilization of the peroxy bleaching agent, although they contain no conventional stabilizers such as phosphonate, magnesium silicate or other complexing agents such as the salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid.
• the detergents and cleaning agents contain known compounds from the group of anionic, nonionic and zwitterionic surfactants as further constituents.
• sulfonates come as anionic surfactants and sulfates and soaps from preferably natural fatty acids or fatty acid mixtures.
• C Tens-C13 alkylbenzenesulfonates, olefin sulfonates, esters of ⁇ -sulfofatty acids or ⁇ -sulfofatty acid disalts are used, for example, as surfactants of the sulfonate type.
• Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from C12-C18 fatty alcohols or from C10-C20 oxo alcohols, and those of secondary alcohols of this chain length.
• the sulfuric acid monoesters of the alcohols reacted with 1 to 6 mol of ethylene oxide (EO) are also suitable.
• Addition products of preferably 2 to 20 moles of EO to 1 mole of an aliphatic compound with essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides are of particular interest as nonionic surfactants.
• polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule that are not or not completely water-soluble are also important, in particular when they are used together with water-soluble nonionic or anionic surfactants.
• alkyl polyglycosides of the general formula RO- (G) x can also be used as nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms, methyl-branched, G is a symbol is a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10.
• the total content of surfactants in the compositions is generally between 5 and 40% by weight. It is preferably 5 to 30% by weight and in particular 8 to 25% by weight.
• detergent and cleaning agent components include foam inhibitors, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts, solvents and water.
• foam inhibitors include foam inhibitors, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts, solvents and water.
• graying inhibitors which are usually used in modern textile detergents, is not necessary and, in particular, is also not preferred.
• Enzymes from the class of proteases, lipases, cellulases and amylases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
• Suitable non-surfactant-like and preferably used foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica. Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
• powdery or granular detergents contain 10 to 30% by weight of surfactants, 30 to 45% by weight of a finely divided, hydrated zeolite with an average particle size of 2.0 to 3.8 ⁇ m, 2 to 10% by weight.
• the detergents according to the invention can be prepared in a conventional manner, for example by mixing, granulating and / or by spray drying. It is possible to incorporate the builders zeolite and solid alkali silicate into the agents individually in a conventional manner and in any order.
• the pourable powder or granular preparations preferably consist of a dry homogeneous mixture of at least 2 powder components, at least the first of which is in the form of spray-dried granules. It is done by a conventional way Spray drying of a slurry available which contains at least the anionic surfactants and optionally nonionic surfactants.
• This slurry preferably additionally contains at least part of the zeolite and / or the silicate.
• the slurry can contain a portion, but not more than 3% by weight and in particular not more than 2% by weight, in each case based on the total finished composition of the amorphous silicates contain.
• the rest of the amorphous alkali silicates present as powder or granules, like the crystalline sheet silicates which may be present, which are in granular form or adsorbed on a carrier which consists, for example, of sodium sulfate, are subsequently mixed into the spray product.
• the zeolite-containing slurry be free of amorphous alkali silicates and that these are subsequently added to the spray-dried product.
• the slurry does not contain zeolite, it is possible to incorporate the entire proportion of the amorphous alkali silicates into the slurry and to spray-dry them.
• the crystalline layered silicates which may be present are preferably not spray-dried, but are added subsequently in granular form or adsorbed onto a carrier.
• the zeolite is then also incorporated into the compositions as a powder or, preferably, as a commercially available compound, for example as Wessalith (R) CS or Wessalith (R) CB (commercial products from Degussa, Federal Republic of Germany).
• zeolite-containing and a silicate-containing slurry it is also possible for a zeolite-containing and a silicate-containing slurry to be spray-dried separately and then mixed. However, it is particularly advantageous if the zeolite-containing slurry and the silicate-containing slurry are introduced into a spray tower at the same time.
• bleaching agents such as perborate are not spray-dried together with the constituents of the first powder component, but are also only added to the spray product afterwards.
• Granular detergents of the following composition were produced and tested.
• the perborate, the bleach activator, the alkali silicate as well as enzyme granulate and silicone oil granulate were subsequently mixed into the spray-dried product from a slurry which contained the remaining constituents.
• the test was carried out under practical conditions in household washing machines (Miele W 717). The washing conditions are specified in more detail in the individual examples.
• the degree of whiteness was measured in a Zeiss reflectometer at 460 nm (suppression of the brightener effect). Remission differences of 2% and more are significant and directly understandable by the consumer.
• Table 1 shows that in the test series a) (detergent without the addition of copper), agents E and V have comparable performances.
• the detergent E according to the invention performed significantly better than V in all soiling.
• the performance difference between E and V in favor of E was even greater .
• Table 1 Trial series % Remission for detergent E V a) Detergent 73.9 74.4 b) Detergent + 5ppm Cu2+ 68.1 63.3 c) Detergent + 10ppm Cu2+ 53.3 47.7
• Washing conditions tap water of 23 ° d, 3.5 kg of clean laundry, dosage of detergent 146 g, 25 washes; all other parameters as in example 1.

Landscapes

• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (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)
• Crystallography & Structural Chemistry (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=6426447

Family Applications (1)

Country Status (6)

Families Citing this family (4)

Family Cites Families (8)

• 1991
  • 1991-03-05 DE DE4106880A patent/DE4106880A1/de not_active Withdrawn
• 1992
  • 1992-02-25 ES ES92905355T patent/ES2079858T3/es not_active Expired - Lifetime
  • 1992-02-25 EP EP92905355A patent/EP0574436B1/de not_active Revoked
  • 1992-02-25 AT AT92905355T patent/ATE129743T1/de not_active IP Right Cessation
  • 1992-02-25 DE DE59204203T patent/DE59204203D1/de not_active Revoked
  • 1992-02-25 WO PCT/EP1992/000390 patent/WO1992015663A1/de not_active Application Discontinuation
  • 1992-02-25 JP JP50465492A patent/JPH06505045A/ja active Pending

Also Published As

Similar Documents

Legal Events