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
  • C11D3/12—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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
  • C11D3/3937—Stabilising agents
  • C11D3/394—Organic compounds

Definitions

• the invention relates to a detergent additive which is present in the mixture with granular detergents or spatially separated from them and is advantageously used in washing processes in which a poor washing result is to be expected as a result of increased water hardness.
• alkali salt should be 5 to 30% by weight and in the examples is 8 to 11.5%.
• these proportions are based on a water-containing zeofite, ie containing 21 to 22% by weight of structural water, which is evident from claim 8 and from the examples according to which the aluminosilicate slurry used contains 61% by weight of zeolite A.
• the technically possible maximum content of a zeolite slurry is 50% zeolite A, based on the anhydrous substance.
• the proportion of polymeric acid, based on water-free zeolite is therefore 6 to 37% by weight and in the examples 9.8 to 14% by weight. It is therefore comparatively high and makes the resources correspondingly expensive.
• a similarly composed softening agent with a reduced polymeric acid content is known from DE 36 14 779-A1.
• the agent also contains citric acid or. their salts and soda.
• the effect of these agents also appears to be increasing, especially when used in very hard water.
• the relatively high proportion of organic substance (10.5% citrate in the example) appears to be in need of improvement with regard to a minimal waste water pollution.
• the soda content can also interfere in some cases due to the formation of insoluble calcium carbonate.
• the object of the invention is a granular to powdery additive to be used in detergents or washing processes, characterized by a content of
• Component A consists of finely crystalline, synthetic, water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 ⁇ m.
• Component B consists of homopolymers of acrylic acid and / or copolymers of acrylic acid with maleic acid, which are in the form of the sodium salts.
• the polyacrylic acid can have, for example, a molecular weight of 2,000 to 200,000, preferably 5,000 to 100,000.
• Component C consists of sodium perborate, which can be present as a monohydrate, tetrahydrate or a mixture thereof.
• the content of the agents and the mixing ratios are based on the monohydrate, even if component B should consist entirely or partially of the tetrahydrate.
• Agents in which the perborate is present as a monohydrate are particularly preferred.
• the weight ratio of A: B is 30: 1 to 4: 1, preferably 14: 1 to 6: 1, that of A: C 10: 1 to 2: 1, preferably 7.5, 1 to 3: 1 and that of B: C 2: 1 to 1:10, preferably 1: 1 to 1: 4, components A and B being counted as anhydrous substances.
• the agents preferably contain the constituents in granular form, the average particle size of the particles being between 0.1 and 1.2 mm and the proportion of dust-like components (below 0.05 mm). less than 1% by weight, in particular less than 0.5% by weight, and the proportion of coarse fractions (over 1.6 mm) should be less than 2% by weight, preferably less than 1% by weight.
• the granular agents preferably consist of a dry, homogeneous mixture of at least two powder components, of which the first component is in the form of spray-dried granules. It can be obtained by spray drying a slurry which contains the zeolite as an aqueous suspension in a mixture with the sodium salt of the (co) -polymeric acids in the stated mixing ratio.
• This 1st powder component may contain other additives, which, for. B. can advantageously change the granulate structure, the bulk density or the flow behavior.
• additives include, for example, sodium sulfate, which is essentially in water-free form.
• (anhydrously calculated) component D its weight ratio A: D is preferably 20: 1 to 4: 1.
• nonionic surfactants which have an HLB value of at most 12 and which consist of ethoxylation products of linear or methyl-branched (oxo radical) alcohols or also alkyphenols.
• these additives serve to stabilize aqueous zeolite suspensions and can therefore also be present in agents of the type claimed, in the manufacture of which such suspensions are used. Examples of these are C “_ .. alcohols with 3 to 5 EO and C ,. , "-AI-
• E 100: 1 to 20: 1, usually 50: 1 to 30: 1 and therefore only contains small amounts of surfactant, the influence of which on the washing result is correspondingly small.
• the water-soluble salts e.g. B. the sodium salts, of phosphonic acids (component G).
• Suitable phosphonic acids or phosphonic acid salts are 1-hydroxyethane-1,1-diphosphonate, ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate.
• the weight ratio of A: F can be 600: 1 to 40: 1.
• the agents can contain further powder components which are 'mixed with the two powder components mentioned above in dry form.
• a preferred further powder component consists of a powdery to granular peracid precursor. (Bleach activator) from the class of N-acyl compounds and O-acyl compounds.
• suitable N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril.
• N-alkyl-N-sulfonylcarbonamrde N-acylhydantoins
• N-acylated cyclic hydrazides triazoles, urazoles, dketopiperazines, sulfurylamides and imidazolones.
• carboxylic anhydrides such as phthalic anhydride and esters such as Na (iso) nonanoyl phenol sulfonate
• acylated sugars such as glucosopentaacetate are also suitable as O-acyl compounds.
• Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate.
• the bleach activators can be granulated in order to avoid interactions with the perborate and can be coated with water-soluble coating substances.
• Particularly suitable coating agents are water-soluble polymers, for example wise cellulose ethers, such as carboxymethyl cellulose (as sodium salt), or carbon chain polymers, such as the (co) -polymeric polycarboxylic acids mentioned under B and their salts, and also polyvinyl alcohol and mixtures of water-soluble polymers.
• Agents of the specified composition can accordingly have the following composition:
• polymeric polycarboxylate derived from acrylic acid and its copolymers with maleic acid in the form of the sodium salts
• G 0 to 10% by weight of a peracid precursor, with the proviso that the amounts, with the exception of component C, are based on anhydrous substance and the amount of component C is based on monohydrate and the total amount of bound water, the is contained in the components with the exception of C, is up to 20 wt .-%.
• compositions preferably have the following composition: A) 45 to 55% by weight of finely crystalline, synthetic zeolite of the NaA type, B) 3 to 7.5% by weight of the sodium salt of an acrylic acid-maleic acid copolymer in a weight ratio of 10: 1 to 1: 1 and a molecular weight of 20,000 to 150,000,
• components A, B and D to F are preferably combined in a spray-dried powder component (1st powder component).
• the components C and G form two separate powder components, which are associated with the 1st Powder components are mixed in dry form.
• agents of the claimed composition show a better effect with regard to the binding of calcium salts and the enhancement of the builder effect than conventional agents which have higher proportions of "classic” softening agents.
• Zeolites, soda, polymeric polycarboxylates and polyacids such as citric acid are considered to be "classic” softening agents.
• perborates, in combination with some of the "classic” softening agents mentioned advantageously support their specific action and exert a builder effect, provided the water used has a high calcium hardness.
• the agents still have a pronounced bleaching action, which is particularly useful when the consumer underdoses the heavy-duty detergent containing bleach and does not use any other additives.
• the agents according to the invention and conventional detergents are used simultaneously, the following advantages result: the washing power, in particular with regard to the prevention of graying of the fabric and ash, is considerably improved, especially if the conventional detergent is underdosed in relation to the water hardness,
• the synthetic zeolite used (calculated anhydrous) had a particle size between 0.5 and 8 ⁇ m.
• the polycarboxylate consisted of the Na salt of a copolymer of acrylic acid and maleic acid with a molecular weight of approx. 70,000 (Sokalan CP5) and in Example 3 from a Na polyacrylate with a molecular weight of 20,000.
• EDTMP stands for the hexasodium salt of ethylenediaminetetra-methylenephosphonic acid.
• TAED stands for tetraacetylethylenediamine.
• CMC is the sodium salt of carboxymethyl cellulose and served as a coating substance for the TAED according to the information in EP 37026. In comparative experiment V2, CMC served as a granulating aid for the overall product.
• the application test was carried out in a practical manner in a household washing machine with a horizontally arranged laundry drum (type Miele W 433) with the use of a commercially available detergent.
• the composition of this agent was (in% by weight)
• Test soiling I - VI I kaolin / soot / skin fat on cotton
• the other test conditions are shown in the following table.
• the column "target” indicates the dosage of the detergent W compared to the correct target value 1.
• the addition of softening agents according to the invention according to Example 1 is marked with B1 ge.
• VI and V2 designate additives according to comparative experiment VI and V2.

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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)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (5)

• 1988
  • 1988-05-02 DE DE19883814855 patent/DE3814855A1/de not_active Withdrawn
• 1989
  • 1989-04-24 WO PCT/EP1989/000444 patent/WO1989010953A1/de not_active Application Discontinuation
  • 1989-04-24 EP EP89107371A patent/EP0340590A1/de not_active Withdrawn
  • 1989-04-24 EP EP19890904809 patent/EP0423132A1/de active Pending
• 1990
  • 1990-08-07 DK DK188390A patent/DK188390D0/da not_active Application Discontinuation

Patent Citations (5)

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