EP0571436B1 - Additif granule pour produits de lavage et de nettoyage - Google Patents

Additif granule pour produits de lavage et de nettoyage Download PDF

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Publication number
EP0571436B1
EP0571436B1 EP92904218A EP92904218A EP0571436B1 EP 0571436 B1 EP0571436 B1 EP 0571436B1 EP 92904218 A EP92904218 A EP 92904218A EP 92904218 A EP92904218 A EP 92904218A EP 0571436 B1 EP0571436 B1 EP 0571436B1
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EP
European Patent Office
Prior art keywords
weight
water
granules
spray
additive
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.)
Expired - Lifetime
Application number
EP92904218A
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German (de)
English (en)
Other versions
EP0571436A1 (fr
Inventor
Lothar Pioch
Wolfgang Seiter
Otto Koch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0571436A1 publication Critical patent/EP0571436A1/fr
Application granted granted Critical
Publication of EP0571436B1 publication Critical patent/EP0571436B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D3/16—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

Definitions

  • the invention relates to a granular additive for detergents and cleaning agents and to a method for producing these additives.
  • the additives are usually stored separately from granular detergents and cleaning agents and, if required, used together with these in washing or cleaning processes. In the sense of an additional builder effect, they improve the cleaning ability of the actual washing and cleaning agent and prevent the formation of hard limescale deposits on the heating elements or on the textile fiber.
  • the detergents can be added to granular detergents and cleaning agents or processed together with them, thereby advantageously influencing their pouring properties and washing-in behavior or enabling trouble-free further processing.
  • Known agents of this type often contain salts of polymeric aliphatic carboxylic acids. These include, in particular, salts of polyacrylic acid and polymethacrylic acid and salts of copolymers of these two acids with maleic acid and / or vinyl esters. There are no difficulties in producing storage-stable granules which contain up to about 15% by weight of such polymer salts. However, since the salts of the polymeric polycarboxylates are hygroscopic, mixtures with higher proportions of such salts cannot readily be converted into storage-stable and free-flowing granules, especially not if they do not contain any water-binding or water-repellent mixture components.
  • German patent application 21 00 500 proposes to use the polymers as free acids or partially neutralized salts with a degree of neutralization of at most 60% or to convert them from their aqueous solutions into granular products by hot spray drying.
  • Agents that contained a higher proportion of neutralized salts showed under after only one week of storage Room temperature conditions a strong softening.
  • the polymeric carboxylic acids only develop their full effect as completely neutralized salts.
  • the alkaline agent required for neutralization must therefore be subsequently added to the acidic granules.
  • German patent application 36 04 223 discloses granular additives for detergents and cleaning agents which contain 20 to 80% by weight of homo- or copolymeric (meth) acrylic acids or, if appropriate, their water-soluble salts.
  • the problem of the hygroscopicity of such concentrated agents could be solved by the agents additionally containing 20 to 80% by weight of nitrilotriacetic acid (NTA) or salts thereof.
  • NTA nitrilotriacetic acid
  • Other components of detergents and cleaning agents for example sodium sulfate and / or sodium aluminum silicates, can additionally be present in the agents up to 20% by weight.
  • the invention relates to a granular additive that 40 to 75% by weight of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, 1 to 35% by weight of synthetic, finely crystalline, zeolite containing bound water, 2 to 20 wt .-% sodium sulfate (calculated anhydrous) and 1 to 15 wt .-% water, but contains no nitrilotriacetic acid or sodium or potassium salts of nitrilotriacetic acid.
  • Suitable homopolymers are sodium salts of polymethacrylic acid and preferably polyacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acids). If only homopolymeric polyacrylic acids (in salt form) are used, their relative molecular mass is preferably 1,000 to 80,000 (based on acid) in the interest of good flowability and storage stability.
  • Suitable copolymers are those of acrylic acid with methacrylic acid and preferably copolymers of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
  • Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Mixtures of different homo- and copolymers can also be used with advantage, in particular mixtures of homopolymeric acrylic acid and the copolymers of 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid described above.
  • Such mixtures which are characterized by favorable grain properties and high storage stability, can consist, for example, of 10 to 50% by weight of homopolymeric acrylic acid and 90 to 50% by weight of acrylic acid-maleic acid copolymers.
  • Highly polymeric polyacrylic acids can also be used in these mixtures which, when used alone, have a slightly greater tendency to stick or melt than the low molecular weight polyacrylates.
  • the content of homopolymeric or copolymeric (meth) acrylates in the additives is preferably 45 to 65% by weight and in particular 50 to 62% by weight.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. It can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, this may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C12-C18 alcohols with 2 to 5 glycol ether groups. Suitable zeolites have an average particle size of less than 10 »m (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The zeolite content of the additives is preferably 8 to 30% by weight and in particular 10 to 25% by weight.
  • the sodium sulfate is used in anhydrous form, preferably in amounts of 4 to 15% by weight and in particular 7 to 15% by weight.
  • zeolite for example from 3 to 10% by weight
  • the content of water in the additives which is not bound by the zeolite is preferably not more than 12% by weight, based on the additive, and is in particular in the range from 3 to 11% by weight.
  • the additives can have sodium carbonate in anhydrous form in amounts not exceeding 20% by weight.
  • the additives contain 3 to 15% by weight and in particular 4 to 12% by weight of anhydrous sodium carbonate.
  • the additives can contain small amounts, for example 0.5 to 3% by weight, based on the additive, of surfactants, such as soap, sulfonates (for example dodecylbenzenesulfonate), organic sulfates (for example fatty alkyl sulfates) or alkypolyglycosides.
  • surfactants such as soap, sulfonates (for example dodecylbenzenesulfonate), organic sulfates (for example fatty alkyl sulfates) or alkypolyglycosides.
  • the additives can also contain small amounts of further constituents, such as dyes and color pigments, and can be colored uniformly or speckled.
  • the proportion of such constituents is in each case well below 1% by weight.
  • the average grain size of the granular additive is usually 0.2 to 1.2 mm, the proportion of the granules being below 0.1 mm not more than 10% by weight and above 2 mm not more than 20% by weight (sieve analysis ).
  • at least 75% by weight, in particular at least 85% by weight, of the granules have a size of 0.2 to 1.6 mm, the proportion of the granules having a grain size between 0.1 and 0.05 mm no longer than 4% by weight, in particular not more than 3% by weight and the proportion of the grains between 1.6 and 2.4 mm not more than 20% by weight, preferably not more than 10% by weight and in particular is not more than 6% by weight. Larger proportions of fine grain generally lead to a deterioration in the induction behavior.
  • the production of the granules can, for example, be reduced by intensive mixing of the dry constituents with participation Amounts of liquid, in particular water, are carried out in conventional granulating devices.
  • spray drying of an aqueous slurry is preferred.
  • the slurry concentration is preferably between 50 and 68% by weight (non-aqueous fraction) and in particular between 55 and 60% by weight, the viscosity of the paste being decisive, which should not exceed 10,000 mPa ⁇ s and advantageously 2,500 to Is 6,000 mPa ⁇ s. (The viscosity is measured in the low pressure part of the spray tower at temperatures between 60 and 100 ° C using a truncated cone viscometer).
  • the temperature of the slurry is usually between 50 and 100 ° C.
  • the pressure at the spray nozzles is generally 30 to 80 bar, preferably 40 to 70 bar.
  • the temperature of the counter-current dry gases in the entrance zone of the spray tower, ie in the so-called ring channel is advantageously between 200 and 320 ° C, in particular between 220 and 300 ° C. In the area of the tower outlet it should be between 90 and 130 ° C, preferably between 100 and 125 ° C.
  • Such comparatively high operating temperatures are advantageous for the production of a perfect product and, despite the high proportion of organic substance in the spray product, are not critical, since the self-ignition temperature is above 330 ° C., usually even above 350 ° C.
  • Conventional spray drying systems spray nozzles or spray disks can be used for spray drying, the spray nozzles being able to be arranged in one or more levels.
  • the spray material leaving the tower can, if necessary after cooling with flowing air, be immediately further processed or packaged.
  • the granules are exceptionally free-flowing and can be washed into washing machines and dishwashers without leaving any residue and retain these advantageous properties even after a long storage period.
  • the granules according to the invention usually have a bulk density of 240 to 450 g / l, usually one of 320 to 400 g / l. If small amounts, for example 0.5 to 3% by weight, of surfactants, such as soaps, sulfonates, organic sulfates or alkyl polyglycosides, were added to the granules before the spray drying, the bulk density may be lower by amounts of 50 to 150 g / l than without this addition.
  • surfactants such as soaps, sulfonates, organic sulfates or alkyl polyglycosides
  • granules with a higher bulk density in particular those of 500 to 900 g / l, are claimed.
  • the bulk weight can be increased in a manner known per se by compacting the light granules, for which purpose in principle all techniques are suitable which are carried out under pressure and, if appropriate, with the addition of a small amount of liquid, for example by roller compacting, pelleting, extrusion or tableting.
  • roller compacting pressing by means of rollers, for example at a pressure between 100 and 200 bar, is preferred.
  • liquid binders preferably water and / or nonionic, in particular ethoxylated, nonionic surfactants, paste-like anionic surfactants and paraffin oil can be added to the granular additives.
  • binder the content of which, based on the compacted granulate, advantageously does not exceed 10% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight, improves the plasticizability of the light additive and increases the density of the compacted additive.
  • the binders can be mixed with the light additive or sprayed onto the light granulate, for example by spraying the powder stream fed to the roller with water or aqueous surfactant solutions. If water is selected as the binder, water can be omitted if the granules obtained, for example, by spray drying have not been completely dried, so that a residual moisture, for example 6 to 15% by weight of water, is retained in the spray-dried granules. The further processing of such slightly moist spray granules is a preferred method of working.
  • the compacting can also be carried out in a screw press or in a granulating device after the addition of appropriate amounts of liquid.
  • the active substance content of the non-dried compacts slightly decreases according to the amount of liquid added.
  • the compacted granules are also free-flowing and their storage stability under unfavorable conditions, for example in a humid atmosphere, also exceeds the spray-dried products.
  • a granular additive of the composition 60.0% acrylic acid-maleic acid copolymer (molecular weight 70,000) in the form of the Na salt, 16.0% zeolite NaA, spray dried (20% by weight bound water), 10.6% sodium sulfate (anhydrous), 8.0% sodium carbonate (anhydrous), 5.4% water was made as follows: A slurry heated to 77 ° C., which contained the aforementioned solids and 47.0% by weight of water and had a viscosity of 2,500 mPa ⁇ s (60 ° C.; truncated cone viscometer from Brabender, Duisburg, Federal Republic of Germany), was also used sprayed at a pressure of 40 bar via nozzles in a drying tower.
  • the counter-current dry gas had a temperature of 210 ° C in the ring channel and 120 ° C in the area of the tower outlet.
  • the spray product was extremely free-flowing and had a bulk density of 320 g / l.
  • the following particle size distribution was determined by sieve analysis (> greater than, ⁇ less than) mm > 1.6 > 0.8 > 0.4 > 0.2 > 0.1 ⁇ 0.1 % By weight 2nd 19th 43 26 8th 2nd
  • the dust content ( ⁇ 0.05 mm) was less than 0.02% by weight.
  • the product proved to be stable in storage and quickly and completely redispersible in cold water.
  • the parts with a grain size of more than 1.6 mm and less than 0.1 mm were separated off by sieving.
  • Example 1 a free-flowing, storage-stable granulate of the following composition was produced by spray drying: 50.0% by weight Na salt of the acrylic acid-maleic acid copolymer, 20.0% by weight of zeolite NaA, spray-dried, 10.0% by weight sodium sulfate (anhydrous), 9.0% by weight sodium carbonate (anhydrous), 11.0 wt% water.
  • the dust content was less than 0.02% by weight.
  • the spray product showed an equally good flowability as the product according to Example 1.
  • APG stands for an alkyl polyglucoside, derived from linear C10 ⁇ 14 alkyl chains and with an average degree of oligomerization of the glucose residue of 1.4.
  • the product made with this addition draws is characterized by an above-average degree of whiteness and a comparatively low bulk density.
  • the product according to Example 3 requires a somewhat lower product throughput per unit of time in the drying tower because of its somewhat difficult drying properties. All granules were free-flowing and stable in storage and proved to be completely and quickly redispersible when introduced into cold tap water.
  • the granules according to Examples 1 and 2 were fed to a roller compactor.
  • the roller pressure was 150 bar.
  • the lower-water granules were sprayed with 4% by weight of water before the pressing, while the more water-rich product was compacted according to Example 2.
  • the pressed material was continuously in one Hammer basket grinder crushed.
  • Granules with a grain size greater than 1.6 mm and less than 0.2 mm were sieved.
  • the screened fine and coarse fractions were fed back into the powder stream to be compacted. The result was hard-grained, easily pourable, abrasion-resistant chip granules with the following powder specifications.

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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)

Claims (7)

  1. Additif granulé pour produits de lavage et de nettoyage, contenant:
    de 40 à 75% en poids de sel sodique d'au moins un acide acrylique ou méthacrylique homopolymère ou copolymère,
    de 1 à 35% en poids de zéolithe synthétique, finement cristalline, contenant de l'eau liée,
    de 2 à 20% en poids de sulfate de sodium (calculé sous forme anhydre), et
    de 1 à 15% en poids d'eau, mais pas d'acide nitrilotriacétique ni de sel sodique ou potassique de l'acide nitrilotriacétique.
  2. Additif selon la revendication 1, caractérisé par une teneur de :
    de 45 à 65% en poids d'acrylate ou de méthacrylate homopolymère ou copolymère,
    de 8 à 30% en poids de zéolithe contenant de l'eau,
    de 4 à 15% en poids de sulfate de sodium (calculé à l'état anhydre),
    de 3 à 15% en poids de carbonate de sodium (calculé à l'état anhydre), et
    de 3 à 11% en poids d'eau.
  3. Additif selon la revendication 1 ou 2, caractérisé en ce qu'au moins 75% en poids et, de préférence, au moins 85% en poids des granulés présentent une dimension de 0,2 à 1,6 mm, avec une fraction des granulés ayant une taille des grains comprise entre 0,1 et 0,05 mm ne dépassant pas 4% en poids et une fraction des granulés ayant une taille des grains entre 1,6 et 2,4 mm ne dépassant pas 10% en poids, avec un poids en vrac compris entre 320 et 400 g/l.
  4. Additif selon la revendication 1 ou 2, caractérisé en ce qu'il contient de 2 à 8% en poids de liant liquide et qu'il présente un poids en vrac compris entre 650 et 800 g/l.
  5. Procédé de préparation d'additifs granulés pour produits de lavage et de nettoyage, dans lequel l'additif contient:
    de 40 à 75% en poids de sel sodique d'au moins un acide acrylique ou méthacrylique homopolymère ou copolymère,
    de 1 à 35% en poids de zéolithe synthétique, finement cristalline contenant de l'eau liée,
    de 2 à 20% en poids de sulfate de sodium (calculé sous forme anhydre), et
    de 1 à 15% en poids d'eau, mais pas d'acide nitrilotriacétique ni de sel sodique ou potassique de l'acide nitrilotriacétique,
    caractérisé en ce qu'il est préparé par séchage par pulvérisation.
  6. Procédé selon la revendication 5, caractérisé en ce que le granulé séché par pulvérisation est compacté sous pression.
  7. Procédé selon la revendication 6, caractérisé en ce que l'on humidifie avec de l'eau le granulé déterminé séché par pulvérisation en vue de la compaction et/ou que l'on utilise un granulé séché par pulvérisation ayant une teneur en eau augmentée.
EP92904218A 1991-02-11 1992-02-03 Additif granule pour produits de lavage et de nettoyage Expired - Lifetime EP0571436B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4104085 1991-02-11
DE4104085A DE4104085A1 (de) 1991-02-11 1991-02-11 Granulares additiv fuer wasch- und reinigungsmittel
PCT/EP1992/000227 WO1992013937A1 (fr) 1991-02-11 1992-02-03 Additif granule pour produits de lavage et de nettoyage

Publications (2)

Publication Number Publication Date
EP0571436A1 EP0571436A1 (fr) 1993-12-01
EP0571436B1 true EP0571436B1 (fr) 1995-06-21

Family

ID=6424804

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92904218A Expired - Lifetime EP0571436B1 (fr) 1991-02-11 1992-02-03 Additif granule pour produits de lavage et de nettoyage

Country Status (5)

Country Link
EP (1) EP0571436B1 (fr)
AT (1) ATE124081T1 (fr)
DE (2) DE4104085A1 (fr)
ES (1) ES2073291T3 (fr)
WO (1) WO1992013937A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4404279A1 (de) * 1994-02-10 1995-08-17 Henkel Kgaa Tablette mit Buildersubstanzen
DE19651072A1 (de) * 1996-12-09 1998-06-10 Henkel Kgaa Additiv für Wasch- oder Reinigungsmittel
EP1529834A1 (fr) * 2003-11-10 2005-05-11 The Procter & Gamble Company Particules de détergent
EP1529833A1 (fr) * 2003-11-10 2005-05-11 The Procter & Gamble Company Particules de détergent

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3604223A1 (de) * 1985-02-14 1986-08-14 Basf Ag, 67063 Ludwigshafen Zusaetze fuer wasch- und reinigungsmittel
GB8626082D0 (en) * 1986-10-31 1986-12-03 Unilever Plc Detergent powders
GB8922179D0 (en) * 1989-10-02 1989-11-15 Rohm & Haas Polymer-containing granulates

Also Published As

Publication number Publication date
ES2073291T3 (es) 1995-08-01
DE4104085A1 (de) 1992-08-13
WO1992013937A1 (fr) 1992-08-20
ATE124081T1 (de) 1995-07-15
EP0571436A1 (fr) 1993-12-01
DE59202625D1 (de) 1995-07-27

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