EP0544670B1 - Additif d'avivage seche par pulverisation pour agents de lavage - Google Patents

Additif d'avivage seche par pulverisation pour agents de lavage Download PDF

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Publication number
EP0544670B1
EP0544670B1 EP91906393A EP91906393A EP0544670B1 EP 0544670 B1 EP0544670 B1 EP 0544670B1 EP 91906393 A EP91906393 A EP 91906393A EP 91906393 A EP91906393 A EP 91906393A EP 0544670 B1 EP0544670 B1 EP 0544670B1
Authority
EP
European Patent Office
Prior art keywords
weight
additive
component
spray
detergent
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
EP91906393A
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German (de)
English (en)
Other versions
EP0544670A1 (fr
Inventor
Lothar Pioch
Elmar Wilms
Wolfgang Seiter
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 EP0544670A1 publication Critical patent/EP0544670A1/fr
Application granted granted Critical
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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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite 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
    • C11D3/16—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 present invention relates to the production of a granular detergent additive which, due to its content of layered silicates, enhances, i.e. has fabric softening properties. Due to the high proportion of ingredients with builder properties, it also has washing properties.
  • Detergent additives of the type mentioned are advantageously added to granular detergents in order to modify and improve their properties.
  • the agents according to the invention consist of easily soluble granules which are very resistant to abrasion and breakage and are therefore very suitable for further processing on detergent and cleaning agent mixtures. They have a pronounced adsorption capacity for liquid to pasty detergent components, which can be easily introduced into detergent granules without affecting their free-flowing properties.
  • DE-A 35 41 410 discloses textile-softening agglomerates of bentonite and sodium sulfate containing 1 part by weight of sodium sulfate to 3 to 5 parts by weight of bentonite.
  • the sodium sulfate acts as a granulation aid. Its comparatively high proportion is a considerable disadvantage since it has no washing and cleaning properties and increases the salt content in the waste water.
  • the production of the means. is carried out by granulating the constituents with simultaneous spraying on of water, which is followed by drying of the moist granules by means of hot air, for example in a fluidized bed dryer (fluid bed dryer).
  • Detergent builders are known from EP-A 279 040 which contain 50 to 80% by weight of finely crystalline zeolite, 5 to 25% by weight of bentonite and 0.5 to 5% by weight of cellulose ether as binders. In addition, up to 5% by weight of sodium sulfate, up to 1% by weight of alkali and up to 5% by weight of nonionic surfactants can be present.
  • the compositions are said to be prepared by spray drying an aqueous slurry. None is said about the Aviva effect of the funds. If it is present at all, it can only be very small, since in practice (examples) the bentonite content is comparatively low at a maximum of 8% by weight and special layered silicates with an anti-sagging effect are not disclosed.
  • the object of the present invention is to provide means and a suitable method for their production, by means of which a sufficient active ingredient content and thus a good softening effect and favorable grain properties are achieved.
  • the layered silicates can contain hydrogen, alkali and alkaline earth ions, in particular Na+ and Ca++.
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the state of swelling or the type of processing.
  • the particle size is in the range from 0.05 to 25 ⁇ m, usually less than 10 ⁇ m.
  • Layered silicates are preferably used which are largely free of strongly coloring iron ions and calcium ions, for example due to an alkali treatment.
  • the layer silicate content of the agents is 12.5 to 20% by weight, preferably 14 to 20% by weight and in particular 15 to 20% by weight.
  • the component (B) which is present in proportions of 50 to 65% by weight, preferably 52 to 62% by weight, consists of synthetic zeolite A-type sodium aluminosilicate containing bound water. Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% particles smaller than 10 ⁇ m. Your calcium binding capacity, that is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g.
  • the sodium sulfate (C) improves the granulability of the starting mixtures and the dispersing and dissolving behavior of the granules in the wash water. Its content is preferably 3 to 7% by weight.
  • the proportions refer to anhydrous salt. However, this implies that some of the moisture contained in the granules may be bound to this salt as water of hydration.
  • the component (D) consists of a homopolymeric and / or copolymeric carboxylic acid in the form of the sodium salt.
  • Suitable homopolymers are polyacrylic acid and polymethacrylic acid.
  • Suitable copolymers are those of acrylic acid or methacrylic acid with maleic acid.
  • copolymers of acrylic acid or methacrylic acid with maleic acid such as are described, for example, in EP 25 551 B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
  • the molecular weight of the homo- or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000.
  • polyacid or its salts With increasing proportion of polyacid or its salts, the resistance of the grains to abrasion increases. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases. Mixtures with 2 to 7% by weight of sodium salt of polyacid have optimal abrasion properties. In addition to improving the grain structure, the polymers also do one improved builder effect of the mixtures when used.
  • the water content of the granules includes the water which is bound to the zeolite (18 to 22% by weight, based on zeolite) and is adsorbed by the layered silicate, and also the water of hydration of the salts. It is usually 10 to 25% by weight, in particular 12 to 20% by weight.
  • the agents can contain small amounts of compounds which can be added during the production and processing of the synthetic zeolites in order to increase the stability of the aqueous zeolite dispersions (master batch).
  • additives which can be introduced into the compositions with the zeolite, are described in document DE 25 27 388 cited above.
  • These can be nonionic surfactants containing polyglycol ether groups, for example primary alcohols having 12 to 18 carbon atoms reacted with 2 to 7 mol of ethylene oxide.
  • the proportion of stabilizers introduced into the composition via such zeolite dispersions can be, for example, 0.05 to 2% by weight, depending on the proportion of the zeolite.
  • this component is not necessary for the desired properties of the granules.
  • Further optional constituents are dyes or color pigments, which can be added to the agents during the granulation in proportions of, for example, 0.01 to 1% by weight in order to cover up a possible gray or brownish intrinsic color of the layered silicates. After adding the granules to a granular detergent, they give it a visually appealing, color-speckled appearance.
  • White pigments can also be used in the same way and use optical brighteners if white granules and a uniform white mixed product are required.
  • Dyes which are degraded in the subsequent washing process are particularly suitable, so that there is no undesired dyeing of the textiles.
  • Examples include the dyes duasyn acid blue (R) and duasyn acid green (R) .
  • the granules can be used to adsorb liquid or pasty detergent constituents and to be incorporated into detergent granules without loss of free-flowing properties.
  • these are fatty acid alkanolamides (which can bring about an additional softening effect or increase washing power) and in particular nonionic surfactants of the polyglycol ether derivative type.
  • the proportion of nonionic surfactants, based on the adsorbate, can be up to 30% by weight.
  • oil-like additives such as perfumes or foam-suppressing substances from the class of paraffins, microparaffins, long-chain bisacyl diamines and silicones and mixtures thereof can also be adsorbed on the grains.
  • the agents are produced by spray drying an aqueous, paste-like batch (slurry) of the constituents by means of heated gases (combustion gases) in conventional drying towers. Since the combustion air, which is widely used as a dry gas, contains comparatively high proportions of carbon dioxide, it can be advantageous be if you add small amounts of sodium hydroxide to the slurry before spraying in order to counteract a pH reduction by a corresponding alkali excess.
  • the recommended proportions of NaOH are usually between 0.1 and 1% by weight.
  • the aqueous batch contains 50 to 65% by weight of anhydrous ingredients. Its temperature is advantageously 50 to 90 ° C and its viscosity at this working temperature up to 25,000 mPa ⁇ s, usually 12,000 to 20,000 mPa ⁇ s.
  • the atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar.
  • the drying gas which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent.
  • the inlet temperature measured in the ring channel (ie immediately before entering the lower part of the tower), is 180 to 300 ° C., preferably 220 to 280 ° C. .
  • the exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 110 ° C., preferably 60 to 100 ° C.
  • the granules produced in this way are notable for very good redispersibility in the aqueous wash liquor. With regard to their reviving effect, they are largely identical to agents of the same type produced in other ways.
  • the average grain size of the agent produced by spray drying is usually 0.2 to 1.2 mm.
  • at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.0 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 2% by weight .-%, in particular less than 1% by weight and the proportion of the grains above 1.5 mm is not more than 15% by weight, in particular not more than 10% by weight.
  • Larger amounts of fine grain favor dust formation when mixed with other powder components and should therefore be avoided.
  • Larger proportions of coarse grain cause a lower bulk density and make the product appear visually inconsistent, but are otherwise not disadvantageous.
  • the bulk density of the spray-dried compositions is 500 to 700 g / l, mostly 550 to 650 g / l.
  • the agent consists essentially of rounded grains, which have a very good flow behavior. This very good flow behavior is still present even if the grains have been impregnated with larger proportions of liquid, semi-liquid or solid nonionic surfactants.
  • the proportion of these adsorbed components can be 5 to 30% by weight, preferably 10 to 25% by weight, based on the adsorbate.
  • Example 2 The formulation according to Example 2 was sprayable using stirrers with high torque and a high spray pressure.
  • the recipes according to Examples 1 and 3 could be prepared and spray dried without any particular technical effort.
  • the counter-current drying gases had an inlet temperature in the ring channel of 263 ° C (example 1 and 3) or 267 ° C (example 2).
  • the temperature in the area of the tower outlet in front of the dust filters was 71 ° C to 72 ° C (Examples 1 and 3) and 76 ° C (Example 2).
  • the atomization pressure was 40 bar in Example 1 and 3 and 49 bar in Example 2.
  • the spray products obtained were free-flowing with an average particle size of 0.35 mm and a dust content (less than 0.05 mm) of less than 0.1% by weight. Grain fractions of over 2 mm were not present.
  • the bulk density was 590 g / l in Example 1, 550 g / l in Example 2 and 590 g / l in Example 3. All spray products could contain 5 to 30% by weight (based on the end product) of liquid nonionic in a spray mixing apparatus Surfactants (coconut fatty alcohol + 5E0, C12 ⁇ 14-oxo alcohol + 7 E0) are applied, the bulk density increasing to 650 to 780 g / l. The flow behavior of the adsorbates obtained in this way was still good compared to the granules used.
  • the granules were mixed with a granular detergent to give an agent of the following composition (in% by weight): 7.2% sodium dodecylbenzenesulfonate 4.8% C12 ⁇ 18 fatty alcohol + 7E0 1.5% tallow soap (Na salt) 10.5% zeolite (anhydrous) 7.0% sodium carbonate 2.5% hydroxyethane diphosphonate (Na salt) 2.2% copolymer corresponding to (D) 1.3% Na carboxymethyl cellulose 2.5% sodium silicate (1: 3.3) 0.3% optical brightener 10.5% sodium perborate monohydrate 2.6% tetraacetyethylene diamine 1.5% enzyme granulate (enzyme content 0.7%) 0.1% fragrance 35.0% granules according to Examples 1-3 Rest of water

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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 (9)

  1. Additif d'avivage granuleux pour agents de lavage, renfermant
    (A) 12,5 à 20 % en poids d'un silicate stratifié,
    (B) 52 à 65 % en poids de zéolithe synthétique en fins cristaux (proportion par rapport à la substance anhydre),
    (C) 2 à 8 % en poids de sulfate de sodium (proportion par rapport à la substance anhydre),
    (D) 1,5 à 8 % en poids de sel sodique d'un acide (méth)acrylique homopolymère ou copolymère,
    (E) 0 à 30 % en poids de tensioactifs non ioniques de la classe des polyglycoléthers,
    restant: eau.
  2. Agent selon la revendication 1, dans lequel le constituant (A) se compose de montmorillonite, d'hectorite ou de saponite et est présent en proportions de 14 à 20 % en poids.
  3. Agent selon la revendication 1 ou 2, renfermant 52 à 62 % en poids du constituant (B).
  4. Agent selon une ou plusieurs des revendications 1 à 3, renfermant 3 à 7 % en poids du constituant (C).
  5. Agent selon une ou plusieurs des revendications 1 à 4, dans lequel le constituant (D) se compose du sel sodique de l'acide acrylique homopolymère et/ou de son copolymère avec l'acide maléique.
  6. Agent selon les revendications 1 et 5, dans lequel la proportion du constituant (D) atteint 2 à 7 % en poids.
  7. Procédé de fabrication de l'agent selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que l'on sèche par pulvérisation une préparation aqueuse des constituants renfermant 50 à 65 % en poids d'ingrédients anhydres, à l'aide de gaz circulants, qui présentent une température d'entrée de 180 à 300 °C et une température de sortie de 50 à 110 °C.
  8. Utilisation d'un agent selon l'une ou plusieurs des revendications 1 à 6 comme adsorbant pour les constituants liquides ou pateux d'agents de lavage, en particulier pour les tensioactifs non ioniques.
  9. Utilisation d'un agent selon l'une ou plusieurs des revendications 1 à 6 et 8, comme constituant de mélange dans des agents de lavage granuleux.
EP91906393A 1990-03-26 1991-03-18 Additif d'avivage seche par pulverisation pour agents de lavage Expired - Lifetime EP0544670B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4009618 1990-03-26
DE4009618A DE4009618A1 (de) 1990-03-26 1990-03-26 Spruehgetrocknetes, avivierend wirkendes waschmitteladditiv
PCT/EP1991/000514 WO1991014762A1 (fr) 1990-03-26 1991-03-18 Additif d'avivage seche par pulverisation pour agents de lavage

Publications (2)

Publication Number Publication Date
EP0544670A1 EP0544670A1 (fr) 1993-06-09
EP0544670B1 true EP0544670B1 (fr) 1994-07-20

Family

ID=6403046

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91906393A Expired - Lifetime EP0544670B1 (fr) 1990-03-26 1991-03-18 Additif d'avivage seche par pulverisation pour agents de lavage

Country Status (5)

Country Link
EP (1) EP0544670B1 (fr)
AT (1) ATE108823T1 (fr)
DE (2) DE4009618A1 (fr)
ES (1) ES2056643T3 (fr)
WO (1) WO1991014762A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996018714A1 (fr) * 1994-12-15 1996-06-20 Nippon Shokubai Co., Ltd. Adjuvant pour detergent, son procede de fabrication et composition detergente le contenant
GB2297977A (en) * 1995-02-07 1996-08-21 Procter & Gamble Detergent composition containing Zeolite MAP
DE19538028A1 (de) * 1995-10-12 1997-04-17 Sued Chemie Ag Waschmittelzusatz
DE19538029A1 (de) * 1995-10-12 1997-04-17 Sued Chemie Ag Waschmittelzusatz
ATE246722T1 (de) * 1997-09-17 2003-08-15 Ciba Sc Holding Ag Antimikrobieller waschmittelzusatz
EP0903401B1 (fr) * 1997-09-17 2003-08-06 Ciba SC Holding AG Additif antimicrobien pour détergents
DE19756696A1 (de) 1997-12-19 1999-07-01 Clariant Gmbh Schichtsilikathaltige Wasch- und Reinigungsmittelkomponente
DE19819187A1 (de) * 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
GB0102736D0 (en) * 2001-02-05 2001-03-21 Crosfield Joseph & Sons Disintegrants and a process for their manufacture
EP3318622B1 (fr) 2016-11-04 2023-07-05 Sociedad Anónima Minera Catalano-Aragonesa Particules colorées pour détergents et leur procédé de production

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1844794A1 (fr) * 2001-02-22 2007-10-17 PSIMEDICA Limited Implants de silicon comprenant un radionucleide et/ou des medicaments cytotoxiques et son utilisation pour le traitement du cancer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3444960A1 (de) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf Koerniges adsorptionsmittel
DE3702764A1 (de) * 1987-01-30 1988-08-11 Degussa Waschmittelbuilder
DE3931871A1 (de) * 1989-09-23 1991-04-04 Henkel Kgaa Granulares, phosphatfreies wasserenthaertungsmittel
DE3936405A1 (de) * 1989-11-02 1991-05-08 Henkel Kgaa Koerniges, nichtionische tenside enthaltendes additiv fuer wasch- und reinigungsmittel mit verbessertem einspuelverhalten

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1844794A1 (fr) * 2001-02-22 2007-10-17 PSIMEDICA Limited Implants de silicon comprenant un radionucleide et/ou des medicaments cytotoxiques et son utilisation pour le traitement du cancer

Also Published As

Publication number Publication date
DE4009618A1 (de) 1991-10-02
ATE108823T1 (de) 1994-08-15
ES2056643T3 (es) 1994-10-01
DE59102283D1 (de) 1994-08-25
EP0544670A1 (fr) 1993-06-09
WO1991014762A1 (fr) 1991-10-03

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