[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP0344629A1 - Composition adsorbente granulaire avec une capacité de dégagement ameliorée - Google Patents

Composition adsorbente granulaire avec une capacité de dégagement ameliorée Download PDF

Info

Publication number
EP0344629A1
EP0344629A1 EP89109494A EP89109494A EP0344629A1 EP 0344629 A1 EP0344629 A1 EP 0344629A1 EP 89109494 A EP89109494 A EP 89109494A EP 89109494 A EP89109494 A EP 89109494A EP 0344629 A1 EP0344629 A1 EP 0344629A1
Authority
EP
European Patent Office
Prior art keywords
weight
water
composition according
adsorbent
sodium
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.)
Granted
Application number
EP89109494A
Other languages
German (de)
English (en)
Other versions
EP0344629B1 (fr
Inventor
Elmar Dr. Wilms
Lothar Pioch
Günther Dr. Vogt
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT89109494T priority Critical patent/ATE98294T1/de
Publication of EP0344629A1 publication Critical patent/EP0344629A1/fr
Application granted granted Critical
Publication of EP0344629B1 publication Critical patent/EP0344629B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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 adsorbent with a high absorption capacity for liquid to pasty detergent and cleaning agent components, in particular liquid or, when heated, melting nonionic surfactants, which is particularly suitable for use in phosphate-free or low-phosphate detergents and cleaning agents. It has a significantly improved flushing behavior, i. H. it does not form undissolved residues in the washing-in devices of automatic washing machines and moreover improves the washing-in behavior of detergent mixtures in such devices.
  • nonionic surfactants have a very high cleaning ability, which makes them particularly suitable for use in cold detergents or 60 ° C. detergents.
  • their proportion cannot be increased significantly beyond 8 to 10 percent by weight in the generally customary production of detergents by means of spray drying, since otherwise there is excessive smoke formation in the exhaust air from the spray towers and poor pouring properties of the spray powder.
  • Processes have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance.
  • Absorbent carrier grains which consist of several components and are usually produced by spray drying, are e.g. B. from US 3 849 327, US 3 886 098 and US 3 838 027 and US 4 269 722 (DE 27 42 683) known.
  • these carrier grains developed especially for the adsorption of nonionic surfactants, contain considerable amounts of phosphates, which limits their possible uses.
  • Phosphate-free carrier grains are known from DE 32 06 265. They consist of 25 to 52% sodium carbonate or hydrogen carbonate, 10 to 50% zeolite, 0 to 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate.
  • the high proportion of carbonate favors the formation of calcium carbonate in hard water and thus the formation of incrustations on the textile fiber or the heating elements in the washing machine. Furthermore, the absorption capacity of the carrier grains cited above is limited. With proportions of more than 25% by weight of mixed liquid or sticky nonionic surfactants, the free-flowing properties of the products decrease considerably and are unsatisfactory above 30% by weight.
  • EP 184 794 discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight zeolite, 0.1 contains up to 8% by weight of sodium silicate, 3 to 15% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight of nonionic surfactants and is available by spray drying. Practice has shown that in Washing machines with poorly designed induction devices do not completely detach the products in the course of the induction phase and leave residues.
  • Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% particles smaller than 10 ⁇ m. Their average particle size (volume distribution, measurement method: Coulter Counter) is in the range from 1 to 10 ⁇ m. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g. The zeolites can still contain excess alkali from their production.
  • the component (b) consists of a water-soluble soap, preferably a sodium soap, which is derived from saturated fatty acids with 12 to 24, preferably 14 to 22 carbon atoms, and mixtures thereof with oleic acid, the proportion of saturated fatty acids being at least 50% by weight. -%, preferably at least 75% by weight.
  • a water-soluble soap preferably a sodium soap, which is derived from saturated fatty acids with 12 to 24, preferably 14 to 22 carbon atoms, and mixtures thereof with oleic acid, the proportion of saturated fatty acids being at least 50% by weight. -%, preferably at least 75% by weight.
  • Examples are soaps made from coconut oil, tallow oil and hardened rapeseed oil fatty acids, hardened fish oil fatty acids and mixtures thereof. Their proportion is 1.0 to 6, preferably 1.5 to 5 and in particular 2 to 4% by weight.
  • the component (c) consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts being preferred.
  • Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid.
  • Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
  • copolymeric acids in which one of the components has no acid function the proportion thereof, in the interest of sufficient water solubility, is not more than 70 mole percent, preferably less than 50 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as described in more detail 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 2,000 to 150,000, preferably 5,000 to 100,000.
  • Their proportion of the adsorbent is 1 to 12% by weight, preferably 1.5 to 8% by weight and in particular 2 to 5% by weight, calculated as the sodium salt.
  • the resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases. Mixtures with 2 to 5% by weight of sodium salt of polyacid have optimal abrasion properties.
  • the weight ratio of soap (b) to polymeric acid sodium salt (c) is in the range from 2.5: 1 to 1: 5, in particular in the range from 1.5: 1 to 1: 4 . These areas are characterized by good induction results. Stronger Deviations, especially higher soap contents at the expense of the polymer acid content, lead to less favorable values.
  • the sodium sulfate (component d), calculated as an anhydrous substance, is present in proportions from 0 to 25% by weight, preferably from 0.5 to 22 and in particular from 3 to 20% by weight.
  • the sodium sulfate can contribute to a considerable improvement in the grain structure and the flushing behavior of the agents and at the same time increases their bulk density, which results in the possibility of saving packaging and transport volume.
  • the adsorbent can contain nonionic surfactants in proportions of up to 5% by weight, preferably 0 to 4% by weight, and in particular 0.3 to 3% by weight.
  • Suitable nonionic surfactants are, in particular, ethoxylation products of linear or methyl-branched (oxo radical) alcohols with 12 to 18 carbon atoms and 3 to 10 ethylene glycol ether groups. Also useful are ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides, which correspond to the fatty alcohol ethoxylates described with regard to the number of carbon atoms in the hydrophobic radical and the glycol ether groups.
  • Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups can also be used.
  • block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics are also suitable.
  • the nonionic surfactants can then be present if aqueous zeolite dispersions in which these surfactants function as dispersion stabilizers are used in the production of the granular adsorbents. In individual cases, the nonionic surfactants can also be completely or partially replaced by other dispersion stabilizers, as described in DE 25 27 388 (US 4,072,622).
  • the difference of up to 100% by weight is due to water, which is present in bound form and as moisture, the main amount being bound to the zeolite.
  • a proportion of the water which is about 8 to 18 wt .-% (based on the agent), can be removed at a drying temperature of 145 ° C.
  • Another portion which is between 4 and 8% by weight, depending on the zeolite portion, is released at the annealing temperature (800 ° C.) and corresponds to the water stored in the crystal lattice of the zeolite.
  • the average grain size of the adsorbent is 0.2 to 1.2 mm, the proportion of the grains being less than 0.05 mm less than 1% by weight, preferably less than 0.5% by weight and not more than 2 mm Is 5% by weight.
  • at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.1 to 1.2 mm, the proportion of the grains between 0.1 and 0.05 mm preferably not more than 3 %
  • the proportion of the grains between 0.1 and 0.2 by less than 20% by weight, in particular less than 10% by weight and the proportion of the grains between 1, 2 and 2 mm is not more than 10% by weight, in particular not more than 5% by weight.
  • the bulk density of the adsorbent is 350 to 680 g / l, preferably 400 to 650 g / l.
  • the agent essentially consists of rounded grains, which have a very good flow behavior. This very good flow behavior is still present when the grains are impregnated with large proportions of liquid or semi-liquid detergent components, especially nonionic surfactants.
  • the proportion of these adsorbed components can be 10 to 35% by weight, preferably 15 to 30% by weight, based on the adsorbate.
  • the invention further relates to a method for producing the granular adsorbent according to the invention.
  • This The process is characterized in that an aqueous mixture comprising the components (a) to (c) and, if appropriate, the components (d), (e) and additional alkali metal hydroxide, with a total of 40 to 55% by weight of anhydrously calculated ingredients Sprayed nozzles into a drop room and dried to a moisture content of 8 to 18% by weight that can be removed at 145 ° C. by means of drying gases which have an inlet temperature of 150 to 280 ° C. and an outlet temperature of 50 to 120 ° C.
  • the aqueous batch can be prepared by mixing the dry or water-containing constituents with the addition of the water required for liquefaction.
  • the zeolite can be used as a spray-dried powder or granulate or as a water-containing filter cake or as an aqueous dispersion. If spray-dried zeolite granules are used as the starting material, these may already contain polymers and / or the sodium sulfate or a proportion thereof. Instead of the soap or the salts of the polymeric carboxylic acids, the corresponding free acids can also be incorporated and the alkali required for salt formation can be added separately.
  • alkali metal hydroxide in particular NaOH
  • NaOH alkali metal hydroxide
  • the addition of NaOH, which ensures a sufficient alkali reserve, can be, for example, up to 3% by weight. In general, 0.2 to 1% by weight is sufficient. can be made without the formation of fine fractions or coarser agglomerates.
  • Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be present in proportions of 0.03 to 3, preferably 0.05 to 2% by weight, based on that with the additive loaded adsorbents are used. For example, B.
  • finely powdered zeolites silica airgel (Aerosil (R) ), colorless or colored pigments, such as titanium dioxide and other powder materials already proposed for powdering granules or detergent particles, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxylmethyl cellulose.
  • a treatment is generally not necessary, especially since the washability is not improved thereby.
  • the additives to be adsorbed can consist of known nonionic surfactants, as are usually used in washing and cleaning agents.
  • suitable additives are organic solvents, with which the cleaning ability of detergents and cleaning agents is improved, in particular with regard to greasy soiling, and which can be incorporated into a granular cleaning agent without problems in this way.
  • sensitive substances such as enzymes, biocides, fragrances, bleach activators, softening agents, optical brighteners and anionic or cationic surfactants can be added to the adsorbents after they have been dissolved or dispersed in organic solvents or the liquid or melted nonionic surfactants. These substances come together with the solvent or dispersant in the porous grain and are thus protected against interactions with other powder components.
  • Preferred detergent constituents which are bound to the adsorbent and are present together with this as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of the polyglycol ethers, derived from alcohols having 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
  • EO ethylene oxide
  • PO propylene oxide
  • the number of EO or PO groups corresponds to the statistical mean for technical alkoxylates.
  • ethoxylated fatty alcohols examples include C12 ⁇ 18 coconut alcohols with 3 to 12 EO, C16 ⁇ 18 tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures. From the series of ethoxylated oxo alcohols, for example, those of the composition C12 ⁇ 15 + 5 to 10 EO and C14-C15 + 6 to 12 EO are suitable.
  • Mixtures of low and highly ethoxylated alcohols are distinguished by increased detergency against both greasy and mineral stains, for example those made from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or C13 ⁇ 15 oxo alcohol + 3 to 5 EO and C12 ⁇ 14-oxo alcohol + 8 to 12 EO.
  • Agents in which the adsorbed nonionic surfactants have both long hydrophobic residues and higher degrees of ethoxylation have particularly favorable flushing properties.
  • nonionic surfactants additionally contain a compound which is difficult or not soluble in water, but does have a dispersible polar, hydrophobic radical. Examples of this are free, soap-forming fatty acids.
  • Partial esters of polyhydric alcohols such as partial glycerides and fatty acid glycol esters, fatty acid amides, fatty acid partial amides of alkylenediamines and hydroxyalkylalkylenediamines, fatty amines, quaternary ammonium bases or their salts, fatty alcohols and poorly soluble anionic surfactants, such as the di-salts of alphasulfo fatty acids. Mixtures of such poorly soluble or insoluble compounds can also be used.
  • the number of carbon atoms in the hydrophobic radicals should be at least 10, usually 12 to 18.
  • the quantitative ratios of nonionic surfactant to sparingly soluble additional compound is 99: 1 to 70:30. It is essential for the success that the nonionic surfactant and additive are mixed together beforehand. A successive application of the individual substances to the adsorbent does not lead to an improvement in the solubility and flushing behavior.
  • Preferred examples of this group are coconut oil, tallow and rapeseed oil fatty acids, which can also be hardened, mixtures of tallow fatty acid partial glyceride and the tallow fatty acid partial amide of hydroxyethyl-ethylenediamine, di-tallow-alkyl-dimethyl-ammonium chloride and the disodium salt of alpha-sulfo fatty acids derived from hardened C12 ⁇ 18 fatty acids.
  • the granular adsorbents impregnated with the nonionic surfactants or with the mixtures of nonionic surfactant and additive can be mixed with further powdery to granular detergents or detergent components, such as, for example are obtainable by spray drying or granulation, or can also be mixed with bleaches or with bleach-containing detergents of known composition in any ratio.
  • granular detergents or detergent components such as, for example are obtainable by spray drying or granulation
  • bleaches or with bleach-containing detergents of known composition in any ratio.
  • their good flowability and their high grain stability are of great advantage, since an undesirable formation of abrasion and dust is avoided.
  • the powder mixtures are in turn stable in storage and do not tend to clump or exude the nonionic surfactant. When used, they are particularly easy to flush in compared to known agents.
  • the zeolite used had a calcium binding capacity of 1 65 mg CaO / g and an average particle size of 3 ⁇ m, with no proportions above 20 ⁇ m. It was used as an aqueous dispersion containing 48% by weight of anhydrous zeolite, 1.5% by weight of component (s) and 53.1% by weight of water. A copolymer of acrylic acid and maleic acid with a molecular weight of 70,000 (Sokalan (R) ) in the form of the sodium salt was used as the polycarboxylic acid.
  • Sokalan (R) Sokalan
  • the liter weight was 563 g / l.
  • Dry sea sand with the following grain spectrum was chosen as the reference substance. mm over 1.5 to 0.8 to 0.4 up to 0.2 to 0.1 % By weight 0.2 11.9 54.7 30.1 3.1
  • the run-off time of the dry sand after opening the outflow opening was set at 100%.
  • the pourability of the products according to the invention is given in%, based on this 100% value. Values above 75% are considered very good.
  • the adsorbent had a flushing grade of A 5.
  • 2 series of tests were carried out, with the impregnated adsorbent without the addition of a detergent and a mixture of 25 parts of the impregnated adsorbent and 75 parts of a detergent, consisting of 50 parts of tower spray powder, 20 parts of sodium perborate and 5 parts of other granular constituents Defoamers, enzymes, fragrances and bleach activators (called "with W").
  • the tower spray powder had the following composition (in% by weight): 17.6% n-dodecylbenzenesulfonate (Na salt) 2.5% Tallow soap (Na salt) 4.0% Tallow alcohol + 14 EO 20.5% Zeolite NaA (calculated anhydrous) 15.0% soda 5.0% Copolymer (b) 0.5% Na hydroxyethane diphosphonate 3.0% Sodium silicate 1: 3.3 1.6% Carboxymethyl cellulose 18.0% Sodium sulfate 12.3% water
  • Example 2 granular granules of the following composition were produced (in% by weight): (a) 60.0 % Containing zeolite (calculated as anhydrous) 0.35 % free NaOH (b) 5.2 % Acrylic acid-maleic acid copolymer (Na salt) (c) 2.0 % Na tallow soap (d) 13.2 % Sodium sulfate (e) 1.85 % Tallow fatty alcohol + 5EO (f) 17.4 % water
  • the liter weight was 590 g / l.
  • the sieve analysis showed the following grain distribution: mm over 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 3rd 41 50 6 -
  • Example 2 As described in Example 1, 84 pbw of the adsorbent were impregnated in a spray mixer with 16 pbw of a molten surfactant mixture according to Example 2. The bulk weight of the product was 710 g / l, the flow behavior 80% and the wash-in test A8. A mixture of 20 pbw of these granules, 80 pbw of the spray-dried detergent used in Examples 1-4, 15 pbw of sodium perborate and 5 pbw of other granular constituents gave the induction test value A6 under the same test conditions.
  • a granular adsorbent prepared as described in Example 1 had the following composition (in% by weight): (a) 60.0% Zeolite, alkalized with 0.8% NaOH (b) 3.0% Tallow coconut soap 1: 1 (Na salt) (c) 2.2% Acrylic acid-maleic acid copolymer (Na salt) (d) 15.2% Na sulfate (e) 1.8% Valley alcohol + 5EO (f) 17.0% water
  • the product had a bulk density of 580 g / l with the following particle size distribution: mm over 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 8th 38 50 4th 0
  • aqueous slurry was prepared using spray dried zeolite granules. These granules consisted of a mixture of zeolite (with one removed at annealing temperature baren water content of 20 wt .-%) and from anhydrous sodium sulfate. Na polyacrylate (MW 32,000), coconut tallow soap and sodium hydroxide were also added to the slurry. The water content of the slurry was 52.5% by weight (including the water bound to the zeolite). The slurry, which had a temperature of 88 ° C., was spray-dried in the spray tower by the countercurrent method, the drying gases having an inlet temperature of 130 ° C. and an outlet temperature of 67 ° C.
  • the granules had the following composition (in% by weight): 59.0% Zeolite (anhydrous) 0.6% NaOH 2.4% Soap 2.5% Na polyacrylate 18.0% Sodium sulfate 17.5% water Grain size 1.2 to 0.1 mm, average grain size 0.3 g / l, bulk density 600 g / l.
  • a wash-in grade of B2 resulted and after mixing with a washing powder according to Example 6, a wash-in grade of A8.

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP89109494A 1988-06-03 1989-05-26 Composition adsorbente granulaire avec une capacité de dégagement ameliorée Expired - Lifetime EP0344629B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89109494T ATE98294T1 (de) 1988-06-03 1989-05-26 Koerniges adsorptionsmittel mit verbessertem einspuelverhalten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3818829 1988-06-03
DE3818829A DE3818829A1 (de) 1988-06-03 1988-06-03 Koerniges adsorptionsmittel mit verbessertem einspuelverhalten

Publications (2)

Publication Number Publication Date
EP0344629A1 true EP0344629A1 (fr) 1989-12-06
EP0344629B1 EP0344629B1 (fr) 1993-12-08

Family

ID=6355727

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89109494A Expired - Lifetime EP0344629B1 (fr) 1988-06-03 1989-05-26 Composition adsorbente granulaire avec une capacité de dégagement ameliorée
EP89906072A Pending EP0424403A1 (fr) 1988-06-03 1989-05-26 Adsorbant granulaire a facilite amelioree de rincage

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP89906072A Pending EP0424403A1 (fr) 1988-06-03 1989-05-26 Adsorbant granulaire a facilite amelioree de rincage

Country Status (9)

Country Link
US (1) US5139693A (fr)
EP (2) EP0344629B1 (fr)
JP (1) JP2633045B2 (fr)
KR (1) KR960012274B1 (fr)
AT (1) ATE98294T1 (fr)
DE (2) DE3818829A1 (fr)
DK (1) DK272790A (fr)
ES (1) ES2047059T3 (fr)
WO (1) WO1989012087A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0419970A2 (fr) * 1989-09-23 1991-04-03 Henkel KGaA Produit granulaire, exempt de phosphate, pour adoucir l'eau
EP0425277A2 (fr) * 1989-10-27 1991-05-02 Unilever Plc Compositions détergentes
EP0425804A2 (fr) * 1989-11-02 1991-05-08 Henkel KGaA Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées
GB2239513A (en) * 1989-12-29 1991-07-03 Carello Spa Vehicle headlight
WO1992007060A1 (fr) * 1990-10-18 1992-04-30 Unilever N.V. Compositions detergentes
EP0520582A1 (fr) * 1991-06-28 1992-12-30 Colgate-Palmolive Company Compositions détergentes à base de zéolithe séchées par pulvérisation
WO1994018294A1 (fr) * 1993-02-15 1994-08-18 Henkel Kommanditgesellschaft Auf Aktien Additif pour detergent, contenant des tensioactifs et des adjuvants
EP0653481A1 (fr) * 1993-11-11 1995-05-17 The Procter & Gamble Company Composition de détergent granulaire
US5723428A (en) * 1993-11-24 1998-03-03 Lever Brothers Company Detergent compositions and process for preparing them
EP2009086A1 (fr) 2007-06-26 2008-12-31 Sociedad Anonima Minera Catalano-Aragonesa (Samca) Procédé de coloration de minéraux non-adsorbants et le produit ainsi obtenu

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5756445A (en) * 1993-11-11 1998-05-26 The Proctor & Gamble Company Granular detergent composition comprising a low bulk density component
ES2141336T3 (es) * 1994-02-18 2000-03-16 Henkel Ecolab Gmbh & Co Ohg Procedimiento para la obtencion de granulados secados por pulverizacion.
DE19500644B4 (de) * 1995-01-12 2010-09-09 Henkel Ag & Co. Kgaa Sprühgetrocknetes Waschmittel oder Komponente hierfür
WO1999029829A1 (fr) * 1997-12-10 1999-06-17 Kao Corporation Particules detergentes et leur procede de preparation
DE19842054A1 (de) * 1998-09-15 2000-03-16 Bayer Ag Verwendung von wasserlöslichen polymeren Polycarboxylaten in Reinigerformulierungen mit abrasiver Wirkung
JP4063431B2 (ja) * 1998-12-28 2008-03-19 花王株式会社 高嵩密度洗剤粒子群
US6849590B1 (en) * 1998-12-28 2005-02-01 Kao Corporation Process for producing granules for supporting surfactant
DE60019533T2 (de) * 1999-06-14 2006-02-23 Kao Corp. Verfahren zur herstellung einkerniger waschmittelteilchen
KR100432925B1 (ko) * 1999-06-14 2004-05-28 카오카부시키가이샤 계면활성제 지지용 과립군 및 그의 제법
JP3352977B2 (ja) * 1999-06-15 2002-12-03 花王株式会社 固形状洗剤
KR100346812B1 (ko) * 1999-08-28 2002-08-03 주식회사 엘지씨아이 정제형 세제 조성물
US7976941B2 (en) * 1999-08-31 2011-07-12 Momentive Performance Materials Inc. Boron nitride particles of spherical geometry and process for making thereof
US6713088B2 (en) * 1999-08-31 2004-03-30 General Electric Company Low viscosity filler composition of boron nitride particles of spherical geometry and process
US6894019B2 (en) 2000-12-18 2005-05-17 Kao Corporation Base particles and detergent particles
US20030203832A1 (en) * 2002-04-26 2003-10-30 The Procter & Gamble Company Low organic spray drying process and composition formed thereby
DE102004035552A1 (de) * 2004-07-22 2006-02-16 Henkel Kgaa Niotensid und/oder Parfüm aufweisende sodafreie Partikel zur Anwendung in Wasch- oder Reinigungsmitteln
WO2006048142A2 (fr) 2004-11-02 2006-05-11 Henkel Kommanditgesellschaft Auf Aktien Granulats / agglomerats pour detergents ou produits de nettoyage
JP5705525B2 (ja) * 2010-12-16 2015-04-22 花王株式会社 ゼオライト複合粒子群
JP2015091992A (ja) * 2015-01-27 2015-05-14 三浦工業株式会社 殺菌性洗浄剤

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0050894A1 (fr) * 1980-10-29 1982-05-05 THE PROCTER & GAMBLE COMPANY Compositions pour l'adoucissement de l'eau à base d'aluminosilicates et compositions détergentes les contenant
DE3316513A1 (de) * 1983-05-06 1984-11-08 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Abriebfeste granulate auf basis von alkalialuminiumsilikat
EP0184794A2 (fr) * 1984-12-10 1986-06-18 Henkel Kommanditgesellschaft auf Aktien Produit adsorbant granulé
US4683073A (en) * 1985-02-09 1987-07-28 Manfred Diehl Builder for washing agents
EP0289767A2 (fr) * 1987-05-06 1988-11-09 Degussa Aktiengesellschaft Produit absorbant granulé

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886098A (en) * 1971-03-15 1975-05-27 Colgate Palmolive Co Manufacture of free flowing particulate detergent composition containing nonionic detergent
US3849327A (en) * 1971-11-30 1974-11-19 Colgate Palmolive Co Manufacture of free-flowing particulate heavy duty synthetic detergent composition containing nonionic detergent and anti-redeposition agent
US4605509A (en) * 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
US4136051A (en) * 1974-02-25 1979-01-23 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation
AT338948B (de) * 1974-10-10 1977-09-26 Henkel & Cie Gmbh Pulverformige wasch- und reinigungsmittel und verfahren zu ihrer herstellung
DE2903058A1 (de) * 1978-02-01 1979-08-09 Unilever Nv Verfahren zur herstellung von waschmittelpulver
DE3514364A1 (de) * 1985-04-20 1986-10-23 Henkel KGaA, 4000 Düsseldorf Koerniges waschmittel mit verbessertem reinigungsvermoegen
DE3545947A1 (de) * 1985-12-23 1987-07-02 Henkel Kgaa Phosphatfreies, granulares waschmittel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0050894A1 (fr) * 1980-10-29 1982-05-05 THE PROCTER & GAMBLE COMPANY Compositions pour l'adoucissement de l'eau à base d'aluminosilicates et compositions détergentes les contenant
DE3316513A1 (de) * 1983-05-06 1984-11-08 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Abriebfeste granulate auf basis von alkalialuminiumsilikat
EP0184794A2 (fr) * 1984-12-10 1986-06-18 Henkel Kommanditgesellschaft auf Aktien Produit adsorbant granulé
US4683073A (en) * 1985-02-09 1987-07-28 Manfred Diehl Builder for washing agents
EP0289767A2 (fr) * 1987-05-06 1988-11-09 Degussa Aktiengesellschaft Produit absorbant granulé

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0419970A3 (en) * 1989-09-23 1991-06-26 Henkel Kommanditgesellschaft Auf Aktien Granular, phosphate free water softening agent
EP0419970A2 (fr) * 1989-09-23 1991-04-03 Henkel KGaA Produit granulaire, exempt de phosphate, pour adoucir l'eau
EP0425277A3 (en) * 1989-10-27 1991-07-24 Unilever Plc Detergent compositions
EP0425277A2 (fr) * 1989-10-27 1991-05-02 Unilever Plc Compositions détergentes
EP0425804A2 (fr) * 1989-11-02 1991-05-08 Henkel KGaA Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées
EP0425804A3 (en) * 1989-11-02 1991-07-03 Henkel Kommanditgesellschaft Auf Aktien Granular additive containing nonionic surfactents for detergent and cleaning agents with improved rinsing properties
GB2239513A (en) * 1989-12-29 1991-07-03 Carello Spa Vehicle headlight
GB2239513B (en) * 1989-12-29 1993-06-09 Carello Spa Aimable beam vehicle headlight
WO1992007060A1 (fr) * 1990-10-18 1992-04-30 Unilever N.V. Compositions detergentes
EP0520582A1 (fr) * 1991-06-28 1992-12-30 Colgate-Palmolive Company Compositions détergentes à base de zéolithe séchées par pulvérisation
WO1994018294A1 (fr) * 1993-02-15 1994-08-18 Henkel Kommanditgesellschaft Auf Aktien Additif pour detergent, contenant des tensioactifs et des adjuvants
EP0653481A1 (fr) * 1993-11-11 1995-05-17 The Procter & Gamble Company Composition de détergent granulaire
US5723428A (en) * 1993-11-24 1998-03-03 Lever Brothers Company Detergent compositions and process for preparing them
EP2009086A1 (fr) 2007-06-26 2008-12-31 Sociedad Anonima Minera Catalano-Aragonesa (Samca) Procédé de coloration de minéraux non-adsorbants et le produit ainsi obtenu

Also Published As

Publication number Publication date
JP2633045B2 (ja) 1997-07-23
WO1989012087A1 (fr) 1989-12-14
ATE98294T1 (de) 1993-12-15
ES2047059T3 (es) 1994-02-16
EP0424403A1 (fr) 1991-05-02
DK272790D0 (da) 1990-11-15
EP0344629B1 (fr) 1993-12-08
DE58906340D1 (de) 1994-01-20
JPH03504734A (ja) 1991-10-17
US5139693A (en) 1992-08-18
DK272790A (da) 1990-11-15
KR960012274B1 (ko) 1996-09-18
DE3818829A1 (de) 1989-12-14
KR900701993A (ko) 1990-12-05

Similar Documents

Publication Publication Date Title
EP0344629B1 (fr) Composition adsorbente granulaire avec une capacité de dégagement ameliorée
EP0184794B1 (fr) Produit adsorbant granulé
DE69216191T2 (de) Waschmittelpulver und Verfahren zu deren Herstellung
DE3545947A1 (de) Phosphatfreies, granulares waschmittel
EP0364881A2 (fr) Préparation de granulés contenant des agents tensio-actifs
AT394380B (de) Teilchenfoermiges und weichmachendes grobwaschmittel fuer textilien, verfahren zu seiner herstellung, agglomerierte bentonitteilchen fuer das waschmittel und verfahren zu ihrer herstellung
EP0368137B1 (fr) Méthode de préparation de granules en zéolite de haute densité
EP0167916A2 (fr) Procédé de préparation d'un adjuvant de détergent non ionique séché par pulvérisation
EP0425804B1 (fr) Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées
DE2753680C2 (de) Verfahren zur Herstellung pulverförmiger, organische Siliciumpolymere enthaltender Waschmittel mit verbesserten Lösungseigenschaften
EP0354331A1 (fr) Additif de détergent avec une capacite de degagement amelioree
EP0560802B2 (fr) Procede de fabrication de granulats de zeolite
EP0034194B1 (fr) Procédé pour la fabrication de détergents granulés dispersifs pour le lavage et le nettoyage, contenant des agents tensio-actifs non-ioniques
EP0473622B1 (fr) Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive
DE3516548A1 (de) Teilchenfoermiges waschmittelprodukt mit einem gehalt an builder und nichtionischem tensid
WO1991009927A1 (fr) Additif d'agent de lavage granulaire, a effet avivant et procede pour sa fabrication
EP0633923B1 (fr) Additif granulaire sans phosphate contenant des tensioactifs non ioniques pour produits de lavage et detergents
DE2837504C2 (de) Verfahren zur Herstellung eines schüttfähigen, nichtionische Tenside enthaltenden Wasch- und Reinigungsmittelgranulates
EP0605436B1 (fr) Procede de preparation de granules de zeolithe

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): ES

17P Request for examination filed

Effective date: 19900602

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL

XX Miscellaneous (additional remarks)

Free format text: VERBUNDEN MIT 89906072.7/0424403 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) DURCH ENTSCHEIDUNG VOM 03.07.91.

17Q First examination report despatched

Effective date: 19920708

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL

REF Corresponds to:

Ref document number: 98294

Country of ref document: AT

Date of ref document: 19931215

Kind code of ref document: T

XX Miscellaneous (additional remarks)

Free format text: VERBUNDEN MIT 89906072.7/0424403 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) DURCH ENTSCHEIDUNG VOM 03.07.91.

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19931215

REF Corresponds to:

Ref document number: 58906340

Country of ref document: DE

Date of ref document: 19940120

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2047059

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940526

EPTA Lu: last paid annual fee
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940526

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19960601

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19961231

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20010514

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20010518

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010522

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20010530

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20010531

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20010717

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020527

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030131

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20021201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030611

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050526