EP0419970A2 - Produit granulaire, exempt de phosphate, pour adoucir l'eau - Google Patents

Produit granulaire, exempt de phosphate, pour adoucir l'eau Download PDF

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Publication number
EP0419970A2
EP0419970A2 EP90117748A EP90117748A EP0419970A2 EP 0419970 A2 EP0419970 A2 EP 0419970A2 EP 90117748 A EP90117748 A EP 90117748A EP 90117748 A EP90117748 A EP 90117748A EP 0419970 A2 EP0419970 A2 EP 0419970A2
Authority
EP
European Patent Office
Prior art keywords
weight
composition according
water
component
granular
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.)
Withdrawn
Application number
EP90117748A
Other languages
German (de)
English (en)
Other versions
EP0419970A3 (en
Inventor
Horst Dr. Upadek
Karl Schwadtke
Wolfgang Dr. Seiter
Lothar Pioch
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
Publication of EP0419970A2 publication Critical patent/EP0419970A2/fr
Publication of EP0419970A3 publication Critical patent/EP0419970A3/de
Withdrawn legal-status Critical Current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
    • 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 a granular, phosphate-free water softening agent which is particularly suitable as an additive to the wash liquor in hard water areas and is capable of replacing the polymer phosphates normally used for this purpose.
  • Agents of this type are suitable for pretreating hard water intended for washing, rinsing and cleaning purposes. They are usually stored separately from granular detergents and cleaning agents and, if required, used together with them in washing or dishwashing processes. In the sense of an additional builder effect, they improve their cleaning ability and prevent the formation of hard limescale deposits on the heating elements or on the textile fiber.
  • the agents can also be admixed a priori. They are then present in these agents as granular powder, whereby they have an advantageous influence on their pouring properties and in particular also on the induction behavior when used in household machines.
  • DE 33 16 513-A1 discloses abrasion-resistant granules of zeolite and homo- or copolymeric carboxylic acids which can be used as detergent additives or as softeners. As further components, they can include organic complexing agents, such as Contain aminopolycarboxylic acids.
  • the zeolite content is 30 to 75% by weight and that of homo- or copolymeric carboxylic acid is at least 5% by weight, between 8 and 11.5% by weight being used in the examples.
  • the moisture content should preferably not be more than 4% by weight.
  • a disadvantage of these agents is the relatively poor washing-in behavior of the granules when used in automatic washing machines. This property causes considerable portions to remain undissolved in the induction devices and settle there as moist sludge or dried-up crusts.
  • Another granular, phosphate-free softening agent containing 50 to 60 wt .-% zeolite, 3 to 5 wt .-% polymeric acid, 4 to 15 wt .-% sodium citrate and 4 to 12 wt .-% sodium carbonate (balance: water) is from EP-A-24 39 08 known.
  • the washing-in behavior of these agents is still not completely satisfactory in machines with poorly designed washing-in devices.
  • DE-A-27 90 40 describes a granular detergent builder which consists of 50 to 80% by weight of zeolite, 5 to 25% by weight of bentonite, 0.5 to 5% by weight of a cellulose ether and optionally small amounts of sodium sulfate, alkalis and nonionic surfactants. These agents also do not yet achieve the desired good induction marks.
  • Phosphate-free is understood to mean an agent which contains less than 0.1% of inorganic phosphorus.
  • 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.
  • Useful sheet silicates are known, for example, from US 3,966,629, US 4,062,647 (DE 23 34 899-B2), EP 26 529 A1 and EP 28 432 A1.
  • Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • the content of layered silicates in the agents is 2 to 10% by weight, preferably 3 to 7% by weight.
  • the component (c) 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, as described, for example, in EP 25 551-B1, have proven 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 homopolymers or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000. Their proportion of the average is 5 to 15% by weight and preferably 7 to 12% by weight.
  • Constituent (d) is sodium sulfate, the proportion of which, calculated on anhydrous salt, is 1 to 10% by weight, preferably 2 to 8% by weight.
  • the sodium sulfate, calculated as an anhydrous salt improves both the granule properties and the flushing behavior in the amounts stated.
  • the agents can contain small amounts of surface-active 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).
  • Such additives which are introduced into the compositions with the zeolite, are described in DE 25 27 388-B2.
  • These can be nonionic surfactants containing polyglycol ethers, for example primary alcohols with 12 to 18 carbon atoms reacted with 2 to 7 moles of ethylene oxide.
  • the proportion of stabilizers introduced into the composition via such zeolite dispersions can be, for example, 0.5 to 3% by weight.
  • this component is not necessary for the desired properties of the water softener.
  • the water content of the detergents depends on the drying conditions.
  • the water content which can be removed at a drying temperature of 145 ° C. is about 8 to 18% by weight, mostly 10 to 16% by weight.
  • Other amounts of water bound by the zeolite or layered silicate that are released at higher temperatures are not included in this amount. Obtain this by calcining the zeolite or layered silicate at temperatures of 800 ° C a share, the water content of the agents is a total of 12 to 25% by weight.
  • the average grain size of the agent is usually 0.2 to 1.2 mm, the proportion of the grains being below 0.1 mm not more than 2% by weight and above 2 mm not more than 5% by weight.
  • at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.6 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 5% by weight .-%, in particular not more than 3 wt .-% and the proportion of grains between 1.6 to 2 mm is also not more than 15 wt .-%, in particular not more than 7 wt .-%. Larger proportions of fine grain generally lead to a deterioration in the induction behavior and should therefore be avoided.
  • the agents are preferably produced by spray drying an aqueous, liquid to pasty batch (slurry) of the constituents by means of heated gases (combustion gases) in customary drying towers. Since the combustion air, which is widely used as a dry gas, contains comparatively high proportions of carbon dioxide, it may be advantageous to add small amounts of sodium hydroxide to the slurry before spraying, in order to counteract a pH reduction by a corresponding excess of alkali. The recommended proportions of NaOH are usually between 0.1 and 1% by weight.
  • the minor components that can be added to the agents during production include fragrances and dyes or color pigments with which the intrinsic odor and the intrinsic color of individual active ingredients, in particular the layered silicate, can be covered.
  • the agents are used in washing and cleaning processes when there is increased water hardness, the amounts used depending on the water hardness. They are generally 0.5 to 8 g / l, usually 1 to 5 g / l.
  • the agent can be added to the washing liquid before or together with the detergent. In modern household washing machines with a programmed rinse cycle, the agent is expediently used together with the detergent.
  • the granules had a bulk density of 600 g / l.
  • the sieve analysis showed the following grain distribution:
  • 5% by weight of the product was sprayed with 0.07% by weight of a green dye (pigmosol green), which was dissolved in water, and the colored material was again combined with the main amount, with an optically appealing color speckling being achieved.
  • a green dye pigmosol green
  • the application test was carried out in a practical way in a household washing machine with a horizontally arranged washing drum (type Miele W 433) with the use of a commercial detergent.
  • the composition of this detergent was (in% by weight): Na dodecylbenzenesulfonate 8.0 Fatty alcohol ethoxylate 5.8 Tallow soap 1.5 Cellulose ether 0.8 opt.
  • 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 B1.
  • dosage % Remission W Should additive I. II III IV 0 ⁇ 82 g 0.6 - 65.2 67.0 70.0 78.7 70.2 82 g 0.6 66 g B1 73.9 79.2 81.0 81.8 78.5 140 g 1 - 74.5 77.9 81.1 82.4 78.9
  • Household washing machine (AEG Turnette AS R ), Detergents, additives and conditions as described in the previous example, Ashing of the cotton fabric after 25 washing cycles. dosage W Should additive % Ashes 82 g 0.6 - 2.8 82 g 0.6 66 g B1 0.6 140 g 1.0 - 2.6

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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)
EP19900117748 1989-09-23 1990-09-14 Granular, phosphate free water softening agent Withdrawn EP0419970A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19893931871 DE3931871A1 (de) 1989-09-23 1989-09-23 Granulares, phosphatfreies wasserenthaertungsmittel
DE3931871 1989-09-23

Publications (2)

Publication Number Publication Date
EP0419970A2 true EP0419970A2 (fr) 1991-04-03
EP0419970A3 EP0419970A3 (en) 1991-06-26

Family

ID=6390094

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900117748 Withdrawn EP0419970A3 (en) 1989-09-23 1990-09-14 Granular, phosphate free water softening agent

Country Status (2)

Country Link
EP (1) EP0419970A3 (fr)
DE (1) DE3931871A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991014762A1 (fr) * 1990-03-26 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Additif d'avivage seche par pulverisation pour agents de lavage
WO1993025651A1 (fr) * 1992-06-18 1993-12-23 Unilever N.V. Composition pour le lavage de la vaisselle en machine
EP0622449A3 (fr) * 1993-04-28 1994-12-21 Huels Chemische Werke Ag Compositions pour adoucir l'eau.
WO2002062933A1 (fr) * 2001-02-05 2002-08-15 INEOS SILICAS LIMITED (formerly known as CROSFIELD LTD.) Desintegrants et procede de fabrication de ceux-ci

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
DE3627773A1 (de) * 1986-08-16 1988-02-18 Hoechst Ag Phosphatfreies geschirrspuelmittel
DE3702764A1 (de) * 1987-01-30 1988-08-11 Degussa Waschmittelbuilder
DE3818829A1 (de) * 1988-06-03 1989-12-14 Henkel Kgaa Koerniges adsorptionsmittel mit verbessertem einspuelverhalten

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991014762A1 (fr) * 1990-03-26 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Additif d'avivage seche par pulverisation pour agents de lavage
WO1993025651A1 (fr) * 1992-06-18 1993-12-23 Unilever N.V. Composition pour le lavage de la vaisselle en machine
EP0622449A3 (fr) * 1993-04-28 1994-12-21 Huels Chemische Werke Ag Compositions pour adoucir l'eau.
US5575946A (en) * 1993-04-28 1996-11-19 Chemische Fabrik Stockhausen Gmbh Water-softening compositions
WO2002062933A1 (fr) * 2001-02-05 2002-08-15 INEOS SILICAS LIMITED (formerly known as CROSFIELD LTD.) Desintegrants et procede de fabrication de ceux-ci

Also Published As

Publication number Publication date
EP0419970A3 (en) 1991-06-26
DE3931871A1 (de) 1991-04-04

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