EP0460035B1 - Adoucisseur d'eau sous forme granulaire a pulverulente - Google Patents

Adoucisseur d'eau sous forme granulaire a pulverulente Download PDF

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Publication number
EP0460035B1
EP0460035B1 EP90903797A EP90903797A EP0460035B1 EP 0460035 B1 EP0460035 B1 EP 0460035B1 EP 90903797 A EP90903797 A EP 90903797A EP 90903797 A EP90903797 A EP 90903797A EP 0460035 B1 EP0460035 B1 EP 0460035B1
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EP
European Patent Office
Prior art keywords
weight
ratio
monohydrate
sodium
expressed
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
EP90903797A
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German (de)
English (en)
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EP0460035A1 (fr
Inventor
Jörg Poethkow
Horst Upadek
Martina Kihn-Bortulinski
Gerhard Stoll
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT90903797T priority Critical patent/ATE82317T1/de
Publication of EP0460035A1 publication Critical patent/EP0460035A1/fr
Application granted granted Critical
Publication of EP0460035B1 publication Critical patent/EP0460035B1/fr
Anticipated expiration legal-status Critical
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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the invention relates to a water softener, which is used in addition to a detergent to improve the washing result, especially if a poor washing result is to be expected with high water hardness.
  • German patent application 36 14 779 discloses a softening agent with a similar composition based on zeolite, polymeric polycarboxylate, sodium citrate, soda and preferably carboxymethyl cellulose.
  • German patent application 38 14 855 (EP-A-0.340.590, state of the art according to Art 54 (3) (4) EPC) is a detergent additive which can be used as a softening agent and is based on zeolite, polymeric polycarboxylates and sodium perborate.
  • the component (A) consists of finely crystalline, synthetic, water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg Ca0 / g (according to the information in German patent application 24 12 837).
  • the average particle size is in the range from 1 to 10 ⁇ m (measurement method: Coulter counter).
  • Component (B) consists of homopolymers of acrylic acid and / or copolymers of acrylic acid with maleic acid, which are in the form of the sodium salts.
  • the polyacrylic acid can have, for example, a molecular weight of 2,000 to 200,000, preferably 5,000 to 100,000. They have proven to be particularly suitable Copolymers of acrylic acid or methacrylic acid with maleic acid have been found to be characterized, for example, in EP-A-0.025.551. These are copolymers which contain 40 to 90% by weight of acrylic acid. Copolymers in which 50 to 85% by weight of acrylic acid and 50 to 15% by weight of maleic acid are present are particularly preferred.
  • Component (C) consists of sodium perborate, which can be present as a monohydrate, tetrahydrate or as a mixture of these.
  • the content of the agents and the mixing ratios are based on the perborate monohydrate, even if the component (C) should consist entirely or partially of the tetrahydrate.
  • Preferred agents are those in which the oxygen-containing bleaching agent is present as a perborate monohydrate.
  • Component (D) consists of linear 1,2-alkanediols with a chain length of 10 to 18 carbon atoms, which can be ethoxylated with 0 to 3 ethoxy units.
  • diols with C10 to C14 chain numbers ie 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 1,2-tridecanediol and 1,2- Tetradecanediol and their ethoxylates, the number of ethoxy groups being limited to a maximum of 3.
  • the 1,2-alkanediols can also be used in a mixture with their ethoxylated derivatives, the degree of ethoxylation corresponding to a statistical distribution. In general, these are terminally ethoxylated derivatives. 1,2-Dodecanediol and the ethoxylated diols 1,2-dodecanediol.1EO and 1,2-dodecanediol.2EO are particularly preferred.
  • 1,2-alkanediols The production of 1,2-alkanediols is known. It is carried out in particular by reacting epoxidized 1,2-alkenes with water at temperatures from 180 to 250 ° C. and a pressure of 15 to 40 bar, as described in German application 38 14 850.
  • the ethoxylated derivatives of 1,2-alkanediols can be obtained in a manner known per se by reaction with ethylene oxide under the action of customary alkaline catalysts or using calcined hydrotalcites, as described in German application 38 13 910.
  • the latter method has the advantage that the reaction products have a narrow bandwidth or homolog distribution, the distribution curve being very close to that calculated according to Poisson.
  • the weight ratio of (A) to (B) is 30: 1 to 4: 1, preferably 14: 1 to 5: 1, that of (A) to (C) 30: 1 to 1.6: 1, preferably 11: 1 to 3: 1, that from (A) to (D) 55: 1 to 4: 1, preferably 28: 1 to 7.5: 1, that from (B) to (C) 5: 1 to 1:12 , 5, preferably 1.6: 1 to 1: 4, that of (B) to (D) 10: 1 to 1: 5, preferably 4: 1 to 1: 4, and that of (C) to (D) 25: 1 to 1: 5, preferably 7.5: 1 to 1: 1, the components (A), (B) and (D) being counted as anhydrous substances.
  • the agents preferably used in granular form consist of a dry, homogeneous mixture of at least two powder components, of which the first component is in the form of spray-dried granules. It can be obtained by spray drying a slurry which contains the zeolite as an aqueous suspension in a mixture with the sodium salt of the (co) -polymeric acids in the stated mixing ratio.
  • This first powder component can contain further additives which, for example, can advantageously change the granulate structure, the bulk density or the flow behavior.
  • additives include, for example, sodium sulfate, which is essentially in anhydrous form. Referred to as (anhydrously calculated) component (E), its weight ratio (A): (E) is preferably 20: 1 to 4: 1.
  • the agents according to the invention can also contain these stabilizers.
  • Stabilizers frequently used in practice are ethoxylated linear or methyl-branched (oxo radical) alcohols, for example C12-C16 alcohols with 3 to 5 ethylene oxide groups (EO) and C16-C18 alcohols (tallow alcohol) with 4 to 7 EO. This applies to both detergents and softeners.
  • the stabilizing agents can be contained in the claimed agents in amounts of approximately 1 to 2% by weight.
  • perborate (C) is not spray-dried together with the constituents of the first powder component, but is only subsequently mixed into the spray product. It thus forms the base powder for the second powder component.
  • Component (D) can be mixed with each powder component of the water softening agent according to the invention, if appropriate after previous granulation or spray drying, and with the mixture of the powder components mentioned and then granulated. However, a certain powder component of the additive is preferably treated in this way and this surfactant-containing premix is then combined with the other powder components.
  • a spray product made of (A + B) and sodium sulfate (E) are particularly suitable for this purpose.
  • the weight ratio of (D) to (E) can be 5: 1 to 1: 30.
  • the agents can also contain further powder components which are neither suitable for processing together with the perborate nor for hot spray drying and which are likewise mixed in a dry form with the aforementioned powder components.
  • These include bleach activators, in particular powdery to granular peracid precursors from the class of N-acyl compounds and O-acyl compounds.
  • suitable N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylethylenediamine (TAED), and acylated glycolurils, for example tetraacetylglycoluril.
  • acylated sugars such as glucose pentaacetate are also suitable as O-acyl compounds.
  • Preferred bleach activators are tetraacetylethylenediamine and glucose pentaacetate.
  • the bleach activators can be granulated and coated with water-soluble coating substances in order to avoid premature interaction with perborate.
  • Particularly suitable coating agents are water-soluble polymers, for example cellulose ethers, such as carboxymethyl cellulose (as sodium salt), or carbon chain polymers, such as the (co) -polymeric polycarboxylic acids and their salts mentioned under (B).
  • the agents of the claimed composition show a better effect than conventional agents with higher proportions of "classic” softening agents in terms of binding calcium salts and enhancing the builder effect.
  • Zeolites, soda, polymeric polycarboxylates and polyacids such as citric acid are considered “classic” softeners. It has not previously been known of perborates that, in combination with some of the "classic” softening agents mentioned, they advantageously support their specific action and have a builder effect, provided the water used has a high calcium hardness.
  • Agent No. 1 contained a conventional detergent booster of the QAV type
  • agent No. 2 and agent No. 3 contained 1,2-dodecanediol and 1,2-dodecanediol.2EO, respectively, which were mixed with the mixture of the other powder components and granulated .
  • 1,2-dodecanediol.2EO had been applied to perborate monohydrate.
  • the synthetic zeolite used (calculated anhydrous) had a particle size between 0.5 and 8 microns.
  • the agents 1 to 4 of the polycarboxylate consisted of the sodium salt of a copolymer of acrylic acid and maleic acid with a molecular weight of approximately 70,000 (Sokalan CP5 (R) ).
  • ingredients of the first powder component obtained by spray drying an aqueous slurry.
  • the granules had a grain size of 0.1 to 0.8 mm (average grain size 0.4 mm).
  • TAED stands for tetraacetylethylenediamine.
  • CMC is the sodium salt of carboxymethyl cellulose and was used as a coating substance for the TAED according to the information in European patent application 37 026.
  • composition of the detergent was (in% by weight):
  • the target dosage for water hardness range 4 (28 ° d) is 234 g per washing machine.
  • An underdosing is typical, in which only 70% of the target value is used (164 g).

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un adoucisseur d'eau sous forme granulaire à pulvérulente qui s'utilise conjointement avec un détergent ou pour le lavage et qui renferme (A) une zéolite synthétique hydratée à cristaux fins, du type NaA, (B) des polycarboxylates polymères dérivés d'acides acryliques ainsi que leurs copolymères avec de l'acide maléique sous forme de sel de sodium, (C) du perborate de sodium sous forme de monohydrate et/ou tétrahydrate et (D) au moins un 1,2-alcanediol linéaire d'une longueur de chaîne C10 à C18 et/ou leurs produits d'éthoxylation avec 3 groupes éthoxy au maximum. L'adoucisseur est constitué d'un mélange sec d'au moins deux composants pulvérulents; le premier composant renferme les constituants (A) et (B) sous forme d'un granulat séché par pulvérisation, et le deuxième composant pulvérulent contient du perborate de sodium (C). Le constituant (D) peut être mélangé avec chaque composant pulvérulent ou avec un mélange de ceux-ci ou bien être granulé.

Claims (7)

  1. Agent en grains ou en poudre adoucissant l'eau, qui peut être utilisé comme additif aux produits de lessive ou dans un procédé de lessivage, caractérisé par une teneur en
    (A) zéolithe de type NaA finement cristalline et synthétique contenant de l'eau de constitution,
    (B) polycarboxylates polymères dérivés de l'acide acrylique ainsi que de ses copolymères avec l'acide maléique sous forme de sels sodiques,
    (C) perborate de sodium (sous forme de monohydrate et/ou de tétrahydrate ),
    (D) un ou plusieurs 1,2-alcanediol(s) linéaire(s) dont la longueur de chaîne est comprise entre C₁₀ et C₁₈ et ou leurs produits d'éthoxylation, avec de préférence 1 à 3 groupes éthoxy,
    dans lequel les rapports pondéraux de (A) à (B) sont compris entre 30:1 et 4:1; de (A) à (C) entre 30:1 et 1,6:1; de (A) à (D) de 55:1 et 4:1; de (B) à (C) entre 5:1 et 1:12,5; de (B) à (D) entre 10:1 et 1:5 et de (C) à (D) entre 25:1 et 1:5, avec pour condition que les teneurs des constituants (A) (B) et (D) doivent être calculées sous forme de substances anhydres et que la teneur en (C) doit être calculée sous forme de monohydrate.
  2. Agent selon la revendication 1, caractérisé en ce que les proportions pondérales de (A) à (B) sont comprises entre 14:1 et 5:1; de (A) à (C) de 11:1 à 3:1; de (A) à (D) de 28:1 à 7,5:1; de (B) à (C) de 1,6:1 à 1:4; de (B) à (D) de 4:1 à 1:4 et de (C) à (D) de 7,5:1 à 1:1.
  3. Agent selon la revendication 1 ou 2, caractérisé en ce qu'il est constitué d'un mélange sec d'au moins deux composants pulvérulents, dans lesquels le premier composant se présente sous forme d'un granulé sec par pulvérisation et contient les constituants (A) et (B) tandis que le deuxième constituant pulvérulent contient du perborate de sodium.
  4. Agent selon de l'une des revendications 1 à 3, caractérisé par une teneur en sulfate de sodium (E) (calculée sous forme de substance anhydre) avec un rapport de (A) : (E) compris entre 20:1 et 4:3.
  5. Agent selon l'une des revendications 1 à 4, caractérisé par un teneur en
    (A) de 40 à 60 % en poids de zéolithe synthétique finement cristalline de type NaA,
    (B) de 2 à 10% en poids de polycarboxylate polymère dérivé de l'acide acrylique et de ses copolymères avec l'acide maléique sous forme de sels sodiques,
    (C) de 2 à 25% en poids de perborate de sodium sous forme de monohydrate ou de tétrahydrate (calculés sous forme de monohydrate),
    (D) de 1 à 10% en poids d'un ou plusieurs 1,2-alcanediols linéaires ayant une longueur de chaîne allant de C₁₀ à C₁₈ et avec 0 à 3 groupes éthoxy,
    (E) de 0 à 30% en poids de sulfate de sodium.
    (F) de 0 à 10% en poids d'un précurseur d'un peracide,
    (G) de 0 à 2% en poids d'un alcool en C₁₂-C₁₈ linéaire ou méthylé ayant réagi avec 3 à 7 moles d'oxyde d'éthylène,
    dans lequel les quantités, à l'exception du constituant (C), se rapportent à des substances anhydres et dans lequel la quantité totale d'eau liée contenue dans les constituants à l'exception de (C) est égale au maximum à 20% en poids.
  6. Agent selon la revendication 5, caractérisé par une teneur en
    (A) de 45 à 55% en poids de zéolithe synthétique finement cristalline de type NaA,
    (B) de 4 à 8% en poids du sel sodique d'un copolymère d'acide acrylique et d'acide-maléique, avec un rapport pondéral compris entre 10:1 et 1:1 et ayant un poids moléculaire de 20 000 à 150 000,
    (C) de 5 à 15% en poids de perborate de sodium, calculé sur le monohydrate,
    (D) de 2 à 6% en poids d'un ou de plusieurs 1,2-alcanediols linéaires ayant une longueur de chaîne allant de C₁₀ à C₁₄ et avec de 0 à 3 groupes éthoxy , en préférant tout particulièrement le 1,2-dodécanediol et le 1,2-dodécanediol·2EO,
    (E) de 2 à 20% en poids de sulfate de sodium,
    (F) de 2 à 8% en poids de tétraacétylènediamine,
    (G) de 1 à 2% en poids d'un alcool en C₁₂-C₁₈ linéaire ayant réagi avec 3 à 7 moles d'oxyde d'éthylène
  7. Utilisation d'un agent d'adoucissement de l'eau en grains ou en poudre ayant une teneur en
    (A) zéolithe de type NaA finement cristalline et synthétique contenant de l'eau de constitution,
    (B) polycarboxylates polymères dérivés de l'acide acrylique ainsi que de ses copolymères avec l'acide maléique sous forme de sels sodiques,
    (C) perborate de sodium (sous forme de monohydrate et/ou de tétrahydrate ),
    (D) un ou plusieurs 1,2-alcanediol(s) linéaire(s) dont la longueur de chaîne est comprise entre C₁₀ et C₁₈ et ou leurs produits d'éthoxylation, avec de préférence 1 à 3 groupes éthoxy,
    dans lequel les rapports pondéraux de (A) à (B) sont compris entre 30:1 et 4:1, ceux de (A) à (C) entre 30:1 et 1,6:1; ceux de (A) à (D) entre 55:1 et 4:1; ceux de (B) à (C) entre 5:1 et 1:12,5; ceux de (B) à (D) entre 10:1 et 1:5 et ceux de (C) à (D) entre 25:1 et 1:5, avec pour condition que les teneurs des constituants (A), (B) et (D) doivent être calculées sous forme de substances anhydres et que le constituant (C) est calculé sous forme de monohydrate,à utiliser comme additif à des produits de lessive ou pour les procédés de lessivage.
EP90903797A 1989-02-22 1990-02-14 Adoucisseur d'eau sous forme granulaire a pulverulente Expired - Lifetime EP0460035B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90903797T ATE82317T1 (de) 1989-02-22 1990-02-14 Koerniges bis pulverfoermiges wasserenthaertungsmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3905423 1989-02-22
DE3905423A DE3905423A1 (de) 1989-02-22 1989-02-22 Koerniges bis pulverfoermiges wasserenthaertungsmittel

Publications (2)

Publication Number Publication Date
EP0460035A1 EP0460035A1 (fr) 1991-12-11
EP0460035B1 true EP0460035B1 (fr) 1992-11-11

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EP90903797A Expired - Lifetime EP0460035B1 (fr) 1989-02-22 1990-02-14 Adoucisseur d'eau sous forme granulaire a pulverulente

Country Status (4)

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EP (1) EP0460035B1 (fr)
DE (2) DE3905423A1 (fr)
ES (1) ES2053182T3 (fr)
WO (1) WO1990010054A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024089139A1 (fr) * 2022-10-25 2024-05-02 Symrise Ag Détergents et compositions de nettoyage à performances de blanchiment améliorées
WO2024089071A1 (fr) * 2022-10-25 2024-05-02 Symrise Ag Composition de traitement textile anti-jaunissement
WO2024088521A1 (fr) * 2022-10-25 2024-05-02 Symrise Ag Détergents et compositions de nettoyage présentant des propriétés anti-redéposition améliorées

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK167363B1 (da) * 1991-04-12 1993-10-18 Cleantabs As Toejvaskemiddel
DE19961660A1 (de) * 1999-12-21 2001-07-12 Henkel Kgaa Pflegemittel für Wasch- und Geschirrspülmaschinen
US20110021410A1 (en) * 2009-07-27 2011-01-27 Ecolab Usa Inc. Novel formulation of a ware washing solid controlling hardness

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT336751B (de) * 1974-10-03 1977-05-25 Henkel & Cie Gmbh Wasch-, reinigungs- und bleichmittel, insbesondere zum waschen und bleichen von textilien
DE2547389A1 (de) * 1975-10-23 1977-05-05 Henkel & Cie Gmbh Phosphatfreies waschmittel
DE3424987A1 (de) * 1984-07-06 1986-02-06 Unilever N.V., Rotterdam Verfahren zur herstellung eines pulverfoermigen waschmittels mit erhoehtem schuettgewicht
DE3814855A1 (de) * 1988-05-02 1989-11-16 Henkel Kgaa Waschmitteladditiv

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024089139A1 (fr) * 2022-10-25 2024-05-02 Symrise Ag Détergents et compositions de nettoyage à performances de blanchiment améliorées
WO2024089071A1 (fr) * 2022-10-25 2024-05-02 Symrise Ag Composition de traitement textile anti-jaunissement
WO2024088521A1 (fr) * 2022-10-25 2024-05-02 Symrise Ag Détergents et compositions de nettoyage présentant des propriétés anti-redéposition améliorées

Also Published As

Publication number Publication date
DE3905423A1 (de) 1990-08-23
DE59000471D1 (de) 1992-12-17
WO1990010054A1 (fr) 1990-09-07
ES2053182T3 (es) 1994-07-16
EP0460035A1 (fr) 1991-12-11

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