WO1990010054A1 - 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
WO1990010054A1
WO1990010054A1 PCT/EP1990/000238 EP9000238W WO9010054A1 WO 1990010054 A1 WO1990010054 A1 WO 1990010054A1 EP 9000238 W EP9000238 W EP 9000238W WO 9010054 A1 WO9010054 A1 WO 9010054A1
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WO
WIPO (PCT)
Prior art keywords
weight
monohydrate
sodium
linear
component
Prior art date
Application number
PCT/EP1990/000238
Other languages
German (de)
English (en)
Inventor
Jörg Poethkow
Horst Upadek
Martina Kihn-Botulinski
Gerhard Stoll
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE9090903797T priority Critical patent/DE59000471D1/de
Priority to AT90903797T priority patent/ATE82317T1/de
Publication of WO1990010054A1 publication Critical patent/WO1990010054A1/fr

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
    • C11D3/16—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 softening agent which is used in addition to a detergent to improve the washing result, in particular if a poor washing result is to be expected with high water hardness.
  • German patent application 33 16 513 discloses granules which contain zeolites and polymeric polycarboxylates and can be used as softening agents.
  • the content of homo- or copolymeric polycarboxylic acid or its alkali salt should be 5 to 30% by weight, based on the hydrated zeolite.
  • German patent application 36 14 779 discloses a similarly composed softening agent based on zeolite, polymeric polycarboxylate, sodium citrate, soda and preferably carboxymethyl cellulose.
  • German patent application 38 14 855 relates to a detergent additive which can be used as a softening agent and is based on zeolite, polymeric polycarboxylates and sodium perborate.
  • the invention accordingly relates to a granular to powdery water softening agent which can be used as an additive with detergents or for washing processes, characterized by a content of
  • 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 CaO / 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 present 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 proven, as are characterized, for example, in European patent application 25 551. These are copolymers containing 40 to 90% by weight of acrylic acid. Those 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. Arithmetically, the content of the compositions 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 Cirj to Ci4 chain numbers ie 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 1,2-tridecanediol and, have proven to be particularly suitable detergent boosters 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. Particularly preferred are 1,2-dodecanediol and the ethoxylated diols 1,2-dodecanediol Leo and l, 2-dodecanediol "2E0.
  • 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 of 180 to 250 ° C. and a pressure of 15 to 40 bar, as described in German application 3814850.
  • 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 hydrotalites, 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 coming 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 constituents (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 pouring behavior.
  • additives include, for example, sodium sulfate, which is essentially in water-free form. Referred to as (water-free) component (E), its weight ratio (A): (E) is preferably 20: 1 to 4: 1. Because zeolites are preferably used in stabilized aqueous suspensions, 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 Ci2-Ci6 alcohols with 3 to 5 ethylene oxide groups (EO) and Ci6-Ci8 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.
  • Constituent (D) can be mixed with any powder component of the water softening agent according to the invention, if appropriate after previous granulation or spray drying, or with the mixture of the powder components mentioned and then granulated. However, a certain powder constituent of the additive is preferably treated in this way and this surfactant-containing premix is then combined with the other powder constituents.
  • 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.
  • compositions 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 dry form with the powder components mentioned above.
  • bleach activators in particular powdery to granular peracid precursors from the class of N-acyl compounds and O-acyl compounds.
  • N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylethylenediamine (TAED), and acylated glycolurils, for example tetraacetylglycoluril.
  • TAED tetraacetylethylenediamine
  • glycolurils for example tetraacetylglycoluril.
  • carboxylic anhydrides such as phthalic anhydride and esters such as Na (iso) nonanoylphenol sulfonate
  • acylated sugars such as glucose pentaacetate are also suitable as O-acyl compounds.
  • Preferred bleach activators are tetraacetyl ethylene diamine and glucose pentaacetate. The bleach activators can be granulated and coated with water-soluble coating substances to avoid premature interaction with perborate.
  • Particularly suitable coating agents are water-soluble polymers, for example cellulose ethers, such as carboxymethylcellulose (as sodium salt), or carbon chain polymers, such as the (co) -polymeric polycarboxylic acids and their salts mentioned under (B).
  • cellulose ethers such as carboxymethylcellulose (as sodium salt)
  • carbon chain polymers such as the (co) -polymeric polycarboxylic acids and their salts mentioned under (B).
  • Agents of the stated composition can therefore have the following composition:
  • (G) 0 to 2% by weight of a linear or methyl-branched C 1 -C 8 alcohol reacted with 3 to 7 moles of ethylene oxide, the amounts, with the exception of component (C), being based on anhydrous substance and the total amount bound water, which is contained in the components with the exception of (C), is up to 20 wt .-%.
  • compositions preferably have the following composition:
  • the agents of the claimed composition show a better action than conventional agents which have higher proportions of "classic” softening agents.
  • Zeolites, soda, polymeric polycarboxylates and polyacids such as citric acid are considered to be “classic” softening agents.
  • 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.
  • the agents according to the invention in addition to a pronounced bleaching action through the addition of a detergency booster (D), also have a substantially improved primary washing power, which is particularly useful when the consumer underdoses the bleach-containing heavy duty detergent and none further additives used.
  • the primary washing power and the prevention of tissue graying and fabric ash are considerably improved, in particular if the conventional detergent is underdosed in relation to the water hardness, an additional bleaching effect is achieved, and the waste water is much less compared to a conventional washing process with high water hardness burdened, both against a washing process in which the conventional detergent is dosed accordingly high, as well as in a washing process with underdosing of the detergent and compensation with a conventional water softener.
  • Agent No. 1 contained a conventional detergent booster of the QAV type
  • agent No. 2 and agent No. 3 contained 1,2-dodecandiol and 1,2-dodecanediol-2E0, respectively, which were mixed with the mixture of the other powder components and were granulated.
  • 2-dodecanediol was l, applied to perborate 2E0 wor ⁇ to.
  • compositions No. 1 to No. 4 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 )).
  • 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 in accordance with the information in European patent application 37026.
  • the application test was carried out in a launderometer as well as in a household washing machine with a horizontally arranged washing drum (type Miele W 760) using a commercially available phosphate-free detergent.
  • Tables 2 to 4 it must be taken into account that in tests, both in the launderometer and in the washing machine, remission differences of 2% and more can be understood by the consumer (optical evaluation with Zeiss reflectometer at 465 nm; Suppression of the brightener effect). In contrast, differences of 0.5 grades are already significant in the visual assessment (maximum grade 6.0 means no brightening).
  • the composition of the detergent was (in% by weight):
  • Washing conditions Washing machine Miele W 760 washing temperature 60 ° C single eye method
  • V mascara refined on polyester / cotton
  • 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 setpoint 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.
PCT/EP1990/000238 1989-02-22 1990-02-14 Adoucisseur d'eau sous forme granulaire a pulverulente WO1990010054A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE9090903797T DE59000471D1 (de) 1989-02-22 1990-02-14 Koerniges bis pulverfoermiges wasserenthaertungsmittel.
AT90903797T ATE82317T1 (de) 1989-02-22 1990-02-14 Koerniges bis pulverfoermiges wasserenthaertungsmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3905423.3 1989-02-22
DE3905423A DE3905423A1 (de) 1989-02-22 1989-02-22 Koerniges bis pulverfoermiges wasserenthaertungsmittel

Publications (1)

Publication Number Publication Date
WO1990010054A1 true WO1990010054A1 (fr) 1990-09-07

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ID=6374663

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/000238 WO1990010054A1 (fr) 1989-02-22 1990-02-14 Adoucisseur d'eau sous forme granulaire a pulverulente

Country Status (4)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107012023A (zh) * 2009-07-27 2017-08-04 埃科莱布美国股份有限公司 器具清洗固体控制硬度的新制剂

Families Citing this family (5)

* 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
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
WO2024089139A1 (fr) * 2022-10-25 2024-05-02 Symrise Ag Détergents et compositions de nettoyage à performances de blanchiment améliorées

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2547389A1 (de) * 1975-10-23 1977-05-05 Henkel & Cie Gmbh Phosphatfreies waschmittel
AT336751B (de) * 1974-10-03 1977-05-25 Henkel & Cie Gmbh Wasch-, reinigungs- und bleichmittel, insbesondere zum waschen und bleichen von textilien
EP0168102A2 (fr) * 1984-07-06 1986-01-15 Unilever N.V. Procédé de préparation d'une composition détergente en poudre à densité en vrac élevée
EP0340590A1 (fr) * 1988-05-02 1989-11-08 Henkel Kommanditgesellschaft auf Aktien Additif pour détergent

Patent Citations (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
EP0168102A2 (fr) * 1984-07-06 1986-01-15 Unilever N.V. Procédé de préparation d'une composition détergente en poudre à densité en vrac élevée
EP0340590A1 (fr) * 1988-05-02 1989-11-08 Henkel Kommanditgesellschaft auf Aktien Additif pour détergent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107012023A (zh) * 2009-07-27 2017-08-04 埃科莱布美国股份有限公司 器具清洗固体控制硬度的新制剂

Also Published As

Publication number Publication date
DE3905423A1 (de) 1990-08-23
EP0460035A1 (fr) 1991-12-11
EP0460035B1 (fr) 1992-11-11
ES2053182T3 (es) 1994-07-16
DE59000471D1 (de) 1992-12-17

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