EP0054094B1 - Gegen Chlorabspaltung stabile Reinigungsmittelzusammensetzungen und Mittel zu deren Herstellung - Google Patents

Gegen Chlorabspaltung stabile Reinigungsmittelzusammensetzungen und Mittel zu deren Herstellung Download PDF

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Publication number
EP0054094B1
EP0054094B1 EP80850189A EP80850189A EP0054094B1 EP 0054094 B1 EP0054094 B1 EP 0054094B1 EP 80850189 A EP80850189 A EP 80850189A EP 80850189 A EP80850189 A EP 80850189A EP 0054094 B1 EP0054094 B1 EP 0054094B1
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European Patent Office
Prior art keywords
weight
triazine trione
alkali metal
amount
chlorinated triazine
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EP80850189A
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English (en)
French (fr)
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EP0054094A1 (de
Inventor
Krister Holmberg
Ingvar Nilsson
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Nouryon Pulp and Performance Chemicals AB
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Eka AB
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Priority to AT80850189T priority Critical patent/ATE14452T1/de
Priority to DE8080850189T priority patent/DE3070906D1/de
Priority to EP80850189A priority patent/EP0054094B1/de
Publication of EP0054094A1 publication Critical patent/EP0054094A1/de
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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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3958—Bleaching agents combined with phosphates

Definitions

  • This invention relates to detergent compositions stable to chlorine separation suitable as machine dish washing detergents or industrial detergents, and to agents for producing said compositions.
  • Machine dish washing detergent compositions for example consist mainly of
  • the alkali metal phosphate usually sodium tripolyphosphate, primarily serves as complexing agent for calcium and magnesium ions.
  • the alkali metal silicate normally is a sodium silicate having a molar ratio Si0 2 :Na 2 O of 3.50 to 0.75. Usually, use is made of so-called sodium metasilicate, which implies that said ratio lies about 1.
  • the purpose of the silicate is to provide a high pH, which is needed int. al. for hydrolysis of edible fat rests, and to have a corrosion preventing effect.
  • the sodium metasilicate may be either practically anhydrous or be present as a hydrate with crystal bound water.
  • the commercially most usual hydrate is the crystal form called pentahydrate.
  • This product is usually written as Si02. N 82 0 - 5H 2 0, but actually is a tetrahydrate of the salt Na 2 H 2 SiO 4 .
  • This crystal form is hereinafter called "pentahydrate”.
  • the pentahydrate offers several advantages over the anhydrous sodium metasilicate in machine dish washing detergent compositions, int. al. because it is more readily soluble and considerably cheaper.
  • the introduction of water into a machine dish washing detergent composition in powder form entails problems regarding the stability of the organic chlorine compounds. These readily hydrolyzed compounds in fact give off chlorine gas in a moist environment, which amounts to a considerable technical problem. For these reasons, use is preferably made of anhydrous sodium metasilicate in said products.
  • the surfactant usually is a low-foaming non-ionic surfactant, preferably a block polymer of ethylene and propylene oxide. Its task is to contribute to wetting and emulsification simultaneously as it shall have an antifoaming effect on for example proteins.
  • the organic chlorine compound or chlorine carrier functions as an oxidative bleaching agent which has the task of attacking deposits of int. al. coffee, tea and fruit juices.
  • the economically most favourable chlorine carrier is trichloroisocyanuric acid, but it is very instable and gives off chlorine too easily to permit being used in practice. Salts of dichloroisocyanuric acid are therefore used in most cases and the sodium salt has, primarily for economical reasons, been most widely utilized.
  • machine dish washing detergents often also contain varying quantities of alkalimetal carbonates and bicarbonates, corrosion inhibitors, dyes and perfume.
  • Trichloroisocyanuric acid also has been stabilized for instance by means of an olefin having a carbon-carbon double bond, one carbon atom of said double bond being tertiary (cf. British Patent 848,397).
  • an olefin having a carbon-carbon double bond one carbon atom of said double bond being tertiary (cf. British Patent 848,397).
  • Common to all of these methods is that even though they imply a certain improvement as to stability to chlorine separation, the result is far from satisfactory.
  • sodium metasilicate pentahydrate in detergents an uncontrolled discharge of chlorine gas therefore still is a production-technical problem for the industries producing the detergents and also an important practical problem for the consumer because of chlorine smell and lower bleaching effects.
  • This invention thus relates to a detergent composition
  • a detergent composition comprising alkali metal phosphate, alkali metal silicate, a surfactant, a chlorinated triazine trione of formula (1) wherein X is Cl, Na or K, or when X is Na, the dihydrate thereof, and optionally conventional additives.
  • Said composition is characterized in that the chlorinated triazine trione of formula (I) is in the form of granules, said granules having a size of about 0.5 to 5 mm and being coated with a thin hydrophobic layer of a diester of phthalic acid or adipic acid with an alcohol having 4-18 carbon atoms in an amount of 3-9% by weight, calculated on the amount of chlorinated triazine trione of formula (I).
  • the invention further relates to an agent for producing the detergent composition, said agent being characterized in that it consists of granules of chlorinated triazine trione of formula (I) wherein X is CL, Na or K, or the dihydrate of the triazine trione of formula (I) when X is Na, said granules having a size of about 0.5 to 5 mm and being coated with a thin hydrophobic layer of a diester of phthalic acid or adipic acid with an alcohol having 4-18 carbon atoms in an amount of 3-9% by weight, calculated on the amount of the chlorinated triazine trione of formula (I).
  • composition according to the invention comprise a machine dish washing detergent composition and an industrial detergent composition, respectively.
  • the surface-treatment of the chlorinated triazine trione is preferably performed such that the hydrophobic substance in liquid form or dissolved in a readily volatile solvent is added by portions under some kind of agitation to the granulate chlorinated triazine trione which is thereby coated with a thin film of hydrophobic material effectively protecting the labile chlorine compound from contact with water.
  • the hydrophobic film-forming substances utilized in the surface-treatment are diesters of certain carboxylic acids, particularly phthalic acid or adipic acid, which surprisingly have proved to yield excellent results.
  • the diesters preferably utilized in the invention are diesters of phthalic acid or adipic acid with an alcohol having 4-18 carbon atoms, preferably a straight or branched alcohol having 6-12 carbon atoms.
  • the following diesters have proved to be particularly useful:
  • the most important physical property required in the diesters utilized for the surface-treatment is that they shall be sufficiently water-repellent in order that also a thin layer of the diester shall provide a fully satisfactory moisture protection for the enclosed chlorine compound. Further, it is advantageous if the diester is liquid at room temperature or has a melting point not too far above said temperature, preferably below 70°C. Use can also be made of diesters having a higher melting point, in which case these are first dissolved in a volatile solvent whereupon the surface-treatment proper is performed and the solvent is finally driven off by heating of the granulate surface-treated product.
  • the diesters Naturally, it is also of great importance for the diesters to have a good adhesion to the granulate chlorine compound.
  • the chlorinated triazine compounds of formula I comprise
  • a complex between K-dichlorocyanurate and trichloroisocyanuric acid is also well suited for use with the present invention.
  • the surface-treatment provides an effect already an astonishingly small amounts of the hydrophobic substance. For most of the substances tested a content of 3-9% by weight calculated on the chlorinated triazine trione has proved to be sufficient. In most cases it has even been found disadvantageous to exceed that amount as this results in the surface-treated product becoming sticky and having a tendency of aggregating.
  • a machine dish washing detergent composition being an embodiment of the present invention has the following constitution as regards its essential components (the percentages are percentages by weight):
  • An industrial detergent composition being another embodiment of the present invention has the following constitution (the percentages are percentages by weight):
  • Example 3 it is possible to produce with the aid of the above-described surface-treating method a detergent composition based on sodium metasilicate pentahydrate which is at least equally stable to chlorine separation as a corresponding product based on anhydrous sodium metasilicate and a non-treated organic chlorine compound.
  • the amount stated of hydrophobic material for the surface treatment usually 5-8% of the amount of organic chlorine compound, usually constitutes but 0.05­0.25% of the total detergent composition.
  • the additional cost of said raw product and of the extra operation the surface treatment involves, is small compared with the savings in raw material costs realized by turning from anhydrous metasilicate to the pentahydrate thereof.
  • Another advantage gained by the surface-treating method indicated thus resides in the possibility of being able to replace the anhydrous metasilicate in detergents with the corresponding pentahydrate, retaining the stability to chlorine separation of the detergents.
  • An alternative application of the surface-treating method is to provide compositions based on anhydrous metasilicate and a surface-treated organic chlorine compound, said compositions being extremely stable to chlorine separation.
  • such a formulation will be relatively expensive and may probably be used only for special purposes.
  • the surface-treating agent was added by portions under vigorous agitation to the granulate chlorine compound. After finished addition the agitation was continued for a further 2-3 minutes. Low viscous substances were added at room temperature whereas high viscous substances as well as solid compounds were first heated to' suitable viscosity. The surface treating agent was added in an amount of 7%, and in some cases also 5%, calculated on the chlorine compound. A reference test was made, in which the surface-treating agent was replaced by soda which is totally inert in this connection.
  • the chlorine content of the various dish washing detergent compositions which thus differ only with regard to the surface-treatment of sodium dichloroisocyanurate, was determined as a function of the storage time.
  • the surface-treating agent was added by portions under vigorous agitation to the granulate chlorine compound. After finished addition agitation was continued for a further 2-3 minutes. Low viscous substances were hereby added at room temperature whereas high viscous substances as well as solid compounds were first heated to a suitable viscosity. The surface-treating agent was added in an amount of 6%, calculated on the chlorine compound. A reference test was made in which the surface-treating agent had been replaced by soda which is entirely inert in this connection.
  • the chlorine content of the different machine dish washing detergent compositions which thus differ only with regard to the surface-treatment of trichloroisocyanuric acid, was determined as a function of the storage time.
  • the effect of a surface-treatment of sodium dichloroisocyanurate for detergents stored at 30°C/85% relative moisture was examined.
  • the samples are stored in board cartons treated with polyethylene.
  • the chlorine content was determined by titration according to the iodine-thiosulphate method.
  • the surface-treating agent was added by portions under vigorous agitation to the granulate chlorine compound. After finished addition agitation was continued for a further 2-3 minutes. Low viscous substances were hereby added at room temperature whereas high viscous substances as well as solid compounds were first heated to a suitable viscosity. The surface treating agent was added in an amount of 7%, calculated on the chlorine compound. A reference test was made, in which the surface treating agent was replaced by soda which is entirely inert in this connection.
  • the chlorine content of the different detergent compositions which thus differed only with regard to the surface-treatment of sodium dichloroisocyanurate, was determined as a function of the storage time.

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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)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (8)

1. Reinigungsmittelzusammensetzung, umfassend Alkalimetallphosphat, Alkalimetallsilikat, einen oberflächenaktiven Stoff, ein chloriertes Triazintrion der Formel
Figure imgb0013
in der X=CI, Na oder K, oder, wenn X=Na, das Dihydrat davon, sowie falls erwünscht herkömmliche Zusätze, dadurch gekennzeichnet, dass das chlorierte Triazintrion der Formel (I) die Form von Körnchen aufweist, die eine Grösse von etwa 0,5-5 mm besitzen und mit einer dünnen hydrophoben Schicht eines Diesters von Phthalsäure oder Adipinsäure mit einem Alkohol mit4-18 Kohlenstoffatomen in einer Menge von 3-9 Gew.-%,-bezogen auf die Menge des chlorierten Triazintrions der Formel (I), überzogen sind.
2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass der Alkohol ein geradkettiger oder verzweigt kettiger Alkohol mit 6-12 Kohlenstoffatomen ist.
3. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass die hydrophobe Schicht eine Fraktion von Diestern von Phthalsäure und Alkoholen mit 6-10 Kohlenstoffatomen, di-(2- Äthylhexyl)phthalat, Diisodecylphthalat, di-(2-Äthylhexyl)adipat und/oder Diisodecyladipat umfasst.
4. Geschirrspülmaschinen-Reinigungsmittelzusammensetzung nach einem oder mehreren der Ansprüche 1-3, dadurch gekennzeichnet, dass sie
25-60 Gew.-% Alkalimetallphosphat,
30-70 Gew.-% Alkalimetallsilikat,
0,5-3 Gew.-% eines oberflächenaktiven Stoffes,
1-5 Gew.-% chlorierten Triazintrions,
3-9 Gew.-% Diester, bezogen auf die Menge chlorierten Triazintrions,
0-40 Gew.-% herkömmlicher Zusätze umfasst.
5. Industrielle Reinigungsmittelzusammensetzung nach einem oder mehreren der Ansprüche 1-3, dadurch gekennzeichnet, dass sie
25-60 Gew.-% Alkalimetallphosphat,
20-70 Gew.-% Alkalimetallsilikat,
0-30 Gew.-% Alkalimetallhydroxyd,
0,5-3 Gew.-% eines oberflächenaktiven Stoffes,
1-10 Gew.-% chlorierten Triazintrions,
3-9 Gew.-% Diester, berechnet auf die Menge des chlorierten Triazintrions,
0-40 Gew.-% herkömmlicher Zusätze enthält.
6. Mittel zur Herstellung einer Reinigungsmittelzusammensetzung, dadurch gekennzeichnet, dass das Mittel Körnchen von chloriertem Triazintrion der Formel
Figure imgb0014
umfasst, wo X=CI, Na oder K, oder das Dihydrat des Triazintrions der Formel (1), wenn X=Na, wobei die genannten Körnchen eine Grösse von etwa 0,5-5 mm aufweisen und mit einer dünnen hydrophoben Schicht eines Diesters von Phthalsäure oder Adipinsäure mit einem Alkohol mit 4-18 Kohlenstoffatomen in einer Menge von 3-9 Gew.-%, bezogen auf die Menge des chlorierten Triazontrions der Formel (1), überzogen sind.
7. Mittel nach Anspruch 6, dadurch gekennzeichnet, dass der Alkohol ein geradkettiger oder verzweigt kettiger Alkohol mit 6-12 Kohlenstoffatomen ist.
8. Mittel nach Anspruch 6, dadurch gekennzeichnet, dass die hydrophobe Schicht eine Fraktion von Diestern von Phthalsäure und Alkoholen mit 6-10 Kohlenstoffatomen, di-(2-Äthylhexyl)phthalat, Diisodecylphthalat, di-(2-Äthylhexyl)adipat und/oder Diisodecyladipat umfasst.
EP80850189A 1980-12-11 1980-12-11 Gegen Chlorabspaltung stabile Reinigungsmittelzusammensetzungen und Mittel zu deren Herstellung Expired EP0054094B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT80850189T ATE14452T1 (de) 1980-12-11 1980-12-11 Gegen chlorabspaltung stabile reinigungsmittelzusammensetzungen und mittel zu deren herstellung.
DE8080850189T DE3070906D1 (en) 1980-12-11 1980-12-11 Detergent compositions stable to chlorine separation, and agents for producing same
EP80850189A EP0054094B1 (de) 1980-12-11 1980-12-11 Gegen Chlorabspaltung stabile Reinigungsmittelzusammensetzungen und Mittel zu deren Herstellung

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP80850189A EP0054094B1 (de) 1980-12-11 1980-12-11 Gegen Chlorabspaltung stabile Reinigungsmittelzusammensetzungen und Mittel zu deren Herstellung

Publications (2)

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EP0054094A1 EP0054094A1 (de) 1982-06-23
EP0054094B1 true EP0054094B1 (de) 1985-07-24

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2548684B1 (fr) * 1983-07-08 1986-08-22 Charbonnages Ste Chimique Compositions detergentes contenant un derive chloroisocyanurique convenant pour le lavage de la vaisselle en machine a laver et leur procede de preparation
FR2548683B1 (fr) * 1983-07-08 1986-02-21 Charbonnages Ste Chimique Nouvelles compositions de lessive convenant pour le lavage de la vaisselle en machine a laver

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL238043A (de) * 1958-04-14
US3390092A (en) * 1965-03-30 1968-06-25 Fmc Corp Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
US3761416A (en) * 1971-04-19 1973-09-25 Monsanto Co Composite particles and process for preparing same
IT1020170B (it) * 1973-10-06 1977-12-20 Benckiser Gmbh Joh A Detersivi a cloro stabile
ZA775615B (en) * 1976-10-26 1978-08-30 Stauffer Chemical Co Hard surface cleaning composition

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EP0054094A1 (de) 1982-06-23
DE3070906D1 (en) 1985-08-29
ATE14452T1 (de) 1985-08-15

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