EP0548019B1 - Storage-stable bleach dispersion - Google Patents

Storage-stable bleach dispersion Download PDF

Info

Publication number
EP0548019B1
EP0548019B1 EP92810974A EP92810974A EP0548019B1 EP 0548019 B1 EP0548019 B1 EP 0548019B1 EP 92810974 A EP92810974 A EP 92810974A EP 92810974 A EP92810974 A EP 92810974A EP 0548019 B1 EP0548019 B1 EP 0548019B1
Authority
EP
European Patent Office
Prior art keywords
weight
shelf life
long shelf
life according
dispersion
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
EP92810974A
Other languages
German (de)
French (fr)
Other versions
EP0548019A2 (en
EP0548019A3 (en
Inventor
Claude Dr. Eckhardt
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.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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 Ciba Geigy AG, Ciba Spezialitaetenchemie Holding AG filed Critical Ciba Geigy AG
Publication of EP0548019A2 publication Critical patent/EP0548019A2/en
Publication of EP0548019A3 publication Critical patent/EP0548019A3/en
Application granted granted Critical
Publication of EP0548019B1 publication Critical patent/EP0548019B1/en
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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • 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
    • C11D3/3947—Liquid compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D06L4/636—Optical bleaching or brightening in aqueous solvents with disperse brighteners

Definitions

  • the invention relates to a storage-stable bleach dispersion, which in addition to at least a peracid, a peracid-forming system or its salts, one or more optical brighteners of the bis-benzofuranyl type contains, as well as the production and use of these Bleach dispersion for simultaneous bleaching and lightening of fabrics in the Household and in industry, at temperatures from + 10 ° C or higher.
  • the invention thus relates to an aqueous storage-stable bleaching agent dispersion containing 2 to 70% by weight, based on the total weight of the formulation, one or more peracids, peracid-forming systems or their salts, and 0.01 to 1% by weight of an optical brightener or a mixture of optical brighteners, characterized in that the optical brighteners are bis-benzofuranyl brighteners of the formula (1) are in which R 1 and R 2 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, benzyloxy or phenoxy, R 3 C 1 -C 4 alkyl, halogen or phenyl, M hydrogen or an equivalent of a non-chromophoric cation and n is 1 to 4; that hydrogen peroxide, diperoxyalkyl dicarboxylic acids, phthaloamino peracids or sulfonyl pers acids are used as peracids; and that as peracid-
  • C 1 -C 4 alkyl and C 1 -C 4 alkoxy are methyl, ethyl, butyl and tert-butyl as well as methoxy, ethoxy and butoxy.
  • sodium and potassium are preferred for the alkali metal ions.
  • R 1 is hydrogen, methyl or methoxy and R 3 is methyl, ethyl or phenyl, the optical brighteners of the formulas (3), (4) and (5) is of particular importance.
  • the optical brightener content is 0.01 to 1% by weight, preferably 0.05 to 0.25 % By weight, based on the total weight of the formulation.
  • optical brighteners of formulas (1) to (5) are known and can e.g. according to EP-A-395 588.
  • the peracids present in the bleach dispersions, peracid-generating systems or their salts are in an amount of 2 to 70 wt.% And preferably in an amount of 5 to 40% by weight, based on the total weight of the Formulation, added.
  • Hydrogen peroxide comes into question as inorganic peracids.
  • Hydrogen peroxide and diperoxyalkyldicarboxylic acids such as that are preferred Diperoxydodecanedicarboxylic acid, or a mixture thereof.
  • Tetraacetylethylenediarnin TAED
  • NOBS Nonoyloxybenzenesulfonate
  • i-NOBS iso-nonoyloxybenzenesulfonate
  • Sulfonate phenyl benzoates can be used.
  • a catalyst or one Catalyst mixture can be added.
  • Suitable catalysts are, for example, transition metal compounds such as copper, cobalt and manganese compounds. Examples include CuSO 4 , cobalt-amine complexes or manganese complexes with multidentate ligands.
  • Suitable sulfonates are, for example, water-soluble salts of alkylphenyl sulfonates, paraffin sulfonates, ⁇ -olefin sulfonates, fatty acid monoglycerol sulfonates, 2-acyloxy-alkane-1-sulfonates and ⁇ -alkyloxy-alkane sulfonates, as mentioned in GB-A-2 141 754.
  • Examples include sodium pentadecyl sulfonate or dioctyl sulfosuccinate, and especially the C 9 -C 15 alkylphenyl sulfonates.
  • nonionic surfactants are compounds which are characterized by the Condensation of ethylene oxide, propylene oxide or a mixture of both with one Hydrocarbon bearing an active hydrogen atom is formed.
  • alkyl or alkylene, mono- or polyglucosides are suitable. These preferably have alkyl or alkylene groups with 9 to 15 carbon atoms and 1-10 glucoside units. Examples include nonyldiglucoside and allyl (C 12 -C 15 ) poly (1-10) glucoside. Sorbitan esters such as polyoxyethylene sorbitan monopalmitate, fatty acid ethanolamides such as coconut fatty acid diethanolamide and fatty acid ethanolamine oxides such as tetradecylamine oxide can also be used.
  • Saturated and unsaturated carboxylic acids such as e.g. Oil, caprine, Lauric, myristic, coconut, palm kernel acid or salts thereof, e.g. the sodium, Potassium or ammonium salts are used, the coconut fatty acid derivatives are particularly preferred.
  • Examples of the group of phosphonates and polyphosphonates are e.g. Aminotrimethylphosphonic acid, Aminotriethylphosphonic acid, ethylenediaminetetramethylphosphonic acid and diethylenediaminetetramethylphosphonic acid and compounds such as they are described in US-A4 321 165.
  • additives such as further surfactants, Emulsifiers, thickeners, foam regulators, stabilizers, odor improvers, Sequestering agents, salts or dyes.
  • the bleach dispersion is produced by using the optical brightener (s) as a moist press cake or dry powder with one or more peracids or peracid-forming systems together with water and possibly other additives mixed and homogenized.
  • the bleach dispersion thus obtained is for months stable and does not sediment.
  • the optical brightener can be incorporated without visible sedimentation and its After neutralizing the oxidizing agent with hydrosulfite, the amount is determined spectroscopically to 100% of the amount used. The dispersion obtained is stable.
  • the bleach dispersions according to Examples 1 and 2 are at 14 days stored at a temperature of 20 ° C in the dark. When determining the Optical brightener content in both cases results in a content of 100% of the Baseline.
  • the optical brightener content is 85% after 3 days at 26 ° C Output quantity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

A storage-stable bleach dispersion which, besides at least one peracid or the salts thereof, contains one or more optical brighteners of the bis-benzofuranyl type, and the production and use of this dispersion for the simultaneous bleaching and brightening, domestically or industrially, of fabrics at temperatures of +10 DEG C or above are described.

Description

Die Erfindung betrifft eine lagerstabile Bleichmittel-Dispersion, die neben mindestens einer Persäure, eines Persäurebildenden Systems oder deren Salzen, einen oder mehrere optische Aufheller vom Bis-benzofuranyl-Typ enthält, sowie die Herstellung und Verwendung dieser Bleichmittel-Dispersion zum gleichzeitigen Bleichen und Aufhellen von Geweben im Haushalt und in der Industrie, bei Temperaturen ab +10°C oder höher.The invention relates to a storage-stable bleach dispersion, which in addition to at least a peracid, a peracid-forming system or its salts, one or more optical brighteners of the bis-benzofuranyl type contains, as well as the production and use of these Bleach dispersion for simultaneous bleaching and lightening of fabrics in the Household and in industry, at temperatures from + 10 ° C or higher.

Kombinationen von optischen Aufhellern mit Persäuren sind bereits vielfach im Einsatz. Durch den Wunsch bunte Textilien nicht mehr separat zu waschen, sowie aus Energiespar-Gründen, wird in vielen Ländern die Wäsche nicht mehr bei 90 bis 95°C oder durch Kochen sondern bei tieferen Temperaturen gewaschen bzw. gebleicht. Um bei diesen Temperaturen gute Bleicheffekte zu erzielen, war man gezwungen zu Persäuren mit stärkerer Bleichwirkung überzugehen (EP-A-145 438, GB-2 141 754, GB-2 141 755, US-4 028 263). Insbesondere werden Bleichmittel, z.B. flüssige Bleichmittel-Formulierungen angeboten, die separat dem Waschbad zugegeben werden. Diese Produkte enthalten hohe Konzentrationen an Oxidationsmitteln, wie z.B. Persäuren, die konventionelle optische Aufheller im Waschbad zerstören können.Combinations of optical brighteners with peracids are already widely used. Due to the desire not to wash colored textiles separately, as well as for energy saving reasons, in many countries the laundry is no longer at 90 to 95 ° C or through Cooking but washed or bleached at lower temperatures. To be with these To achieve good bleaching effects at temperatures, one was forced to use peracids more bleaching effect (EP-A-145 438, GB-2 141 754, GB-2 141 755, U.S. 4,028,263). In particular, bleaches, e.g. liquid bleach formulations offered, which are added separately to the wash bath. This Products contain high concentrations of oxidizing agents, e.g. Peracids can destroy conventional optical brighteners in the wash bath.

Es wurde nun gefunden, dass Bis-benzofuranyl-Verbindungen, die am heterocyclischen Ring substituiert sind, überlegene optische Aufhelleigenschaften zeigen und in flüssigen Bleichmittel-Dispersionen eine ausgezeichnete Stabilität gegenüber den zugesetzten Persäuren aufweisen. Diese speziellen Bis-benzofuranyl-Verbindungen können in konzentrierte Bleichmittel eingearbeitet werden. Sie zeigen darin gute Aufhelleffekte und sind bei 20°C über Monate stabil oder werden höchstens in einer in der Praxis nicht störenden Menge abgebaut.It has now been found that bis-benzofuranyl compounds that are heterocyclic Ring substituted, show superior optical brightening properties and in liquid Bleach dispersions have excellent stability against the added Have peracids. These special bis-benzofuranyl compounds can be found in concentrated bleach can be incorporated. They show good lightening effects and are stable at 20 ° C for months or at most will not be in practice in one disruptive amount reduced.

Diese speziellen Bis-benzofuranyl-Verbindungen sind teilweise als Komponenten eines flüssigen Waschmittel in EP-A-394998 beschrieben. Das flüssige Waschmittel kann auch Bleichmittel, vorzugsweise Perborat, enthalten. In EP-A-364027 sind andere Bis-benzofuranyl-Verbindungen als Komponenten einer Bleichmittel-Dispersion offenbart. These special bis-benzofuranyl compounds are partly as components of one liquid detergent described in EP-A-394998. The liquid detergent can also Bleach, preferably perborate, contain. There are others in EP-A-364027 Bis-benzofuranyl compounds as components of a bleach dispersion disclosed.

Gegenstand der Erfindung ist somit eine wässrige lagerstabile Bleichmittel-Dispersion enthaltend 2 bis 70 Gew.%, bezogen auf das Gesamtgewicht der Formulierung, einer oder mehrerer Persäuren, persäurebildender Systeme oder deren Salze, sowie 0,01 bis 1 Gew.% eines optischen Aufhellers oder einer Mischung von optischen Aufhellern, dadurch gekennzeichnet, dass die optischen Aufheller Bis-benzofuranyl-Aufheller der Formel (1)

Figure 00020001
sind, worin R1 und R2 unabhängig voneinander Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, Halogen, Benzyloxy oder Phenoxy, R3 C1-C4-Alkyl, Halogen oder Phenyl, M Wasserstoff oder ein Äquivalent eines nicht chromophoren Kations und n 1 bis 4 bedeuten; dass als Persäuren Wasserstoffperoxid, Diperoxyalkyldicarbonsäuren, Phthaloaminopersäuren oder Sulfonylpersäuren verwendet werden; und dass als persäurebildende Systeme oder deren Salze, Tetraacetylethylendiamin, Salze des Nonoyloxybenzolsulfonats, des iso-Nonoyloxybenzolsulfonats oder Sulfonat-phenylbenzoate verwendet werden.The invention thus relates to an aqueous storage-stable bleaching agent dispersion containing 2 to 70% by weight, based on the total weight of the formulation, one or more peracids, peracid-forming systems or their salts, and 0.01 to 1% by weight of an optical brightener or a mixture of optical brighteners, characterized in that the optical brighteners are bis-benzofuranyl brighteners of the formula (1)
Figure 00020001
are in which R 1 and R 2 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, benzyloxy or phenoxy, R 3 C 1 -C 4 alkyl, halogen or phenyl, M hydrogen or an equivalent of a non-chromophoric cation and n is 1 to 4; that hydrogen peroxide, diperoxyalkyl dicarboxylic acids, phthaloamino peracids or sulfonyl pers acids are used as peracids; and that as peracid-forming systems or their salts, tetraacetylethylenediamine, salts of nonoyloxybenzenesulfonate, iso-nonoyloxybenzenesulfonate or sulfonate-phenylbenzoates are used.

Bevorzugte Bleichmittel enthalten einen optischen Aufheller der Formel (2)

Figure 00020002
worin

  • R1 Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, Halogen, Benzyloxy oder Phenoxy und
  • R3 C1-C4-Alkyl, Halogen oder Phenyl und
  • M Wasserstoff, Alkalimetallion oder Ammoniumion
    • bedeutet.Preferred bleaching agents contain an optical brightener of the formula (2)
    Figure 00020002
    wherein
  • R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, benzyloxy or phenoxy and
  • R 3 is C 1 -C 4 alkyl, halogen or phenyl and
  • M is hydrogen, alkali metal ion or ammonium ion
    • means.

    Beispiele für C1-C4-Alkyl und C1-C4-Alkoxy sind Methyl, Ethyl, Butyl und tert-Butyl sowie Methoxy, Ethoxy und Butoxy. Bei den Alkalimetallionen sind aus praktischen Überlegungen Natrium und Kalium bevorzugt. Examples of C 1 -C 4 alkyl and C 1 -C 4 alkoxy are methyl, ethyl, butyl and tert-butyl as well as methoxy, ethoxy and butoxy. For practical reasons, sodium and potassium are preferred for the alkali metal ions.

    In besonders bevorzugten optischen Aufhellern der Formel (2) steht R1 für Wasserstoff, Methyl oder Methoxy und R3 für Methyl, Ethyl oder Phenyl, wobei den optischen Aufhellern der Formeln (3), (4) und (5)

    Figure 00030001
    Figure 00030002
    Figure 00030003
    besondere Bedeutung zukommt.In particularly preferred optical brighteners of the formula (2), R 1 is hydrogen, methyl or methoxy and R 3 is methyl, ethyl or phenyl, the optical brighteners of the formulas (3), (4) and (5)
    Figure 00030001
    Figure 00030002
    Figure 00030003
    is of particular importance.

    Der Gehalt an optischem Aufheller beträgt 0,01 bis 1 Gew.%, vorzugsweise 0,05 bis 0,25 Gew.%, bezogen auf das Gesamtgewicht der Formulierung.The optical brightener content is 0.01 to 1% by weight, preferably 0.05 to 0.25 % By weight, based on the total weight of the formulation.

    Die optischen Aufheller der Formeln (1) bis (5) sind bekannt und können z.B. gemäss EP-A-395 588 hergestellt werden.The optical brighteners of formulas (1) to (5) are known and can e.g. according to EP-A-395 588.

    Die in den Bleichmittel-Dispersionen vorhandenen Persäuren, persäurebildenden Systeme oder deren Salze werden in einer Menge von 2 bis 70 Gew.% und bevorzugt in einer Menge von 5 bis 40 Gew.%, bezogen auf das Gesamtgewicht der Formulierung, zugesetzt.The peracids present in the bleach dispersions, peracid-generating systems or their salts are in an amount of 2 to 70 wt.% And preferably in an amount of 5 to 40% by weight, based on the total weight of the Formulation, added.

    Als anorganischen Persäuren kommt in Frage Wasserstoffperoxid.Hydrogen peroxide comes into question as inorganic peracids.

    Es können jedoch auch organische Systeme die eine oder mehrere Peroxideruppen, wie z-B.

    Figure 00030004
    enthalten eingesetzt werden. Beispiele hiefür sind :

    • Diperoxyalkyldicarbonsäuren der allgemeinen Formel
      Figure 00040001
      worin R' = Wasserstoff oder C1-C4-Alkyl und n = 5 bis 15 ist,
    • Phthaloaminopersäuren wie sie z.B. in der EP-A-325 288 beschrieben sind, und
    • Sulfonylpersäuren wie sie z.B. in der US-A-5 004 558 und US-A-4 822 510 beschrieben sind.
    However, organic systems can also contain one or more peroxide groups, such as, for example.
    Figure 00030004
    included. Examples are:
    • Diperoxyalkyldicarboxylic acids of the general formula
      Figure 00040001
      wherein R '= hydrogen or C 1 -C 4 alkyl and n = 5 to 15,
    • Phthaloamino acids as described, for example, in EP-A-325 288, and
    • Sulfonyl peracids as described, for example, in US-A-5 004 558 and US-A-4 822 510.

    Bevorzugt sind hierbei Wasserstoffperoxid und Diperoxyalkyldicarbonsäuren, wie die Diperoxydodecandicarbonsäure, oder Mischung davon.Hydrogen peroxide and diperoxyalkyldicarboxylic acids such as that are preferred Diperoxydodecanedicarboxylic acid, or a mixture thereof.

    Anstelle der Persäuren oder zu deren Unterstützung können als persäurebildende Systeme Tetraacetylethylendiarnin (TAED), Salze des Nonoyloxybenzolsulfonats (NOBS), des iso-Nonoyloxybenzolsulfonats (i-NOBS) oder Sulfonat-phenylbenzoate verwendet werden.Instead of the peracids or to support them can be used as peracid-forming systems Tetraacetylethylenediarnin (TAED), salts of Nonoyloxybenzenesulfonate (NOBS), iso-nonoyloxybenzenesulfonate (i-NOBS) or Sulfonate phenyl benzoates can be used.

    Zur Aktivierung der Persäuren können 0,01 bis 5 Gew.% und bevorzugt 0,05 bis 2 Gew.%, bezogen auf das Gesamtgewicht der Formulierungen, eines Katalysators oder eines Katalysatorengemisches zugesetzt werden.To activate the peracids, 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the formulations, a catalyst or one Catalyst mixture can be added.

    Geeignete Katalysatoren sind z.B. Übergangsmetallverbindungen wie Kupfer-, Kobalt- und Mangan-Verbindungen. Als Beispiele seien CuSO4, Kobalt-Amin-Komplexe oder Mangan-Komplexe mit mehrzähnigen Liganden genannt.Suitable catalysts are, for example, transition metal compounds such as copper, cobalt and manganese compounds. Examples include CuSO 4 , cobalt-amine complexes or manganese complexes with multidentate ligands.

    Die Bleichmittel-Dispersion kann darüberhinaus noch weitere Zusätze enthalten wie :

  • a) 0 bis 10 Gew.%, vorzugsweise 3 bis 7 Gew.% eines oder mehrerer Sulfonate,
  • b) 0 bis 10 Gew.%, vorzugsweise 1 bis 8 Gew.% eines oder mehrerer nichtionischer Tenside,
  • c) 0 bis 5 Gew.%, vorzugsweise 0 bis 3 Gew.% einer oder mehrerer Fettsäuren und
  • d) 0 bis 1 Gew.%, vorzugsweise 0 bis 0,5 Gew.% eines oder mehrerer Phosphonate.
    • The bleach dispersion can also contain other additives such as:
  • a) 0 to 10% by weight, preferably 3 to 7% by weight, of one or more sulfonates,
  • b) 0 to 10% by weight, preferably 1 to 8% by weight, of one or more nonionic surfactants,
  • c) 0 to 5% by weight, preferably 0 to 3% by weight, of one or more fatty acids and
  • d) 0 to 1% by weight, preferably 0 to 0.5% by weight, of one or more phosphonates.

    • In Frage kommende Sulfonate sind z.B. wasserlösliche Salze von Alkylphenylsulfonaten, Paraffinsulfonaten, α-Olefinsulfonaten, Fettsäuremonoglycerinsulfonaten, 2-Acyloxy-Alkan-1-sulfonaten und β-Alkyloxy-Alkansulfonaten, wie sie in der GB-A-2 141 754 genannt sind. Beispielhaft seien Natriumpentadecylsulfonat oder Sulfobernsteinsäuredioctylester und besonders die C9-C15-Alkylphenylsulfonate genannt.Suitable sulfonates are, for example, water-soluble salts of alkylphenyl sulfonates, paraffin sulfonates, α-olefin sulfonates, fatty acid monoglycerol sulfonates, 2-acyloxy-alkane-1-sulfonates and β-alkyloxy-alkane sulfonates, as mentioned in GB-A-2 141 754. Examples include sodium pentadecyl sulfonate or dioctyl sulfosuccinate, and especially the C 9 -C 15 alkylphenyl sulfonates.

    Als Beispiele für nichtionische Tenside seien Verbindungen genannt, die durch die Kondensation von Ethylenoxid, Propylenoxid oder einem Gemisch aus beiden mit einem Kohlenwasserstoff, der ein aktives Wasserstoffatom trägt, entstehen.Examples of nonionic surfactants are compounds which are characterized by the Condensation of ethylene oxide, propylene oxide or a mixture of both with one Hydrocarbon bearing an active hydrogen atom is formed.

    Beispiele für Kohlenwasserstoffe mit einem aktiven Wasserstoffatom sind :

    • niedermolekulare, aliphatische Polyole,
    • gesättigte und/oder ungesättigte Fettalkohole mit 8 bis 22 C-Atomen,
    • Alkylphenole mit 4 bis 12 C-Atomen im Alkylrest,
    • Hydroxybiphenyle,
    • gesättigte und ungesättigte Fettamine mit 8 bis 22 C-Atomen,
    • gesättigte und ungesättigte Fettsäuren mit 8 bis 22 C-Atomen, oder
    • gesättigte und ungesättigte Fettsäure-(N,N-bis-hydroxyalkyl)amide,
    wobei auf 1 Mol der genannten Verbindungen vorzugsweise 4 bis 100 Mol Ethylenoxid und/oder Propylenoxid kommen. Als Beispiele seien die Fettalkoholethoxylate genannt. Es können aber auch Gemische dieser Umsetzungsprodukte untereinander verwendet werden. Diese Gemische erhält man durch Mischen einzelner Umsetzungsprodukte oder direkt durch Ethoxylierung eines Gemisches der den Umsetzungsprodukten zugrundeliegenden Verbindungen.Examples of hydrocarbons with an active hydrogen atom are:
    • low molecular weight, aliphatic polyols,
    • saturated and / or unsaturated fatty alcohols with 8 to 22 carbon atoms,
    • Alkylphenols with 4 to 12 carbon atoms in the alkyl radical,
    • Hydroxybiphenyls,
    • saturated and unsaturated fatty amines with 8 to 22 carbon atoms,
    • saturated and unsaturated fatty acids with 8 to 22 carbon atoms, or
    • saturated and unsaturated fatty acid (N, N-bis-hydroxyalkyl) amides,
    wherein for 1 mol of the compounds mentioned there are preferably 4 to 100 mol of ethylene oxide and / or propylene oxide. Examples include the fatty alcohol ethoxylates. Mixtures of these reaction products with one another can also be used. These mixtures are obtained by mixing individual reaction products or directly by ethoxylating a mixture of the compounds on which the reaction products are based.

    Desweiteren kommen Alkyl- oder Alkylen-, mono- oder polyglucoside in Frage. Diese weisen bevorzugt Alkyl- oder Alkylengruppen mit 9 bis 15 Kohlenstoffatomen sowie 1-10 Glucosideinheiten auf. Beispiele hierfür sind Nonyldiglucosid und Allyl(C12-C15)-poly(1-10)-glucosid. Weiterhin können Sorbitanester wie z.B. Polyoxyethylensorbitanmonopalmitat, Fettsäureethanolamide wie z.B. Kokosfettsäurediethanolamid und Fettsäureethanolaminoxide wie z.B. Tetradecylaminoxid verwendet werden.Furthermore, alkyl or alkylene, mono- or polyglucosides are suitable. These preferably have alkyl or alkylene groups with 9 to 15 carbon atoms and 1-10 glucoside units. Examples include nonyldiglucoside and allyl (C 12 -C 15 ) poly (1-10) glucoside. Sorbitan esters such as polyoxyethylene sorbitan monopalmitate, fatty acid ethanolamides such as coconut fatty acid diethanolamide and fatty acid ethanolamine oxides such as tetradecylamine oxide can also be used.

    Als Fettsäuren können gesättigte und ungesättigte Carbonsäuren wie z.B. Öl-, Kaprin-, Laurin-, Myristin-, Kokosnuss-, Palmkernsäure oder deren Salze, z.B. die Natrium-, Kalium- oder Ammoniumsalze, eingesetzt werden, wobei die Kokosfettsäurederivate besonders bevorzugt sind.Saturated and unsaturated carboxylic acids such as e.g. Oil, caprine, Lauric, myristic, coconut, palm kernel acid or salts thereof, e.g. the sodium, Potassium or ammonium salts are used, the coconut fatty acid derivatives are particularly preferred.

    Beispiele für die Gruppe der Phosphonate und Polyphosphonate sind z.B. Aminotrimethylphosphonsäure, Aminotriethylphosphonsäure, Ethylendiamintetramethylphosphonsäure und Diethylendiamintetramethylphosphonsäure sowie Verbindungen, wie sie in der US-A4 321 165 beschrieben sind.Examples of the group of phosphonates and polyphosphonates are e.g. Aminotrimethylphosphonic acid, Aminotriethylphosphonic acid, ethylenediaminetetramethylphosphonic acid and diethylenediaminetetramethylphosphonic acid and compounds such as they are described in US-A4 321 165.

    Neben diesen Zusätzen sind noch weitere Zusätze möglich, wie weitere Tenside, Emulgatoren, Verdicker, Schaumregulatoren, Stabilisatoren, Geruchsverbesserer, Sequestriermittel, Salze oder Farbstoffe.In addition to these additives, other additives are possible, such as further surfactants, Emulsifiers, thickeners, foam regulators, stabilizers, odor improvers, Sequestering agents, salts or dyes.

    Hergestellt wird die Bleichmittel-Dispersion indem man den oder die optischen Aufheller als feuchten Presskuchen oder trockenes Pulver mit einer oder mehreren Persäuren oder persäurebildenen Systemen zusammen mit Wasser und gegebenenfalls weiteren Zusätzen vermischt und homogenisiert. Die so erhaltene Bleichmittel-Dispersion ist über Monate stabil und sedimentiert nicht.The bleach dispersion is produced by using the optical brightener (s) as a moist press cake or dry powder with one or more peracids or peracid-forming systems together with water and possibly other additives mixed and homogenized. The bleach dispersion thus obtained is for months stable and does not sediment.

    Dank der erfindungsgemässen Kombination der Persäuren mit den spezifischen Aufhellern ist es möglich eine flüssige Bleichmitteldispersion anzubieten, die dem üblichen Standard entspricht, ab +10°C, bevorzugt im Bereich +10°C bis +60°C und besonders bevorzugt im Bereich +15°C bis +40°C, einsetzbar ist und zusätzlich eine erhöhte Lagerstabilität besitzt.Thanks to the combination of peracids according to the invention with the specific Brighteners it is possible to offer a liquid bleach dispersion that usual standard, from + 10 ° C, preferably in the range + 10 ° C to + 60 ° C and particularly preferably in the range from + 15 ° C to + 40 ° C, and in addition a has increased storage stability.

    In den nachfolgenden Beispielen beziehen sich Teile und Prozente auf das Gewicht. Die Temperatur ist in Celsiusgraden angegeben.In the examples below, parts and percentages are by weight. The Temperature is given in degrees Celsius.

    Die nachfolgenden Beispiele erläutern die Erfindung ohne sie darauf zu beschränken.The following examples illustrate the invention without restricting it thereto.

    Beispiel 1:Example 1:

    Es wird eine Formulierung mit folgender Zusammensetzung hergestellt :

    Figure 00060001
    Figure 00070001
    A formulation with the following composition is produced:
    Figure 00060001
    Figure 00070001

    Dazu werden alle Komponenten bis auf die Persäure und den optischen Aufheller unter Rühren in erwärmtes deionisiertes Wasser gegeben. Nach dem Abkühlen auf Raumtemperatur werden die Persäure und der optische Aufheller zugegeben.For this purpose, all components except the peracid and the optical brightener are under Stir into warmed deionized water. After cooling down The peracid and the optical brightener are added at room temperature.

    Der optische Aufheller lässt sich ohne sichtbares Sedimentieren einarbeiten und seine Menge wird, nach der Neutralisation des Oxidationsmittels mit Hydrosulfit, spektroskopisch zu 100 % der eingesetzten Menge bestimmt. Die erhaltene Dispersion ist stabil.The optical brightener can be incorporated without visible sedimentation and its After neutralizing the oxidizing agent with hydrosulfite, the amount is determined spectroscopically to 100% of the amount used. The dispersion obtained is stable.

    Beispiel 2:Example 2:

    Wie Beispiel 1, wobei jedoch als optischer Aufheller ein solcher der Formel (4)

    Figure 00070002
    verwendet wird. Man erhält ein gleich gutes Ergebnis.As example 1, but with an optical brightener of formula (4)
    Figure 00070002
    is used. You get an equally good result.

    Beispiel 3:Example 3:

    Die Bleichmittel-Dispersionen gemäss Beispielen 1 und 2 werden während 14 Tagen bei einer Temperatur von 20°C unter Lichtabschluss gelagert. Bei der Bestimmung des Gehaltes an optischen Aufheller ergibt sich in beiden Fällen ein Gehalt von 100% des Ausgangswertes.The bleach dispersions according to Examples 1 and 2 are at 14 days stored at a temperature of 20 ° C in the dark. When determining the Optical brightener content in both cases results in a content of 100% of the Baseline.

    Beispiel 4: (Vergleichsbeispiel)Example 4: (comparative example)

    Wie Beispiel 1, wobei jedoch als optischer Aufheller ein solcher der Formel (6)

    Figure 00080001
    (EP-A-345 765) verwendet wird. Nach 14-tägiger Lagerung bei 20°C unter Lichtabschluss liegt hier der Gehalt an optischen Aufheller nur noch bei 15% des Ausgangswertes.As example 1, but with an optical brightener of the formula (6)
    Figure 00080001
    (EP-A-345 765) is used. After 14 days of storage at 20 ° C with the exclusion of light, the optical brightener content here is only 15% of the initial value.

    Beispiel 5:Example 5:

    Es wird wie in den Beispielen 1, 2 und 4 verfahren, mit dem einzigen Unterschied, dass die Lagerung der Formulierung bei 37°C erfolgt. Bei der Bestimmung des Gehaltes an optischen Aufheller ergeben sich die in Tabelle 1 aufgeführten Werte. Optischer Aufheller Gehalt an optischem Aufheller nach 14 Tagen bei 37°C (3) 70% (4) 80% (6) 0% The procedure is as in Examples 1, 2 and 4, with the only difference that the formulation is stored at 37 ° C. When determining the optical brightener content, the values listed in Table 1 are obtained. Optical brightener Optical brightener content after 14 days at 37 ° C (3) 70% (4) 80% (6) 0%

    Beispiel 6:Example 6:

    Wie Beispiel 1, wobei jedoch als optischer Aufheller ein solcher der Formel (5)

    Figure 00080002
    verwendet wird.As example 1, but with an optical brightener of formula (5)
    Figure 00080002
    is used.

    Der Gehalt an optischem Aufheller beträgt nach 3 Tagen bei 26°C 85 % der Ausgangsmenge.The optical brightener content is 85% after 3 days at 26 ° C Output quantity.

    Claims (18)

    1. A bleach dispersion of long shelf life comprising 2 to 70% by weight, relative to the total weight of the formulation, of one or more peracids, peracid-forming systems or salts thereof and 0.01 to 1% by weight of a fluorescent whitener or a mixture of fluorescent whiteners, characterized in that the fluorescent whitener is a bis(benzofuranyl) whitener of the formula (1)
      Figure 00140001
      in which R1 and R2, independently of one another, are hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, benzyloxy or phenoxy, R3 is C1-C4alkyl, halogen or phenyl, M is hydrogen or one equivalent of a non-chromophoric cation and n is 1 to 4; and in that the peracids used are hydrogen peroxide, diperoxyalkyldicarboxylic acids, phthalaminoperacids or sulfonyl peracids; and in that the peracid-forming systems or salts thereof used are tetraacetylethylenediamine, salts of nonoyloxybenzenesulfonate, of isononoyloxybenzenesulfonate or sulfonatophenyl benzoates.
    2. A bleach dispersion of long shelf life according to claim 1, characterized in that it comprises a fluorescent whitener of the formula (2)
      Figure 00140002
      in which R1 is hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, benzyloxy or phenoxy and R3 is C1-C4alkyl, halogen or phenyl and M is hydrogen, an alkali metal ion or an ammonium ion.
    3. A bleach dispersion of long shelf life according to claim 2, characterized in that it comprises a fluorescent whitener of the formula (2)
      Figure 00150001
      in which R1 is hydrogen, methyl or methoxy and R3 is methyl, ethyl or phenyl and M is hydrogen or an alkali metal ion.
    4. A bleach dispersion of long shelf life according to claim 3, characterized in that it comprises a fluorescent whitener of the formula (3)
      Figure 00150002
    5. A bleach dispersion of long shelf life according to claim 3, characterized in that it comprises a fluorescent whitener of the formula (4)
      Figure 00150003
    6. A bleach dispersion of long shelf life according to claim 3, characterized in that it comprises a fluorescent whitener of the formula (5)
      Figure 00150004
    7. A bleach dispersion of long shelf life according to claim 1, characterized in that the fluorescent whitener content is 0.05 to 0.25% by weight, relative to the total weight of the formulation.
    8. A bleach dispersion of long shelf life according to claim 1, characterized in that the content of peracids, peracid-forming systems or salts thereof is 5 to 40% by weight, relative to the total weight of the formulation.
    9. A bleach dispersion of long shelf life according to claim 1, characterized in that the peracids used are hydrogen peroxide, diperoxydodecanedicarboxylic acid or a mixture of both.
    10. A bleach dispersion of long shelf life according to claim 1, characterized in that it contains 0.01 to 5% by weight, relative to the total weight of the formulation, of a catalyst or a catalyst mixture.
    11. A bleach dispersion of long shelf life according to claim 10, characterized in that it contains 0.05 to 2% by weight, relative to the total weight of the formulation, of a catalyst or a catalyst mixture.
    12. A bleach dispersion of long shelf life according to claim 10, characterized in that the catalyst is from the group of the transition metal compounds.
    13. A bleach dispersion of long shelf life according to claim 12, characterized in that the catalyst is a copper compound, cobalt compound or manganese compound.
    14. A bleach dispersion of high shelf life according to claim 13, characterized in that it comprises, relative to the total weight of the formulation,
      a) 0 to 10% by weight of one or more sulfonates,
      b) 0 to 10% by weight of one or more nonionic surfactants,
      c) 0 to 5% by weight of one or more fatty acids and
      d) 0 to 1% by weight of one or more phosphonates.
    15. A bleach dispersion of long shelf life according to claim 1, characterized in that it comprises, relative to the total weight of the formulation,
      a) 5 to 10% by weight of hydrogen peroxide,
      b) 3 to 7% by weight of diperoxydodecanedicarboxylic acid,
      c) 0.05 to 0.25% by weight of a fluorescent whitener of the formula (3), (4) or (5)
      Figure 00170001
      Figure 00170002
      Figure 00170003
      d) 0 to 7% by weight of a secondary alkyl sulfonate,
      e) 1 to 8% by weight of a nonionic alcohol ethoxylate,
      f) 0 to 3% by weight of a coconut fatty acid derivative,
      g) 0 to 0.5% by weight of a phosphonate.
    16. A bleach dispersion of long shelf life according to claim 1, characterized in that it comprises further additives, such as surfactants, emulsifiers, thickeners, foam regulators, stabilisers, odour improvers, sequestering agents, salts or dyes.
    17. A process for the preparation of a bleach dispersion according to claim 1, characterized in that it comprises mixing the fluorescent whitener or whiteners as a moist press cake or a dry powder with one or more peracids or the peracid-forming systems together with water and, if desired, further additives and homogenising the mixture.
    18. The use of the bleach dispersion according to claim 1 for bleaching textiles starting from 10°C.
    EP92810974A 1991-12-19 1992-12-10 Storage-stable bleach dispersion Expired - Lifetime EP0548019B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    CH377791 1991-12-19
    CH3777/91 1991-12-19

    Publications (3)

    Publication Number Publication Date
    EP0548019A2 EP0548019A2 (en) 1993-06-23
    EP0548019A3 EP0548019A3 (en) 1995-06-14
    EP0548019B1 true EP0548019B1 (en) 1998-06-24

    Family

    ID=4263268

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP92810974A Expired - Lifetime EP0548019B1 (en) 1991-12-19 1992-12-10 Storage-stable bleach dispersion

    Country Status (12)

    Country Link
    US (1) US5449477A (en)
    EP (1) EP0548019B1 (en)
    JP (1) JPH05271691A (en)
    KR (1) KR930013349A (en)
    AT (1) ATE167699T1 (en)
    AU (1) AU660747B2 (en)
    BR (1) BR9205072A (en)
    DE (1) DE59209385D1 (en)
    ES (1) ES2118804T3 (en)
    MX (1) MX9207050A (en)
    NZ (1) NZ245506A (en)
    ZA (1) ZA929832B (en)

    Families Citing this family (12)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CH684485A5 (en) * 1992-11-17 1994-09-30 Ciba Geigy Ag Liquid detergent.
    GB9224052D0 (en) * 1992-11-17 1993-01-06 Unilever Plc Non aqueous liquid detergent compositions
    US5968881A (en) * 1995-02-02 1999-10-19 The Procter & Gamble Company Phosphate built automatic dishwashing compositions comprising catalysts
    EP0832176B1 (en) * 1995-06-16 2001-07-11 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt catalysts
    WO1997000311A1 (en) * 1995-06-16 1997-01-03 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
    US5703034A (en) * 1995-10-30 1997-12-30 The Procter & Gamble Company Bleach catalyst particles
    GB9611063D0 (en) * 1996-05-28 1996-07-31 Warwick Int Group Concentrated alkaline isotropic detergent liquid with bleach
    DE19700799C2 (en) * 1997-01-13 1999-02-04 Henkel Kgaa Aqueous textile bleach
    US6584988B1 (en) * 1998-10-30 2003-07-01 Cognis Corp. Process for removing contaminants from water
    TWI400330B (en) 2005-12-28 2013-07-01 Kao Corp Liquid detergent
    JP5197949B2 (en) * 2006-12-21 2013-05-15 ライオン株式会社 Bleaching goods
    JP5342757B2 (en) * 2007-07-26 2013-11-13 ライオン株式会社 Liquid bleach composition

    Citations (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0293040A1 (en) * 1987-05-27 1988-11-30 The Procter & Gamble Company Liquid detergent containing solid peroxygen bleach

    Family Cites Families (30)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB1286459A (en) * 1968-12-12 1972-08-23 Unilever Ltd Detergent compositions
    BE787576A (en) * 1971-08-13 1973-02-14 Hoechst Ag BENZOFURANE DERIVATIVES AND THEIR USE AS OPTICAL BLASTERS
    US4002423A (en) * 1971-08-13 1977-01-11 Hoechst Aktiengesellschaft Benzofuran derivatives process for their preparation and their use as optical brighteners
    US3994879A (en) * 1972-12-18 1976-11-30 Hoechst Aktiengesellschaft Process for the preparation of benzofuran compounds
    US4028263A (en) * 1973-08-24 1977-06-07 Colgate-Palmolive Company Bleaching and brightening detergent composition
    DE2857161A1 (en) * 1977-06-29 1980-03-06 Procter & Gamble DETERGENT AND CLEANING AGENT
    GB8316760D0 (en) * 1983-06-20 1983-07-20 Unilever Plc Detergent bleach compositions
    GB2141755B (en) * 1983-06-20 1987-01-07 Unilever Plc Detergent bleach compositions
    GB8332682D0 (en) * 1983-12-07 1984-01-11 Procter & Gamble Laundry additive products
    US4659519A (en) * 1984-07-02 1987-04-21 The Clorox Company Process for synthesizing alkyl monoperoxysuccinic acid bleaching compositions
    GB8603961D0 (en) * 1986-02-18 1986-03-26 Interox Chemicals Ltd Concentrated liquid composition
    US4735740A (en) * 1986-10-03 1988-04-05 The Clorox Company Diperoxyacid precursors and method
    US5004558A (en) * 1986-11-03 1991-04-02 Monsanto Company Sulfone peroxycarboxylic acids
    US4778618A (en) * 1986-11-06 1988-10-18 The Clorox Company Glycolate ester peracid precursors
    ES2029345T3 (en) * 1987-08-26 1992-08-01 Ciba-Geigy Ag OPTICAL DISPERSION BLEACHERS.
    US5230820A (en) * 1987-11-23 1993-07-27 Ciba-Geigy Corporation Storage-stable bleaching detergents containing bis-benzofuranyl fluoescent whitening agents
    ES2065328T3 (en) * 1987-11-26 1995-02-16 Ciba Geigy Ag STABLE DETERGENTS CONTAINING OPTIC BLEACHES.
    DE3850232D1 (en) * 1987-12-23 1994-07-21 Ciba Geigy Stable detergents containing optical brighteners.
    IT1233846B (en) * 1988-01-20 1992-04-21 Ausimont Spa IMMEDIATE AROMATIC PEROXIDES
    EP0333248A3 (en) * 1988-03-17 1990-08-29 Unilever N.V. Bleach precursors and their use in bleaching and/or detergent composition
    US4822510A (en) * 1988-03-25 1989-04-18 Lever Brothers Company Stably suspended 4,4'-sulfonylbisperoxybenzoic acid bleach in an aqueous liquid
    US5030244A (en) * 1988-06-08 1991-07-09 Ciba-Geigy Corporation Preparation of granules of dyes, optical whiteners or photoactivators from an aqueous suspension of naphthalene sulfonic acid-formaldehyde condensate dispersant
    JPH0259406A (en) * 1988-08-25 1990-02-28 Sankyo Kasei Kk Production of anhydrous sodium sulfide crystal
    GB8824108D0 (en) * 1988-10-14 1988-11-23 Unilever Plc Bleaching & detergent compositions
    US5326491A (en) * 1989-04-28 1994-07-05 Ciba-Geigy Corporation Detergents containing certain sulfonated dibenzofuranylbiphenyls
    US5279772A (en) * 1989-04-28 1994-01-18 Ciba-Geigy Corporation Liquid detergents containing specifically disulfonated dibenzofuranyl-biphenyls as flourescent whitening agents
    ES2055399T3 (en) * 1989-04-28 1994-08-16 Ciba Geigy Ag DIBENZOFURANILBIFENILOS.
    EP0394998B1 (en) * 1989-04-28 1996-03-27 Ciba-Geigy Ag Liquid detergent
    US5078907A (en) * 1989-11-01 1992-01-07 Lever Brothers Company, Division Of Conopco, Inc. Unsymmetrical dicarboxylic esters as bleach precursors
    US5055218A (en) * 1990-04-13 1991-10-08 The Procter & Gamble Company Bleach granules containing an amidoperoxyacid

    Patent Citations (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0293040A1 (en) * 1987-05-27 1988-11-30 The Procter & Gamble Company Liquid detergent containing solid peroxygen bleach

    Also Published As

    Publication number Publication date
    JPH05271691A (en) 1993-10-19
    US5449477A (en) 1995-09-12
    ZA929832B (en) 1993-06-21
    EP0548019A2 (en) 1993-06-23
    DE59209385D1 (en) 1998-07-30
    AU3028392A (en) 1993-06-24
    ES2118804T3 (en) 1998-10-01
    AU660747B2 (en) 1995-07-06
    BR9205072A (en) 1993-06-22
    MX9207050A (en) 1993-06-01
    NZ245506A (en) 1994-12-22
    KR930013349A (en) 1993-07-21
    ATE167699T1 (en) 1998-07-15
    EP0548019A3 (en) 1995-06-14

    Similar Documents

    Publication Publication Date Title
    EP0548019B1 (en) Storage-stable bleach dispersion
    DE2422691A1 (en) STABLE BLEACHING AGENTS
    DE4493996B4 (en) New sulfonates, process for their preparation and their use in a bleaching composition
    EP0210952A1 (en) Aqueous, alkaline, silicate-containing composition for the bleaching of cellulosic fibres in the presence of percompounds
    EP0024340B1 (en) Washing process
    EP0011166B1 (en) Liquid, cold-stable detergent concentrate and its use
    EP0082823B1 (en) Process for bleaching fibrous materials with oligomers of phosphonic acids as stabilizing agents in alcaline, peroxide-containing bleaching baths
    CH642677A5 (en) Bleach and detergent.
    EP0172534A2 (en) Liquid cleaning agent
    EP0601967B1 (en) Liquid detergent composition
    DE2365172A1 (en) BLEACHING AGENTS FOR DETERGENTS AND DETERGENTS
    CH650764A5 (en) ALKYL-polyoxyalkylene CARBOXYLATE.
    EP0210132B2 (en) Aqueous, alkaline, silicate-containing composition for the bleaching of cellulosic fibres in the presence of percompounds
    DE2128945A1 (en) Bleach
    EP0011715B1 (en) Liquid, cold-stable two-component washing agent and washing process
    EP0409846A1 (en) Activators for inorganic percompounds
    EP0112801A1 (en) Magnesium complexes of oligomeric phosphonic-acid esters, process for their preparation and their use as stabilizers in bleaching baths containing alcaline peroxide
    DE2539349C2 (en) Laundry treatment agents
    DE1289815B (en) Stable aqueous bleach solution
    US2119523A (en) Pyrophosphate ester bleaching agent
    EP0116887A2 (en) Organic cyanamides compounds as activators for inorganic percompounds
    DE60133821T2 (en) METHOD FOR THE OPTICAL LIGHTING OF COTTON
    US3704262A (en) Surfactant for electrolyte-containing processing solutions
    EP0626944B1 (en) Thiodiglycol derivatives, process for producing them and their use for softening textiles
    DE1519479C3 (en) Process for the optical brightening of fiber material made of optionally esterified cellulose or of polyamide

    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: A2

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

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

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

    17P Request for examination filed

    Effective date: 19951110

    17Q First examination report despatched

    Effective date: 19960924

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: CIBA SC HOLDING AG

    RAP3 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC.

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    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 DK ES FR GB GR IT LI LU NL SE

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

    Ref country code: GR

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

    Effective date: 19980624

    REF Corresponds to:

    Ref document number: 167699

    Country of ref document: AT

    Date of ref document: 19980715

    Kind code of ref document: T

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    ET Fr: translation filed
    REF Corresponds to:

    Ref document number: 59209385

    Country of ref document: DE

    Date of ref document: 19980730

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

    Effective date: 19980713

    ITF It: translation for a ep patent filed

    Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

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

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 19980924

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 19980924

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2118804

    Country of ref document: ES

    Kind code of ref document: T3

    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: 19981210

    Ref country code: GB

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

    Effective date: 19981210

    Ref country code: AT

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

    Effective date: 19981210

    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: 19981231

    Ref country code: CH

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

    Effective date: 19981231

    Ref country code: BE

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

    Effective date: 19981231

    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
    BERE Be: lapsed

    Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC.

    Effective date: 19981231

    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: 19990701

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 19981210

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    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: 19990831

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

    Effective date: 19990701

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    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: 19991001

    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: 19991211

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20000114

    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

    Effective date: 20051210