EP0604366A1 - Formulation stable au stockage de mélanges d'azurants optiques - Google Patents

Formulation stable au stockage de mélanges d'azurants optiques Download PDF

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Publication number
EP0604366A1
EP0604366A1 EP93810877A EP93810877A EP0604366A1 EP 0604366 A1 EP0604366 A1 EP 0604366A1 EP 93810877 A EP93810877 A EP 93810877A EP 93810877 A EP93810877 A EP 93810877A EP 0604366 A1 EP0604366 A1 EP 0604366A1
Authority
EP
European Patent Office
Prior art keywords
weight
brightener
storage
stable
brightener formulation
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.)
Granted
Application number
EP93810877A
Other languages
German (de)
English (en)
Other versions
EP0604366B1 (fr
Inventor
Josef Zelger
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 EP0604366A1 publication Critical patent/EP0604366A1/fr
Application granted granted Critical
Publication of EP0604366B1 publication Critical patent/EP0604366B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D06L4/621—Optical bleaching or brightening in aqueous solvents with anionic brighteners
    • 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
    • D06L4/65—Optical bleaching or brightening with mixtures of optical brighteners
    • 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
    • D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners

Definitions

  • the present invention relates to storage-stable optical brightener formulations, a process for their preparation and their use.
  • Optical brighteners are usually marketed preferably in the form of aqueous solutions or suspensions.
  • aqueous solutions or suspensions e.g. the wet filter cake or the dry powder slurried with water.
  • the suspensions thus obtained are then mixed with dispersing and thickening agents to increase homogeneity, wettability and stability.
  • An electrolyte is often added as a further auxiliary.
  • the auxiliaries used hitherto could not prevent sedimentation of the brighteners and / or a high increase in viscosity, especially at high storage temperatures, over a longer period of time.
  • These new formulations are suspensions and are stable at a temperature of -5 ° C to 60 ° C for at least 6 months, preferably at 0 to 40 ° C for at least 6 months.
  • the compounds of formula (1) come as secondary or tertiary amino e.g. with C1-C4alkyl, C1-C4alkoxy, sulfo, halogen, cyano, or carboxy, one or more substituted phenylamine; Morpholine, piperidine, methylamine, ethylamine, propylamine, butylamine, ⁇ -hydroxyethylamine, ⁇ -hydroxypropylamine, ⁇ -cyanoethylamine, dimethylamine, diethylamine, dipropylamine, bis- ⁇ -hydroxyethylamine, N-methyl-N-ethylamine, N- Methyl-N- ⁇ -hydroxyethylamine, N-ethyl-N- ⁇ -hydroxyethylamine, N-methyl-N- ⁇ -hydroxypropylamine, N-ethyl-N- ⁇ -hydroxypropylamine, benzylamine, N- ⁇ -hydroxyethylbenzylamine, N
  • unsubstituted, mono- or disubstituted alkoxy examples include methoxy, ethoxy, n-propoxy, i-propoxy, butoxy, ⁇ -hydroxy-ethoxy, ⁇ -methoxy-ethoxy and ⁇ -ethoxy-ethoxy.
  • optical brighteners of the formula (1) in which X and Y, which may be identical or different, are phenylamino, which is optionally mono- or di-substituted by alkyl having 1 or 2 carbon atoms; further preferred radicals for X and Y are morpholino, alkylamino having 1 to 4 carbon atoms, which may be substituted by hydroxyl; or alkoxy with 1 to 4 carbon atoms. Damn preferably hydrogen or a salt-forming cation.
  • Optical brighteners of the formula (1) are particularly preferred, in which X and Y, which can be identical or different, are phenylamino, morpholino or alkylamino having 1 to 4 carbon atoms, which can be substituted by hydroxyl.
  • M is preferably hydrogen or a salt-forming cation.
  • optical brighteners of the formulas (1) are those of the formulas in which M represents an alkali metal ion, and in the case of this optical brightener a content of 0.05 to 5% by weight, based on the total weight of the slurry, of a strong electrolyte is expedient; and (3) where M denotes an alkali metal ion.
  • Particularly preferred brighteners are the compounds of the formulas (2).
  • halogens are fluorine, chlorine and bromine, but especially chlorine.
  • C1-C4-alkyl in the alkylamino radicals are unbranched and branched alkyl such as methyl, ethyl, n- and iso-propyl, n-, sec- and tert-butyl. These C1-C4 alkyls can in turn be substituted with e.g. Aryl- (phenyl, naphthyl), C1-C4 alkoxy, OH, halogen, sulfo or CN.
  • Salt-forming cations M are, for example, alkali metal, ammonium or amine salt ions.
  • Amine salt ions are preferred those of the formula H+NR1R2R3 in which R1, R2 and R3 independently of one another are alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl or in which R1 and R2 together are the addition to a 5-7-membered saturated nitrogen heterocycle , which may additionally contain a nitrogen or oxygen atom as a ring member, for example a piperidine, piperazine, pyrrolidine, imidazoline or morpholine ring, while R3 is hydrogen.
  • Preferred salt-forming cations are alkali metal cations, Na+ and K+ being particularly preferred.
  • electrolytes e.g. one or more alkali metal salts and salts of lower carboxylic acids can be used.
  • electrolytes are sodium sulfate, sodium phosphate, sodium carbonate, sodium formate or one of the corresponding potassium salts and mixtures of these electrolytes, and also small amounts of sodium chloride.
  • the carbonates, phosphates and formates are preferred.
  • the amount of electrolyte can be 0.05 to 15% by weight, preferably 0.1 to 5% by weight and particularly preferably 0.1 to 1.0% by weight, based on the total weight of the formulation.
  • anionic polysaccharides which can be used according to the invention belong to the group of modified polysaccharides which can be derived from cellulose, starch or from the heteropolysaccharides, which may contain further monosaccharides such as mannose and glucuronic acid in the side chains.
  • anionic polysaccharides are sodium alginate, carboxymethylated guar, carboxymethyl cellulose, carboxymethyl starch, carboxymethylated locust bean gum and, particularly preferably, xanthan, and also mixtures of these polysaccharides.
  • the amount of polysaccharide is 0 to 1% by weight, a range of 0 to 0.5% by weight being preferred and a range of 0.05-0.2% by weight being particularly preferred, in each case based on the total weight of the formulation . However, with very highly concentrated or very low concentrated formulations, these ranges can be exceeded.
  • Dispersants which can be used are those of the anionic or nonionic type. Examples include alkyl benzene, alkyl or Alkenylethersulfonatsalze, saturated or unsaturated fatty acids, alkyl or Alkylenethercarboxylsalze, sulfofatty or esters, Phosphatester, polyoxyethylene alkyl or alkenyl, polyoxyethylene alkyl vinyl ether, polyoxypropylene alkyl or alkenyl, Polyoxybutylenalkyl- or alkenyl ether, higher fatty acid or Alkylene oxide adducts, sucrose / fatty acid esters, fatty acid / glycol monoesters, alkylamine oxides and condensation products of aromatic sulfonic acids with formaldehyde as well as lignin sulfonates or mixtures of the above-mentioned dispersants.
  • condensation products of aromatic sulfonic acids with formaldehyde and lignin sulfonates are preferred.
  • Condensation products of naphthalenesulfonic acids or phenolsulfonic acids (benzene, cresolsulfonic acid) with formaldehyde and ditolyl ether sulfonic acids with formaldehyde are particularly preferred.
  • These condensation products are usually in the form of alkali metal, alkaline earth metal or ammonium salts.
  • the content of dispersant is 0.2 to 20% by weight, based on the total weight of the formulation, preferably 0.1 to 10% by weight and particularly preferably 0.2 to 5% by weight.
  • the brightener formulation according to the invention can optionally contain further additives; examples are preservatives such as chloroacetamide, triazine derivatives or benzoisothiazolines, Mg / Al silicates, odor improvers and antifreezes, e.g. Propylene glycol called.
  • preservatives such as chloroacetamide, triazine derivatives or benzoisothiazolines, Mg / Al silicates, odor improvers and antifreezes, e.g. Propylene glycol called.
  • Mg / Al silicates examples are bentonite, montmorillonite, zeolites and highly disperse silicas. They are usually added in an amount of 0.2-1% by weight, based on the total weight of the brightener formulation.
  • Formulations according to the invention are obtained by adding the moist presscakes or the dry powders of the anionic optical brighteners, which contain at least one sulfonic acid residue, in an amount of 15 to 60% by weight, preferably 15 to 45% by weight and particularly preferably 19-40 % By weight, based on the total weight of the formulation; with 0.01 to 1% by weight of anionic polysaccharide; 0.05 to 5 wt% electrolyte; 0.2 to 20 wt% dispersant; if necessary with further additives; as well as mixed with water and homogenized at room temperature or higher temperatures (20-100 ° C), e.g. by intensive stirring or with a dissolver disc. If necessary, wet grinding can also be connected.
  • the desired content of anionic optical brighteners in the suspension can be adjusted either by adding water, aqueous electrolyte, or further dry brightener powder to the moist filter cake. This setting can be made before, during or after the addition of the anionic polysaccharide.
  • the new optical brightener formulations are used primarily in the incorporation into detergents, e.g. by allowing the required amount of the optical brightener formulation according to the invention to flow in, from a container into a mixing device which contains a suspension of the detergent or the dispersant.
  • the present invention accordingly also relates to a process for the production of solid and liquid detergents, and to the detergents obtained thereafter, characterized in that e.g. a suspension for detergents of conventional detergents, mixed with an inventive suspension of brighteners, and dried.
  • the drying process can e.g. done by a spray drying process.
  • the brightener formulation according to the invention can be used for the production of liquid detergents.
  • Percentages refer to the total weight of the formulation.
  • the components listed below are mixed and homogenized with stirring at 20 ° C. 36.0% by weight of the optical brightener of the formula (2); 0.5 wt% NaCl; 1.0% by weight of the condensation product of ditolyl ether sulfonic acids with formaldehyde; 0.2% by weight chloroacetamide; 0.1% by weight of an anionic polysaccharide; Rest on 100% deionized water.
  • the brightener formulations obtained remain liquid and, after standing for two months at -5 ° C., room temperature or 40 ° C., do not form any deposits.
  • the components listed below are mixed and homogenized with stirring at 20 ° C. 19.0% by weight of the optical brightener of the formula (2); 5.0 wt% NaCl; 1.3% by weight Na2SO4; 0.01% by weight of the condensation product of ditolyl ether sulfonic acids with formaldehyde; 0.3 wt% chloroacetamide; 0.2% by weight of an anionic polysaccharide; Rest on 100% deionized water.
  • the brightener formulations obtained remain liquid and do not form any deposits after standing at room temperature or 40 ° C. for one month.
  • the components listed below are mixed and homogenized with stirring at 20 ° C. 19.0% by weight of the optical brightener of the formula (2); 2.0 wt% NaCl; 0.05% by weight of the condensation product of ditolyl ether sulfonic acids with formaldehyde; 0.3 wt% chloroacetamide; 0.2% by weight of an anionic polysaccharide; Rest on 100% deionized water.
  • the brightener formulations obtained remain liquid and do not form any deposits after standing at room temperature or 40 ° C. for one month.
  • the components listed below are mixed and homogenized with stirring at 20 ° C. 40.0% by weight of the optical brightener of the formula (2); 1.05 wt% NaCl; 0.25% by weight of the condensation product of ditolyl ether sulfonic acids with formaldehyde; Rest on 100% deionized water.
  • the brightener formulations obtained remain liquid and do not form any deposits after standing for one month at room temperature.
  • the components listed below are mixed and homogenized with stirring at 20 ° C. 40.0% by weight of the optical brightener of the formula (2); 2.1% by weight NaCl; 0.17% by weight of the condensation product of ditolyl ether sulfonic acids with formaldehyde; Rest on 100% deionized water.
  • the brightener formulations obtained remain liquid and do not form any deposits after standing for one month at room temperature.
  • the components listed below are mixed and homogenized with stirring at 20 ° C. 40.0% by weight of the optical brightener of the formula (2); 5.3% by weight NaCl; 0.08% by weight of the condensation product of ditolyl ether sulfonic acids with formaldehyde; Rest on 100% deionized water.
  • the brightener formulations obtained remain liquid and do not form any deposits after standing for one month at room temperature.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
EP93810877A 1992-12-22 1993-12-14 Formulation stable au stockage de mélanges d'azurants optiques Expired - Lifetime EP0604366B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH3940/92 1992-12-22
CH394092 1992-12-22
CH03940/92A CH686959A5 (de) 1992-12-22 1992-12-22 Lagerstabile Formulierung von optischen Aufhellern.

Publications (2)

Publication Number Publication Date
EP0604366A1 true EP0604366A1 (fr) 1994-06-29
EP0604366B1 EP0604366B1 (fr) 2001-08-29

Family

ID=4266761

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93810877A Expired - Lifetime EP0604366B1 (fr) 1992-12-22 1993-12-14 Formulation stable au stockage de mélanges d'azurants optiques

Country Status (12)

Country Link
US (1) US5429767A (fr)
EP (1) EP0604366B1 (fr)
JP (1) JP3542624B2 (fr)
KR (1) KR100302934B1 (fr)
AT (1) ATE204931T1 (fr)
BR (1) BR9305181A (fr)
CA (1) CA2111915A1 (fr)
CH (1) CH686959A5 (fr)
DE (1) DE59310203D1 (fr)
ES (1) ES2161709T3 (fr)
MX (1) MX9307731A (fr)
TW (1) TW240242B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0837124A3 (fr) * 1996-10-15 1999-01-20 Ciba SC Holding AG Formulation d'agent de blanchiment fluorescent
WO2004111330A1 (fr) * 2003-06-11 2004-12-23 Ciba Specialty Chemicals Holding Inc. Formulations de blanchiment fluorescentes stables au stockage

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5852015A (en) * 1997-01-27 1998-12-22 American Cyanamid Company Triazine containing anionic compounds useful as antiviral agents
ES2208855T3 (es) * 1996-10-10 2004-06-16 Ciba Specialty Chemicals Holding Inc. Dispersiones de blanqueantes opticos.
US6806366B2 (en) * 2001-02-02 2004-10-19 Wyeth Preparation and purification of antiviral disulfonic acid disodium salt
EP1392925A1 (fr) * 2001-05-29 2004-03-03 Ciba SC Holding AG Composition de blanchiment fluorescent du papier
US7531107B2 (en) * 2003-09-19 2009-05-12 Ciba Specialty Chemicals Corporation Aqueous solutions of fluorescent whitening agents
US20120255541A1 (en) * 2011-04-11 2012-10-11 Reynold Hendrickson Integrated Modular Mounting Apparatus

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2367803A1 (fr) * 1976-10-14 1978-05-12 Ciba Geigy Ag Procede pour fabriquer des azurant
EP0008669A1 (fr) * 1978-08-04 1980-03-19 Hoechst Aktiengesellschaft Préparations d'agents de blanchiment optique stables à la couleur et procédé pour leur fabrication
EP0033913A2 (fr) * 1980-02-07 1981-08-19 Hoechst Aktiengesellschaft Procédé de fabrication de préparations pigmentaires et leur utilisation
EP0235080A1 (fr) * 1986-01-31 1987-09-02 Ciba-Geigy Ag Adjuvant de teinture et son utilisation dans la teinture ou l'azurage optique de matériaux fibreux synthétiques contenant de l'azote
EP0323399A1 (fr) * 1987-11-27 1989-07-05 Ciba-Geigy Ag Dispersion d'agent de blanchiment optique
EP0345765A1 (fr) * 1988-06-08 1989-12-13 Ciba-Geigy Ag Procédé de fabrication de granulés
EP0542677A1 (fr) * 1991-11-07 1993-05-19 Ciba-Geigy Ag Formulation stable au stockage de mélanges d'azurants optiques

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4752298A (en) * 1985-11-25 1988-06-21 Ciba-Geigy Corporation Storage-stable formulations of water-insoluble or sparingly water-soluble dyes with electrolyte-sensitive thickeners: polyacrylic acid
US5205960A (en) * 1987-12-09 1993-04-27 S. C. Johnson & Son, Inc. Method of making clear, stable prespotter laundry detergent
BR9000850A (pt) * 1989-02-28 1991-02-05 Ciba Geigy Ag Formulacao aclaradora estavel a armazenagem,processo para sua preparacao e aplicacao
US5057236A (en) * 1990-06-20 1991-10-15 The Clorox Company Surfactant ion pair fluorescent whitener compositions
US5234617A (en) * 1992-04-20 1993-08-10 Kathleen B. Hunter Aqueous liquid bleach compositions with fluorescent whitening agent and polyvinyl pyrrolidone or polyvinyl alcohol

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2367803A1 (fr) * 1976-10-14 1978-05-12 Ciba Geigy Ag Procede pour fabriquer des azurant
EP0008669A1 (fr) * 1978-08-04 1980-03-19 Hoechst Aktiengesellschaft Préparations d'agents de blanchiment optique stables à la couleur et procédé pour leur fabrication
EP0033913A2 (fr) * 1980-02-07 1981-08-19 Hoechst Aktiengesellschaft Procédé de fabrication de préparations pigmentaires et leur utilisation
EP0235080A1 (fr) * 1986-01-31 1987-09-02 Ciba-Geigy Ag Adjuvant de teinture et son utilisation dans la teinture ou l'azurage optique de matériaux fibreux synthétiques contenant de l'azote
EP0323399A1 (fr) * 1987-11-27 1989-07-05 Ciba-Geigy Ag Dispersion d'agent de blanchiment optique
EP0345765A1 (fr) * 1988-06-08 1989-12-13 Ciba-Geigy Ag Procédé de fabrication de granulés
EP0542677A1 (fr) * 1991-11-07 1993-05-19 Ciba-Geigy Ag Formulation stable au stockage de mélanges d'azurants optiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 105, no. 18, 3 November 1986, Columbus, Ohio, US; abstract no. 154612z, ZWIERZYNSKI ET AL: "Preparation of uniform 1,3,5-triazine-based fluorescent brightener compositions" *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0837124A3 (fr) * 1996-10-15 1999-01-20 Ciba SC Holding AG Formulation d'agent de blanchiment fluorescent
WO2004111330A1 (fr) * 2003-06-11 2004-12-23 Ciba Specialty Chemicals Holding Inc. Formulations de blanchiment fluorescentes stables au stockage
AU2004247892B2 (en) * 2003-06-11 2009-09-17 Basf Se Storage-stable fluorescent whitener formulations

Also Published As

Publication number Publication date
US5429767A (en) 1995-07-04
DE59310203D1 (de) 2001-10-04
BR9305181A (pt) 1994-06-28
ATE204931T1 (de) 2001-09-15
KR100302934B1 (ko) 2001-12-15
JP3542624B2 (ja) 2004-07-14
MX9307731A (es) 1994-06-30
EP0604366B1 (fr) 2001-08-29
TW240242B (fr) 1995-02-11
CA2111915A1 (fr) 1994-06-23
ES2161709T3 (es) 2001-12-16
KR940015074A (ko) 1994-07-20
CH686959A5 (de) 1996-08-15
JPH06220353A (ja) 1994-08-09

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