US3663538A - Cationic derivatives of 4,4' - bis-(s-triazinylamino)-stilbene -2,2'-disulfonic acid,process for the preparation thereof and application as optical brighteners - Google Patents

Cationic derivatives of 4,4' - bis-(s-triazinylamino)-stilbene -2,2'-disulfonic acid,process for the preparation thereof and application as optical brighteners Download PDF

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US3663538A
US3663538A US839640A US3663538DA US3663538A US 3663538 A US3663538 A US 3663538A US 839640 A US839640 A US 839640A US 3663538D A US3663538D A US 3663538DA US 3663538 A US3663538 A US 3663538A
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Karl Heinz Lebkucher
Ehrenfried Nischwitz
Erich Schinzel
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/68—Triazinylamino stilbenes
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • 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

Definitions

  • Y and Z represent neutral or negatively charged substituents
  • M represents a cation.
  • the soluble alkali metal salts and equally the salts of the 4,4 bis (s triazinylamino) stilbene- 2,2-disulfonic acid with amines dissociate in aqueous solution to a large extent into their ions, and that also the free disulfonic acids are dissociated, at least partially, into hydrogen ions and brightener anions, provided they are soluble in water.
  • substrate ionic relation indicated in formula A is maintained. This is equally true for substrates such as cellulose fibers on which these brighteners are absorbed substantively, and for substrates with basic groups, such as polyamide and protein fibers on which the brightening anion is bound mainly in heteropolar manner on cationic centres.
  • anionic brighteners there may be distinguished such water-soluble derivatives of the 4,4- bis (s triazinylamino) stilbene 2,2 disulfonic acid in which the active brightener molecule is present as a
  • Y and Z represent electro-neutral bridge members and X represents an anion.
  • the present invention relates to compounds of the type B and to a process for their preparation, and it demonstrates the clear advantages on some fields of application of these cationic derivatives over the above-mentioned anionic brighteners.
  • the reaction product obtained is further condensed at temperatures of from about 40 to about 100 C., preferably at 40 to about C. with at least 2, preferably with 4 mols, of a diamine of the Formula III wherein A, R R and R have the meanings given above, the reaction product obtained is separated with 2 mols of the compound wherein R has the meaning given above and X represents a radical that may be split off as anion, in the form of an inner salt of the general Formula IV wherein R R R R R R R", A and A have the meanings given above, and the compounds of the Formula IV are reacted with at least 2 mols of a compound of the formula wherein R has the meaning given above and X represents a radical that may be split off as anion.
  • the sodium salt of the 4,4'-bis-(2,4"-dichloro-s-triazinylamino-(6") )-stilbene-2,2'-disulfonic acid obtained from 1 mol of 4,4'-diamino-stilbene-2,2-disulfonic acid and 2 mols of cyanuric acid chloride is combined, if the diarnines II and III are identical, with at least 4 mols, preferably with 6 mols, of this diamine.
  • the inner salts IV wherein R represents a lower alkyl group can also be precipitated from the strongly alkalineaqueous or aqueous-alcoholic solution of the sodium salts IVa by addition of 2 equivalents of an alkylating agent such as, for example, dimethyl sulfate. These salts too mu be easily determined analytically.
  • the aqueous solution of the sodium salts IVa is combined with such a quantity of acid that the internal salts of the Formula IV (R' zhydrogen) which have precipitated intermediately are dissolved again.
  • diamines of the Formulae II and III there may preferably be used:
  • N,N-diethyl-1,2-diaminoethane N,N-di-n-propyl-1,2-diaminoethane, N,N-di-n-butyl-1,2-diaminoethane, N,N-di-n-pentyl-1,2-diaminoethane, N,N-diethyl-N'-methyl-l,Z-diaminoethane, N,N,N'-triethyll ,Z-diaminoethane, N,N-di-n-butyl-N'-ethyl-1,2-diaminoethane, 1-diethylamino-Z-amino-n-propane,
  • the three last-mentioned substances are starting products for the preparation of compounds of the Formula I, wherein A or A are substituted by non-chromophoric groups, i.e by halogen atoms.
  • non-chromophoric groups i.e by halogen atoms.
  • Other non-chromophoric groups that may be used are cyano groups, lower alkoxy groups and lower carboxylic acid-alkyl ester groups.
  • the compounds I of the present invention wherein R and R represent hydrogen are obtained by stirring the internal salts IV in water and dissolving them by addition of 2 equivalents of acid. It is advantageous, in order to obtain completely clear and stable solutions, to increase the amount of acid slightly and to adjust to a pH-value of about 5.
  • AS acids strong inorganic acids, such as hydrochloric acid or sulfuric acid, may be used; organic acids, however, such as formic acid, acetic acid, propionic acid or oxalic acid, are also suitable.
  • the compounds of the Formula I may be obtained in solid form by evaporation of their aqueous solutions under mild conditions. In practice, however, concentrated brightener solutions are preferred to powders since they are easier to handle. Therefore, it is advantageous to dispense with the evaporation.
  • the content of the solutions of the compounds I is mostly referred to the internal salts IV.
  • the compounds I of the present invention wherein R and R represent a lower alkyl group or an aralkyl group, are prepared from the internal salts IV, wherein R represents hydrogen, by stirring the salts IV in water with 2 equivalents of sodium hydroxide solution and treating them with at least 4 to about 8 equivalents of an alkylating agent.
  • a (greater) excess of alkylating agent might be used, but is in general of no advantage.
  • alkylating agents there may be used the esters of sulfuric acid, such as dimethyl sulfate or diethylsulfate, or the esters of aromatic sulfonic acid, such as the p-toluene-sulfonic acidmethyl ester.
  • Alkyl or aralkyl halides such as methyl chloride, methyl bromide, ethyl bromide, butyl bromide, benzyl chloride and benzyl bromide may also be used as alkylating agents.
  • Some compounds of the general Formula I are relatively difficultly soluble in the presence of salts and precipitate from the alkylating solution. Their isolation is carried out in the usual manner by suction-filtering and washing with a solution of sodium chloride. If desired or required, a reprecipitation from water may be effected.
  • Concentrated aqueous solutions of the products I of the present invention may also be obtained by additlon of 2 equivalents of an inorganic and/or an organic acid to the internal salts IV wherein R" represents a lower alkyl u %ll'th6fm0l6, we have found that the compounds of the general Formula I of the present invention are especially suited as optical brighteners for fibrous material, 1n particular for cellulose materials and in an especially advantageous manner for the brightening of paper.
  • the compounds of the present invention which are either in liquid form or dissolved water, are added to the paper pulp in the hollander, optionally before the addition of other auxiliary agents such as, for example, rosin size, aluminium sulfate etc., and by mixing thoroughly the pulp in order to disperse the brightener homogeneously, before forming the sheets in generally known manner on a wire.
  • auxiliary agents such as, for example, rosin size, aluminium sulfate etc.
  • the compounds of the present invention are clearly superior, in their brightening effect, both in non-sized as in sized and loaded papers, to the anionic brighteners of the type A hitherto used.
  • the cationic brighteners of the present invention show an equally very good brightening effect when used in coating mixtures for paper.
  • the compounds of the general Formula I of the present invention show a particularly good brightening effect when used together with cationic softening agents for fabrics and knit fabrics of cellulose fibers and fibers of regenerated cellulose.
  • These laundry refining agents generally consist of fatty acid ammonium compounds, for example distearyl-dimethyl-ammonium chloride, and are used in laundry in the last rinsing operation in order to obtain soft and downy linen. By this treatment, however, the linen turns yellow to a certain degree. By addition of the compounds of the present invention, this yellowing can be avoided to a large extent.
  • anionic optical brighteners of type A are incompatible with cationic softening agents and are blocked in their action to a large extent.
  • the products of the present invention show, when applied onto cellulose fibers, very good brightening elfects, especially when used in a strongly acid medium, for example at a pH-value of 1 to 2.
  • the new cationic brightners may be used sucessfully together with auxiliary agents for the crease-proofing of cellulose fibers, for example with reactance resins, such as dimethylol-ethyleneurea, dimethylol-propylene-urea, dimethylol-monoalkylcarbamate and others. Particularly high degrees of whiteness are obtained if the condensation of the synthetic resins is effected at a pH-value of 1 to 2, as it is usual in moist or wet cross-linking.
  • EXAMPLE 1 A solution of 36.7 parts by weight of cyanuric acid chloride in 200 parts by volume of acetone was allowed to run into 700 parts by volume of ice water. To this suspension, a solution of 38.1 parts by weight of 4,4'-diamino-stilbene-2,2'-disulfonic acid (96.8% strength) in 400 parts by volume of water and 100 parts by volume of 2 N-sodium hydroxide solution was added dropwise, at a temperature in the range of from 0 to 5 C., and by simultaneous addition of about 90 parts by volume of 2 N- sodium carbonate solution, the pH-value was maintained at 2.5-3.5. When, by indirect diazotation no more diamino-stilbene-disulfonic acid could be detected, the reaction mixture was adjusted to a pH-value of 7 by means of 2 N-sodium carbonate solution.
  • the sodium salt was dissolved in 1500 parts by volume of water at a temperature of from 50 to 55 C. and the pH-value of the strongly alkaline solution was adjusted to pH 10 by means of concentrated hydrochloric acid.
  • the internal salt (1) (Table 1) that had precipitated crystallized upon further stirring at 15 C.
  • the salt was sepparated by suction-filtration, washed with water until it was free from chlorine ions and dried in vacuo at 60 C. 87 parts by weight of the compound (1) were obtained, corresponding to a yield of 88.5% of the theory.
  • EXAMPLE 2 78 parts by weight of N,N-diethyl-l,3-diaminopropane were added to the suspension of the sodium salt of 4,4- bis-(2",4"-dichloro-s-triazinylamino-(6") )-stilbene 2,2- disulfonic acid, prepared according to Example 1, the whole was heated slowly to 40 C. and maintained, while stirring, for 4 hours at this temperature. The reaction mixture was then heated to 95 C., while acetone was distilling off, and boiled for 5 hours under reflux.
  • the mixture was diluted with 2000 parts by volume of water, the reaction product that had precipitated was dissolved by addition of about 30 parts by volume of a 33% sodium hydroxide solution, clarified after addition of 20 parts by weight of kieselguhr, and the clear filtrate was combined with 230 parts by weight of sodium chloride.
  • the sodium salt of the 4,4'-bis-(2,4"-('y-diethylaminopropylamino) s triazinylamino-(6") )-stilbene-2,2'-disulfonic acid that had precipitated was stirred at room temperature, suction-filtered and washed with a 20% sodium chloride solution.
  • the sodium salt was dissolved in 2000 parts by volume of water at room temperature and to the resulting solution there were added dropwise 50 parts by volume of concentrated hydrochloric acid until the precipitate formed was dissolved.
  • the mixture was clarified by filtration and the filtrate was mixed with 100 parts by weight of sodium carbonate until it showed, with phenol-phthalene, a definitely alkaline reaction.
  • the internal salt (2) (Table 1) which first precipitated in greasy form, was decanted several times with water, until no more chlorine ions could be detected. After drying in vacuo at 60 C., 62 parts by weight of compound (2) in solid form were obtained (60% of the theory).
  • 60 parts by weight of the internal salt 2) were dissolved in 150 parts by volume of water by addition of 7.5 parts by volume of formic acid, at a pH-value of 5.
  • the solution of the compound (37) (Table 2) was filled up with 8 water to the amount of 300 parts by weight (20% solution, referred to the internal salt).
  • EXAMPLE 4 95 parts by weight of 1-diethylamino-4-amino-pentane were added to the suspension of the sodium salt of 4,4- bis-(2",4"-dichloro-s-triazinylamino-(6")) stilbene 2, 2'-disulfonic acid, prepared according to Example 1, the mixture was heated slowly to 40 C. and maintained at this temperature for 4 hours, while stirring. The reaction mixture was then heated to 95 C., while acetone was distilling off, and boiled for 5 hours under reflux.
  • Example 1 prepared according to Example 1. The mixture was stirred for 2 hours at room temperature, then heated to 40 C. and kept for 4 hours at this temperature. By adding dropwise 66 parts by volume of 2 N-sodium carbonate solution, the pH-value was maintained at 7. Then 46.5 parts by weight of p-diethylamino-ethylamine were added, the reaction mixture was heated to 95 C., while acetone was distilling olf, and boiled for 5 hours under reflux. It was then cooled to room temperature, the supernatant was decanted from the reaction product which had precipitated in resinous form, and the reaction product was dissolved by addition of 500 parts by volume of 2 N-hydrochloric acid and 1000 parts by volume of water.
  • EXAMPLE 6 A solution of 27.2 parts by weight of 3-amino-dimethylaniline in 50 parts by 'volume of acetone were added to the suspension of the sodium salt of 4,4'-bis-(2",4"- dichloro-s-triazinylamino (6")) stilbene-2,2-disulfonic acid, prepared according to Example 1. The mixture was stirred for 2 hours at room temperature, then heated to 40 C. and kept for 4 hours at this temperature. By adding dropwise about 100 parts by volume of 2 N-sodium carbonate solution, the pH-value was constantly maintained at 7. Then 46.4 parts by weight of fl-diethylaminoethylamine were added, the reaction mixture was heated to 75-80" C.
  • the reaction product which crystallized during cooling, was suction-filtered, crushed to small pieces and washed with water on a suction filter until it was free from chlorine ions.
  • the material obtained from the suction filter was introduced into 2000 parts by volume of water, 100 parts by volume of 2 N-sodium hydroxide solution were added and, after short stirring, a solution was obtained from which small impurities were removed by suction-filtering. 25.2 parts by weight of dimethyl sulfate were added dropwise in about 5 minutes to the clarified solution, the internal salt (7) (Table 1) precipitating thereupon.
  • the suspension obtained was heated to 60 C.
  • EXAMPLE 7 A solution of 32.8 parts by weight of 4-aminodiethylaniline in 50 parts by volume of acetone was added to the suspension of the sodium salt of 4,4-bis-(2",4"-dichlorotriazinylamino-(6)) stilbene-2,2'-disulfonic acid, prepared according to Example 1. The mixture was stirred for 2 hours at room temperature, then heated to 40 C. and kept at this temperature for 2 hours. By adding dropwise 35 parts by volume of 2 N-sodium carbonate, the pH was constantly maintained at 7. Then, 46.4 parts by weight of fi-diethylamino-ethylamine were added, the reaction mixture was heated to C. while acetone was distilled off, and boiled for 5 hours under reflux.
  • the crystalline reaction product was suction-filtered and washed twice with water.
  • the material obtained from the suction filter was introduced into 1000 parts by volume of water, dissolved by addition of 40 parts by volume of concentrated hydrochloric acid, and the solution obtained was clarified, after stirring, with 5 parts by weight of kieselguhr.
  • the filtrate was mixed with parts by weight of sodium carbonate, stirring was continued for 3 hours at room temperature, the crystalline internal salt (6) (Table l) was suction-filtered, washed until it was free from chlorine ions and dried at 60 C. in vacuo. 105.5 parts by weight were obtained, corresponding to 98% of the theory.
  • EXAMPLE 8 A solution of 32.8 parts by weight of 4-amino-diethylaniline in 50 parts by volume of acetone was added to the suspension of the sodium salt of 4,4'-bis-(2",4"-dichloro-s-triazinylamino (6)) stilbene 2,2-disulfonic acid, prepared according to Example 1. The mixture was stirred for 2 hours at room temperautre, then heated to 40 C. and kept for 2 hours at this temperature. By dropwise adding about 50 parts by volume of 2 N-sodium carbonate solution, the pH-value was constantly maintained at 7. Then 46.4 parts by Weight of B-diethylamino-ethyl amine were added, the reaction mixture was heated to 7580 C.
  • EXAMPLE 14 100 parts of dry bleached soft wood sulfite pulp were adjusted, in a 4% aqueous suspension, in a hollander, to a beating degree of 40 SR. This suspension was combined with 15%, referred to the fiber weight, of china clay, mixed thoroughly, and then combined with 0.3%, referred to the fiber weight, of compound (41) which had been previously dissolved in water in a dilution of 1:100, and again thoroughly mixed. After further addition of 3% by weight, referred to the fiber weight, of resin size, the suspension was adjusted to a pH of 4.5 by means of aluminum sulfate and mixed until it was homogeneous.
  • EXAMPLE 15 There was prepared in known manner a paper coating mass (casein coating mass) having the following composition:
  • the coating mass so prepared was applied by means of a coating blade on wood-free paper having a weight of 90 g./m.
  • the dry coating amounted to 20 g./m. of paper.
  • the paper was then dried and calendered in the usual manner.
  • Bleached white cotton fabrics were washed in the usual manner with a commercial brightener-containing detergent, then rinsed warm and cold, the last rinsing bath containing 4% of softening agent referred to the weight of the dry fabrics.
  • the fabric was squeezed between rollers with a squeezing elfect of 70%.
  • the fabric was rolled up, wrapped in a foil and allowed to stand for 20 hours at room temperature and then rinsed in water at 40 C., with addition of sodium carbonate, until it showed neutral reaction.
  • the fabric treated in this manner showed an excellent degree of whiteness.
  • a compound according to claim 1 wherein A and A each is an alkylene of 2 to 5 carbon atoms, phenylene, toluylene or chlorophenylene, R and R each is hydrogen, R R R and R each is lower alkyl or phenyl, or R and R and/ or R and R together with the nitrogen atom is morpholino or piperidino, R and R each is hydrogen, methyl or 'benzyl, and X is chloride, methosulfate, toluene sulfonate or formate.

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  • Oil, Petroleum & Natural Gas (AREA)
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US839640A 1968-07-22 1969-07-07 Cationic derivatives of 4,4' - bis-(s-triazinylamino)-stilbene -2,2'-disulfonic acid,process for the preparation thereof and application as optical brighteners Expired - Lifetime US3663538A (en)

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CH1095368A CH525991A (de) 1968-07-22 1968-07-22 Verfahren zum optischen Aufhellen von Textilmaterialien, insbesondere aus natürlicher oder regenerierter Cellulose

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892675A (en) * 1973-01-23 1975-07-01 Ici Ltd Coating compositions
US3951965A (en) * 1973-09-21 1976-04-20 Hoechst Aktiengesellschaft Bis-triazinyl-amino)-stilbene-disulfonic acid derivatives
US3970647A (en) * 1973-02-16 1976-07-20 Sandoz Ltd. Bis-(triazinylamino)stilbene compounds
US4012378A (en) * 1972-02-11 1977-03-15 Imperial Chemical Industries Limited Reactive dyestuffs
DE2915323A1 (de) * 1978-04-26 1979-11-08 Sandoz Ag Basische bzw. kationische, sulfonsaeuregruppenhaltige monoazo- oder disazoverbindungen
US4478598A (en) * 1981-02-26 1984-10-23 Ciba-Geigy Corporation Amphoteric styrene derivatives useful as fluorescent brighteners
US5945396A (en) * 1996-12-24 1999-08-31 Ciba Specialty Chemicals Corporation Compounds
JP3220285B2 (ja) 1993-05-18 2001-10-22 富士写真フイルム株式会社 ジアミノスチルベン系化合物及びそれを用いた画像形成方法
US20030010459A1 (en) * 1999-12-22 2003-01-16 Farrar John Martin Cationically modified white pigments, their production and use
WO2005019189A1 (en) * 2003-08-21 2005-03-03 Ciba Specialty Chemicals Holding Inc. Optical brighteners
US20050161184A1 (en) * 2002-03-19 2005-07-28 Goetz Scheffler Amphoteric and cationic fluorescent whitening agents
US7019134B2 (en) * 1999-12-22 2006-03-28 Clariant Finance (Bvi) Limited Amphoteric optical brighteners, their aqueous solutions, their production and their use
WO2011146604A3 (en) * 2010-05-18 2012-02-02 Milliken & Company Optical brighteners and compositions comprising the same
US8262743B2 (en) 2010-05-18 2012-09-11 Milliken & Company Optical brighteners and compositions comprising the same
USD835859S1 (en) 2017-04-19 2018-12-11 Gramercy Products, Inc. Ring

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE4600T1 (de) * 1979-09-21 1983-09-15 The Procter & Gamble Company Wasch- und weichmittelzusammensetzungen und verfahren zu ihrer herstellung.
RU2413719C2 (ru) * 2008-11-28 2011-03-10 Альбина Ивановна Леонтьева Способ получения белофора кд-2

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012378A (en) * 1972-02-11 1977-03-15 Imperial Chemical Industries Limited Reactive dyestuffs
US3892675A (en) * 1973-01-23 1975-07-01 Ici Ltd Coating compositions
US3970647A (en) * 1973-02-16 1976-07-20 Sandoz Ltd. Bis-(triazinylamino)stilbene compounds
US3951965A (en) * 1973-09-21 1976-04-20 Hoechst Aktiengesellschaft Bis-triazinyl-amino)-stilbene-disulfonic acid derivatives
US4367172A (en) * 1978-04-26 1983-01-04 Sandoz Ltd. Disazo dyes containing at least one sulfo group and at least two basic or cationic groups
US4273707A (en) * 1978-04-26 1981-06-16 Sandoz Ltd. Monoazo and disazo dyes containing at least one sulfo group and at least two basic or cationic groups
DE2915323A1 (de) * 1978-04-26 1979-11-08 Sandoz Ag Basische bzw. kationische, sulfonsaeuregruppenhaltige monoazo- oder disazoverbindungen
US4478598A (en) * 1981-02-26 1984-10-23 Ciba-Geigy Corporation Amphoteric styrene derivatives useful as fluorescent brighteners
JP3220285B2 (ja) 1993-05-18 2001-10-22 富士写真フイルム株式会社 ジアミノスチルベン系化合物及びそれを用いた画像形成方法
US5945396A (en) * 1996-12-24 1999-08-31 Ciba Specialty Chemicals Corporation Compounds
CN1118461C (zh) * 1996-12-24 2003-08-20 希巴特殊化学控股公司 紫外线吸收剂及其用途
US20030010459A1 (en) * 1999-12-22 2003-01-16 Farrar John Martin Cationically modified white pigments, their production and use
US7019134B2 (en) * 1999-12-22 2006-03-28 Clariant Finance (Bvi) Limited Amphoteric optical brighteners, their aqueous solutions, their production and their use
US6911116B2 (en) 1999-12-22 2005-06-28 Clariant Finance (Bvi) Limited Cationically modified white pigments, their production and use
US20050161184A1 (en) * 2002-03-19 2005-07-28 Goetz Scheffler Amphoteric and cationic fluorescent whitening agents
WO2005019189A1 (en) * 2003-08-21 2005-03-03 Ciba Specialty Chemicals Holding Inc. Optical brighteners
US20060197060A1 (en) * 2003-08-21 2006-09-07 Goetz Scheffler Optical brighteners
US7166564B2 (en) 2003-08-21 2007-01-23 Ciba Specialty Chemicals Corp. Optical brighteners
WO2011146604A3 (en) * 2010-05-18 2012-02-02 Milliken & Company Optical brighteners and compositions comprising the same
US8262743B2 (en) 2010-05-18 2012-09-11 Milliken & Company Optical brighteners and compositions comprising the same
US8262744B2 (en) 2010-05-18 2012-09-11 Milliken & Company Optical brighteners and compositions comprising the same
CN102906239A (zh) * 2010-05-18 2013-01-30 美利肯公司 荧光增白剂及含有其的组合物
US8454711B2 (en) 2010-05-18 2013-06-04 Milliken & Company Optical brighteners and compositions comprising the same
JP2013531706A (ja) * 2010-05-18 2013-08-08 ミリケン・アンド・カンパニー 蛍光増白剤およびそれを含む組成物
US8740997B2 (en) 2010-05-18 2014-06-03 Milliken & Company Optical brighteners and compositions comprising the same
US9018151B2 (en) 2010-05-18 2015-04-28 Milliken & Company Optical brighteners and compositions comprising the same
CN102906239B (zh) * 2010-05-18 2015-09-09 美利肯公司 荧光增白剂及含有其的组合物
USD835859S1 (en) 2017-04-19 2018-12-11 Gramercy Products, Inc. Ring

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AT294751B (de) 1971-12-10
DE1930307A1 (de) 1970-02-12
CH1095368A4 (enrdf_load_stackoverflow) 1972-03-30
FR2013466A1 (enrdf_load_stackoverflow) 1970-04-03
DE1930307B2 (de) 1978-06-15
SE346539B (enrdf_load_stackoverflow) 1972-07-10
BE736364A (enrdf_load_stackoverflow) 1970-01-22
DK137755C (enrdf_load_stackoverflow) 1978-10-09
GB1274545A (en) 1972-05-17
DE1930307C3 (de) 1979-03-15
DK137755B (da) 1978-05-01
CH525991A (de) 1972-03-30
NL6911208A (enrdf_load_stackoverflow) 1970-01-26
NO125051B (enrdf_load_stackoverflow) 1972-07-10
CH534170A (de) 1973-02-28

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