Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/14—Styryl dyes
  • C09B23/148—Stilbene dyes containing the moiety -C6H5-CH=CH-C6H5
• • 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

Definitions

• Stilbene compounds suitable for the brightening of textiles in combination with cationic softeners, of paper and of weakly acidic substrates. They have the formula wherein X and Y independently of one another each represents an optionally substituted phenylamino radical or a radical of the formula T and Z each represents the radical of the Formula 11, R is hydrogen or lower alkyl R2 is OH, 'CN, COCmH2m+1,
• the invention thus provides novel stilbene compounds of the formula N N t some SO Me N I x I Y wherein X and Y independently of one another each represents an optionally substituted phenylamino radical or a radical of the formula 1 zh-r T and Z each represents the radical of the Formula H or IH,
• R represents hydrogen or a low molecular weight alkyl radical which may optionally be substituted with hydroxy, alkoxy, cyano, aminocarbonyl, phenyl, phenoxy or cresoxy radicals,
• R represents hydrogen or a low molecular weight alkyl radical
• R represents hydroxy, a cyano, CO-C H or COOR radical
• R and R independently of one another each represents a low molecular alkyl or hydroxyalkyl radical or R and R together with the nitrogen atom represent a saturated heterocyclic radical
• R and R independently of one another each represents a hydrogen atom or a low molecular alkylor hydroxyalkyl radical or R and R together with the nitrogen atom represent a saturated heterocyclic radical,
• R represents a low molecular alkyl radical which may optionally be substituted with hydroxy, alkoxy, phenoxy, cresoxy or phenyl,
• Me represents an equivalent of an alkali or alkaline earth metal or ammonium radical
• Anion represents a colourless anion
• n a number from 1 to 3
• n 1 or 2 and 2 represents a number from 2 to 6,
• the nitro group is then reduced or the acylamino group hydrolysed and the amino group reacted with 1 mol of a cyanuric halide and the dihalogenotriazinyl compound is reacted in any desired sequence with (d) 0 to 1 mol of an optionally substituted aminobenzene and (e) 1 to 2 mols of an amine of the Formula IV or a mixture of amines of the Formula IV, with the proviso that the amines mentioned at (d) and (e) total 2 mols,
• reaction product is optionally reacted with an acid or a quaternizing agent.
• optionally substituted aminobenzenes are the following: aminobenzene and its deriati-ves which may contain in the 2-, 3- and/or 4-position low molecular weight alkylor alkoxy groups, halogen atoms, cyano groups, alkylsulphonyl groups, optionally monoor disubstituted sulphonic acid amide groups or acylamino groups, for example 2-, 3- or 4-methyl, 2,4, 2,5-, 2,6- or 3,5- dimethyl-, 2,4,6- or 2,4,5-trimethyl l aminobenzene, 4-ethyl-, 4-iso-propyl-, 4-n-propyl-, 4-n-butyl, 4-tert.- butyl-, 4-n-amyl-l-amino benzene, 2-, 3- or 4-chlor0-laminobenzene, 2,4- or 2,5-dichloro- 1 -aminobenzene, 4- fluoroor 4-bromo 1-aminobenzene
• acylamino groups optionally substituted are benzoylamino-, phenylsulphonylamino-, alkylsulphonylaminoand especially the alkanoylaminoand alkoxycarbonylamino groups, for example benzoylamino, 4-methylor 4-chlorobenzo'ylamino, phenyland 4-methylphenylsulphonylamino, methyl-, ethyland n-propylsulphonylamino, propionylamino, butyrylamino, acetylamino, methoxycarbonylamino, ethoxycarbonylamino.
• Suitable aminobenzenes with such substituents are, for example, 4 propionylamino-, 4-acetylamino-, 3-acetylamino-, 4-methoxycarbonylaminoor 4-ethoxycarbonylamino-l-aminobenzene.
• aminobenzenes may also be substituted at the nitrogen atom, for example, as in the following compounds: N-methyl-, N-ethylor N-2-hydroxyethylaminobenzene, 3-methyl-l-N-methylor -N-ethylaminobenzene.
• Am inobenzenes which are preferably used are: aminobenzene, l-amino-2-, -3- or -4-methylor -chlorobenzene, 1-amino-2- or -4-methoxyor -ethoxybenzene.
• the radical A is a low molecular weight alkyl radical which contains the substituent designated as R for example 2-hydroxyethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 2-oxopropyl, 2-oxobutyl, 3-oxobutyl, aminocarbonylmeth'yl, Z-aminocarbonylethyl, 2-dimethylaminocarbonylethyl, 2 diethylaminocarbonylethyl, Z-moropholinocarbonylethyl, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2 n butoxycarbonylethyl, 2-(2'-hydrox'yethoxycarbonyl)-ethyl, 2 (2'-hydroxyprop0xycarbonyl)-ethyl, 2-(3'-hydroxypropoxycarbonyl)-ethyl, 2-(2'- methoxyethoxycarbonyl)-ethy
• the radical of the amine of the Formula IV is exemplified by 2-dimethylamino-, 2-diethylamino-, Z-N-methyl N ethylamino-, 2 di n butylamino-, 2-di-(2-hydroxyethyl)- amino, Z-N-methyl N (2'-hydroxyethyl)-amino-, 2-N- ethyl N (2'-hydroxyethyl)-amino-, 2-m0rph0lin0- or 2-piperidino-eth'ylamino, 3-di-ethylamino-propyl-Z-amino, 3-dimethylamino-, 3-diethylamino-, 3-N-methyl-N-ethylamino-, 3 N methyl-N-n-propylamino-, 3-N-ethyl-N-nbutylamino-, 3 di n propylamino-, 3-di-n-butyla
• Preferred amines of the Formula IV are, for example, N- (3-dimethylaminopropyl N- 3-diethylaminopropyl N- 3-di-n-butylaminopropyl) N- 3-morpholinopropyl) N-( S-piperidino-propyl) N- 3-N'-ethyl-N'-methylaminopropyl)-N-aminocarbonylmethyl-amine, -N-(2'-cyanoethyl)-amine, -N-(2-aminocarbonylethyl)-amine, -N-(2'-dimethylaminocarbonylethyl)-amine, -N-(2'-diethylaminocarbonylethyl)-amine, -N-(2-morpholinocarbonylethyl)- amine, -N-(2-ethoxycarbonylethyl)-amine, -N-(2'-methoxycarbonyleth
• T'he amines of the Formula 'IV required as intermediate products may be obtained, for example, by the reaction of amines of the formula with acrylonitrile, optionally substituted acrylic acid alk'yl esters and acrylic acid amides or with the corresponding methacrylic acid derivatives, with alkylene oxides (especially ethyleneand propylene oxide) or with vinyl-alkyl tketones (vinyl-methyl ketone), at temperatures of from -100 C. (20-60).
• Suitable quaternizing agents are for example, esters of sulphuric acid, e.g. dimethylsulphate or diethylsulphate, or the esters of aromatic or aliphatic sulphonic acids, e.g. benzene-, 4-methylbenzeneor 4-chlorobenzenesulphonic acid methyl ester, -ethyl ester or n-but'yl ester, methane-, ethane-, l-propaneor 2-propanesulphonic acid methyl ester or -ethyl ester.
• alkylating agents there are suitable also alkyland aralkylhalides, e.g.
• alkylating agent alkylhalides with from 1 to 5 carbon atoms which are substituted with hydroxyl, alkoxy, phenoxy, cresoxy, cyano or preferably with aminocarbonyl groups, e.g.
• the reaction with cyanuric halides e.g. cyanuric bromide and especially cyanuric chloride
• the 4,4'-diaminostilbene-2,2'-disulphonic acid or with a water soluble salt thereof is effected with aqueous medium when the cyanuric halide is merely suspended in water, or in aqueous-organic medium when the cyanuric halide is first dissolved in an organic solvent (benzene, toluene, chlorobenzene, acetone) and the solution is added dropwise to an aqueous solution of the 4,4'-diaminostilbene-2,2'-disulphonic acid.
• an organic solvent benzene, toluene, chlorobenzene, acetone
• the addition of a dispersing agent may increase the reaction velocity.
• the replacement of the first halogen atom of the cyanuric halide is carried out at temperatures of from 0 to C. and pH values of from 3 to 7.
• the replacement of the second halogen atom [introduction of an optionally substituted phenylamino residue or of a residue of the Formula II] is suitably effected in the temperature range of from to 60 C. and at a weakly acid to weakly alkaline reaction, for example at pH values of from 4 to 8, while for the replacement of the third halogen atom [introduction of a residue of the Formula II] the temperature is advantageously kept to 80 to 100 C. and the pH value between 4 and 10.
• the hydrogen halide liberated during the reaction is neutralized with alkalis, for example an alkali metal hydroxide or carbonate, or tertiary organic amines, e.g. triethanolarnine.
• alkalis for example an alkali metal hydroxide or carbonate, or tertiary organic amines, e.g. triethanolarnine.
• the isolation of the unquaternized brightener produced according to the invention may be effected by salting out, acidifying or evaporating the reaction solution, whereby pulverulent products result.
• a solubilizing agent such as for example a polyvalent alcohol [ethyleneor propylene glycol, dior tri-ethylene glycol, polyethylene glycol, dior tri-propylene glycol, 1,3-dihydroxypropane, 1,4dihydroxybutane, 2,3-dihydroxybutane, 2-methy1 2,4 dihydroxypentane, glycerine, hexanetriol, bis-(2'-hydroxyethyl)-sulphide], ether alcohol [2-methoxy-, 2-ethoxyor 2-n-butoxy-ethanol, 2-(2'-ethoxy-ethoxy)-ethanol, 2-(2- n-butoxyethoxy)-ethanol], a sulphoxide or s
• the quaternization may be effected in aqueous, aqueous-organic or organic suspension or solution at temperatures of from 0 to 100 C. and pH values of from 4 to 8, preferably at 20-60 C. and in the pH range of from 6 to 8. All tertiary amino groups or only some of them may be quaternized, at least 1 mol of the quaternizing agent being used for each tertiary amino group to be quaternized.
• a volatile quaternization agent e.g. methylchloride, methylbromide, ethylbrornide
• any excess of quarternizating agent is destroyed by the addition of sodium hydroxide solution and stirring the mixture at about 60 C. until the pH value no longer changes.
• the above mentioned polyvalent alcohols, ether alcohols, sulphoxides, sulphones and amides or their mixtures with water are suitable reaction media for the quaternization.
• the compounds with tertiary amino groups are stirred in water or a mixture of water and a solvent mentioned for the quaternization of 1 mol of acid is added for each tertiary amino group to be protonized.
• Working is advantageously effected at 0 to 100 C., preferably at 20 to C., in such a way that all tertiary amino groups present are protonized and the pH value of the solution or suspension is adjusted to about 3 to 5.
• the isolation of the protonized or quaternized compounds may be effected in the above described manner.
• Valuable brighteners correspond to the formula X and Y independently of one another each represents a phenylaminoor methylphenylamino radical or a radical of the formula (VII) T and Z each represents a radical of the Formula VII or of the Formula VIII and Me, R, R R and R have the above significance.
• Particularly valuable brighteners are those of Formula VI, wherein R [in the Formulae VII and VIII] represents an optionally monoor disubstituted aminocarbonyl radical.
• the new brighteners produced according to the invention are suitable in the non-quaternized form and especially in the quaternized form for the brightening of textiles in combination with cationic softeners which may optionally also contain antistatically effective agents. Thanks to their excellent drawing ability on to cellulose fibres in the cold in the presence of cationic softeners they are especially suitable for use in soft rinsing agents which have been used in households for some time.
• the quantities of brightener to be used amounts to
• the brighteners of the invention afford the possibility to industry to combine simply and economically brightening and improvement of handle. Furthermore, they improve the appearance of weakly acid substrates, preferably of inorganic nature, e.g. silica, clay, kaolin etc, which is of especial importance in the paper industry.
• weakly acid substrates preferably of inorganic nature, e.g. silica, clay, kaolin etc, which is of especial importance in the paper industry.
• a likewise very good brightening effect is shown by the brighteners according to the invention when used as coating compositions for papers.
• Those of the brighteners according to the invention which contain 4 quaternized amino groups may likewise be applied to cellulose fibres from strongly acid medium, for example at pH values of from 1 to2, and show good brightening effects. They may be used together with auxiliaries for crease-proofing cellulose fibres, for example with resins such as dimethylolethylene urea, dimethylolpropylene urea, dimethylol-4,5-dihydroxyethylene urea, dimethylolmonoalkyl-carbamate and others.
• the condensation of synthetic resins is effected in a pH value range of from 1 to 2 which is usual in moist or wet cross-linking.
• EXAMPLE 1 A solution of 190 parts cyanuric chloride in 635 parts acetone is run into 2000 parts of ice water during 10 minutes. A solution of 185 parts of 4,4'-diaminostilbene- 2,2'-disulphonic acid and 106 parts of anhydrous sodium carbonate in 1500 parts of water is then added dropwise at to 5 while stirring during one hour into the resulting suspension. In this way a suspension results which contains 355 parts of the sodium salt of 4,4'-bis-(2",4"-dichloro-1",3",5"-triazinyl-6"-amino) stilbene 2,2-disulphonic acid.
• the resulting brightener corresponds to the formula
• the required propionic acid amide is produced by adding 71 parts of acrylic amide to parts of B-diethylaminopropylamine at 40 and continuing stirring for one hour at this temperature.
• the product is separated out in the warmth in the form of a viscous mass and is completely separated by the addition of sodium chloride g./ litre).
• the brightener is suctioned off, washed with dilute sodium chloride solution and dried. It constitutes a light yellow powder which is very effective, in combination with cationic softeners, for brightening cotton and alone for brightening weakly acid substrates, e.g. silica, clay or kaolin.
• the brightener produced as above corresponds to the formula H H; HEN-m0 JH,-N o,H
• amines are produced, for example, by the reaction of 3-[di-(2'-hydroxyethyl)-amino]-propylamine or of B-di-n-butylaminopropylamine with acrylic acid amide in the manner described in Example 1.
• the resulting product contains as active component a compound of the formula 5 eners as are the products described in Examples 1 to 3.
• EXAMPLE 5 A solution of 19 parts of cyanuric chloride in 100 parts of acetone is run into 200 parts of a mixture consisting of equal parts of ice and water. A solution, neutralized with sodium hydroxide, of parts of 4nitro-4'-aminostilbene- 2,2'-disulphonic acid in 400 parts of water is added drop- I HgN-O C-C Hz-CHr-N in addition to small quantities of the symmetric compounds containing two phenylamino residues or two 2- methylphenylamino residues and is as elfective as the symmetrically substituted brightener described in Example 1.
• EXAMPLE 4 To the suspension, produced'as in Example 1, of 355 parts of intermediate product from cyanuric halide and 4,4-diaminostilbene-2,2-disulphonic acid in a mixture of acetone and water there are added first, while stirring at 10-12", 46.5 parts of aminobenzene and then 53.5 parts of 1-amino-2-methylbenzene, the procedure being as in Example 3. After the presence of the aromatic primary amines is no longer detectable, 215 parts of ;S-(3'-morpholinopropylamino)-propionic acid amide are added at 40 to the suspension and the mixture is heated for 5 hours to -400 while simultaneously adding dropwise 400 parts of 10% sodium hydroxide solution. The product is completely separated ofi by salting out g. of sodium chloride/litre) and worked up in the usual way.
• the brightener present in the form of a yellow powder contains mainly the compound of the formula SOaNa S OaNa SOaNB wise during 10 minutes at 0-5 while stirring to the resulting suspension.
• a solution 35 of 5.5 parts of sodium carbonate in 50 parts of water is added dropwise in such a way that the reaction product is always weakly acid to neutral (pH value 6 to 7).
• 9.3 parts of aminobenzene the temperature is raised during about one hour to 35 and stirring is continued at this temperature until aminobenzene can no longer be detected with the diazo test, which occurs after 1-2 hours.
• This solution is added pound of the Formula X or 79.5 parts 1 mol) of the dropwise during 10 minutes at 010 to a suspension compound bearing di-(n-butyD-amino groups instead of which has been obtained by mixing 19 parts of cyanuric the di-ethylamino groups (last paragraph of Example 2) chloride, dissolved in 100 parts of acetone, with 100 parts and 25.2 parts of dimethylsulphate and quadruple of ice and 100 parts of water.
• the resulting hydrochloric quaternized compounds result.
• the product is ettective as a brightener in manner similar to the product obtained according to Exam- By replacmg the bnghtener of Formula XV by the l 3 EXAMPLE 6
• I other brightener described in the last paragraph of Ex- 57'6 parts of 2420 of the compound of the ample 2 which contains dI-(n-butyD-aminO groups inmula IX are stirred into 547 parts of dirnethylformamide stead of d1(fl'hydroxyethyn'ammo groups a snmlafly at room temperature and a clear solution is produced by protonized brightener is Producedadding 29 parts of water.
• 105 "do--. .do.. N-(2-n-butoxycarbonylethyl)-N- N-(2-n-butoxycarbonylethyl)-N- Na (3-diethylau1in0pr0pyl)-amin0. (3-diethylaminopropyl)amino. 106 do do.
• N-(3"-diethylaminopropyD-amino. 110 do-.. dodo N-(2-n-buty1aminocarbonylethyl)-N- Na (3 -diethylarninopropyl) -amino.
• 111 ..do 4-chlorophenyl do N-(2-aminocarbonylethyl)-N-(3- Na diethylaminopropyD-amino.
• Table 3 contains quaternized or protomzed compounds TABLE 3C0nt1m1ed which are made from the stilbene compounds of the presmbene ceding examples 1n accordance with the details of Exam- 5335 ples 6 to 9. They are characterized by the startmg com- MEX? Quaternizing agent (acid M01 pound, the quaternization agent or acid and the number of mols of quaternization agent or acid Which are reacted with 1 mol of starting material.
• distearyl-dimethylammonium chloride it is possible to likewise use other cationic compounds, for example on a basis of l-methyl-l-alkanoylaminoethyl-Z- alkylimidazoliniummethylsulphate or a condensation product of stearic acid and N-p-hydroxyethylethylenediamine in the form of a salt.
• Example of Use A which preparation contains 4% of the brightener described in Example 1 (based on softener), so that the rinsing liquor contains 0.5 g. of softener per litre.
• Treatment in the cold is effected for 15 minutes (liquor ratio 1:40), centrifuging is efiected and ironing.
• the other part of the washed cotton material (B) is treated for purposes of comparison in similar manner in a rinsing bath containing softening agent, but without the addition of the brightener according to the invention.
• the Samples A and B are compared in daylight. Whereas Sam ple B appears clearly more yellow than before the treatment with the softener, the Sample A appears clearly brighter than the Sample B and also brighter than material which has not been treated in a rinsing bath containing softener.
• the brightener in accordance with the invention combined with cationic softeners is capable of increasing the whiteness degree of cotton material despite the already present anionic brightener, a result which was in no way to be expected.
• Example 7 (second compound)
• Example 8 Example 9 (last paragraph) mc-oc-cm-cm N I
• Example 136 Example 150 c so;
• R represents a low molecular alkyl radical which may optionally be substituted with hydroxy, alkoxy, phenoxy, cresoxy, or phenyl,
• Me represents an alkali metal, ammonium, or an equivalent of an alkaline earth metal
• Anion represents a colourless anion
• n a number from 1 to 3
• a stilbene compound according to claim 2 wherein 23 4.
• the stilbene compound according to claim 1 of the formula 1 13.

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• 1969
  • 1969-12-11 CH CH1842569A patent/CH529770A/de not_active IP Right Cessation
• 1970
  • 1970-12-07 DE DE19702060085 patent/DE2060085A1/de active Pending
  • 1970-12-07 US US00095935A patent/US3757010A/en not_active Expired - Lifetime
  • 1970-12-09 ES ES386268A patent/ES386268A1/es not_active Expired
  • 1970-12-10 FR FR7044483A patent/FR2073529A5/fr not_active Expired
  • 1970-12-10 JP JP45110044A patent/JPS527011B1/ja active Pending
  • 1970-12-10 NL NL7018032A patent/NL7018032A/xx unknown
  • 1970-12-10 GB GB58647/70A patent/GB1299120A/en not_active Expired
  • 1970-12-10 BE BE760178A patent/BE760178A/xx unknown
  • 1970-12-11 ZA ZA708379A patent/ZA708379B/xx unknown
• 1972
  • 1972-11-10 JP JP47112819A patent/JPS4924127B1/ja active Pending

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