DE1469229A1 - Optical brighteners based on derivatives of 4,4-diamino-2,2-stilbene disulfonic acid - Google Patents

Description

DR. ELISABETH JUNG. DR. VOLKER VO88IUS. DIPL.-ING. GERHARD COLDEWEY PATCNTANWXLTf

■ MONCHENJS ■ 8IEQE89TnA88E2 · · T (LErON 34 It «7. TILtQRAMM.ADDRESS: IN VENT / M ONCHEN

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P 14 69 229 ο 6
(G 40329 XVe / 81)
UoZ. C 624 / R-366/2

GENERAL ANILINE & FILM CORPORATION
New York, NoYo, VoSt.A.

"Optical brighteners based on -70η derivatives of 4 f.4 ^? " Diamino-2,2 · ~ s ti.lbendisulfoneäure "

Priority: April 12, 1963, V.St.A., No. 272 525

Numerous optical brighteners are known which are produced from diaminostilbene disulfonic acid and cyanuric chloride and further conversion of amino compounds. These brighteners are not soluble mostly in acidic medium, they ie fall slightly in dilute mineral acid and therefore can not be used for optical bleaching when using cationic finishing agents for cellulosic materials · Ana dtr French patent 1,277,193 and GDR patent 20,794 are optisohe Brighteners are known which I also derive from condensation products except 4,4'-diamino, 2'-atilbene disulphonic acid and triazine compounds

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MÖNCHEN »1« JANKKCMTO; OiUTBCHt IANX A. O. MÖNCHEN. LIOPClO * Tr ..> 1 KtO.

The invention relates to optical brighteners of the general formula

in which H is a hydrogen atom or an alkali metal cation, e.g. is a lithium, sodium or potassium cation, η is 1 or 2, Y has a hydrogen atom, a methyl or ethyl group and Z means a -CHgCOCM group or -CHgCHgSOjM group.

The new brighteners ^ are soluble in an acidic medium, i.e. in a Pu value of less than 2, and they are particularly suitable for optical bleaching together with cationic butchering agents, for cellulose materials »together with alum and resin sizing agents for paper production, with casein ~ clay coatings for paper and for other purposes to achieve a lightening for cellulose materials The brighteners according to the invention are particularly suitable for the optical bleaching of cellulose materials, However, they can also be used for materials containing ke rat, such as wool, casein or polyamides.

The brighteners identified above are produced by condensation of 1 mole of 4,4'-diamino-2,2'-stilbene disulfone " acid with 2 moles of cyanuric chloride. The product obtained in this way is then with 2 moles of aniline mono- or diaulfonic acid

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and then with 2 hol taurine, H-He thy itaurine, N ~ ethyl taurine, glycine, N-methylglycine or N-ethylglycine condensed '

Preferably, the preparation is carried out in the order listed above, but may vary v / ground »ZB _0, the cyanuric chloride first with the anilinesulfonic acid, then with taurine, N-methyltaurine, N-Äthyltaurin, glycine, N-methylglycine or H-λthy1glycin, and abaohlieesend be condensed with 4 »4 ^l -Diamino-2,2'-stilbene disulfonic acid«

Examples of usable aniline mono- or di-sulfonic acids are o-, m ~ and p-aminobenoleulfonic acid, 4-Araino * -l, 3-benBoldisulfonic acid and

2-Ajalno-1,4-benzenedi8ulfonic acid.

Pie examples explain the invention. Ropes refer to the weight, unless otherwise stated

Example 1

»Atrium-4,4'-bie / 4- (HHae tny l-N-2-sulfoäthylamino) - 6-p-sulf o anilino-6-triazin ~ 2-ylaminq7-2,2 ^l -stilbene diulfonate of the formula

CH ₃ - n- CH ₂ OH ₂ -SO ₃ Na

was made as follows

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15 g of cyanuric chloride were dissolved in 65 ml of acetone at 30 ⁰ C. This solution was poured into a slurry of 100 g pieces of egg and 20 ml of water with stirring. At a temperature of -8 bit 2 ⁰ C gradually 148 ml (0.04 Hol) jC of a 10-weight aqueous solution of 4,4'-diamino-2 _f 2 ^l -stilbendisulfonsäure added while the _pH value with 25 ml of a 20 # aqueous sodium carbonate solution was kept neutral (Congo Delta). The mixture was stirred for 1 hour at about ⁰ ° C. until no more amine could be detected. 15.6 g (0.08 mol) of p-aminobenzenesulfonic acid sodium salt were then added, and the mixture was stirred at 35 ° C. for 5 hours, the powert being kept slightly alkaline with phenolphthalein by adding 16 ml of 20 μg sodium hydroxide solution. Then 38.6 g (0.088 mol) of 31.7% aqueous methyl taurine solution were added. The mixture

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was 3 hours at 65 C and then a further 6 hours at 95 0 stirred, the Pg value by adding 16 ml of 20% sodium hydroxide solution was kept strongly phenolphthalein-alkaline. Finally the mixture was treated with activated charcoal, filtered and evaporated to dryness.

Use of the brightener on cotton

A piece of cotton cloth weighing about 100 g was padded as usual with an aqueous suspension which dissolved 1.43 g of a cationic synthetic plasticizer based on a fatty acid amino acid compound and 0.07 g of the above-described in 100 ml of water Contained brightener. The impregnated cotton cloth was then pressed out with rubber whales and dried. Djeee treatment results in an uptake of 1 ^ wetting agent and G, 05 $ AuChelXer _o

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The cotton cloth that was treated had a much lighter appearance than an identical piece of cotton cloth that had been padded with an aqueous solution containing only 1.43 g of the cationic material synthetic Weiohmaohers contained »

Use of the brightener in clay coatings for paper 166 g caseinj 47.7 ml concentrated ammonium hydroxide and 300 ml water were mixed together and stirred at 55 - 66 ° C until dissolved. After cooling to room temperature, the mixture was diluted with water to 1 liter.

A coating was produced from 80 g of clay, 20 g of calcium carbonate, 66.3 ml of the casein solution (11 g of 100% casein) and 4 g of a latex made from a styrene-butadiene copolymer. This mixture was diluted to 250 g with water and then 1 g of the brightener was added. On paper, a coating of 20 wt _o was - £, based on the weight of the trookenen paper, the above mixture is applied and dried anschlieseend ο

The lightness of this brightener on paper was excellent. The paper coating consisted of several paper coatings made in a similar manner, but using five known brighteners of the following general formula: think:

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R ^ is a hydrogen atom or the group -C ₂ H.OH, Rg is the group -C ₂ H ^ OH or a phenyl group, or R ₁ and R "together with the nitrogen atom form a morpholine ring.

Example 2

Sodium 4,4'-bi8 ~ / 4- (H-methyl-ii-2-sulfoethylamino) -6-m ~ sulfo ~ anilino-3-triazin-2-ylaniineq / 2i2 ^l -stilbene diaulfonate was used as in Example 1 , but with 0.08 mol of sodium m-aminobenzenesulfonic acid instead of 0.08 Hol p-aminobenzenesulfonic acid, sodium salt ο

example 3

Hatriura-4,4'-bis - ^ - (N-methyl »H-2-sulfoethylamino) -6-o-sulfoanilino-s-triazin-2-ylamino7-2,2» s tilbene disulfonate

NHCHgCOONa

- H-N

SO _{x well}

was according to Beiopiel 1, but with 0.08 mol of o-aminobenzenesulfonic acid sodium salt instead of 0.08 mole of p-aminobenzoloule

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f onic acid 4iatriua> salt and instead of methyl taurine with 6.6 g (0.06 mol) glycine prepared as a 30 ^ 6% aqueous solution.

The brighteners obtained according to Examples 2 and 3 had the same lightfastness on cotton and in clay covers for paper like the brightener according to Example 1.

Beis piel 4

Sodium ~ 4,4 'bie ~ / 4- (methyl-H-2-sulfoethylamino) -6- (2,4-dieulfoanilino) ~ e-triazin-2-ylamin7-2,2'-stilbene disulfonate was according to Example 1, however, instead of 18.5 g of sodium p-aminobenzenesulfonate, it was prepared using 23.8 g (0.08 mol) of Hatriua-4-amino-1 _f 3-benzenedieulfonate.

Applicatio n d dung he Au fheller genäse Examples 3 and 4 in paper with rosin sizing agents and alum

0.2 g of the brighteners according to Examples 3 and 4 were dissolved separately in 100 ml of water. 30 g of bleached sulfite paper pulp (10 1 » dry) were weighed into two separate 1 liter vessels made of stainless steel (vessels 1 and 2) and 100 μl of cold water (20 ° C.) were then added. The slurry in each vial was stirred with a stainless steel stirrer. 10 ml of each solution of the two brighteners were added to container 1 and 2, respectively. Stirring was continued for 1 minute, after which 5 ml of resin size solution were added each time (the resin size solution was prepared by diluting 17 parts of a commercially available resin size with a Feetatoff content of 70J6 with water to 1 liter). The contents of the two Gefäeee was stirred for 1 Hinute and then with 5 ml of a 1.5 ^ sodium alum solution was added, followed by stirring for further 20 minutes wurdo _c The thus treated

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Papleraaeee was entnoumen the vessels, often by a 17.5 filter sieve with a Masohengrögse τοπ 0.147 βα filtered, ge * - Gautscht, pressed and wiped filter papers and Pilestüoken With a steam-heated drum dryer as well as clean sheets of paper. The dried Pftfiere - paper 1 and 2 - had a distinct pink color in the case of similar types of paper produced, however, without the use of the brighteners according to the invention, not found could be

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Compare attempts '.

In each case 2 g of the brightener obtained according to Example 1 (compound A) and the brightener known from French patent specification 1,277,193p example 1 (compound. B) and of the known brightener (compound C) of the formula

were dissolved in 1 liter of water given Mt sulfuric acid, the p _H was adjusted to ~ 2 »Hit rosin size and alum impregnated paper was dipped in the solutions and allowed to dry anscblieesend. The brightening achieved was determined with the aid of a fluorescence photoimeter . The following results were obtained:

Connection, reading & evert, brightening

A ·: 50

B 31

0 22

The effect achieved with compound A can already be achieved Recognize daylight well *

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Claims (1)

Patent claim Optical brighteners of the general 3? Ormel ΙΙ _Κ · ·· SUN.M MO ₁ S f ■ in which H is a hydrogen atom or an alkali metal cation, ZoB _{0 is} a lithium, sodium or potassium cation »η has the value 1 or 2, Y is a hydrogen atom, a methyl or ethyl group and 2 iron -CHgCOOM group or -CH ₂ CH ₂ SOxK group means. * 909848/1316