DE1237525B - Optical brightener - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

l / GERMAN

PATENT OFFICE

LEGAL LETTERING

ft

Int. Cl .:

German class:

Number: 1237525

File number: F 35895IV c / 8 i

Filing date: February 1, 1962

Open date: March 30, 1967

It has been found that derivatives of aminostilbene, which optionally substituted the remainder of a Aminoaryl- / S-oxyäthylsulfons via a 1,3,5-triazine ring bound, are excellent optical brighteners.

Derivatives of the aminostilbene of the type mentioned above are compounds of the general type Formula I.

Optical brightener

O ₂ S

H ₂ C

H ₂ C

HO

HN

N N

ν /

CH = CH -

in the Z hydrogen or a water-solubilizing group, e.g. B. a carboxyl group, a sulfonic acid amide group, an alkyl sulfone group, a / I-oxyethyl sulfone group, preferably a sulfonic acid group, R a hydrogen atom, an alkyl or alkoxyl radical and X the radical of a primary or secondary aliphatic amine, preferably one with solubilizing groups, e.g. B. the Mean residue of aliphatic aminosulfonic acids such as taurine and methyltaurine.

The new aminostilbene descendants, which are characterized primarily by a very brilliant shade of white, great Characterized by abundance and good lightfastness, they are suitable for the optical brightening of structures of all kinds, for example foils, films, felts or textiles, such as fibers, threads, flakes, fabrics and knitted from natural, regenerated and synthetic material, as well as leather and Paper. However, particularly good effects are obtained with the optical brightening of structures made of native or regenerated cellulose.

The compounds can be a component of optically brightening mixtures of all kinds, such as, for example Detergents, dishwashing detergents or finishing agents, they are notifying parties:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning, Frankfurt / M.

Named as inventor:

Dr. Erich Schinzel, Frankfurt / M.-Höchst;

Dr. Rolf Austrup,

Sulzbach via Frankfurt / M.-Höchst;

Dr. Karl-Heinz Lebkücher, Hofheim (Taunus)

but can also use the substances to be lightened during the manufacturing process of the same or treatment baths, z. B. washing liquors, whitening baths, bleaching baths and pulp can be added.

A particular technical advantage is that the new derivatives of the aminostilbene also In high concentrations give brilliant lightening and also with high concentration on the ones to be lightened Formed show only a slight reduction in their fluorescence capacity. This attribute is particularly valuable for use in washing liquors, as it is also used in high quantities and if the washing process is repeated many times, one caused by the accumulation of the brightener There is no need to fear a reduction in the degree of whiteness. Another one to highlight Those derivatives of the aminostilbene which, bound via a 1,3,5-triazine ring, show the advantages of such aminoaryl-jS-oxyäthylsulfonen contain, whose benzene nucleus is substituted by alkyl and alkoxyl groups, as these new brighteners in addition to a very brilliant white shade showing high acid fastness and good compatibility with high-performance finishing catalysts, which, as is known, lead to a reduction in the fluorescence capacity of the usual products. These properties make these new products valuable whiteners for the paper industry and allow their use in finishing processes in the textile industry.

Compared to the connections known from the German Auslegeschriften 1 098 485 and 1 090 168 show the process of the present

709 547/379

Invention to be used products have a more brilliant whiteness and are characterized in particular from the fact that, in contrast to the known compounds, they are also used in high concentrations suffer only an extremely small reduction in their fluorescence capacity and none Green cast in the white effect occurs.

The new atninostilbene derivatives of the formula I can by various processes known per se getting produced. You can, for example, cyanuric acid chloride with a derivative of Aminostilbene, an optionally substituted aminoaryl - /? - oxyäthylsulfon and a primary or secondary aliphatic amine, which preferably contains solubilizing groups, in any Implement the order.

Of particular technical interest is the condensation of 2 moles of cyanuric acid chloride with 1 mole of 4,4'-diaminostilbene-2,2'-disulfonic acid, 2 moles of an aminoaryl- / i-oxyethylsulfone and 2 moles of one primary or secondary aliphatic amine, which preferably contains solubilizing groups.

Examples of aminoaryl / 3-oxyethyl sulfones are the 4-aminophenyl - ^ - oxyäthylsulfon, 3-aminophenyl - /? - oxyethyl sulfone, 3-amino-4-methylphenyl / i-oxyethyl sulfone, 3-amino-6-methylphenyl- / i-oxyethyl sulfone and the S-amino ^ methoxyphenyl / 3-oxyethylsulfone into consideration.

Of the primary or secondary aliphatic amines, which are preferably a solubilizing agent Group include ethylamine, isopropylamine, butylamine, dimethylamine, diethylamine, glycocoll, Called taurine and methyl taurine.

The previously explained reaction of the cyanuric acid chloride is preferably carried out in an aqueous or in an organic medium. You can use inert organic solvents and / or diluents, especially those that are miscible with water, z. B. acetone, dioxane, dimethyl sulfoxide or dimethylformamide, use alone, in a mixture with each other or with water. The hydrochloric acid released during the reactions is neutralized by adding alkaline agents, e.g. B. sodium bicarbonate, sodium carbonate or dilute aqueous sodium or potassium hydroxide solution, or they are bound by adding mineral acid binding agents, such as salts of weak acids and strong bases, e.g. B. sodium acetate, or by an excess of an organic amino compound. For the preparation of the primary condensation products of cyanuric acid chloride, it is expedient to choose lower temperatures, for example between 0 and + 10 ° C. The compounds obtained are then set at a slightly elevated temperature, e.g. B. between 10 and 40 ⁰ C to secondary condensation products, from which one finally at a higher temperature, z. B. 60 to 100 ⁰ C, wins the desired tertiary condensation products. The compound of the general formula II mentioned below in Example 1 can be prepared in the following manner:

A solution of 18.4 parts of cyanuric chloride in

100 parts of acetone are left with cooling in a mixture of 300 parts of ice and 500 parts of water come in. At 0 ° to 5 ° C., a solution of 20.7 parts of 4,4'-diamino-stilbene-2,2'-disulfonic acid is added to this mixture Sodium in 150 parts of water was added dropwise and the reaction mixture by simultaneous Dropwise addition of 10% soda solution kept weakly acidic to Congo paper. The mixture is subsequently stirred at 0 to 5 ° C. until no more primary aromatic amino groups are formed by diazotization can be proven.

The resulting suspension of 4,4'-bis (2 ", 4" -dichlorotriazinyl- (6 ") - amino) stilbene-2,2'-disulfonic acid is mixed with a solution of 20.1 parts of 3-aminophenyl - /? - oxyethylsulphone in 200 parts of water are added dropwise at 5 to 10 ° C. and kept neutral by simultaneous dropwise addition of 10% sodium carbonate solution until no more primary aromatic amino group can be detected by diazotization. triazinyl- (6 ") -amino] -stilbene-2,2'-disulfonic acid is allowed to flow in a solution of 62.4 parts of N-methyltaurine (66.8%) in 150 parts of water and heated to 95, while acetone is distilled off ^C. C. The temperature is maintained at 98 to 100 ° C. for 5 hours, nitrated and the reaction product crystallizes by cooling and adding 15% NaCl Brightener II washed neutral with 15% NaCl solution ^{is dried at 60 5} C in a vacuum.

The parts and percentages given in the text are weight units.

example

A bleached cotton fabric is 20 minutes at 40 ° C in aqueous liquor, the 0.2% of the following link

CH ₃

NaO ₃ SCH ₂ CH ₂ N-rj ^{/ N} V-HN NN

NH SO ₂ CH ₂ CH ₂ OH

contains, treated.

CH =

SO ₃ Na

After rinsing and drying, the treated cotton fabric compared to an untreated one a much nicer shade of white.

Instead of the compound II, the following substances III to XII can be used with the same success will.

NaO ₃ SCH ₂ CH ₂ N - | f ¹ V- HN - <^ f-

N N ^ Y

NH

CH = SOaNa

SO ₂ CH ₂ CH ₂ OH

NaO ₃ SCH ₂ CH ₂ N -ji V-NH

N N

NH

CH =

SO ₃ Na
SO ₂ CH ₂ CH ₂ OH

IVR = H VR = CH ₃

NaO ₃ SCH ₂ CH ₂ N -] f ^N VN N

NH

CH =

SO ₃ Na
CH ₃

SO ₂ CH ₂ CH ₂ OH

VIR = H VII R = CH ₃

(C ₂ Hs) ₂ N

N N

CH = SO ₃ Na

SO2CH2CH2OH

NaO ₃ SCH ₂ CH ₂ N -ff ^N V-NH

N N

CH =

SO ₃ Na
SO ₂ CH ₂ CH ₂ OH

CH ₃

IXR = H XR = CH ₃

NaO ₃ SCH ₂ CH ₂ N - | f ^N V - NH

CH =

SO ₃ Na
SO ₂ CH ₂ CH ₂ OH

N N

NH

The compounds III to III do not show any whitener accumulation marks in similar washes Way how to make the connection II. js but stayed pure white.

XIR = H
XII R = CH ₃

Example 2

A desized cotton raw fabric is in the liquor ratio 1:20 for 3 hours at 85 C. bleached with a solution that

2 g / l sodium silicate,

1 g / 1 sodium hydroxide solution,

0.5 g / l alkyl aryl sulfonate,

2 cm ³ / l of hydrogen peroxide (35%) and 0.2 g / l of compound V

contains. After rinsing and drying, the fabric shows an excellent degree of whiteness, without Use of the optical brightener cannot be achieved.

The white measurements were made with a Zeiss-Elrepho device carried out and compared to magnesium oxide as a standard, at one wavelength of 460 Γημ a value of 98%.

25th

30th

Example 3

35

0.2% of the aminostilbene derivative of the formula II is added to a sulphite pulp pulp. This out of this Paper produced in the usual way shows brilliant white (Zeiss-Elrepho value: 100.3%).

Example 4

A fabric made of polycaprolactam is heated for 20 minutes at 60 ° C. in a liquor ratio of 1:20 with a solution of

0.5 ml / l formic acid (85%) and 0.2 g / l of compound III

treated. The result is an increase in whiteness from 76% (raw fabric) to 87%.

Example 5

A detergent is produced with the following composition and sprayed at 250 C:

10% condensation product from oleyl alcohol

and about 10 moles of ethylene oxide, 35% polyphosphonate,

2% soap powder,
15% sodium metasilicate, 10% sodium perborate,

3% magnesium silicate,

3.5% carboxymethyl cellulose, 0.05% compound II. 21.45% common fillers.

This detergent is used to machine white cotton poplin shirts in a drum washing machine washed several times. The shirts also showed

55 Example 6
Bleached nettle is used in a bath that

50 g / l of a polyvinyl acetate dispersion and
3.2 g / I of compound IX contains,

treated.

It is then squeezed off to 100% liquor pick-up and dried. The fabric does not show any Yellowing, but has an extensive and luminous white effect.

Example 7

A bleached wool flannel that still has a certain yellow tinge is used in the liquor ratio of 1:20 with a solution of

0.5 ml / 1 formic acid (85%) and
0.2 g / l of compound II

treated for 30 minutes at 45 ° C.

As a result of this treatment, it shows a significant improvement in the degree of whiteness.

Example 8

A bleached cotton poplin with a urea-formaldehyde precondensate is used for the finishing process and ammonium nitrate impregnated. The solution also contains 1.5 g / l of compound II.

The fabric is then squeezed off to 100% liquor pick-up and the resin is condensed out at 150.degree. A brilliant bluish white and good crease resistance are achieved here.

Claims (1)

Claim: Use of derivatives of the aminostilbene of the general formula R ^ -χ _KT / - \ C VHN-if ^ Y HN-C V-CH = CH-I O ₂ S ^x - ^/ H ₂ C
HO R> ™ N N SO2 CH ₂ CH ₂ OH 9 10 in the Z hydrogen or a water-soluble one of a primary or secondary aliphatic making group, e.g. B. means a carboxyl group, amine, the preferably solubilizing contains a sulfonamide group, an alkyl sulfone group, groups as optical brighteners. a ß-Oxyäthylsulfongruppe, but preferably a sulfonic acid group, R a hydrogen atom, 5 publications considered: an alkyl or alkoxyl radical and X the radical Deutsche Auslegeschriften Nr. 1 090168,1098 485. When the registration was announced, a test report with four sample cards was displayed. 709 547/379 3.67 © Bundesdruckerei Berlin