CH668774A5 - Autolube antifriktionskomposition. - Google Patents

Description

1

2nd

Optical brighteners from the series of 4,4'-bis (triazinyl) It has now been found that new compounds of the amino) -stilbene-2,2'-disulfonic acid compounds have been found since Formula 1

known for a long time.

R-N- (ch2) 2-s-z

(1),

Z-s- (ch2) 2-n ~ r in which X is a chlorine atom or a group of the formula yR '

-N <^, -O-R3 or -NR- (CH2) 2-S-Z

20th

R

is in which

R1 for a hydrogen atom, an alkyl or alkenyl radical with up to 20 C atoms optionally substituted by non-chromophoric radicals, cycloalkyl radical with 4 to 8 C atoms, aryl radical or heterocyclic radical,

R2 represents a hydrogen atom or a lower alkyl radical optionally substituted by non-chromophoric radicals or

R1 and R2 together with the N atom represent a hydrogenated 5- or membered ring,

R3 represents a lower alkyl, phenyl or naphthyl radical which is optionally substituted by non-chromophoric radicals, and

M is a hydrogen atom or a colorless cation, Z M, S03M or a bond to another S atom and

R represents a hydrogen atom, a lower alkyl radical or together with Z a methylene group,

represent interesting optical brighteners for textile materials.

Compounds of formula 1 in which X is a chlorine atom or a group of the formula are preferred

-NR'R2, -O-R3 or -NR- (CH2) 2-S-Z

is in which

R1 for an alkyl group with 1-20 C atoms;

a lower alkyl group substituted by optionally esterified hydroxyl, lower alkoxy, lower dialkylamino, optionally functionally modified carboxy or sulfo or a phenyl group;

an alkenyl group with 2-20 C atoms;

a cycloalkyl group with 4-8 C atoms;

a phenyl or naphthyl group optionally substituted by 1 to 4 identical or different substituents from the series lower alkyl, lower alkoxy, optionally functionally modified carboxy or sulfo group and halogen atoms,

R2 represents a hydrogen atom or a lower alkyl radical which is optionally substituted by an optionally esterified hydroxyl group or an optionally functionally modified carboxy or sulfo group,

R1 and R2 together with the N atom for a piperidino or morpholino group,

R3 is a lower alkyl radical optionally substituted by an optionally esterified hydroxy, lower alkoxy, a lower hydroxyalkoxy group optionally etherified with a low molecular weight alkanol, lower dialkylamino or phenyl group, or a lower alkyl group, optionally by one or two identical or different substituents -, Lower alkoxy, optionally functionally modified carboxy or sulfo group and halogen atoms substituted phenyl radical and

M is a hydrogen or alkali metal ion, an ammonium ion or an equivalent of an alkaline earth metal or aluminum,

Z M, SO3M or a bond to another S atom and

R represents a hydrogen atom, a lower alkyl radical or together with Z a methylene group, and in particular compounds of the formula 1, in which

X is a chlorine atom or a group of the formula

30th

35

40

-NR'R2, -O-R3 or -NR- (CH2) 2-S-Z

is in which

R1 is a lower alkyl group which is optionally substituted by a hydroxyl, carboxy or sulfo group or a phenyl radical which is optionally substituted by one or two identical or different substituents from the series methyl, methoxy, carboxy, sulfo or chlorine,

R2 is a hydrogen atom, a lower alkyl radical optionally substituted by a hydroxyl, carboxy or sulfo group or together with R1 and the N atom for a piperidino or morpholino group,

R3 is a lower alkyl radical optionally substituted by a hydroxyl or phenyl group or a phenyl radical optionally substituted by one or two identical or different substituents from the series methyl, methoxy, carboxy, sulfo or chlorine,

M is a hydrogen or alkali metal ion,

Z M, SO3M or a bond to another S atom and

R represents a hydrogen atom or together with Z a methylene group.

Compounds of formula 2 are of particular interest

50

55

60

65

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3rd

4th

wherein X, R and M have the meaning given above.

“Lower” or “low molecular weight” in connection with aliphatic radicals are to be understood in particular as those having up to 4 carbon atoms.

“Non-chromophore” or “non-coloring” substituents are those which have no or no significant absorption in the visible range, in particular - preferably lower - alkyl, alkenyl and alkoxy radicals, acyl radicals, halogen atoms, preferably chlorine and bromine atoms, lower Mono- and dialkylamino residues and the trialkylammonium groups derived therefrom with colorless anions, optionally acylated hydroxyl and amino groups, optionally functionally modified carboxy and sulfo residues, and aryl residues, in particular phenyl residues. Of course, the radicals mentioned can in turn be substituted by such non-chromophoric radicals, such as, for example, lower alkyl radicals by halogen atoms, hydroxyl radicals or the amino radicals mentioned, optionally functionally modified carboxy groups or phenyl groups or phenyl radicals by lower alkyl or alkoxy groups, acyl radicals, halogen atoms or optionally functionally modified carboxy or sulfo groups are substituted one or more times.

If a hydroxy group or amino group can be “esterified” or “acylated” or “acyl residues” are mentioned, this should primarily be understood to mean an acyl residue which is derived from a low molecular weight aliphatic carboxylic acid or an optionally substituted benzoic acid, in particular lower alkanoyl residues and the benzoyl residue.

A “functionally modified” carboxy group is to be understood in particular as meaning its salts with colorless cations, esters with non-chromophoric alcohol residues, amides, the N atom of which can be substituted once or twice by non-chromophoric residues, and the cyano group. Lower esters are preferred among the esters, the alkyl group of which can be substituted by hydroxyl and lower dialkylamino groups.

The above statements with regard to the salts, esters and amides apply correspondingly to a “functionally modified” sulfo group.

The compounds of formula 2 to be used according to the invention can be prepared by adding 2 moles of aminoethylthiosulfuric acid of formula 3

R-NH-CH2-CH2-S-S03H (3),

in which R is preferably a hydrogen atom, in water-containing solvents in the presence of acid acceptors with 2 mol of cyanuric chloride, 1 mol of 4,4'-diaminostilbene-2,2'-disulfonic acid and 2 mol of an amine or alcohol or phenol XH among the conventional conditions gradually condensed. The order of these condensation stages depends on the reactivity of the reactants. If X = C1, the aminoethylthiosulfuric acid is used in the second reaction stage and the third chlorine atom is left in the molecule. These compounds according to the general formula II are isolated in a known manner as salts or as free acids. By reacting the free acids with suitable amines, for example, easily water-soluble ammonium salts can be obtained.

In formula 1 and 2, the residues of the following amines are particularly suitable for X:

Orthanilic acid, chloroaniline sulfo acids, chloroaniline disulfo-20 acids, amides of the aniline sulfo acids, differently substituted here and below, which are substituted on the benzene nucleus, dichloroanilines, 4,5-dichloroaniline-2 sulfo acid, toluidines, toluidine sulfo acids, toluidine disulfonic acids, chlorotoluidene sulfino acids, chlorotoluidine sulfo acids, chlorotoluidine sulfono acids methyl-3-chlorobenzene-25 4,6-disulfonic acid, anisidine, 6-chloro-4-amino-l-methoxy-benzene-3-sulfonic acid, phenetidine, N-methyltoluidine, N-methylanisidine, N-methylphenetidine, aminobenzoic acids , Aminobenzoic acid esters, aminobenzoic acid amides, aminophthalic acids, aminophthalic acid esters, naphthyl-30 amines, N-methylbenzylamine, 2-aminopyridine, 2-amino-thiazole, 2-aminobenzothiazole, pyrrolidine, piperidine, hydroxypiperidine, hexamethyleneimine, piperazine, niperazine, n

2-methylmorpholine, 2,6-dimethylmorpholine, 3-aminopropionitrile, 2 - (/? - hydroxy-ethoxy) -ethylamine, 2- (di-

35 methylamino) ethylamine, 2- (diethanolamino) ethylamine, n- or iso-propylamine, propanolamine, isopropanolamine,

3-methoxypropylamine, 3- (dimethylamino) propylamine, 3- (diethanolamino) propylamine, n-butylamine, n-hexylamine, cyclohexylamine, stearylamine, allylamine, 2-methyl

40 amino-ethylthiosulfuric acid, N-ethylglycine, diethylamine-2,2'-disulfonic acid, imino-diacetic acid, dipropylamine, diisopropylamine, diisopropanolamine, N-butylethanolamine, di-n-butylamine.

Furthermore, X can be the residue of a phenol which is optionally substituted by non-45 coloring or fluorescence-free groups or the residue of an alcohol such as. B. dimethylamino ethanol, propanol, isopropanol, n-butanol, ethylene glycol, butyl glycol and diglycol.

Of particular interest are compounds of formula 50 in which X represents the residues of the following amines or alcohols: aminoethylthiosulfuric acid, aniline, metanilic acid, sulfanilic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, aniline 3,5-disulfonic acid, chloroaniline, N-methylaniline, aminobenzonitrile, benzylamine, 55 morpholine, methylamine, ethylamine, ethanolamine, taurine, glycine, dimethylamine, diethylamine, diethanolamine, N-methylethanolamine, N-methyl-taurine, sarcosine , Methanol, ethanol, methyl glycol and lower diglycol monoalkyl ether.

60 The following are possible for M: the hydrogen ion, an alkali metal cation, an ammonium ion which is derived from ammonia or from a nitrogenous organic compound of basic character, and also an equivalent of an alkaline earth metal or aluminum 65 Cations. Examples of suitable basic nitrogen-containing organic compounds are: guanidines, S-alkyl- and S-aryl-isothioureas such as. B. S-benzyl isothiourea, aromatic amines such as aniline or

6687/74

p-toluidine, but especially primary, secondary or tertiary aliphatic amines, u. a. Triethylamine, ethanolamine, diethanolamine, triethanolamine and morpholine. The salts of these amines are particularly suitable for the production of high-percentage liquid formulations of the compounds according to the invention.

~ \

The corresponding mercaptans of formula 4 are obtained from the abovementioned compounds of formula 2 by acid hydrolysis

-TV »

ir-ch2-ch2

-4>

iTR-CHg-CHg-SM

where R, X and M have the meaning given above.

Furthermore, the corresponding polydisulfides (Z = bond to another S atom) can easily be prepared from the compounds of the formula 2 by treatment with water-soluble sulfides, such as ammonium hydrogen sulfide or sodium sulfide. These form in the event

that in the compounds of formula 2 the grouping -NR-CH2CH2-S-SO3M occurs twice in the molecule, linear or cyclic polydisulfides which, depending on the number of sulfo groups contained in the molecule and the average molecular weight, are sparingly soluble, swellable or also genuine are soluble.

X and M have the meaning given above.

These subsequent reactions on the aminoethylthiosulfuric acid group can also be carried out retrospectively on the textile substrate after the brightening agents of the formula 2 have been applied or can be carried out in the dyeing liquor. By means of the action of sodium sulfide or suitable additives which develop alkali sulfides at elevated temperature, the brightener is fixed during the lightening process or in the course of an aftertreatment process, with the formation of a polydisulfide crosslinking. Here, wet-fast brightenings can be achieved. Furthermore, the compounds of the formulas 2 and 4 to be used according to the invention can be used in an acidic medium by the action of aldehydes and ketones, for example B.

crosslink on the substrate using formaldehyde or substances that release formaldehyde.

Analog optical brighteners are already known from Japanese Patent Application No. 7 204 742. However, these compounds contain phosphoric acid ester groups instead of the aminoethylthiosulfuric acid groups in the present case, so that the advantage of polydisulfide crosslinking is absent in the previously known compounds.

The aminoethylthiosulfuric acid group thus allows the brightening agents of formula 2 to be used according to the invention under special application conditions and, of course, also under the generally customary application

In the case of compounds of the formula 2 which contain the radical -NR-CH2CH2-S-S03M 4 times, the treatment with sodium sulfide under heat leads to a polydisulfide with spatial crosslinking, which is very sparingly soluble in water.

The polydisulfides mentioned can also be easily obtained by oxidation of the mercapto compounds of the formula 4. 25 The action of formaldehyde / hydrochloric acid on the compounds of the formula 2, in which R denotes a hydrogen atom, converts the aminoethylthiosulfuric acid group into a thiazolidine group. The compounds of the general formula 5 are thus accessible in which

(5),

apply conditions. However, the compounds of the formulas 4 and 5 to be used according to the invention and the poly disulphides can also be isolated in substance and used in lightening processes.

The process according to the invention can be used, for example, to lighten cotton, regenerated cellulose, wool or synthetic polyamides and polyurethanes. The textile materials to be lightened can be in a wide variety of processing forms (e.g. fibers, threads, fabrics, knitted fabrics, nonwovens, etc.).

However, preference is given to optically lightening textile materials made from natural and regenerated cellulose and from synthetic 55 polyamides by the process according to the invention.

The compounds to be used according to the invention are furthermore distinguished by excellent resistance to reductive bleaching agents such as, for. B. sodium di-60 thionite.

The process according to the invention is suitable in the case when M in the formulas 1, 2, 4 and 5 and in corresponding polydisulfides M is hydrogen or an ammonium ion which is derived from an organic nitrogen base, for optical brightening from non-aqueous solvent systems.

The process according to the invention can also be carried out simultaneously with the high refinement of the fiber materials with synthetic resins and

6687/74

7

8th

Resin pre-condensates are carried out. The crosslinking of the synthetic resins can be carried out in a customary manner in a wide pH range from pH 0 to 10. The compounds of formula 2 to be used according to the invention, in which X is the rest of a sulfoaniline, in particular the rest of 2,5-disulfoaniline, are particularly suitable for optically brightening cellulose materials from acidic crosslinking baths, as is the case for wash and wear. -Equipment of cellulose fibers is common. With a brightener content of up to 4 g brightener per liter, the liquors are stable even at low pH values of 0-1 and provide very good whiteness.

The process according to the invention is particularly distinguished in the block drying process on cotton, where excellent degrees of whiteness are achieved.

Furthermore, the compounds of formula 2 to be used according to the invention, in which X represents the residue of a lower aliphatic or saturated heterocyclic amine, are particularly to be emphasized. On polyamide, these produce excellent degrees of whiteness of high brilliance in the usual 5 temperature range from 40 to 130 ° C. The use of sodium dithionite provides an additional increase in whiteness.

The amount of the compounds to be used according to the invention, based on the material to be optically brightened, can vary within wide limits depending on the area of use and the desired effect and is generally between about 0.01 and about 2%.

The following examples illustrate the present invention:

Nv NwN

Table (see general formula 2, M = Na)

: TH-CKo-CHo-S-S0, Ha dà $

Y

] fii-ch „ch, s-s0, i: a

à d $

No.

101

102

103

^ Abs.max '[mu] f-

O- ™ -

^ 3-nh-

s0, Na 5

358

355

: - £> nh-

355

5.70

6.22

6.24

104

105

nh-

357

355

6.40

5.80

106

107

108

109

110 1 I 1

H3C-NH- (ho-CH2-CH2) 2N-Na03S-S-CH2CH, -NH-h3c-o-

O

Cl-

353 355 355 353

353 353

6.05 5.88 5.21 5.77

5.50 5.87

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9

10th

production method

example 1

The solution of 18.44 parts by weight of cyanuric chloride in 100 parts by volume of acetone is rapidly run into 400 parts by volume of water at 0 ° C. with stirring. The solution of 18.52 parts by weight of 4,4r-diamino-stilbene-2,2'-disulphonic acid in 55 parts by volume of 2N Nairon lye and 100 parts by volume of water is then dissolved within 20 minutes at a temperature of 0 to + 5 ° C and a pH of Value of 2.5-3 added dropwise. The pH value is kept constant by the simultaneous dropwise addition of 2N soda solution. The mixture is then stirred at about 5 ° C and pH 2.5-3 for about an hour until no more diaminostilbenedisulfonic acid can be detected. The mixture is then adjusted to pH 5 with a little soda solution and the solution of 9.31 parts by weight of aniline in 50 parts by volume of acetone is added dropwise at 15 ° C. in the course of 15 minutes, the pH being kept at 5-5.5 by dropwise addition of 2N soda solution becomes. The mixture is then slowly heated to 40 ° C. and the above pH is kept constant at this temperature for about two hours until aniline is no longer detectable. Then it is adjusted to pH 7 with sodium carbonate solution, the solution of 31.44 parts by weight of aminoethylthiosulfuric acid in 180 parts by volume of water and 8.00 parts by weight of sodium hydroxide are added all at once, heated and aqueous acetone is distilled off until the temperature has reached 100 ° C. The mixture is then stirred under reflux for two hours, the pH being kept at 8-9 by adding sodium carbonate solution. The clear solution is mixed with 135 parts by weight of sodium chloride in the cold. The separated product is filtered off with suction, washed neutral with 20% sodium chloride solution and dried at 60 ° C. 48.20 parts by weight of compound (101), table, 100 '; calculated with a residual moisture (determined according to Karl Fischer) and a content of sodium chloride (determined by titration of the ionic chlorine).

Example 2

The procedure is as described in Example 1, but in the second condensation stage, instead of the solution of aniline in acetone, a solution of 17.32 parts by weight of metanilic acid in 60 parts by volume of 2N sodium hydroxide solution and 100 parts by volume of water is added dropwise. After salting out with sodium chloride, washing neutral with saturated sodium chloride solution and drying, 51.75 parts by weight of compound (102), Table, KKKrig are calculated, with a residual moisture content and a content of sodium chloride.

Example 3

When the reaction according to Example 2 is carried out, but using sulfanilic acid instead of mctanilic acid, 45.30 parts by weight of compound (103), calculated as a table, are obtained.

Example 4

The solution of 18.44 parts by weight of cyanuric chloride in 100 parts by volume of acetone is rapidly run into 400 parts by volume of water at 0 ° C. with stirring. The solution of 25.33 parts by weight of aniline-2,5-disulfonic acid in 70 parts by volume of 2N sodium hydroxide solution and 100 parts by volume of water is then added dropwise at from 0 to 5 ° C. and pH 4 over the course of about 1 hour. The pH is kept constant by adding 2N soda solution. The mixture is then stirred for about 4-5 hours at 0-5 ° C and pH 4 until aniline-2,5-disulfonic acid can no longer be detected. It is then adjusted to pH 7 with sodium carbonate solution and the solution of 18.52 parts by weight of 4,4'-diaminostibene is added dropwise.

2,2'-disulfonic acid in 55 parts by volume of 2N sodium hydroxide solution and 100 parts by volume of water in 10 minutes at pH 6.5-7, heated and stirred for 3-4 hours at 35 ° C and pH 6.5 to 7 until the diaminostilbene disulfonic acid is no longer detectable. The pH is kept constant by dropwise addition of 2N soda solution. The solution of 31.44 parts by weight of aminoethylthiosulfuric acid in 180 parts by volume of water and 8.00 parts by weight of sodium hydroxide is then added all at once and the process is continued as described in Example 1. After salting out with sodium chloride, suction filtration, washing with saturated sodium chloride solution and drying, 49.10 parts by weight of compound (104), table, calculated 100%, are obtained.

15 Example 5

The first condensation stage is carried out as described in Example 1. In the second condensation stage, the solution of 8.71 parts by weight of morpholine in 50 parts by volume of acetone is added dropwise in the course of 15 minutes at 10 to 20 ° C. and a pH of 5.5 to 6.5. The mixture is then stirred for a further 31/2 hours at room temperature, the pH mentioned being kept constant by dropwise addition of 2N sodium carbonate solution. The pH is then adjusted to 7 and the condensation is carried out with amino-25-ethylthiosulfuric acid as indicated in Example 1. It is finally salted out with sodium chloride at room temperature. After suction, washing and drying, 45.80 parts by weight of compound (105) are obtained,

Table, calculated 100%.

30th

Example 6

18.44 parts by weight of cyanuric chloride are reacted with 18.52 parts by weight of 4,4'-diaminostilbene-2,2'-disufoic acid as described in Example 1. The solution of 15.72 parts by weight of aminoethylthiosulfuric acid in 90 parts by volume of water and 4.00 parts by weight of sodium hydroxide is then added dropwise at pH 6.5 to 7. The pH is then kept constant and the mixture is stirred at 40 ° C. for 4 hours. 40 100 parts by weight of 42% strength aqueous methylamine solution are then added and, after the acetone has been distilled off, the mixture is boiled under reflux for 3 hours. By adding 220 parts by weight of sodium chloride to the clear solution, the product is salted out at about 60 ° C. and then isolated as usual. 45 are obtained, 38.40 parts by weight of the compound (106), table, calculated 100%.

Example 7

The first and second condensation stages are carried out as indicated in Example 6. Then, in place of methylamine, 12.00 parts by weight of diethanolamine are added and, after acetone has been distilled off, the mixture is boiled under pH 8 for a further 2 hours. By adding sodium chloride to the clear solution, the product is brought to separation in the heat. Finally, 45.40 parts by weight of the compound (107), table, calculated as 100%.

Example 8

The first and second condensation stages are carried out as indicated in 60 Example 6, then in the third stage instead of methylamine, the solution of 15.72 parts by weight of aminoethylthiosulfuric acid in 90 parts by volume of water and 4.00 parts by weight of sodium hydroxide is added, and the mixture is followed Distill off acetone for 2 hours at pH 8, boiled under reflux. It is filtered and the filtrate is evaporated to dryness in vacuo. 60.70 parts by weight of compound (108), table, calculated 100% are obtained.

11

12

Example 9

36.80 parts by weight of cyanuric chloride at 30 ° C. are introduced into the mixture of 200 parts by volume of methanol, 25 parts by volume of water and 33.60 parts by weight of sodium bicarbonate. The mixture is stirred for 30 minutes at this temperature, then mixed with 250 parts by volume of water, suction filtered, washed neutral with water and dried. This gives 26.14 parts by weight of 2,4-dichloro-6-methoxy-s-triazine, mp. 87-88 ° C.

18.00 parts by weight of the 2,4-dichloro-6-methoxy-s-triazine thus prepared are dissolved in 100 parts by volume of acetone. 400 parts by volume of water are added at room temperature and the solution of 18.52 parts by weight of 4,4'-di-aminostilbene-2,2'-disufoic acid in 55 parts by volume of 2N sodium hydroxide solution and 100 parts by volume of water are added dropwise at room temperature in the course of 30 minutes , the pH being kept at 5 to 6 by simultaneous addition of 2N soda solution. It is then heated to 35 to 40 ° C. and stirred for a further 1 hour at this temperature and pH 5 to 6 until diaminostilbene disulfonic acid can no longer be detected. The solution of 31.44 parts by weight of aminoethylthiosulfuric acid in 180 parts by volume of water and 8.00 parts by weight of sodium hydroxide is then added, the mixture is heated up, aqueous acetone is distilled off until the temperature has reached 100 ° C. and the mixture is then boiled under reflux for 2 hours, with the pH is kept at 8 to 8.5 by adding 2N sodium carbonate solution.

After clarifying with kieselguhr, filtering and salting out with sodium chloride, the product is filtered off with suction, washed with sodium chloride solution and dried. 38.75 parts by weight of compound (109), table, calculated 100%, are obtained.

Example 10

The first condensation stage is carried out as described in Example 1 with 18.44 parts by weight of cyanuric chloride and 18.52 parts by weight of 4,4'-diaminostilbene-2,2'-disulfonic acid. The pH is then adjusted to 6.5 and the solution of 9.41 parts by weight of phenol in 60 parts by volume of water and 4.00 parts by weight of sodium hydroxide is added dropwise at pH 6.5-7 within 20 minutes, the temperature being allowed to slowly rise to room temperature . The mixture is then stirred for a further 3 hours at room temperature and then for 2 hours at 40 ° C., the pH being kept at 6.5-7 by the dropwise addition of 2N sodium carbonate solution.

Then, as indicated in Example 1, the solution of 10 31.44 parts by weight of aminoethylthiosulfuric acid is added. The procedure is continued as in Example 1 and finally salted out at about 50 ° C. with sodium chloride. 37.80 parts by weight of compound (100), table, calculated 100%, are obtained.

15

Example 11

The condensation with 18.44 parts by weight of cyanuric chloride and 18.52 parts by weight of 4,4'-diaminostilbene-2,2'-disulfonic acid in the first stage and 15.72 parts by weight of 20 parts of aminoethylthiosulfuric acid in the second stage is carried out as in Example 6, carried out. After a reaction time of four hours at 40 ° C. and pH 6.5-7, the mixture is salted out with sodium chloride and worked up as usual. 43.20 parts by weight of compound (111), 25 tables, calculated 100% are obtained.

Example 12

11.09 parts by weight of compound (101), table, are concentrated in a mixture of 70 parts by volume of ethanol and 30 parts by volume. Hydrochloric acid boiled under nitrogen atmosphere 4 '/ 2 hours with stirring and reflux. It is allowed to cool while passing nitrogen through, suction filtered, washed neutral with water and free of chlorine and sulfate ions and dried over P205. 35 8.00 parts by weight of the compound (201) are obtained.

NH

■ N>

nh-ch2-cii2-sh

Example 13

14.40 parts by weight of compound (101), table, are dissolved in 210 parts by volume of water with the addition of 8 parts by volume of 2N sodium carbonate solution and filtered. 130 parts by volume of a 0.1 molar, aqueous sodium sulfide solution are added dropwise to the filtrate at 65 to 70 ° C. with stirring in the course of 20 minutes, a yellow, finely divided precipitation occurring. The mixture is then stirred for 2 hours while slowly cooling to room temperature. A loose, yellow, easily absorbable powder is obtained, which is washed neutral with water and Cl-free. After drying, 10.00 parts by weight of the corresponding polydisulfide compound are obtained.

Example 14

6.57 parts by weight of compound (103), Table 1, are dissolved in 80 parts by volume of water. At 60 ° C 50 parts by volume of a 0.1 molar aqueous sodium sulfide

im- ^ y

(201)

îh-ch2-ch2-sh

50

55

Solution added dropwise. Then it is stirred for 1 hour at 80 ° C and finally salted out at 60-70 ° C with sodium chloride. 4.75 parts by weight of the corresponding poly-disulfide compound are obtained.

eo

Example 15

22.18 parts by weight of compound (101), table, are pasted in 120 parts by weight of aqueous formaldehyde solution (40%) at room temperature. Then 15 parts by volume are concentrated. Hydrochloric acid added dropwise with stirring. The mixture is stirred for 5 hours at room temperature, then suction filtered, washed first with 2N hydrochloric acid and then with water 65. The filter cake is dissolved in water with the addition of soda solution in the heat. It is clarified with diatomaceous earth and sodium chloride is added to the heat. After cooling, the product is filtered off with suction, washed with water and dried. 14.00 parts by weight of compound (202) are obtained.

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<3 *

H

13

14

NH

-Q- Cil - CH- ~ ^ 3 ~ nh

S0o Na yN

O

SCyïa

«5

Use Example 1 Pull-Out Process on Cotton 50 g of bleached cotton jerseys were treated at a 1:20 liquor ratio with aqueous liquors, which were composed as follows:

0.20% of compounds (101), (201) or (202),

based on the weight of the goods, 5.0 g / 1 Glauber's salt, 2.0 g / 1 of a commercial plasticizer of the long-chain (essentially C] 6) fatty acid ethanolamine ester type.

The treatment was started below 40 ° C., the temperature was raised to 50 ° C. within 10 minutes after the goods had been introduced, and the treatment was continued at this temperature for 20 minutes. This was followed by the final drying of the knitted cotton. Rinsing is not necessary. This treatment resulted in very good lightening effects with high brilliance.

Application Example 2 Block Drying Process on Cotton Bleached cotton batiste was padded on the foulard with aqueous liquors, each of which

1.5 g / 1 of the compounds (102), (104) or (201), 0.5 g / 1 of a wetting agent based on nonylphenol polyglycol ether (with an average of 9 ethylene glycol units) and 10.0 g / 1 of a commercially available Contain plasticizers based on a long-chain fatty acid polyglycol ester (with an average of 3-6 ethylene glycol units).

The liquor absorption of the fabric was adjusted to about 70% of the dry weight of the fabric by squeezing between the paddle rollers. Immediately afterwards, the goods were dried by a tenter frame at 105 ° C. This treatment gave the goods very good lightening effects.

Example of Application 3 Dry Crosslinking on Cotton 500 g of bleached cotton shirt poplins were impregnated on the laboratory foulard with aqueous liquors of the following composition:

180 g / 1 dimethylol propylene urea, 27 g / 1 magnesium chloride hexahydrate, 20 g / 1 commercial plasticizer based on a long-chain (essentially C16) trimethyl-olalkyl urea, 30 g / 1 commercial additive based on polyethylene dispersion, 2 g / 1 nonylphenol oxyethylate (with an average of 9 ethylene glycol units), 1.5 g / 1 compound (102) or (104).

The goods were squeezed between rolls to a liquor intake of approximately 70% of the dry weight. The drying was then carried out on the stenter at 105 ° C. Condensation was also carried out on the stenter, the condensation temperature was 155 ° C., the condensation time was 3 minutes. With this operation, very good brightening effects of high brilliance were achieved on the cotton poplin.

Example of Application 4 15 Wet Crosslinking on Cotton

Sections of bleached cotton damask were impregnated with aqueous liquors on the foulard, which had the following composition:

300 g / 1 l, 3-dimethylol-4-methoxy-5,5-dimethyl-20 propylene urea, 100 ml / 1 hydrochloric acid, approx. 36%, 2 g / 1 nonylphenol oxyethylate (with an average of 9 ethylene glycol units), 1.5 g / 1 of compound (102) or (104).

After squeezing to about 70% liquor absorption (based on the dry weight of the goods), the fabric was rolled up with low tension, wrapped tightly in polyethylene film and stored for 20 hours at room temperature.

After this time, the web was washed in baths of the following composition:

1st bath:

cold water

2nd bath:

cold water and 10 g / 1 soda, calcined

3rd bath:

Water 40-60 ° C, 1 g / 1 nonylphenol oxyethylate (with an average of 9 ethylene glycol units), 2 g / 1 soda, calcined

4. Bath:

Water, 40-50 ° C

After the last wash bath, the product was squeezed off well and then wet-in-wet with 50 g / l of a commercial plasticizer based on a long-chain (essentially Ci6) trimethylolalkylurea. The final drying on the stenter at 110 ° C completed the finishing process. Very good lightening effects were obtained.

30th

35

45

50

Example of use 5 Pull-out aftertreatment process on cotton Bleached cotton tricot was treated in aqueous liquors (liquor ratio 1:20) for 60 minutes at 85 ° C. with:

0.20% of compounds (101) and (201), based on the weight of the goods, 5 g / 1 Glauber's salt.

After the treatment time, the goods were spun off and then treated for 30 minutes at 85 ° C in baths 13, which with

5 g / 1 sodium sulfide, crystallized (60-62% Na2S) and 200 g / 1 table salt were charged.

Rinse (cold) and re-soap with 1 g / 1 nonylphenolox-60 ethylate (with an average of 9 ethylene glycol units) and 0.5 g / 1 soda, calc. at 98 ° C followed. After rinsing again, the usual drying took place. The treatment according to this regulation brought very good lightening effects.

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Example of Application 6 Two-Bath Block Air Passage Method on Cotton Cotton fabric was padded on the padder with an aqueous liquor which contained the following constituents:

6687/74

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1.4 g / 1 compound (101), 50 g / 1 urea, 100 g / 1 alginate thickener (4%), 1 g / 1 commercial wetting agent based on dibutylnaphthalenesulfonate.

The liquor absorption in the bleached cotton fabric used was about 70% of the dry weight after squeezing. After padding, the mixture was dried at 105 ° C. for 3 minutes.

The dry goods were then sealed (at room temperature and a liquor absorption of approx. 80%) with an aqueous solution which

Contained 20 g / 1 sodium sulfide (approx. 60-62% Na2S), 10 ml / 1 formaldehyde, 33% and 200 g / 1 sodium sulfate (anhydrous).

After an air cycle of 30 seconds, the goods were rinsed cold and hot and then soaped at the boil with a bath containing 1 g / 1 nonylphenol oxyethylate (with an average of 9 ethylene glycol units) and 0.5 g / 1 soda ash, calcined. Finally, after cold and hot rinsing, the usual drying followed. Very good lightening effects were also obtained by this process.

Application example 7 Block steaming method on cotton

Bleached cotton poplin was impregnated with fleets which had the following composition:

2.0 g / 1 of the compounds (101) or (201), 50 g / 1 urea, dissolved in hot water. After cooling, these liquors were added

50 g / 1 thiourea, 20 g / 1 sodium hydrogen carbonate and 10 g / 1 m-nitrobenzenesulfonic acid sodium were added.

By squeezing between rollers, a liquor absorption of about 70% of the dry weight of the goods was set. Then it was steamed at about 98 ° C for 10 minutes to fix the brightener. The aftertreatment of the Gewkbe sections was carried out by warm rinsing and boiling soaping with 1 g / 1 nonylphenol oxyethylate (with an average of 9 ethylene glycol units) and 0.5 g / 1 soda ash, calcined, and rinsing again. It was dried as usual. Very good lightening effects resulted.

Example of use 8 Extending process on viscose staple fiber fabric

Fabric made of viscose staple fiber was treated with a liquor ratio of 1:20 in the exhaust process with an aqueous liquor which had the following composition:

0.16% of compound (102), based on the weight of the goods, 5.0 g / 1 Glauber's salt.

The goods were introduced into the liquor at approx. 40 ° C., the liquor temperature was then raised to 60 ° C. within 10 minutes and treated at this temperature for a further 30 minutes. Rinsing and normal drying complete the process. The recovery effect obtained was good.

Application example 9 pull-out method on wool

Woolen fabric was prewashed as follows:

Fleet 1:30

I g / 1 isotridecanol oxyethylate (with an average of 8 ethylene glycol units), 0.5 ml / 1 ammonia solution (25%),

30 minutes, 40-45 ° C.

The goods were then bleached according to the following recipe:

Fleet I: 40

20 ml / 1 hydrogen peroxide (approx. 35%), 1.5 g / 1 tetra-sodium pyrophosphate, crystalline, and addition of ammonia solution (25%) to pH 9.5.

The bleaching lasted 4 hours at 40-45 ° C, then it was rinsed warm and cold.

The goods were lightened with:

2 g / 1 commercially available reductive bleach based on 5 sodium dithionite, 0.15% of compound (201) based on the weight of the goods at a pH of 5.5 (formic acid). After 2 hours of treatment at 50 ° C, rinsing and drying took place as usual. There was a clear brightening effect.

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Example of use 10 Extraction process on polyamide 6

1 kg of polyamide 6 knitted fabric was mixed with a liquor ratio of 1:20 on a laboratory reel skid with 0.17%

13 of the compound (105) dissolved in water or 0.15% of the compound (106) dissolved in water treated in the exhaust process (percentages based on the weight of the goods).

The pH of the aqueous liquor was 4.0 (oxalic acid) and the temperature was maintained at 20 80 ° ç. The treatment period was 30 minutes rinsed and dried as usual. This way of working resulted in very good lightening effects.

Application example 11 25 HT process on polyamide 6

20 kg of shirt fabric made of knitted polyamide 6 were treated on a tree dyeing machine with 0.17% of the compound (105) dissolved in water or 0.15% of the compound dissolved in water (106) (percentages based on the weight of the goods).

Brightening was carried out at a liquor ratio of 1:20, the liquors were adjusted to a pH of 4.0 with oxalic acid. They contained 0.5 g / 1 of a nonylphenol oxyethylate (with an average of 10 ethylene glycol units). The treatment temperature was 120 ° C, the treatment time 45 minutes. Rinsing and drying were carried out as usual. Very good lightening effects were obtained.

40 Application example 12

HT process on polyamides 20 kg of knitted fabric made of polyamide 6 or 6.6 threads were each on an HT tree dyeing machine at a liquor ratio of 1:10 with 0.17% of the aqueous solution 45 of compound (105) or (1.1 5 '; the aqueous solution of compound (106), based on the weight of the goods treated.

The aqueous treatment liquors contained 2.0 g / 1 of a reduction bleaching agent based on sodium dithionite,

50 0.5 g / 1 of a nonylphenol oxyethylate (with an average of 10 ethylene glycol units) and were adjusted to a pH of 4.0 with oxalic acid. The goods were treated at 120 ° C for 45 minutes. It was completed as usual. This way of working brought excellent brightening effects of high brilliance to the 55 goods used.

Example of use 13 Extending process on polyurethane knitted fabric made from commercially available polyurethane elastomer 60 threads

2 g / 1 nonylphenol oxyethylate (with average

9 ethylene glycol units) and 2 g / 1 of commercially available high molecular weight sodium polyphosphate at 80 ° C and a liquor ratio of 1.30 '/ 2 hours and then rinsed. The brightening of the goods followed. The work was carried out with an aqueous liquor of the following composition:

Fleet 1:20

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0.5 g / 1 nonylphenol oxyethylate (with an average of 9 ethylene glycol units), 2.0 g / 1 commercially available reduction bleach based on sodium dithionite, 0.16% of compound (105), based on the weight of the product, formic acid to pH 4.0.

After the goods had been introduced, the liquor was heated to 80 ° C. in the course of 10 minutes and the treatment at this temperature was continued for a further 20 minutes.

It was completed as usual. The elastic material was brightened very well using this procedure.