DE1619071A1 - Process for finishing and whitening textiles - Google Patents

Description

Dr.F.Zumstein-Dr.EAssmonn 3-2456 *

Dr. R. Koenigsbergar Dipl. Phys. R. Holzbauer

Patent attorneys Munich 2, Bräuhäusstralje 4 / III

Process for finishing and whitening textiles.

The invention relates to the permanent press method finished and tinted textiles and cellulose fibers, Process for the manufacture of these articles, suitable for this process «optical whiteners and process for their manufacture.

The optical brightening of cellulose fibers in any one Processing status, be it in the form of yarns, woven or knitted fabrics, before or after the conventional finishing of such textiles, as well as in use in washing or rinsing laundry, presents no fundamental technical problems, albeit improvements, for example with regard to light fastness, color tone and brilliance of the brighteners, are still quite desirable. .

In contrast to this fact, the modern resin finishing of textiles for the purpose of achieving dimensional stability, the .untei terms such as wash-and-wear and no-iron are particularly well-known and popular in America, are tasks that are more difficult to solve and sometimes still unsolved are.' This is particularly true for ^: the newly emerging finishing of textiles using the so-called permanent press process. One of these methods is that cotton fabrics intended for textile processing are impregnated with a mixture of resin-like precondensates, preferably based on acid amide-formal resin, especially of the type Kohlensaü ^ eeiamid-formal resin, a hardening catalyst, as well as softening agents and then under mild conditions

dried . The tissue so equipped _ ^

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then goes to the garment manufacturer, is cut and sewn into pieces of clothing. The garment is then pressed at a temperature of about 120 ⁰ C and then the resin is condensed by a heat treatment for about 15 minutes at 160-180 ⁰ C and cured. Compared to the older resin finish of textiles of the wash-and-wear type, the permanent press finish, which has become particularly known under the protected name KORATBON from the company Köret, San Francisco, USA, is characterized by a significantly improved dimensional stability after repeated washing the end. There is also the version of the permanent press process known as pre-curing. being networked before assembly and pressing after assembly, in question.

Particularly suitable resins for the permanent Bress finish are compounds from the group of dimethylol-Ν, Ν'-alkyleneureas and, for example, commercial products that are protected under protected names such as. "KNITTEX EVERFIT LE" Company chemical plant Pfersee, A ^u gsburg (Federal Republic of Germany); "FIXAPEiET CPN" from the Badische Anilin- und Sodafabrik (BASF) in Ludwigshafen (Federal Republic of Germany), or "PEBMAFRESH Beactant 183" from the Warwick Chemical Corporation in Wood River Junction (USA) are available for purchase. Other resins used in practice are alkyl carbamates, dimethyloltriazone, dimethylolhexpyrimidone, 1,3-diglycidylglycerol, and imidazolidone / triazine mixed condensates. The activity of the hardening catalyst plays a major role in the permanent press process. Only highly effective hardeners can be used} zinc nitrate is preferred over zinc chloride or magnesium chloride, which are generally not entirely satisfactory.

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Unfortunately, it has been shown that zinc nitrate, under the necessary working conditions, is far from common with all conventional catalysts causes strongest yellowing of the textile material. It’s about it in the permanent press finishing of white goods for the purpose of preservation an appealing aspect of the goods inevitably that Whiteners are used because the yellowing is neither

wash out or remove by chemical bleaching lässii.

It has also been shown that the preferred whiteners for cellulose fibers from the class of 4,4'-bis- (triazinylamino) -stilbene-2,2'-disulfonic acids, which top products in terms of affinity of fiber, luminosity and hue of fluorescence contains, cannot be used, because apparently the zinc nitrate under the reaction conditions of the resin hardening changes the whitener in such a way that a strong brown coloration occurs during the subsequent exposure. The treated White goods are unusable because the tan is not a one-off or repeated washing, or can be removed by oxidative or reductive chemical bleaching. : Although it is possible to reduce the browning in the light by choosing a different curing catalyst; but also the essential one The advantage of the new finishing process is the high dimensional stability of the equipped goods if repeated several times

Lost laundry. Many other well-known whiteners fail, be it due to insufficient affinity for cellulose, inadequate Improvement of the degree of whiteness, causing undesired color casts or because of insufficient resistance under the working conditions. The whiteness of the resins used also only leads to

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unsatisfactory results and, moreover, requires an undesirable one Post-treatment of the shape-stabilized goods. In particular, their treatment with the effective whiteners of 4,4'-bis (triazinylamino ) -stilbene-2, 2'-disulfonic acid series is ineffective due to a lack of affinity for the resin-laden fibers. This is why the Permanent press equipment practically limited to pre-dyed fibers. However, there is a great need for a form-stable and wash-resistant finish, especially with white goods such as blouses and shirts .

It has now been found that, surprisingly, textiles are finished using the permanent press process: and at the same time can be tinted white if you look at the goods in front of or in the impregnation with curable resins or resin precursors, curing catalyst and optionally containing plasticizer aqueous preparation, followed by drying, shaping and curing a stilbyl-naphthotriazole compound of the general Formula I winds up,.:

Shark

(D

in what formula

one of the symbols Y ,, Y ₂ ^anc * ^ 3 ^^ - ^e sulfonic acid group and the

the other two are hydrogen and "Hai" is halogen up to atomic number 35.

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The halogen substituent, d-.h. Fluorine, bromine or chlorine in formula I can be in ο- or m-position to Vinylene bridge are located; ' a particularly favorable influence he exercises in meta position.

Especially preferred white tones therefore correspond to the general formula II

Shark

in which the symbols have the meaning given under formula I.

The second sulfonic acid group is advantageously in position Y ₂ *. ^In particularly valuable whiteners according to the invention, both of the last-mentioned features apply, and finally, chlorine is the preferred halogen substituent "Hai".

The soluble salts of whiteners of the general formulas I or II are primarily the alkali metal salts; but ammonium salts, especially N-substituted ammonium salts of strong nitrogen bases, can also be used can be used, for example alkane oil amine salts.

The new, particularly valuable stilbyl naphthotriazole compounds of the general formula II are obtained by methods known per se, for example by coupling the diazo compounds a 4-amino-stilbene compound of the general ' Formula III

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(III)

SO ₃ H Hal

with coupling in the o-position to a primary amino group 1- or 2-aminonaphthalene-monosulfonic acid of the general Formula] V:

(IV)

In the * formulas III and IV, "Hai" and Υ _χ , Y ₂ and Y _{3 have} the meanings and emphasis given above and of Q, and Q ₂ means one of the amino groups and the other of the coupling conditions through the stilbylazo group Replaceable hydrogen. The o-aminoazo dyes obtainable in this way are then oxidized to the corresponding stilbyltriazole compounds of the general formula II by methods known per se, for example with oxygen or oxygen-containing gas mixtures such as air, in the presence of copper tetramine salts or with soluble salts of hypochlorous acid such as Sodium, potassium or calcium hypochlorite. .

The new stilbylnaphthotriazole compounds of the formula II represent pale yellow colored powders in the form of their water-soluble alkali salts, which dissolve well in water and are among the have good affinity for cellulose under normal dyeing conditions,

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They are primarily used to whiten cellulose fibers in aqueous liquors and can especially also be used in impregnation liquors for the dimensionally stable finishing of Cellulose fabric used according to the permanent press process will.

The whitening agents of the formula I used according to the invention are absorbed when finishing cellulose fabric by the permanent press process in the usual amounts of 0.01 to 0.3 $ active substance based on the fiber weight by, for example, impregnating them in amounts of 0.1 up to 3.0 g per liter, which ^{contain 100 - 250 g N, N 1} -dimethylol-ethylene-dihydroxy urea and 5-20 g zinc nitrate per liter, 'added, the goods are impregnated on the padder with a squeezing effect of about 70- 100 $ liquor, based on the dry weight of the fabric, this dries at 60-80 ⁿ , then made up, ironed and hardened.

Further details can be found in the following examples which illustrate the subject matter of the invention. Unless otherwise noted, the parts denote parts by weight. The temperatures are given in degrees Celsius .

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example 1

A cotton fabric is on a padder with a suspension containing 180 g of a dimethylol-dihydroxy-ethylene urea (KNITTEX everfit LE from Chem. Fabrik Pfersee, Augsburg, Germany), 10 g zinc nitrate and 1.0 g of the whitening agent of the formula:

Clv.

CH = CH - <ζ _> - N-: NaSOC J /

Impregnated in 1000 ml of water at 25 °, squeezed off (squeezing effect approx. 70 %) and dried at 60 °. The fabric finished in this way is then treated for 15 minutes at 160 ° for condensation and crosslinking of the resin. The result is a fabric which, on the one hand, is dimensionally stable and, on the other hand, has a brilliant catfish tint. A fabric tinted white in this way can be exposed to light without the risk of browning.

A weaker lightening effect is obtained when instead of 1.0 g only 0.5 g of the whitening agent is used.

If, in the above example, the cotton fabric is replaced by a rayon fabric, the fabric treated in this way also becomes strong lightened, retains its shape and does not turn brown in light. A mixed fabric made of cotton and polyester is also used or made of cotton and synthetic polyamide fibers, the cellulose content is also strongly lightened. For brightening the Polyester or polyamide parts are used in a separate one Pretreatment of a brightener specifically suitable for these fibers.

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A similar shade of white is obtained if, in the above example, the 0.5 g of the di-sodium salt of 2- (3 ' ^M -chloro-stilbyl-4 ") naphtho-1', 2 ': 4.5) -1, 2,3-triazole-2 ", 5'-disulfonic acid by equal parts of the ^{disodium salt of 2- (3 III} -chloro-stilbyl-4 ^II ) - (naphtho-

-1 2 3-l ^l , 2 ^l : 4,5S ^ triazol-2 ^rl , 4 ^l -or. - 2 ", 6 · -disulfonic acid or the 2- (3 '" -

—1 2 3 * ■ Fluorstilbyl-4 ") - (naphtho-1 ', 2 ·: 4.5) _/ ftriazol-2", 5 · -disulphonic acid.

Also used as a lightening agent is 0.5 g of the " ^{disodium salt of 2- (2 I} " -chloro-stilbyl-4 ") - (naphtho- ^l , 2 ¹ : 4.5) -1,2,3-triazole -2 ", 5'-disulfonic acid. Or the disodium salt of 2- (2 ^IM -Chlor-

-1? 2? 3_1

stilbyl-4 ") - (naphtho-1 ¹ , 2 ': 4.5) / ttiflazol-2", 4' -or. -2 ", O ¹ -disulfonic acid is used, one obtains somewhat less brilliant white tones.

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Example 2

A cotton fabric is placed on a padder with a suspension containing 150 g of dimethylol-oxy-propylene-urea the formula

OH ₂ -OH

N - ₀
O = G _x CIi-OH

C]

H ₂ -OH

12 g of zinc nitrate and 1.0 g of the whitening agent of the formula

CH = CH - <\ _>
NaSO, N

SCLNa

Impregnated in 1000 ml of water at 25 °, squeezed off (quenching effect approx. 70 %) and dried at 60 °. The fabric finished in this way then becomes condensation; and crosslinking the resin treated for 15 minutes at 165-168 °. A fabric is obtained in this way, which on the one hand is dimensionally stable and on the other hand has a brilliant white tint. A fabric tinted white in this way can be exposed to light without the risk of browning.

A similar but weaker white tint is obtained} if in the above example instead of the disodium salt of 2- (3 ^"g -phlor-stilbyl-4") - (naphtho-l ^l, 2 's4,5) -l, 2,3 -triazole-2 ", 5'-disulforic acid as a whitening agent, 0.5 g of the disodium

salt of 2- (2 "'- chloro-stilbyl-4") - (naphtho-1 «, 2»' »4,5) -l, 2,3-triazol-2", 5 ^l -disulfonic acid is used.

Furthermore, in the above example, the dimethylol-ossy-propyleneurea by 200 g of dimethylol methyl earbamate of the formula

CH ₂ -OH

CH - O-CO-N

⁵ N) H ₂ -OH

replaces werefe ^ u You also get a dimensionally stable, white-tinted one Fabric without the tanning effect in the light. . ,

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Example 3

A cotton fabric is placed on a padder with a suspension containing 200 g of a mixture of 70 parts Dimethylol ethylene urea of the formula

CH ₂ -OH
N CH,

-CH,

CH ₂ -OH

and _v 30 parts of hexantethylol melamine, 8 g of zinc nitrate and 1.0 g of the whitening agent of the formula

CIn

NaSO

SO-Na

Impregnated in 1000 ml of water at 25 °, squeezed off (squeezing effect approx. 70 %) and dried at 60 °. The fabric finished in this way is then treated for 15 minutes at 165-170 ° for condensation and crosslinking. The result is a fabric that is dimensionally stable on the one hand and has a brilliant white shade on the other. A fabric tinted white in this way can be exposed to light without the risk of browning.

A similar but weaker shade of white is obtained if, in the above example, instead of the disodium salt of 2- (3 "'- chlorostilbyl-4 ^ll ) - (naphtho-l', 2 ^l : 4.5) -l, 2.3 -triazol-2 ", 5 ^l -disulfonic acid as a lightening agent 0.5 g of the disodium salt of 2- (2 ^lth -Chlor stilbyl-4") - (naphtho-1 ·, ^ J ⁹ 4? 5 ¹ ) 1/3, 3-iriazol-2 ", 5 · -disulfonic acid

is used.

Furthermore, in the above example, the mixture of dimethylolethylene urea and replacing hexamethylol melamine with 190 g of dimethylol propylene urea. A dimensionally stable, White-tinted fabric without braid inserts in the light.

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Example 4

A mixed fabric of 65 % polyethylene glycol terephthalate and ¹ 35 % cotton is placed on a padder with a suspension containing 190 g of a dimethylol-dihydroxy-ethylene urea (KNITTEX. Everfit LE from Chem. Fabrik Pfersee, Augsburg, Germany), 10 g of zinc nitrate, 1 , 0 g des'brightener of the formula

CH = CH Na SO

S0, well y

and 0.6 g of the creamer of the formula

in 1000 ml of water, impregnated at 25 °, squeezed off (squeezing effect approx. 65 %) and dried at 90-92 °. The fabric is then exposed to a temperature of 140-150 ° for 5 minutes for polymerization. The fabric treated in this way can now optionally be made up.

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For the final form stabilization, the fabric is only used during Steamed for 15-20 seconds and then for 15-20 seconds at 205-215 ° and a pressure of approx. 800 g / cm to break open the existing and subsequent new formation of the cross-linking pressed.

The result is a fabric that is dimensionally stable on the one hand and on the other hand has a white tint. Such a whitewashed one Tissue can be exposed to light without the risk of browning.

A weaker whitening effect is obtained if, in the above example, instead of 1.0 g: only 0.5 g of the brightener is used, and the rest of the procedure is the same Lightening agent used disodium salt of 2 ^f (3 "'- chlorostilbyl-4") - (naphtho-l ¹ , 2': 4,5) -l, 2,3-triazol-2 ^l t, 5 ¹ -disulfonic acid 0 , 5 g of the ^{disodium salt of 2- (3 in} -Chlor-sti3 £ byl-4 ^II ) - (naphthol ', 2': 4,5) -l, 2,3-triazol-2 ", 4'- or -2 ", 6'-disulfonic acid, etc. der 2 ^I (2 "'- chloro-stilbyl-4") - (naphtho-1 ^t , 2 ": 4,5) -1, 2,3-triazol-2", 4 ^ or -2 ^1!, 5'- or -2 ", 6'-disulfonic acid can be used.

Furthermore, in the above example, the dimethyl ^; ol dihydroxyethylene urea can be replaced by 180 g of a mixture consisting of 70 parts of dimethyl oil ethylene urea and 30 parts of hexamethylol melamine or by 200 g of dimethylol methyl carfaamate. In this way, a dimensionally stable, white-aged fabric is also obtained, which does not show any signs of browning in the light.

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If, instead of the zinc nitrate mentioned in the above example as a curing catalyst, the same amounts of zinc chloride are used or magnesium chloride and otherwise works according to the method described above, one also obtains white-tinted ones Tissue. Fabrics treated in this way have a lower dimensional stability, but also do not produce any in the light Signs of browning.

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example

A solution of the sodium salt of 31.0 g of 4-amino-3'-chlorostilbene-2-sulfonic acid and 7.1 g of sodium nitrite in 800 ml of water is enlaced at a temperature of 8-10 ° into a solution of 12, 8 g. Hydrochloric acid indirectly dlazotiert in 120 ml of water. The mixture is then stirred for a further 30 minutes at 8-10 °, the excess nitrite is then removed with a little sulfamic acid and the diazo suspension at a temperature of 12-15 ° to form a solution of 22.4 g of 2-AmInO-HaPh ^ aUn-O-SuIfOnSaUrC , 4.1 g of sodium hydroxide in 600 ml of water were added. The pH of the coupling is kept at about 4.5 and the temperature at 20-25 ° by adding crystallized sodium acetate. After the coupling is complete, the o-amino-azo dye is completely salted out by adding 140 g of sodium chloride, filtered off and washed out with 10% sodium chloride solution. The moist dye is then dissolved in 1000 m of hot water with the addition of sodium hydroxide solution dissolved until it is clearly phenolphthalein alkaline and then treated with a solution of 2.5 g of crystallized copper sulfate in 100 ml of water and 10 g of monoethanol alcohol. The o-amino-azo compound is then added

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1619U71

oxidized with vigorous stirring by introducing a vigorous stream of air at a temperature of 92-95 ° to the stilbylnaphtho- 'trlazole compound. After the red color of the o-amino-azo dye has disappeared, excess aqueous sodium sulfide is added to the solution, the precipitated copper sulfide is separated off by a clarifying filtration, the copper residue is washed with 250 ml of hot water and the combined filtrates are heated again to 95 °. To remove any coloring products, 5 - 10 g of sodium hydrosulphite are added until the solution remains lighter and 5 % sodium chloride is then added to the solution. After stirring at room temperature for 4 hours, the precipitated product is filtered off and treated with * 5 * % Ig '€ v Nätriumchloridlösung washed. for further purification, can be recrystallized or reprecipitated from water if necessary, the compound either #igem 50 from aqueous n-propanol. the product obtained is dried in vacuum at 120 125 °.

The disodium salt of 2- (3 ^III -chloro-stilbyl-4 ") - '. (Naphtho-1', 2 ': 4.5) -1,2,3-triazole-2", 5 · is obtained -disulfionic acid as a yellowish, water-soluble powder with a melting point of over 3.00 °. :;

The compound obtained is a valuable lightening agent for whitening cellulose fibers, fibers made from synthetic polyamides, soap, soap powders and detergents. The above-mentioned compound is particularly suitable for whitening * cellulose fibers that are subsequently or simultaneously with. a resin and at the same time impregnated with zinc nitrate as a catalyst, dried, possibly partially condensed andl further after a

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1b19U71

carried out assembly "at temperatures of 1-60 - 180 ° be condensed and networked.

• Compounds with similar properties and sometimes slightly different nuances can be obtained by replacing 2-amino-naphthalene-5-sulfonic acid with equal amounts of 2-amino-naphthalene-6- or -7-sulfonic acid, or l- Amino-naphthalene-4-sulfonic acid replaced, · in this case the disodium salt of 2- (3 "'- ChlorstilbyX-4") - (naphtho-1 ^r , 2 ^l : 4.5) -l, 2 is obtained _y 3-triazole-2 ", 6 ^I -, or -2", 7 ', or -2 ", 4'-disulfonic acid as a yellowish to pale yellowish powder with a melting point of over 300 °.

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ORlGfNAl INSPECHD

Claims (7)

Claims 1. Process for finishing and whitening textiles according to the permanent press process by impregnating with Aqueous preparations containing curable resins or resin precursors and curing catalyst, drying, shaping and curing, characterized in that a stilbylnaphthotriazole compound is applied to the goods to be finished before or during the impregnation the general formula I is raised, Shark (D in what formula one of the symbols Yp Y ₂ ^una - ^ 3 ^the sulfonic acid group and the the other two are hydrogen and "Hai" is halogen up to atomic number 35. 10 9 8 11/2113 1619U71 2. Procedure according to. Claim 1, characterized in that "Hai" takes the meta position in relation to the vinyl bridge. 3. The method according to claim 2, characterized in that "shark" means chlorine. 4. The method according to claim 1, characterized in that Y _{2 is} the sulfonic acid group and Y and Y _{3 are} hydrogen. 5.. Stilbylnaphthotriazole compounds of the formula II λ Hal SO ₃ H in which one of Y ₁ , Y ₂ and Y _{3 is} the sulfonic acid group and the others are hydrogen and "Hai" are halogen up to atomic number 35. 109811/2113 1619U71 CU / 6. Compound / according to claim 5, in which "shark" is chlorine means. 7. Process for the preparation of stilbylnaphthotriazole compounds of the formula II, characterized in that the diazo compound of a 4-amino-3'-halostilbene-2-sulfonic acid with halogen up to atomic number 35 with an aminonaphthalene monosulfonic acid coupling in o-position to the amino group of the general formula IV (IT) in which one of Υη, Y2 and Y ^ the sulfonic acid group and one of Q. and Q2 is the amino group and the remaining symbols Mean hydrogen, couples to the o-aminoazo dye and this according to methods known per se to form the naphthotriazo! Compound of the formula II is oxidized. J. R.. G e i g y A. 109811/2113