DE3109828A1 - WHITE-TONED SPIDERS FOR THE PRODUCTION OF CELLULOSE REGENERATE FIBERS - Google Patents

Abstract

1. Whitener-containing spinning dopes for the production of regenerated cellulose fibres, characterised in that they contain virtually water-insoluble lowmolecular brightener salts of the formula see diagramm : EP0060439,P8,F4 wherein A denotes the anion of a high-affinity anionic whitener for cellulose, R1 denotes optionally substituted alkyl, alkenyl, aralkyl, aryl or cycloalkyl, R2 , R3 or R4 independently of one another denote hydrogen or R1 , or either 2 or 3 of these radicals jointly form, with the inclusion of the N atom, a heterocyclic structure, and n denotes an integer > 0.

Description

• · · · · • · · m • · - • · · • ft 3109828 CHAFT 5090 Leverkusen, Bayerwerk

BAYER AKTIENGESELLSCHAFT

Central area

Patents, trademarks and licenses K / AB / kl-c March 13, 198t

Spinning masses containing whitener for the production of regenerated cellulose fibers

In the spin dyeing of artificial cellulose fibers the dyes used are subject to the most diverse chemical stresses, which are unusual in this Combination are not given in any other dyeing process. For example, the dyes need to a high degree both acid and alkali-resistant, in order to allow treatment in the various spinning baths survive unscathed.

For this reason, pigments have so far been used almost exclusively as color bodies in this spin-dyeing factory. Whitener for spin dyeing regenerated cellulose fibers have not yet been able to establish themselves on the market. The usual cotton whiteners fail here completely, since they meet the above-mentioned drastic stresses have not grown.

It has therefore already been proposed (cf. DE-PS 1 096 321 = GB-PS 815 742), water-soluble cellulose brighteners to lye by reaction with polymeric amines and the water-insoluble ones obtained in the process

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Incorporate lightening agents into spinning masses for the production of white-tinted cellulose synthetic fibers.

It has been found, however, that these brightening lacquers although they are acid and alkali stable, they only provide unsatisfactory lightening effects.

Surprisingly, it has now been found that regenerated cellulose fibers can be used after the spin dyeing method without the disadvantages mentioned, it can turn white if you use spinning pulp uses the low molecular weight brightener salts which are practically insoluble in water (i.e. which do not contain polymeric groups) the formula

? 3

contain,

wherein

A is the anion of a high-affinity anionic cellulose whitener,

optionally substituted alkyl, alkenyl, aralkyl, Aryl or cycloalkyl,

R ₃ and R, independently of one another, are hydrogen or R ₁ , or 2 or 3 of these radicals are taken together

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Inclusion of the N atom form a heterocycle, and η is an integer > 0 mean.

Suitable heterocycles which can be formed by 2 of the radicals R ₂ ~ ^R 3 are saturated 5- or 6-membered types, such as morpholine, piperidine, pyrrolidine and others

Suitable heterocycles which can be formed by 3 of these radicals are saturated types, in particular Pyridine.

Suitable alkyl radicals are in particular those with 1-20 C atoms which _{can be substituted by CN, OH, halogen, C 1} -C ₄ -AlkOXy or C.-C.-alkylcarbonylamino.

Suitable alkenyl radicals are in particular those with 2 up to 10 carbon atoms.

Suitable aralkyl radicals are phenyl-C.-C_-alkyl radicals.

Suitable aryl radicals are phenyl radicals which can be substituted by halogen, C.-C.-alkyl or C ^ -C ₄ -alkoxy.

Suitable cycloalkyl radicals are above all cyclohexyl radicals. "Halogen" is preferably understood to mean Cl and Br.

Suitable cellulose whiteners, of which the rest A derives are Bistriazolylstxlben-, Bistüben- and especially bistriazinylamino beebend disulfonic acids.

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Examples of suitable radicals A are those of the formula

, X-

_N N- /

N) -NH- / VcH-CH-ZVNH- ^ tt ^(II)

"2

wherein

X ₁ amino, methylamino, ethylamino, dimethylamino, diethylamino, 2-hydroxy-ethylamino, 3-hydroxypropylamino, di- (2-hydroxy-ethyl) amino, di- (2-hydroxy-propyl) amino, 2-sulfo-ethylamino, Morpholino, anilino, chloroanilino, sulfoanilino, methylanilino or disulfoanilino and

x is hydroxy, methoxy, ethoxy, methoxyethoxy, chlorine or X ₁ ,

as well as those of the formula

(III)

wherein

χ and X _{4 are} hydrogen, methyl, ethyl, phenyl or sulfophenyl,

as well as the formula Le A 20 923

■ · BI

• ♦ «·

- sr -

3109823

CH = CH-

(IV)

worm

X ₅ denotes hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or sulfo.

In the preparation of the compounds of the formula I, it is expedient to proceed in such a way that optical brighteners are used according to the formulas II-IV as sulfonic acids or their water-soluble salts, in particular their alkali salts, with low molecular weight basic nitrogen compounds of the formula V

R.

R ₁ -N ~ R "

(V)

wherein Y is a colorless, non-fluorescent anion or OH ', is converted.

The reaction takes place in water and / or organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, glycol, Glykolmethylether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, at temperatures from 20 ⁰ C to the reflux temperature of the corresponding Lö solution smitte1.

The sparingly soluble brightener salts obtained in this way can be used directly or after prior fine grinding or liquid formation can be used as a lightening agent.

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fm a *

The dispersions according to the invention can be prepared as follows will:

The press cake and / or powder are added after adding a surfactant and optionally water vigorous stirring homogenized. Thereafter, increasing the amount of surfactant, if necessary to the total amount required for the stability of the dispersion.

The suspension obtained is then pre-crushed and wet-ground.

The pre-comminution can be carried out using stone or toothed colloid mills.

The subsequent wet comminution can take place in colloid oscillating, cone and vibromillers as well as in dissolvers or in sub-micron dispersers. However, continuous agitator mills with grinding media, preferably those made of SiO ₂ with a diameter of 0.2-5 mm, are preferably used.

After the grinding treatment, additional amounts of surface-active substances or even hydrotropes can optionally be added Substances such as ethylene glycol or glycerine, preservatives, wetting agents, defoamers and / or water can be added, unless this is done at an earlier point in time, e.g. before grinding took place.

Another possibility according to the invention in water sparingly or insoluble whitening agents and their

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-A ti

Producing dispersions represents the combination of Reaction and grinding process:

For this purpose, the alkali salts of the brighteners according to formula II-IV are used together with the basic nitrogen compounds of formula V as well as water and surface-active Wet-shredded substances after homogenization and pre-shredding.

The complete reaction of the brightener salts II-IV with the basic nitrogen compounds V takes place in the grinding apparatus / preferably in a continuous agitator _{mill with SiO 2} grinding media.

The inventive prepared by the two processes Dispersions contain 1-25%, preferably 5-20%, of the substances according to the invention that are difficult or difficult to react with in water. insoluble brightener salts, 1-50%, preferably 5-20% surfactants, 0-15% preservatives and water, with some of the water being hydrotoped Substances can be replaced (% = weight percent).

All conventional, cationic and non-ionic surface-active substances can be used as surface-active substances into consideration, as described for example in DE-OS 2 334 769, pages 8-10 (corresponds to GB-PS 1 417 071) are.

Preference is given to using nonionic surfactants.

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· ♦ ·· I *

'Ί'"' · ^: ' 31 09823

The compounds of the formula (I) show more or less in the dissolved or finely divided state pronounced fluorescence. They are suitable for tinting natural and synthetic spinning masses white, especially of regenerated cellulose fibers such as viscose and rayon and their mixtures with aromatic ones Polyesters and polyamides. They are also suitable for lightening plastics such as polyvinyl chloride, Polyethylene and polycarbonate.

The amount of the compounds I used depends on the desired lightening effect. Generally enough 0.01-0.5 percent by weight of pure active substance (based on the fiber material to be lightened).

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3103828

example 1

10 g of the optical brightener of the formula

(D

-N

• V *

ON SO ₃ Na ^ y

and 10 g of benzyl-n-dodecyldimethylammonium chloride are refluxed in 100 ml of water for 30 min. It is then filtered off at approx. 60 ^° C. and. washed with 6O ⁰ C warm water. After drying i. Vac. 14.5 g of the quaternary ammonium salt of opt are obtained. Brightener of the above formula, of melting point: 258-259 ⁰ C, which can be recrystallized in n-butanol. The substance is insoluble in water and, when incorporated into viscose spinning masses, shows excellent whitening effects on the fiber.

Example 2

In the same way as described in Example 1, the brightener of the formula (1) is reacted with 7.5 g of benzyl • dimethylphenylammonium chloride. This gives 12.2 g of light yellow crystals of melting point: 259-260 ⁰ C, which can be recrystallized from ethylene glycol.

The substance is practically insoluble in water and, when incorporated into viscose, shows excellent white effects,

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Example 3

9.6 g of the opt. Brighteners of the formula

(2)

are refluxed for 1 hour with 6 g of benzyldimethylphenylammonium chloride in 200 ml of water. Filtration at about 50-60 ⁰ C and drying in vacuo. gives 8 g of a pale yellow crystalline powder of m.p .: 212-215 ° C _f which can be recrystallized from n-butanol. Brilliant white effects on rayon fibers.

Example 4

6 g of the whitening agent of the formula

-CH = CH

SO ₃ Na

(3)

are refluxed for 1 hour with 10 g of benzyldodecyldimethylammonium chloride in 100 ml of water. Filtration and drying i. Vac. provides 10.3 g of almost colorless crystals of mp .: 268-270 ⁰ C, which can be recrystallized from ethylene glycol.

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Example 5

7 g of the opt. Brighteners of the formula N

-CH = CH
SO ₃ Na SO ₃ Na

are heated with 10 g of benzyl-dodecyl-dimethylammonium chloride in 120 ml dimethylformamide for 2 hours under reflux, and filtered after cooling to 10 ⁰ C .. This gives 8.7 g of pale yellow crystals of m.p .: 182-184 ° C, consisting of ethylene glycol can be recrystallized.

Example 6
8.5 g of the optical brightener of the formula

(5)

CH ₃ -HN

are dissolved in 100 ml of water and then refluxed with 10 g of benzyldimethylphenylammonium chloride for 2 hours. Cooling and suction supplies 13g of yellowish crystals of mp .: 224-226 ⁰ C, which can be recrystallized from ethylene glycol.

Example 7

10 g of the optical brightener of the formula (1) and 3 g of triethylamine hydrochloride in 150 ml of water are added for 1 hour.

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ara heated to reflux, cooled and filtered off. Yellowish Crystals that can be redissolved from methylglycol.

Example 8

In the same way as in the previous ones
Examples described, one obtains further sparingly soluble quaternary ammonium salts of opt. Brighteners obtained by reacting compounds of the formula

with ammonium salts of the formula

CH-,

¹² (7)

can be obtained.

The following table contains the residues of the starting compounds (6) and (7) used.

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OCH ₃ N (C ₂ H ₄ OH) ₂

OCH.

NH (CH ₂ CH ₂ SO ₃ Na)

NH-CgH ₅ NH (C ₂ H ₄ OH)

CH-

CH-

^C 6 ^H 5

NH (C ₀ H ₇₁ OH) 24

CH ₂ -C ₆ H ₅

12th NH-Cg ^H 5 NH CH ₃ 2 ^CH 2 ~ ^C 6 ^H 5 ^C 12 ^H 25 13th NH-C ₆ ^H 5 NH C ₂ H ₅ ^C 6 ^H 5 CH ₂ -CgH ₅ 14th nh- {o N (C ₂ H ₄ OH) ^C 6 ^H 5 ^CH 2 ~ ^C 6 ^H 5 SOgNa OH) 15th NH ₂ NH ₂ CH ₂ -CgH ₅ ^C 14 ^H 29 16 OCH ₃ NCH ₃ (C ₂ H ₄ CH ₃ ^C 12 ^H 25 17th NH ₂ NH-C ₅ H ₅ CH ₂ -CgH ₅ ^CH 2 ^C 6 ^H 5 18th NH-C--
ο ^H 5 NH-C ₃ H ₅ ^C 6 ^H 5 ^C 12 ^H 25

NH-CcH ₁ . NH (C ₀ H.OH)

OD 2 4

^C 2 ^H 4 " ^C 6 ^H 5 ^C 2 ^H 4 ~ ^C 6 ^H 5

NH-CcH ₁ , NCH, (C ₀ H ₄ OH) CH, whether J 2 4 J

^C 2 ^H 4 ~ ^C 6 ^H 5

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■ *;: 3109823

- 4-4 -

Example 9

20 g of the water-insoluble whitening salt prepared according to Example 1 are added together with 20 g of emulsifier W and 60 g of water are homogenized and pre-comminuted with a toothed colloid mill. The suspension is then wet-crushed at room temperature with 4 passes in a bead mill. The resulting stable dispersion is easy to work into the spinning masses and shows also excellent whitening effects on the spun fiber.

Example 10

16 g of the opt. Brighteners of the formula 1 from Example 1 are mixed with 12.8 g of benzyldimethylphenylammonium chloride, 16 g of emulsifier W and 55.2 g of water homogenize while stirring

^ ⁵ sized and pre-crushed with a tooth grinder. The suspension is wet-ground at room temperature and 4 passes in a bead mill. The resulting stable dispersion is easy to incorporate into the spinning mass and shows excellent whitening effects on the spun fiber.

Example 11

16 g of the optical brightener of the formula 1 from Example 1 are mixed with 16 g of benzyldodecyldimethylammonium chloride, 16 g of emulsifier W and 52 g of water are homogenized with stirring and pre-comminuted with a toothed colloid mill .. The suspension is in crushed wet in a pearl mill.

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Example 12

The brightener salts, which are sparingly soluble or insoluble in water, can be prepared in the same way as described in Example 9 Examples 4, 5 and 6 and the compounds (8) - (20) described in Example 8 to form stable dispersions form.

Example 13

In the same way as described in Examples 10 and 11, the starting products (8) - (20) described in Example 8 can also be converted and stabilized Form dispersions.

Example 14

1 kg of viscose (7% cellulose dissolved as xanthate in sodium hydroxide solution) is shaken well with 1.2% Dispersion (16% based on active ingredient), the preparation of which is described in Example 9 or 11, added; It is stirred well for 6 min. (70 rpm), deaerated at approx. 200 torr for 60 min. and then in a. Coagulation bath, consisting of sulfuric acid (8%), sodium sulfate (16%) and zinc sulfate (3%), spun off and usually worked up. An influence the spinning baths could not be found either in the acidic or in the alkaline range.

A comparison of the lightening with equivalent amounts of the starting compound (1) shows that one is with the precipitated quaternary ammonium salt gets higher degrees of whiteness.

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In the same way, the corresponding amount of the pure active ingredient from Example 1 can also be used and to be spun.

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Claims (1)

Claims 1. Spinning masses containing whitener for the production of regenerated cellulose fibers, characterized in that that the low molecular weight brightener salts of the formula which are practically insoluble in water ? 3 contain, in which A is the anion of a high-affinity anionic Cellu loose whiteners optionally substituted alkyl, alkenyl, aralkyl, aryl or cycloalkyl, ₃ or R ₄ independently of one another are hydrogen or R ₁ , or 2 or 3 of these radicals each together form a heterocycle including the N atom, and an integer mean. 2) spinning masses according to claim 1, characterized in that that they, as brightener salts, are those of the given formula, in which Le A 20 923 for a remainder of the formula (ID wherein Amino, Methy1amino, Ethylamino, Dimethylamine, Diethylamino, 2-hydroxyethylamino, 3-hydroxypropylamino, Di (2-hydroxy-ethyl) amino, di (2-hydroxy-propy1) amino, 2-sulfo-ethylamino, morpholino, anilino, chloroanilino, suIfoanilino, Methylanilino or 2-disulfoanilino and X-, hydroxy, methoxy, ethoxy, methoxyethoxy, chlorine or X ₁ mean, stands. 3) spinning masses according to claim 1, characterized in that it is a compound of the formula NH tJ ^ t = -CH = \ (■ CH 2 \ - CH ^ -N-CH-3, 3 ^C 12 ^H 25 contain. Le A 20 923 4) spinning masses according to claim 1, characterized in that it is a compound of the formula NH -CH = SCU CH 2 \ ~ CH-j-N-CH, 3 ι 3 contain. 5) spinning masses according to claim 1 _r, characterized in that they contain those of the formula given as brightener salts, in which A for a remainder of the formula VS-CH = CH- / 'A— U M_rH = srw- and X denotes hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or sulfo. 6) Process for the production of spinning masses according to claim 1, characterized in that one optical Formula lightener Le A 20 923 A ^{n (} - ^} / h7 ⁽⁺⁾ - η or their water-soluble salts with η equivalents of a basic nitrogen compound of the formula R ₁ -NR ₂ wherein Y is a colorless, non-fluorescent, water-soluble agent Anion or OH ~ means, converts the resulting, practically in water insoluble brightener salt isolated and incorporated into a viscose dope. Process according to Claim 6, characterized in that the sparingly soluble brightener salt is used subjected to wet grinding in the presence of surfactants. 8) Method according to claim 6, characterized in that the optical brightener together with the basic nitrogen compound and the surfactants subjected to wet grinding. Le A 20 923