DE19533218A1 - Hydrophilic modified poly:isocyanate use as curing agent during sizing and opt. dyeing with indigo - Google Patents

Abstract

The claims concern the use of hydrophilic modified polyisocyanates (I) in combination with (a) sizes (II) cured with (I) for producing permanently sized yarns and (b) (II) and indigo for 1-stage sizing and dyeing of yarns or dyeing and printing of fabrics.

Description

The invention relates to the use of hydrophilically modified Polyisocyanates together with sizing agents that are combined with the hydro phil modified polyisocyanates are crosslinkable, for the manufacture processing of permanently sized yarns and the use of Indigo in the sizes for one-step finishing and dyeing of yarn or for dyeing and printing fabrics.

Textile yarns consisting of a large number of individual threads and which are used as warp yarns in a weaving process usually treated with a sizing agent to the individual to connect threads of the yarns together. This treatment ver strengthens and solidifies the warp yarns and makes them for the webpro more abrasion resistant. Filament yarns, especially those with fine deniers from individual filaments with a titer in the range from 4 to 0.1 dtex, need one for processing in the weaving mill very special mechanical protection to rely on high performance weaving seem to be able to be woven non-destructively.

Known synthetic sizing agents are, for example, poly vinyl alcohols, polyacrylates and polyesters, cf. US-A 4,268,654, US-A 3 519 477 and DE-B 20 04 676. The sizing agents are usually washed out of the fabrics after the weaving process. The fabrics are then dyed, printed, coated or otherwise treated.

DE-A 42 17 716 describes the use of polyisocyanate mixed with an average NCO functionality of 1.8 to 4.2 and a content of aliphatically bound isocyanate groups of 12.0 to 21.5% by weight as a crosslinker for use in textile pastes ten binders known. The polyisocyanates can optionally also be modified hydrophilically.

The present invention has for its object yarn al of a permanent nature and possibly together with to color the finishing.

The object is achieved with the use of hydrophilically modified polyisocyanates

• (a) in combination with sizing agents with the hydrophilic modified polyisocyanates are crosslinkable, for the manufacture processing of permanently sized yarns,
• (b) in combination with the sizing agents mentioned under (a) and indigo for single-stage sizing and dyeing of yarns or for dyeing and printing fabrics.

As the basis for the hydrophilic modes to be used according to the invention fected polyisocyanates serve conventional diisocyanates and / or usual higher functional polyisocyanates with a medium NCO functionality from 2.0 to 4.5. These components can alone or in a mixture.

Examples of common diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diiso cyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, Dodecamethylene diisocyanate, tetradecamethylene diisocyanate, tri methylhexane diisocyanate or tetramethylhexane diisocyanate, cyclo aliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanato cyclohexane, 4,4′-di (isocyanatocyclohexyl) methane, 1-isocyanato 3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (Isophorondiiso cyanate) or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, Tetramethylxylylene diisocyanate, p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 1,3- or 1,4-phenylenediiso cyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diiso cyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-di methyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate or Diphenyl ether 4,4'-diisocyanate. Mixtures of the ge called diisocyanates are present. Of these, alipha are preferred table diisocyanates, especially hexamethylene diisocyanate and Isophorone diisocyanate.

The usual higher functional polyisocyanates are suitable for for example triisocyanates such as 2,4,6-triisocyanatotoluene or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, Tri and higher polyisocyanates by phosgenation of corresponding aniline / formaldehyde condensates are obtained and Represent polyphenyl polyisocyanates having methylene bridges.

Of particular interest are the usual aliphatic radio tional polyisocyanates of the following groups:

• (1) Isocyanurate group-containing polyisocyanates from aliphati and / or cycloaliphatic diisocyanates. Especially the corresponding isocyanato isocya are preferred  nurates based on hexamethylene diisocyanate and isophorondi isocyanate. The present isocyanurates are especially simple tris-isocyanatoalkyl or triiso cyanatocycloalkyl isocyanurates, which cyclic trimers of Represent diisocyanates, or mixtures with their higher, homologues with more than one isocyanurate ring. The Isocyanato isocyanurates generally have an NCO content from 10 to 30% by weight, in particular 15 to 25% by weight, and a average NCO functionality from 2.6 to 4.5.
• (2) Uretdione diisocyanates with aliphatic and / or cycloali phatic bound isocyanate groups, preferably from hexa derived methylene diisocyanate or isophorone diisocyanate. At Uretdione diisocyanates are cyclic dimers sation products of diisocyanates.
• (3) Biuret group-containing polyisocyanates with aliphatic bound isocyanate groups, especially tris (6-isocyanato hexyl) biuret or its mixtures with its higher homo lied. These have biuret polyisocyanates generally an NCO content of 18 to 25 wt .-% and a average NCO functionality from 3 to 4.5.
• (4) Polyiso containing urethane and / or allophanate groups cyanates with aliphatic or cycloaliphatic bound Isocyanate groups, as for example by reacting excess amounts of hexamethylene diisocyanate or Isophorone diisocyanate with simple polyhydric alcohols such as Trimethylolpropane, glycerin, 1,2-dihydroxypropane or their Mixtures can be obtained. This urethane and / or Polyisocyanates containing allophanate groups have in all mean an NCO content of 12 to 20 wt .-% and average NCO functionality from 2.5 to 3.
• (5) Polyisocyanates containing oxadiazinetrione groups, preferably example of hexamethylene diisocyanate or isophorone diisocyanate derived. Such poly containing oxadiazinetrione groups Isocyanates can be produced from diisocyanate and carbon dioxide.
• (6) Uretonimine modified polyisocyanates. For the use according to the invention, aliphatic diiso Cyanates and aliphatic higher functional polyisocyanates preferred.

The described diisocyanates and / or more functionalized Polyisocyanates become non-ionic hydrophilic for conversion modified polyisocyanates used for the inventive tion are particularly preferred, with NCO-reactive compounds implemented, the hydrophilic structural elements with not ionic groups or with polar groups that are not in ions groups can be transferred. That’s it Diisocyanate or polyisocyanate in a stoichiometric excess before so the resulting hydrophilically modified polyisocyanate still has free NCO groups.

As such, NCO-reactive compounds with hydrophilic Structural elements come primarily from hydroxyl-terminated groups Polyethers of the general formula

R¹-X- (AO) _n -H (I),

in the
R¹ is C₁ to C₂₀ alkyl, in particular C₁ to C₄ alkyl, or C₂ to C₂₀ alkenyl, cyclopentyl, cyclohexyl, glycidyl, oxethyl, phenyl, tolyl, benzyl, furfuryl or tetrahydrofurfuryl,
X denotes sulfur or in particular oxygen,
A means propylene or, above all, ethylene, and in particular mixed ethoxylated and propoxylated compounds can also occur in blocks, and
n stands for a number from 5 to 120, in particular 10 to 25,
into consideration.

This is particularly preferably to C₁ to C₄-alkanol started with ethylene oxide or propylene oxide polyethers average molecular weights of 250 to 7000, in particular 450 until 1500.

One can radio from the described diisocyanates and / or higher tionalized polyisocyanates also first by reaction with a deficit of hydroxyl-terminated polyesters other hydroxyl-terminated polyethers or on polyols, e.g. B. ethylene glycol, trimethylolpropane or butanediol, prepolymers generate and then these prepolymers or  simultaneously with the polyethers I in deficit to the hydrophilic implement modified polyisocyanates with free NCO groups.

It is also possible to produce non-ionically hydrophilically modified polyisocyanates from diisocyanate or polyisocyanate and polyalkylene glycols of the formula HO- (AO) _n -H, in which A and n have the meanings given above. Both terminal OH groups of the polyalkylene glycol react with isocyanate.

The enumerated types of non-ionic hydrophilic modified Polyisocyanates are described in DE-A 24 47 135, DE-A 26 10 552, DE-A 29 08 844, EP-A 0 13 112, EP-A 019 844, DE-A 40 36 927, DE-A 41 36 618, EP-B 206 059, EP-A 464 781 and EP-A 516 361 described in more detail.

The described diisocyanates and / or more functionalized Polyisocyanates become anionically hydrophilic for conversion modified polyisocyanates with NCO-reactive compounds vice versa sets, the hydrophilic anionic groups, in particular Acid groups such as carboxyl groups, sulfonic acid groups or Phosphonic acid groups. The diisocyanate or Polyisocyanate in a stoichiometric excess, so that resulting hydrophilically modified polyisocyanate is still free Has NCO groups.

As such, NCO-reactive compounds with anionic groups come especially hydroxycarboxylic acids like 2-hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid or hydroxyl pivaline acid and 2,2-bis- and 2,2,2-tris (hydroxymethyl) alkanoic acids, e.g. B. 2,2-bis (hydroxymethyl) acetic acid, 2,2-bis (hydroxy methyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid or 2,2,2-tris (hydroxymethyl) acetic acid. The carboxyl Groups can be partially or completely by a base be neutralized to in a water soluble or water dispersible form. This is preferred as the base have a tertiary amine, which is known to Isocyanate is inert.

The described diisocyanates and / or more functionalized Polyisocyanates can also be mixed with a non-ionic hydrophilically modifying and anionically hydrophobically modifying the compounds which are added sequentially or simultaneously are implemented, for example with a deficit the polyethers I and the described hydroxycarboxylic acids.  

The listed types of anionically hydrophilic modified polyiso Cyanates are in the documents DE-A 40 01 783, DE-A 41 13 160 and DE-A 41 42 275 described in more detail.

The described diisocyanates and / or more functionalized Polyisocyanates become cationically hydrophilic for conversion modified polyisocyanates with NCO-reactive compounds vice versa sets, the chemically built alkylatable or protonatable Ent functions with the formation of a cationic center hold. In particular, such functions are tertiary nitrogen atoms which are known to be inert to isocyanate and can be easily quaternized or protonated. At the order Settlement of diisocyanate or polyisocyanate with this NCO reak tive compounds exist in excess so that the resulting hydrophilically modified polyisocyanate is still free Has NCO groups.

As such NCO-reactive compounds with tertiary nitrogen Atoms come preferably amino alcohols of the general formula

in the
R² and R³ are linear or branched C₁ to C₂₀ alkyl, in particular C₁ to C₅ alkyl, or together with the N atom form a five- or six-membered ring which also contain an O atom or a tertiary N atom can, in particular a piperidine, morpholine, piperazine, pyrrolidine, oxazoline or dihydrooxazine ring, where the radicals R² and R³ can additionally carry hydroxyl groups, in particular in each case one hydroxyl group, and
R⁴ denotes a C₂ to C₁₀ alkylene group, in particular a C₂ to C₆ alkylene group, which can be linear or branched,
into consideration.

Particularly suitable amino alcohols II are N-methyldiethanolamine, N-methyldi (iso) propanolamine, N-butyldiethanolamine, N-butyl di (iso) propanolamine, N-stearyldiethanolamine, N-stearyl di (iso) propanolamine, N, N-dimethylethanolamine, N, N-Dime  thyl (iso) propanolamine, N, N-diethylethanolamine, N, N-Di ethyl (iso) propanolamine, N, N-dibutylethanolamine, N, N-Dibu tyl (iso) propanolamine, triethanolamine, tri (iso) propanolamine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine, N-methyl-N ′ - (2-hydroxyethyl) piperazine, N-methyl-N ′ - (2-hydroxy propyl) piperazine, N-methyl-N ′ - (4-hydroxybutyl) piperazine, 2-hydroxyethyl oxazoline, 2-hydroxypropyl oxazoline, 3-hydroxy propyl oxazoline, 2-hydroxyethyl dihydrooxazine, 2-hydroxypropyl dihydrooxazin or 3-hydroxypropyl-dihydrooxazin.

Furthermore come as such NCO-reactive compounds with ter tertiary nitrogen atoms preferably diamines of the general form mel IIIa or IIIb

in which R² to R⁴ have the meanings given above and R⁵ C₁- to C₅-alkyl or with R² a five- or six-membered Ring, in particular a piperazine ring forms.

Particularly suitable diamines IIIa are N, N-dimethylethylene diamine, N, N-diethyl-ethylenediamine, N, N-dimethyl-1,3-diamino 2,2-dimethylpropane, N, N-diethyl-1,3-propylenediamine, N- (3-amino propyl) morpholine, N- (2-aminopropyl) morpholine, N- (3-amino propyl) piperidine, N- (2-aminopropyl) piperidine, 4-amino-1- (N, N-di ethylamino) pentane, 2-amino-1- (N, N-dimethylamino) propane, 2-amino-1- (N, N-diethylamino) propane or 2-amino-1- (N, N-diethyl amino) -2-methylpropane.

N, N, N'-trimethylethylene are particularly suitable as diamines IIIb diamine, N, N, N'-triethylethylenediamine, N-methylpiperazine or N-ethylpiperazine.

Poly can also be used as NCO-reactive compounds ether (poly) ole with built-in tertiary nitrogen atoms, the by propoxylation and / or ethoxylation of amine nitrogen having starter molecules can be used will. Such polyether (poly) ole are, for example Propoxylation and ethoxylation products of ammonia, Ethanolamine, diethanolamine, ethylenediamine or N-methylaniline.  

Other NCO-reactive compounds that can be used are tertiary stick Polyester and polyamide resins that have atoms of matter, tertiary Polyols containing urethane groups and nitrogen atoms Polyhydroxypolyacrylates containing tertiary nitrogen atoms.

The described diisocyanates and / or more functionalized Polyisocyanates can also be mixed with a non-ionic hydrophilically modifying and cationically modifying hydrophilically the compounds which are added sequentially or simultaneously are implemented, for example with a deficit the polyethers I and the amino alcohols II or the diamines IIIa or IIIb. Mixtures of non-ionic hydrophilic modifications Renden and anionically hydrophilic modifying compounds possible.

The listed types of cationically hydrophilically modified poly Isocyanates are in the documents DE-A 42 03 510 and EP-A 531 820 described in more detail.

The content of the hydrophilically modified used according to the invention ten polyisocyanates on hydrophilic components, which over their NCO-reactive groups with the described diisocyanates and / or higher functionalized polyisocyanates to the vorlie products have reacted, is usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight, in particular 1.0 to 20 wt .-%, based on the weight of the product. If it is purely non-ionically hydrophilically modified polyisocyanates, This content is usually 1 to 40% by weight, preferably 3 to 30% by weight, in particular 5 to 20% by weight, is concerned on the other hand, by purely anionically or cationically hydrophilically modified Polyisocyanates, this content is usually 0.1 to 10% by weight, preferably 0.5 to 7% by weight, in particular 1.0 to 3% by weight.

Based on the amount of free NCO groups in the present Product is the proportion of hydrophilic components in generally 0.5 to 300 wt .-%, preferably 2 to 200 wt .-%, ins particularly 5 to 120% by weight. If it is purely non-ionic hydrophilically modified polyisocyanates, this is Proportion usually 5 to 300 wt .-%, preferably 15 to 200% by weight, in particular 30 to 120% by weight, are here gene for purely anionically or cationically hydrophilically modified Polyisocyanates, this proportion is usually 0.5 to 50% by weight, preferably 2 to 25% by weight, in particular 5 to 10% by weight.  

Since the hydrophilically modified polyisocyanates mentioned in aqueous media can be used is sufficient for one appropriate dispersibility of the polyisocyanates. Preferential act wisely within the group of the described hydrophilic mo identified polyisocyanates from certain reaction products Di- or polyisocyanates and hydroxyl-terminated poly ethers (polyether alcohols) such as the compounds I as an emulsifier for this purpose.

Synthetic and native sizes are used as sizing agents medium into consideration.

As a native sizing agent modified with the hydrophilically modified For example, starches are suitable for crosslinking polyisocyanates ken and their derivatives such. B. Starch ether and starch ester, Ga lactomannones and their derivatives such as B. Galactomannanester and ether, carboxymethyl cellulose and proteins.

As a synthetic sizing agent with the hydrophilic modifi graced polyisocyanates are crosslinkable, for example Polyurethanes, polyacrylates, polyesters, polyvinyl alcohols or Mixtures of the sizing agents mentioned. This Substance classes have functional groups with Iso cyanates react. The hydrophilically modified polyisocyanates are thus included as crosslinkers for the functional groups to understand the sizing agent. Contain these sizing agents for example as a functional group at least one primary or secondary amino group, hydroxyl group, carboxyl group or Nitrile group. However, you can also create multiple functional groups contained in the molecule, e.g. B. hydroxyl groups and carboxyl groups. The sizing agents are preferably in the form of aqueous Dispersions used. The solids content of the aqueous Dispersions is, for example, 2 to 60% by weight, preferably 5 to 30% by weight. Sizing agents containing functional groups are commercially available.

Particularly preferred sizing agents are polyurethanes, polyester as well as polyacrylates. The polyacrylates are, for example, by Polymerization of acrylic acid and / or methacrylic acid and against optionally also from comonomers such as acrylic esters, in particular other acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid n-propyl ester, acrylic acid isopropyl ester, acrylic acid n-butyl ester and isobutyl acrylate, acrylonitrile, methacrylonitrile, acrylamide and Methacrylamide available. The polyacrylates preferably contain at least 3% by weight of polymerized acrylic acid and / or Methacrylic acid. As comonomers for the production of the polyacrylates  you can also use hydroxyalkyl acrylates such as hydroxyethyl acrylate, Use hydroxypropyl acrylate and hydroxyisobutylacrylate.

Polyester sizes are produced, for example, by that aromatic carboxylic acids such as phthalic acid, terephthal acid, isophthalic acid or sulfoisophthalic acid with at least dihydric alcohols condensed and the condensation products processed into an aqueous dispersion. With condensation are preferably mixtures of several aromatic carbon acids, e.g. B. phthalic acid and sulfoisophthalic acid.

Polyurethanes suitable as sizing agents are, for example in DE-A-26 45 779 and in US-A-4 092 286. At Games for this are aqueous dispersions of polyether polyurethane NEN or polyester polyurethanes.

Polyvinyl alcohol sizes are, for example, by polymer sieren of vinyl acetate and subsequent partial or complete hydrolysis of the polyvinyl acetate to vinyl alcohol units ent holding polymers produced. Vinyl acetate can with others Monomers such as acrylic acid, acrylonitrile, styrene, acrylic esters or Mixtures of the monomers mentioned are copolymerized. The Copolymers can then also be hydrolyzed, whereby polymers containing vinyl alcohol units are formed. The containing suitable vinyl alcohol units as sizing agents For example, polymers have a vinyl alcohol content units of at least 30 mol%.

In order to permanently size yarns, they are mixed from hydrophilically modified polyisocyanates and at least one of the above-mentioned sizing agents. The blends who preferably immediately after their manufacture or internally half of about 10, preferably up to 4 hours after the preparation lung consumed. Contain 1000 g of such a mixture for example 10 to 500, preferably 50 to 400 g / l at least a functional sizing agent, preferably a polyure thans and 1 to 50, preferably 5 to 40 g / l of a hydrophilic mo differentiated polyisocyanate. The used as sizing agents Mixtures can also contain conventional auxiliaries that are used when finishing. For example 1000 g of a mixture used for finishing 2 to 10 g / l an anti-roll coating agent, e.g. B. a mixture of alkoxy laten, 1 to 10, preferably 1 to 3 g / l of a wetting agent, 0 up to 5 g / l of a defoamer and 0 to 60, preferably 3 to Contain 40 g / l of a wax dispersion.  

Such mixtures are usually finished on applied the yarns. The yarn is impregnated for example in a temperature range from 5 to 100, preferably as 20 to 50 ° C instead. The fleet intake is übli Usually 20 to 150%, preferably 90 to 120%. The impregnated For example, yarn is ge at temperatures of 80 to 180 ° C. dries.

At temperatures in the range of approx. Room temperature to 190 ° C, preferably from 80 to 140 ° C, a reaction occurs between the hy drophil modified polyisocyanates and the functional group pen containing sizing agents. It forms on the Garnish a firm coating, which can also be cannot be removed. Depending on the chosen th temperature is the condensation of hydrophilically modified Sizing containing polyisocyanates and functional groups average on the yarns usually within 1 second to 5 mi grooves, preferably 5 seconds to 1 minute. The ge size and dried yarn has a dry, not small handle. It usually becomes 1 to before use in weaving 5, preferably stored for 1 to 2 days, with one subsequent condensation station entry.

With the mixture to be used according to the invention, all Yarns are sized. You can also use natural or syn synthetic fibers or fiber mixtures. Before preferably, one finishes with the one to be used according to the invention Blend yarns made from cellulose fibers or from blends of Cellulose fibers with synthetic fibers, e.g. B. polyester fibers or polyamide fibers. Using the mixtures described above all textile fibers can be permanently sized, e.g. B. apart from the yarns already mentioned above, you can just as well Yarns made from wool, silk, rayon, rayon, hemp, jute, polyamide or permanently polishing polyacrylonitrile. According to the invention Using sizing agent mixtures are also suitable for permanent sizing of yarns from non-textile fibers such as Glass fibers, carbon fibers, fibers of melamine-formaldehyde con densates, aramid fibers, polypropylene fibers, polyester fibers, Polyacrylonitrile fibers, polyamide fibers and / or wool fibers.

The yarns to be sized can be in undyed or in ge colored state according to the invention are permanently sized. For example, cotton yarn dyed with indigo or from fiber mixtures of cotton and polyester fibers or Polyamide fibers are processed according to the invention.  

There is a variant of the above-described sizing process in that one modified to the size from hydrophilic Contain polyisocyanates and at least one functional group tendency sizing agents, preferably polyurethanes, indigo sets and sizing the yarns in one process step and colors. Such a mixture can also be used for dyeing fabrics ben can be used. Another variant is the Ver use of such a mixture for printing on fabrics. At the Printing contains the mixtures to be used according to the invention gene preferably another thickener. Unless the creek contain blends of indigo, it can be used for yarns or Fabrics made from natural or synthetic fibers or from fiber Mixing and dyeing mixtures permanently.

The production of permanently sized and colored with indigo Textiles are particularly interesting for the production of free time wear, e.g. B. Blue jeans pants. Such articles are post the making of an intensive wash in the presence of pumice stone and aggressive chemicals (hypochlorite, permanganate, enzyme) un to give them the look of worn clothing. The technical term for this is "wash down". With the "wash down" one strives for a maximum difference in color depth, d. H. huge Color contrast between the exposed tissue areas, e.g. B. to the Seams with strong lightening and the tissue areas in protected layer with less brightening. So far it has been extreme Difficulties with maximum color contrast, the overall brightening to minimize the garment. So you strive for the farthest ongoing dye removal at an exposed position at under protection and preservation of the dark overall impression of the Textile.

For example, subject to ge according to the invention plain and indigo-dyed stone laundry textiles, so surprisingly you get the desired and so far hardly or maximum contrast that cannot be produced, which is called dark wash-down is called. This means that the exposed Ge the webs are mechanically scrubbed white, while the proportion of the tissue surface due to the protective function of the Sizing agent is not discolored. In the permanently sneaked Tissues and fabrics dyed with indigo are added to the fact that they stand up better after the aggressive washing process have as Jeans-Ar manufactured by conventional processes article. This is a better and easier assembly the fabric to garments is guaranteed.  

The mixture of hydrophilic modified to be used according to the invention graced polyisocyanates and functional groups Sizing agents are usually used in an amount of 0.1 to 40, preferably 1 to 30 wt .-%, each based on the solid fabrics used on the warp yarn. If along with that Finishing also staining in a single process step the warp threads or the fabric to be reached contain the Mixtures of hydrophilic modified to be used according to the invention graced isocyanates and functional groups Sizing agents per 1000 g of aqueous dispersion, for example 1 up to 300 g / l, preferably 5 to 200 g / l indigo.

Examples

Polyiso was the hydrophilically modified polyisocyanate cyanate 1 used, which was prepared as follows:

Polyisocyanate 1 (nonionically modified)

1000 g of one by trimerizing part of the isocyanate Groups of 1,6-diisocyanatohexane, isocyanurate group-containing polyisocyanate, which consists essentially of Tris (6-isocyanatohexyl) isocyanurate and its higher homologues existed, with an NCO content of 22.2%, a content of monome rem diisocyanate of less than 0.3%, a viscosity at 23 ° C. of 1.9 Pa · s and an average NCO functionality of approx. 3.3 were heated to 50 ° C. 80.8 g of one at 50 ° C. were added heated monofunctional polyethylene started on n-butanol noxide polyether with a molecular weight of 1120 g / mol. Man warmed to 110 ° C and stirred for 2.5 h. After cooling, one obtained clear resin with an NCO content of 18.9% and a viscosity at 23 ° C of 2700 mPas.

Polyurethane 1: commercially available polyester polyurethane in the form of a 40% aqueous dispersion (PERAPRET PU)
Anti roll coating 1: commercially available aqueous mixture of alkoxylates
Wetting agent 1: commercially available triisobutyl phosphate.

For those sneaked according to the examples and comparative examples The yarn abrasion values were evaluated according to Zweigle true, which is used to assess the weave of staple fiber warp yarns are used. The scouring values according to Zweigle are determined by placing 15 yarns on the device with one load of 10 g (yarns with yarn number <Nm 20) or 20 g (yarns with yarn  number <Nm 20) and the threads on emery paper as long scrubs until they tear. The tearing of the yarn is over a light barrier registered and recorded. As a measurand is the mean of the first 10 torn yarns.

example 1

Cotton warp yarn (Nm 13.1) was sized on a laboratory sizing machine with a size fleet containing the following components:
200 g / l polyurethane 1
20 g / l polyisocyanate 1
3 g / l wetting agent 1
5 6 g / l anti roll coating agent 1
0.2 g / l of a commercially available defoamer.

The size requirement was 12.1%. Checking the Plain ten yarns on scouring tours to Zweigle gave a value of 3,295, while a value of 518 found.

Comparative Example 1

The yarn described in Example 1 was modified with a Sized potato starch (135 g / l TISSALIS G 115, sizing circulation 12.6%) and checked as above. The scouring tours after Zweigle was 2,087.

Example 2

Example 1 was repeated with the only exception that one add 50 g / l indigo (Brilliantindigo 4BD) to the wash liquor sat. The size requirement was 12.8%. For the simple Yarn, Zweigle abrasion cycles of 3,182 were measured.

Comparative Example 2

Example 2 was repeated with the exception that the yarn with
400 g / l of a commercially available polyacrylate size (size CE) and
50 g / l brilliant indigo 4BD
mediated, the mediation requirement being 13.2%. For the sized yarn, abrasion cycles according to Zweigle of 2,113 were measured.

Example 3

Example 1 was repeated with the only exception that one with the plain cotton yarn Nm 50 described there arbitrated. The sizing run was 11.9%. For the ge plain yarn, scrubbing tours to Zweigle from 987 were determined telt, while for the unrefined raw yarn scouring tours of 109 were found.

Comparative Example 3

Cotton warp yarn Nm 50 was with that in Comparative Example 1 written sizing fleet. The sizing pad was 11.9%. Zweigle were used for the warp yarn Scouring tours of 888 found.

Example 4

Example 2 was repeated with the only exception that one a Nm 50 cotton warp yarn was used. The size requirement was 12.2%. The plain warp yarn proved abrasion Zweigle from 1,008.

Comparative Example 4

The size float described in Comparative Example 2, the In digo was used to size Nm 50 cotton warp yarn used. The size requirement was 12.5%. For the ge plain warp yarns were scrubbing tours to Zweigle from 915 measured.

Claims (9)

1. Use of hydrophilically modified polyisocyanates

• (a) in combination with sizing agents that can be crosslinked with the hydro phil modified polyisocyanates for the production of permanently sized yarns,
• (b) in combination with the sizes mentioned under (a) and indigo for single-step size and dyeing of yarns or for dyeing and printing on fabrics.

2. Use according to claim 1, characterized in that one as crosslinkable sizing agents, polyurethanes, polyacrylates, Polyester, polyvinyl alcohols or mixtures thereof are used. 3. Use according to claim 1, characterized in that one hydrophilic modified polyisocyanates based on aliphati diisocyanates and aliphatic more functional Uses polyisocyanates. 4. Use according to claim 1, characterized in that one uses nonionically hydrophilic modified polyisocyanates. 5. Use according to claim 1, characterized in that nonionically hydrophilically modified polyisocyanates are used, the hydroxyl-terminated polyethers of the formula R¹-X- (AO) _n -H (I) in which
R¹ is C₁- to C₂₀-alkyl or C₂- to C₂₀-alkenyl, cyclo pentyl, cyclohexyl, glycidyl, oxethyl, phenyl, tolyl, benzyl, furfuryl or tetrahydrofurfuryl,
X denotes sulfur or oxygen,
A means propylene and / or ethylene and
n stands for a number from 5 to 120,
built-in included. 6. Use according to any one of claims 1 to 5, characterized records that yarns from natural or synthetic Fibers or fiber blends are permanently sized. 7. Use according to one of claims 1 to 5, characterized characterized in that yarns made of cellulose fibers or Mixtures of cellulose fibers with synthetic fibers per manent arbitration. 8. Use according to one of claims 1 to 5, characterized characterized in that yarns made of cellulose fibers or Mixtures of cellulose fibers with synthetic fibers in a process stage with an aqueous liquor permanently finishes and colors the at least one hydrophilic modifi graced polyisocyanate, at least one polyurethane and indigo contains. 9. Use according to one of claims 1 to 5, characterized records that yarns made of glass fibers, carbon fibers, Fa from melamine-formaldehyde condensates, aramid fibers, poly propylene fibers, polyester fibers, polyacrylic fibers, polyamide fibers and / or wool fibers with an aqueous liquor perma nent mediates that at least one hydrophilically modified Contains polyisocyanate in the form of an aqueous dispersion.