DE1419556A1 - Process for dyeing fiber and film structures - Google Patents

Description

Lawyer L F. Drissl

Munich 23,

^^ ^^ D ₀ 801/481

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April 20, 1961

A method for dyeing τοη lai fiber and

Formation of foils.

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The technique of dyeing «τοη textiles let already high, developed * nevertheless there is a great need »dl · Color fastness τοη textiles to light, washing, chemical cleaning, atmospheric and other the color destructive influences to improve. Likewise leaves the Warmth of dyed textiles, i.e. the resistance against mechanical abrasion, often something to be desired.

of fiberglass and dies · Tasks occur mainly when dyeing / synthetic

Textile fibers, especially those that are consistently hydrophobic and therefore in the The aqueous dye liquors used do not swell. Sas Aufslehen of dyes on this kind τοη fibers has been hitherto with the help of chemical swelling agents or carriers or awakened by using high temperatures and pressures.

However, these agents *** M ± MtianX * X ± 9Wtwttw are expensive, often toxic

and difficult to remove. The fiber is also commonly used at damaged during their use or removal

Dyeing at high temperatures requires la general

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expensive equipment that allows working at overpressure.

It has now been found that, when dyeing fiber and film structures, the disadvantages described are practically avoided if the structures are mixed with aqueous solutions or dispersions of water-miscible copolymers, consisting essentially of units, before, during or after the application of the dyes of the general formula χί "(Z R ¹ ) ό ± '£ " 0 ^ _, where Y is an (OH) or (OR) group (R = an alkyl radical with fewer than 4 carbon atoms), R ¹ aliphatic hydrocarbon radical with 1 or more than 2 carbon atoms and a grade of η + 1, η an integer and at least 1, Z a monovalent, ^{bonded to R 1} by a carbon-nitrogen bond and made up of carbon, nitrogen and a radical consisting of hydrogen atoms with at least two amino groups, the ratio of the carbon atoms to the IT atoms in the substituent -S ¹ Z _{n being} less than 6: 1, R "a monovalent hydrocarbon radical free of aliphatic multiple bonds, χ 0, 1 or 2, ζ 0, 1 or r 2 and the sum of χ + ζ 0, 1 or 2, and units of the general formula R "'SiY _m O. _"" , where R ^{IM is} a monovalent hydrocarbon radical which, if aryl radicals are present, can be halogenated , y 0, 1, 2 or 3, m 0, 1 or 2 and the sum of y + m 1, 2 or 3 and Y has the meaning given above, the copolymers being at least 5 % by weight > polyaminoalkylsilicon units, on average at least one organic group bonded to the Si atom by a Si-G bond per Si atom

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and contain at least 0.5 Grew. $ amine-S ticks toff, or brings their water-soluble salts into contact.

The * method according to the invention can be used with all organic, natural and synthetic textile fibers.

The greatest advantages in using the method according to the invention arise when dyeing glass fibers and hydrophobic, synthetic organic textile fibers. The term "hydrophobic fibers" does not only include fibers that are specific chemical treatment have been subjected to make them strong to make water-repellent, although the inventive method in these

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Cases also τοη large part of the gate 1st. This designation also includes those fibers which, when immersed in distilled water, have a relatively greater negative surface potential than pure natural cellulose fibers (cf. J. Soc. Dyers Colourists, 21 1 ° ² 0955)) »and / or those that are only very have small intermediate channels · Both properties have the effect that iceine or only slight swelling occurs in aqueous media.

Typical examples door hydrophobic synthetic fibers are ap £ rn, Aerylfasern (at least 65 5 * Aorylnitrileinheiten) modified · Aorylfaeern (at least 35 but less than 85 ^ acrylonitrile), polyester fibers (at least 65 J * a petitioner a "weiwertigen alcohol and terephthalic acid) »Acetate fibers (cellulose acetate and triacetate), saran (at least 60 pounds of yinylidene chloride), hytril (at least

Poly 85 J * long-chain vinylidene nitrile), nylon (long-chain Polyamide with recurring amide groups in the chain) »vinyon (at least 85 ^ vinyl chloride units) and olefin (at least 85 # ethylene, propylene or other olefin units). These type designations and descriptions are for Pasern those who τοη the USA Federal Trade Commission im Recognized in connection with the Textile Fiber Products Identification Aot rom Sept. 2, 1958 and published in "Textile World", Vol. 109 » Vr. 7t since · 44 (July 1959) are reproduced. Fibers of the mentioned type are in the trade for example under the trademarks "Orion", "Zefran", "Acrilan", "Dacron", "Terylene",

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"Darvan *," Dynel "and * Arnel * and often among yours Type designations, feebeispielawe1; β as * Nylön ^ © the "66" and "Saran" available.

For natural cellulose fiber such as cotton ^ _f linen and wood fibers »it acidic dyes are poorly dyeable because aie have only ~ HO groups as functional '' groups, is the erflndungsgeiaäSe procedure auefe using acid Färbetoffen draäglicht"

Other hydrophobic types of textile, with άβκ, βι: atm örfindegememem method can be used, & ind withapJeleweise metal yarns _t like Lame, or the under- the Ha / idel & naraer "Ιλιγκα" vnü. "Metion" available vJ-arn «eomi ^ di <s verßc'ai & ü ^ n ^ n KcE-M ^ atiuaeji of Ms tall- and organ! beschiohtetea ·. iSetall or uit metal coated tesi iCuns ^ stoffeii best * Ben. All bej don hftr.öp.l & abi ichen mo talTIlsijiif λ yarns ro rwendeten Metai} ^ eip ^ u sdob for di «erfliidvoi ^ sge-nsäSe treatment, but ΑΓύΐϋ1ί ^» Μ _{κ is best suited}

The method according to the invention can be used independently of the mechanical processing shape of the fibers, ie. as can unprocessed fibers, twisted _t crimped or drawn yarns, and knitted, woven or braided ürseugniese and Filse 3? orm etüoken of cloths or finished Heidung ^ are treated thereafter. Some of the above synthetic polymers are offered not only in Paeerfora, but not in the form of films or foils ·

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For example, those under the trade name "Mylar" films obtainable have essentially the same composition like "Dacron". The process according to the invention is of course also suitable for dyeing these films.

Anyone can use the method according to the invention Textile dye can be used. The term "dye refers to all textile dyes, i.e. both on real colors as well as on those dyes that are sometimes referred to as "pigments" or "lacquers". Dyes are commonly used from different points of view classified, for example according to color, origin (e.g. "natural dyes" such as madder and indigo, or synthetic

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Dyes, such as "tar dyes ¹¹ ), chemical structure (azo, anthraquinone, triphenylmethane dyes), after use in dyeing (acidic, basic, direct, stain, vat and development" .. ₍ lacquer and pigment - Dyes), or according to the most important types of fiber in which they are used (eg acetate dyes) Dyes from all of these classes can be used in the process according to the invention.

In the following list of examples, chemical names for dyes are used according to the classification of the "Society of Dyers and Colourists" »Mono-, Di-, Tries- and Tetrakisazo, nitroso, nitro, stilbene, pyrazolone, ketimine, Di- and tri-phenylmethane, xanthine, acridine, quinoline, thiazole, Indamine, indophenol, azine, aniline black, oxazine, thiazine, Sulphide, hydroxyketone, hydroxylaotone, anthraquinone (acid, For * and vat dyes), arylohinone and indigoid dye.

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The most important chromophoric (coloring) groups in the ones Dyes are the Azo »(Jl-H-), Tnio- (C« S), Hitroeo- (N »0) and azoxy- (-1UH) groups, - together with the weaker aitro-

0 (-HO ₂ ) * carbonyl (-C-0) and ethenyl (-CC-) groups. she The most important auxochrome (color-strengthening) groups are the -H (CH ^) ₂ -, -IiHCH ₅ -, -SH ₂ -, -OH and -OCH ^ groups.

The method according to the invention can be used particularly well in connection with acidic dyes. These dyes are mostly in the form of water-soluble, containing 30 * Na groups Salts in trade. They are used in liquors with a pH between 2 and 8 which is adjusted with acids such as sulfuric, formic or acetic acid or with salts such as ammonium sulfate will. That under the name used in the "Color Index" of the "Society of Dyers and Colourists of Bradford, England" "CI. Add Red 5" known product is a representative example of an acidic dye ·

Tiele metallizable dyes, ie organic dyes which form complexes with metals such as chromium, such as chromium or stain dyes, are acidic dyes. The metal can be added to the liquor before the dye (Torchromierung), together with the dye (Metaohrom- or ^c hromatYerfahren) or after dye (Sachohromierung). Examples of dyes that can be used in any of the three methods mentioned are those below Designations "CI. Mordant Yellow 1 ^M ," CI Mordant Had 9 "and" CI. Mordant Brown 12 "products available. Chrome«

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for example sodium biohroaate, let the most common Pickling agents, but sometimes others are also used Metal salts such as copper sulfate, aluminum sulfate, iron sulfate and tin chloride.

Also acidic paraffin in "pre-metallized" form, ie in form of parbetoff-metal-complexes available. Examples are "0.1. Aoid Yellow 98", ^M CI Acid Green 35 "and" CI Acid Blue 158 ". Many of these substances are soluble in water. Those in which a metal atom is linked to a dye molecule, so-called "1: 1 complexes", are used in acidic plots. Neutral dye types are also available as complex compounds with a dye / metal ratio of 21.

Since the method according to the invention is also suitable in connection with nouns or direct Parbatoffs, these Parbetoffes usually contain aroaatlache in a stretched arrangement Binge I can set coplanar and sodium sulfonate groups. All examples of such perfumes are those on Bens! din-lokinä lag «.

Most »of the direct Parbatoffees as well as many acidic and Disperse dyes belong to the group of azo dyes. Azo dyes are produced by doping a primary aromatic asine with nitrous acid obtained Diasoniumaalz with an aromatic amine or a hydroxy compound such as naphthol AS is coupled. Azo dyes can contain the solubilizing group -S0, Ha or insoluble pigments. One speaks of development

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lung dye if an insoluble dye is generated directly on the fiber. Here you can use the fibers first sit the coupling compound and then impregnate with the Diazoniuasalz, so that one directly on the fiber Implementation of the two substances takes place. The primary aromatic amines can also be diasotized directly on the fiber and couple. All of these working methods can be combined can be used with the method according to the invention.

most of time

The "dispersion" or "acetate" dyes, which are only slightly soluble in water and contain amino groups, are dispersed in neutral or slightly alkaline baths, preferably using dispersants such as soap. The disperse dyes, originally mainly used in dyeing τοη acetate fibers ▼, are now used in almost all synthetic fibers. They can also be used in connection with the method according to the invention. These dyes belong to various chemical classes, for example to anthraquinones, aminoazo, pyrazolone or indophenol dyes. Examples of dyes of this type are "CI Disperse Violet 4", "CI Disperse Yellow 14% ^w 0.I. Disperse Orange 3 "

Vat dyes can also be used in connection with the method according to the invention these are insoluble compounds belonging to the class of the anthraquinones, indigoid or thioindigoid. she have C-O groups that can be converted into C-OH groups by reducing agents such as sodium hydroeulfite. the

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Reduced fora is known as Leukoforn and is soluble in caustic soda solutions to form τοη O-Olfa groups. After de « The leuco compounds are applied to the textiles slt air or other oxidizing agents such as sodium perborate or hydrogen peroxide is oxidized to the original dye. The dyeing process is then generally terminated by treating the textile fibers in a hot soap solution or other Exposure to cleaning solution. Soluble vat dyes are also available. They are usually located in fora Salts clay sulfuric acid ester! the Leukoforn of the relevant Dye gate »i.e. they contain C-O-SO-Ha groups.

They are also usable sulfur dyes of complex organic sulfur-containing compounds. Like the vat dyes, the sulfur dyes must also be reduced before their application. The Reduk-

where at

tion takes place in an alkaline medium, «Äts ^ xxwrwjprtmMgxMot at the same time
Va ^ S / as a reducing agent and to adjust the alkaline pH

the so-called reactive dyes can be used will. Such dyes contain solubilizing groups, an organic moiety with chromophoric groups as well Substituents such as halogen, in particular chlorine, which can react with cellulose OH groups.

Si «" basic "dyes are another large class of dyes, which can be seen in connection with the invention Driving is suitable. Sa see here about dyes which the so-called "colored * part of the dye molecule

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contains a positive charge when the dye is in solution. These dyes are generally marketed in the form of chloride or sulfate salts of the basic organic molecule that forms the colored part of the dye. Examples of color salts of this type are those with the group -MH ₅ Cl, e.g. * CI Basic Orange 2 ". Since basic dyes are often quickly absorbed from the liquor, they are used in conjunction with buckets of sizing agents. In particular with vegetable fibers such as cotton, the basic dyes are used in the sail after 41 * fibers are present with an acidic material, such as coarse änm _t gefc * jl: "t marSe",

Resin- bound pigments are used in conjunction with am- i-iijycmägßen processes . Is 2üsa ^ .t $ ühang with these pigments iet fcöufjg one "HB ^ -Sahl, a 3s ** iohnung the Amtirlcan Aesoclaticri of ^r i« xiliL0 Oässffiiets tmü , example © for fl> .m ^ Kti are RuS, "Msnj cyanine blue or -grüß, i ^f ltra; aas ^t lnblai3, ^ ifJon & xydb ^ Äujj o4er -red, metallized Azübraur < ₀ BeÄ ^ i'-ii ^ orar ^ e ai # r -gelt ·? ^ .yromorange or -gelb, Titandiloxydl » " ivtXmya _f lBdoXm <it »niexii ^ä> j *« i- ^: n & Lithooolgelb »Zur Ersseugujng & ix \ &» e *>? t-: tm »th color shade we-ifer aft Miechimgen different pigments are used * PigiseaSe are often marketed in the form of neutral or allraiiöehsr wäfcrig ^ y dispersions.

In connection with old Terfaluea, steeped in invention as coloring substances both subaiaiuseia and uniform Mixtures of several substances in single or multi-level

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procedure, i.e. according to the usual working methods. The dyes can, for example, be in the form of two or more initially more or less colorless substances are applied separately. Usual dyeing auxiliaries, such as mordants, soaps or synthetic surface-active substances, so-called detergents, can also be used will. Palis desired, dyes can be applied from solutions in organic solvents, but there are according to the invention, as well as generally in technology, the in Water-dispersible dyes are preferred. These include substances that form real solutions in knowledge, as well as those that which are insoluble or only very slightly soluble in water and are therefore produced as aqueous, mostly with the aid of surface-active agents Suspensions are applied. In general, water-soluble dyes are preferred.

In the organosiloxane copolymers used according to the invention, the average ratio of at least 1: 1 of the number of R '- + R " ¹ - + (Z _n R') groups to Si atoms can be up to 5, preferably it is up to 5 however, from 1 to about 2.05 inclusive, most suitably there are χ 0 or 1, y 2 and ζ 0 or 1, and at least 15 grains of poly-aminoalkyl-substituted siloxane units.

In those used in the method according to the invention Interpolymers, R 'can have any aliphatic configuration

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from any arrangement; and number of Iu'ethyl, vinyl,

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!.! ethylene, vinylen, -GH and -C-G groups within the have claimed area.

All nitrogen atoms are preferably located in the Z radical in amino or nitrile groups.

The term "amino groups" includes primary amino, secondary amino (including imino) and tertiary amino groups.

The reads Ii "preferably contains a maximum of 18 O atoms. Examples of suitable radicals R "are alkyl radicals, such as methyl, ethyl, propyl, isopropyl, butyl and octadecyl radicals, aryl radicals, such as phenyl, xenyl and baphthyl radicals, alkaryl radicals, such as iolyl and xylyl radicals, aralkyl radicals such as benzyl radicals, as well as cycloaliphatic radicals, such as cyclohexyl radicals. The methyl, ethyl and phenyl radicals are preferred.

The radicals Y in the above formulas mean (OH) - and / or (Ου) - · ".teste, where R is an alkyl radical with less than 4 carbon atoms, i.e. a methyl, ethyl, propyl or isopropyl radical.

Examples of radicals R "'include both all those which have already been mentioned above in connection with the radical R ", as well as alkenyl and alkynyl radicals, v / ie vinyl, allyl, cyelo

Al

hexenyl and propargyl radicals, as well as halogenated TR radicals, such as

and bromophenyl, dichlorophenyl, chlorxenyl oil, 06, oU-trifluorotolyl

Methyl, phenyl and vinyl radicals are preferred. The radicals R, R ', R ", R" ¹ , Z and Y in the siloxanes can be the same or

to be different.

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The preferred method of making the according to the invention

copolymers used is in the patent (patent

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message - <J. .V. < ... '' * (DC 799/479)). Corresponding quantities of polyaminoalkylalkoxysilanes are then supplied by Porrael

Rn (Z ₁ -R ') Si (OE), __ or their partial hydrolysates with organosiloxanes]! ^{xn 0} ^ noticeable

the formula R "· Si (OH) _1n P _{4 m} , in which m 'is a % & ttßSBS &. amount of silicon-bonded hydroxyl groups, for example 1 to 5% by weight,

OH, corresponds, implemented according to the following simplified equation: SSiOR + HOSiS> ^ SiOSiS + RAW.

This reaction is accelerated in two ways by heating, for example to 100 to 200 ⁰ O. Inert solvents can optionally also be used.

The alcohol formed in the reaction can be removed by distillation; thus the G-ewphr exists that real Mixed polymers are formed. Depending on the ratio of the respondents and the amount of RO and HO groups present therein, the mixed polymer can unreacted RO and / or Have HO groups. If necessary, an excess of RO groups can be partially eliminated by adding water to the reaction mixture or fully hydrolyzed depending on the amount of water used will. An excess of HO groups can be caused to condense, for example, by heating the copolymer. As well as the reaction of silane with siloxane as well as {at \ £ ery alcohol formed following hydrolysis can, if so desired, completely or partially in the reaction product

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stay. In aqueous and / or alcoholic solutions or dispersions the interpolymer is in a state of equilibrium. The determination of the exact number of silicon-bonded HO or RO grouping is therefore usually not possible.

Another process for producing the copolymers used according to the invention consists in the mixed hydrolysis of the above-mentioned polyaminoalkylalkoxysilanes with alkoxysilanes

the formula R ^m Si (OR),. The production of such mixed hydrolyzation τ · —y

sate can be done in the usual way. It is in the patent ........

(Patent application D 31 145 IVb / 39c) or in the latter French patent corresponding to 1 230 and 1 230 821.

For the production of the copolymers used according to the invention Polyaminoalkylalkoxysilanes used can according to

those in the patent (application D 31 145 IVb / 39c) and

in the process described in patent 1,090,399.

The polyaminoalkylsilanes can accordingly be prepared by reacting a polyamine with a halohydrocarbonalkoxysilane be prepared in which the halogen atom (s) is located on one in the OC. position or at least in the V * position to the Si atom O atom are bound. In these reactions, a nitrogen atom in the polyamine replaces a halogen atom in the halogenated hydrocarbon radical with elimination of hydrogen halide. The reaction is expediently carried out at temperatures from 50 to 200 ° under anhydrous conditions and with a molar excess

carried out on polyamine.

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Any aliphatic, cycloaliphatic or aromatic polyamines having at least 2 amino groups, one of which contains at least one hydrogen atom, can be used here. Examples of these include ethylenediasin, diethylenetrlamine, 1 # 6-Eiaminonexan, 5-aminoethyl-1 _v 6-dlaminohexane, Ι, ϊ'-Diaethylhexaiaethylendiemin, cadaverine, piperaxine, dl-1,2-propanedioain, methylhydraein, 1-aminoguanidine, 2 Pyrazoline, triaminobenaol , pentaminobenzene, benaylhydraxine, 5-4i «tbyl-p-phenylenediaaain,!, H-biiethyl-p-phenylenediamine and 3-o-tolylenediaain.

They can be produced by the known addition of a halogenated aliphatic hydrocarbon with at least one aliphatic bond to a Balogeneilan, example of the formula R ** _x 9iH01. _χ »in which E" and χ have the meaning given above, and subsequent reaction with one or more alcohols of the formula ROH are prepared · Examples of halogenated «hydrocarbons are allylbroaid, allyl iodide, methallyl chloride, propargyl chloride, 1-chloro-2-ethylbutene" 2, 5-Broia-pentadiene-1,3 and 16-Bro "-2,6-dimethylhexadeoen-2" The balogen hydrocarbons can contain more than one halogen atom, such as 3,4-dibromobutene and 3-chloro-2-chloromethylpropene -1, DAFL can react derived daron radicals with more than one Amlnwasserstoff, that η is greater than 1 · preferably should not ale a halogen atom per carbon atom rorliegen. Bt ^ ax

* rm »r> no halogen atom may be arranged in such a way that after the addition of the halogenated hydrocarbons

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a halogen atom is bonded to a carbon atom which is in β-3 position to the silicon.

In a second process for the preparation of the halocarbon silanes, alkyl halosilanes are halogenated with elemental halogen and then reacted with an alcohol. This method is mainly used when R ^{f is} a methylene radical.

The radical (R ¹ Z) can be of any length, provided that the ratio of carbon to nitrogen is less than 6: 1. However, the R 'radicals preferably contain no more than 18 carbon atoms and in particular 1 or 3 to 5 carbon atoms. The preferred 2 radicals contain 1 to 8 carbon atoms; η is preferably 1, 2 or 3.

The salts are formed by treating the polyaminoalkyl copolymers with an acid in the liquid phase. The acid can be organic or inorganic. Preferably she is Soluble in water, such as hydrochloric, hydrobromic, nitric, acetic, formic, propionic and lactic acids. The salts are generally only used in cases where the Alkalinity of the amino groups is undesirable or if a higher one Degree of water solubility in the organosilicon compound is desired will. ._ .. _ "_ .. .., .--- ■

__D. The amount of acids used to make the salts is preferably equivalent to the amino nitrogen atoms in the organosiloxane. Of course, less can also be used if necessary Acid can be used so that partial salts with solubility properties between those of the free aminoalkylorganosiloxane

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and the whole salt. An excess over the equivalent amount of acid can also be used so long as an excessively large excess of acid does not interfere with the use of the salt.

The aminoalkylorganosiloxanes and their salts are water-soluble. The term "water-soluble" in this context is intended to mean both water-soluble and self-emulsifying substances to the same extent

used include. In general, however, the salts according to the invention form true solutions in water. The same goes for those Organosiloxanes which, although not salts, contain a sufficient number of polyaminoalkyl-substituted polymer units. For example, the salts of copolymers of dimethylsiloxane and 20 to 25 percent by weight a polyaminoalkylsiloxane units real solutions in water. The salts with a smaller amount of polyaminoalkyl units, e.g. mixed polymers Dimethylsiloxane and 5 to 20 wt. 70 polyaminoalkylsiloxane units are generally self-emulsifying, i.e. they do not form real solutions, but they do form permanent emulsions with Y / asaer even without the addition of an emulsifier.

Are organosilicon compounds in the process according to the invention Applied to the textile fibers before the actual dyeing process, it is preferable to apply the fibers before the Dyeing to dry. Drying can take place at room temperature, but the treated fibers are preferably heated Temperatures of, for example, about 50 to 210. Such a heat treatment also improves the color fastness.

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This pretreatment is a preferred embodiment of the invention. However, good results are obtained by mixing the organosilicon compound, water and dye and applying this mixture to the fibers. The fibers are then dried and all further treatments are carried out, which are required for the particular dye used. This way of working can be done on untreated textile fibers «, or on Fibers are used that are already silicon compounds with the Amino'or gano have been pretreated.

A third embodiment consists in that one the fibers are first colored using one of the usual methods and then treating the colored product with the organosilicon compound.

In each of the procedures described above for the use of dye and / or organosilicon compound can the usual methods, such as padding, spraying or immersion in a liquor, are used. If .desired, can the products dyed according to the invention are provided with further finishes, for example to make them water-repellent or to make it crease-resistant or to give the finished fabrics a softer feel. The most useful are often after-r Actions with organosilicon compounds, as described in German patents 925 225, 878 791, 1 010 943 and 1,046,564. The inventive method is also suitable for dyeing textiles that have been pretreated according to the above-mentioned German patents.

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The aqueous solutions or dispersions of the copolymers mentioned or their salts can be applied to the textile fibers in any concentration. Preferably For example, organosilicon concentrations in the range from about 0.1 to 5.0% by weight, especially from 0.3 to 2.0%, are used. These concentrations generally lead to an intake of 0.2 to 0.8 w / s of organosilicon compound. It is often advisable to use a water-miscible solvent, e.g. lower aliphatic alcohols, dioxane or tetrahydrofuran, to be used in order to achieve more homogeneous solutions or Emulsions to arrive.

Production of the copolymers to be used according to the invention

A mixture of 75 g (CH ₃ O) ₅ Si (CHg) ₅ HHCH ₂ NH ₂ and 25 g of a polymer of the formula (HO) (CH ₃ ) ₂ SiOJjCH ₅ ) ₂ Sio] _a Si (CH ₅ ) ₂ (OH ), in which a has an average value corresponding to a content of 3.5% by weight of HO groups, with 1.01 mol of CH ^ O groups and 0.05 mol of HO groups, is heated to 150 ° under reflux. _{8.65 g of H 2} O (0.48 mol), ie the _{amount equivalent to the difference of 0.96 mol between the CH 5} O and the HO groups, and 75 g of 02H ₁ -OH, are added to the cooled reaction mixture. sufficient for an approximately 50% solution of the copolymer. About a third of the alcohol is removed by distillation and then a 50% concentration is restored. The ethanol solution obtained in this way contains a siloxane of about 75 wt. #.

₂ ) ₅ Si (OCH ₃ ) ₂ 0 ₅ _ _z - and 25 wt. & (CH ^ SiO units.

"ΊΓ"

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The value ζ can in this i.Iischpolymerlösung due to the Do not measure the alcohol present as a solvent, theoretically it should be between 0 and 1. The alcoholic Solution is completely soluble in water. This is a Most of the remaining silicon-bonded liethoxy groups

Dries "on the paser

hydrolyzed. Saraijiii one this aqueous solution

, so hydrolysis and condensation are practically completed, so that the mixed polymer consists essentially only of (OH, J ₉ SiO and HH ₀ GH ₀ CH ₉ ITH (CH ₉ USiO ₁ , - units.

ever. cc C c. · j I, y

By adding 40.5 g of glacial acetic acid (0.676 mol) to the cooled one 50 dgen alcohol solution (1 hol acid per gram atom nitrogen) the Ilischpolymer is converted into the salt.

Similar copolymers and salts of the type described above are obtained with the same starting materials and using the same procedure, but the weight ratios being 10/90, 25/75, 50/50 and 90/10 instead of 75/25. Corresponding mixed polymers with a weight ratio of 50/50 are produced by using the same procedure, with (CH ₅ 0 ^ 31 (OH ₂ ) 3HHGH ₂ GH ₂ NH ₂ -, (GH ₅ O) ₂ GH ₅ SiCH ₂ GHCH ₅ ÖH ₂ riHGH ₂ CH ₂ M ₂ or (CH ₃ 0) ₅ 3i (CH ₂ ) ₅ HHGH ₂ GH ₂ I ^; l (GH ₂ aH ₂ GIi) ₂ instead of (GH ₃ OJ ₅ Si (OH ₂ ) 3NHOH ₂ CH ₂ HH ₂ is used.

Unless otherwise specified, all parts and percentages in the following examples are by weight.

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EXAMPLE 1

By mixing 98 parts of water with 2 parts of each of the 50% alcohol solutions of the various copolymers and salts described above under "Preparation of the copolymers to be used according to the invention", solutions were obtained which each contained 1 ^a / o of the copolymers with the G- Weight ratios 10/90, 25/75, 50/50, 75/25 or 90/10 - the designation "10/90" etc. always refers to the theoretical ratio of NH ₂ OH ₂ OH ₂ NH (CH ₂ ) ^ SiO ₁ ^ - to (CH ₅ ) ₂ Si0 units - or 1 <fo of copolymers with a weight ratio of 50/50, the polyaminoalkyl-substituted units being NH ₂ CH ₂ CH ₂ NH (CH ₂ ). * Si CH ₅ O-, NH ₂ CH ₂ CH ₂ NHCH ₂ CH (CH ₅ ) CH ₂ Si (CH ₅ ) O- or (ITCCH ₉ CH ₉ KNCH ₉ CH ₉ NH (CH ₀ 5, SiO ₁ , - units , or 1 ^c ß> of the corresponding acetate salts of these different polymers

manufactured.
contained _f / All salts and all copolymers with the exception of those with the weight ratio 10/90 formed true aqueous solutions. The latter gave a stable emulsion.

A number of fabric samples made from undyed polyacrylonitrile known under the trade name "Orion", under the trade name "Dacron" known polyester from polyethylene glycol and terephthalic acid, nylon, acetate, cotton,

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and fiberglass
· Silk, wool, juice Tlskose'wurden in each one of the solutions and immersed · ansohliefiend directed through nip rolls in each "Pail was the inclusion of Organoeiliciumverbindung about 0.5%, based on the weight of the fabric. The Orion samples were dried for 5 minutes at 127 °, all other samples for 20 minutes at 107 °. Samples of each treated fabric were then dyed with different colors * as described below.

Part A

They pretreated fabric were each immersed for 30 minutes in maintained at 77 ⁰ C solutions each containing 3 parts of acidic or metallized acid dye, 2 parts Aaaonlumaoetat and 100 parts of water, besogen on the weight of the tissue sample contained. It was then rinsed with cold water and allowed to dry at room temperature. The following dyes were used (color index calculations are attached in brackets) ι Gibalan Black BLd, Srioeehtbraun 5 GL, Supranolorange BA (CX. AoId Orange 45) _r Pontaoyl green BI (Add Green 3), Kigrosin SSB Extra (CZ. Acid Black 2), Oaloooid Real Light Orange 2 G (CI. Acid Orange 10), Brioanthracene Blue 4 OIL (CX.AoId Blue 23) ι Gyeoland Dunkelgrün BL (CI.Aoid Green 35), Kitoneohtorange GH (CI. Acid Orange 22), Brilliant Crocein 3 BA (CI. Acid Red 73), Kiton Red S (CI. Acid Red 7), Cibal Yellow OL (Ci.AeId Yellow 114), Oibalanorange RLW (Q.I, Acid Orange 86),

2 Cibalan Brown / BL (CI. Acid Brown 45), Cibalan Bordeaux GBL (CI.

Acid Red 213), CaI eof as t Braun MF (CI. Add Brown 97) and Caloofast Olivbraun G (CI. Add Brown 93) · Gate-treated fabric samples were also stained with Keolangelb BE, the same

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Was applied operation old _f except that in the dye solution in place of the Salces 4 parts H ₂ SO ^ were rerwendet "

Each of the treated tissue samples had a good stain deep β and a good "dye loot" from any dye, alright traded polyacrylonitrile ("Orion"), cotton and polyester

as well as fiber optic

("Daoi» n "-) (öewebe was only weakened by the same fleets or not colored at all, i.e. it turned out to be light at best tinted·

PART B ''

Direct dyes were applied to the goal-treated fabrics Solutions each of 0.55 parts of dye, 100 parts of barrel and 0.5 parts of τοη known under the trade name "Tergitol TMM" Trlmethylnonyläther clay polyethylene glycol padded. The dyed fabrics were then heated to 127 ° for 5 minutes, rinsed in cold water and dried at tree temperature. The dyes used were Chloranthine-Fast Orange ÖRLL (CX. Direct Orange 34), Chlorantin-Bchtrot 5 BRL (CI. Direct Red 80), Chlorantin-Eohtblau 2 RLL (CI.Direct Blue 80) and Oaloomin-Hiamelblau FF Extra Cone (CI.Direct Blue 1). Every Tissue sample had good color depth and color yield. while, untreated polyacrylonitrile, polyester and wool fabrics * * xrar were slightly tinted «

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Solutions τοη each 0.55 parts of Realrtivfarstoff, parts of Waeeer and 0.5 parts of iergitöl TMIf were padded onto the goal-treated fabric. After drying for 5 hours at 127 ° C., the fabrics were washed with soapy water at 56 °, rinsed with cold water and dried at room temperature , the Remazol dyes QeIb β and Hot B, as well as the Proeiön dyes Brilliantolau R, Soap R, Brilliatttroi 5% and 2 B _t Brilliantgelb 6 α and Druckgrün 5 β. Every tissue sample had good color depth and color yield, while not ror-

G-glass fiber fabric ~ _t

treated a / Orion "and" Dacron "only took on a slight tint.

TBIL D

The disperse dyes Bastone Red B (CI. Disperse M 30) and Kastone Orange 3 R (CI. Disperse Orange 17} were applied to the treated fabrics by means of the dipping process described in section A. Each fabric sample was thoroughly dyed and not just tinted, although the received · Color depth was not as satisfactory as in the experiments described in Part k The C above.

Very good results have been achieved with paper or fabrics aiii acrylic, modified aoryl, polyteter, saran, hytil or Polyethylene fiber after the pre-treatment described above and coloring according to parts A to D. .

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A single bathing process would be carried out as follows: Solutions of 2 and 2 parts each would be used to prepare 2.44 parts of each of the five-hole surfaces of the Sb / SÖ-kiächpolymereh and 100 parts of water samples each of the untreated fabrics used according to Example ί padded, the samples dried at ßäümiemperatur, heated for 5 min. At 127 °, washed in warm soapy water, rinsed with cold ¥ / water and dried again at room temperature. Probion blue 3 G · lind Procion red B would be used as reactive dyes. All Grewebeprbbeh used received a satisfactory coloration. A greater stability of the liquor in this system was obtained by adding NHiOH up to a concentration of 10 % »

BBiGAME 5

In the preparation of copolymers described before Example 1, the following compounds were used _{instead of the compound (GH 5} OUSi (CHgJ ₅ NHCHgCHgNH _2):

/ jri τι λ ^ Γ Ti Q4 (OXX \ WTJr ¹ TI PTT WTT fP TT Π \ C TT C3-i f Γ »ΤΤ 1 TJTTfTT ΠΤΤ WtT

(CH ₅ O) ₅ SiGH ₂ OH ₂ CHNHCH ₂ CH ₂ NH ₂ , (CH ₅ O) ₅ SiCH ₂ NHC ₆ H ₄ N (GH ₅ ) ₂ ,

GH ₂ NHCH ₂ GH ₂ NH ₂

(CH ₅ O) ₅ Si (GH ₂ ) 3NH (CH ₂ JgNH ₂ , (CH ₅ O) ₅ Si (CHg) ₅ NHCgH ₅ (IiHg) ₂ or (CH ₅ O) ₅ Si (CH ₂ J ₅ NGH ₅ (CH ₂ ) gNHCH _5. When using the copolymers and salts obtained in Behahclin and dyeing according to the procedures described in Example 1, comparable results were obtained *

3ÖS3Ö 1 / Ö3 ί1

EXAMPLE 4

different 1% of the copolymer

Di β / aqueous solutions jrom flrgiuiuiiilljclnmjf iwrbinfluiii ^ Biax. according to

Example 1 were each with, formic, adipic, hydrochloric or nitric acid in the number of nitrogen atoms mixed equivalent amounts, and applied to the treatment of the fabrics used according to Example 1 by the method described in this example. The fabrics dyed according to the procedures described in Example 1 were approximately the same Properties with regard to color depth and color structure yield.

EXAMPLE 5

The fabrics pretreated with organosilicon compounds according to Example 1 were each padded with various pigment dyes in the form of aqueous suspensions of about 5 parts of the commercially available pigment dispersions and 95 parts of water. Haoh padding, the fabrics were dried at laumtemperatur and heated for 5 min. At ⁰ C 12T. Each sample had good color depth and color yield · Equivalent results were obtained obtained with a single bath process, with the untreated

1.0 weave with a solution of £ ^ S ropes from each of the

■ copolymers

iditome according to example 1 and 94.5 files water,

in which 5 parts of the commercially available pigment dispersions were dispersed, padded, then air-dried and heated to 121 ° for 5 minutes. The pigment dispersions used in these two dyeing processes were the alkaline types Aridye Gray K, Aridye Yellow I _9, Aridye Yellow K (AATCC designation RB 92), Aridye Brown R (RB 31) and

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I H I 3OOD

Jf

Primal Burgundy, as well as the neutral Aridye SXN dispersions Brown R, Red B, Yellow R, blue and green G 2 B. These pigment dispersions contain about 25 - 60 wt ° ß> solids..

EXAMPLE 6

By heating the aminosilane of the formula

(QH ₅ OJ ₅ Si (CH ₂ J ₅ NHCH ₂ CH ₂ NH ₂ with the features specified in the following alkoxysilanes in the respective conditions at 50 to 100 ⁰ C and slowly adding water to a the still existing alkoxy equivalent amount, various copolymers manufactured.

A. 25 parts aminosilane / 75 parts (CJH ₅ ) ₂ Si (OC ₂ H ₅ J ₂

B. 50 ^H "/ 25 ×" (CH _{5) 2} Si (OC ₂ H _{5) 2/25} parts

CH ₅ Si (OC ₂ H ₅ J ₅

C. 54 ". ^M / 46 parts CH ₂ = CHSi (OC ₂ H ₅ J ₅

D. 50 ^"H / 25 ^fl CH ₅ C ₆ H ₅ Si (OC ₂ H ₅ J _2/25 parts

GL ₂ I ₆ H ₅ Si (OC ₂ H ₅ J ₅

E. 70 " ^M / 30 parts CgH ₅ Si (OC ₂ H ₅ J ₅

F. 70 ■ "" / 10 ^M (CH ₅ J ₂ Si (OC ₂ H ₅ J _2/10 parts

CH ₅ Si (OC ₂ H ₅ J _5/10 parts (CH ₅ J ₅ SiOC ₂ H. ₅

Then each time with water to a concentration of 1 $> Organosiloxane ^! f irr and each solution neutralized with 1 mole of acetic acid per gram atom of nitrogen.

When using these solutions in the in Example 1 about the same results were obtained.

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The preparation of the various polyaminoalkylalkoxy bilanes used in the preparation of the copolymers used in the above examples is described in the patents and patent applications cited above. The compound (OH ₅ O) ₅ SiCOH ₂ ) 3HHGH ₂ IT (CH ₂ OH ₂ OiI) ₂ can be obtained by mixing 3 moles of acrylonitrile with 1 mole of (OH ₅ O) ₅ Si (CHg) ₅ MHOH ₂ CHgHS ₂ , external cooling to 55 ^{0 0} until the reaction subsides, 4 hours of heat to about 95 ° and subsequent evaporation of the constituents which boil up to a vessel temperature of 168 ° / 15 mm Hg, in particular the unreacted acrylonitrile, as brown, oily

25th

Liquid to be obtained from n- ^ 1.4615 "

BATH

CCC3Ü 1/0 5 SI

Claims (1)

A process for dyeing fiber and film structures, characterized in that the structures are mixed with aqueous solutions up to dispersions of misohypolymers, consisting essentially of units of the general formula R. ^rt _x (2 _tt R ·) SiY _a O ^ _XÄgs , where Y is an (OH) - or (OR) -Iieate (R = alkyl radical with less than 4 atoms), H · an aliphatic hydrocarbon radical with 1 or more than 2 G atoms and a valence of η + 1 »η an integer and at least 1» 2 a monovalent heat, ^{bonded to H 1} by a carbon-nitrogen bond, consisting of carbon, nitrogen and hydrogen atoms and containing at least 2 amino groups where the ratio of O atoms to N atoms in the subatituent -H ¹ ^ _{n is} less than 6 i 1, R ^{M is} a monovalent hydrocarbon radical free of aliphatic multiple bonds, χ 0, 1 or 2, β 0, 1 or 2 and the sum of χ + α ö, 1 or 2 it st, and polymeric units of the general formula R ^nt _y 3iY _ffl Q ^ _yMa> where 1 ^{MI is} a monovalent carbon dioxide which, if arylreates are present, can be halogenated, t has the above meaning, y 0, 1, 2 or 3, m 0, "1 or 2 and the sum of y + m 1, 2 or 3, the copolymers being at least 5 wt. S090Q1 / QSM I'M 300D on average at least one through C-Si bond to the Silicon-bonded organic group per Si atom and contain at least 0.5% by weight of amine nitrogen, or their water-soluble ones Bringing salts into contact. ZZZj Λ / V-SAA