DE2101222A1 - Anionic auxiliaries for dyeing and opticalbr - - Google Patents

Abstract

Before, during or after dyeing or optical brightening, fibres or other shaped articles of basic modified polymers having a paraffinic main chain, pref. modified polyolefins, pref. polypropylene, or polyacrylonitrile, are treated with water-soluble cpds. (I) R-(A-X)n p BH(1-p) -(SO3H)q (where R is H or a 1-18C opt. unsatd. branched or sbustd. aliphatic group; A is opt. substd. arylene or (ar)alkylene; B is benzene or diphenyl opt. substd. by alk)enyl, alkoxy, alkylthio, alkylamino, alkylcarbonyl, alkylcarbonyl-alkylene, or amide, or diphenyl carrying 1 or 2 higher alkyl groups; X is -O-, -S-, sulphoxide or sulphonyl, or if A is aromatic, also -CH2-, or -CH2-NH-CO-NH-CH2-1 n is integer 1-3; p is zero or 1; q is integer 1-3; and if X is -CH2-NH-CO-NH-CH2-, B can carry OH groups; and if n >1, the groups -A-X- can be different). Level dyeings of improved light-stability are obtained.

Description

Coloring and / or optical brightening of moldings made from basic modified polymers.

It is known base modified polypropylene in the presence of Alkylbenzosulfonic acid in which the alkyl radical contains less than 8 carbon atoms, such as dodecylbenzenesulfonic acid, with anionic dyes after the exhaust process to color. These auxiliary sulfonic acids have the disadvantage that they foam strongly, which has an adverse effect on the dyeing process in the exhaust process Results.

It has now been found that when using anionic auxiliaries of the formula (I) below, better results can be achieved because when using these agents foam less, particularly good results in terms of lightfastness submissive and have a better equalizing effect.

The invention now relates to a process for dyeing and / or optical brighteners by the exhaust process or by printing fibers or other shaped bodies made of base-modified polymers containing a paraffinic main chain with anionic dyes and / or optical brighteners. The process is characterized in that before, during or after dyeing or optical brightening with water-soluble compounds of the formula where R is hydrogen or an optionally unsaturated, branched or substituted, aliphatic radical containing 1 to 18 carbon atoms, A is an optionally substituted arylene, aralkylene or low molecular weight alkylene group, B is an optionally substituted by halogen atoms or low molecular weight alkyl, alkenyl, alkoxy -, alkylthio, alkylamino, alkyl carbonyl, alkylcarbonylalkylene groups or amide radicals substituted benzene or diphenyl radical or a diphenyl radical bearing 1 or 2 higher molecular weight alkyl radicals, X oxygen, sulfur or cLne SulSoxid- or sulfonyl group or, if A is aromatic, also a methylene group or a group of the formula -CH2-NH-CO-NH-CH2-, n is an integer from 1 to 3, p is 0 or 1 and q is an integer from 1 to 3, where, if X is a radical of the formula - CH2-NH-CO-NH-CH2-, B can also carry OII groups and, if n is greater than 1, each radical -AX- can have its own meaning.

Benzene or diphenyl derivatives can be used as compounds of the formula (I) into consideration, which can also carry substituents such as Ilalogenatoms, e.g. chlorine, lower alkyl groups, e.g. methyl, ethyl, propyl, iso-propyl, n-, sec.-, iso- or tert-butyl, and n- or iso-amyl, alkoxy groups, e.g.

Methoxy or ethoxy, or the corresponding thio derivatives, alkylamino, Alkylcarbonyl, alkylcarbonylalkylene in which alkyl and alkylene have 1 to 6 carbon atoms contain aliphatic or aromatic amide radicals, with -A- also hydroxyl groups and can carry ester residues. For example, the following compounds may be mentioned: benzosulfonic acid, Alkylbenzosulphonic acids, the alkyl radicals of which contain 1 to 3 carbon atoms, e.g. Toluenesulphonic acids, o-, m- and p-xylenesulronic acids, n- and iso-propylbenzenesulphonic acids, n-, sec-, iso- and tert-butylbenzenesulfonic acids, mono-, di-, tri- and tetra-ethylbenzenesul fonic acids t diphenyl and diphenyl ether sulfonic acids, e.g. diphenyl mono - and disulfonic acid, diphenyl ether mono- and disulfonic acid, diphenyl oxide mono- or disulfonic acid, diphenylphenyl ether mono- or disulfonic acid or the corresponding ThSoäthersulfonsäuren or derivative, which one or two optionally branched, Carry alkyl radicals containing 6 to 18 carbon atoms, such as alkyldiphenyl, Alkyldiphenyläther-, Altyldiphenylthioäthermono- or disulfonic acid, wherein Allcyl Hexyl, cyclohexyl, oxtyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, Hexadecyl or octadecyl or didodecyldiphenylmono- or disulfonic acid; Mono- or di- (tri-, tetra- or pentapropylene) -diphenyläthersulfonsäuren, as they e.g. in German Patent N ° 1 094 911; are described, wherein alkyldiphenylsulfonic acids analogous to the corresponding alkyldiphenyl ether sulfonic acids according to the German patent 1,094,914 can be manufactured; Phenylsulfonsulfonic acids, as e.g. Condensation of diphenyl ether, diphenylene oxide, diphenyl phenyl ether sulfonic acids or the corresponding thio derivatives, e.g. those in the French patents Compounds described in 1,513,945 and 1,513,946; Wondensation products from phenolsulphonic acids, Urea and formaldehyde as described, for example, in German Patent 1,142,173 are ; Condensation products from diphenyl sulfonic acid, diphenyl ether mono- or disulfonic acid and formaldehyde. Pure or technical mixtures of sulfonic acids are also suitable of the formula (I) 3 as they are optionally alkylated, for example, in the sulronation of mixtures Benzoles or diphenyls or their derivatives are formed.

Diphenyl and diphenyl ether sulfonic acids are preferably used, especially dodecyldiphenylmono- and disulfonic acid and mono- and didodecyldiphenyläUllermono- and disulfonic acid, where the dodecyl radical can be straight-chain or branched, also the product referred to in French Patent 1,513,945 as "Phénylsulfone K". or the product described in Example 1 of German Patent 1,142,173.

As a mixture, it is also advantageous to use, for example, those that are through Sulphonation of the by-products of the work-up or synthesis of phenols, diphenyl or low molecular weight alkylbenzenes are formed; it is, for example, the by-products the synthesis of ethyl and / or methylbenzenes, e.g. of xylylene, of ethylbenzene or of phenol. Such mixtures are sulfonated in a general manner known way.

As mixtures of alkylbenzenes or their optionally substituted Derivatives, for example, can also be suitable fractions of petroleum, especially petroleum with a high content of aromatics can be used.

As substrates, colored with the help of the aids mentioned above or can be optically brightened, fibers or other shaped bodies are suitable from base-modified polymers that contain a paraffinic main chain. Polyolefins are mainly suitable as polymers, e.g. polypropylene, polyethylene, Polystyrene and polyacrylonitrile or copolymers with such Polymers. Basically modifying agents are mainly low molecular ones open-chain or cyclic, optionally polymerized or oligomerized Amines alone or together with resins, e.g. epichlorohydrin resins or with phosphoric acid derivatives mentioned. Such polymers are e.g.

in "American Dyestuff Reporter", 54 (1965) 4, p.34-41 and 175 p.41-45, in Dutch patent application 6 810 175 and in Italian patent 826 240 mentioned.

The polymers can be used during, during or after the manufacture Processing, e.g. into fibers or other shaped bodies, e.g. foils or films, be modified basic. The fibers can be processed together with fibers of other types be, e.g.

with cellulose, wool, polyamide or spandex (polyurethane) fibers. You can do it alone or with others.

Fibers in loose form or in any form, e.g. as threads (individual Threads, strands, packages), fleece, felt, knitted, woven, velvety, carpets etc. processed and processed. Other moldings, such as films, can also be used or films, including elastic fabrics, contain basic modified polymers, that are mixed with other polymers.

Commercially known, base modified polyacrylonitrile fibers are e.g. "Acrilan N" (registered trademark Chemstrand Ltd) and Leacryl N (registered trademark ACSA, Italy), basic modified polypropylene fibers are e.g. Meraklon DL, Meraklon DO (protected trademarks, Polymer Spa Montecatini-Edison), Polycrest SDR-3 (protected US Rubber Co. brand).

For dyeing (here and in the following under the term 11Färben " optical brightening is also meant) of the substrates mentioned with the substrates according to the invention Aids, both by the exhaust process and by printing, are suitable anionic dyes in general as well as optical brighteners with anionic ones Character.

Suitable anionic dyes are, for example, acid dyes, direct dyes, Reactive dyes, 1: 1 and 1: 2 metal complex dyes, some of which are also possible come that contain no SO »H or COOH groups, or metalizable anionic ones Dyes, such dyes are, for example, in 1, Color Index "(1956) under the designations "Acid Dye11," Direct Dye "," Reactive Dye "and" Mordant Dye "and more "Solubilized Vat Dye" defined; you can also use fluorescent acidic dyes use or optical brighteners of an anionic character, alone or in a mixture with dyes. But you can also use a dye component of anionic character Apply to the substrate and process them on the substrate to the finished dye.

The substrates can be pretreated with the auxiliaries according to the invention and if necessary only after intermediate drying, but preferably without intermediate drying, dye, you can add the auxiliaries to the dye liquor or the printing pastes or the auxiliaries can be added to the extracted liquors at the end of the dyeing process.

One works both for pretreatment and for dyeing preferably in an aqueous medium, but you can also use an aqueous-organic medium or work alone in an organic medium, the organic means being preferred at least partially water-soluble agents, e.g. the following alcohols are possible, e.g. glycerine, n-, sec.-, iso- and tert. -Butyl alcohol, n-amyl, iso-amyl, n-hexyl, Cyclohexyl, benzyl, and phenylethyl alcohol; Ether alcohols, e.g. phenoxyethanol, Methoxyethanol; Ethylene glycols, propylene glycols; Dioxane; Ketones, e.g. acetylacetone, Methyl isobutyl ketone, cyclohexanone; Esters, e.g. Butyl acetate, ethyl acetate; Methylamides, e.g., dimethylformamide, dimethylacetamide, phosphoric acid tris (dimethylamide); further Dimethyl sulfoxide or tetramethylene sulfone.

The treatment of the substrate with the aid, in the presence or absence of dyes and / or optical brighteners1 is preferably found in aqueous, neutral to acidic medium instead, preferably at pH values of 2 to 5, wherein both organic and inorganic acids are used as acids or also acidic salts, e.g. formic acid, acetic acid, sulfuric acid, ammonium sulfate or -acetate. You can also add other aids, e.g. braking equipment (whereby as braking equipment those means are to be understood which induce a gradual drawing up of the dye enable the fiber, such as the condensation product of 1 mole of 3- (stearylamino) propylamine with 90 mol (ethylene oxide) or non-ionic or weakly basic leveling agents, as they are common in the dye works.

The substrate is before geous with the aid according to the invention in amounts of 0.5 to 30%, preferably 1 to 15 », based on the substrate, in weakly acidic solution, optionally together with a braking agent or a leveling agent at temperatures from 70 to 1200 ° C., advantageously from 800 to 115 ° C., preferably at the boiling point of the medium, treated and can after a careful, even drying or in the moist or wet state with dyes and / or optical brighteners be treated further.

The pre-treated goods are dyed using the exhaust process according to known methods, preferably in compliance with those for the pretreatment conditions given above. After dyeing, it is rinsed and kept at temperatures dried at a maximum of 1150 c.

If the above conditions are observed, one can with advantage Add auxiliary and dye (or optical brightener) at the same time and in color in a single process.

The substrate can also be used in the absence of the auxiliary according to the invention dye and the auxiliary according to the invention at the end of the F8XDung the drawn one Add the dye bath and use it to treat the dyed goods.

The pretreated goods can also be printed using conventional methods, with the possible heat treatment of the print not exceeding 115-1200C should be.

The auxiliary according to the invention can be used together with the dye and / or the optical brightener of the printing paste, e.g.

Mix in amounts of 0.5 to 5%, based on the printing paste and print and treat in the usual way, not exceeding 1l5-1200C shall be.

Dye components can be applied to the pretreated substrate and processed further to dyes by known methods.

The colorations obtained according to the invention are irrelevant and are good Fastness properties, e.g. fastness to rubbing (dry and wet), fastness to shampoo tests, fastness to dry cleaning (perchlorethylene), Fastness to steam setting (e.g. at 115 ° C), fastness to washing (e.g. at 600) and especially good lightfastness.

In the following examples, parts mean parts by weight and Percent weight percent; the temperatures are given in degrees Celsius and the lightfastness was measured with Xenotest.

Bcispi el i 100 parts of a base modified polypropylene existing yarn are dyed in 4000 parts of an aqueous dye liquor, the 0.1 part of 4- (2 "-amino-8" -hydroxynaphthyl-1 "-azo) -4'-dodecycloxy-carbonylamino) -2,2'-dimethyl-1,1'-diphenyl-5 ', 6 '' -disulphonsaures Sodium, 4 parts of 85% formic acid and 4 parts of the sulfonation product , "Polyethylbenzene" contains as sodium salt.

The yarn is placed in the dye bath at 400. One heated within from 40 minutes to 980 and stains for 1 hour at this temperature. After rinsing and troclmen a level red coloration is obtained compared to that in the absence the dyeing obtained according to the invention has a lightfastness higher by one note owns.

"Polyethylbenzene" is a component involved in the synthesis of ethylbenzene By-product and contains 1.4% ethylbenzene, 4.7 ffi sec.

Buthylbenzene, 84.4% diethylbenzene, 4.8% 1,3,5-triethylbenzene, 2.1 % 1,2,4-triethylbenzene, 0.2 ffi tetraethylbenzene; 100 parts of this mixture will be sulfonated with 260 parts of 100% sulfuric acid by known methods.

Example 2 silane proceeds as in Example 1, but replaces the 4 parts of the sulfonation product from "polyethylene benzene" as the sodium salt by the same Amount of the sodium salt of the sulfonation product from 154 parts of diphenyl (1 mol) with 196 parts of H2S04 (2 moles). A level dyeing of its lightfastness is obtained by 1-2 notes. is better than the same way but in the absence of the invention Aid by means of the coloration obtained, examples, l 3 The procedure described in Example 1 is followed, but replaces the 4 parts of the sulfonation product from 1, "polyethylbenzene" as the sodium salt by the same amount of the sodium salt of the sulfonation product from 170 parts Diphenyl ether (1 mol) with 196 parts of H2S04 (2 mol). A level coloring is obtained, whose lightfastness is 1-2 grades better than that in the same way but in the absence the dye obtained from the auxiliary according to the invention.

B e i s p i e 1 e 4 and 5 In example 1, the 4 parts of the Sulfonierungsproduk tes from "Polyäthylbenzol" as the sodium salt by the same Amount of dodecyldiphenylether mono- or disulfonic acid sodium, one obtains a level coloring, the lightfastness of which is 4 grades better than that of the same way but coloration obtained in the absence of the additive according to the invention.

B e 1 s p i e 1 e 6 and 7 100 parts of a base modified Polypropylene existing yarn are used in 4000 parts of an aqueous dye liquor colored, the 0.1 part of the sodium salt of 4,4'-bis (4 "-amino-3" -sulfoanthraquinonyl-1 "-amino) -1,1'-diphenylmethane, 4 parts of 85% formic acid and 4 parts of dodecyldiphenylether mono- or disulfonic acid Contains sodium. The coloring and the aftertreatment are carried out as indicated in Example 1. Level blue dyeings are obtained, the lightfastness of which is two grades better than that of the under the same conditions but in the absence of the auxiliaries according to the invention colorations obtained.

Example 8 Example 1 is repeated with 4000 parts of a dye liquor, the 0.1 part of the disodium salt of 1,4-bis- (2,6'-dimethyl-3'-sulfophenylamino) -6,7-dichloroanthraquinone, 4 parts of 85% formic acid and 2 parts of the in French patent 1,513,945 as "Phénylsulfone K" named product contains.

A level blue dyeing is obtained, its lightfastness by two Grades is better than that for comparison in the same way but in the absence of the dyeing obtained according to the invention.

B e i s i e l 9 100 parts of a base-modified Polyaerylnitrii existing yarn are dyed in 4000 parts of an aqueous dye liquor, the 0.1 part of the disodium salt of 1,4-bis- (2 '4', 6'-trimethyl-3'-bromo-5'-sulfophenylamino) -anthraehinone and 2 parts 85 Sige contains formic acid. You teach the yarn 400 in the dyebath and heated to 980 within 40 minutes. The dye is dyed 30 minutes at this temperature, then cools the bath down to 80 ° and gives another 2 Parts of 85% formic acid and 4 parts of sodium dodecyldiphenyläthcrdisulronsaures added. It is heated again to 980 and treated at this temperature for 15 minutes. After rinsing and drying, you get a blue level coloring that is around two notes is more lightfast than that obtained in the absence of the auxiliary according to the invention Coloring.

B e 1 s p 1 e 1 10 The procedure described in Example 9, with the difference that 0.1 part of the dye used in Examples 6 and 7 is used as the dye used. A blue level coloring is obtained which is two grades better than the coloration obtained in the absence of the additive according to the invention.

B e 1 s p i e 1 11 100 parts of a base-modified polypropylene existing yarn earth dyed in 4000 parts of an aqueous dye liquor, the Contains 0.1 part of the dye given in Example 1 and 3 parts of ammonium acetate. The yarn is introduced into the dyebath at 400 and heated within 40 minutes to 980. The dyeing is carried out for 30-45 minutes at this temperature, then the bath is cooled to 800 from and gives 4 parts of the obtained according to Example 1 of German Patent 1,142,173 Product and 4 parts of 85% formic acid added. It is heated again to 980 and treated at this temperature for 15 minutes. A red, level coloring is obtained, whose lightfastness is two grades better than that for comparison in the absence the dye obtained according to the invention.

Example 11, but using as Dye 0.05 part of the 1: 2 cobalt complex of 1- (2'-hydroxy-5'-nitrophenylazo) 2-hydroxy-3-acetylamino-5-methylbenzene and, as an auxiliary, 4 parts of dodecyldiphenylethersulfonic acid Sodium.

A level brown coloration is obtained which is now 1-2 notes lightfast is than that obtained for comparison in the absence of the auxiliary according to the invention Coloring.

The diphenyl ether derivatives used in Examples 4-7, 9, 10 and 12 can e.g. according to the information of the German patent 1 096 914 (example 1 or 2) getting produced.

Claims (10)

patent claims 1. A process for dyeing and / or optical brightening by the exhaust process or by printing fibers or their moldings made of base-modified polymers containing a paraffinic main chain, with anionic dyes and / or optical brighteners, characterized in that before, during or after dyeing or optical brightening with water-soluble compounds of the formula where R is hydrogen or an optionally unsaturated, branched or substituted aliphatic radical containing 1 to 18 carbon atoms, A is an optionally substituted arylene, aralkylene or low molecular weight alkylene group, 13 is an optionally substituted by low molecular weight alkyl, alkenyl, alkoxy, Alkylthio, alkyl: amino, alkylcarbonyl or alkylcarbonylalkylene groups or amide radicals B-substituted benzene or diphenyl radical, or a diphenyl radical bearing 1 or 2 higher molecular weight alkyl radicals, X oxygen, sulfur or a SulSoxide or SL1l? LO-nyl group or, if A is aromatic is also a methylene group or a Cr group of the formula --CH2-NH-CO-NH-CH2-, n is an integer from 1 to 3, p is 0 or 1 and q is an integer from 1 to 3, where, if X is a radical of the formula -CH2-NH-CO-NH-CH2-, B can also carry OH groups and, if n is greater than 1, the radicals -AX- are identical or different. II. Those colored and / or optically lightened according to claim I Fibers or moldings. Dependent claims 1. The method according to claim 1, characterized in that that one uses compounds of the formula (I) in which A and B each optionally contain one benzene or diphenyl radicals bearing low molecular weight alkyl groups, R dodecyl, X is oxygen, n and p are each 0 or 1 and q is 1 or 2. 2. The method according to claim 1, characterized in that compounds of the formula is used, in which Y is -O- or -S-, m is 1 or 2 and n is 1 or 2. 3. The method according to claim I, characterized in that one Diphenylether sulfonic acids are used as compounds of the formula (I). 4. The method according to claim I, characterized in that one Didodecyldiphenyläthersulfonsäuren used. 5. The method according to claim 1, characterized in that one adding the compounds of formula (I) to the dyebath. 6 * Method according to claim I, characterized in that one the fibers or moldings after dyeing with the compounds of formula (I) im same bath treated. 7. The method according to claim I, characterized. that one uses fibers made from basic modified polyolefins. 8. The method according to claim I, characterized in that one Uses fibers made from basic modified polypropylene, 9. Method according to claim I, characterized in that fibers made from base-modified polyacrylonitrile begins. 10.Verfahren according to claim I, characterized in that one dyes with reactive, acid, direct or 1: 2 metal complex dyes.