DE2103764B2 - Process for the production of pad dyeings or prints and means for carrying out the process - Google Patents

Description

45

The production of pigment dispersions in organic solvents and their use in so Printing inks, paints or colored lacquers are already known (cf. GB-PS 12 26 616). This dyeing process relate, however, to the application of insoluble pigments to a substrate by means of a hardenable carrier, the after curing or crosslinking, holds the dye coating on the substrate

It has now been found that pad dyeings or prints of excellent quality on woven, knitted or non-woven fabrics made from fully or semi-synthetic, hydrophobic, high molecular weight organic substances are obtained by organic dyes in the presence of 0.5-10 parts of alkyd resins, based on the amount of dye , in between 80 and 150 ⁰ C boiling, preferably halogenated hydrocarbons or alcohols, the solubility of the dyes in the hydrocarbons or alcohols at room temperature is less than 5 g / l, then the substrates mentioned with the obtained dispersions pad or printed and the Dyes fixed on the substrates

Fully synthetic, hydrophobic, high molecular weight organic substances are used here in particular the linear, aromatic polyesters, the polyamides (e.g. nylon 6, nylon 7, nylon 11, nylon 66, nylon 76, Nylon 226, nylon 610 or nylon 6/66), polypropylene and polyacrylonitrile understood; among the corresponding semi-synthetic materials above all cellulose 2 · / 2- and cellulose triacetate These materials can can also be mixed with other fiber materials, e.g. cellulose (cellulose-polyester or polyamide mixed fabric).

The grinding is mostly carried out in ball or sand mills, and suitable apparatus is general to those skilled in the art It is known that milling takes place until the size of the dye particles is between about 0.01 to 10 μ or preferably between 0.1 and 5 μ is then the dispersion obtained by sieving from the balls or from Separated sand

The alkyd resins required for the production of durable dispersions are z. B. in "Encyclopedia of Polymer Science and Technology "(John Wiley and Sons, London, Sidney, 1964), vol. 1, pp. 663-734 described. These alkyd resins are oligomeric polyesters made from organic polyhydroxy compounds with in the main polybasic acids. The acid number becomes small when there is an excess of polyalcohols held. Most of these alkyd resins also contain triglycerides in the form of non-drying vegetable substances oil, in this case the resins are often used dissolved in xylene because of their high viscosity

Both those free of sulfonic acid and carboxylic acid groups and also come as organic dyes Acidic group-containing dyes are contemplated The dyes can be metallized. The selection will usually according to the known criteria of dyeing by the exhaust process in aqueous dispersion or solution take place. For polyester materials, therefore, the water-insoluble (that is, of the called acidic groups free) dyes preferred.

The dye dispersions produced in this way are usually very concentrated and are used for the dyeing process in the generally diluted by further addition of organic liquid. They are in a concentrated form Dispersions stable for a long time.

The halogenated hydrocarbons to be used according to the invention are above all carbon tetrachloride, trichlorethylene, perchlorethylene, trichloroethane, tetrachloroethane, dichloropropane, dichlorobutane. The unsubstituted hydrocarbons are z. B. hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene (mixture) and examples of alcohols are ethanol or isopropanol. These solvents can all be used as long as the dyes are ^{not noticeably soluble in them at room temperature (up to about 25 °} C.), that is to say less than about 5 g / l.

Since these organic liquids require significantly less heat than water for evaporation, the new dyeing process is considerable more economical than dyeing with aqueous dispersions.

The organic liquids can easily be recovered by condensation and thus reused.

Very often it is beneficial in making the

Dispersions other auxiliaries, e.g. alkylene oxide adducts, especially those of the general formula

HO- (CH ₂ CH ₂ O) ₀ -ZCHCH ₂ O ^ - (CH ₂ CH ₂ Ok-H CH ₃

whose molecular weight is between about 500 and 5000 to be added. Even the addition of very little Quantities of oleum, 0.5 to 5 g / l, on the one hand the electrical charging of the dye particles and, on the other hand, the conductivity of the medium through formation favorably influenced by »charge transfer IC complexes«, can be beneficial.

Ethyl cellulose, for example, is used as a thickening agent for the application of the dispersions. Further auxiliaries of this type are, in particular, hydrophobic substances, for example pyrogenic, squat-disperse silicas, which have a specific surface area between 80 and 400 m ² per gram.

It is also often beneficial to use small amounts (about 2 to

20 parts per 1000 parts of solvent) of a neutral, inert acid derivative, e.g. B. an amide, in particular an amide derived from a carboxylic acid having 1 to 3 carbon atoms, such as dimethylformamide or dimethylacetamide, or phosphoric acid tri- (dimethylamide) to be used.

When dyeing polyester-cotton blends in particular, it is beneficial to use this as much as possible anhydrous liquors a solubilizer (for the residual water that is still present during dyeing) add, e.g. a mixture (1 + 1) of a calcium alkylarylsulfonate and a water-soluble one Polyglycol ether.

Suitable calcium alkylarylsulfonates are, for. B. Calcium alkyl benzenesulfonates with about 10 to 15 carbon atoms in the alkyl radical (calcium-decyl-, -dodecyl- or pentadecylbenzene sulfonate) or calcium monoalkyl or dialkylnaphthalene sulfonates with about 8 to 10 carbon atoms in the alkyl radical or in the Alkyl residues (calcium dibutyl or calcium nonyl naphthalene sulfonate). As water-soluble polyglycol ethers, for. B. consider the adducts of about 7 to 20 moles Ethylene oxide to saturated or unsaturated fatty alcohols with about 10 to 18 carbon atoms (laurylhepta- or octaglycol ether, oleylpentadecaglycol ether) or monoalkyl or dialkylphenols with about 8 to

21 carbon atoms in the alkyl radical or in the alkyl radicals (iso-octylphenyl or nonylphenyl decaglycol ether, Di-isoamylphenyldodecaglycol ether, dodecylphenyldodecaglycol ether).

It is of course advantageous to pad the dyes in pure form, that is, without padding them only for dyeing or printing in aqueous medium cheap coupage means, because these coupage means in the organic solvents used are insoluble.

For padding, up to about 150 g of dye are used per liter of padding liquor and for printing up to to about 150 g of dye per kilogram of printing paste. The amount of alkyd resin used is between 0.05 and 10, preferably between 0.2 and 5 parts by weight per part by weight of dye.

Solvent-resistant equipment is preferably used for padding. The organic liquids are generally removed by evaporation after padding from the substrate in closed, heated rooms which are provided with condensation devices. The fixing of the dye is carried out in a generally known manner, for example by heating in water vapor, the solvent vapor or air, in the temperature range 100-230 ⁰ C.

ίο In general, the dyeings or prints after fixing with the solvent used for impregnation treated so, the excess Dye and the alkyd resin remaining on the fiber are removed.

υ In the following examples, the parts mean Parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

example 1

1 part of the dye of the formula 2fi-Didilor-4-mtro- 4 '- (N-0-cyanäthyl-N-acetoxyäthylamino) -1,1' -azobenzene is in 4 parts of perchlorethylene with 1 part of a mixture of 45 parts of alkyd resin, 273 parts

Ethyl glycol acetate and 27.7 parts of ethyl acetate mixed, ground in a ball mill to a fine dispersion and mixed with 10 parts of perchlorethylene The alkyd resin used is a phthalic acid glycerol ester with 43.5% phthalic anhydride and 33% coconut oil content The acid number is between 6 and 10.

In a fleet consisting of 3 parts of the dispersion thus obtained, 15 parts of a 7% solution of ethyl cellulose in perchlorethylene, 1 part of dimethylacetamide and 80 parts of perchlorethylene, a polyester fiber fabric is padded to 60% Cewichtszunähme squeezed at 70 ⁰ C dried with hot air for 1 Fixed at 210 ° for a minute, rinsed in perchlorethylene and dried

After soapy at 70 ^° C. with a 0.2% strength aqueous solution of a polyglycol ether, rinsing with distilled water and drying, a level yellow-brown dyeing with excellent wash and rub fastness is obtained.

All other things being equal, the

mentioned dye 1 part of the 1: 2 chromium complex the mixture (1: 1) of the dyes 1- (2'-hydroxy-4'-nitrophenylazo) -2-hydroxynaphthalene and 1- (2'-hydroxy-5'-nitrophenylazo) -2-hydroxynaphthalene are used and applied to a nylon 66 fabric. You get a deep black dyeing with excellent fastness properties.

Example 2

1 part of the dye of the formula l-amino-2-phenoxy-4-hydroxyanthraquinone is in 4 parts of perchlorethylene with 1 part of a mixture of 50 parts of alkyd resin 68% phthalate and 32% coconut oil, and 50 parts xylene mixed in a sand mill to a fine one Grind the dispersion and add 10 parts of perchlorethylene. The acid number of the alkyd resin is between 6 and 10.

With a liquor consisting of 3 parts of the dispersion obtained in this way, 15 parts of a 7% solution of ethyl cellulose in perchlorethylene, and 82 parts of perchlorethylene, a fabric is produced that consists of an intimate mixture of polyester and cotton in a ratio of 67: 33 is impregnated on 70% weight gain squeezed, at 120 ⁰ C dried and finally fixed with hot air for 1 minute at 210 ⁰ C.

After a conventional reductive cleaning, thorough rinsing and drying, one obtains a Dyeing with excellent wash and rubbing fastness, the cotton part is white and the polyester part has an intense red shade

Instead of the dyes mentioned, it is also possible to use the same amounts of the dyes of the following formulas can be used:

l-phenylamino ^ -nitro ^ -phenylaminosulfonyl-

benzene (light yellow),

4- (4'-Hydrophenyl) -azo-l, 1 '-azobenzene (yellow), 2-cyano-4-nitro-4 '- (N - /? - cyanoethyl-N-jJ-acetoxy-

äthylamir.o) -l, l'-azobenzene (red), 2-chloro-4-nitro-4 '- (N-ethyl-N-0-cyanoethyl-

amino) -1,1'-azobenzene (red), 1 -Methylamino-4 - /? - hydroxyethylamino-

anthraquinone (blue), 2-bromo-4-nitro-4'-N - /? - cyanoethyl N - /? - hydroxy-

ethylamino-l, l'-azobenzene (scarlet red) or 1,4-bis- (l ^# -hydroxybutyl-2'-amino) -

anthraquinone (blue) or the dye of the formula

Example 4

0.5 part of the 1: 2 cobalt complex and 0.5 part of the 1: 2 chromium complex of the substance of the formula

H O NH

Br

Br

(blue)

HN Ο

Example 3

According to the procedure of Example 1, 1 part of the 1: 2 chromium complex of the dye becomes the formula

OH

-CH,

Cl

, / NIC ₆ H ₅

ground in a sand mill to a fine dispersion and this finally by filtering and washing out freed from sand with 10 parts of perchlorethylene.

4 parts of the dispersion thus obtained are mixed with 15 parts of a 7% solution of ethyl cellulose in perchlorethylene, 1 part of dimethylacetamide and 80 parts of perchlorethylene offset with this liquor is a nylon filament fabric padded, squeezed to 60% dry weight gain, at 70 ⁰ C -Dried and fixed with hot air for one minute at 20O ⁰ C, soaped and rinsed as indicated in Example 1. A level, red coloration without the slightest streakiness is obtained.

OH

OH

O ₂ N

N = N

are as indicated in Example 3 and Example 1, dispersed and thus described a KJotzflotte prepared with this liquor is a nylon carpet pad-dyed squeezed dried for two minutes at 205 ⁰ C set in a hot air stream, and as described in Example 1, treated further Man receives a level blue-gray coloration in 100% dye yield and excellent color penetration.

Example 5

1 part of the »dye mixture of 50% of the dye of the formula

HO O NH,

OH

H ₂ NO OH

and 50% of the dye of the formula

HO O NH ₂

OCH ₃

H ₂ NO OH

is 4 parts of perchlorethylene with 1 part of a mixture of 50 parts of alkyd resin with 49% synthetic fatty acids (remainder phthalate) and 50 parts of xylene mixed in a sand mill to a fine dispersion and mixed with 10 parts of perchlorethylene. With a liquor consisting of 3 parts of the dispersion thus obtained, 15 parts of a 7% solution of ethyl cellulose in perchlorethylene, 1 part a mixture (1: 1) of calcium dodecylbenzenesulfonate and isooctylphenyl decaglycol ether and 81 parts Perchlorethylene, is a fabric made from a mixture of polyester and weft in warp and weft Cotton fibers in a ratio of 67: 33 are imprä gniert at 70% weight gain squeezed off at 120 ° C dried and finally fixed with hot air for 1 minute at 210 ⁰ C. After a usual practice purification gives a dyeing having excellent fastness properties, which is uncolored and BaumwoUanteil whose polyester content has an intense blue shade

Instead of the dye mixture mentioned, it is also possible to use 1 part of one of the following dyes can be used:

2,6-dichloro-4-nitro-4 '<N - /? - cyanoethyl-N-1S-acetoxyethylamino) -1.1 '-azobenzene (yellow-brown),

2-chloro-4-methylsulfonyl-2'-acetylariiino-

H ₅ C-NH-COO-CH ₂ -CH ₂

4'-diethylamino-l, 1'-azobenzene (red), 2-cyano-4-nitro-4 '- (N - /? - cyanoethyl-N - /? - acetoxy-

äthylamino) -l, 1 'azobenzene (red) or the dye of the formula

CN

(yellow)

Claims (5)

Patent claims: 1. A process for the production of pad dyeing or prints on woven, knitted or non-woven fabrics from fully or semi-synthetic, hydrophobic, high molecular weight organic substances with dye dispersions, characterized in that organic dyes are used in the presence of 0.5-10 parts of alkyd resins, based on the amount of dye , ground in preferably halogenated hydrocarbons or alcohols boiling between 80 and 150 ^° C., the solubility of the dyes in the hydrocarbons or alcohols at room temperature being less than 5 g / l, then the substrates mentioned are padded or printed with the dispersions obtained and fixed the dyes on the substrates 2. The method according to claim I, characterized characterized in that the halogenated hydrocarbons used are carbon tetrachloride, trichlorethylene, Perchlorethylene, trichloroethane, tetrachloroethane, Dichloropropane or dichlorobutane is used 3. The method according to claim 1, characterized in that the hydrocarbons Hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene or xylene are used 4. The method according to claim 1, characterized in that the alcohols or ethanol Isopropanol is used. 5. Means for performing the method according to claim 1, characterized in that it consists of organic dyes, 0.5-10 parts of alkyd resin, based on the amount of dye, between 80 and 150 ° C boiling, preferably halogenated hydrocarbons or alcohols and optionally other auxiliaries and the dyes in the hydrocarbons or alcohols a solubility at room temperature of less than 5 g / l.