DE2410185B2 - DYE PREPARATIONS AND THEIR USE - Google Patents

Description

wherein

R ¹ denotes an optionally substituted alkyl, cycloalkyl or aryl radical, as it remains after removal of π isocyanate groups from a corresponding n-valent isocyanate,
π is a number from 1 to 6,

R ² -R ^{5 are} independently hydrogen, lower alkyl, optionally substituted phenyl or chloromethyl,

χ for the numbers 0 to 100 and

y stand for the numbers 0 to 50 and

R ⁶ O-aryl, O-aralkyl, O-alkaryl. O-CO-alkyl, O-CO-aryl, NH-CO-alkyl, NH-SO ₂ -alkyl or O-alkyl means, with the proviso that χ and y do not represent the number 0 at the same time, unless that R ^{6 is} O-alkyl or O-alkaryl,

c) a phthalic acid C _r C ₈ dialkyl ester and

d) a fatty acid ester of ethoxylated novolaks

contain.

2. Dye preparations according to claim 1, characterized in that they contain as dyes those whose maximum solubility in tetrachlorethylene at 25 ⁰ C is 10 g / 1 kg.

3. Dyestuff preparations according to claim 1, characterized in that they are used as dispersants the formula

R ⁷ [-NHCO- (O-CHR ⁸ -CH ₂ ), - R ⁹ ] _m

R ⁷ denotes an alkyl or aryl radical containing one or two isocyanuric acid radicals, optionally substituted by methyl groups, as remains after removal of m isocyanate groups from a corresponding n-valent isocyanate,
m is the number 3 or 4,

R ⁸ denotes hydrogen or methyl, ζ denotes the numbers 0 to 30 and R ⁹ O-alkyl, O-CO-alkyl with 8-20 carbon atoms in each case in the alkyl radical or O-phenylalkyl with 6-15 carbon atoms in the alkyl radical means,

with the proviso that ζ is 1 to 30 when R ^{9 is} O-CO-alkyl or O-phenylalkyl.

4. Process for dyeing textile materials made from organic materials that are immiscible with water Solvents in the exhaust process, characterized in that dye preparations according to Claim 1 used.

5. Process for dyeing textile materials made from organic, water-immiscible materials Solvents in the continuous process, characterized in that dye preparations according to Claim 1 used.

6. The method according to claim 4, characterized in that the organic solvent uses a halogenated aliphatic hydrocarbon.

7. The method according to claim 4, characterized in that the organic solvent Tetrachlorethylene uses.

40

The invention relates to dye preparations for dyeing textile materials made of organic, with Water immiscible solvents. The preparations are characterized in that they

a) sparingly soluble or insoluble in tetrachlorethylene

Dyes,
b) dispersants of the formula

R '[- NHCO- (O-CHR ² -CHR ³ ). _V - (O-CHR ⁴ -CHR ⁵ ) ,, - R ⁶ L

wherein

an optionally substituted alkyl, cycloalkyl or aryl radical, as it remains after removal of η isocyanate groups from a corresponding n-valent isocyanate,

π is a number from 1 to 6,

R ² -R ^{5 are} independently hydrogen, lower alkyl, optionally substituted phenyl or chloromethyl,

χ for the numbers 0 to 100 and

y stand for the numbers 0 to 50 and

R «O-aryl, O-aralkyl, O-alkaryl, O-CO-alkyl, O-CO-aryl, NH-CO-alkyl means NH-SO ₂ -alkyl or O-alkyl with the proviso that χ and y not simultaneously stand for the number 0, unless R ^b denotes O-alkyl or O-alkary, and

c) a phthalic acid Ci-Ce dialkyl ester and

d) a fatty acid ester of ethoxylated novolaks

contain.

24 IO

Suitable alkyl radicals R ¹ are those with 1-18 carbon atoms; Suitable cycloalkyl ^{radicals R 1} are above all cyclohexyl radicals and suitable aryl radicals Ri are phenyl and naphthyl radicals, it being possible for the radicals mentioned to contain, for example, urethane, uretdione or isocyanuric acid radicals. The aryl radicals and cycloalkyl radicals can preferably _{carry C 1 -C 4} -alkyl or chlorine substituents.

Are in the formula (I) mentioned

η preferably for 2 to 5, A- preferably for 1 to 30 and
y is preferably from 0 to 20.

Suitable -O-alkyl-, -NHCO-alkyl-, -NHSO ₂ -alkyl and - OCO-alkyl radicals R ⁵ are those having 1 to 30, preferably 8-20, carbon atoms in the alkyl rust.

The aryl radicals mentioned in any connection with R ⁵ are preferably phenyl and naphthyl radicals, which _{can be substituted by C r} C ₄ alkyl, chlorine, C _{1 -C 4} alkoxy, hydroxy, and others.

Suitable O-aralkyl or O-alkaryl radicals R ⁵ preferably have 6-15 carbon atoms in the alkyl radical.

Dispersants of the formula (1) to be used with particular preference correspond to the formula

25th

35

R ⁷ C-NHCO- (O-CHR ⁸ -CH ₂ ) ₂ -R ⁹ ] _m (II)

R ⁷ denotes an alkyl or aryl radical containing one or two isocyanuric acid radicals, optionally substituted by methyl groups, as remains after removal of m isocyanate groups from a corresponding n-valent isocyanate,

m is the number 3 or 4,

R ^{8 is} hydrogen or methyl,

ζ stands for the numbers 0 to 30 and

R ⁹ denotes O-alkyl, O-CO-alkyl, each with 8-20 carbon atoms in the alkyl radical or O-phenylalkyl with 6-15 carbon atoms in the alkyl radical,

with the proviso that ζ is 1 to 30 when R ^{9 is} O - CO-alkyl or O-phenylalkyl.

Those dyes and whiteners are considered to be sparingly soluble if their solubility is at room temperature Does not exceed 10 g / 1000 g tetrachlorethylene.

The dyes which can be used in the dye preparations according to the invention can be of all dye classes belong to, such as B. the classes of diarylmethane, triarylmethane, xanthene, azine, oxazine or thiazine dyes and in particular the azo, anthraquinone, nitro, phthalocyanine, methane, styryl, stilbene, Naphthoperinone, quinophthalone, or 5-amino-8-hydroxy-M-naphthoquinoneimine dye classes. Metal complex dyes of copper, nickel, chromium, cobalt, iron and aluminum are also suitable. Even Whiteners, as a special class of colorants, come into consideration. do

All customary derivatives of stilbene, coumarin, carbostyrene, 1,3-diarylpyrazoline, 4-naphthalic acid imide, benzoxoline, Pyrazole, thiazole, odiazole and the triazine system are mentioned. (15

The particle size of the dyes should be less than 10 μ, preferably between 1 and 2 μ.

Preferred dyes are azo dyes, including optionally metallized mono- and disazo dyes are to be understood.

The dispersing auxiliaries to be used according to the invention are known as such (see. For example US-PS 26 95 913 and 2946 767) or easy accessible by reacting substances containing isocyanate groups or blocked isocyanates with monohydroxy compounds. As suitable aliphatic, cycloaliphatic and aromatic compounds containing isocyanate groups may be mentioned:

Phenyl isocyanate, methyl isocyanate,

Cyclohexyl isocyanal, stearyl isocyanate,

Hexamethylene diisocyanate,

Cyclohexane-1,4-diisocyanate,

2,4- and 2,6-toluene diisocyanate

and their mixtures,

isophorone diisocyanate,

(l-isocyanatomethyl-5-isocyanato-

1,3,3-trimethylcyclohexane),

Phorondiisocyanate

(2,2,4- or 2,4,4-trimethylhexamethylene

diisocyanate-1,6),

1,5-naphthalene diisocyanate,

1, S-cyclopentylene diisocyanate,

m- and p-phenylene diisocyanate,

2,4,6-toluene triisocyanate,

4,4 ', 4 "-triphenylmethane triisocyanate,

1,3- and 1,4-xylylene diisocyanate,

S.S'-dimethyl ^^ '- diphenylmethane diisocyanate,

4,4'-diphenyl methane diisocyanate,

3,3'-dimethylbiphenylene diisocyanate,

4,4'-biphenylene diisocyanate,

Thuric diisocyanate,

1 - phenoxy-2,4'-phenylene diisocyanate,

1 -tert-butyl ^^ - phenylene diisocyanate,

Methylene-bis-4,4'-cyclohexyl diisocyanate,

1 -Chlor · 2,4-phenylene diisocyanate and

4,4'-diphenyl ether diisocyanate.
It is known from the chemistry of isocyanates to produce higher molecular weight and, if appropriate, higher functional polyisocyanates from low molecular weight base bodies by polymerization reaction to give uretdiones or isocyanurate derivatives. Examples include the uretdione from 2 moles of 2,4-toluene diisocyanate and the isocyanurate ring-containing polymerization products from 2,4- and 2,6-toluene diisocyanate or hexamethylene diisocyanate, such as a system containing an average of 2 isocyanurate rings in the molecule and formed from 5 moles of toluene diisocyanate or a corresponding derivative from an average of 2 moles of toluene diisocyanate and 3 moles of hexamethylene diisocyanate. These, as well as the isocyanates described below, are eminently suitable for the preparation of the dispersing auxiliaries according to the invention.

According to a further construction method, it is possible from di- or polyisocyanates by partial hydrolysis to produce higher biuret-linked systems via the carbamic acid and amine stage, such as Legs biuret-linked compound which is formally obtained from 3 moles of hexamethylene diisocyanate with the addition of one mole Water and splitting off of one mole of carbon dioxide has arisen.

Substances containing isocyanate groups which are also united are obtained in the reaction of diols or polyols with di- or polyfunctional isocyanates if the molar ratio of hydroxy compound to isocyanate is chosen so that with the statistically educated

Reaction products always remain free NCO functions and have a molecular weight of 2000-3000 is not exceeded. All of the above-described di- and polyisocyanates can in this way with di- and Polyols, such as, for example, mono- and polyethylene glycol, propanediols, butanediols, neopentyl glycol and others Pentanediols, adipol and other hexanediols, cyclohexanediols, 1,4-dihydroxymethylcyclohexane, perhydrobisphenol-A, Glycerin, trimethylolethane, trimethylolpropane and other hexanediols and pentaerythritol, among the ι ο are implemented. The reactions of di- and are preferred Polyols with toluene diisocyanate in which 1 mol of the diisocyanate is used for reaction per OH function comes.

Isocyanate-containing substances which are also outstandingly suitable for building up the dispersants according to the invention are obtained by using di- and polyisocyanates, such as all of the previously described pure or created by building reactions, with monoalcoholic compounds of this kind lets react that at least one isocyanate group per mole is retained. All of them come as mono-alcohols Alcohols with 1 to 30 carbon atoms are possible. This procedure increases the functionality of the Isocyanates used are reduced, but it is possible with the preferred use of alcohols with more than 7 carbon atoms to increase the hydrophobicity of the remainder Ri considerably.

As already mentioned above, they can contain isocyanate groups Compounds in free or masked form react. For capping one normally uses phenols, acid amides, especially caprolactam, oximes and enol compounds.

As monohydroxy compounds, which by reactions with the isocyanate-containing substances to the invention A large number of products can be used for dispersing aids. This is what it is are essentially alkoxylates of alcohols, phenols, carboxylic acids, carboxamides and sulfonamides. Excellent auxiliaries are also obtained if the alcohols are converted by oneself.

Suitable alcohols which can be used directly or after alkoxylation are all saturated or unsaturated aliphatic and cycloaliphatic as well as araliphatic hydroxy compounds with 1-30 C atoms, but preferably with more than 8 C atoms, which are pure or in the form of mixtures Reduction of fatty acids or fatty acid esters obtained from vegetable oils, such as. B. coconut, peanut, palm, Soy, flaxseed, corn or castor oil, or from animal oils or fats, such as. B. fish oil, whale oil, Tallow or lard produced by oxo synthesis, the Ziegler process or by paraffin oxidation are available. The following should be mentioned here as an example:

1-octanol, iso-ethanol, 2-ethyl-1-hexanol,

2-ethyl-4-methylpentanol- (1),

2,2-dimethyl-1-hexanol, 1-nonanol.

Trimethyl-1-hexanol do

(2,4,4,3,5,5 and mixtures),

1-dccanol, 1-dodecanol, iso-dodccanols,

Isotridecanol, t-tetradccanol, 1-1 lexadccanol,

Isohexadecanol, I-octadecanol,

Iso-octadecanol, 3,3,5-trimethylcyclohexanol, ds

4- tcrt.- Buty! -Cyclohexanol, 2- Hydroxydecalin,

l, 7,7-trimethylnorbornanol- (2).

Olev alcohol, eicosenyl alcohol, benzyl alcohol,

1- and 2-phenylethanol and
3-phenyl-1-propanol.

Of the phenols which can be used for the preparation of the alkoxylates, the following may be mentioned: phenol, mono- and polyhalogenated phenols, naphthols, 2- and 4-hydroxydiphenyl, 3-benzyl-4-hydroxydiphenyl, with 1-15 C-atoms alkylated phenols, such as. B. cresols, ethylphenols, but preferably with 6-15 carbon atoms alkylated phenols, such as. B. isooctylphenol, nonylphenols and dodecylphenols.

The alkoxylatable acids are saturated and unsaturated aliphatic carboxylic acids with 1-30 C atoms, but preferably those with 10-22 C atoms, are available, such as caprine, Lauric, palmitic, stearic, behen, ricinol, ricin, Linoleic or linolenic acid, or mixtures of saturated and / or unsaturated aliphatic carboxylic acids, the incurred in the oxidation of paraffin and the synthesis of oxo or those obtained by saponification of vegetable and animal species Fats are obtained. Furthermore, for the alkoxylation, cycloaliphatic and aromatic carboxylic acids, preferably in the range between 10 and 22 carbon atoms, are used, such. B. cyclohexaricarboxylic acid, abietic acid, tert-butylbenzoic acid and p-nonylbenzoic acid.

Of the acid amides which can be used for alkoxylation in the context of the invention, the carboxamides of the above-described carboxylic acids in the preferred carbon number range and preferably 8-22 Alkyl sulfonamides containing carbon atoms are recommended.

To prepare the alkoxylates, the compounds to be alkoxylated are reacted with alkylene oxides by known processes. Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, 1,2- and 2,3-epoxybutane, 2,3-epoxypentane, styrene oxide or epichlorohydrin, but preferably the first two mentioned. In the majority of cases, only one alkylene oxide, namely ethylene oxide, is used, ie y = 0 in the general formula given above. To increase the hydrophobicity on the part of the radical R ₄ , however, it is sometimes advisable to propoxylate the alkoxylatable compound first and only then to ethoxylate it.

The monohydroxy compounds are combined with the isocyanate-containing substances in the usual way dispersants according to the invention implemented. The reaction can take place in inert solvents or else can be carried out without solvents. Any catalysts effective in urethane formation can be used will. The substances are solid or liquid, depending on the starting materials.

Products with a wide variety of molecular weights can be produced using the manufacturing processes described above achieve. However, it has been shown that products with optimal effect in the molecular weight range between 500 and 10,000. It can also be said that polyurethane group-containing Substances are even more effective than monourethangrup- (lenhaltige.

The dye preparations according to the invention are advantageously produced in such a way that that the components are mixed well together and in a crusher, e.g. B. one Agitator ball mill, a steel ball mill or a kneader, carefully ground or knead. For better grinding, organic solvents are usually used as grinding media, like them

24

10

ζ. B. mentioned above. The use of such substances can in principle when used the urethane-containing dispersing aids can be dispensed with, but in many cases this is reasonable Adjustment of the viscosity of the dye preparations and, for reasons of cost, a combination of those according to the invention Mixtures of substances with the organic solvents described above are recommended. Also the Use of aids known from the technical point of view of dyeing, such as B. thickener is possible. ι ο

The preparations according to the invention can optionally also contain further additives, such as aliphatic Contain halogenated hydrocarbons, water or aliphatic alcohols. Preferably the preparations are but anhydrous.

To produce the preparations according to the invention, <*> * ·. Low volatility solvents and the dispersants described are used in such an amount that one part of dye accounts for about 0-20 parts of solvent and about 0.1-20 parts of dispersant. The preparations according to the invention usually contain 5, preferably 10-40% dye, based on the weight of the dye preparation.

The polyurethane-containing preparations according to the invention are distinguished, in particular from corresponding preparations based on polyureas according to US Pat. No. 3,728,301, by good storage stability. They are therefore ideal for the preparation of baths for dyeing textile materials from organic, water-immiscible solvents, such as aliphatic halogenated hydrocarbons, in particular trichlorethylene, tetrachlorethylene and 1,1,1-trichloropropane. When diluted with halogenated hydrocarbons, e.g. B. tetrachlorethylene, dispersions that are stable even under dyeing conditions, ie at high temperatures. Therefore, when dyeing with the dye baths prepared by means of the dye preparations according to the invention, extremely uniform dyeings are obtained and contamination of the dyeing trays through smearing of the dyes is avoided.

The preparations by means of the dye according to the invention Halohydrocarbon dye baths produced, in particular tetrachlorethylene, are suitable for Dyeing of all fiber materials which can be dyed with the dyes contained in the dye preparations are, according to the continuous process and especially after the peeling process.

Suitable fiber materials are: Fiber materials made of cellulose, e.g. cotton, or regenerated Cellulose such as viscose and rayon; Polyacrylonitrile; Polyesters, such as cellulose ^ '/ j-acetate, cellulose triacetate, and polyesters, such as polyethylene glycol terephthalates, or polyesters made from 1,4-bis (hydroxymethyl) cyclohexane and terephthalic acid; and polyamides, such as natural Polyamides, e.g. B. wool and silk, and synthetic polyamides, such as polyhexamelhylenediamine adipate, polycaprolactam or poly-w-aminoundecanoic acid; or Polyurethanes.

The specified in the following examples (> o

Parts are weight styles.

Example I.

To a solution of 546 ζ of a PolyäthcrcMcrs 1 mol of oleic acid and 10 mol of ethylene oxide in 1 1 of acetone fts 87 g of an isomeric mixture of 80 parts of 2,4- and 20 parts of 2,6-tolene are obtained at room temperature isoeyanate added dropwise. To complete the reaction is refluxed for 3 hours. The solvent is then distilled off. One receives a pale yellow viscous oil. which is soluble in organic solvents such as perchlorethylene and dibutyl phthalate is.

Example 2

To a solution of 147 g of a biuret-linked triisocyanate which formally consists of 3 mol of hexamethylene diisocyanate was formed by reaction with one mole of water with the elimination of one mole of carbon dioxide, 744 g of a polyglycol ether made from 11 mol of ethylene oxide are added dropwise to 500 ml of ethyl acetate at room temperature and 1 mole of 3-benzyl-4-hydroxy-bisphenyl. It is then refluxed for 3 hours and the solvent distilled. A pale yellow, viscous oil is obtained as the reaction product.

Example 3

In a solution of 217.6 g of a polyether ester Oleic acid and 6 mol of ethylene oxide in 200 ml of ethyl acetate are 158.4 g of a 2,4-toluene diisocyanate polymer which is 55% strength in ethyl acetate, in which an average of 5 moles of toluene diisocyanate have been polymerized to give a tetraisocyanate containing 2 isocyanurate rings, added dropwise and the mixture then heated to reflux for 1 hour. After distilling off the solvent a highly viscous yellow-brown oil is obtained.

Example 4

In a solution of 74.4 g of dodecanol in 300 ml of acetone, 158.4 g of the 55% strength, in Example 3 tetraisocyanate described was added dropwise. The mixture is refluxed for 2 hours and then the solvent is distilled off. A colorless solid reaction product is obtained.

Example 5

Analogously to Example 3, 395 g of the 55% strength tetraisocyanate based on toluene diisocyanal are added 528 g of a nonylphenol alkoxylated with 10 moles of ethylene oxide are reacted. As a reaction product is a slightly clear, highly viscous oil isolated.

Example 6

As in Example 3, 197.5 g of the 55% tetraisocyanate are reacted with 135.5 g of stcaryl alcohol. After working up, a colorless, semi-wax-poor product is obtained.

• Example 7

10 parts of the disperse dye

N = N

N- (CjIi ₁ OCONHj) ₂

are made with 20 parts of the example 2! Surfactant, 10 parts of a fatty acid ester of a novolak athoxylicrungsproduktes (in DT-OS 21 43 993, Beispic 1, described) and 60 parts of dibutyl phthalate and ground in a PcrlmUhlc. There The resulting dispersion concentrate is liquid, has excellent storage stability and leads to dilution with Tetra chloroethylene to heat-stable dispersions that see good for dyeing synthetic fiber materials.

709 627/4 £

An equivalent dye preparation is obtained if, instead of the disperse dye used, the the same amount of the following disperse dyes is used.

NH

SO ₂ -NH-

OH

C ₂ H ₄ CN

C ₂ H ₄ OCONH ₂

Example 8

IS

10 parts of the disperse dye according to Example 7 are with 20 parts of the surfactant prepared according to Example 5, 10 parts of a fatty acid ester of a novolak

ethoxylation product (in DT-OS 21 43 993, Example I, described) and 60 parts of dibutyl phthalate in a sand mill. The dispersion obtained is liquid and has excellent storage stability. By diluting of the dye preparation obtained with tetrachlorethylene gives a stable dispersion which is very good for dyeing synthetic fiber materials - especially polyethylene terephthalate fibers - after the exhaust process.

100 parts of a fabric made of textured polyethylene terephthalate fibers are placed at room temperature without pre-cleaning in a dyebath which has been prepared by diluting 5 parts of the dye preparation described with 1600 parts of tetrachlorethylene. The bath is heated rapidly to 120 ° C. with vigorous liquor circulation and held at this temperature for 30 minutes. It is then ^{cooled to 90 °} C. and the dye liquor is separated off. No dye precipitations whatsoever are observed in the dyeing machine or on the textile material. This is easily rinsed off the still adhering dye liquor with fresh tetrachlorethylene. After drying, a strong, uniform wine-red color is obtained.

Claims (1)

Patent claims: 1. Dye preparations for dyeing · textile materials made from organic materials, but not with water miscible solvents, characterized in that they a) dyes that are sparingly soluble or insoluble in tetrachlorethylene, b) dispersants of the formula R '[- NHCO- (O — CHR ² -CHR ^J ) _X - (O — CHR ⁴ - CUR ⁵ ) ,, - R ⁶ ] ,,