CH624984A5 - Dye preparations - Google Patents

Description

The invention relates to aqueous preparations of 50 water-insoluble dyes, which are characterized in that they contain water-soluble N-hydroxyalkylureas.

The N-hydroxyalkyl urea compounds correspond e.g. Formula 55

R2

I.

r (nh-co-n -rjoh) ,, (i)

wherein

R is an n-valent, optionally substituted and counteracted 60 R? R3

optionally alkyl, cycloal I I interrupted by heteroatoms

kyl- or aryl radical means as it is after removal of n iso-HO-C H-CH2 CH2-C H-OH

cyanate groups from a corresponding n-valent isocyanate \ /

remains, N-CONH- (CH2) 6-NH-CO-N

R, for an alkylene radical, 65 / \

R2 represents hydrogen, an alkyl radical or the radical -RjOH HO-C H-CH2 CH2-C H-OH

and x '

n stands for a number from 1 to 5. * R3

3rd

624 984

CH /

3 NH-CO-Nn ^

? 3

CH 2 -CH-OH

ch9-ch-oh

^ i

R-,

CH. CH.

NH CO

CH.

CH - NH-CO-N

* 3

H

/ CH2-CH-OH

^ CH - CH-OH R,

, CH -CH-OH

N \

XCH -CH-OH

^ i

R-,

(where R3 = H or CH3;

R2 = H or CH3C H-)

R.

The following drying-out preventing agent is very particularly preferred:

Mixtures, isophorone diisocyanate (l-isocyanatomethyl-5-isocyanato-l, 3,3-trimethylcyclohexane.

According to a construction method for the production of higher poly-isocyanates, it is possible to produce higher urea- or biuret-linked systems from di- or polyisocyanates by partial hydrolysis via the stage of carbamic acid and amine, e.g. a biuret-linked compound that is formally formed from 3 moles of hexamethylene diisocyanate with the addition of 1 mole of water and elimination of 1 mole of carbon dioxide. 10 The polyisocyanate thus obtained is suitable for the production of preferred hydroxyalkyl ureas.

Likewise suitable substances containing isocyanate groups are obtained in the reaction of di- or polyols with di- or polyfunctional isocyanates if the molar ratio of hy-15-hydroxy compound to the isocyanate is chosen such that free NCO functions are always present in the statistically formed reaction products, so for example reaction products of 1 mole of trimethylolpropane with 3 moles of tolylene di-isocyanate or isophorone diisocyanate.

20 Possible water-insoluble dyes are, for example:

1. Pigment dyes such as organic pigments of the azo, anthraquinone, azaporphine, thioindigo or polycyclic series, and also the quinacridone, dioxazine, naphthalene series

25 tracarboxylic acid or perlyentetracarboxylic acid series, as are known from the Color Index, 2nd edition, or inorganic pigments, such as zinc sulfides, cadmium sulfides or selenides, ultramarine, titanium dioxide, iron oxides, nickel or chromium titanium yellow, chromium oxides, chromate pigments and carbon black as well as their mixes.

2. Disperse dyes. These include water-insoluble or practically insoluble polyester and polyamide dyes, in particular those from the azo, anthraquinone, methine, quinophthalone and aminocoumarin series, as described, for example, in

35 Color Index 3rd Edition (1971), Volume 2, page 2483-2741. Disperse dyes for the purposes of this invention are also water-insoluble optical brighteners, for example those of the coumarin, stilbene, naphthalimide or carbostyryl series.

These preferably include subliming dyes in the range of 160-220 ° C, as are usually used in transfer printing (cf. e.g. GB-PS 1 221 126).

Examples include:

O

O

HO-CH2-CH2

HO-CH2-CH2

N-C -NH (CH2) 6-NH-C -N;

CH2CH2OH

• CH2CH2OH

The hydroxyalkylureas to be used according to the invention are known in part from the literature, e.g. DOS 2 106 726, or can be prepared by conventional methods known from the literature from hydroxyalkylamines and compounds containing isocyanate groups (Houben-Weyl, Vol. 8, pp. 157-158).

The reactions can be carried out without solvents or in solvents, advantageously in water.

Suitable aliphatic, cycloaliphatic and aromatic compounds containing isocyanate groups may be mentioned:

Cyclohexane-l, 4-diisocyanate, phorone diisocyanate (2,2,4- or 2,4,4-trimethyl-hexamethylene-diisocyanate-l, 6), 1,3-cy-clopentylene diisocyanate, m- and p-phenylene diisocyanate, 2,4,6-tolylene triisocyanate, 4,4'-, 1,3- and 1,4-xylene diisocyanate, durene diisocyanate, l-tert-butyl-2,4-phenylene diisocyanate, l-chloro-2,4-phenylene diisocyanate and however, preferably phenyl isocyanate, methyl isocyanate, cyclohexyl isocyanate, hexamethylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and the like

C.I. Disperse Yellow

60

No. 12712

45 C.I. Disperse Yellow

3rd

No. 11855

C.I. Disperse Red

5

No. 11215

C.I. Disperse Red

13

No. 11115

C.I. Disperse Red

4th

No. 60755

C.I. Disperse violet

1

No. 61100

50 C.I. Disperse Blue

19th

No. 61110

C.I. Disperse Blue

14

No. 61500

C.I. Disperse Blue

3rd

No. 61505

C.I. Disperse Blue

26

No. 63305

55

60

65

Sublimable carbinol bases and carbinol-based derivatives (especially ether) of cationic dyes are also suitable (cf. DT-OS 2 323 538.2 324 017.2 325 154 and 2 325 155).

The preparations can also contain customary auxiliaries, such as mold prevention agents and surfactants.

Suitable surfactants are anionic, nonionic or cationic surfactants or mixtures thereof. Examples of anionic surfactants are:

sulfated alkylene oxide adducts, sulfated partially esterified polyhydric alcohols, alkyl sulfonates, sodium dialkylsulfosuccinates, alkylbenzenesulfonates, condensation products from naphthalenesulfonic acids and formaldehyde, ligninsulfonates and oxyligninsulfonates as well as condensation products from ditolyl

624 984

ether, formaldehyde and sulfuric acid, or condensation products of m-cresol, 2-naphthol-6-suIfonic acid, formaldehyde and sodium sulfite.

Ethylene oxide adducts and adducts of propylene oxide and ethylene oxide are preferably used as nonionic surfactants. Ethylene oxide adducts are reaction products of 3 to 60 moles of ethylene oxide and, for example, alkylphenols, long-chain alcohols, long-chain amines or long-chain carboxylic acids and polypropylene glycols. A large part of these compounds is described in N. Schönfeldt, surface active addition products of ethylene oxide, Wissenschaftliche Verlagsgesellschaft Stuttgart, 1959. Adducts of 10 to 20 moles of ethylene oxide nonylphenol, phenylethylphenol or benzylhydroxydiphenyl and, in particular, oxyethylation products with 10 to 20 moles of ethylene oxide of compounds obtained by condensation of chromates containing phenolic OH groups or their ethers with formaldehyde and amines are preferred contain at least 2 NH groups which are reactive towards formaldehyde, are obtainable, in particular from compounds having the recurring structural unit of the formula

R is an alkylene or cycloalkylene radical which is optionally interrupted by O, S, NR4, CO, arylene or cycloalkylene, Rj and R2 are hydrogen, alkyl or hydroxyalkyl, R3 is hydrogen, alkyl, cycloalkyl, alkoxy, carboxy or alkoxycarbonyl and

R4 is alkyl or hydroxyalkyl.

Such connections are e.g. in U.S. Patent 3,166,516, U.S. Patent 3,278,637 and DT-OS 2,421,606.

Other non-ionic surfactants include Fatty acid esters of polyhydric alcohols such as glycerol, sorbitol, pentaerythritol and glucose and sucrose are also considered. Also optionally substituted fatty acid amides and polyamines.

Suitable cationic surfactants are long-chain ammonium compounds of the zephirol type.

The dye dispersions are prepared by conventional methods by wet grinding, e.g. in the kneader, ball mills,

high-speed agitator ball mills, dissolvers, corundum disk mills or rotor-stator mills. They contain 20-65% preferably 30-50% dye, 3-25, preferably 5-15% N-hydroxyalkylurea, 1-25%, preferably 5, 5 -15% surfactant and 10-50 preferably 20-40% water (the percentages are percentages by weight).

The preparations according to the invention have good flocculation stability, good flowability and, above all, good water retention.

In comparison to known additives for dyeing off preparation to prevent drying out, the urea compounds added according to the invention have the advantage of not increasing the viscosity of the preparation.

15 Example 1

1472 g (14 mol) of diethanolamine are distilled in 2648 g. Submitted water. 1176 g (7 mol) of hexamethylene diisocyanate are added dropwise to this solution with stirring such that a reaction temperature of less than 30 ° is maintained. After the addition, the mixture is stirred at 60 ° C. for 2 hours. A clear, almost colorless 50 percent is obtained. Solution of the addition product.

Example 2

25 133 g (1 mol) of diisopropanolamine are distilled in 292.3 g. Submitted water. While stirring, 159.3 (0.33 mol) of a biuret-linked triisocyanate (formally from 3 mol of hexamethylene diisocyanate by adding 1 mol of water, with the elimination of 1 mol of CO 2), (tri-product 30 Desmodur N®, BAYER AG) is produced in this way added dropwise that a reaction temperature below 30 0 is maintained. After the addition, the mixture is stirred at 60 ° C. for 2 hours. A clear, oily solution of the addition product is obtained.

35 Example 3

61 g (1 mol) of ethanolamine are distilled in 118 g. Submitted water. 57 g (1 mol) of methyl isocyanate are added dropwise to this solution with stirring such that a reaction temperature of less than 30 ° is maintained. After the addition, the mixture is stirred at 60 ° C. for 40 hours. A clear, colorless, thin solution of the addition product is obtained.

Example 4 A mixture consisting of 45 a) 50% of the dye Disperse Yellow 54 (C.I. 27020); b) 8% of the nonionic surfactant with the following constitution

0- (CHo-CHo-0) -H

2 2 x (CH2-CH2-0) z-H

-ch2-n- (ch2) 6-n-ch2-

(ch2-ch2-0) y-h

3-4,

where x, y and z together represent about 60;

c) 5% of the anti-drying agent obtained according to Example 1;

d) 0.6% of commercially available preservatives;

e) 36.4% of water is homogenized by stirring and then ground in a 65 continuously working commercial agitator body mill, which contains glass beads of 0.3-0.5 mm 0 as grinding media, up to a dye distribution of less than 5 n. A well flowable preparation is obtained.

5

624 984

Example 5 A mixture consisting of a) 45% of the dry dye of the formula

0

ho h3c

-C-NH- ^ ~ ^ -N = N-f "^

d) 5% of the drying-out preventing agent described in Example 1 e) 49.4% of water is homogenized by stirring and then ground in a 5 continuously working agitator body mill with glass beads of 0.3-0.5 mm until the particles -size less than 5 jx.

ch.

b) 5% of the nonionic ten-

Example 7 io A mixture consisting of a) 50% of the dry dye l-amino-2-bromo-4-hydroxy-anthraquinone b) 10% of the nonionic surfactant described in Example 1 c) 0.5% of the anionic dispersant of the constitution 15 c) 0.6% of commercially available preservatives d) 5% of the drying-out preventing agent described in Example 1 e) 34.4% of water is homogenized by stirring and then in a

20 continuously working agitator body mills with glass beads of 0.3-0.5 mm 0 until the particle size is less than 5 n.

sids

1-C12H25

O

e so

3 h3n-ch2-ch2-oh d) 0.6% of commercially available preservatives e) 5% of the drying-out preventing agent described in Example 1 f) 43.9% of water is homogenized by stirring and then in a continuously working commercially available stirrer body mill with glass beads from 0.3 to 0.5 mm 0 milled until the particle size is less than 5 | x.

Example 6 A mixture consisting of a) 40% of the dry dye of the formula

° 2n ~ ^ ~~ ^ - ~ -tw

\ = / \ = / C2H4CN

30th

25 Example 8

A mixture consisting of a) 50% of the dry dye l-hydroxy-4-p-tolylamino-noanthraquinone b) 8% of the nonionic surfactant described in Example 4 c) 0.6% of commercially available preservatives d) 5% of that in Example 1 described drying prevention agent e) 36.4% water

35 is homogenized by stirring and then ground in a continuously operating agitator body mill with glass beads of 0.3-0.5 mm 0 until the particle size becomes smaller than 5 | x.

The preparations 40 prepared according to Examples 3-8 are excellently suitable for the production of printing inks for transfer printing.

sids b) 5% of the nonionic ten- described in Example 4

s c) 0.6% commercially available preservatives

Example 9 A mixture consisting of 4J a) 40% of the dry pigment Pigment Yellow 14 (C.I. 21 095)

ch3-CO ^

C1

/ = \ y = \ / co-ch3

, ch-n = n- £ j-c ^ -n = n-ch

Cl b) 12% of a nonionic surfactant, prepared by reacting 14 mol of ethylene oxide with 1 mol of a compound which was obtained by reacting hydroxybiphenyl with benzyl chloride c) 10% of the drying-out preventing agent described in Example 1 d) 0.6 % commercial preservatives and e) 37.4% water is processed into a homogeneous paste in the dispersion kneader: dye, surfactant and a small part of the water are kneaded in the dispersion kneader for 10 minutes in such a way that a temperature of 70 ° C is reached.

65 The mixture is then diluted with the remaining water, preservative and drying agent in the kneader.

CO-CH / X ^ -N = N-CH / '

Ci Vo-NH- ^)

ch3o

624 984

Example 10 A mixture consisting of a) 35% of the dry pigment Yellow 17 (C.I. 21105)

och3

b) 10% of the surfactant described in Example 9 c) 10% of the anti-drying agent described in Example 1 d) 0.6% of commercially available preservatives and e) 39.4% water

20 is processed in the dispersion kneader in the manner described in Example 9.

The preparations prepared according to Examples 9 and 10 are excellently suitable for the production of printing inks for textile printing.

C.

Claims (3)

624 984 1. Aqueous preparations of water-insoluble dyes, characterized in that the preparations contain water-soluble N-hydroxyalkylureas. 2. Preparations according to claim 1, characterized in that they are N-hydroxyalkylureas of the formula r2 r (nh-co-n -r, oh) n (I) 10th contain what mean R is an n-valent, optionally substituted and optionally interrupted by heteroatoms alkyl, cycloalkyl or aryl radical, as it remains after removal of n isocyanate groups from a corresponding n-valent isocyanate, 15 Rj an alkylene radical, R2 is hydrogen, an alkyl radical or the radical -R, OH and n is a number from 1 to 5. 3. Preparations according to claim 2, characterized in that they contain N-hydroxyalkylureas of the given formula, in which R represents an n-valent QQ alkyl radical which is optionally interrupted by urea or biuret groups, a cyclohexyl or cyclopentyl radical which is optionally substituted by methyl groups or a phenyl radical optionally substituted by Q-C4-alkyl, chlorine, bromine, fluorine or Q-Cj-Alko- 25 xy, R, for -CH2-C H-I R3 R2 for H or Rj, 30 R3 is H or CH3 and n is 1, 2 or 3. 4. Preparations according to claim 1, characterized in that these are the compound of the formula O O Suitable alkyl radicals R are e.g. those with 1 to 18 carbon atoms; suitable cycloalkyl radicals R are e.g. those with 5 or 6 ring carbon atoms, and suitable aryl radicals R are in particular phenyl and naphthyl radicals, the radicals mentioned being able to contain, for example, urethane, urea, uretdione, biuret or isocyanuric acid radicals. The aryl radicals and cycloalkyl radicals can preferably carry C] -C4-alkyl or chlorine substituents. Preferred ureas are those of the formula (I) in which R is an n-valent Cj-Q-alkyl radical which is optionally interrupted by urea or biuret groups, a cyclohexyl or cyclopentyl radical which is optionally substituted by methyl groups or an optionally substituted by C [-C4-alkyl , Chlorine, bromine, fluorine or C] -C4-alkoxy substituted phenyl radical, Rj for -CH2-C H-I R3 R2 for H or Rj R3 is H or CH3 and n is 1, 2 or 3. Particularly preferred radicals R which remain after removal of an isocyanate group are the methyl, cyclohexyl and phenyl radicals, preferred radicals R which remain after removal of two isocyanate groups are the hexamethylene, the cyclohexylene and the phenylene radical, the listed ones Residues with 1 to 3 methyl groups can be substituted. Preferred radicals R, which remain after removal of three isocyanate groups, are alkylene, cycloalkylene and arylene radicals containing urethane, urea or biuret groups. The following particularly suitable N-hydroxyalkylureas may be mentioned as examples: .R, 35 CH3-NH-CO-N; \ HO-CH2-CH- ho-ch2-ch2 ' N-C -NH (CH2) 6-NH-C -N; / \ ch2ch2oh ch2ch2oh ch2-ch-oh R. 40 contain. 5. Preparations according to claim 1, characterized in that they contain sublimable dyes. 6. Use of the preparations according to claim 5 for the production of printing inks for printing on print carriers 45 for transfer printing. CftH t-NH-CO-N Ri CH2-CH-OH I. R3 C6Hn-NH-CO-N; R2 ^ CHj-CH-OH R 2nd PATENT CLAIMS • 3