DE2529568A1 - SOLID COLD-WATER-SOLUBLE COLORANT AND OPTICAL BRIGHTENER PREPARATIONS - Google Patents

Description

Lawyer File 26 I96 July 2, 1975

Solid dye and optical brighteners soluble in cold water

preparations

The invention relates to solid cold-water-soluble dye and optical brightener preparations, processes for their production and their use.

It is known that many dyes are difficult to dissolve in water and are difficult to wet, as well as in the Adding water forms lumps, which not only makes the preparation of dye liquors more difficult, but also makes it more difficult often designed to be very time-consuming. Furthermore, many metal complex dyes have a much too low solubility to be to be able to produce concentrated stock solution. To circumvent this problem, the dyes are made with dispersants and wetting agents treated.

To improve the cold water solubility of dyes, For example, it was proposed in DOS 1.619.375 to convert basic dyes into a granulate form via a urea melt. With these granulates, however, dye decomposition can occur due to the high temperature of the melt, appear; Furthermore, these granules have an unpleasant ammoniacal odor, originating from the known one Release of ammonia from the urea melt.

Another disadvantage of the use of urea is the limited solubility of the dyes in the Melt. This allows the necessary for practical purposes

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agile higher concentration of the dye cannot be achieved in many cases.

It is known that liquid and solid aprotic polar substances have a very good solubility for various Have organic and inorganic compounds. It has now been found that highly concentrated dye and Optical brightener melt products with considerably increased cold water solubility can be obtained by using dyes or optical brighteners, for example, first dissolve the obtained in an aprotic polar substance at higher temperatures Solution mixed with a substance containing proton donor groups, which with the aprotic-polar compound is capable of forming hydrogen bonds, so that a solid Forms adduct, which contains the dye or optical brightener.

Substances that enable the formation of hydrogen bonds contain groups in the molecule that are capable of forming hydrogen bonds. Include such groupings naturally hydrogen atoms, which simultaneously with two Atoms can interact. Examples of such groupings are the NH ^ group, the -NH group, the OH group, the -COOH group, the SO ^ H group, the carbonamide and sulfonamide groups, such as the SO ^ NHR group, where R can be hydrogen or another substituent. Such groupings can be present once or several times in the molecule.

For example, these substances are acid amides, such as urea, thiourea, benzamide and nicotinic acid amide; acids such as maleic acid and benzoic acid; and amines such as ethylenediamine. It is also possible to use mixtures of these Substances to use.

The aprotic polar compounds capable of forming adducts contain in particular electronegative elements, such as fluorine, chlorine, oxygen, sulfur and nitrogen, to which the hydrogen of the proton-releasing substance is bound

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is, where the hydrogen atom to the positive and the electronegative Element becomes the negative end of a dipole.

The aprotic polar compounds exhibiting these properties can be liquid or, in particular, solid.

For example:

a) phosphoric acid and thiophosphoric acid derivatives, such as hexamethylphosphoric acid triamide, trimethyl phosphate, dimethylraethane phosphonate, Monomorpholino-tetramethylphosphoric acid triamide, diethyltetramethylphosphoric acid triamide, trimethylphosphine oxide and decyldimethylphosphine oxide;

b) urea and thiourea derivatives, such as tetramethylurea, Morpholinocarboxylic acid (4) -N, N-dimethylamide and dimorpholinocarbonyl;

c) pyrrolidones and thiopyrrolidones, such as N-methylpyrrolidone;

d) Acyl or aryl amides, such as dimethylacetamide, nicotinic acid dimethylamide and dimethylbenzamide;

e) amine oxides;

f) sulphoxides, such as dimethyl sulphoxide;

g) sulphones, such as dimethyl sulphone;
h) phosphines;

i) Dicarboxamides, such as Ν, Ν, Ν ', N'-tetraalkyldicarboxamide, for example Ν, Ν, Ν ¹ , N'-tetramethylfumaric acid ^{amide, Ν, Ν, Ν', N 1} -tetramethylsuccinic acid amide, Ν, Ν, Ν ', N '-Tetramethylterephthalic acid amide, Ν, Ν, Ν ¹ , N'-tetramethylphthalic acid amide and Ν, Ν, Ν', Ν ¹ -tetramethyl isophthalic acid amide and dithiocarboxylic acid amide; k) Oxamides and thiooxamide derivatives, hydantoin and imidazolidone derivatives and purine derivatives.

It is also possible that mixtures of such compounds are used.

Further additives can be added to the adducts. These mainly serve to improve the properties of these Preparations. For example, other coupage agents can be added, which can be used to adjust the dye strength or Serve the strength of the optical brightener, then dispersant

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both anionic, nonionic and cationic Nature, which serve the dispersion stability and hygroscopic agents, which reduce the hygroscopicity.

All of these additives can be used in amounts of 1 to 10% by weight. to be available.

The dyes that can be converted into a better cold-water-soluble form are, for example, acidic dyes, Reactive dyes, 1: 1 or 1: 2 metal complex dyes and basic dyes.

The anionic and cationic optical brighteners included here can belong to the most varied classes of compounds, such as, for example, the 4,4'-bis- (triazinylamino) -stilbene-2,2 ^f -disulfonic acids, 4,4'-bis- (1,2,3 -triazol-2-yl) -stilbene-2,2 ¹ -disulfonic acids, 1,3-diphenylpyrazolines, distyryl-4,4'-biphenylene and distyryl-1,4-benzenes, benzofuran derivatives with conjugation-extending radicals in the 2-position , Mono- and bis-benzoxazole derivatives, mono- and bis-benzimidazole derivatives, stilbenes with heterocyclic substituents in the 4- or 4,4'-position (preferably stilbenyl-naphthtriazoles), monomethine cyanines, naphthalimides (preferably with ether substitution in 4- or 4 , 5-position), 4-styryl-4 ^! - [2-aryl-1,2,3-triazol-4-yl-ethenyl] -biphenylene, as well as compounds with 1,2,4-oxdiazole groups,

This cold-water-soluble form can be produced in various ways. For example, one solves the solid dye or optical brightener optionally also in the form of an aqueous press cake or in the form of a aqueous solution in the substance capable of forming hydrogen bonds or in the aprotic polar substance, the Solution can also take place via a melt and then adds the polar substance in the event that the dye is in the for The substance capable of forming hydrogen bonds has been dissolved, or this substance is added if the dye is in the aprotic state polar substance has been dissolved. Becomes the watery press cake

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or the aqueous solution is used, the water must then be removed.

If it is a melt, the melting temperature is largely dependent on the boiling point of the polar compound and the melting point of the resulting adduct and moves approximately in the temperature range of 100 to 200 ⁰ C. This melt can subsequently by known methods, for example by sputtering or Schuppieren solidified to be brought. However, it is also possible to solidify the melt and then convert it into granules.

The melts can also, for example, be poured into molds and, after cooling, crushed, the molds being dimensioned in this way It can be that the shaped bodies, such as tablets or balls, have a certain weight and are therefore certain for dosing Dye amounts are suitable. When crushing the melt, it is useful, for example, to produce flakes, there due to their large surface, these loosen particularly quickly and easily.

However, it is also possible to use the dye or the optical brightener in an adduct, e.g. in a 1: 1 adduct from the aprotic polar substance and the proton-donor compound, e.g. to dissolve in the melt.

In all cases adducts are formed which form the dye or optical brighteners finely divided.

According to the invention, it is therefore a matter of preparations in which a dye or optical brightener is contained in an adduct in finely divided form, which are adducts an aprotic polar substance containing a proton donor group Compound which is capable of hydrogen bonding acts.

The adducts make it possible that the dyes used bzxtf. optical brighteners have a much better water solubility, especially cold water solubility. For example, 13 g of the adduct in the distributed dye in 1 liter of water of 20 ⁰ C, while when using the crude dye or optical brightener dissolve

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only 2 g in 1 liter of water of 20 ⁰ C solve, which means that the solubility in cold water is increased by about 6-7fache. They also have the property that they are of dye or optical brightener very concentrated by this is or optical brighteners in amounts from about 30 to wt.%, In particular 40 to 50 Gew.7 _o in the adduct present and Have it made in a dust-free form.

The adducts according to the invention are used primarily for the preparation of aqueous dye liquors and optical brightener liquors or printing pastes, which are then used for dyeing and printing or for optical brightening of the most diverse Materials can be used.

The following examples serve to illustrate the invention without restricting it to Temperatures are given in degrees Celsius.

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example 1

20 g of the dye of the formula

N / A

are with 17 g of urea and 10 g of Hexamethylphosphorsäirretriamid heated at 130 ° for 20 to 30 minutes. The low viscosity melt obtained is applied to an aluminum plate poured and the immediately solidified mass crushed after some time, an adduct of urea and hexamethylphosphoric triamide which contains 42.5 percent by weight of dye and which is very soluble in cold water is.

6 g of this adduct are demineralized in 200 ml Water is dissolved or dispersed at 20 ° while stirring for 2 minutes. The solution or dispersion is through a Schleicher-Schuell 1450 CV paper filter (diameter 7 cm) filtered, being on no residue remains on the filter. The filtered solution or the dispersion is left to stand overnight at 20 ° and filtered again through an identical paper filter, it remains no residue on the paper.

Dissolve instead of the adduct the equivalent amount (2.55 g) of the starting dye alone, which with 200 ml of demineralized Treated water and then filtered off, 2.2 g of residue remain on the filter paper, from which it can be seen that through the distribution of the dye in the adduct, the solubility of the dye is significantly improved.

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Example 2

39 g of the dye according to Example 1 and 37.8 g of urea are dissolved in 25.5 ml of dimethylacetamide at 120 °. As soon as a thin, homogeneous melt has formed, it is placed on a cold aluminum plate at 110 ° poured. The solidified mass is crushed. The adduct contains 38.7 percent by weight of the dye and has a very good cold water solubility and wettability in water.

Example 3

40 g of the dye according to Example 1 and 40 g of urea are in a mixture of 19.5 g of hexamethylphosphoric triamide and 6.5 g of dimethyl methanephosphonate at the melting temperature dissolved. After adding 4 g of polyethylene oxide (Carbowax 4000), the melt is left at 130 ° for a further 30 minutes. The thin one Melt solidifies immediately after it has been poured onto an aluminum plate. The crushed adduct contains 36.4 percent by weight of the dye and has excellent solubility in cold water.

Example 4

12 g of the dye according to Example 1, 7 ml of hexamethylphosphoric acid triamide, 8.5 g of urea and 0.85 g of Carbowax 4000 are dissolved or suspended in 12 ml of water at 110 °. To After stirring for 30 minutes, the water is removed under vacuum. The remaining mass solidifies immediately on cooling. The pulverized Adduct, containing 42.3 percent by weight of the dye, has excellent properties compared to the starting dye Cold water solubility.

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• 4.

Example 5

10 g of the dye of the formula

252S568

are heated together with 2 g of hexamethylphosphorus muretriamide and 12 g of nicotinic acid amide at 140 ° for about 10 minutes. the Low-viscosity melt is left to solidify and then the hard product is crushed. One receives a Adduct containing 41.7% by weight of the dye which has very good cold water solubility.

Example 6

10.3 g of the dye according to Example 5 are at 175 ° dissolved in 7.2 g of hexamethylphosphoric triamide. The concentrated dye solution is then cooled down to 130 ° and slowly added 7.4 g of urea. The thin liquid melt solidifies immediately when it cools down. The adduct containing 41 ^ 4 percent by weight of the dye, has a very good Cold water solubility.

Example 7

40 g of the dye according to Example 5, 22 g of hexamethylphosphoric triamide and 28 g of thiourea are mixed with 80 ml of water and refluxed for 20 minutes. The water is then removed under vacuum between 80 and 105 °. The remaining mass solidifies immediately when

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Cooling down. The powdered adduct, which is 44.4 percent by weight of the dye contains excellent wettability in water and very good solubility in cold water.

Example 8

Is used instead of the dry dye according to the Example 5, 80 g of the technically easily accessible aqueous dye press cake (dry content approx. 50%), proceeds in otherwise as indicated in Example 7, but without water, an adduct that is just as good and with similarly good properties is obtained.

Example 9

4.5 g of the dye of the formula

H ₃ CO ₂ S

N / A

H ₃ CO ₂ S

are with 2.7 g of urea and 2.4 g of hexamethylphosphoric triamide heated at 140 ° for about 20 minutes. The low viscosity melt is then poured onto an aluminum plate, whereby the mass immediately solidifies. The resulting adduct contains 46.9 percent by weight of the dye and has crushed granules an excellent solubility in water / compared to the solubility of the pure dye.

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Example 10

4 g of the dye of the formula

0 NH,

CH ₂ NHCO CHo

are in 4 g of dimorpholinocarbonyl and 4.8 g of urea Melted 140 °. The solidified melt, containing 31.3 percent by weight of the dye, gives a rapidly soluble in water or dispersible product.

If hexamethylphosphoric acid triamide is used instead of dimorpholinourea with otherwise the same procedure, in this way one obtains an adduct with equally good properties.

Example 11

5 g of the dye of the formula

NCH (CH.)
H ^J

are together with 2 g of dimorpholinocarbonyl and 10.25 g of urea melted at 140 °. The cooled mass, containing 30 percent by weight of the dye, gives one in water quickly soluble or dispersible adduct, which solubility is 5 times greater than that of the sole dye.

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Example 12

33 g aqueous press cake of the dye of the formula

SO ₃ H

= N- <yy> -OCH ₃

(20 g dry content), 6 g Hexamethylphosphorsäuretriamidj 8.3 g of thiourea, 0.7 g of sodium hexametaphosphate and 15 ml of water are added. Then the solution is approx. Heated for 20 minutes at 110 ° and then removed the water under vacuum. The dry powder (35 g) containing 57.1 Percentage by weight of the dye shows a very good wettability in water compared to the untreated dye and very good cold water liquor.

Example 13

If in Example 12 hexamethylphosphoric acid triamide is replaced by equal amounts of N-methylpyrrolidone and the Water at 95 °, an equally good product is obtained.

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Example 14

15 g of the dye of the formula

NHCH.

CH ₃

NHCH ₀ CH ₀ CH ₀ -N-CH ζ ζ ζ 1

SO ₄ CH ₃

are at 110 ° in a 1: 1 adduct of hexamethylphosphoric triamide and thiourea melted. The thin liquid melt is poured onto an aluminum plate fast fixed. The comminuted adduct, containing 37 percent by weight of the dye, has very good cold water solubility and wettability in water.

Example 15

120 g of thiourea are dissolved in 120 ml of dimethylacetamide at about 110 °. The solution will solidify cast an aluminum plate. 30 g of this adduct are mixed with 20 g of the optical brightener of the formula ^ V-NH

T

HN- ^ V-CH = CH

ο ο

heated at 130 °. The thin, homogeneous suspension of the optical brightener in the adduct becomes fast after cooling fixed. An adduct is obtained which contains 40 percent by weight of the optical brightener and which is a much better one Has dispersibility in water as the starting product.

NaOoS '

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If one proceeds as indicated in the example, however, the 20 g of the optical brightener are replaced by the same amounts of the following optical brighteners, adducts with improved dispersibility in water are also obtained compared to the adducts Output Optical Brighteners:

Cl- / ~ V CH = CH

NaO ₃ S

- Cl

SO ₃ Na

CH ₃ SO ₄

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Claims (9)

2523568 claims 1. Solid dye or optical brightener preparations which are soluble in cold water containing a dye or optical brightener in an adduct of a for hydrogen bridge formation capable substance and an aprotic polar compound and optionally other additives. 2. Solid, cold water-soluble preparations according to claim 1, characterized in that they contain substances capable of _{forming hydrogen bonds which contain an -NH 2} , -OH, -COOH, -SO ₃ H or an -SO ₂ NH ₂ group in the molecule . 3. Solid, cold-water-soluble preparations according to claim 1, characterized in that they are used as hydrogen bridge formation capable substances contain urea, thiourea or nicotinic acid amide. 4. Solid, cold water-soluble preparations according to claim 1, characterized in that they are used as the aprotic polar compound phosphoric acid and thiophosphoric acid derivatives, urea and Contain thiourea derivatives, pyrrolidones and thiopyrrolidones and acyl or aryl amides. 5. Solid, cold water-soluble preparations according to claim 4, characterized in that they are used as an aprotic polar compound Hexamethylphosphoric acid triamide, dimorpholinocarbonyl, N-methyl-pyrrolidone or dimethylacetamide. 6. Solid, cold-water-soluble preparations according to the claims 1 to 5, characterized in that they contain 30 to 60% by weight, in particular 40 to 50% by weight, of a dye or optical brightener included. 509883/1016 7. Solid preparations which are soluble in cold water according to the claims 1 to 6, characterized in that the dyes used are acidic dyes, reactive dyes, 1: 1 or 1: 2 metal complex dyes or basic dyes, and as optical brighteners anionic or cationic, such as stilbene derivatives, Pyrazoline derivatives, benzofuran derivatives, benzoxazole derivatives, Benzimidazole derivatives, monomethine cyanines, naphthalimide derivatives, and compounds with 1,2,4-oxdiazole groups contain. 8. Process for the production of the solid, cold-water-soluble preparations according to claims 1 to 7, characterized in that that the dye or optical brightener either in powder form or in the form of an aqueous solution or of the press cake in those capable of forming hydrogen bonds Substance or in the aprotic polar substance, whereby the solution can also take place via a melt, dissolved and then the aprotic polar compound is added in the event that the dye is in the substance capable of forming hydrogen bonds was dissolved, or this substance is added if the dye has been dissolved in the aprotic polar substance, and after separation of the water forms an adduct, which contains the dye or optical brightener in fine distribution. 9. Use of the solid, cold-water-soluble preparations according to claims 1 to 7 or the cold water-soluble preparations obtained according to the method of claim 8 for the preparation of dye liquors and optical brightener liquors or printing pastes on an aqueous basis and the application same for dyeing and printing or optically brightening materials. 509883/1016