CH615212A5 - Process for preparing dust-free dye or optical brightener granules - Google Patents

Description

The invention relates to a process for the preparation of mono- or dibenzimidazolyl compounds and naphthalene-free dye or optical brightener granules acidimides, naphthotriazole and v-triazole derivatives.

as well as the dust-free 50 produced by the process. All of these dyes or optical brighteners can be dye or optical brightener granules. already in a spray-dried or in conventional

Powdery dyes or optical brighteners, which are available in neil quality and as raw material. It should be mentioned in this grinding and mixing process or via the atomization connection that this drying process must be standardized, in order to be suitable for today's grain enlargement not only to satisfy dusting pro-commercial forms. Widely used to convert 55 products into non-dusting, but also for this is the dedusting method, which is used on a liquid-solid to e.g. B. weaken dye concentrations or fabric liability based. Here, the liquid dedusting agent is a higher or lower color strength for dyes an z. B. sprayed onto the powder surface, with liquid inlets.

form bridges between the particles and thus usable according to the invention are such aids:

Effectively stick together. 60 soften or melt in a range from 50 to 150 ° C.

A typical dust-binding agent is «Essotex» (mine - in this context, e.g. urea, milk-ral oil), which has the disadvantage, however, that in water only emulsified sugar, ethoxylated (1.8 or 3 mol ethylene oxide ) To be coconut fat. But even among water-soluble dust alcohol sulfate, sodium dodecylbenzenesulfonate (WAS 83%), there are only a few who have or develop no disadvantageous properties - lauryl pyridinium chloride, glucose, dextrose (hydrate dextrose). Often the dedusting effect is 65 dextrin (blonde quality), sorbitol (e.g. Karion, Merck AG, because the liquid from the surface in Germany), salts containing water of crystallization, such as sodium carbonate, diffuse, or one occurs Clumping of the phosphate-10-hydrate, sodium acetate-3-hydrate and disodium hydrogen-verse due to excessive adhesion. Since the dust-binding agent we-phosphate-2-hydrate, polyethylene glycol with a molecular

3rd

515 212

important over 3000 and citric acid.

Particularly good results are obtained with dextrin and sorbitol. The individual adhesive or mixture of adhesives is added in an amount of at least 10 percent by weight, based on the dye to be granulated or optical brightener. In addition to this adhesive, other additives can also be present, such as coupants in particular in amounts of 0.1 to 50 percent by weight, based on the dye to be granulated or optical brighteners, such as sodium chloride or sodium sulfate, or also wetting agents, dispersants acidic range, gas-releasing substances (NaHCCh), alkaline agents or acid carriers (sulfamic acid). It is important that mixtures of substances are particularly suitable for particle enlargement which show 15 softening phenomena at a temperature of above 50 ° C., in particular 65 and 95 ° C.

The actual process of particle enlargement consists of the following operations:

- Production of the homogeneous, granulated mixture of dye or optical brightener, adhesive and, if necessary, the further additives;

Heating this mixture with mixing or rolling motion to at least 50 ° C, preferably 65 to 95 ° C, for about 5 to 30 minutes;

- crushing the resulting lumps; 25th

- Cool while moving the granules to approx. 50 ° C.

The size of the granules can vary depending on the amount of adhesive in the range of 100 mm to 20 mm.

Technically, this measure z. B. in a tumble dryer, in a Conaform dryer or in a Lödige 30 mixer.

By means of this process it is thus possible to convert dusting dyes or optical brighteners, in particular in powder form, with an initial fineness of approximately 1 to 150 μm into a granular, non-dusting form with a grain size of approximately 35 100 (in to 20 mm, which is compared to that Basic goods have the following advantages:

- effective dedusting without added liquid;

- abrasion-resistant granules;

- no dust loss; 40

- persistent dust-binding effect;

- reducing the adhesion of the particles to each other;

- no fine fraction in the end product;

- Improved pouring and flow behavior or improved flowability by increasing the grain size;

- no loss of water solubility;

- improved appearance (aspect);

- Separation is prevented.

In addition to these advantages, the granules are required to have sufficient strength and separability. These and similar properties can be transferred to the product using formulation aids. The division can be improved by easily soluble, gas-evolving or swelling substances that are added to the granulate.

A higher strength is achieved if the granulation is carried out with the addition of salt.

This very versatile process provides a product that is easier to handle than powder quality in terms of processing, packaging and dosing. It is particularly important that this method can be used in particular for basic and acidic dyes.

The size of the granules largely depends on the content of the adhesive and on the weight of the powder. A high adhesive content favors the formation of large granules. The granules obtained by the process have a residual moisture content of about 2 to 5 percent by weight.

Since the granulation is the last step in the processing of the product, the properties and the active content should correspond to the type. If this is not the case, a correction granulation can be carried out.

The dye or optical brightener granules obtained are used for a wide variety of applications, such as. B. for dyeing and printing or optical brightening of a wide variety of materials in a known manner from aqueous or organic liquor.

The following examples illustrate the invention without limiting it. Temperatures are given in degrees Celsius, parts (T) mean parts by weight; “UpM” means revolutions per minute and “dust-free” should be understood to mean that the product contains no particles with a particle size of 1 to 60 n.

example 1

Dry, spray-dried dye of the formula ch3o

(

C-N = N

f ~ \

CH.

N-CH2CH20H

C2H5

e

ZnCl,

©

is weakened with a granulable coupage from 300% to 100% as follows: 200 parts of a mixture with a grain size of 2 to 100 (in, consisting of 33.3 parts of the above dye, 36.0 parts of sodium sulfate calc, 27.0 parts Dextrin blond (Provenance Schrobenhausen, residual moisture 10%), 3.0 T sorbitol (Provenance Hefti), 0.7 T sulfamic acid are homogenized in a mixer and then granulated in a rotating round-bottom flask (30 rpm), which is placed in an 80 ° Warm heating bath is immersed, the powder warms from room temperature to about 70 ° in the course of 20 minutes, the granulation also taking place at the same time, and is then cooled to 50 °.

This gives a dye granulate with a grain size of about 900 to 1000 μm, which is very low in dust and whose concentration has been weakened.

Example 2

33.0 T sodium sulfate (ground), 26.0 T dextrin blond (Schrobenhausen, residual moisture 10%) and 8.0 T Karion are mixed in a Braun mixer for 1 minute and crushed. Then this mixture together with 33.0 T of powdery dye (raw material) of the formula

60

65

615212

4th

Cl

/

n = n ho -

(Particle size 10 to 50 µm), mixed in a pelletizing flask for 10 minutes and the flask rotation set to 30 rpm. This pelletizing flask is then immersed in a 90 ° warm heating bath, the contents heating up to approximately 80 °. The granulation is complete after about 30 minutes. Allow to cool and fill at a product temperature of 503.

20th

A non-dusting dye granulate with a particle size of about 100 to 2000 p.m. is obtained.

Example 3

91.0 T of the already granulated but dusting dye of the formula are placed in a pelletizing flask

XC-N = N- ^ \ N

yH \ T-CH2CH20H

i2h5

©

ZnCl '

o mixed with 9.0 T dextrin blond (Schrobenhausen, residual moisture 10%).

The pelletizing flask, half of which is immersed in a 90 ° warm heating bath, should not exceed a speed of 30 rpm. The mixture warms to 85 ° within 25 minutes.

The granulation is then stopped, the granules are cooled to 50 ° and discharged.

Dust-free dye granules are obtained.

Example 4

89.0 T of the already granulated dye of the formula according to Example 3 (particle size mm) with 7.0 T of the same dye, but spray-dried (particle size 50 to 150 μm) and 4.0 T of blond dextrin (Schrobenhausen, Residual moisture 10%) mixed.

While rotating (30 rpm) the pelletizing flask, which is immersed in a 90 ° warm heating bath, the mixture is heated to 85 ° for 35 minutes.

After reaching this temperature, the granulate is immediately cooled to 50 ° and discharged.

A dust-free dye granulate (particle size 100 to 1000 μm) is obtained.

40

Example 5

29.0 dextrin blond (Schrobenhausen, residual moisture 10%) are mixed with 12.0 T Karion in a Braun mixer for about 1 minute and crushed.

45 The mixture is then 59.0 T of the dye of the formula

(ground raw material, conventionally dried, particle size 1 to 100 yy.m), mixed in a round bottom flask at room temperature for 10 minutes (flask revolutions ~ 30 rpm).

After mixing, half of the flask is immersed in the 90 ° hot heating bath. With a piston revolution of 30 rpm, granulation takes place within 30 minutes. The product temperature rises to ~ 80 °. The granules are allowed to cool to 50 ° and are filled.

60 A granulated, dust-free dye with a particle size of 0.1 to 2 mm is obtained.

If instead of the 59.0 T of the above dye the same amounts of the dyes listed in the following table are used with the same procedure, the result is 65-free dust-free granules.

5

table

615 212

Example No.

dye

6

ch3 ° ^ ys-C-N = n / ~ y ^ ch3

\ = / xCHo 1 j l c2h5

©

Cl 0

7

r chq i i 3

f '? / ~ \ _ / C2H5

1 2 5 l ch3

©

ZnCl30

8th

1 / II • Ii 3 0. / ^ 0-C N Cr nN "'

° "7 ° fs

ó "ó, 0>"

N = N

<9

Na ®

9

S03

T "-TTch3

0 ^ / V 0-1 N Cr N "^

° 7 o / V

j ^ j-N = N-j ^ j \. ^

<^^> - N = N dj

© © 2 Na ®

615 212

6

Example No.

dye

10th

, -s ° 2-f> ° - (3rd

c2h5 n oh nh-s0o- / ~ v ch ~ Uli 2 \ / 3

n

1i03s s03h

11

c2h5s02-o ~ n = h i, —n— ch3

- \ X N "h ho- ^

1: 2 Cr complex

12

no2 so3h ° 2n ^> nh-ff nh- ^ ~ ^)

13

q- c00c10h21

n = n-c-c-ch "

ii ff «3

ho - C n XN '

so- ^ h

14

oh ho na03s- / \ -n = n- /%

ö ö

02n

615212

Example No.

dye

15

r s0ochq r i2 3] ©

| j_}] = N C-C0NH - / ^>

0 ^ ^ 0 - = - ch3 ct

Cl ^ Co ^ Na ® h-c-c-0 1 0

^ j ^ -hnc0- c - -n = n s02c2h5

16

^ so ^ h

(~ \ 0-s09 h0- / ~ ^>

nh2

17th

nh0 oh ho n = n—, £ 00h

/ ~ i_ kj-n = n- / yoh nh ^ j> - n = n- | ^ j- n = n- ^ jh oh v w / so ^ h Cu complex

Example 18

30.0 T blond dextrin (Schrobenhausen), 30.0 T sodium sulfate (ground), 3.5 T karion and 0.5 T sulfamic acid are comminuted and mixed in a Braun mixer in about 1 minute.

The mixture obtained is mixed with 36.6 parts of the spray-dried, but still dusting dye of the formula according to Example 1 (particle size 50 to 150 μm) in a pelletizing flask. For homogeneous mixing, the pelletizing flask is rotated at 30 rpm for 5 minutes. Then this flask is immersed in the 900 warm heating bath. Granulation is carried out for 20 minutes while rotating at 30 rpm. The heating bath is then removed and the granules are cooled in the rotating flask. When the product temperature has dropped to 50 °, the granulate is filled. A dust-free dye granulate (particle size 100 to 1000 µm) is obtained.

Example 19

41.0 T sodium chloride and 17.0 T Karion are combined in one

50

Braun Mixer crushed and mixed in about 1 minute. This mixture is then mixed with 42.0 T of the atomically dried, but still dusting dye of the formula given in Example 15 (particle size 10 to 50 μm) in a granulating flask with a spiral insert within 5 minutes, and then half in an 80 ° Warm heating bath immersed and set in rotating motion (30 rpm). The granulation is complete in 5 to 10 minutes. After about 10 minutes, the granulate has cooled to 50 ° so that it can be discharged 60. A dust-free dye granulate (particle size 100 to 1000 μm) is obtained.

Example 20

65 22.0 T blond dextrin (Schrobenhausen), 17.0 T sodium sulfate (ground) and 6.0 T karion are comminuted and mixed in a Braun mixer in about 1 minute.

The mixture obtained is oven-dried with 55.0 T of the

615212

8th

th dye of the formula given in Example 7 (particle size 50 to 150 (im)) in a pelletizing flask and mixed for 5 minutes. The flask is then half immersed in a 90 ° warm heating bath and set in rotating motion. By the rotating movement (30th Rpm) and exposure to heat (maximum product temperature 85 °), the powder mixture is granulated in 15 minutes.

The granulate can be cooled in the rotating piston. As soon as the granulate temperature has dropped to 50 °, the product is filled. A dust-free dye granulate (particle size 100 to 1000 p.m) is obtained.

Example 21

60.0 T blond dextrin (Schrobenhausen), 6.5 T Karion and 0.5 T sulfamic acid (50 to 150 (im)) are crushed and mixed in a Braun mixer in approx. 1 minute.

The mixture obtained is placed together with 33.0 T of the atomically dried but dusting dye of the formula given in Example 6 (particle size 50 (im)) in a pelletizing flask and mixed for 5 minutes, then half of the flask is placed in a 100 ° warm one With a piston speed of 30 rpm and a product temperature of 95 °, the granulation takes place within 20 minutes.

The heating bath is then removed so that the flask can cool in air. The granulate has a temperature of 50 ° within 10 minutes and can be filled. A dust-free dye granulate (particle size 100 to 1000 (im)) is obtained.

Example 22

20.0 T blond dextrin (Schrobenhausen, particle size 5 to 50 (im), 40.0 T sodium sulfate (ground), 4.5 T karion and 0.5 T sulfamic acid are mixed in a Braun mixer for 1 minute and crushed.

This mixture is then mixed in a granulating flask with 35.0 T of the spray-dried dye of the formula given in Example 1 (particle size 50 to 150 (im). Homogenization is achieved at 30 rpm within 10 minutes. which rotates at 30 rpm, immersed in a 90 ° warm heating bath. Within 30 minutes the product warms up to 80 °. Now the granulation can be ended. The granulate is cooled to 50 ° and discharged. A dust-free dye granulate (particle size 100 to 2000 (im).

5 Example 23

60.0 T blond dextrin (Schrobenhausen), 6.5 T Karion and 0.5 T sulfamic acid are crushed and mixed in a Braun mixer in about 1 minute.

The mixture obtained is then placed in a granulating flask together with 33.0 parts of the spray-dried dye of the formula given in Example 6 (particle size 50 (im)) and mixed for 5 minutes, and the flask is then half-immersed in a 100 ° C. heating bath At a speed of the piston of 30 rpm and i5 a product temperature of 95 °, the granulation takes place within 20 minutes.

The heating bath is removed so that the flask can cool in the air. The granulate has a temperature of 50 ° within 10 minutes and can be filled. 20 dust-free dye granules (particle size 100 to 1000 (im)) are obtained.

Example 24

42.0 T sodium chloride and 16.0 T Karion are crushed and mixed in about 25 minutes in a 25 Bràun mixer.

42.0 T of the atomically dried but dusting dye of the formula given in Example 15 (particle size 10 to 50 (im)) are then added and mixed to this mixture within 5 minutes in a pelletizing flask.30 Half of the flask is then heated to 80 ° The heating bath is immersed and rotated (30 rpm). The granulation is completed in 5 to 10 minutes and the product warms up to a maximum of 75 °.

The flask is then removed from the heating bath to the air 35. After 10 minutes, the granulate has cooled to 50 ° so that it can be discharged. A dust-free dye granulate (particle size 100 to 1000 (im)) is obtained.

Example 25

46.0 T of the conventionally dried dye of the formula

40

ch30

N

I.

ch

^ c-n = n-n h ^ \ n02

ch3 ~

©

Cl

©

(Particle size 1 to 26 (im), 10.5 T sodium sulfate (ground), 34.0 T dextrin blond (Schrobenhausen, residual moisture 10%) and 10.0 T sorbitol (Hefti, particle size 50 to 150 (im) are combined in one Braun mixer blended and chopped for approx. 1 minute.

This mixture is then placed in a granulating flask. Then the flask, which rotates at 30 rpm, is immersed in a 90 ° warm heating bath. Spherical particles larger than 300 (im. The 60th

Granules are cooled to 50 ° in a rotating flask and then discharged. A non-dusting 55 dye granulate with a particle size of ~ 300 (im.

Example 26

56.0 T of the conventionally dried dye of the formula ch,

jun-n-tv n "

N / A

ch.

ch.

ch,

©

Cl

©

9

615 212

(Particle sizes 3 to 50 (im), 16.0 TN atrium sulfate (ground), 22.0 T dextrin blond (Schrobenhausen, residual moisture 10%) and 6.0 T sorbitol (Hefti, residual moisture 1%) are mixed in a Braun mixer mixed and chopped for approx. 1 minute.

The mixture obtained is then placed in a pelletizing flask which is heated in a 100 ° warm heating bath. At a piston speed of 30 rpm, the granulation takes place within 20 minutes. The granules are cooled in the rotating flask. Bottling is possible at a product temperature of 50 °. A dust-free dye granulate with a grain size of ~ 500 µm is obtained.

Example 27

22.0 T blond dextrin (Schrobenhausen), 17.0 T sodium sulfate (ground) and 6.0 T karion are comminuted and mixed in a Braun mixer in about 1 minute.

The mixture is then placed in a pelletizing flask with 55.0 T of the oven-dried dye of the formula given in Example 7 (particle size 50 to 150 μm) and mixed for 5 minutes. Then the piston is half in

5 submerged the 90 ° warm heating bath and set it in rotating motion. Due to the rotating movement (30 rpm) and exposure to heat (maximum product temperature 85 °), the powder mixture is granulated in 15 minutes.

The granulate can be cooled in the rotating piston.

10 As soon as the granule temperature has dropped to 50 °, the filling is started. A dust-free dye granulate (particle size 100 to 1000 μm) is obtained.

Example 28

's 32.0 T of the conventionally dried dye of the formula

©

r ~

oc2h5

/ VNv \

(c2h5) 2n / ^ n (c2h5) 2

(Particle size 26 µm), 25.0 T sodium sulfate (ground), 33.0 T dextrin blond (Schrobenhausen, residual moisture 10%) and 10.0 T sorbitol (residual moisture 1%) are mixed in the receptacle of the Braun mixer. The mixture is then mixed in portions in a vessel more intensively.

The parts of the mixture are then combined and placed in a granulating flask which is immersed in a 100 ° warm heating bath. At a piston speed of 30 rpm

the grain builds up within 20 minutes.

The heating bath is removed, the product is cooled to 50 ° under piston rotation and then bottled.

Dust-free dye granules are obtained.

Example 29

Spray-dried optical brightener of the formula

35

is granulated as follows: 100.0 T of a mixture consisting of 50.0 T of the optical brightener mentioned above (particle size 1 to 50 (im), residual moisture 7.2%) and 50.0 T of urea (particle size 50 to 100 μm), Residual moisture 3.2%), are mixed in a mixer. The granulation is then carried out in a rotating round-bottom flask (30 rpm) which is immersed in a 70 ° warm heating bath. A grain (1 to 2 mm) builds up within 30 minutes. After cooling to 50 °, the granules are discharged. A dust-free optical brightener is obtained.

G

Claims (9)

615 212 1. Process for the production of dust-free dye or see the particles can be recycled, an optical brightener granules, characterized in that deterioration of the pourability cannot be avoided. Both dyes or optical brighteners in the dry state properties - effective long-lasting dust binding with at least 10% by weight, based on good flowability - cannot be given to the Proauf the dye or optical brightener, at least one product. In addition, liquid dust-binding agent adhesive, which softens between 50 to 150 ° C or only achieves a certain dust binding, which also melts, mixes and homogenizes, and then does not heat up by mixing or rolling with min - can be exceeded. at least 50 ° C this by particle enlargement into a 10 A method has now been found which converts to dust-like, non-dusting form and leads to free products under movement and which, surprisingly, cools them down. does not have the disadvantages mentioned above. 2. The method according to claim 1, characterized in that this method is based on a grain enlargement of the particles corresponding to dye or optical brightener powder and is characterized in that with the adhesive by means of a rolling movement with heating, dyes or optical brighteners in the dry state at 65 to 95 ° C in a granular non-dusting form in the presence of at least 10 percent by weight at least. an adhesive that softens between 50 to 150 ° C 2nd PATENT CLAIMS with liquids to increase the liability between 3. The method according to claim 1, characterized, melts, and optionally further additives are mixed and that dyes or optical brighteners are homogenized with an adhesive and then mixed by heating to a medium and other additives. 2. <at least 50 ° C this by particle enlargement into a solid 4. The method according to claim 3, characterized in that some non-dusting form is converted. that as additional additives 0.1 to 50 percent by weight, it is also expedient that the particle size of all of the genes on the dye or optical brightener on coupé agents components is in a narrow range in order to use one. to ensure even grain build-up. 5. The method according to claims 1 to 4, characterized 25 under dyes here are all possible classes to indicate that the granules obtained are then, both coloristically and chemically, which u. a. for being crushed. an aqueous or organic application is suitable. - 6. Process according to claims 1 to 5, characterized by way of example are sulfur dyes, vat dyes, characterized in that urea, water of crystallization 'pickling dyes, chromating dyes, dispersion dyes containing salts such as sodium carbonate-10-hydrate, sodium acetate 30 and direct dyes, these dyes may contain fiber 3-hydrate or disodium hydrogenphosphate 2-hydrate or poly-reactive groups in the molecule. It goes without saying that ethylene glycol with a molecular weight of more than 3000 or food dyes and, for example, leather dyes, citric acid and in particular dextrin (blonde quality) are also included. This method is particularly interesting when sorbitol is used. application to basic and acid dyes. 7. Application of the method according to claim 1 based on 35 chemically, z. B. nitroso, nitro, see or acidic dyes. Monoazo, disazo, trisazo, polyazo, stilbene, carotenoid, 8. The diphenylmethane, trìarylmethane, xanthene, acridine, quinoline, granular non-dusting dye or optical brightener methine, thiazole, indamine, indophenol, azine, oxazine obtained by the process according to claim 1 -, Thia granules. zinc, lactone, aminoketone, hydroxyketone, anthraquinone, 9. dye or optical brightener granules according to 40 indigoids and phthalocyanine dyes and by 1: 1 or claim 8, obtained by the process according to one of the 1: 2 metal complex dyes. Claims 2-6. Any brightener classes of this type can also be used as optical brighteners which are used for whitening. For example, there are stilbene compounds, such as cyanuric derivatives of 4,4'-diaminostilbene-2,2-disulfonic acid or distyryl biphenyls, coumarins, benzocoumarins, pyrazines, pyrazolines, oxazines, mono- or dibenzoxazolyl ,