DE2038560A1 - Process for the production of pigment dyes - Google Patents

Description

DR. BERQ DIPL-ING. STAPF PATENT LAWYERS

? ΓΠ Pi R R Ω

Munich a, HiLBLESTRASSE ao £ uooaou

CIBA AKTIENGESELLSCHAFT ₁ BASEl (SWITZERLAND)

Case 6832 / E '.

Germany

Attorney's file 19 836 . 'Munich, August 3rd, 1970

Process for the production of pigment dyes.

There has already been a procedure for. Manufacture of pigments proposed, which is characterized in that an aminotriazine-aldehyde condensation product is used as the dye carrier used (see Swiss patent specification 196 35 ^) · Das Atninotriazine-aldehyde condensation product is before, during or hardened after association with the dye and then finely ground. Both water-soluble and fine-grained, water-insoluble Dyes are used.

.0.09887 / 1893. . _ ■, _NSP £ CtED

- 2 - ·. . 2033560

Despite its obvious advantage, an overpass simple, soluble substances in insoluble, extract-resistant Pigments, this process has not found any industrial application. The reason for this is as follows: The particle size and the particle shape of the pigment is also determined in this process by a mechanical comminution process. It is known that even the most efficient grinding machines cannot reduce the particle size below 1 micron. The particles obtained by mechanical comminution generally have a broad size distribution and are irregular Forms on. This is particularly true for hardened aminotriazine-aldehyde condensation products too, which, because of their brittleness and glassy character, become irregular when they are married Splinters of very different sizes are smashed. This inhomogeneity in shape and size has a number of disadvantages The result of using such products as color pigments:

a) Their adhesion to textile fibers with binders is low; They are easily rubbed off. They are therefore not suitable for textile printing.

b) They reduce the strength of synthetic fibers when they are dyed in bulk with such color pigments.

c) If they are used to color paints, matt films result.

d) As the mechanical strength of rubber and plastic items is already lowered in a significant way by very small proportions of coarse, irregular particles

009887/1893

BATH ORIGINAL

Rubber and plastic items with the mentioned color pins have been colored, decreased mechanical strength.

All these parts are eliminated by the method according to the invention, and many things are characterized by this is that one consists of a single-phase, aqueous system, which

en / one, or ', several' aminoplast formers, one / or more aldehydes, or the polycondensation products of amino-ρ lcj-stb ilanes with aldehydes as well as a protective colloid or a surface-active copper; -elöst contains, before, during or "inch of the Association rr.ifc a water-soluble dye is a finely disperse,"'-eflirbtos., insoluble, fusible ^, vernrt:; Ves Ar _t. "; .r.oplact forms.

In the Re.jel the formed is then colored Aminoplast separated from the aqueous phase, dried and desa -; lomerized.

For some applications, however, it is not necessary the aminoplast obtained by FSllim ■ odor Gelierun -

watering and drying, for example one can produce colored ones 'Papers or, for some textile applications, aqueous suspensions of the - if necessary, neutralized and deagglomerated, Vion directly to the dye-containing film gels. on In this way, costly process steps and energy costs can be saved.

BATH ORIGINAL 009887 / 1S23

Aminoplast formers are understood in particular to mean: urea, thiourea, dicyandiamide, melamine and

Guanamines of the general formula

R = C _{1 -C 1} Q alkyl, C _{1 -C 1} Q alkenyl, cycloalkyl, aryl, aralkyl.

Examples of such guanamines are acetoguanamine / benzoguanamine, tetrahydrobenzoguanamine and phenylacetoguanamine.

The formaldehyde can partly be replaced by other aldehydes such as acetaldehyde, isobutyraldehyde, acrolein, crotonaldehyde and benzaldehyde are replaced.

There are practically no restrictions on the choice of the water-soluble dye. There can be dyes various classes are used, e.g. mono- or polyazo dyes, both metal-free and metal complexes, for example copper, nickel, chromium or cobalt complexes of azo dyes, anthraquinone, perinone, nitro, methine, Azomethine, azoporphine, quinophthalene, oxazene, dioxazine xanthene or triphenylmethane dyes. Optical brighteners can also be used instead of the dyes. The dyes must be soluble in water. The water solubility of the dyes can be effected in a number of ways, for example by Use of a suitable number of customary water-solubilizing groups, such as sulfonic acid, carboxylic acid, disulfimide, carbon

009887/1893

amide or sulfonamide groups, or else also.by Presence of several hydroxyl groups. There are also the well-known 2: 1 chromium or cobalt complexes of azo or azomethine dyes into consideration, whose water solubility in addition to any sulfonamide, sulfone or Acy! amino groups due to the salt-like character of the Complex is conditional.

Also basic dyes, whose solubility is due to the presence of a tertiary or quaternary amino group or an oxonium group, come for the invention | appropriate procedures under consideration. Unless working in very dilute solutions is considered uneconomical, A water solubility of the dye of a few percent is sufficient. The lightfastness of the pigment is, to a high degree, through determines the lightfastness of the water-soluble dye. The melamine-formaldehyde or the urea-formaldehyde component the pigment has excellent lightfastness.

0098 87/1893

Protective colloids are understood to mean macromolecular, water-soluble substances that increase the viscosity of water. They preferably have the character of a polyelectrolyte. Examples of substances that are excellent as protective colloids are: synthetic substances such as alkali salts of polymers and copolymers of acrylic acid, methacrylic acid, fumaric and

Maleic acid: polyoxyethylene glycols, natural substances such as gelatin, Agar-agar / tragacanth and alginic acid, as well as modified natural substances, such as methyl cellulose, ß-hydroxyethyl cellulose, hydroxypropyl cellulose

and sodium carboxymethyl cellulose.

Among surface-active substances or surfactants are

/gene. Understood substances that reduce the surface tension of water / Anionic, cationic or non-ionic surfactants can be used. Examples of anionic surfactants are petroleum alcohol sulfonates, alkylarylsulfomates, salts of sulfosuccinic acid esters, and monoglyceride sulfates. The halides or methyl sulfates of quaternary ammonium bases which carry _{at least one alkyl radical J ^ C, 2 can be used as cationic surfactants.} Effective non-ionic surfactants are, for example, the polyalkylene ethers of fatty alcohols or

Phenols.

The electron microscopic examination of the after this

Pigment particles produced by the process shows their exact spherical

its size / / e ciently shaped form and the evenness /. The coefficient of variation / of the particle diameter is in all cases below 20 percent, in most cases it is only 10 percent or even less.

009887/1893

The following factors determine the mean particle diameter:

(a) molar ratio and concentration of aminoplast former and of the aldehyde.

(b) Type and concentration of the protective colloid or surfactant.

(c) pH value or acid concentration in the crosslinking reaction.

With the help of these parameters one has it in hand, particles with diameters between 25O-10000 8 or a specific one Surface from 2 to 200 m2 / gr. to produce "made to measure". This is a decisive advantage of this Procedure. One is d-amit of the random factors with which ™ mechanical crushing processes are tainted independently. Particle size range of organic pigments becomes light accessible, which is now difficult to achieve with the means belonging to the state of the art. One can, and this is it most important point, adjust the particle size to the intended use and the substrate. For example one can choose a particle size that provides a maximum gloss and high opacity of paints, while others Particle size ranges are ideal for printing textiles or for dyeing synthetic fibers in bulk suitable. The type of aminoplast former also plays a major role. For example, with urea-formaldehyde pigments transparent PVC films are obtained, while melamine-formaldehyde. Pigments of the same particle size cause severe clouding.

Process for the preparation and properties of such colorless, highly dispersed, crosslinked condensation :

009887/1893

polymers based on melamine formaldehyde and urea formaldehyde are described in the literature (see British patent specification

I 0 ^} [J) k '} 6 and American patent specification j5 4? .8 607; further

^II Makromol.Chemie ^ l20, 68-86 (1968). It has been shown how specific the reactions that lead to submicron particles are. In previously unpublished laboratory tests it was shown that even relatively small amounts of polar substances, such as alcohols, phenols, or amines and, in particular, inorganic salts, cause particle enlargement and strong particle conglomeration. Based on this experience, it was to be expected that the crosslinking reactions, which lead to particles in the submicron range, will also be sensitively disturbed by dyes. The fact that it is possible to produce polymeric pigment dyes in the form of uniform, spherical micron and submicron particles with a dye content of up to kO '/ o must therefore be regarded as extremely surprising. With a suitable choice of the soluble dye, color pigments of high yield are obtained. The dye is generally very tightly bound and, despite the large surface area of the particles (up to 200 m "/ g), cannot be extracted with water or solvents. In many cases it even withstands extraction with dilute acids or alkalis.

The determination of the mean particle diameter · by Counting electron micrographs is a time consuming and arduous job. A suitable measure for characterization the dispersity of the pigment dyes according to the invention

009887/1893

Is the specific surface. From it, the mean particle diameter can be determined according to

³ ■ y-ψ- ■ ^s2

(cf. "Macromol.Chemie" 120, 68-86 (1968). In this, A stands for the specific surface area, m for the mean particle mass and S for the standard deviation. The specific surface area can easily be determined by the so-called BET method or can be determined more easily according to "Haul and Dümbgen" (cf. Chem.Ing.Technik 32 [1960] 349 and Chem.Ing. Technik 35 [1936] 586).

The new pigments can be used for pigmenting high molecular weight organic material, e.g. cellulose ethers and esters, super polyamides or super polyurethanes or polyesters, acetyl cellulose, nitrocellulose, natural resins or condensation resins, e.g. aminoplasts, in particular urea and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters g, rubber, casein, silicone and silicone resins, singly or in mixtures.

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages by weight and temperatures are given in degrees Celsius.

009897/1893

Example 1.

Production of a blue, highly dispersed pigment based on melamine-formaldehyde.

a) precondensate

200 parts of 30 # aqueous formaldehyde solution are used heated to 70 and adjusted to pH = 7. One carries under Stir in 126 parts of melamine and keep pH = 7 constant by adding a little 10 $ HpSOu. After the melamine has dissolved condensation is carried out for 50 minutes at pH = 7 and 70 ° and cooled the precondensate to 40 °.

009887/1 893

b) dye dissolution

4.65 parts of an anthraquinone dye of the formula

0 NH ₉

Il I SO ₃ Na

are dissolved in 88 parts of water.

c) The reaction vessel is equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a pH measuring probe which controls the flow of 10% sulfuric acid via a pH meter and a solenoid valve. 848 parts of deionized water and 0.93 parts of a high molecular weight sodium lumarboxymethyl cellulose are initially charged, and the mixture is stirred, heated to 95 ° C. and adjusted to pH 6.5. Combine 81.5 parts of according to Example 1 a) prepared precondensate with the dye solution according to Example 1 b) and dropwise ä this mixture under agitation, with pH = 6.5 is maintained by automatic addition of 10 $ lUSOj. A deep blue precipitate forms. The mixture is allowed to react for 60 minutes at pH = 4 and 95 ° C., cooled to room temperature and adjusted to pH = 6 with 10 ^ strength sodium carbonate solution. The precipitate is filtered off with suction and washed with 3000 parts of water. Both filtrate and wash water are absolutely colorless. The pigment is ^{dried overnight at 0} C in a stream of air and, after cooling, by means of

009887/1893

BAD ORiGtNAU

disagglomerated by a high-speed pin mill.

38 parts of a deep blue, fine powder with a specific surface area of 132 m ~ / g are obtained. The electron micrograph shows uniform, spherical particles with a mean diameter of 280 A. The dye content is 12.2 ^ fo. The dye does not bleed out when boiled for 2 hours in water, 5% soda solution and 25% sulfuric acid. It cannot be extracted with trichlorethylene either.

Dyeings of excellent wash and rub fastness are obtained if the color pigment is used in the roller printing process on cotton, acetate silk, rayon, polyester (polyethylene terephthalate) or nylon fabric applied. The color pigment is also suitable for coloring vulcanizates Natural or synthetic rubber.

Example 2

18.6 parts of a chromated azo dye of the following formula

are dissolved in 352.5 parts of water. You mix these up Solution with 16-5 parts of a melamine-formaldehyde precondensate, which is prepared according to the information in Example 1 a).

009887/1893

BATH ORIGINAL

A solution of 1.86 parts of high molecular weight sodium carboxymethyl cellulose in 1700 parts of water is heated to 95 ° C. and the pH is adjusted to 6.5. The above dye precondensate ^{solution is instilled in static pH at 6.5 and} 95 ° C. while stirring, and the mixture is left to react for 1 hour at pH 6.5 and for a further hour at pH 4. It is cooled to room temperature, made neutral and worked up as described in Example 1. · ·

84 parts of color pigment are obtained with the following characteristics:

Effective dye content: 22 #

Specific surface: 37.5 m / g

Average particle diameter: 68O Å

Lacquer films made from a melamine-formaldehyde stoving lacquer etherified with butanol, which contain this color pigment have an excellent gloss, good covering power and good durability.

» Example 3

/ 4 "'-., A solution of 25.3 parts of copper phthalocyanine-3,4, 4 ¹ ^ / tetrasulfoni, 31 * 5 parts of an 8 $ aqueous tragacanth and 2010 parts V / ater to this solution is prepared at 95 ° C is added dropwise a precondensate which has 30 $ aqueous formaldehyde and 63 parts of melamine for 20 minutes at pH = 8.5 and 85 ⁰ C prepared from 100 parts. the solution is then deep blue-green, but clear. Within 10 minutes 150 parts by volume of 10% sulfuric acid are added dropwise with stirring at 95 ° C. At pH = 5> 1, a precipitate begins to form after the addition of HpSO ^ has ended

009887/1893

the pH value 3.45 ..

After cooling, it is neutralized and worked up as described in Example 1. 95 parts of colored pigment are obtained with the following characteristics:
Effective Dye Content: $ 26.6

Specific surface: 7.2 m / g

The pigment shows good resistance to extraction against boiling water (< $ 0.001), boiling $ 5 HgSO. (<"$ 0.001), 5 $ soda solution (<0.001 $) and trichlorethylene (O). It is particularly suitable as a lacquer pigment, with high-gloss, permanent Lacquer films made from acrylic lacquer resin, cellulose acetate and melamine-formaldehyde stoving lacquer can be obtained.

The color pigment is also suitable for printing textiles. With suitable binders, prints of excellent quality are obtained Fastness to washing and rubbing on cotton, acetate silk, nylon, polyester (polyethylene terephthalate) and polyacrylonitrile fabrics.

Example 4 ^k

The procedure is as in Example 3 »but instead of the Cu-phthalocyanine tetrasulfonic acid 25.3 parts of the blue anthraquinone dye of Formula 4, Table III.

009887/1893

96 parts of pigment are obtained with the following characteristics: Effective dye content: 26.%

Average particle size: 1.16 μια

Specific surface: 15.0 m / g

Extraction resistance:

Boiling water: < 0.01 %

¹¹ 5 # H ₂ SO ₁₁ : <0.0001 <f>

"■ 5% Ua ₂ CO ₃ : 0 % ·

¹¹ trichlorethylene: O ^

The pigment dye is suitable as a lacquer pigment.

In the following Table I is the preparation of further Melamine-formaldehyde resin pigments according to the method laid down in Examples 1 to 3. All necessary Information can be found in the table.

ORIGlNAL BATHROOM

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Table I.

σ σ co οο

No. Parts
melamine Parts
CH ₂ O 30 # protection
colloid Parts
Color
material Color
material
Tabel
III No. PH resin
concentra
tion % yield
Parts colour dye
salary in
Pigment % Spec.
Upper
area
m2 / g 1 31.5 50 Sodium-
carboxy
methyl-
cellulose 9.3 1 4.0 5 42 blue 22.5 185 2 31.5 50 ti 13.9 1 4.0 5 48 blue 29.2 205 3 31.5 50 It 2.3 1 4.0 5 38 blue 6.1 54.5 4th 63 100 Il 18.6 2 4.0 5 89 yellow 21.0 142 5 63 100 Il 18.6 4th 4.0 5 92 blue 20.4 30th 6th 63 100 Il 18.6 5 4.0 5 89 blue 21 19th 7th 63 100 Il 22.4 6th 4.0 5 87 Red 28.8 220 8th 63 100 Tragacanth 25.3 6th 3.3 4th 87 Red 29.1 7.6 9 63 100 Il 25.3 7th 3.4 4th 91 green
blue 27.8 8th 10 63 100 Il 25.3 1 3.1 4th 88 blue 28.8 210 11 63 100 It 25.3 3 3.4. 4th 91 Red 27.8 10 12th 63 100 It 25.3 5 2.8 4th 96 blue 26.4 167 13th 63 100 ti 25.3 2 3.1 4th 88 yellow 28.7 9

Table I.

CO CO CO

No. Parts
melamine Parts
CH ₂ O $ 30 Protection-
colloid Parts
Color
material dye
Table III
No. PH resin
concentra
tion % yield
Parts colour dye
salary in.
Pigment % Spec.
Upper
area
m2 / g i4: 63 100 Tragacanth 25.3 8th 3.3 .4 88 blue 28.7 6th 15th 63 100 ti 25.3 32 3.5 4th 95 blue 26.6 7th 16 50.4 80 dd 20.2 31 3.4 4th 74 yellow 27.4 13th 17th 63 100 It 24 9 3.3 4th 83 green 28.9 9 18th 63 100 dd 24 11 3.3 4th 77 yellow 22.9 11 19th 63 100 It 24 20th 3.3 4th 82 vio
lett 29.7 7th 20th 63 100 dd 24 10 3.2 .4 86 green 27.9 7th 21 63 100 dd 24 · 15 ' 3.2 4th 84 Red 28.6 7th 22nd 63 100 It 24 17th 3.2 4th 85 blue 28.0 7th 23 63 100 dd 24 18th 3.1 4th 85 blue 28.2 10 24 63 100 dd 24 13th 3.4 4th 79 yellow 25.3 8th 25th
26th 63
63 100
100 ' ti
It 24
24 <H KN
CM CM 3.3
3.1 4th
4th 84
77 vio
lett
green 28.7
23.4 10
11 27 63 100 dd 24- 24 3.4 4th .78 ' yellow 24.4 10 28 63 100 · dd 24 14th 3.4 4th 79 Red 25.3 6th

Table I.

Parts
melamine Parts
CH ₂ O 30 # Protection
colloid Parts
Color
material dye
Table III
No. pH Resin-
Concentration
tion % yield
Parts colour dye
salary in
Pigment % 33.7 Spec.
Upper
area
m2 / g No. 63 100 Tragacanth 24 12th 3.2 4th 74 yellow 20.3 27.6 10 29 63 100 tt- 24 19th 3.3 4th 78 blue 24.4 24.4 9 30th 63 100 It 24 22nd 3.1 4th 83 orange 28.9 27 8th 31 63 100 Il 31 33 3.8 4th 87 Crowd
laugh 35.6 30.6 57 32 63 100 Il 31 34 3.8 4th 85 purple 36.5 30th 7th 33 63 100 Il 31 35 3.5 4th 83 Red 29.6 6th 34 63 100 It 31 36 3.5 4th 76 Red 7th 35 63 100 It 24 9 2.5 4th 98 green 7th 36 63 100 Il 24 9 2.8 4th 89 green 7th 37 63 100 It 13.5 25th 3.3 4th 44 blue - 38 63 100 It 27 26th 3.5 4th 90 Red δ 39 63 100 Il 34
(80 # ig 27
) 3.5 4th 91 Red 5.5 40

Table I.

No. Parts
melamine Parts
CH ₀ O 50 #
d Protection-
colloid Parts
Color
material dye
Table III
No. PH Ha rz
concentrated
tion % yield
Parts colour dye
salary in
Pigment % Spec.
Upper
area
m2 / g 41 56 90 Tragacanth 42 50 5.2 4th 35 blue 29.4 9 42 ^ 100 52 28. 5.2 4th 92 yellow 29.4 6th 45 65 100 » 27 29 5.0 4th 99 yellow 29.2 10 44 65 100 t! 50.5 26th 5.0 8th 102 Red 29.8 8th 45 65 100 tf 51 16 2.9 8th 99 Red 28.1 9

GO CX)

Example 5

Production of a yellow, highly dispersed pigment based on urea-formaldehyde:

A solution of 60 parts of urea, 150 parts of 30% aqueous formaldehyde, 2.1 parts of sodium dodecylbenzenesulfonate in 215 parts of water is condensed for 2 hours at pH = 7 and 70 °. This precondensate is mixed rapidly with a solution of 3, 24 parts of sulfamic acid and 12.9
Parts of the dye of the formula 2 in Table III

009887/1893 '

It is formed within I5 seconds a hard gel, allowed to react for 3 hours at which one 65 ⁰ C. It is crushed in a cutting granulator, mixed with the same amount of water and neutralized with a 10% aqueous soda solution. It is filtered off, rewashed a little, dried at 110 ° C. in a stream of air and deagglomerated using a high-speed pin mill.

85 parts of color pigment are obtained with the following characteristics:

Effective dye content: 15.2 #

Specific surface: 19 m / g

Average particle diameter: about 800 Å

Extraction resistance:
Boiling water: <0.1 %

H ₂ SO ₄ : 0 £ ■

" 5% Na ₂ CO ₅ : <0.01 Ji.

If the pigment obtained is used to dye polyvinyl chloride, for example, films of excellent quality are obtained Transparency, depth of color and homogeneity. The pigment is also suitable for dyeing paper in bulk or as Printing ink.

The following Table II describes the production of further pigments according to the information in this example All the necessary information can be found in the table.

009 887/18 93

Table II

ο ο co OO 00

00 (O to

No. Parts
urea Parts
CH ₂ O 30 # Parts
dye dye
Table III
No. Parts
yield colour dye
salary in
Pigment % Spec.
Upper
area
m2 / g 1 60 150 24 24 79 yellow -25 6th 2 βο 150 24 17th 90 blue -25 10 3 60 150 · 12.9 1 87 blue 14.8 14th 4th 60 150 12.9 5 83 blue 15.5 - 5 60 150 12.7 6th 86 Red 14.8 14th 6th 60 150 12.7 4th 82 blue 15.5 12th 7th 60 150 12.7 7th 74 green Blue 17.2 12th 8th 60 150 24 5 87 blue -23 15th 9 60 150 24 2 90 yellow -23 41 10 60 150 24 1 88 blue -23 49

ro ro

ro CD co co cn CD CD

Table III

Structural formulas of the dyes used

O ^NH 2

O IiH

SO well

NH,

NH ₂

N N I! · I C C

N = N-C C -C -CH.

Ii Il ^: SCLH £ N wf V

1 ^C1

SO ₃ H

OH

O ₀ NIK = NCC-CH-2 \ A / "μ 3

CN HCfV

(Cr / ₂ )

SO H

0 NH

0 NH

- <Z> -C

009887/1893

λ U 3 8 5 6 O

Of ₂

Il 30 H

0 NH

NH-

N N

^ΰ0 3 ^Η N

NH

N N

C C

^ n η / ^ / \ tjtj

3 HO NH N N = N

HN

N N

SO H

C C

^Χ
i

Cu phthalocyanine tetrasulfonic acid

ο im.

0 UH

CH

NH ₂ H

3 • 30 H.

009,887 / ¹ H? 3

O NH-O-CH

CH,

SO ₃ H

SO ₃ H

SO ₃ H

11) HO "S- <CI> -N = N-

Cl

-N = N-

S0, H

HO '

HO

Cl

3 "■ 009887/1893

2Ü33560

CH CONH-

SO, H NH ₀ ι 2

SO H

CH CONH-C> -N = N-

SO ₃ H

16) 4,4'-diamino- !, 1-dianthraquinony 1-3,3'-disulfonic acid

NH,

HO S-

SO H

NH-

-NHCOCH.

CH ₃ SO ₃ H

NH.

SO H

CH.

O NH-

CH

NHCOCH.

^{! H} 5 O ₃ H

009887/1893

2033560

if

O Il C

NH

CH.

SO H

^l 2

CH.,

KH

CH .. CH j5

CH

OH

OCH

NH,

₂ H

(Co / 2)

NO ₂ SO H

CH.

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2Ü38560

HO S

HO S

O-Cu — O -N = N-

CH.

SO ₂ OCH,

0 N = N- <Z> -NH—

j HO S " ^{vv N} 30 H -Co

OH

HO ^ SC "> -N = NN
-N ^H0 3 ^S

• Nile CO

SO ^ H C-OH

J Il

-N = N-C-CO-NH

-CH = CH- <~ r> -NO SO ₃ H SO H

SO, H
1 3 I> -N = N jKN = N- < - ^ HO ₃ S Γ
HO, S < j ^ Vn = N-C SO H

009887/1893

2033560

SO ₂ H

-N = N-

SO TALL

N N

I ii

-C C-N ^ /

cco-

■ SO H

O NH

OH

H ₂ NSO ₂

A N = N-C

U ■

C-CH

(Cr /,)

Cl

NH-

0 Cu

A-N = N γ HO ₃ S SO ₃ H

SO ₃ H N
/ \ v

-C C-NH.

Il I ' NN

Eq

-SO ₃ H

Cr-O-C N

II II N = N-C C-CH

Cl

009887/1893

2U33560

0 gr

Cl

CH.

OC CO

NH,

009887/1893

- 31 Example 6.

A precondensate is produced by dissolving 31.5 parts of melamine in 50 parts of a 30% aqueous solution Formaldehyde solution at p "8.5 and 85. After that it will be immediately

ri

cooled to 'to ^0.

A solution of 24 parts of the blue dye of formula 37, Table III, in 970 parts of water containing 1.8 parts of polyvinyl alcohol to ρ “6.0 at 95 ° brings. The precondensate is added dropwise under these conditions and with stirring. It is left for 2 hours at p “4.0

post-react, the pigment is filtered off and dried for 6 hours at 160. After the deagglomeration in a high-speed Pin mill you get 53 parts of a deep blue

ο pigment with a specific surface area of 60.8 m / g.

The table below further protective colloids are mentioned in column I, the place according to the data of this example are used by polyvinyl ύ can. Column II gives the yield and column III of the specific surface area of the pigment obtained.

BAD ORfGiNAL

009887/1893

2Ü38560

Protective colloid Yield in
share _o specific 0ber-
f Iac he in n \ '/ & 1. Polyethylene oxide 56 31.6 2. Sodium alginate 52 42.1
* 3. ß-hydroxypropyl
cellulose 48 42.7

ORIGINAL INSPECTED

009887/1893

2Ü33560

Example 7 »

A 'precondensate is produced by 2 hours

Heat at p "7.0 and 70 ° from
η

450 parts of 30% aqueous formaldehyde solution, l80 parts of urea,

645 parts of water and

2.25 parts of Emulphor 0 (condensation product from

Oleyl alcohol and ethylene oxide).

3 dye solutions are prepared containing 3 * 24 parts of sulfamic acid in 100 parts of water

a) 0.38 b) 1.53 c) 6.5 parts rhodamine B.

1/3 of the precondensate is mixed with one of the 3 dyes solutions mixed rapidly at 50. It is formed within Bright red gels that retain their shape in a few seconds. It is allowed to post-react for 2 hours at 65 °, granulated and slurried in the j

double the volume of water. It is adjusted to p "with 10% soda solution , filtered, dried at 130 and deagglomerated using a pin mill. Bright red, fluorescent color pigments are obtained ♦

yield
Parts specific surface
no / g a) 74 3.6 b) 74 2.4 c) 79 1.2

0098 87/1893 ORIGINAL INSPECTED

2 υ YY 5 6

Example 8.

The procedure is as in Example 7, but instead of 2.25 parts of Emulphor 0, 5.15 parts of sodium carboxymethyl cellulose are used and Dye No. 58 of Table III. Bright yellow fluorescent color pigments are obtained.

Parts
dye pigment
yield
(Parts) specific
surface
(m2 / g) a) 0.58 54 58.5 b) 1.55 68 42.9 c) 6.50 75 59.2.

ORlGiNAL INSPECTED

009887/1893

Claims (1)

Claims. Γ. Process for the production of pigment dyes, characterized in that a single-phase aqueous system which contains one or more aminoplast formers, one or more aldehydes or the still soluble polycondensation products of aminoplast formers with aldehydes and a protective colloid or a surface-active substance is dissolved before, during or g after encryption Agreement with a water-soluble dye a finely disperse colored, insoluble, infusible, cross-linked aminoplast forms. 2. The method according to claim 1, characterized in that that ir.an uses melamine as an aminoplast former. 5. Process according to Claims 1 to 2, characterized in that the aldehyde used is formaldehyde. Λ H. Process according to Claims 1 and 2, characterized in that a soluble melamine-formaldehyde is used as the starting material. 5. The method according to claim 1, characterized in that that urea is used as an aminoplast binder. 009887/3 BAD ORfGiNAL 2Ü38560 6. The method according to claims 1 and 5 *, characterized in that that a soluble urea-formaldehyde precondensate is assumed. 7. The method according to claims 1 to 6, characterized in that one starts from an approximately neutral, one-phase aqueous solution of the aminoplast former and the aldehyde or their still soluble polycondensation products, and that the colored aminoplast is formed by adding an acid. 8. The method according to claims 1 to 7, characterized in that the colored aminoplast of the separates aqueous phase, dries and deagglomerates. 9 · Colored crosslinked aminoplasts, characterized that they consist of spherical primary particles more evenly Large with a specific surface area of 2 to 200 m / g exist. 10. Colored crosslinked aminoplasts which fluoresce in daylight according to claim 9- 009887/1893