DE2338759A1 - Pigments from soluble dyes deposited in crystal lattices - from aq. suspensions at controlled pH - Google Patents

Abstract

Pigments consisting of a colourless inorganic carrier with an organic dye deposited in the crystal structure. The dyes may be vat, development, oil-soluble dyes, organic pigments, metal complex dyes or pref. substantive, acid, reactive or dispersion dyes. The carrier is pref. Al2O3, ZnO or MgO. Amount of dye is pref. 3-150% of carrier weight. The method is used in the pigmenting of paints, printing inks, macro-molecular materials, etc. Dyed with no pigment properties but which are intense, brilliant and light-fast may be used. They are held so strongly by the carrier that they cannot be extracted by usual solvents.

Description

Bayer Aktiengesellschaft

Central area of patents, trademarks and licenses

509 Leverkusen. Bayerwerk Jo / Bre

30. JuJM9? 3

Pigments

The invention relates to pigments made from colorless, inorganic carrier materials and organic dyes exist, processes for their production and their use for pigmenting printing inks, paints and plastics.

The pigments are characterized in that the organic dyes are in the lattice of the colorless, inorganic carrier materials are stored. The binding of the dyes to the inorganic carrier material is so strong that they with the for printing inks and varnishes and for the processing of plastics common solvents not from the inorganic carrier can be extracted.

This makes it possible to choose from soluble dyes or dyes, which have no pigment properties, but which are strongly colored, brilliant and lightfast, brilliant, strongly colored and to produce lightfast color bodies that are suitable for a wide variety of pigment applications.

Suitable dyes are, for example, substantive dyes, acidic dyes, reactive dyes, vat dyes, Disperse dyes, developing dyes, oil-soluble dyes, organic pigments and metal complex dyes.

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Dyes of the application classes mentioned are, for example, in Ullmanns Encyclopadie der techn. Chemie, 7th volume (1956), 84-188 listed. They can constitutionally belong to the most diverse classes, for example the azo, anthraquinone, Phthalocyanine or policy series.

Substantive dyes, acidic dyes, Reactive dyes and disperse dyes.

Suitable colorless inorganic carrier materials are, for example:

Titanium dioxide (anatase, rutile), barium sulfate, aluminum silicate (bentonite), calcium carbonate (chalk), slate flour, clays, quartz, mica _for talc, magnesium silicate, magnesium carbonate, types of kaolin such as china clay, devolite, Dixie clay or white crown clay, zinc oxides, powdered silica, aluminum oxides, magnesium oxides and Aerosil (colloidal silica).

Aluminum oxides, zinc oxides and magnesium oxides are particularly preferred.

The pigments are produced by suspending the inorganic carrier material in a dye liquor which dissolves or finely disperses the desired dye or, in the case of vat and developer materials, the dye precursor in an amount between 3 and 150 %, preferably 10 and 80 %, based on the amount of carrier material and which is adjusted to a pH which is lower than the pH of the carrier material in water.

For each carrier material there is an optimal pH range in which the dye uptake is greatest.

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For aluminum oxide, the range is between 0.5 and 2, for Zinc oxide between 6 and 6.5 and for magnesium oxide between 8 and 9.5.

The most favorable pH range for optimal staining is determined by preparing a series of aqueous carrier material suspensions with increasing pH values. The same amount of colorants is added to each suspension, preferably 5% by weight, based on the carrier material used, stirs vigorously and observes the samples until they are completely discolored the aqueous phase. The pH range at which the decolorization of the aqueous phase takes place most rapidly is that for the coloration most favorable for the inorganic carrier material.

The dyeing is preferably carried out from aqueous liquor, but solutions and dispersions of dyes in organic substances can also be used Find solvents use. The coloring of the inorganic carrier material can take place in a temperature range between 10 and 140 ° C, but preferably in a range between 60 and 120 ° C. After staining the colored pigment is separated off and washed repeatedly.

The colored pigments obtainable by the process according to the invention surprisingly show good resistance to both aqueous and organic solvents and a good dispersibility. The lightfastness and color strength largely correspond to the results obtained in the pigments Dyes. On the basis of this property profile, the colored pigments according to the invention can be used for the production of printing inks, Lacquers and for pigmenting macromolecular materials are used.

The new colored pigments can be used alone or mixed with other pigments.

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Example 1 , / f _%

30 g finely divided aluminum oxide (type L from Martinswerk, Erft) are suspended in 100 ml of water. The suspension is adjusted to pH 1 with dilute hydrochloric acid. In addition a solution of 50 g of the reactive dye of the formula is added

^ : so ^ H)

Cu-Pc

in 10 ml of water and reflux the mixture with vigorous stirring for 1 hour. The filtrate is then separated off and slurried the stained alumina twice in boiling water. The blue pigment is at 100 C in a vacuum drying cabinet dried. The dye absorption is 10096. A lightfast, varnishfast and readily dispersible pigment is obtained. The applied dye can Do not remove with boiling water or organic solvents.

It can be seen from electron spectroscopy that

the dye is completely embedded in the aluminum crystals and was not adsorbed on the surface.

Example 2-9

As in Example 1, the following dyes are used for coloring performed. Color-fast pigments of the specified shade with the specified dye content are obtained:

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example

lot
G

Formula of the dye hue

Red

Red

OH NH. NV ^S0 2 ^CH 3

N = N

8 SO ₃ H,

Cl Cl bluish red

HO ₃ S

SO ₃ H

15th

O ₃ H OH NH ₂ dark blue

15 / (SO ₃ H) ₂ CuPcC

Cl

14 cl

SO ₂ CH ₃

blue

CO-NH

NH-CO

SO ₃ H

N = N-SO ₂ CH ₃

, COOH

yellow

CH,

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example

Amount g

Formula of the dye

SO ₃ H

- U = N -

SO ₃ H ^S0 3 ^H

16

CH, Cl

- / ~ Vn = n

SO ₂ CH ₃

Examples 10-12

hue

yellow

yellow

30 g of finely divided aluminum oxide (type L, Martinswerk, Erft) are used as in Example 1 with 11 g of the noun dye of the formula

N = N

SO ₃ H

colored. The dye is completely absorbed. Man receives a bright yellow, lightfast pigment that is fast to paint over.

The following noun dyes also result in coloring of aluminum oxide colorfast pigments:

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example

Amount g

Formula of the dye

hue

violet

yellow

So ₃ H

Examples 13-15

30 g of finely divided aluminum oxide (type L, Martinswerk, Erft) are as in Example 1 with 14.4 g of the acidic dye the formula

CH,

-so.

N CH

stained. The dye is completely absorbed. Man receives a lightfast and overpaintable red pigment.

The following acidic dyes also produce color-fast pigments when coloring aluminum oxide:

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example

Amount g

-fr *

^ ormel of the dye

hue

21.3

2 ⁿ 5

yellow

25.4

CH

I,

H * C

yellow

HO-

Examples 16-19

30 g finely divided aluminum oxide (type L, Martinswerk, Erft) are as in Example 1 with 20 g of the disperse dye of the formula

0 NH

/ \\_NS,

0 OH

stained. The dye is completely absorbed. Man receives a bright red pigment.

The following disperse dyes also produce color-fast pigments when coloring aluminum oxide:

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at
game lot
G Formula of the dye hue 17th 30th O 2 violet ⁰ NH-
2

50

NO,

Red Yellow

Example 20

30 g of finely divided aluminum oxide (type L, Martinswerk, Erft) are as in Example 1 with 7.5 g of the vat dye formula

0 0

colored in the presence of an anionic dispersant. A lightfast, overpaintable, red pigment is obtained,

Example 21

30 g of finely divided aluminum oxide (type L, Martinswerk, Erft) are as in Example 1 with 8 g of the pigment formula

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colored in the form of an aqueous fine paste. One receives a lightfast, bright red pigment.

Examples 22-24

30 g finely divided aluminum oxide (type L, Martinswerk, Erft) are suspended in 100 ml of diethyl sulfoxide. The suspension is adjusted to pH 1. A suspension of 30 g of the pigment of the formula is added to this

0ONH

in 20 ml of dimethyl sulfoxide and the mixture is boiled for 1 hour at 90 ^° C. with vigorous stirring. After cooling, the FII appeared is separated off and the red pigment was washed twice with dimethyl sulfoxide and dried at 100 ⁰ C in vacuo. The dye is completely absorbed. The bright red pigment is lightfast and easy to disperse.

The following pigments have also been used successfully to color aluminum oxide.

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example

Amount g

Formula of the dye

hue

50

15.3

OCH,

OCH,

N = N

HN-CO

N = N

OCH,

N = N

Red

yellow

Example 25

1 g of 2-hydroxy-3-naphtholic acid anilide is added as a phenolic coupling component to a suspension of 5 g of aluminum oxide (type L, Martinswerk, Erft) in 30 ml of water. The mixture is stirred for 10 minutes. The aluminum oxide is then separated off and suspended ^{at 5 °} C. in a solution of 1 g of 2,5-dichloroaniline sulfate (as a diazonium salt solution) in 30 ml of water. The suspension is stirred vigorously for 15 minutes and then heated for 10 minutes in order to destroy unreacted diazonium salt. The red pigment is then filtered off with suction and washed twice with water. A lightfast, readily dispersible, red pigment is obtained.

Example 26

Analogously to Example 25, from 2-hydroxy-3-naphtholic acid (2,4-dimethoxy-5-chloroanilide) and diazotized 2-methoxy-4-diethylsulfamoylaniline, another colorfast red pigment to win.

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Example 27

10 g of aluminum oxide (type L, Martinswerk, Erft) are suspended in 40 ml of water. A solution of 1 g of linked tetrabromine indigo in 20 ml of water is added. The mixture is heated to 80 ⁰ C and treated with a solution of 1 g of sodium nitrate in 10 ml of water and längsam adjusted to pH1. The suspension is refluxed for 1 hour with vigorous stirring. The olive green pigment is separated off and washed twice with water. The dye is completely absorbed from the liquor. The pigment is dried at 80 ° C. in a vacuum. A readily dispersible pigment is obtained.

Example 28

10 g of aluminum oxide (type L, Martinswerk, Erft) are as in Example 27 with 1 g of the vetted dye of the formula

Cl

stained. The dye is completely absorbed. Man receives an olive-green, easily dispersible pigment.

Example 29

A solution of 1.8 g of the reactive dye of the formula is added to a suspension of 10 g of magnesium oxide in 100 ml of water

. (SO ₃ H) ₂

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in 10 ml of water. The mixture is adjusted to pH 9 with dilute hydrochloric acid and refluxed for 1 hour with vigorous stirring cooked. The colored magnesium oxide is then filtered off and washed twice with warm water. The dye is taken up completely. You get a lightfast, Overcoatable and easily dispersible, blue-green pigment. The stored dye can neither with boiling Water can still be separated from the magnesium oxide using organic solvents.

Examples 30-32

10 g of magnesium oxide were as in Example 29 with 1 g of the acidic Dye of the formula

H ₃ C-CONH

stained. The dye is completely absorbed. You get a well dispersible, lightfast red pigment. The following acidic dyes also result in coloring strong, lightfast pigments of magnesium oxide:

example

Amount g

Formula of the dye

hue

' ^xV 0C ₂ H ₅

32

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Red

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Example 33

10 g of magnesium oxide were as in Example 29 with 1.5 g of the noun dye of the formula

stained. The dye uptake was complete. Man receives a lightfast and varnish-resistant violet pigment.

Example 34

Analogously to Example 33, 1.3 g of the dye of the formula are obtained

SO ₃ H HO ₃

a yellow pigment.

Example 35

10 g of magnesium oxide are as in Example 31 with 1.3 g of the Disperse dye of the formula

CH ₉ -CH ₀ -OH N = N - // \ VN - ^ ^ ²

-S

colored. A lightfast, light red pigment is obtained.

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Examples 36-38

IS-

10 g of zinc oxide are suspended in 100 ml of water. Thereafter the suspension is adjusted to pH 6 with dilute hydrochloric acid. 1.1 g of a solution of the reactive dye are added to this the formula

Cl

* "» 13f

COOH

SO3H

in 10 ml of water. The mixture is refluxed for 1 hour with vigorous stirring. The colored zinc oxide is then filtered off with suction and washed twice with warm water. The dye is completely absorbed. The result is a lightfast, easily dispersible and paint-fast,
yellow pigment. The stored dye cannot be reassembled with boiling water or organic solvents
be washed out.

Other strong and lightfast pigments are obtained with the following reactive dyes

example

Amount g

Formula of the dye

hue

(SO ₃ H)

green Blue

J (

SO ₃ H)

₃ H) ₂

green

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Examples 39-41

10 g of zinc oxide are as in Example 36 with 3 g of the acidic dye the formula

/ A-SO ^ -O-V V-C

SO ₃ H

colored. The dye is completely absorbed. Man receives a lightfast and overpaintable red pigment.

When coloring zinc oxide, the following acidic dyes also result in lightfast and varnish-fast pigments:

example

Amount g

Formula of the dye

hue

1.6

1.6

SO,

Cl N = N

N = N - </ \> - OC ₂ H ₅

yellow

yellow

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Examples 42-44

10 g of zinc oxide were as in Example 36 with 1 g of the noun dye the formula

NH-CO-NH r {\ // - 0CH,

Ν = ν 'U /;

HO

stained. The dye is completely absorbed. Man receives a lightfast and varnish-resistant violet pigment,

The following noun dyes also result in coloring Pigments valuable from zinc oxide:

at
game lot
G &
3 ^pp formula of Dye hue ^ SO ₃ H HO ₃ S ^ I ^ 43 1.1 E. H\ -Ν ^ / ον ^ ~ Ύ ^ HO ₃ ^ SO ₃ H 44 1.4 SO ₃ H yellow HO Γκ> - <ο> -
> »CH 3 Ho ₃ S k:

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Example 45 . μλ

10 g of zinc oxide are as in Example 36 with 1.5 g of the disperse dye the formula

CH ₉ -CH ₉ -OH

CH -CH ₉ -OH ₂ 2

colored. A lightfast, light red pigment is obtained. Example 46

10 g of zinc oxide were as in Example 36 with 3 g of the pigment the formula

Cl

Cl

colored. The dye is completely absorbed. Man receives a lightfast, bright red pigment.

Example 47

10 g of zinc oxide are suspended in 100 ml of diethyl sulfoxide and the suspension is adjusted to pH 6 with dilute hydrochloric acid. A suspension of 5 g of the im Example 46 used pigment in 20 ml of dimethyl sulfoxide and reflux the mixture with vigorous stirring. The red pigment is then suctioned off and twice with dimethyl sulfoxide washed. The dye is completely absorbed, A lightfast, bright red pigment is obtained.

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Example 48

r I Wl s

In the same way, 4.7 g of the dye of the formula OH becomes OH

a lightfast, yellow pigment obtained. Example 49

a) 8 g of the pigment obtained according to Example 1 are rubbed with a stoving varnish made from 25 g of coconut oil alkyd resin (40% coconut oil), 10 g of melamine resin, 50 ml of toluene and 7 ml of glycol monomethyl ether on an automatic Hoover-Muller grinder. It carries the mixture to be painted on substrate, curing the coating by baking at 130 ⁰ C and receives blue, opaque strong coatings excellent Uberlackierechtheit and excellent light and weather fastness.

Pigmented stoving enamels with the same fastness properties are obtained by adding 15-25 g of the specified alkyd resin or one Alkyd resin based on cottonseed oil, ricinine oil, Castor oil or synthetic fatty acids are used and instead of the specified amount of melamine resin 10-15 g of the mentioned Melamine resin or a condensation product of formaldehyde with urea or with benzoguanamine is used.

b) Instead of the specified amount of pigment, 1 to 10 g of a mixture of titanium dioxide (rutile type) with pigment is rubbed Ratio 0.5-50: 1 in those given in Example 1a

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Varnish, one obtains varnishes with the same fastness properties and with increasing titanium dioxide content with the same further processing after white shifted blue hue.

Example 50

In 100 g of a nitrocellulose lacquer made from 44 g of collodion wool (low viscosity, 35%, butanol moist), 5 g dibutyl phthalate, 40 ml of ethyl acetate, 20 ml of toluene, 4 ml of n-butanol and 10 ml of glycol monomethyl ether are 6 g of the example 1 obtained pigment rubbed. After spreading and drying, you get blue paintwork with excellent light and fastness to overcoating.

The same results are obtained when using nitrocellulose lacquers with 10-15 g nitrocellulose content and 5-10 g plasticizer content and 70 - 85 g solvent mixture, preferably using aliphatic esters such as ethyl acetate, Butyl acetate and aromatics such as toluene and xylene and smaller proportions of aliphatic ethers such as glycol ethers and alcohols such as Butanol. Plasticizers can be understood as meaning, for example: phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, Phosphoric acid esters, castor oil alone or in combination with oil-modified alkyd resins.

Coatings with similar fastness properties are obtained when using other physically drying fuel, zapon and nitro lacquers, air-drying oil, synthetic resin and nitro combination paints, oven- and air-drying epoxy resin paints, optionally in combination with urea, melamine, alkyd or phenolic resins.

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Example 51 * *
-JIf *

5 g of the pigment obtained according to Example 1 are in 100 g of a paraffin-free drying unsaturated polyester resin ground in a porcelain ball mill. With the grinding, 10 g of monostyrene, 5 g of melamine-formaldehyde resin and 1 g a paste of 40 g of cyclohexanone peroxide and 60 g of dibutyl phthalate and finally 4 g of dryer solution (10 ^ iges cobalt naphthenate in white spirit) and 1 g silicone oil solution (1% in xylene) added. You apply the mixture to primed wood, and you get a high-gloss, waterproof and weatherproof blue paint with excellent lightfastness.

Instead of the reactive varnish based on unsaturated polyester resin, amine-containing epoxy resin varnishes with dipropylenetriamine are used as an amine component, one obtains blue coatings with excellent weather and bloom fastness, the good acid fastness The dye also allows the use of acid-hardening varnishes made with 10% alcoholic hydrochloric acid hardened.

Example 52

100 g of a 65% solution of an aliphatic polyester with about 8 % free hydroxyl groups in glycol monoethyl ether acetate are rubbed with 5 g of the pigment obtained in Example 1 and then with 44 g of a 67 % solution of the reaction product of 1 mole of trimethylol propane with 3 Moles of toluene diisocyanate mixed well. After application of the mixture and reaction of the components, high-gloss polyurethane coatings with excellent blooming, light and weather fastness result without impairing the pot life.

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Pigmentations of similar fastness are obtained when using other two-component lacquers based on aromatic or aliphatic isocyanates and polyethers or polyesters containing hydroxyl groups, as well as with moisture-drying, Polyisocyanate lacquers resulting in polyurea lacquers.

Example 53

5 g of a fine dough obtained by kneading 50 g of the pigment obtained in Example 1 with 15 S of an aryl polyglycol ether emulsifier and 35 ml of water are mixed with 10 g of heavy spar as filler, 10 g of titanium dioxide (rutile type) as a white pigment and 40 g of an aqueous emulsion paint , containing approx. 50% polyvinyl acetate, mixed. The paint is spread and, after drying, blue paints are obtained which are very good fastness to lime and cement as well as excellent fastness to weather and light.

The fine dough obtained by kneading is equally suitable for pigmenting clear polyvinyl acetate emulsion paints, for emulsion paints that contain copolymers of styrene and maleic acid as binders, as well as emulsion paints based on polyvinyl propionate, polymethacrylate or Butadi e ns tyr ο1.

Example 54

10 g of the pigment dough mentioned in Example 53 are mixed with a mixture of 5 g of chalk and 5 g of 20 # glue solution mixed. A blue wallpaper coating color is obtained with which coatings of excellent lightfastness are achieved.

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Other non-ionic substances can also be used to produce the pigment dough Emulsifiers such as the reaction products of nonylphenol with ethylene oxide or ionic wetting agents such as the Sodium salts of alkylarylsulfonsäjran., E.g. of dinaphthylmethane disulfonic acid, Sodium salts of substituted sulfofatty acid esters and sodium salts of paraffin sulfonic acids in Combination with alkyl polyglycol ethers can be used.

Example 55

A mixture of 65 g of polyvinyl chloride, 35 g of diisooctyl phthalate, 2 g of dibutyltin mercaptide, 0.5 g of titanium dioxide and 0.5 g of the pigment described in Example 1 is dyed on a roll mill at 165 ⁰ C. The result is an intensely blue-colored mass which can be used to produce films or moldings. The dyeing is characterized by excellent light fastness and very good plasticizer fastness.

Example 56

0.2 g of the pigment obtained according to Example 1 are mixed with 100 g of polyethylene, polypropylene or polystyrene granules. The mixture can either be ^{sprayed directly in an injection molding machine at 220 to 280 °} C., or processed into colored rods in an extruder or into colored skins on the mixing roller mill. The rods or skins are, if necessary, granulated and injected in an injection molding machine. The blue briquettes have very good light and migration fastness. .

Similarly, at 280-300 ° C, optionally under a nitrogen atmosphere,. synthetic polyamides Caprolactam or adipic acid and hexamethylenediamine or the condensates of terephthalic acid and ethylene glycol are colored will.

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Example 57

1 g of the pigment obtained according to Example 1, 10 g of titanium dioxide (rutile type) and 100 g of a powdered copolymer based on acrylonitrile-butadiene-styrene are mixed a and colored on a roller mill at 140-180 ° C. One obtains a blue coat, which is granulated and in an injection molding machine at 200 - 250 ⁰ C is sprayed. Blue moldings are obtained with very good light and migration fastness and excellent heat resistance.

In a similar manner, but at temperatures of 180-220 ⁰ C and without the addition of titanium dioxide plastics are colored based on cellulose acetate, cellulose butyrate and their mixtures with similar fastnesses.

Example 58

0.2 g of the pigment obtained in Example 1 are in finely divided form with 100 g of a plastic polycarbonate-based mixed in an extruder or in a kneading screw at 250 280 ⁰ C and processed into granulate. A blue, transparent granulate of excellent lightfastness and heat resistance is obtained.

Example 59

90 g of a weakly branched polypropylene glycol with a molecular weight of 2500 and a hydroxyl number of 56, 0.25 g of endoethylene piperazine, 0.3 g of tin (II) octoate, 1.0 g of a polyether siloxane, 3.5 ml of water, 12, 0 g of a grind of 10 g of the pigment obtained according to Example 1 in 50 ml of the specified polypropylene glycol are mixed well with one another and then intimately mixed with 45 g of tolylene diisocyanate (80% 2,4- and 20 % 2,6-isomer) and in poured a mold.

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The mixture becomes cloudy after 6 hours and the foam formation he follows. After 70 seconds, an intensely blue-colored, soft polyurethane foam has formed, its Pigmentation has excellent lightfastness.

Example 60

90 g of a weakly branched polyester of adipic acid, diethylene glycol and trimethylolpropane with a molecular weight of 2000 and a hydroxyl number of 60 are mixed with the following components: 1.2 g of dimethylbenzylamine, 2.5 g of sodium castor oil sulfate, 2.0 g of an oxethylated, benzylated one Oxidiphenyls, 1.75 g of water, 12 g of a paste, prepared by rubbing 10 g of the pigment obtained according to Example 1 in 50 ml of the polyester indicated above. After mixing, 40 g of tolylene diisocyanate (65 96 2,4- and 35 % 2,6-isomer) are stirred in and the mixture is poured into a mold and foamed. After 60 seconds, a blue-colored, soft polyurethane foam has formed, the color of which is characterized by very good lightfastness.

Example 61

With a printing ink prepared by rubbing 35 g of the pigment obtained in Example 1 and 65 g of linseed oil and adding 1 g of siccative (co-naphthenate, 50 % in white spirit), blue offset prints of high brilliance and color strength and very good light are obtained - and preserve paint fastness.

Use of this printing ink in letterpress, light, stone or steel engraving leads to blue prints with similar fastness properties. If the pigment for coloring Blechdruck- or low viscosity gravure printing inks or printing inks, is obtained blue prints similar fastnesses.

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Example 62 »/
^c * ·?% »

A printing paste is prepared from 10 g of the fine pigment paste specified in Example 53, 100 g of 3% tragacanth, 100 g of an aqueous 50% egg albumin solution and 25 g of a nonionic wetting agent. A textile fiber fabric is printed, steamed at 100 ^° C. and a blue print is obtained which is distinguished by excellent fastness properties, in particular light fastness. Instead of tragacanth and egg albumin, other binders which can be used for fixing to the fiber, for example those based on synthetic resin, British gum or cellulose glycolate, can be used in the printing approach.

Example 63

A mixture of 100 g Crepe bright, 2.6 g of sulfur, 1 g of stearic acid, 1 g of mercaptobenzothiazole, 0.2 g of hexamethylenetetramine, 5 g of zinc oxide, 60 g of chalk and 2 g of titanium dioxide (anatase) is on a roll mill at 50 ⁰ C colored with 2 g of the pigment obtained according to Example 1 and then vulcanized at 140 ° C. for 12 minutes. A blue-colored vulcanizate of very good lightfastness is obtained.

Example 64

100 g of a 20% aqueous paste of the pigment prepared according to Example 1 are added to 22.5 l of an aqueous, approximately 9% viscose solution in the stirrer. The colored mass is stirred for 15 minutes, then deaerated and subjected to a spinning and desulfurization process. Blue-colored threads or films with very good lightfastness are obtained.

Pigmented threads or films of similar fastness are obtained if a 20-pound solution dyed with the dyestuff described in Example 1, which has been finely divided

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of acetyl cellulose in acetone or 15-25 % solution of polyacrylonitrile in dimethylformamide is subjected to a dry spinning process.

Example 65

10 kg of a paper pulp containing 4 g of cellulose per 100 g are treated in the Hollander for about 2 hours. While During this time, 4 g of resin glue, then 3o g of an approximately 15% pigment dispersion, des is added every quarter of an hour pigment obtained according to Example 1 with 4.3 g of dinaphthylmethanedisulfonic acid and 22 ml of water, then 5 g of aluminum sulfate. Receives after completion on the paper machine a blue-colored paper of excellent lightfastness.

Example 66

The blue-pigmented paper produced according to Example 65 is mixed with the 55 # solution of a urea-formaldehyde resin soaked in n-butanol and baked at 140 ° C. You get a blue laminate paper of very good migration and excellent Lightfastness.

A laminate paper with the same fastness properties is obtained by laminating a paper that is gravure with a Printing ink was printed which contained the fine pigment paste and water-soluble or saponifiable binders specified in Example 53 contains.

Instead of the pigment obtained according to Example 1, those in Examples 2-48 can also be used in Examples 49-66 Use specified pigments with success in a completely analogous manner.

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Claims (10)

Patent claims: 1. Pigments, consisting of a colorless, inorganic carrier material and one in the crystals of the inorganic Organic dye embedded in the carrier material. 2. Pigments according to claim 1, characterized in that the organic dye belongs to one of the following classes: Noun dyes, acidic dyes, reactive dyes, Vat dyes, disperse dyes, developing dyes, Oil-soluble dyes, organic pigments, metal complex dyes . 3. Pigments according spoke 1, characterized in that the organic dye belongs to one of the following classes : nouns dyes, acidic dyes, reactive dyes, disperse dyes. 4. Pigments according to claim 1, in which the inorganic carrier material is aluminum oxide, zinc oxide or magnesium oxide. 5. A process for the preparation of pigments according to claim 1, characterized in that the inorganic carrier material is suspended in a dye liquor which contains the organic dye or the dye precursor dissolved or finely dispersed and which is adjusted to a pH which is lower than the pH of the The carrier material is in water. 6. The method according to sensing 5, characterized in that the dye is used in an amount of 3-150% based on the carrier material. Le A 14 9-4 - 28 - 509807 / ί 9ί / 7. The method according to claim 5 »characterized in that aluminum oxide at a pH of 0.5 to 2 in a dye liquor suspended. 8. The method nach.Anspruch 5, characterized in that one Zinc oxide suspended in a dye liquor at a pH of 5 to 6.5. 9. The method according to claim 5 »characterized in that one Magnesium oxide suspended in a dye liquor at a pH of 8 to 9.5. 10. Use of the pigments according to claim 1, e.g. for manufacture of printing inks and varnishes and for pigmenting macromolecular materials. Le A 14 984 - 29 - ORIGINAL INSPECTED 509807/0967