DE2635214A1 - PREPARATIONS OF PHTHALOCYANINES EASILY DISPERSIBLE IN WATER - Google Patents

Description

BASF Aktiengesellschaft

3 26352U

Our reference: O. Z. 32 125 Noe / Be 67OO Ludwigshafen, 03.08.1976

Preparations of phthalocyanines which are easily dispersible in water

The invention relates to new ones which are readily dispersible in water Preparations of phthalocyanines, as well as their production and their use.

Water-dispersible preparations of phthalocyanine pigments are known. These are mixtures of Phthalocyanine pigments with one or more water-soluble surface-active auxiliaries, usually used as dispersants be used. Such agents are, for example, condensation products from phenols such as phenol or cresol, formaldehyde and / or phenolsulphonic acids and sodium sulphite or condensation products from ß-naphthalenesulphonic acid with formaldehyde, as well as mixtures of such compounds. So that the phthalocyanine pigment contained in such preparations in water or water-containing media is readily dispersible, these preparations must have larger amounts of the surface-active auxiliaries contain: usually 30 to 40 percent by weight of phthalocyanine pigment and βθ to 70 percent by weight of auxiliary surfactants. These preparations are generally produced in such a way that the pigment, which has been produced in finely divided form by falling over, is also produced knead or grind the aids until the desired fine distribution is achieved. The kneaded material is then dried and ground into powder. In addition to the relatively low content of phthalocyanine pigments and the complex and cumbersome The way in which they are produced, such preparations also have application-related disadvantages: they cause too much during drying a significant proportion of pigment agglomerates that are not redispersible or redispersible only with great effort, e.g. in mass coloring cause uneven coloration of paper; in addition, the high content of the surface-active agents in the aqueous Medium the formation of so stable dispersions that the coloring capacity of such a liquor for the paper pulp

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coloring or for coloring leather only by special additional Measures how the addition of salt can be fully exploited.

Surprisingly, it has now been found that phthalocyanines are easily dispersible in water if preparations are used which - based on the preparation - (a) 70 to 95 percent by weight of finely divided phthalocyanine pigment whose primary particles are on average smaller than 0.3 μm, and ( b) 30 to 5 percent by weight of one or more alkylarylsulfonic acids with k to 20 carbon atoms in the alkyl, the sum of the alkyl carbon atoms being at least 8 and the sulfonic acids optionally in the form of their water-soluble salts.

The powdery phthalocyanine preparations according to the invention are with water and also with a number of organic solvents such as petroleum ether, gasoline, cyclohexane, pentane, benzene, toluene, xylene, chlorobenzene, carbon tetrachloride, Perchlorethylene, trichlorethylene, diethyl ether, tetrahydrofuran, Dioxane extremely easily wettable. A simple sprinkling in and, if necessary, gentle stirring is sufficient a glass rod to achieve a completely even distribution in water. The fine distribution is so extensive that a solution is simulated: the dispersion is clear and translucent. For example, a 3 weight percent dispersion can be which has been produced with the pigment preparations according to the invention, through 2 superimposed paper filters (CV 1 450 from Schleicher & Schüll) practical Filter without leaving any residue. However, there are no real solutions, as observed when shining through with monochromatic light the Tyndall effect, which is characteristic of colloidal solutions. Those with the pigment preparations according to the invention The aqueous dispersions obtained are also very stable. You can cook them or for a longer time, e.g. some Store at room temperature for weeks to a few months without a significant amount of pigment settling. on the other hand The phthalocyanine pigments in the preparations according to the invention behave in the form of the aqueous dispersions

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but like substantive dyes: they are quantitatively absorbed spontaneously on wool or cotton or on paper pulp, so that colorless dye liquors run off during processing.

The preparations according to the invention contain (a) 70 to 95, preferably 75 to 90 percent by weight - based on the preparation - of finely divided phthalocyanines and (b) 5 to 30, preferably 10 to 25 percent by weight of one or more alkylarylsulfonic acids.

The phthalocyanines (a) are metal-free phthalocyanines, copper phthalocyanines of the α- and ß-modification, their mixtures as well as halogen copper phthalocyanines such as polychloropper phthalocyanine with up to "16 chlorine atoms in the molecule or polychlorobromo-copper phthalocyanine with up to ΐβ chlorine and bromine atoms in the molecule. Of the phthalocyanines mentioned are metal-free phthalocyanine, copper phthalocyanine, which can contain up to 3 percent by weight of chlorine, and hexadecachlorocopper phthalocyanine preferred.

In order for the phthalocyanine to be easily dispersible in the preparation, it must be in a very fine distribution, i.e. the mean particle size of the primary borrowings must be below 1 / µm, preferably 0.5 / µm and below. To very much In order to obtain colorations of pure shade and strong color, it is necessary that the mean particle size of the primary particles is below 0.1 / µm.

For the purposes of the present invention, alkylarylsulfonic acids (b) are sulfonated alkylbenzenes on the aromatic nucleus and / or alky! naphthalenes understood. The benzene or naphthalene nucleus carries 1 to 3 *, preferably 1 or 2 alkyl groups, with 4 to 20 carbon atoms, the sum of the carbon atoms at least 8 is. The alkyl groups preferably contain 8 to 20, in particular 8 to 12, carbon atoms. As alkylbenzenes or alkylnaphthalenes, on which the sulfonic acids are based are, for example, to be mentioned individually: dibutylbenzene, octylbenzene, nonylbenzene, Decylbenzene, hexadecylbenzene, dodecylbenzene, dibutylnaphthalene,

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Octylnaphthalene, nonylnaphthalene, decylnaphthalene, dodecylnaphthalene, Octadecylnaphthalene, hexadecylnaphthalene, octadecylbenzene. Of the hydrocarbons mentioned, the sulfonic acids of octylbenzene, nonylbenzene, decylbenzene, Dodecylbenzene and dibutylnaphthalene are preferred. The sulfonic acids of dodecylbenzene are particularly preferred, of octylbenzene and decylbenzene.

Although the alkylbenzenesulfonic acids, Z ₀ B ₀ dodecylbenzenesulfonic acid, are generally liquid at room temperature, the pigment preparations according to the invention are in powder form. Only at a content of more than 40 percent by weight (based on the preparation) of dodecylbenzenesulfonic acid do such preparations begin to become pasty at room temperature. However, this has no effect on the easy dispersibility in water. Since preparations with a content of more than 30 percent by weight of alkylarylsulfonic acids no longer have any advantages over those with up to 30 percent of sulfonic acids, preparations with a higher content of alkylarylsulfonic acid are of little interest in application technology because of the lower content of pigment. Examples are pigment preparations of 75 to 87 percent by weight of a copper phthalocyanine of the β-modification, the primary particles of which have an average size of below 0.1 Aim , and 13 to 25 percent by weight of dodecylbenzenesulfonic acid and preparations of 75 to 80 percent by weight of a hexadecachlorocopper phthalocyanine, the mean primary particle size of which is below 0.1 / µm, and 20 to 25 percent by weight of dodecylbenzenesulfonic acid. Naturally, the preparations according to the invention can also contain small amounts of inert neutral substances which, for example, may have arisen as by-products in the production of the pigment or in the work-up of the pigment and which have not been completely separated off during isolation. Such inert, neutral substances can be, for example, neutral salts such as ammonium sulfate, sodium sulfate or by-products which do not interfere with color. The content of these substances should, however, be as low as possible and is preferably less than 1, in particular less than 0.1 percent by weight, based on the preparation.

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The phthalocyanine preparations according to the invention are prepared by thoroughly mixing finely divided phthalocyanines (a), the primary particles of which are smaller than 1 μm, preferably smaller than 0.1, with the alkylarylsulfonic acid or a mixture of these sulfonic acids; Phthalocyanines whose mean primary particle size is 0.1 lum and below are particularly preferred.

The finely divided phthalocyanines are preferably prepared by grinding the crude pigments in the absence of grinding aids preserved in mills such as ball mills, oscillating mills, planetary ball mills and other grinding units = the grinding process is finished, when the primary particle size is below 1 / µm, preferably 0.3 / µm and below. Regarding the color strength Preparations that are optimal and the color purity are obtained if one grinds until the primary particle size is im Mean is 0.1 / µm and below. In the grist, the fine primary particles form agglomerates of up to 100 μm in size. The milling process generally lasts between 2 and 48 hours, preferably between 4 and 20 hours, depending on the one used Grinding unit and the phthalocyanine used «The optimum grinding time can easily be determined: during the grinding process samples are taken, which are then mixed with the sulfonic acid in the desired manner. From the mixes the solid preparation of the sample is then isolated and its apparent solubility in water, e.g. using the Filter test determined.

If the milling time is too long, the millbase can be converted back into the alkylarylsulphonic acid become insoluble. This means that preparations are obtained which are only partially soluble in water. In this case, stirring for 50 to 120 hours with the Sulphonic acid a preparation "soluble" in water can be obtained.

The finely divided phthalocyanines required can also be obtained by precipitating solutions in sulfuric acid or chlorosulfonic acid can be obtained on water or ice. Finely divided polychloride and polychlorobromide are preferably used in this way.

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copper phthalocyanine produced «Mixing the finely divided Phthalocyanine pigment with the alkylarylsulfonic acid can also be used simultaneously with the production of the finely divided pigment take place. The preparations obtained in this way can be easily wetted with water. However, you get when you put it in water Pigment dispersions in which part of the pigment is not sufficiently finely distributed] i.e. in the filter test a significant part of the pigment remains on the filter.

The preparations according to the invention are advantageous prepared in such a way that the finely divided phthalocyanine and the alkylarylsulfonic acid are converted into an inert one in any order aprotic solvent with a boiling point below Γ55 C is, enters and the mixture as long as between room temperature and the boiling point of the solvent, preferably at Stirring at room temperature until a homogeneous organic dispersion has formed and a dried sample of this dispersion in Water gives a clear dispersion which does not leave a noticeable residue in the filter test. Then the solvent removed from the organic dispersion, e.g. by drying in a drying cabinet. Preferably, the invention Preparation isolated by freeze-drying, since in this way products that are particularly valuable in terms of color are obtained.

Inert aprotic solvents with a boiling point below 135 ° C are mainly aliphatic and halogenated aliphatic hydrocarbons, cycloaliphatic and aromatic hydrocarbons or mixtures thereof. Specifically, for example: pentane, hexane, light gasoline with a boiling range of 30 to 80 ° C, carbon tetrachloride, Trichlorethylene, tetrachlorethylene, ethylene bromide, cyclohexane, benzene, toluene, chlorobenzene and xylene. As solvents are Cyclohexane, benzene, p-xylene and, ethylene bromide preferred because In this case, the pigment preparation can be isolated particularly easily by freeze-drying.

Aliphatic and cycloaliphatic solvents can also be used as solvents Ketones or cyclic ethers are used,

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e.g. acetone, methyl ethyl ketone, cyclohexanone, dioxane and tetrahydrofuran. However, these solvents are less suitable for the stated purpose.

The amount of solvent is not critical and can therefore be varied within a wide range. The lower one The limit is determined by the fact that the mixture of the phthalocyanine (a), the sulfonic acid (b) and the solvent can be mixed thoroughly is. The mixing and homogenizing of the mixture can take place by stirring or by kneading. The upper limit the amount of solvent is generally from 15 to 20 times the amount by weight, based on (a). As the solvent must be removed to isolate the preparation, the amount of solvent will be used for economic reasons keep it as low as possible. In the event that the mixing is to take place with stirring, it is advantageous to use - based on (a) - 1.2 to 6 times the amount by weight of solvent. The use of larger amounts of solvent has no advantages, neither in terms of the properties of the pigment contained in the preparation, even during the homogenization of the mixture.

For example, from a mixture of copper phthalocyanine with an average particle size of less than 0.1 µm, dodecylbenzenesulfonic acid is obtained and p-xylene in a weight ratio of 1: 0.3: 1 * 28 when stirring with a normal blade stirrer, a pourable and flowable mass which forms a homogeneous dispersion. After removing the solvent, the preparation is obtained in which the pigment is sprinkled on water and Shaking is dispersed. The same result is achieved if, based on the pigment, 10 times the amount by weight Solvent applies.

Should the mixing in kneaders or similar mixing machines take place, the lower amount of solvent can be reduced to 0.3 to 0.1 times the amount by weight, based on (a); Preferably, based on (a), 0.5 to 1.0 times the amount by weight of solvent is used. When using

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Smaller amounts of solvent can solidify the mixture into a solid mass, so that this no longer or only with high energy expenditure can be worked through. When working in kheters and similar mixing machines, it is not necessary to that high shear forces occur during mixing, i.e. the mixtures generally only have a low viscosity on.

The obtained after removal of the solvent according to the invention Phthalocyanine preparations react acidic in water. In an aqueous dispersion, this is 1 percent by weight a preparation with 23 percent by weight (based on the preparation) Contains dodecylbenzenesulfonic acid, the pH value 2.2. In the dispersion, the sulfonic acid can be made alkaline by adding active compounds, which give water-soluble salts with the sulfonic acid, are neutralized, during neutralization the distribution of the phthalocyanine in the dispersion is not changed.

The only alkaline compounds that can be considered are those which give water-soluble salts with the sulfonic acid, for example alkali metal hydroxides, alkali metal carbonates, ammonia, primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, it being possible for the alkyl radicals to be further substituted, for example by alkoxy- and / or hydroxyl saturated 5-i 6- or 7-gü ^e drige heterocyclic compounds containing basic nitrogen as a ring member containing, or mixtures thereof.

Examples of suitable alkaline compounds include: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, gaseous ammonia or ammonia dissolved in water , methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine , Dipropylamine, tripropylamine, ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, methoxyethylamine, methoxypropylamine, ethoxyethylamine, ethoxy-

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propylamine, 2'-ethylhexoxypropylamine, propoxypropylamine, butoxypropylamine, Morpholine, piperidine, pyrrolidine or mixtures thereof.

The sulfonic acids contained in the preparations according to the invention can be neutralized after the preparation has been introduced in water or before use. You can also use the sulfonic acids immediately after the preparation of the organic dispersion (i.e. when a dried sample, after being immersed in water, produces a dispersion that Filter test no or practically no residue) neutralize in the organic solvent. In this case primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines or saturated 5-, 6- or 7-membered heterocyclic amines are preferably used for reasons of solubility Compounds that contain basic nitrogen as a ring member, or gaseous ammonia is passed into the dispersion until the stoichiometrically required amount has been absorbed.

After drying, preparations are obtained which have the same good properties as the preparations which which contain free sulfonic acids. Since the preparations according to the invention which contain the sulfonic acids (b) in the form of water-soluble If they contain salts and are non-corrosive to metals, these preparations are particularly preferred.

The preparations according to the invention are for coloring water-thinnable Varnishes, varnish dispersions, printing inks, inks, coating compounds, for mass coloring paper, cardboard, cellulose, Cement or plaster, as well as for the production of solvent-based printing and lacquer inks on the basis of aromatic or aliphatic Suitable for solvents.

The following examples are intended to illustrate the preparations according to the invention, further explain their manufacture and use. The percentages relate to weight.

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example 1

a) In a 4 l vibratory mill, filled with 5 * 5 kg iron balls from Diameter 1 to 2.5 cm, 400 g of copper phthalocyanine of the ß-modification (made from o-phthalonitrile in Nitrobenzene according to the example of DT-AS 1 569 6 * 1-6) 12 hours shaken. This creates from the blue powder, which consists of long crystal needles (length 1 to 100yum), a finely divided blue-black powder with a metallic sheen on the surface of increased bulk density (grist), As can be seen from the X-ray diagram of a sample, the α-modification was partially formed during grinding and that Crystal lattice largely destroyed, which can be seen from the flattening of the diffraction line. The grist consists of 0.1 Aggregates up to 100 μm in size, which are formed from primary particles of 0.05 μm and below (mean size of the Primary particles 0.03 / µm).

b) 280 g of the ground material are introduced into a solution of 84 g of dodecylbenzenesulfonic acid in 360 g of p-xylene at room temperature and the mixture was stirred at room temperature for 16 hours with a standard blade stirrer. The obtained homogeneous, slightly pasty dispersion is spread on a drying tray and dried under reduced pressure. You get a preparation containing 77 percent copper phthalocyanine and 23 percent dodecylbenzenesulfonic acid. The preparation can be pulverized by rubbing with a pestle or by grinding in a coffee grinder.

The preparation behaves as if the pigment were water-soluble. An aqueous "solution" containing 1 percent of the preparation is colored transparent blue and has a pH value of 2.2.

0) Testing the fineness of the dispersion (filter sample): 3 g of preparation b) are made into a paste in 10 ml of cold water, Pour 90 ml of boiling water over it and bring it to the boil for 2 1/2 minutes. After that, the transparent one

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Dye dispersion was sucked off through a Buchner funnel (0 9 cm) with two superimposed paper filters No. CV 1450 from Schleicher & Schüll using a water jet vacuum. The dispersion runs through the filter with practically no residue in less than a minute.

Example 2

In a solution of

110 g dodecylbenzenesulfonic acid in

400 g of p-xylene will be

280 g of the millbase obtained according to Example la) at room temperature entered and the mixture stirred for 16 hours at room temperature. Then it is placed on a drying tray poured on and dried in vacuo to constant weight. A preparation is obtained which 72 percent copper phthalocyanine and 28 percent dodecylbenzenesulfonic acid contains. The dry material can be crushed to a powder with a pestle or in a coffee grinder will.

Filter sample according to Example Ic): The dispersion runs in less than a minute through the filters. Virtually no residue can be seen on the filters.

Example 3

The procedure is as indicated in Example 2, but carries the millbase in a solution of 56 g of dodecylbenzenesulfonic acid 500 grams of p-xylene. After drying, a preparation is obtained that contains 83.4 percent copper phthalocyanine and 16.6 percent Contains dodecylbenzenesulfonic acid.

In the filter sample (see example Ic) the dispersion runs in less than a minute through the filters; Virtually no residue can be seen on the filters.

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Example 4

The procedure is as in Example 1, but the grist is added a solution of 44 g of dodecylbenzenesulfonic acid in 500 g of cyclohexane a. The mixture is stirred for 90 hours at room temperature. The preparation is obtained after drying under reduced pressure.

A 2 percent aqueous dispersion does not leave any residue on the filters during the filter test.

Example 5

a) 400 g copper phthalocyanine (produced by the solvent process from o-phthalonitrile in the presence of Ammonia) are ground according to example la). However, the grinding time is 48 hours. The grist consists of 10 to 100 / um large agglomerates consisting of primary particles of 0.05 / in and below are formed (mean size 0.02yum)

b) 280 g of the ground material 5a) are described as in Example Ib) converted into the preparation by stirring for 90 hours. The preparation obtained is by stirring in Easily dispersible in water.

A ^ percent dispersion runs in the filter sample less than a minute through the filters. No residue can be seen on the filters.

Example 6

200 g Hexadecachlorkupferphthalocyanin are dissolved in 000 g of chlorosulfonic acid at 30 to 5O ⁰ C and the solution at ^ O to 50 ⁰ C.
000 g of water discharged. The amorphous hexadecachlorocopper phthalocyanine obtained in this way is filtered off with suction, washed neutral and free of sulfate. 120 g of a water-moist filter material, dry content 18 %, are obtained.

The suction product is with
100 g of p-xylene are stirred, with hexadecacHbrkupfer-

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phthalocyanine and p-xylene spontaneously form a lump-like, pasty mass and the water is separated off. The water is decanted off and the remaining water in the spaces between the lumps by heating azeotroped at boiling point with p-xylene at 93 ° C. Then the viscous, pasty mass with

g p-xylene and

g of dodecylbenzenesulfonic acid are added and this suspension is ^{stirred at 120 to 130 °} C. for 10 hours. After cooling to room temperature, the mixture is evenly distributed on a drying tray and dried in vacuo. The preparation obtained in this way can be ground to a powder with a pestle or in a coffee grinder.

Example 7 (application example)

Bulk coloring of paper

g of a paper raw material, consisting of 60 % wood pulp and 40 % unbleached sulphite pulp, ml of a 5% resin size solution (corresponding to 2 %, based on paper raw material)

ml of a 10 percent aluminum sulfate solution (6%) and mg of the preparation obtained in Example 1 are slowly stirred in ml of water for 30 minutes at room temperature. Then with

ml of water, the paper pulp is thinned over a flat screen with a mesh width of 30 μm by applying negative pressure vacuumed, rolled and dried. The water that runs out of the sieve is practically colorless. You get a greenish blue colored leaf. The coloring is stronger, purer in color and leveler than coloring, obtained with prior art copper phthalocyanine preparations.

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If, instead of the preparations obtained according to Example 1, the preparations obtained according to Examples 2, 3, 4 or 5 are used, then equally good results are obtained.

If the preparation is replaced by that of Example 6, a sheet of paper is obtained which has a yellowish green color is. Here, too, the wastewater is practically colorless. The color is purer in color, more yellowish and stronger in color than with polycopper phthalocyanine preparations dyeings obtained from the prior art.

Example 8 (application example)

Bulk coloring of paper without additives.

5 g of the paper stock described in Example 7,

60 mg of the preparation obtained according to Example 5 are stirred in 100 ml of water for 30 minutes at room temperature. Thereafter is diluted with 500 ml of water and the paper pulp over a flat screen of 30 μm mesh size by applying negative pressure sucked off; the filter material is rolled and dried. The water that runs out of the sieve is practically colorless. A sheet is obtained which is evenly deeply greenish blue in color.

If one uses instead of the preparation according to the invention Prior art copper phthalocyanine preparations give practically colorless paper sheets.

An equally good result is achieved if the preparation of Example 5 by the according to Examples 1, 2, J>, 4 or

6 received replaced. In the latter case you get a green one Paper.

Example. 9

50 g of the millbase obtained according to Example la) are at

Room temperature in a solution of 15 g of dodecylbenzenesulfonic acid in
Entered 250 g of cyclohexane and the mixture was stirred for 24 hours at room temperature. After that will be

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3.5 g of mono-n-butylamine (corresponding to the amount required for the sulfonic acid) dissolved in

20 g of cyclohexane were added and ΐβ hours at room temperature stirred, the viscosity of the pigment suspension increases somewhat. Then the homogeneous Dispersion evenly distributed on a drying tray and dried under reduced pressure. A product is obtained which can be pulverized in a coffee grinder or with a pestle. In the case of the filter sample (see example Ic)), practically no residue remains on the filters. The aqueous dispersion has a pH of 7 * 4.

Use the same amount instead of n-butylamine tert. Butylamine or see. Butylamine, a preparation with the same properties is obtained. The pH in the aqueous dispersion (3 percent) is 7.2 to 7.4.

Example 10

400 g of the millbase produced according to Example la) are in 2,000 g of cyclohexane and 120 g of dodecylbenzenesulfonic acid were added and the mixture was stirred at room temperature for 48 hours. Then 33 g of dimethylethanolamine are added. The mixture is stirred for 16 hours at room temperature on a drying tray poured and the solvent removed under reduced pressure.

The preparation obtained is completely dispersible in water. In the filter sample (see example Ic)) there is no residue on the filters. The aqueous dispersion (3 percent) has a pH of 6.1.

Example 11

That has been ground in accordance with Example la) 392 g of .beta.-copper phthalocyanine, are βθ in II8 g dodecylbenzenesulfonic acid and 500 g light gasoline with a boiling range up to 8O ⁰ C was added

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and the mixture was stirred for 16 hours at room temperature. The dispersion is then heated to the boil and 300g of light gasoline distilled off with stirring at atmospheric pressure. The residue is then evaporated to dryness under reduced pressure. A dry matter is obtained which is immediately and completely dispersible after pulverization in water. No residue can be seen on the filter during the pilter test.

Example 12

360 g of grist obtained according to Example 5a) are in a Introduced a solution of 90 g of dodecylbenzenesulfonic acid in 1,000 g of trichlorethylene and stirred for 3 hours at room temperature. Then 600 g of trichlorethylene are distilled off at atmospheric pressure and the residue under reduced pressure to Evaporated dry. A dry matter is obtained which after is almost completely dispersible in water after pulverization. In the case of the pilter test according to Example Ic), there is less Residue.

Example 13

50 g of the millbase obtained according to Example 5a) are added to a solution of 5 * 3 g of dodecylbenzenesulfonic acid in 200 g of cyclohexane entered and stirred for 60 hours at room temperature. The mixture is then dried under reduced pressure. The pigment preparation containing 10 percent dodecylbenzenesulfonic acid and contains 90 percent copper phthalocyanine, gives way Example 7 strong, but not entirely homogeneous paper dyeings. One can find one in the pilter test according to example Ic) clearly visible residue.

Example 14

50 g of the millbase obtained according to Example 5a) are in a Solution of 15 g of dibutylnaphthalene monosulfonic acid (which also contains proportions of the corresponding disulfonic acid) in

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g p-xylene entered and stirred βθ hours at room temperature. The mixture is then dried under reduced pressure. The pigment preparation, which contains 77 percent copper phthalocyanine and 2 % of the sulfonic acid mixture, gives good, strong paper colorations according to Example 7, but shows a clear residue in the filter sample according to Example Ic).

Example 15

a) In a 4 l vibratory mill filled with 5.5 kg of iron balls with a diameter of 1 to 2.5 cm, 200 g of copper phthalocyanine are added with 2.7 percent chlorine (made from phthalonitrile and copper (I) chloride using the baking process) for 10 hours shaken. This creates a shiny metallic grist with an increased debris weight, consisting of 0.1 to 100 μm large aggregates formed from amorphous primary particles of 0.05 µm and below.

b) 96 g of the millbase are converted into a solution at room temperature entered of 24 g of dodecylbenzenesulfonic acid in 750 g of p-xylene and the mixture was stirred with a paddle stirrer at room temperature for 96 hours. The obtained homogeneous, light Pourable dispersion is spread on a drying tray and dried under reduced pressure (approx. 1 Torr). You get a preparation containing 80 percent by weight copper phthalocyanine and 20 percent by weight dodecylbenzenesulfonic acid.

The preparation behaves as if the pigment were water-soluble. When testing for water solubility according to Example 1), almost no residue is found on the filter.

Example l6

8.6 g of chlorosulfonic acid are added dropwise to a solution of 14.1 g of n-octylbenzene in 60 g of cyclohexane at room temperature and the mixture is then ^{stirred at 40 to 50 °} C. until the evolution of gas has ended. After that, at room temperature

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diluted with ΐ8θ g cyclohexane and in this solution 80 g grist, which has been produced according to example la) entered. This mixture is stirred for 48 hours at room temperature and then poured onto a drying tray and dried in vacuo. An apparently soluble pigment preparation composed of 16 percent by weight of n-octylbenzenesulfonic acid is obtained which is very easily wettable in water and 84 weight percent copper phthalocyanine. In the filter test according to example Ic) there is almost no residue on the filter.

Example 17

In a 4 liter vibrating mill filled with 5 * 5 kg iron balls with a diameter of 1 to 2.5 cm, 200 g of metal-free phthalocyanine are ground for 20 hours (primary particles £ 0.05 / u, which form agglomerates from 5 to 100 / im) .

80 g of the millbase obtained are introduced into a solution of 20 g of dodecylbenzenesulfonic acid in 400 g of p-xylene and Stirred for 20 hours at room temperature. Then the easily flowable mixture is distributed evenly on a drying tray and dried under reduced pressure. An easily pulverizable pigment preparation consisting of 20 percent is obtained Dodecylbenzenesulfonic acid and 80 percent metal-free phthalocyanine, which are extremely easy to wet with water leaves and gives the paper which is colored very strongly greenish blue in the mass coloring of paper according to Example 7.

Example l8

280 g of the millbase obtained according to Example 5a) are at Room temperature added to a solution of 84 g of dodecylbenzenesulfonic acid in 56o g of p-xylene and the mixture for 26 hours stirred at room temperature. With continued stirring, 4.7 g of gaseous ammonia are passed through a gas inlet pipe in 4 hours initiated at room temperature to saturation, the viscosity of the previously thin mixture increases slightly. Then the mass is evenly spread on a drying tray.

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divides and dried in vacuo. An easily pulverizable one is obtained Pigment preparation that is soluble in water like a Dye behaves, dyes paper pulp excellently and reacts practically neutrally.

709886/0296

Claims (8)

O.Z. 32 125 patent claims 2 6 3 5 2 1 1. Preparations of phthalocyanines which are easily dispersible in water h, containing - based on the preparation - (a) 70 to 95 percent by weight of finely divided phthalocyanine pigment, whose primary particles are on average smaller than 0.3yum, and (b) 30 to 5 percent by weight of one or more alkylarylsulfonic acids with 4 to 20 carbon atoms in the alkyl, the sum of the alkyl carbon atoms being at least 8 and optionally the sulfonic acids are in the form of their water-soluble salts. 2. Preparations according to claim 1, containing 75 to 90 percent by weight (a) and 10 to 25 percent by weight (b). 3. Preparations according to claims 1 or 2, characterized in that (a) has an average primary particle size of 0.1 μm and below. 4. Preparations according to claims 1 to 3 *, characterized in that (a) metal-free phthalocyanine, copper phthalocyanine of the α or ß modification, copper phthalocyanine which contains up to 3 percent by weight of chlorine, polychloro-copper phthalocyanine with up to ΐβ chlorine atoms in the molecule, Polychlorobromo copper phthalocyanine with up to ΐβ bromine and chlorine atoms in the molecule or a mixture thereof. 5. Preparations according to claims 1 to 4, characterized in that (b) is a sulfonic acid of one or more alkylbenzenes or alkylnaphthalenes which are 1 or 2 alkyl having 4 to 12 carbon atoms have and wherein the total number of alkyl carbon atoms is at least 8. 6. Preparations according to claims 1 to 5, characterized in that (b) in the form of the salts with primary aliphatic amines, secondary aliphatic amines, tertiary 709886/0296 - ~ ²¹ ~ ORIGINAL INSPECTED - ο.ζ. 32 125 λ 26352U aliphatic amines, with saturated 5-, 6- or 7-güedrigen heterocycles which contain basic nitrogen as a ring member. 7. Process for the production of the preparations according to Claims 1 to 5, characterized in that the finely divided phthalocyanine pigment (a) and the alkylarylsulfonic acids (b) are introduced in any order in an inert aprotic solvent whose boiling point is below 135 ° C, the mixture is stirred between room temperature and boiling temperature until a homogeneous dispersion has formed which, after drying in water, can be dispersed practically without residue, if necessary the sulfonic acids by adding the stoichiometrically required amount of an aliphatic primary, secondary or tertiary amine, a basic one saturated heterocyclic compound or ammonia and then the solvent is removed from the organic dispersion. 8. Use of the preparations according to Claims 1 to 6 for dyeing aqueous plastic dispersions, aqueous Emulsion paints, water-thinnable paints, inks, printing inks and cellulose fiber material. BASF Aktiengesellschaft - '? 08886/029