DE1270208B - Process for the preparation of pigment dispersions - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

German class:

Number:
File number:
Registration date:
Display day:

C09d

C08g
D 21h

22 g -10/01

39 b-22/01
55c-3/01

P 12 70 208.8-43
November 2, 1957
June 12, 1968

The present invention relates to organic pigment dispersions which are used for coloring Paper, synthetic fibers, plastics and in particular for pigmenting latex paints suitable.

According to the usual process for the preparation of organic pigment dispersions, a mixture from the organic pigment press cake and a water-soluble dispersant, for example sodium alkylarylsulfonate, Sodium alkylnaphthalene sulfonate, alkylnaphthalene sulfonic acid, etc., an intense one subjected to mechanical processing, for example by mixing or kneading. Under these Conditions come about pigment properties, and the product obtained can be used for Dilute to form a paste with water or dry to "form a dispersed powder; nevertheless the products show considerable sensitivity to water when used later therefore cannot be washed undamaged.

Furthermore, from British patent specification 735 534 pigment dispersions are known which are composed of a pigment of a certain, water-soluble polyvinyl resin and a water-insoluble ^{substance melting between 35 and 100 °} C., e.g. B. an opal resin. However, these known dispersions have to be dried in order to finally be available on the market in the form of tablets or beads.

It is now the purpose of the present invention to overcome the shortcomings mentioned and to make organic To create pigment dispersions which have a high color value, excellent resistance to exhibit flocculation and agglomeration and provide water-based paints that do not Show sensitivity to water.

The present invention now relates to a process for the preparation of aqueous pigment dispersions for coloring paper, plastics and especially for pigmenting latex paints Mixing an aqueous mass of an organic pigment with a polymer and is characterized by that the aqueous mass of an organic pigment with a water-soluble or water-miscible polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether or copolymer that by polymerization of 85 to 90 percent by weight of vinyl methyl ether and 10 to 15 percent by weight Vinyl ethyl, vinyl propyl or vinyl butyl ether has been obtained, in proportion to organic pigment Polymer from 10: 1 to 1: 1, kneaded together.

It has been found that it is useful to achieve the inventive purposes that the process for the preparation of
Pigment dispersions

Applicant:

General Aniline and Film Corporation,

New York, N.Y. (V. St. A.)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

6000 Frankfurt, Große Eschenheimer Str. 39

Named as inventor:

Robert Ernest Brouillard, Westfield, N. J .;

Leon Katz, Springfield, N. J .;

James Joseph Gannon,

Florham Park, N.J. (V. St. A.)

Claimed priority:
V. St. v. America November 15, 1956
(622 246)

Mixture in the kneading device has such a viscosity that it forms a stiff kneading mass. Viscosities of up to 1,000,000 cP are possible. The resulting dispersions can before use can be diluted to the desired consistency with water or another solvent.

The dispersions prepared according to the invention are particularly suitable for pigmenting oil-resin systems or aqueous systems. The pigmented end product does not show any sensitivity to water; despite the fact that they contain substantial amounts of an originally water soluble or miscible material can. Any organic pigments can be used in the present invention as long as they are used Medium are insoluble.

According to the invention, the term “polyvinylpyrrolidone” is understood to mean a polymer which is characterized by Polymerization of N-vinyl-2-pyrrolidone, N-vinyl - methyl - pyrrolidone, N - vinyl - 5 - ethyl - pyrrolidone; N-vinyl-S ^ -dimethyl-pyrrolidone, N-vinyl-4-methylpyrrolidone or N-vinyl-4-ethyl-pyrrolidone is obtained has been. Depending on the degree of polymerization, these polymeric N-vinyl-pyrrolidones have molecular

809 559/523

weighed between 500 and 200,000. The K value of this is because no organic solvents are used Polymer is 10 to 100, in particular 30 to or have to be recovered. Likewise can 100. all protective measures are also omitted that were

The polyvinylmers which can be used according to the invention are flammable and unhealthy solder ethyl ethers and copolymers have a molecular weight 5 are necessary.

Cell weight in the range from 1000 to about 200,000. In the examples below, parts are as far as

corresponding to K values in the range from 10 to 60. nothing else is stated, parts by weight.

The polyvinyl alcohol which can be used according to the invention. -I ₁

is water-soluble and has a viscosity of 10 to Example!

70, preferably 30 to 5OcP, determined with a io 214 parts of an aqueous, 38.5% strength paste of a 4 ° / ₀ aqueous solution at 20 ⁰ C. phthalocyanine green and 34 parts of a polyvinyl

From German patent 684 820, aqueous N-pyrrolidones with a K value of 30 are in Paints known that are intimately mixed with water as a binder using a Werner-Pfleiderer mixer. Of the soluble polyvinyl ether or water-soluble mixed jacket is heated with steam until as much water polymerizate from water-soluble vinyl ethers and 15 is driven off that a stiff putty (viscosity water-insoluble vinyl ethers or other water- approx. 250,000 cP) has arisen. You knead this contain insoluble vinyl compounds; furthermore mass are 5 hours long in order to achieve an intimate mixture from German Patent 744 020 paint pigment and resin. Then you pour Color from pigment, aqueous solutions more artificial, enough water to make a flowable paste more organic Binder and possibly also 20 places. The pigment content of this dispersion can, depending Known emulsifiers, which additionally have an aqueous viscosity according to the desired viscosity, in the range of Contains suspension of polyethylene polysulphide. The- 1 to 30% are. In a standard styrene-butadiene type Paints have the latex already mentioned mixed in, the product developed a full one Disadvantage that they have a considerable water-sensitive color without flocculating, and the resulting film and therefore not without unfavorable product impairment with regard to washability can be washed. nits superior.

It is known from US Pat. No. 2,647,094, Beist> iel2

for the production of pigment dispersions

to use soluble copolymers z. B. 200 parts of an aqueous 20% strength are treated

by adding ammonia soluble or partially 30 paste of a phthalocyanine blue and 40 parts can be made soluble. It is an- polyvinyl-N-pyrrolidone with a K value of 20 in give that one used earlier for this purpose in the same way as in Example 1, except that one the Even already water-soluble polymers used mass after the end of the kneading operation for has, but that brings dryness from the corresponding dispersions by being produced by the steam Coatings are sensitive to water. Which conducts steam or hot water in a jacket and that described in this patent, water per se remaining in water by evaporation under atmospheric insolubles Copolymers, on the other hand, should evaporate under spherical pressure or reduced pressure, lead to beneficial results. This literature - this paste can be used for tinting acrylic, polystelle shows that against the use of water vinyl acetate or styrene-butadiene latexes for the soluble polymers for the production of pigments. 40 Formation of films with improved water-resistant dispersions there was a prejudice. It was possible to use it, therefore it was extremely surprising that the inven- Example 3

duly used special water-soluble

or water-miscible polymers to pigment 100 parts of a by diazotizing m-nitro-

Dispersions lead to water-insensitivity to 45 p-toluidine and domes with aceto-acetanilide Deliver coatings. ten azo pigments, 80 parts of polyvinyl alcohol with

Incidentally, the production according to the invention is a viscosity of 30 cP and 400 parts of water of the dispersions, which are merely kneaded in a Werner-Pfleiderer mixer for 2 hours of the corresponding components, kneaded as required. When the dispersion is complete, there are drive to the preparation of the known dispersions 50 to 400 parts of water and mix for about superior as it is simpler. With the known 1 hour until a uniform paste is formed. Pigment dispersions must first form the solid polymer. When mixing the paste in a styrene-butadiene the pigment to be mixed before the latex is enough brief stirring by hand to full Polymer is made soluble. If one uses color strength to develop, namely in the production of this well-known Disper- 55

sions the polymer which has already been made soluble, see Example 4

the desired result will not be obtained. That

The process according to the invention is used in comparison to the procedure used in the same way as in Example 1

already known processes simpler, however, that instead of polyvinyl-N-pyrrolidone one No neutralization stage with ammonia. 60 equivalent amount of polyvinyl methyl ether with one

It is also already known for the same purpose K value of 20. The mass will be about 5 hours Polymers soluble in hydrocarbons are kneaded too long until they are uniform and intimate turn around. However, these are usually a water mixture of pigment and polyvinyl methyl ether insoluble. Compared to the use of pigment has arisen. After adding enough water dispersions in organic solvents, which are still 65 you get a edible green paste, which is a Containing a dissolved polymeric binder gives excellent resistance to flocculation according to the invention has the advantage that in aqueous or agglomeration. The washability Solutions is being worked on. This represents a cheaper rate of the resulting film is better than that of one

Film made by tinting the acrylic latex with an anionic dispersion of phthalocyanine green has been.

Example5 _g

150 parts of an azo pigment in the form of a 25% press cake, prepared by tetrazotizing 3,3'-dichlorobenzidine and coupling with aceto-acetanilide, along with 200 parts of a 50% Grind aqueous solution of polyvinyl methyl ether at 200,000 cP until completely dispersed originated. The paste is then diluted with water until it is flowable. If you put this Product to a polyvinyl acetate latex and tests a film made from it in the usual way Washability, the result is an improved water resistance compared to known products.

Example 6

The procedure is the same as in Example 1, with the exception that instead of 34 parts of polyvinyl-N-pyrrolidone 30 parts of a copolymer of 90 percent by weight vinyl methyl ether and 10 percent by weight Vinyl butyl ether obtained copolymer vinyl alkyl ether is used. When incorporated into a common styrene-butadiene latex, the product shows a full color without flaking and a film produced therefrom has improved washability compared to known products.

Claims (1)

Claim: Process for the preparation of aqueous pigment dispersions for coloring paper and plastics and especially for pigmenting latex paints by mixing an aqueous one Mass of an organic pigment with a polymer, characterized in that that the aqueous mass of an organic pigment with a water-soluble or water-miscible Polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether or copolymer, the by polymerization of 85 to 90 percent by weight of vinyl methyl ether and 10 to 15 percent by weight Vinyl ethyl, vinyl propyl or vinyl butyl ether has been obtained, in the ratio organic Pigment to polymer from 10: 1 to 1: 1, kneaded together. Considered publications:
German Patent Nos. 662 936, 684 820, 020; British Patent No. 735,534;
French Patent Nos. 691 070, 1063 084; U.S. Patent Nos. 2,647,094, 2,649,382.