GB1588777A

GB1588777A - Solid pigment formulation for printing ink and paint systems

Info

Publication number: GB1588777A
Application number: GB27832/77A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1976-07-05
Filing date: 1977-07-04
Publication date: 1981-04-29
Also published as: AU514994B2; FR2357615B1; DK298977A; SE7707735L; IT1086249B; JPS536333A; AU2671977A; FR2357615A1; BR7704360A; NL7707333A; DE2729892C2; CA1111169A; SE433498B; JPS6111979B2; DE2729892A1; ES460376A1

Description

(54) SOLID PIGMENT FORMULATION FOR PRINTING INK AND PAINT SYSTEMS (71) We, CIBA-GEIGY AG, a Swiss Body Corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention relates to a new advantageous solid pigment formulation for, in particular, aqueous, aqueous-alcoholic or alcoholic printing ink and paint systems, which contains a pigment and a polyacrylic resin, containing carboxylic acid groups, as the carrier, but preferably no surface-active compound.

Pigment formulations which consist of a water-insoluble dyestuff and a copolymer of styrene and maleic anhydride and which are suitable for pigmenting printing inks are already known. However, they have the disadvantage that they can be used virtually only for printing paper since they have poor adhesion to other substrates. In addition, it is known to manufacture pigment granules by shaping a molten mixture of surface-active compounds, pigments and water-insoluble acid resins, which become water-soluble after neutralisation, into granules. The pigment formulations manufactured in this manner can be dissolved in aqueous alkali solutions and are suitable for printing paper.

Compared with the abovementioned state of the art, the solid pigment formulation according to the invention is distinguished in printing inks and paints by an excellent adhesion both to paper and to metals and plastics, by a good waterresistance of the films and by high tinctorial strength and gloss. Co-using a surfaceactive compound proves to be disadvantageous because the dispersibility and the gloss thereby decrease and the foam formation increases. the tinctorial strength and transparency are also adversely influenced with increasing concentration of a surface active substance.

The solid pigment formulation according to the invention contains 30 to 70% by weight of pigment and 70 to 30 /n by weight of a polyacrylic resin which is a polymer or copolymer of an acrylic alkyl ester and/or methacrylic alkyl ester containing carboxylic acid groups. The acid number of the polyacrylic resin to be used is appropriately 30 to 300, preferably 50 to 150. Polyacrylic resins containing carboxylic acid groups which are used are preferably those which are obtained by copolymerisation of an acrylic alkyl ester and/or methacrylic aklyl ester with acrylic acid and/or an alkyl, preferably methyl or ethyl, substituted acrylic acid in proportions to produce a resin with an acid number within the range 30 to 300.It is also preferred that the polyacrylic resin to be used is soluble in an aqueous, aqueous-alcoholic or alcoholic medium, if appropriate with the addition of bases.

Such resins are commercially obtainable in the acid form or in the partially or completely neutralised form.

Possible pigments for the formulations according to the invention are both inorganic pigments, for example carbon black, titanium dioxide, zinc sulphide or iron oxides, and organic pigments, in particular those of the phthalocyanine, anthraquinone, perinone, indigoid, thioindigoid, dioxazine, iso-indolinone, perylene, azo and quinacridone series and metal complexes, for example of azo, azomethine or methine dystuffs, their resistance to alkali appropriately being taken into consideration. Mixtures of different pigments can also be used.

In addition to the components to be used according to the invention, the formulations can also contain one or more auxiliaries, such as plasticisers, waxes, stabilisers and fillers.

The new pigment formulations can be manufactured in various manners, for example by adding the pigment to the alkaline polyacrylic resin solution with subsequent precipitation by acidifying, by atomising the pigment/resin solution, or continuously or discontinuously in kneading machines by mixing the waterinsoluble acid resin with the pigment. When the pigment formulation is manufactured by the first mentioned process, alkalis are used and are subsequently neutralised. On the other hand, for the use of the formulations it is necessary to use volatile bases, such as ammonia or amines, so that the printing ink or paint becomes insoluble by the evaporation of the basic aqueous/alcoholic solvent.

When the manufacture is carried out in a kneader, it is possible to precipitate the polyacrylic resin from the aqueous-ammoniacal solution by acidifying directly in the kneader, to decant the water, which has separated out, from the carrier resin melt, to add the pigment, solvent and, optionally, sodium chloride as a grinding auxiliary, to knead to the desired fineness and to work up the mass to give the dry formulation.

The manufacture of the pigment formulation preferably takes place in the absence of surface-active compounds. This term includes wetting agents and surface-active agents, dispersing agents and the like, such as alkali soaps, aminocarboxylic acid soaps, sulphates, sulphonates, fatty acid esters of hydroxyalkanesulphonic acids, phosphate surface-active agents, fatty amine salts, fatty acid derivatives of polyacidic amines or aminoalcohols, quaternised amines, fatty acid esters of polyhydric alcohols, fatty acid alkylolamides, alkylene oxide adducts, ligninsulphonates, fatty acid alkylolamine esters, amidazolyl-fatty acid derivatives, quaternary pyrimidino or imidazole derivatives, betaine derivatives, ethoxylated mercaptans, amides, amines or polypropylene glycols.

Solid formulations with a pigment content of 50 to 60% by weight have shown themselves to be the best products, the polyacrylic resin having an acid number of 60 to 200. Resins with an acid number of 50120 are preferably suitable for formulations which give printing inks, which adhere particularly well, for example, PVC.

The formulations according to the invention can be used for the most diverse printing ink and paint media. Examples which may be mentioned are the printing and lacquering of paper and coated papers, such as wallpapers, decorative papers and packaging, of aluminiun foils, of plasticised and rigid PVC, of polyamide, polystyrene and cellulose acetate film, of Cellophane and lacquered grades of Cellophane (Cellophane is a Registered Trade Mark), of corona-pretreated polyethylene and polyester films and of supports coated with polyvinylidene chloride. The printing processes used are all the known processes, such as gravure printing, flexographic printing, screen printing, letterpress printing, dry offset and offset and the lacquering processes which are used are, for example, so-called roller-coating, spraying, brushing and spreading with a doctor blade.

In the manufacture of printing inks and paints, the formulations according to the invention are incorporated into the solvent or binder solutions, whilst stirring, no additional grinding process for dispersing the pigment being necessary. This takes place, for example, by the following processes: Preparation of a dye concentrate in the solvent, for example in ethanol, isopropanol, water/organic base, water/organic base/alcohol or acrylic monomer or in a binder solution diluted with solvent. The formulation concentration to be chosen depends on the desired viscosity of the concentrate and is dependent, inter alia, on the solvent. Preferred concentrations are about 5 to 20% by weight of pure organic pigment and are correspondingly higher in the case of inorganic pigments.

The concentrates thus obtained can then be mixed with the appropriate clear lacquers and varnishes in the desired ratio.

Direct stirring into the binder solution or the varnish, if appropriate with the addition of a solvent or diluent to adjust the viscosity. Paints and printing inks which can be used directly or delivered directly can be manufactured in this manner.

The present invention also provides a chemically cured or dried printing ink and paint system based on monomeric and/or prepolymeric compounds, having incorporated therein a pigment formulation as hereinbefore described.

A preferred process for the manufacture of paints or printing inks consists in incorporating the formulations according to the invention, in water, aqueous alcohol or alcohol with the addition of ammonia or an amine, for example a mono-, di-, or tri-alkylamine, an alkanolamine or a heterocyclic amine, such as morpholine or piperazine, into the used ink or paint material the carrier resin being dissolved and the pigment being finely dispersed in the application medium.

In the examples which follow, unless otherwise indicated the parts denote parts by weight, the percentages denote percentages by weight and the temperatures are given in degrees centigrade.

Example 1 a) 400 parts of an aqueous/alcoholic solution which contains 30% of a watersoluble acrylic resin in the form of an amine salt (AQUAHYDE 100 from Lawter Chemicals, acid number 76) are introduced into a kneader.

The carrier resin is liberated in its water-insoluble acid form with 29 parts by volume of 25% strength acetic acid at a temperature of 35--40" (pH range 4.85.8). During this procedure, about 220--240 parts of water separate out and are decanted.

The residual water is removed in vacuo and at a temperature of 90 , and the carrier resin is then present as a viscous melt and corresponds to an amount to be processed of 120g.

b) 480 parts of finely ground sodium chloride, 120 parts of the yellow disazo pigment of the formula

and 90 parts of diacetone-alcohol are introduced into the kneader, warmed to 900, and the kneading composition rapidly formed is kneaded for 3 hours at about 60".

c) The kneading composition is broken up by adding 250 parts of saturated sodium chloride solution dropwise and then adding 100 parts of ice and the resulting granules are subjected to wet grinding in a gear colloid mill with about 5,000 parts of water for fine granulation. The granules are then filtered and washed with water until free from solvent and salt. The filter cake is dried in a vacuum cabinet at 800. The dried material is advantageously pressed through a sieve of 0.5 mm mesh width. A yellow formulation with a pigment content of 50 /O is obtained, which disperses perfectly in the printing inks of Application Examples a to h and gives, for example on paper and aluminium foil, glossy prints which-are intensely coloured.

Example 2 a) 500 parts of an aqueous/alcoholic solution which contains 30% of a watersoluble acrylic resin in the form of an amine salt (AQUAHYDE 100, Lawter Chemicals) are diluted with 1,000 parts of water. This solution is introduced in a thin jet into an aqueous solution, containing small amount of acetic acid, of 5,000 parts of water and 65 parts by volume of 80% strength acetic acid, whilst stirring thoroughly (toothed disc, 300 rpm).

The free acid precipitates in the form of fairly fine grains and is filtered off and washed with demineralised water until free from acid. The filter cake is dried at 300 in vacuo and gives an only slightly sintered solid resin.

b) 35 parts of the yellow disazo pigment used in Example 1, 17.5 parts of the solid acrylic resin obtained according to process 2a, 140 parts of finely ground sodium chloride and 25 parts of diacetone-alcohol are kneaded in a kneader for 2 hours at about 60". The kneading composition is broken up by adding 25 parts of ice and the granules are worked up analogously to Example l c. A yellow formulation with the same properties as in Example 1 is obtained.

Example 3 35 parts of the yellow disazo pigment (Pigment Yellow C.I. 55) of the formula

35 parts of AQUAHYDE 100, isolated as a solid resin according to Example 2a, 140 g of finely ground sodium chloride and 15 parts of diacetone-alcohol are kneaded in a kneader for 2 hours at about 600. The breaking up of the kneading composition is effected by means of 25 parts of an ice/sodium chloride mixture and the working up is carried out by a procedure analogous to that described in Example Ic.

A reddish-tinged yellow formulation is obtained, which can be dispersed perfectly in the printing inks of Application Examples a to h and gives, for example on paper and aluminium foils, glossy prints which are intensely coloured.

Example 4 a) Analogously to Example la, 450 parts of AQUAHYDE 100 in an aqueousalcoholic solution are precipitated as the free acid in a kneader and dried.

b) 540 parts of finely ground sodium chloride, 135 parts of the scarlet red disazo pigment of the formula

and 70 parts of diacetone-alcohol are then introduced into the kneader and the composition is kneaded for 3 hours at about 60". Thereafter, the kneading composition is broken up with 250 parts of saturated sodium chloride solution and worked up analogously tto Example lc.

A scarlet red formulation is obtained, which disperses perfectly in the printing inks of Application Examples a to h and gives, for example on paper and aluminium foil, glossy prints which are intensely coloured.

Example 5 A mixture of 144 parts of the yellow disazo pigment used in Example 1, 240 parts of AQUAHYDE 100 in an aqueous/alcoholic solution (acrylic resin content of 30%, corresponding to 72 parts of solid resin), 144 parts of ethyl alcohol and 122 parts of water are ground in a 2 1 bead mill for 24 hours.

The paste, which is capable of flowing, is separated from the grinding bodies and made up to 2,000 parts by volume by adding water. The ground material diluted in this manner is atomised in a spray-drying installation at an air inlet temperature of about 200 and an air outlet temperature of about 8595a. A fine yellow powder formulation with a pigment content of 66.6% is obtained, which has the same properties as the formulation described in Example 1.

Example 6 a) 35 parts of the red disazo pigment of the formula

35 parts of AQUAHYDE 100, obtained from its aqueous-alcoholic solution by evaporation in vacuo and present as the solid amine salt, 140 parts of finely ground sodium chloride and 14 parts of diacetone-alcohol are kneaded in a kneader for I, hours at about 60". The kneading composition is broken up with 20 parts by volume of about 40% strength acetic acid and the granules, suspended in 2,000 parts of water, are subjected to fine grinding in a gear colloid mill and worked up analogously to Example Ic. A red formulation is obtained, which disperses perfectly in the printing inks of Application Examples a to h and gives, for example on paper and aluminium foil, glossy prints which are intensely coloured.

b) After the kneading process, the procedure can also be to break up the composition by adding 70 parts of saturated sodium chloride solution, to finely grind the granules, suspended in 2,000 parts of water, in a gear colloid mill and to stir the resulting formulation suspension in 4,000 parts of water and 10 parts by volume of 80 / , strength acetic acid for about I hour. The granules are then filtered off, washed until free from acid and salts, dried at 6070 in vacuo and passed through a + mm sieve.

A red formulation is obtained with the same properties as the formulation obtained according to Example 6a.

Example 7 A mixture of 100 parts of an aqueous/isopropanolic solution which contains 40% of an acrylic resin in the form of the ammonium salt (ZINPOL 1519 from Zinchem Corp., having an acid number of 93), 50 parts of ethyl alcohol, 150 parts of water and 40 parts of the furnace black PRINTEX 200 (Degussa) ("Printex" is a Registered Trade Mark) is ground in a 1 1 batch sand mill for 13 hours.

Thereafter, the ground material is diluted with 100 parts of water, separated off from the grinding auxiliary and introduced as a thin jet into a solution, containing a small proportion of hydrochloric acid, of 1,000 parts of water and 20 parts by volume of a 15% strength hydrochloric acid. The pigment formulation precipitates in the form of coarse grains. These are filtered off, washed until free from acid and salts, dried at 60 70 in vacuo and then pressed through a + mm sieve.

A black formulation with a pigment content of 50% is obtained, which disperses perfectly in the printing inks of Application Examples a to h and gives, for example on paper and aluminium foil, glossy prints which are intensely coloured.

Example 8 Analogously to Example la, 333 parts of AQUAHYDE 100 (30% of acrylic resin) are precipitated as the free acid in a kneader. After drying, the resulting melt is kneaded in the presence of 600 parts of finely ground sodium chloride and 70 parts of diacetone-alcohol with 100 parts of crude -copper phthalocyanine blue for 4+ hours. The kneading composition is then granulated and worked up analogously to Example lc. A blue formulation with a pigment content of 50% is obtained which has outstanding dispersion and coloristic properties.

Example 9 a) 117 parts of a 30% strength purely aqueous solution of AQUAHYDE 3013 (Lawter Chemicals, acid number 73) are precipitated with 8.5 parts by volume of 25% strength acetic acid in a kneader analogously to Example la.

b) The dry melt is kneaded with 35 parts of the indigoid pigment dyestuff of the formula

140 parts of finely ground sodium chloride and 15 parts of diacetone-alcohol for 24 hours at about 60". The kneading composition is broken up with 75 parts by volume of saturated sodium chloride solution and the granules are worked up analogously to Example Ic. A claret-coloured formulation with a pigment content of 50% is obtained, which disperses perfectly in the printing inks of Application Examples a to h and gives, for example on paper and aluminium foils, glossy prints which are intensely coloured.

Example 10 35 parts of the yellow isoindolinone pigment of the formula

35 parts of a solid resin JONCRYL 677 ("Joncryl" is a Registered Trade Mark of Johnson Wax, acid number 190), which is soluble in aqueous alkalis, 210 parts of finely ground sodium chloride and 25 parts of diacetone-alcohol are kneaded in a kneader for 3 hours at about 60".

The kneading composition is then granulated analogously Example 9b and worked up as in Example lc.

A yellow formulation is obtained which has excellent coloristic and dispersing properties when it is incorporated into the printing inks of Application Examples a to h.

Example 11 The procedure is analogous to Example 10, but the acrylic resin AQUAHYDE 100, separated out in the solid form in Example 2a and dried, is used as the carrier resin instead of JONCRYL 677.

A yellow formulation is obtained, which has excellent dispersing and coloristic properties when it is incorporated into the printing inks of Application Examples a to h.

Example 12 95 parts of the red disazo dyestuff of the formula

95 parts of an acid acrylic copolymer (acid number 72-76, softening point 106O), 570 parts of finely ground sodium chloride and 75 parts of diacetone-alcohol are kneaded in a kneader for 4 hours.

The breaking up of the kneading composition is effected by adding 250 parts of saturated sodium chloride solution. The addition of 100 parts of ice to the cooled composition completes the granulation.

The granules are worked up as described in Example Ic.

A blush-tinged red formulation with a content of pigment of 50% is obtained, which disperses perfectly in the printing inks a-h and gives, for example on paper and aluminium foil, glossy prints which are intensely coloured.

Example 13 The procedure is analogous to Example 12, but using 95 parts of blue ss-copper phthalocyanine pigment (crude material). The kneading composition is kneaded for 6 hours at about 60".

The composition is then granulated as described in Example 12 and worked up analogously to Example Ic.

A blue formulation with a content of pigment of 50% is obtained, which has outstanding dispersing and coloristic properties.

Example 14 90 parts of the furnace black PRINTEX 300 (Degussa), 90 parts of an acid acrylic copolymer (acid number 74, softening point 115 ), 450 parts of finely ground sodium chloride and 80 parts of diacetone-alcohol are kneaded in a kneader for 3 hours at about 600.

The kneading composition is then broken up analogously to Example 12 and the granules are worked up analogously to Example Ic.

A black formulation with a content of pigment of 50% is obtained, which dispersed perfectly in the printing inks of Application Examples a-h and gives, for example on paper and aluminium foils, glossy prints which are deeply coloured.

Example 15 a) The following aqueous pigment/binder mixture is prepared in a 3 litre beaker provided with a toothed disc stirrer of 6 cm diameter: 450 parts of a water-moist press cake containing 27.6% of solids, corresponding to 124 parts of the red disazo dyestuff of the formula

413 parts of an aqueous/alcoholic solution which contains 30% of a watersoluble acrylic resin in the form of its amine salt (AQUAHYDE 100, Lawter Chemicals), corresponding to 124 parts of dry solid resin, and 600 parts of water.

the suspension is stirred for 1 hour at a stirrer speed of 1,200--1,400 rpm.

The homogeneously dispersed pigment/binder suspension is introduced in a thin iet into an aqueous solution, containing a small proportion Qf hydrochloric acid, 3,000 parts by volume of water and 65 parts by volume of a 15% strength hydrochloric acid, whilst stirring thoroughly.

The pigment formulation precursor precipitates in the granular form which can be readily filtered, and is filtered off, washed until free from acid and salts and dried at 800 in vacuo.

b) 240 g of this dry pigment formulation precursor, 480 parts of finely ground sodium chloride and 85 parts of diacetone-alcohol are kneaded in a kneader for 4 hours at about 60".

The kneading composition is then broken up analogously to Example 12 and worked up as described in Example lc.

A red formulation, intensely coloured, with a content of pigment of 50% is obtained, which disperses perfectly in the printing inks a-h and gives, for example on paper and aluminium foils, glossy bright red prints.

Example 16 a) A mixture of 206 parts of an aqueous/alcoholic solution which contains 30% of an acrylic resin in the form of its amine salt (corresponding to 62 parts of the solid resin AQUAHYDE 100, Lawter Chemicals), 62 parts of carbon black Printex 300 (Degussa) and 382 parts of water are ground in a 2 1 batch bead mill for 3 hours.

After separating off the grinding auxiliaries, the ground material is then introduced in a thin jet into an aqueous solution, containing a small proportion of hydrochloric acid, of 1,000 parts of water and 30 parts by volume of 15% strength hydrochloric acid, whilst stirring thoroughly.

The formulation precursor which has precipitated is filtered off, as described in Example 15, washed free from salts and acid and dried at 800 in vacuo.

b) 70 parts of the dried and powdered formulation precursor are introduced in portions into a kneader, preheated to 1450. The melt formed has a temperature of 138". This melt is kneaded for 20 minutes at an external temperature of 115 , and the composition temperature is then 128--133".

The composition is allowed to cool, the solidified melt is broken up in the kneader and the brittle material is powdered whilst the kneader arms are running.

The resulting powder is advantageously pressed through a 0.5 mm sieve.

This batch melt kneading can also be carried out as a continuously running melt kneading process on single-shaft or twin-shaft kneading machines or extruders.

A fine black formulation powder with a content of pigment of 50% is obtained, which disperses perfectly in the printing inks a-h and gives, for example on paper or aluminium foils, glossy prints which are deeply coloured.

The following are mentioned as application examples of pigment/acrylic resin formulations for aqueous and alcoholic printing inks: a. Gravure printing ink for PVC wallpapers and paper wall coverings 8% of a 50% strength pigment formulation according to Example 12, 36% of Geon 351 ("Geon is a Registered Trade Mark and "Geon 351 is an aqueous PVC copolymer emulsion with a solids content of 56%, B.F. Goodrich Chemical Company), 4% of ZINPOL 1519 (40% strength acrylic resin solution in water/isopropanol 1:1, pH 8.5, Zinchem U.S.A), 30% of water, 20% of isopropanol and 2% of 25% strength ammonia.

The printing ink exhibits a printing quality which is superior to organic vinyl copolymer printing inks and also possesses good adhesion to wallpapers coated with PVC. Furthermore, the prints are distinguished by a good ability to be embossed and good abrasion resistance (dry and wet) as well as good resistance to soaps and detergents.

b) Gravure printing ink for decorative paper with melamine resin laminates 10% of a 50% strength pigment formulation according to Example 10, 40 /O of AQUAHYDE 100 (30% of a water-soluble acrylic resin present as the amine salt, Lawter Chemicals, U.S.A.), 20% of isopropanol, 28% of ethylene glycol monoethyl ether and 2% of 25% strength ammonia.

The prints possess a good resistance to bleeding on subsequent impregnation with melamine/formaldehyde precondensate solutions and exhibit good resistances to heat on pressing at 1500C as well as a good fastness to light in the laminate sheets.

c. Flexographic printing ink 1. 15% of a 50 /" strength pigment formulation according to Example 6, 10% of ZINPOL 14 (wax emulsion, ZINCHEM, U.S.A.), 20% of ZINPOL 259 (styrenated shellac emulsion, ZINCHEM), 3% of morpholine and 52% of water.

II. 15% of a 50% strength pigment formulation according to Example 10, 5% of JONCRYL 677 (acrylic resin, acid number about 180---190, Johnson Wax, U.S.A.), 4% of morpholine, 33% of water and 33% of 95% strength ethanol.

These printing inks are suitable for printing paper, prelacquered aluminium foil and corona-pretreated polyethylene film.

d. Paint for the roller lacquering of soft aluminium foil 5% of a 50% strength pigment formulation according to Example 6, 14% of MOWITAL B30H (polyvinylbutyral; "Mowital" is a Registered Trade Mark of Hoechst, Germany), 1% of dibutyl phthalate, 70% of 95% strength ethanol and 10% of ethylglycol.

The paint, applied on a lacquering machine by the roller application process, exhibits a good adhesion and flexibility, high transparency, good resistance to bleeding and good fastness to light.

e. Flexographic printing ink for polyethylene and paper 15% of a 50% strength pigment formulation according to Example 6, 5% of CAP 504--0.2 (cellulose aceto-propionate, Eastman-Kodak, U.S.A.), 15% of water and 65% of isopropanol.

The printing ink is distinguished by rapid surface drying and a good adhesion to corona-pretreated polyethylene film.

f. Dry offset printing ink for metal 20% of a 50% strength pigment formulation according to Example 6, 30% of SETALYN AM 541 (acrylic monomer, Kunsthars-fabriek synthese B.V., Holland), 44% of SETALYN AP 561 (acrylic prepolymer, Kunstharsfabriek Synthese B.V., Holland), 3% of Michler's ketone and 3% of benzophenone.

The printing ink can be printed onto a prelacquered steel sheet by dry offset printing and cured with UV irradiation. The prints have a high gloss and good resistances to water.

g. Gravure printing ink for various printable materials 10% of a 50% strength pigment formulation according to Example 6, 18% of ZINPOL 1519 (50% strength acrylic resin in isopropanol, ZINCHEM), 10% of water, 60% of isopropanol and 2% of 25% strength ammonia.

The printing ink exhibits a good adhesion to the following materials: plasticised PVC, rigid PVC, Cellophane X, Cellophane P, pretreated polyethylene film and prelacquered aluminium foil.

The printing ink can be diluted with water or with alcohols.

h. 2-Component lacquer for lacquering paper by gravare printing 10% of a 50% strength pigment formulation according to Example 6, 30% of AQUAHYDE 100 (Lawter Chemicals), 5% of CIBAMIN M 100 (hexamethylolmelamine; "Cibamin" is a Registered Trade Mark of Ciba-Geigy AG, Switzerland), 2% of morpholine, 52.5% of water/ethanol 1:1 and 0.5% of ptoluenesulphonic acid.

After drying for 2 minutes at 1300C, a lacquering with very good resistance to water and ethanol, a very high softening point, good stability to heat-sealing and good resistance to chemicals is obtained.

WHAT WE CLAIM IS: 1. Solid pigment formulation for printing ink and paint systems, containing a pigment and an acid resin, which contains 30 to 70% by weight of a pigment and 70 to 30% by weight of a polyacrylic resin which is a polymer or copolymer of an acrylic alkyl ester and/or methacrylic alkyl ester containing carboxylic acid groups.

2. Pigment formulation according to Claim 1, which contains no surface-active compound.

3. Pigment formulation according to Claims 1 or 2, in which the polyacrylic resin has an acid number of 30 to 300.

4. Pigment formulation according to any of the preceding claims, in which the polyacrylic resin has an acid number of 50 to 150.

5. Pigment formulation according to any of the preceding claims, which contains one or more auxiliaries, such as plasticisers, waxes, stabilisers and fillers.

6. Pigment formulation according to Claim 1, substantially as described in any of Examples 1 to 16.

7. Process for the manufacture of the pigment formulation according to Claim 1, wherein a pigment is added to and dispersed in an alkaline solution of a polyacrylic resin containing carboxylic acid groups and the pigment formulation is precipitated by acidifying the solution.

8. Process for the manufacture of the pigment formulation according to Claim 1, wherein an aqueous-alcoholic solution, containing a pigment, of a polyacrylic resin containing carboxylic acid groups is atomised.

9. Process for the manufacture of the pigment formulation according to Claim 1, wherein a water-insoluble polyacrylic resin containing carboxylic acid groups is mixed with a pigment in a kneader.

10. Process for the manufacture of a pigment formulation according to Claim 1 substantially as described in any of Examples 1 to 16.

I 1. Pigment formulation according to Claim I whenever prepared by a process according to any of Claims 7 to 10.

12. An aqueous, aqueous-alcoholic, alcoholic or solvent-free printing ink and paint system, having incorporated therein a pigment formulation according to any of Claims 1 to 6 and 11.

13. Chemically cured or dried printing ink and paint system based on monomeric and/or prepolymeric compounds, having incorporated therein a pigment formulation according to any of Claims 1 to 6 and 11.

14. Process for the manufacture of a printing ink and/or paint, wherein the pigment formulation according to Claim 1 is incorporated, in water, an aqueous alcohol or an alcohol optionally with the addition of ammonia or in amine, into the used ink or paint material, the carrier resin being dissolved and the pigment being finely dispersed in the application medium.

15. Process according to Claim 14 wherein the amine is a mono-, di- or trialkylamine, an alkanolamine or a heterocyclic amine.

16. Process according to Claim 15 wherein the heterocyclic amine is morpholine or piperazine.

17. Process according to Claim 14 substantially as described in any of Examples a to h.

18. An aqueous, aqueous-alcoholic, alcoholic or solvent-free printing ink and paint system according to Claim 12 whenever prepared by a process according to any of Claims 14 to 17.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. AQUAHYDE 100 (Lawter Chemicals), 5% of CIBAMIN M 100 (hexamethylolmelamine; "Cibamin" is a Registered Trade Mark of Ciba-Geigy AG, Switzerland), 2% of morpholine, 52.5% of water/ethanol 1:1 and 0.5% of ptoluenesulphonic acid. After drying for 2 minutes at 1300C, a lacquering with very good resistance to water and ethanol, a very high softening point, good stability to heat-sealing and good resistance to chemicals is obtained. WHAT WE CLAIM IS:

1. Solid pigment formulation for printing ink and paint systems, containing a pigment and an acid resin, which contains 30 to 70% by weight of a pigment and 70 to 30% by weight of a polyacrylic resin which is a polymer or copolymer of an acrylic alkyl ester and/or methacrylic alkyl ester containing carboxylic acid groups.