CA1111169A

CA1111169A - Solid pigment formulation for printing ink and paint systems

Info

Publication number: CA1111169A
Application number: CA281,801A
Authority: CA
Inventors: Bernhard Rutimeyer; Gunther Zwahlen; Peter Eckert
Original assignee: Ciba Geigy Investments Ltd
Current assignee: BASF Schweiz AG
Priority date: 1976-07-05
Filing date: 1977-06-30
Publication date: 1981-10-20
Also published as: AU514994B2; FR2357615B1; ES460376A1; BR7704360A; DE2729892C2; FR2357615A1; JPS6111979B2; DK298977A; JPS536333A; GB1588777A; SE433498B; NL7707333A; IT1086249B; SE7707735L; AU2671977A; DE2729892A1

Abstract

Abstract of the Disclosure Solid pigment formulation for printing ink and paint systems, which contains 10 to 90% by weight of a pigment and 90 to 10% by weight of a polyacrylic resin containing carboxy-lic acid group and which imparts to the printing inks and paints excellent adhesion to paper, metals and plastics.

Description

The invention relates to a new advan-tageous solid pig-ment 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 formula-tions 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. ~Iowever, 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 9 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 water-resistance of the films and by high tinctorial strength and gloss. Co-using a surface-active 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 formula-tion according to the inven-tion contains 10 to 90% by weight of pigment and 90 to 10% by weight of a polyacrylic resin containing carboxylic acid groups, preferably 30 to 70% by weight of pigment and 70 to 30% by weight of polyacrylic resin. 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, in particular, those which are obtained by the polymerisation of acrylic acid or of acrylic acid and other acrylic monomers, such as, for example, acrylates. However, it is also possible to use other poly-acrylic compounds, such as polymeric methacrylic or crotonic acids, or similar polymerisable carboxylic acids, if they contain a fairly large numberof carboxylic acidgroups as sub-stituents. It is important, above all, that the poly-acrylic 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, anthra-quinone, perinone, indigoid, thioindigoid, dioxazine, iso-indolinone, perylene, azo and quinacridone series and , . ~ :'' , . ' .

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metal complexes, fQr example of azo, azomethine or methine dyestuffs, 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 other a w~iliaries, 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 precipita-tion by acidifying, by atomising the pigment/resin solution, or continuously or discontinuously in kneading machines by mixing the water-insoluble acid resin with the pigment.
When the pigment formulation is manufactured by the first-mentioned process, alkalis can also be used and are subsequently neutral-ised. On the other hand, for the application 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 manu~acture is carried out in a kneader, it is possible to precipitate the polyacrylic resin from the aqueous-ammoniacal solution by acidi~ying 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.

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The manufacture of the pigment formulation preferablytakes 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, amino-carboxylic 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 alkylol-amine 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 polyacr~lic resin having an acid number of 60 to 200, Resins with an acid number of 50-120 are preferably suitable for formulations which give printing inks, which adhere particularly well, for, for example, PVC.
The formulations according to the invention can be used for the most diverse prirlting 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 aluminium foils, of plasticised and rigid PVC, of polyamide, polystyrene and cellulose acetate film, of cellophane and lacquered grades of cellophane, of corona-pretreated polyethylene and polyester films and of .. . . . . .
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supports coated with polyvinylidene chloride. The print-ing 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 con-centrations are about 5 to 20% by weight of pure organic pig-ment and are correspondingly higher in the case o~ 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 varrl~sh, 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 manu-~actured in this manner.

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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 pipera~ine, into the desired polymer5the carrier resin being dissolved and the pig-ment being finely dispersed in -the application medium.-In the examples which follow, unless otherwise indica-ted the parts denote parts by weight, the percentages denote percentages by weight and the temperatures are given in degrees centigrade.
Example 1 a) 4 parts of an aqueous/alcoholic solution which con-tains 30% of a water-soluble 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 - L~o (pH range ~.R-5~8). During this procedure, about 220-240 parts of water separate out and are decanted, The residual water is removed in vacuo and at a tem-perature of 90, and the carrier resin is then present as a viscous melt and corresponds to an amount to be processed of 120 g.
b') 480 parts of finely ground sodium chloride, 120 parts .
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~ 6 9 of the yellow disazo pigment of the formula ~ NI~CO ~ U = N ~ Cl~ ~ C
Cl CH CO~ o ~ CH3 Cl and 90 parts of diacetone-alcohol are introduced into the kneader, warmed to 90,and the kneading composition rapidly formed is kneaded for 3 hours at about 60.
c) The kneading composi-tion 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 sub-jected 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 80. The dried material is advantageously pressed through a sieve of 0.5 mm mesh width. A yellow formulation with a pigment content of 50% is obtained, which disperses perfectly in the prin-ting inks of Application Examples a to h and gives, for example on paper and aluminium foil, glossy prints which are intensely coloured.
Ei~u~ 2 a) 500 parts of an aqueous/alcoholic solution which con-tains 30% of a water-soluble 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 .. ~ -:- - , ~..................... . .
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jet into an aqueous solution, containing a 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 acidA The filter cake is dried at 30 in ~acuo and gives an only slightly sintered solid resin.
b) 35 parts of the yellow disazo pigment used in E`xample 1, 17.5 parts of the solid acrylic resin obtained according to process 2a, 140 parts of finely ground sodiurn chloride and 25 ,,parts of diacetone-alcohol are kneaded in a kneader for 2 hours at about 60, The kneading composition is ~roken up by adding 25 parts of ice and the granules are worked up analo-gously to Example lc. 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 forrnula CH3 ~ NH~O C1 , ~ONH ~ - CH3 ~H-N--N ~ ~ N=N-~H
CH30C, COCH3 35 parts of AQUAHYDE 100, isolated as a solid resin according to Exarnple 2a, 140 g of finely ground sodiurrl chloride and 15 parts of diacetone-alcohol are kneaded in a kneader for 2 hours _ 9 _ ., .... .. , ~
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at about 50~ 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 lc.
A reddish-tinged yellow formulation is obtained, which can be disp~rsed perfectly in the printing inks of Application Examples a to h and g~ves, 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 aqueous-alcholic solution are precipita-ted as the free acid in a kneader and dried.
b) 540 parts of finely ground sodiurn chloride 135 parts of the scarlet red disazo pigment of the formula NHCO OH C1 Cl HO CONH ~
C ~ N=N ~ =N ~ Cl .
and 70 parts o:f diacetone-alcohol are then in-troduced 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 to Example lc, A scarlet red formulation is obtained, which disperses perfectly in the printing inks of Application Exarnples a -to h and gives, for exarnple on paper and aluminium foil, glossy . .

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prints which are intensely coloured.
Exa~ple 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 par-ts 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 installa-tion at an air inlet tempera-ture of about 200 and an air outlet temperature of about 85-95, A fine yello~ powder formulation with a pig-ment content of 66.6% is obtained, which has the same proper-ties as the formulation described in Example 1.
Example 6 a) 35 parts of the red disazo pigment of the formula Cl HO CONH ~ NHC ~ H C
~N =N ~ C . ~N-N ~

35 parts of AQIJAHYDE 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 1~
hours at about 60. The kneading composition is broken up .

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with 20 parts by volume of about 40/0 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 lc. 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, sus-pended in 2,000 parts of wa-ter, 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 1 hour. The granules are then filtered off, washed until free from acid and salts, dried at 60-70 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.
~xample~ 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) is ground in a 1 l 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% streng-th hydrochloric acid.
The pigment formulation precipitates in the form of coarse grains. These are fil-tered 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 Exarnples 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 acrylicresin)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 phthalocy~nine 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.
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a) 117 parts of a 30% strength purely aqueous solution of AQUAHYDE 3013 (Lawter Chemicals, acid number 73) are precipi-tated 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 Cl Cl '~

C1 Cl.
140 parts of finely ground sodium chloride and 15 parts of diacetone-alcohol for 2~ 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 lc, A claret-coloured formulation with a pigment con-ten-t of 50% is ob-tained, which disperses per-fectly 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 Cl O O C1 C~ ~Cl 35 parts of a solid resin JONCRYL 677 (Johnson Wax, acid number 190), which is soluble in aqueous alkalis, 210 parts of finely ground sodium chloride and 25 parts of diacetone-alco-hol are kneaded in a kneader for 3 hours at about 60.
The kneading composition is then granulated analogously .
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;9 to 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 Cl CH3 HO CONH ~ NHCO OH C ~
~N = N~ C1 ~ ~ CO

~13C-CHH3C-CH

95 parts of an acid acrylic copolymer (acid number 72-76, softening point 106), 570 parts of finely ground sodium chloride and 75 parts of diacetone-alcohol are kneaded in a kneader for 4 hours.
The breaking up o~ the kneading composition is q~ 69 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 lc.
A bluish-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 al~minium foil, glossy prints which are intensely coloured.
Example 13 The procedure is analogous to Example 12, but using 95 parts of blue ~-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 lc.
A blue formulation with a content of pigment of 50% is obtained, which has outstanding dispersing and coloristic properties.
LExample 14 90 parts of the furnac0 black PRINTEX 300 (Degussa), 90 parts of an acid acrylic copolymer (acid number 74, so~tening point 115), 450 parts of finely ground sodium chloride and 80 parts of diacetone-alcohol are kneaded in a kneader for ~ hours at about 60.
The kneading composition is then broken up analogously to Example 12 and the granules are worked up analogously to Example lc.

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. A black formulation wi-th a content of pigment of 50%
is obtained, which disperses perfec-tly in the printing inks of Application Examples a-h and gives, for example on paper and alumini~m foils, glossy prints which are deeply coloured.
Example 15 a) The following aqueous pigment/binder mixture is pre- -pared in a 3 litre beaker provided with a ~too-thed 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 reddisazo dye-stuff o~ the formula CH3 HO ~ CONH ~ NHCO~ OH H3C
~ N = N ~ CH3 ~ N - N
ClCH~CH~OCO ~ ~ CCH2CH2 413 parts of an aqueous/alcoholic solution which con-tains 30% of a water-soluble acrylic resin in the form of i.ts 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 ls introduced in a thin jet into an aqueous solution, contain-ing a small proportion of hydrochloric acid, of 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 ff t washed until free from acid and salts and dried at 80 in vacuo, b~ 240 g of this dry pigment formulation precursor, 480 parts of finely ground sodium chloride and 85 part.s of diace-tone-alcohol are kneaded in a kneader for 4 hours at about 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 solu- ~ .
tion which contains 30% of an acrylic resin in the form of its amine salt (co:rresponding to 62 parts of the solid resin AQUAHYDE lO0, Lawter Chemicals), 62 parts of carbon black Printex 300 (Degussa) and 382 parts of water are ground in a

2 l 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 l,000 parts of water and 30 parts by volume of 15%

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strength hydrochloric acid, whilst s-tirring thoroughly.
The formulation precursor which has precipitated is filtered off, as described in Example 15, washed free from salts and acid and dried at 80 in vacuo.
b) 70 parts of the dried and powdered formulation pre-cursor are introduced in portions into a kneader, prehea-ted to 145. 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 result-ing 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 pig-ment of 50% is obtained, which disperses perfectly in the printing inks a-h and gives, for example on paper or alwninium 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. Gravureprinting_ink for PVC wallpapers and~aper wall coverings 8% of a 50% strength pigment formulation according to Example 12, 36% of Geon 351 (aqueous PVC copolymer emulsion with a solids content of 56%, B.F, Goodrich Chemical Company), , :

~ 9 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 adhes on to wallpapers coated with P~C.
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 printin~ ink for decorative paper with melamine resin laminates 10% of a 50% strength pigment formulation according to Example 10, 40% 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 preconden-sate solutions and exhibit good resistances to heat on press-ing at 150C a~, well as a goo~ fastness to light in the laminate sheets.
c. Flexographic Printin~ ink I. 15% o~ a 50% strength pigment formulation according to Example 6, 10% of ZINPOL 14 (wax emulsion, ZINCHEM, U.S.A.), 20% of ZINPOL 25~ (styrena-ted 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 re~in, 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 lacquerin~ of soft alu~inium foil 5% of a 50% strength pigment formulation according to Example 6, 14% of MOWITAL B30H (poly~inylbutyral, Hoechst, Germany), 1% of dibutyl phthalate, 70% of 95% strength ethanol and 10% of ethylglycol.
The pain-t, applied on a lacquering machine by the roller application process, exhibits a good adhesion and flexibility, high transparency, good resistance to bleeding and good fast-ness to light.
e. Flexo~raphic printin~ ink for pol~ethylene 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 printin~ ink for metal ~ 0% of a 50% strength pigment formulation according to Example 6, 30% of SETALYN AM 541 (acrylic monomer~ Kunsthars-fabriek Synthese B.~., Holland), 44% of SETALYN AP 561 (acrylic prepolymer, Kunstharsfabriek Synthese BoV~ ~ Holland), 3% of '~ , -, .:, ~ 9 Michler'sketone and 3% of benzophenone The printing ink can be printed onto a prelacquered steel sheet by dry offset printing and cured with W irradia-tion The prints have a high gloss and good resistances to water.
g~ Gravure printin~ ink for various printable materials 10% of a 50~0 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 lacquerin~ Paper by ~ravure printin~
10% of a 50% strength pigment formulation according to Example 6, 30% of AQUAHYDE 100 (Lawter Chemicals), 5% of CIBAMIN M 100 ~hexamethylolmelamine, Ciba-Geigy AG, Switzerland), 2% of morpholine, 52.5% of water/ethanol 1:1 and 0.5% of p-toluenesulphonic acid.
After drying for 2 minutes at 130C, a lacquering with very good resistance to water and ethanol, a very high soften-ing point, good stability to heat-sealing and good resistance to chemicals is obtained.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Solid pigment formulation for printing ink and paint systems, containing a pigment and an acid resin, which con-tains 10 to 90% by weight of a pigment and 90 to 10% by weight of a polyacrylic resin containing carboxylic acid groups.

2. Pigment formulation according to Claim 1, which contains 30 to 70% by weight of pigment and 70 to 30% by weight of polyacrylic resin containing carboxylic acid groups.

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

4. Pigment formulation according to Claim 1, in which the polyacrylic resin has an acid number of 50 to 150.

5. Pigment formulation according to Claim 1, which contains one or more auxiliaries.

6. 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 with the addition of ammonia, an amine, an alkanolamine or a heterocyclic amine, into the desired polymer, the carrier resin being dissolved and the pigment being finely dispersed in the application medium.