KR20070017475A - Azo pigment preparations for packaging gravure and flexographic printing - Google Patents

Abstract

The present invention comprises (a) at least one azo pigment, (b) a colophonium having a acid value of at least 320 mgKOH / g or a modified colophonium-based resin, and (c) an ammonium salt of sulfonated diaryl yellow pigment. It relates to an azo pigment formulation.

Description

AZO PIGMENT PREPARATIONS FOR PACKAGING GRAVURE AND FLEXOGRAPHIC PRINTING}

The present invention relates to azo pigments which have been formulated with high acid value specific natural resin derivatives and have improved performance properties, in particular improved flowability, when used in concentrates, for example packaging gravure printing and grid printing inks.

Printing inks, in particular packaging gravure and griddle printing inks, are dispersed in varnishes and solvents at high pigment concentrations. The concentrate produced for the printing ink can be further processed to yield a ready-produced printing ink. Concentrates for printing inks generally have a pigment content of up to 35%. After dispersion, the concentrate is usually stored in a specific container in between, before further processing. The time delay due to storage before conversion to printing ink produces in most cases a concentrate of the printing ink that regenerates the gel structure. This gel structure regeneration is due to the high concentration and interaction of pigment particles bound to each other. In extreme cases, gel structure regeneration causes the ink concentrate to thicken and requires thinning of the solvent and thickened concentrate. Since the change in structure is time dependent, this fluidity effect is called thixotropy.

EP-A-0 796 900 discloses a pigment formulation for water-thinnable printing inks containing a resin having an acid value of 300 mg KOH / g or less. However, in the case of azo pigments, these formulations still exhibit certain thixotropic properties.

It is an object of the present invention to formulate azo pigments which not only have good coloring properties, for example gloss, but are also flowable, in particular during the production of printing ink concentrates, further processing and storage.

The inventors have surprisingly found that the object of the present invention is achieved by the following azo pigment formulation.

Accordingly, the present invention provides azo pigment formulations comprising:

(a) at least one azo pigment, preferably a diaryl yellow pigment,

(b) a resin based on rosin or modified rosin and having an acid value of at least 320 mgKOH / g, preferably at least 330 mgKOH / g; and

(c) Ammonium salts of sulfonated diaryl yellow pigments.

Preferred azo pigment formulations consist essentially of the following ingredients, based on the total weight of the azo pigment formulation:

50% to 90% by weight, in particular 60% to 80% by weight of component (a),

5% to 45% by weight, in particular 10% to 38% by weight of component (b) and

From 0.1% to 20% by weight, in particular from 2% to 10% by weight of component (c).

Useful azo pigments (a) include monoazo, disazo, β-naphthol, Naphtol AS, acetoacetylamino-benzimidazolone, acetoacetylamino-quinazolinidaone and acetoacetylamino-quinoxalindaion ion pigments. Include.

Useful azo pigments include, for example, aniline, 2-nitroaniline, methyl anthranilate, 2,5-dichloroaniline, 2-methyl-4-chloroaniline, 2-trifluoromethyl-4-chloroaniline, 2,4,5-trichloroaniline; 3-amino-4-methylbenzamide, 4-amino-3-chloro-N'-methylbenzamide, o-toluidine, o-diisididine, 2,2 ', 5,5'-tetrachlorobenzidine, 2 And those having an amine component selected from the group consisting of -amino-5-methylbenzenesulfonic acid and 2-amino-4-chloro-5-methylbenzenesulfonic acid. The following amine components are of particular importance in azo pigments: 4-methyl-2-nitrophenylamine, 4-chloro-2-nitrophenylamine, 3,3'-dichlorobiphenyl-4,4'-diamine , 3,3-dimethylbiphenyl-4,4'-diamine, 4-methoxy-2-nitrophenylamine, 2-methoxy-4-nitrophenylamine, 4-amino-2,5- Dimethoxy-N-phenylbenzenesulfonamide, dimethyl 5-aminoisophthalate, anthranilic acid, 2-trifluoromethylphenylamine, dimethyl 2-aminoterephthalate, 1,2-bis (2-aminophenoxy) ethane , 2-amino-4-chloro-5-methylbenzenesulfonic acid, 2-methoxyphenylamine, 4- (4-aminobenzoylamino) benzamide, 2,4-dinitrophenylamine, 3-amino-4 -Chlorobenzamide, 4-nitrophenylamine, 2,5-dichlorophenylamine, 4-methyl-2-nitrophenylamine, 2-chloro-4-nitrophenylamine, 2-methyl-5-knight Rophenylamine, 2-methyl-4-nitrophenyla , 2-methyl-5-nitrophenylamine, 2-amino-4-chloro-5-methylbenzenesulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 2-amino-5-chloro-4-methylbenzenesulfur Phonic acid, 2-amino-5-chloro-4-methylbenzenesulfonic acid, 2-amino-5-methylbenzenesulfonic acid, 2,4,5-trichlorophenylamine, 3-amino-4-methoxy-N- Phenylbenzamide, 4-aminobenzamide, methyl 2-aminobenzoate, 4-amino-5-methoxy-2, N-dimethylbenzenesulfonamide, monomethyl 2-amino-N- (2,5-di Chlorophenyl) terephthalate, butyl 2-aminobenzoate, 2-chloro-5-trifluoromethylphenylamine, 4- (3-amino-4-methylbenzoylamino) benzenesulfonic acid, 4-amino-2,5- Dichloro-N-methylbenzenesulfonamide, 4-amino-2,5-dichloro-N, N-dimethylbenzenesulfonamide, 6-amino-1H-quinazolin-2,4-dione, 4- ( 3-amino-4-methoxybenzoylamino) benzamide and 4-amino-2,5-dimethoxy-N-methyl Benzene-sulfonamide.

Useful azo pigments include, for example, acetoacetarylide of formula (I), 2-hydroxynaphthalene of formula (II), biacetoacetylated diaminophenyl and -biphenyl, wherein the phenyl or biphenyl ring has one , 2, 3 or 4 identical or different radicals CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ , F, Cl, CF ₃ may or may not be substituted), Acetoacetarylide of the binuclear heterocyclic ring of IV and having a binding component selected from the group of pyrazolone of the following formula (V):

[Wherein,

n is a number from 0 to 3,

R ¹ is a C ₁ -C ₄ -alkyl group such as methyl or ethyl; C ₁ -C ₄ -alkoxy groups such as methoxy or ethoxy; Trifluoromethyl group; Nitro groups; Halogen atoms such as fluorine, chlorine or bromine; NHCOCH ₃ group; SO ₃ H group; A SO ₂ NR ¹⁰ R ¹¹ group, wherein R ¹⁰ and R ¹¹ are the same or different and represent hydrogen or C ₁ -C ₄ -alkyl; A COOR ¹⁰ group, wherein R ¹⁰ is as defined above; Or a COONR ¹² R ¹³ group, wherein R ¹² and R ¹³ independently represent hydrogen, C ₁ -C ₄ -alkyl or phenyl, wherein the phenyl ring is C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy , Trifluoromethyl, nitro, halogen, COOR ¹⁰ (R ¹⁰ is as defined above), COONR ¹⁰ R ¹¹ (R ¹⁰ and R ¹¹ are the same or different and as defined above, respectively) One, two or three same or different substituents),

when n is greater than 1, each R ¹ may be the same or different;

[Wherein,

X is hydrogen, a COOH group or a group of formula III],

[Wherein,

n and R ¹ are each as defined above;

[Wherein,

n and R ¹ are each as defined above,

Q ¹ , Q ² and Q ³ are the same or different and N, NR ² , CO, N-CO, NR ² -CO, CO-N, CO-NR ² , CH, N-CH, NR ² -CH, CH-N, CH-NR ² , CH ₂ , N-CH ₂ , NR ² -CH ₂ , CH ₂ -N, CH ₂ -NR ² or SO ₂ , wherein R ² represents a hydrogen atom; C ₁ -C ₄ -alkyl groups such as methyl or ethyl; Or a phenyl group which may be unsubstituted or may be single or multiple substituted by hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, trifluoromethyl, nitro, cyano,

Provided that the combination of two carbon atoms of the phenyl ring with Q ¹ , Q ² and Q ^{3 results} in a saturated or unsaturated five or six membered ring;

[Wherein,

R ³ is a CH ₃ , COOCH ₃ or COOC ₂ H ₅ group,

R ⁴ is CH ₃ , SO ₃ H group or a chlorine atom,

p is a number from 0 to 3,

when p exceeds 1, each R ⁴ may be the same or different].

Diaryl yellow pigments are particularly preferred azo pigments for the purposes of the present invention. Diaryl yellow pigments generally have the structure of formula (I):

Where

Ar ¹ and Ar ² are the same or different and each represents a phenyl group and is unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of halogen, such as chlorine, methyl and methoxy,

X and Y are independently H or Cl.

Preferred yellow pigments for the purposes of the present invention are C.I. Pigment Yellow (PY) 12, 13, 14, 17, 55, 63, 81, 83, 87, 90, 106, 113, 114, 121, 124, 126, 127, 136, 152, 170, 171 , 172, 174, 176 and 188.

Component (b) is preferably a Dieno-Pile component such as a Diels-Alder adduct of rosin and maleic anhydride or fumaric acid, and the rosin is preferably abiotic acid, dehydrobibiic acid It is used in the form of a commercial rosin variant comprising a resin acid selected from the group consisting of laevopimaric acid and palustric acid. Of course, the aforementioned resin acids can also be used by themselves. The Diels-Alder reaction takes place between the laevopimaric acid and the dienophile, which may be formed from other resinic acids, in particular through an equilibrium reaction. Such compounds are known and described in Encyclopedia of Chem. Techn., Vol. 17, 1968, p. 488-490. According to the invention, the resins used have a high acid value of at least 320 mgKOH / g, preferably at least 330 mgKOH / g, in particular at least 340 mgKOH / g. The acid functional groups in the resin are the carboxyl groups of the initial resin acid and the two carboxyl groups or acid anhydride functional groups of the dienophile. Acid anhydride groups can be saponified.

Component (c) may be an ammonium salt, preferably the tetraalkylammonium salt of sulfonated diaryl yellow pigments. The diaryl yellow pigment may be any of the yellow pigments, although PY 12 is particularly preferred. Component (c) should ideally be poorly soluble in water and therefore preferably has only one sulfo group disposed in either the Ar ¹ radical or Ar ² (Formula 1). The alkyl radical of the ammonium ion may be a C ₁ -C ₂₀ -alkyl radical. Preferably, the ammonium ions contain at least one, more preferably two C ₁₀ -C ₂₀ -alkyl radicals. Particularly preferred ammonium ions are dioctadecyldimethylammonium and dihexadecyldimethylammonium. Particularly preferred component (c) is dioctadecyldimethylammonium sulfonate of PY 12. The compounds described as component (c) are known in nature and are disclosed in EP-A-0 076 024.

The azo pigment formulations of the invention further comprise auxiliaries (d) such as dispersants, polyesteramides, anionic, cationic or nonionic surfactants, alcohol oxyalkylates, eg antistatic agents, extenders, standardizers, waxes, antifoams , Dustproof, preservatives, wetting agents, antioxidants, UV absorbers, additionally light-shielding colorants, light stabilizers or combinations thereof. Preference is given to using compounds based on the fatty alcohol-ethylene oxide-propylene oxide adducts described in EP-A-0 587 021. In addition, auxiliaries are typically used in amounts of 0% to 40% by weight, preferably 0.01% to 20% by weight, in particular 0.1% to 10% by weight, based on the total weight of the azo pigment formulation. Shading colorants are typically used in amounts of up to 10 weight percent, typically 0.01 to 10 weight percent, based on the total weight of the azo pigment formulation.

The present invention also provides a method for preparing the azo pigment formulation of the present invention, which method comprises the steps of admixing components (a), (b), (c) and, if necessary, adjuvant (d) with each other. Include. Component (c) and adjuvant (d) are in principle added in at least one step during the preparation of the azo pigment. When component (a) is a diaryl yellow pigment, in the presence of component (c), preferably in an amount of from 0.1% to 20% by weight, based on the total weight of the azo pigment formulation, acetoacetylanilide of the corresponding benzidine By combining with tetrazodiazed diazonium salts, the resulting pigment suspension is combined with an aqueous alkaline solution of component (b) in an amount of 5% to 45% by weight, heated to a temperature of 65 ° C to 150 ° C and acidified It is preferable to precipitate the yellow pigment and to further incorporate adjuvant (d) in an amount of from 0% to 40% by weight, if necessary.

Diazolation of the diazo component, preferably 3,3'-dichlorobenzidine, can be carried out in a conventional manner. The binding component used is advantageously in an aqueous or aqueous-organic suspension, for example acetoacetanilide, acetoacet-o-toluidide, acetoacet-m-toluidide, acetoacet-m-xylida Id, acetoacet-anisidide, acetoacet-2,5-dimethoxy-4-chloroanilide. Azo bonds may occur in the presence of one or more compounds of component (c), in which case the compounds of component (c) may be bound to one or both of the binding suspension or the tetrazonium salt of benzidine as an aqueous suspension or presscake. It may be added, or in this case the reactants described above are added simultaneously. Azo bonds are preferably carried out in an aqueous or aqueous-organic medium, preferably at a pH of 3 to 7, in particular 4 to 6, and at a temperature of 15 ° C. to 30 ° C., in particular 20 ° C. to 30 ° C.

The pigment suspension is then mixed with an aqueous alkali solution of resin (b), for example an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, wherein the amount of resin, based on the pigment, is from 5% to 60% by weight, preferably from 10% to 50% by weight. %to be. The mixture is then heated to a temperature of preferably 65 ° C. to 150 ° C., preferably 80 ° C. to 120 ° C., more preferably 85 ° C. to 100 ° C., for at least 15 minutes, typically 30 minutes to 10 hours. The pH is then preferably adjusted to 2-6, more preferably 3-5 with hydrochloric acid, sulfuric acid or acetic acid and the azo pigment formulation of the invention precipitates. The suspension is filtered, washed to remove salts, dried and polished as necessary.

In a particularly preferred embodiment, 1% to 3% by weight of the fatty alcohol alkoxylates described in the examples of EP-B1-0 587 021 is added to the suspension of azo pigments as adjuvant (d).

The azo pigment formulations of the present invention may be used in natural or synthetic macromolecular organic materials such as plastics, resins, paints, paints, electrophotographic colorants and developers, electret materials, color filters and It is useful for coloring inks, including printing inks, and seeds.

Macromolecular organic materials that can be colored with the azo pigment formulations of the present invention are, for example, cellulose compounds such as cellulose ethers and esters such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural binders, eg Fatty acids, fatty oils, resins and their conversion products, or artificial resins such as polycondensates, polyadducts, addition polymers and addition copolymers, amino resins, in particular urea- and melamine Formaldehyde resins, alkyd resins, acrylic resins, phenoplasts and phenolic resins such as novolak or resole, urea resins, polyvinyls such as polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate Or polyvinyl ethers, polycarbonates, polyolefins such as polystyrene, polyvinyl chloride, poly Ethylene or polypropylene, poly (meth) acrylates and copolymers thereof such as polyacrylic esters or polyacrylonitrile, polyamides, polyesters, polyurethanes, coumarone-indenes and hydrocarbon resins, epoxy resins, Unsaturated synthetic resins (polyesters, acrylates), waxes, aldehydes and ketone resins, gums, rubbers and derivatives thereof and lactice, casein, silicon and silicon resins having various curing mechanisms, individually or in mixtures Exist as. It does not matter whether the aforementioned macromolecular organic compounds are in the form of flexible deformable compositions, melts or in the form of spinning solutions, dispersions, paints, paints or printing inks. Depending on the intended use, it is advantageous to use the azo pigment formulations of the invention in the form of blends or formulations or dispersions. Based on the macromolecular organic material to be colored, the azo pigment formulations of the invention are used in amounts of 0.05% to 30% by weight, preferably 0.1% to 15% by weight. In some cases it is also possible to use crude materials having a BET surface area of more than ² m ² / g, preferably more than 5 m ² / g instead of the corresponding ground and / or finished azo pigment formulations of the invention. Such crude materials can be used to prepare colored concentrates in liquid or solid form, in concentrations of from 5% to 99% by weight, alone or as needed, as a mixture with other crude materials or ready-made pigments.

The azo pigment formulations of the present invention can also be used in electrophotographic toners and developers, for example one- or two-component powder toners (also known as one- or two-way developers), magnetic toners, liquid toners, latex toners. It is useful as a coloring agent in addition polymerization colorant and specialty colorant. Typical colorant binders include additive polymerization, polyaddition and polycondensation resins such as styrene, styrene-acrylates, styrene-butadiene, acrylates, polyesters, phenol-epoxy resins, polysulfones, polyuretes Phosphorus and polyethylene and polypropylene, which may be present separately or in combination, and may each contain additional components such as charge control agents, waxes or flow assistants, or by such additives Can be modified.

The azo pigment formulations of the present invention are electrostatically or electrokinetically used for the surface coating of powders and powder coatings, in particular articles consisting of metals, wood, plastics, glass, ceramics, concrete, textile materials, paper or rubber, for example. It is more useful as a coloring material in powder coatings sprayable with. Useful powder coating resins typically include epoxy resins, carboxyl- and hydroxyl-containing polyester resins, polyurethane and acrylic resins along with conventional curing agents. Combinations of resins may also be used. For example, epoxy resins are frequently used in combination with carboxyl- and hydroxyl-containing polyester resins. Typical curing agent components (depending on the resin system) are, for example, acid anhydrides, imidazoles and dicyandiamides and derivatives thereof, blocked isocyanates, bisacylurethanes, phenols and melamine resins, triglycides Diyl isocyanurate, oxazoline and dicarboxylic acid.

The azo pigment formulations of the present invention are also useful as colorants in inkjet inks on aqueous and non-aqueous bases, microemulsion inks and inks operated by hot melt processes. Inkjet inks generally contain from 0.5% to 15% by weight, preferably from 1.5% to 8% by weight (dry weight) of at least one azo pigment formulation of the invention. Microemulsion inks are based on organic solvents, water and, if desired, additional hydrophobic materials (interface media). Microemulsion inks are generally 0.5% to 15% by weight, preferably 1.5% to 8% by weight of one or more azo pigment formulations of the invention, 5% to 99% by weight of water and 0.5% to 94.5% by weight. % Organic solvent and / or hydrophobic compound. Solvent-based inkjet inks preferably contain 0.5% to 15% by weight of one or more azo pigment formulations of the invention, 85% to 99.5% by weight of organic solvents and / or hydrophobic compounds. Hot melt inks are typically solid at room temperature, liquefied upon heating, and the preferred melting range is based on waxes, fatty acids, fatty alcohols or sulfonamides, from about 60 ° C to about 140 ° C. The hot melt inkjet inks consist essentially of, for example, 20% to 90% by weight of wax and 1% to 10% by weight of one or more of the azo pigment formulations of the present invention. The hot melt inkjet ink contains 0% to 20% by weight of additional polymer ("dyeing solvent"), 0% to 5% by weight of dispersing aid, 0% to 20% by weight of viscosity modifier, 0% to 20% % By weight of plasticizer, 0-10% by weight of tackifying additive, 0-10% by weight of transparency stabilizer (eg to prevent crystallization of wax) and 0-2% by weight It may further comprise% antioxidant.

The azo pigment formulations of the present invention are further useful as colorants for filters and for colorants for electronic inks ("e-inks") or electronic papers ("e-paper"), in addition to sensitization as well as additive generation of color. .

The pigment formulations of the present invention are readily dispersible, for example in conventional gravure printing ink varnishes for gravure and iron plate printing, to provide printing inks with high gloss and particularly good flow properties, ie low thixotropy.

Accordingly, the present invention further provides particularly the use of the disclosed azo pigment formulations for producing printing inks, in particular gravure printing inks and iron plate printing inks.

In the following examples, unless stated otherwise, percentages are by weight.

Example 1

A binding component suspension, pH 5.6, prepared by dissolving 37.6 parts of acetoacet-m-xylideide in 29.4 parts of a 33% aqueous solution of sodium hydroxide in 500 parts of water and then precipitating with 20 parts of 80% acetic acid, EP-A-0 4 parts of the fatty alcohol alkoxylate described in Example 1 of 587 021 and dioctadecyldimethylammonium sulfonate of PY 12 (component (c)) are mixed. The suspension was then subjected to an aqueous solution of about 10% strength 3,3'-dichlorobenzidine tetrazo (3,3'-dichlorobenzidine 23 in dilute HCl) over a period of 2 hours at a temperature of 20 ° C.-25 ° C. and a pH range of 5.6-4. And bis-diazotization of sodium nitrite. The pigment suspension is adjusted to about pH 9 with aqueous sodium hydroxide solution and mixed with a resin solution consisting of 200 parts of water, 22.2 parts of 33% NaOH and 16.9 parts of maleic acid rosin adduct with acid value 360. The temperature of the suspension is raised to 95 ° C. and maintained for 1.5 hours. Diaryl yellow pigment comprising PY 13 at 65 ° C. (cooled with ice), suspension adjusted to pH 5 with hydrochloric acid, filtered, washed to remove salts, dried at 80 ° C. and pin milled. 85 g of formulation is obtained.

Comparative example  1a

Example 1 is repeated except that 85 g of a diaryl yellow pigment formulation comprising P. Y. 13 is obtained using the fumaric acid rosin adduct of acid value 300 as the resin.

Comparative Example 1b

Example 1 is repeated except that 84 g of a diaryl yellow pigment formulation comprising P. Y. 13 is obtained using the maleic acid rosin adduct of acid value 150 as a resin.

Example 2

69.5 parts of N- (4-chloro-2,5-dimethoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide dissolved in 81 parts of 33% aqueous sodium hydroxide solution in 400 parts of water was indirectly precipitated, followed by water 400 3 parts of a fatty alcohol alkoxylate as described in Example 1 of EP-A-0 587 021, prepared by precipitation in 81 parts of 31% hydrochloric acid and 10.2 parts of 80% acetic acid. Mix with The suspension was then followed by an aqueous solution of about 9% strength (3-amino- in dilute HCl) of diazonium chloride of 3-amino-4-methoxy-N-phenyl-benzamide over 1 hour at a temperature of 40 ° C. and a pH range of 5. 44 parts of 4-methoxy-N-phenyl-benzamide and prepared by diazolation of sodium nitrite). The pigment suspension is adjusted to about pH 9 with aqueous sodium hydroxide solution and mixed with 400 parts of water, 32 parts of 33% NaOH and 17 parts of maleic acid rosin adduct with acid number 360. The temperature of the suspension is raised to 95 ° C. and maintained for 2 hours. The suspension is then mixed with 5.5 parts of commercial fatty alcohol alkoxylates described in Example 1 of EP-A-0 587 021. At 65 ° C. (cool with ice), the suspension is adjusted to pH 5 with hydrochloric acid, filtered and washed to remove salts, wherein the presscake is dioctadecyl die of kneaded PY 12 (component (c)) With 1.8 parts of methylammonium sulfonate, dried at 80 ° C. and pin milled to give 134 g of a pigment formulation comprising PR 146.

Comparative Example 2a

Example 2 is repeated except that 136 g of pigment formulation comprising P. R. 146 are obtained using the fumaric acid rosin adduct of acid value 300 as the resin.

Comparative Example 2b

Example 2 is repeated except that 136 g of pigment formulation comprising P. R. 146 are obtained using the maleic acid rosin adduct of acid value 150 as a resin.

Example 3

0.3 parts of nonionic surfactant (nonylphenol oxetylate), 19 parts of 33% aqueous sodium hydroxide solution, 19 parts of 80% acetic acid are added to 600 parts of water with stirring, followed by 64.7 parts of acetoacetanilide at 10 ° C. The suspension is then subjected to an aqueous solution of about 10% 3,3′-dichlorobenzidine tetrazo (3,3′-dichlorobenzidine 23 in dilute HCl) over a period of 2 hours at a temperature of 20 ° C.-25 ° C. and a pH range of 5.6-4. And bisdiazotization of sodium nitrite). The pigment suspension was adjusted to about pH 9 with aqueous sodium hydroxide solution and 0.4 parts of fatty alcohol alkoxylate described in Example 1 of EP-A-0 587 021, 82 parts of water, 6.1 parts of 33% aqueous NaOH and It is mixed with 8.17 parts of maleic acid rosin adduct of acid value 360. The temperature of the suspension is raised to 95 ° C. and maintained for 3 hours. The suspension is then mixed with 1.2 parts of dioctadecyldimethylammonium sulfonate of P. Y. 12 (component (c)). At 65 ° C. (cooled with ice), the suspension is adjusted to pH 5 with hydrochloric acid, filtered, washed to remove salts, dried at 80 ° C. and pin milled to give 65 g of a diaryl yellow pigment formulation comprising PY 12. To obtain.

Comparative Example 3a

Example 3 is repeated except that 65 g of a diaryl yellow pigment formulation comprising P. Y. 12 is obtained using the fumaric acid rosin adduct of acid value 300 as the resin.

Comparative Example 3b

Example 3 is repeated except that 66 g of diaryl yellow pigment formulation comprising P. Y. 12 is obtained using a maleic acid rosin adduct of acid value 150 as the resin.

Example 4

Prepared by indirect precipitation of 49.9 parts of acetoacet (2,5-dimethoxy-4-chloroanilide) dissolved in 25 parts of 33% aqueous sodium hydroxide solution in 200 parts of water, followed by precipitation in 400 parts of water and 23.4 parts of 80% acetic acid. The binding component suspension, pH 5.6, is then mixed with 5 parts of a nonionic surfactant (nonylphenol oxetylate). The suspension was then subjected to an aqueous solution of about 10% strength 3,3'-dichlorobenzidine tetrazo (23 parts DCB in dilute HCl and bisdia of sodium nitrite) over a period of 1 hour at a temperature between 20 ° C and 25 ° C and a pH range of 5.6 to 4.5. Manufactured by coordination). The pigment suspension is adjusted to about pH 9 with aqueous sodium hydroxide solution and mixed with a resin solution consisting of 150 parts of water, 8 parts of NaOH and 9.7 parts of maleic acid rosin adduct with acid value 360. The temperature of the suspension is raised to 95 ° C. and maintained for 0.5 h. The suspension is then mixed with dioctadecyldimethylammonium sulfonate of P. Y. 12 (component (c)). At 65 ° C. (cooled with ice), the suspension is adjusted to pH 4.5 with hydrochloric acid, filtered, washed to remove salts, dried at 70 ° C. and pin milled to give 91 g of diaryl yellow pigment formulation comprising PY 83. To obtain.

Example 4a

Example 4 is repeated except that 92 g of a diaryl yellow pigment formulation comprising P. Y. 83 is obtained using the maleic acid rosin adduct of acid value 340 as a resin.

Comparative Example 4b

Example 4 is repeated except that 91.5 g of a diaryl yellow pigment formulation comprising P. Y. 83 is obtained using the maleic acid rosin adduct of acid value 300 as the resin.

Comparative Example 4c

Example 4 is repeated except that 92 g of a diaryl yellow pigment formulation comprising P. Y. 83 is obtained using the maleic acid rosin adduct of acid value 150 as the resin.

Example 5

A binding component suspension, pH 5.5, prepared by dissolving 39.0 parts of acetoacet-o-anisidide in 48.3 parts of an aqueous 33% sodium hydroxide solution in 200 parts of water and then precipitating with 33 parts of 80% acetic acid, has a temperature of 18 ° C. to 20 ° C. and 5.5 Of about 10% strength aqueous solution of diazonium chloride of 5-nitro-2-aminoanisole over 2 hours in the pH range of 4-4 (30.6 parts of 5-nitro-2-aminoanisole in dilute HCl and sodium nitrite Produced by diazonation). The pigment suspension was adjusted to about pH 9 with aqueous sodium hydroxide solution, a resin solution consisting of 235 parts of water, 17.6 parts of 33% NaOH, 11 parts of maleic acid rosin adduct with acid value 360, and a commercial fatty alcohol alkoxylate having a cloud point of about 40 ° C. Mix with 2 parts. The temperature of the suspension is raised to 95 ° C. and maintained for 0.5 h. At 65 ° C. (cool with ice), the suspension is adjusted to pH 5 with hydrochloric acid, mixed with 5 parts of dioctadecyldimethylammonium sulfonate of PY 12 (component (c)), filtered and washed to give salts. Removed, dried at 80 ° C. and pin milled to yield 85 g of diaryl yellow pigment formulation comprising PY 74.

Comparative Example 5a

Example 5 is repeated except that a fumaric acid rosin adduct of acid value 300 is used as the resin to obtain a diaryl yellow pigment formulation comprising P. Y. 74.

Example

Preparation of Dispersion Concentrate to Measure Thixotropy

This test method is particularly used to test pigments and pigment formulations used to prepare solvent-containing printing ink concentrates with high pigment concentrations:

device:

DIN 53 238 shaking machine: model "Disperser DAS 200 K" discharge stage 1, frequency stage 2 (660 rpm);

Zirconium oxide balls: SAZ bead zirconium oxide 69%, ER 120S, narrow sieve, Ø = 1.0-1.25 mm;

Sieves for separating ink from zirconium oxide balls, eg metal or textile sieves or E-D-Schnellsieb rapid sieve coarse, 1000 μm;

Glass bottle with metal spiral cover (210 ml) Ø 55 mm x 105 mm.

NC alcohol gravure printing varnish of the following composition:

Solvent mixtures of

process:

Vibrating polishing machine

150 g of zirconium oxide balls are filled into a glass bottle, followed by an appropriately weighed-out amount of varnish, solvent mixture and pigment formulation, depending on the pigment formulation (see Table 1). The vial is vibrated on a vibrating machine for 45 minutes (“disperser DAS 200 K” discharge stage 1, frequency stage 2 (660 rpm).

Measurement of the flow curve

The dispersion concentrate is temperature controlled at 23 ° C. Measure the flow curve using a Hake RS 1 Rotational Viscometer:

First rotation (shear ratio γ)-bend-rise, for example from 0 to 250 1 / s in 3 minutes,

Second rotation (shear ratio γ) -bend-fall, for example 0 to 1 / s at 250 in 3 minutes.

Calculation of thixotropy:

The thixotropic value ΔA is measured as the difference in area between the rising curve of the τ axis and the falling curve of the τ axis. This calculation is integrated into the measurement method. According to the invention, very small ΔA values are preferred. The results are summarized in Table 2.

Claims (10)

(a) one or more azo pigments, (b) a resin based on rosin or modified rosin and having an acid value of at least 320 mgKOH / g and (c) ammonium salts of sulfonated diaryl yellow pigments Azo pigment formulation comprising a. The method of claim 1, Azo pigment formulations wherein the azo pigment is a diaryl yellow pigment. The method of claim 2, Diaryl yellow pigments are CI pigment yellow (PY) 12, 13, 14, 17, 55, 63, 81, 83, 87, 90, 106, 113, 114, 121, 124, 126, 127, 136, 152, 170 , 171, 172, 174, 176 and 188 and combinations thereof, azo pigment formulations. The method according to any one of claims 1 to 3, An azo pigment formulation in which the resin has an acid value of at least 330 mgKOH / g. The method according to any one of claims 1 to 4, Azo pigment formulations wherein the resin is a Diels-Alder adduct of rosin and maleic anhydride or fumaric acid. The method according to any one of claims 1 to 5, Azo pigment formulation wherein component (c) is dioctadecyldimethylammonium sulfonate of P. Y. 12. The method according to any one of claims 1 to 6, Based on the total weight of the azo pigment formulation, 50% to 90% by weight of component (a), 5% to 45% by weight of component (b), From 0.1% to 20% by weight of component (c) and In addition, from 0% to 40% by weight of adjuvants (d) Azo pigment formulation consisting essentially of. A process for preparing the azo pigment formulation according to any one of claims 1 to 7 by mixing component (a), component (b), component (c) and, if necessary, adjuvant (d). Coloring inks and seeds, including natural or synthetic macromolecular organic materials such as printing inks including plastics, resins, paints, paints, electrophotographic colorants and developer, electret materials, light filters, and inkjet inks Use of an azo pigment formulation according to any one of claims 1 to 7 for the purpose of The method of claim 9, For coloring printing inks, especially gravure printing inks and griddle printing inks.