JPH0318672B2 - - Google Patents

Description

[Detailed description of the invention] The invention of JP-A-55-139458 is based on formula (A) (In the formula, R ¹ , R ² and R ³ are independently hydrogen,
chlorine, bromine, alkyl containing 1 to 3 carbon atoms, or alkoxy containing 1 to 3 carbon atoms) and (B) water-soluble when partially or totally neutralized with a nitrogen base. () 1 part by weight of maleic anhydride to about 3 to 6 parts by weight of (a) an unsaturated fatty acid containing only two or fewer isolated or conjugated double bond units; or (b) this derived from unsaturated fatty acids such as
(a) an aliphatic or cycloaliphatic polyol or (b) a primary alcohol or a polyol having at least one primary hydroxy group; Synthetic resins consisting of mixtures or partial reaction products of polyhydroxy compounds having at least two primary hydroxyl groups, consisting of low-molecular curable aminoplasts which have been etherified, where components () and and (C) optionally an anionic or nonionic surfactant.

Developing the above inventive idea, the inventors have found that corresponding pigment compositions which do not contain aminoplasts in the water-soluble synthetic resin component have similarly valuable properties.

Therefore, the present invention utilizes the formula (In the formula, R ¹ , R ² and R ³ independently represent a hydrogen atom, a chlorine atom, or an alkyl group containing 1 to 3 carbon atoms, respectively). is soluble in water after partial or complete neutralization and contains only about 3 to 4.5 parts by weight of no more than 2 isolated or conjugated double bond units per part by weight of maleic anhydride. Practically completely combined with unsaturated fatty acids or hydroxyl-free aliphatic polyol-esters containing such fatty acids in combination or hydroxyl-free mixed esters of natural oils and/or resin acids with aliphatic polyols. 5 to 30% by weight of a synthetic resin consisting of a mixture or partial reaction product of the adduct compound obtained by aryl pararosaniline sulfonic acid, present in approximately equivalent ratios to
In pigment compositions based on pigments and resins that are well dispersible and have good tinting power, alkane-polyols, phenol-formaldehyde reaction products are used as polyhydroxyl compounds having at least two primary hydroxyl groups. The present invention relates to the above-mentioned pigment composition, characterized in that the present invention uses a mixture of these compounds or a mixture of these compounds.

It is already known that aqueous presscakes of pigments based on aryl-pararosaniline sulfonic acids form particularly hard agglomerates in simple drying processes due to their strong polarity. When these agglomerates are incorporated into the medium to be colored, such as printing inks, paints or synthetic resins, they have to be broken up again with mechanical energy, which is very costly. If the decomposition is not complete, which often occurs with the shortest possible dispersion times that are customary today, this leads to a number of different problems during the processing of the pigments. This is also particularly true in the case of aqueous pigmentation.

Apart from prints with weak tinting strength or spots, this can lead to premature destruction of, for example, flat prints.
To avoid this difficulty, pigments of this group are often incorporated with surfactants or natural resins. The surface-active substances which are usually used in large quantities as formulation agents do indeed give rise to a rapid increase in color strength upon dispersion in aqueous media, but they have the disadvantage that they lead to troublesome foam formation. This foaming is greatly increased by other superficial substances contained in the final printing ink.

Attempts to achieve high printing speeds result in severe bubble formation, which can cause operational problems to the point where the machine stops.

Powder formulations of aryl-pararosaniline sulfonic acid pigments containing natural or modified natural resins, as described in German Patent Specification No. 1769912, are also useful for dispersibility, tinting strength and incorporation into printing ink compositions. However, it does not meet all the requirements of the printing ink industry.

In view of the above state of the art, the inventors have proposed according to the invention that these pigments can be used in preparations for aqueous systems which can be easily dispersed and do not generate interfering foam, such as pigments with high tinting strength and particle flexibility. It was discovered that it can be turned into powder.

The preparation according to the invention involves the addition of alkali to the pigment of the above formula, advantageously under heating, preferably from 50 to 100%
C. and from the aqueous-alkaline dye solution obtained, after mixing the synthetic resin - preferably as an aqueous or organic solution - and the surface-active substance with the addition of a mineral acid, preferably 2. to 5,
In particular, it is carried out in such a way that the prepared pigment is precipitated at a pH value of 2 to 3.5.

Sodium or potassium hydroxide is most suitable for producing aqueous-alkaline pigment solutions. The dissolution of the pigments is preferably carried out at temperatures of 80-100°C.

As a synthetic resin, in particular, German Patent Specification No.
1302319 by neutralization with ammonia or an organic base, such as natural oils and adducts of maleic anhydride with polyols such as phenol-formaldehyde reaction products and/or alkanes. Those esterified with polyols are suitable. Preferred synthetic resins have a dynamic viscosity of 0.5 to 1.5 Pas, measured as a 30% by weight aqueous solution at 20°C.

The amount of resin used is preferably from 4 to 25% by weight, preferably from 7 to 15% by weight, based on the weight of the dry starting pigment, depending on the pigment and the intended field of use of the formulation.

Furthermore, the pigment preparations according to the invention may contain anionic or nonionic surfactants.

As surface-active substances used are the anionic or nonionic products customary in the dispersion of dyes or pigments. Examples include salts of fatty alcohol sulfonates, alkylaryl sulfonates and sulfosuccinic acid esters, or polyalkylene ethers of fatty alcohols or alkylphenols or naphthols as effective nonionic surfactants, or block polymers of ethylene oxide and propylene oxide. .

It is also possible to use mixtures of surface-active substances during the precipitation step in order to better disperse the synthetic resins used. Additionally, small amounts of organic solvents may be advantageous.

Preferred formulations contain synthetic resin and surfactant in a weight ratio of 1:0.01 to 0.1, especially 1:0.06. Preferred pigment formulations contain 95-70% by weight pigment and 30-5% formulation agent. After drying the wet presscake, a soft product of particles is obtained which can be ground without difficulty and shows no tendency to agglomerate.
The method of the invention is particularly suitable for continuous operation.

The pigment preparations are particularly suitable for use in aqueous printing inks and aqueous coating compositions.

The pigment formulations according to the invention can be dispersed very easily using dispersers customary in the printing ink industry. Water-based printing inks prepared with this pigment formulation give satisfactory printing without the formation of interfering bubbles.

The powdery formulations according to the invention have a very good tinctorial strength, which leaves a relatively large scope for property-improving additives when preparing printing inks. Due to the low resin content and the resulting low influence on the viscosity when preparing aqueous printing inks and aqueous coating compositions, the powdered formulations can be used in many ways.

The formulation according to the invention can be stored indefinitely. This formulation can be easily metered; it can be quantitatively removed from a container and, for example, pneumatically conveyed from a storage container to a processing device and can be metered automatically.

The invention will be explained in detail by the following example.

Example 1 formula 370 parts by weight of a water-wet 27.2% by weight press cake of triphenyl pararosaniline monosulfonic acid represented by is suspended in 1000 parts by weight of water. After addition of 9.5 parts by weight of sodium hydroxide, the mixture is heated to 90-100°C. At this time, the pigment dissolves.

To this hot pigment solution were added dehydrated castor oil, linseed oil, colophonium and glycerin reacted with maleic anhydride and partially saponified with aqueous triethylamine, tricresol-formaldehyde-resin and trimethylolpropane (German patent specification). No. 1302319 Example 2) - dynamic viscosity at 20°C (30% by weight when diluted with distilled water)
%) 0.5-1 pass and runoff time (4DIN No. 53211
No./20℃) with 100-200 seconds - 20 parts by weight is added.

After stirring until completely homogeneous, the prepared pigment is subsequently precipitated with 110 parts by weight of 15% by weight sulfuric acid at a pH of 2.4. The product is filtered off with suction, washed free of salt and dried in a dryer with circulating air for 70-75 minutes.
Dry at °C. 108 parts by weight of a 91% by weight blue pigment formulation are obtained. Grind the pigment preparation. It can be processed very well into water-based printing inks with good tinting strength and with low dispersion costs.

Example 2 Perform as described in Example 1, but with the exception that the formula 21% by weight aqueous press cake of pigment indicated by 476
Use parts by weight. 107 parts by weight of a 91% blue dye powder with a green hue are obtained, which can be processed very easily into bubble-free aqueous printing inks with good tinting strength.

Example 3 Perform as described in Example 1, but with the exception that approximately 50
Using 40 parts by weight of a wt% aqueous resin mixture and 0.7 parts by weight of a reaction product of n-octylphenol and 10 mol of ethylene oxide, the settled aqueous pigment suspension was subsequently dried in a spray dryer with a two-component nozzle. Spray at an inlet temperature of 240°C and an outlet temperature of 80-90°C. A free-flowing powder is thus obtained which can be processed very well into non-foaming aqueous printing inks with good tinting strength at low dispersion costs.

Claims (1)

[Claims] 1 (A) 95-70% by weight formula (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a chlorine atom, or an alkyl group containing 1 to 3 carbon atoms.) and (B) 30 to water soluble when partially or fully neutralized with 5% by weight of an organic nitrogen base;
4.5 parts by weight of (a) unsaturated fatty acids containing no more than two isolated or conjugated double bond units, or (b) containing no hydroxyl groups derived from such unsaturated fatty acids (a); Aliphatic polyol
esters or (c) adducts obtained by virtually complete combination with hydroxyl-free mixed esters of natural oils and/or resin acids and aliphatic polyols; and () having at least two primary hydroxyl groups. Synthetic resins consisting of mixtures or partial reaction products of alkane-polyols, phenol-formaldehyde-reaction products or mixtures of these compounds, where the resin components () and () are present in approximately equivalent amounts with respect to the ester-forming groups. )including,
Pigment formulations based on aryl-pararosaniline sulfonic acid pigments and resins. 2. A pigment preparation according to claim 1, wherein the synthetic resin has a dynamic viscosity of 0.5 to 1.5 Pas, measured as a 30% aqueous solution at 20°C. 3 (A) 95-70% by weight formula (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a chlorine atom, or an alkyl group containing 1 to 3 carbon atoms.) and (B) 30 to water soluble when partially or fully neutralized with 5% by weight of an organic nitrogen base;
4.5 parts by weight of (a) unsaturated fatty acids containing no more than two isolated or conjugated double bond units, or (b) containing no hydroxyl groups derived from such unsaturated fatty acids (a); Aliphatic polyol
esters or (c) adducts obtained by virtually complete combination with hydroxyl-free mixed esters of natural oils and/or resin acids and aliphatic polyols; and () having at least two primary hydroxyl groups. Synthetic resins consisting of mixtures or partial reaction products of alkane-polyols, phenol-formaldehyde-reaction products or mixtures of these compounds, where the resin components () and () are present in approximately equivalent amounts with respect to the ester-forming groups. )including,
In preparing pigment formulations based on aryl-pararosaniline sulfonic acid pigments and resins, the pigments are dissolved in an alkaline-aqueous medium;
Process for the preparation of the above pigment preparation, characterized in that a synthetic resin is added and the pigment preparation is precipitated by addition of a mineral acid. 4. Process for preparing a pigment preparation according to claim 3, in which the pigment preparation is precipitated from an alkaline solution at a pH value of 2 to 5. 5. Process for producing a pigment preparation according to claim 3 or 4, in which the pigment preparation is precipitated at a pH value of 2.0 to 3.5. 6 (A) 95-70% by weight formula (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a chlorine atom, or an alkyl group containing 1 to 3 carbon atoms.) and (B) 30 to water soluble when partially or fully neutralized with 5% by weight of an organic nitrogen base;
4.5 parts by weight of (a) unsaturated fatty acids containing no more than two isolated or conjugated double bond units, or (b) containing no hydroxyl groups derived from such unsaturated fatty acids (a); Aliphatic polyol
esters or (c) adducts obtained by virtually complete combination with hydroxyl-free mixed esters of natural oils and/or resin acids and aliphatic polyols; and () having at least two primary hydroxyl groups. Synthetic resins consisting of mixtures or partial reaction products of alkane-polyols, phenol-formaldehyde-reaction products or mixtures of these compounds, where the resin components () and () are present in approximately equivalent amounts with respect to the ester-forming groups. )including,
A method of using pigment preparations based on aryl-pararosaniline sulfonic acid pigments and resins in aqueous printing inks or aqueous coating compositions.