DK146824B - DISPERSIBLE AND USE OF IT - Google Patents

Description

146824

The present invention relates to a dispersant and its use in the preparation of a pigment dispersion.

From Norwegian Patent Specification No. 131,204, it is known to prepare a pigment dispersion using a dispersant in which a polyester derived from a hydroxycarboxylic acid is bonded to a colored radical. Such agents have the disadvantage that they can only be used to disperse pigments of a similar color or color which cover the color of the dispersant. In addition, pigments are relatively inert substances, often used under conditions that require considerable stability to light, heat and air, while a suitable dispersant of similar color will not necessarily be as stable. This can lead to discoloration or dulling of the pigment's color during use. The present dispersants, which are colorless, do not suffer from these disadvantages and can therefore be used to a greater extent.

According to the invention there is provided a dispersant which is peculiar in that it has the formula;

R-A-B - (OC - X - 0) y - H

or

20 R - A - B - (OC - X - O) χ - CO - T

wherein R is a primary, secondary or tertiary amino group or a salt thereof with an acid or a quaternary ammonium salt group, A is an alkylene or hydroxyalkylene radical containing from 2 to 6 carbon atoms, B is -N- or -O- where T is H or T1 is an alkyl radical, X is a divalent, saturated or unsaturated aliphatic radical containing at least 8 carbon atoms and where there are at least 4 carbon atoms between the -CO- and -O groups, T is a saturated or unsaturated one aliphatic radical containing from 8 to 20 earbon atoms, and y is an integer from 2 to 20.

Examples of radicals represented by t \ include methyl, ethyl, n-propyl, n-butyl and octadecyl. Examples of radicals represented by A include ethylene, trimethylene, tetramethylene, hexamethylene and β-hydroxytrimethylene.

The primary, secondary and tertiary amino groups which represent -10. preferably R is of the formula

-N

Wherein T and T are each independently hydrogen, alkyl, substituted alkyl or cycloalkyl. The salts of said amino group; are salts with colored or colorless acids.

The quaternary amino groups represented by R preferably have the formula: T2 + / 3 -

-N - T W

X 4 T

4 2 wherein T has the same values as T and may be the same or different therefrom and W is a colorless or colored anion.

As examples of radicals represented by T2, and can be mentioned alkyl such as e.g. methyl, ethyl, n-propyl, n-butyl and octadecyl, hydroxy-lower alkyl, e.g. (3-hydroxyethyl and cyclohexyl. Throughout the specification the term "lower alkyl" is used to denote alkyl radicals containing from 1 to 25 carbon atoms.

The acids used to form salts with the amino groups or which may contain the anion W may be any inorganic acid or colorless or colored organic acid such as e.g. hydrochloric acid, sulfuric acid, acetic acid, propionic acid, formic acid, methanesulfonic acid, benzenesulfonic acid, benzoic acid or an organic dye containing at least one sulfonic acid or carboxylic acid group, in particular azo, anthraquinone or phthalocyanine dyes containing at least one sulfonic acid or is described in the third edition of the Color Index, which was released in 1971.

The dispersants of the invention as defined above, wherein R represents a primary, secondary or tertiary amino group, and B is -N- can be prepared by a polyester of the T1 formula H- (OX-CO) -OH or T-CO - (OX-CO) 2 -OH is condensed together with a compound of formula R 1 ABH wherein A has the meaning given above and R is a primary, secondary or tertiary amino group.

This process can conveniently be carried out by stirring the reactants together preferably at a temperature between 50 and 250 ° C, the reaction being preferably carried out in an inert atmosphere. If desired, the reaction may be carried out in an inert organic liquid which is then removed e.g. by distillation after the reaction is complete.

5

Examples of compounds of formula R ABH which can be used in the process include 3-dimethylaminopropylamine and 3-octadecylaminopropylamine. When said compounds contain two groups (as in 3-octadecylaminopropylamine), both of which can react with the polyester, the resulting product is presumably a mixture of two condensates, but such mixtures may also be used.

Said polyesters used according to the invention can f.

30 is obtained by heating a hydroxycarboxylic acid of the formula HO-X-COOH or a mixture of such acids or a mixture of such hydroxycarboxylic acid and a carboxylic acid T-COOH optionally in the presence of an esterification catalyst, preferably at a temperature in the range. 160-200 ° C until the desired molecular weight has been obtained. The esterification process can be followed by measuring the acid number of the product. The preferred polyesters have acid numbers in the range 10-100 mg KOH / g and especially in the range 20-50 mg 5 KOH / g. The water formed by the esterification reaction is removed from the reaction medium. This may conveniently be accomplished by passing a stream of nitrogen over the reaction mixture or preferably by carrying out the reaction in the presence of a solvent, e.g. toluene or xylene and distill off the water when it is daniies. The resulting polyesters can be isolated in the usual manner.

In said hydroxycarboxylic acids, the radical represented by X preferably contains from 12 to 20 carbon atoms, and it is further preferred that there are between 8 and 14 carbon atoms between the carboxylic acid and hydroxy groups. It is also preferred that the hydroxy group is a secondary hydroxy group.

As particular examples of such hydroxycarboxylic acids may be mentioned ricinolic acid, a mixture of 9- and 10-hydroxystearic acids (obtained by sulfonation of an oleic acid followed by hydrolysis) 20 and 12-hydroxystearic acid, and in particular the commercially available hydrogenated castor oil fatty acid, -ric acid contains smaller amounts of stearic acid and palmitic acid.

The carboxylic acids which can be used with the hydroxycarboxylic acids to obtain the polyesters are preferably saturated or unsaturated aliphatic carboxylic acids, especially alkyl and alkenyl carboxylic acids containing a chain of from 8 to 20 carbons. Examples of such acids include lauric acid, palmitic acid, stearic acid and oleic acid.

The dispersing agents as defined above wherein R represents a primary, secondary or tertiary amino group and E is -O- can be prepared by reacting an acid chloride of the polyester of the above formula with a salt of an amine of formula HOAR with a strong acid, where A and R have the previously stated meanings.

This process may conveniently be carried out by heating the acid chloride and salts together optionally in the presence of a catalyst such as p-toluenesulfonic acid and isolating the resulting salt of the ester. If desired, this salt can be converted to the free base by treatment with a base such as sodium hydroxide.

Said acid chloride may conveniently be obtained by the action of thionyl chloride on the acid. Examples of said salts include β-aminoethanol, β-methylaminoethanol and 10β (dimethylamino) ethanol hydrochloride.

Alternatively, dispersants of the formulas listed where A is 2-hydroxypropylene and B is -O- can be prepared by reacting the polyester with epichlorohydrin or epibromohydrin and subsequent treatment with an amine of formula HR importance.

This process may conveniently be carried out by heating the said polyester and the epichlorohydrin and the epibromohydrin together, preferably in the presence of a tertiary amine as catalyst, adding the amine of the formula HR and heating again to complete the reaction.

Examples of said amines include ammonia, methylamine, diethylamine and octadecylamine.

The preferred polyester for use in the above processes is poly (hydroxystearic acid).

The dispersants of the invention, wherein R is a primary, secondary or tertiary amino group, can be converted to the corresponding salts by stirring or grinding the dispersant together with a colorless or colored acid or a salt thereof with a weak base (e.g. an aromatic amine such as p-dodecylaniline) or with a metal (e.g. aluminum) which forms only a weak basic hydroxide in an inert organic liquid, the reaction being carried out at a temperature up to 146824 the point of the organic liquid. The reaction mixture may, if desired, contain a small amount of water, as this sometimes acts as a catalyst for the reaction. The resulting amine salts can then be isolated in the usual manner, but if desired, the resulting solution of the salt can be used directly to prepare dispersions of solids in organic liquids.

The dispersants of the invention, wherein R is a quaternary amino group, can in itself be obtained by treating the corresponding dispersing agents wherein R is a primary, secondary or tertiary amino group with a quaternizing agent such as dimethyl sulfate, the reaction being preferably carried out at elevated temperature, e.g. between 50 and 250 ° C, and preferably in the presence of an organic liquid.

A dispersant according to the invention can be used in the preparation of a pigment dispersion comprising a finely divided dispersion of a pigment having a particle size below 25 microns in an organic liquid dissolved therein containing a dispersant according to the invention. The common and well known methods of preparing dispersions can be used. Thus, the solid, the organic liquid and the dispersant can be mixed in any order, and the mixture can then be subjected to mechanical treatment to reduce the particle size of the solid, e.g. ball milling, bead milling or gravel milling until the dispersion is formed. The treatment is continued until the particle size of the solid 25 is less than 25 microns and preferably less than 10 microns.

When the dispersants are used in the form of their salts, it is not essential to use the preformed salt as this can be prepared in situ concurrent with the preparation of the dispersion by admixing the solid, the organic liquid, the appropriate dispersant containing a primary, secondary or tertiary amino group and subject the mixture to mechanical treatment. It is not important that all of the amino groups be converted to salt form as it has been found that mixtures of the free bases and salts are as effective as dispersants.

7 146824

Alternatively, the solid can be treated to reduce its particle size independently or in admixture with either the organic liquid or dispersant, and the other or other ingredients are then added, after which the dispersion 5 can be obtained by stirring the mixture. As a further alternative, a solution of the dispersant in an organic liquid can be emulsified into an aqueous phase by known aids such as high speed stirring, in the presence of one or more surfactants, and the resulting emulsion added to a aqueous slurry of the solid, after which the organic liquid and water are removed by filtration and drying of the remainder of the solid and dispersant. This residue can then be dispersed in an organic medium.

It is preferred that the amount of dispersant in the dispersions is such that it corresponds to between 5 and 50% by weight and preferably between 10 and 30% by weight of the solid, and the dispersions preferably contain from 5 to 70% by weight. % solids based on the total weight of the dispersion.

The organic liquids used to prepare the dispersions may be any inert organic liquids in which the dispersants are at least partially soluble at room temperatures and which are stable under the subsequent conditions of use of the dispersion. If desired, mixtures of organic liquids may be used. Preferred organic liquids are 25 hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mineral turpentine, n-hexane, cyclohexane, chlorobenzene, carbon tetrachloride and perchlorethylene. However, other organic liquids, e.g. esters such as alkyd resins and flaxseed oils whose viscosity is increased with heat and used as lithographic fixing media. Above all, it is preferred that the organic liquid is a substantially aliphatic petroleum fraction. The organic liquids or mixtures thereof used to prepare the dispersions will generally depend on the subsequent uses to which the dispersions are to be used.

8 146824

The solids are preferably inorganic or organic pigments and may be of any of the recognized pigment classes. Examples of inorganic pigments include titanium dioxide, carbon black, zinc oxide, berlin blue, cadmium sulfide, iron oxides, zinnobes, ultramarine and chromium pigments comprising chromates of lead, zinc, barium and calcium and the various mixtures and modifications thereof, such as the commercially available green yellow. red pigments with the names primrose, lemon, medium, orange, scarlet and red chromium substances.

10 Examples of organic pigments include pigments of the azo, thioindigo, anthraquinone, anthanthrome, isodibenzanthrone or triphendioxazine series, pigment pigments, phthalocyanine pigments such as copper phthalocyanine phenyl ether acetate and its halogenated derivatives, and its halogenated derivatives lacquer colors of acidic, basic and stain colors. Such pigments are described e.g. in the second edition of the Color Index, published in 1956 under the heading "Pigments", and in subsequent authorized additions thereto. Preferred pigments are carbon black and especially copper phthalocyanine and its core halogenated derivatives.

The dispersions which can be prepared using a dispersant of the invention are liquid or semi-liquid materials containing the solid in finely divided and deflocculated form and scanning can be used for any purpose for which dispersions of these particular even solids are commonly used. Thus, the pigment dispersions are of particular value in the production of printing inks by incorporating the dispersions together with other components commonly used in the preparation of such inks. The dispersions are also of value in the preparation of paints, for which purpose the dispersions are incorporated into ordinary alkyd or other resins. The dispersants of the invention may alternatively be used as dispersants in the preparation of dispersions of other dyes, e.g. acidic dyes, disperse dyes and basic dyes, such as those described in the second edition of the Color Index, in organic liquids, such dispersions being used for solvent dyeing textiles.

The invention is illustrated by the following examples in which all parts and percentages refer to weight.

A polyester was prepared as follows:

Polyester A

A mixture of 348 parts of xylene and 3350 parts of a commercial grade 12-hydroxystearic acid (with acid and hydroxy numbers of 182 mg KOH / g and 160 mg KOH / g respectively) is stirred for 22 hours at 190-200 ° C, the water being which is formed by the reaction is separated from the xylene in the distillate which is then sent back to the reaction medium. After 152 parts of water have been collected, the xylene is removed by heating to 200 ° C in a stream of nitrogen. The resulting pale amber liquid has an acid number of 35.0 mg 15 KOH / g.

Example 1

A mixture of 1600 parts of polyester A and 102 parts of 3-dimethylaminopropylamine is stirred for 2 1/2 hours at 160 ° C under a reflux condenser and in a stream of nitrogen. 10 parts by volume of the mixture are distilled off, the temperature is raised to 190 ° C over 20 minutes and maintained at 190-200 ° C for 2 hours and 45 minutes. The resulting slightly amber, viscous liquid partially solidifies upon cooling.

Infrared analysis of the product shows bands at 1655 and 1540 cm 2, corresponding to the presence of a -CONH group. Titration of the product with perchloric acid, with or without formaldehyde, shows the presence of 0.557 equivalents of one tertiary amino group per 1000 g of product. The acid number of the product is 12.3 mg KOH / g.

146824 ίο

Example 2 13.5 parts of dimethyl sulfate are added to 183 parts of the product of Example 1 at 44 ° C, with the temperature of the mixture rising to 72 ° C. The mixture is then stirred for 1 1/2 hours at 90-100 ° C.

5 The product is a slightly amber, viscous liquid which forms a rubber upon cooling.

Infrared analysis of the product shows bands at 750, 1015, 1062 and 1240 cm -1 due to the presence of the CH 3 SO 4 anion and bands at 1545 and 1660 cm -1 due to the -CONH group.

Example 3

A mixture of 900 parts of polyester A and 300 parts of a commercial grade of 3-octadecylaminopropylamine is stirred for 5 1/2 hours at 160-165 ° C in an inert atmosphere. The mixture is then cooled to give a slightly amber solid which consists essentially of a mixture of the compounds of the formula polyester chain -CONH (C C) NHNH-octadecyl ^ octadecyl and polyester chain -CON ^ ^ (ch₂) ) 3hh2

Infrared analysis shows the presence of bands at 3310, 1645 and 1550 cm 1 corresponding to the -CONH group. Titration with perchloric acid in acetic acid shows that the product contains an equivalent of an amino or substituted amino group in 1455 g. The acid number of the product is 5.7 mg KOH / g.

Example 4

A mixture of 160 parts of polyester A, 0.39 parts of dodecyldimethyl-25 amine and 9.2 parts of epichlorohydrin is stirred for 3 hours at 150-155 ° C, during which time the acid number of the product has dropped to 4.05 mg KOH / g.

A mixture of 50 parts of the product above and 2.17 parts of diethylamine is stirred for 19 hours at 100 ° C. Titration of the resulting product with perchloric acid shows that 78.5% of the dimethylamine has reacted with the chloromethyl group to form a product consisting essentially of / C 2 H 5 polyester chain -COOCH 2 CHOH. CH2N .HC1

Xc2H5

Example 5

A mixture of 3 parts of lead sulphochromat, 0.2 parts of copper phthalocyanine disulphonic acid, 1.3 parts of the product of Examples 1 and 5.5 parts of a petroleum fraction boiling at 100-120 ° C, ball-milled for 16 hours. forming a liquid, finely divided and well-deflocculated dispersion of the pigment suitable for use in paints or in gravure ink. Similar dispersions are obtained when the pigment above is replaced by any of the following: a) Copper polychlorophthalocyanine b) "Tioxide RCR" which is a coated form of rutile titanium dioxide c) Phosphomolybdowolframate from C.I. "Basic Blue 7" (C.1.42595) d) 4.10 — fibromanthranthron e) indanthron.

Example 6

A mixture of 3 parts of copper polychlorophthalocyanine, 1.3 parts of the product of Example 1, o, 2 parts of 1-naphthylamine-5-sulfonic acid and 5.5 parts of a petroleum fraction boiling at 100-120 ° C is ball milled in 16 hours to form a liquid, 25 finely divided and well flocculated dispersion of the pigment. Similar dispersions are obtained when 0.2 parts of l-naphthylamine-5-sulfonic acid is replaced by 0.2 parts of the following: a) commercially available mixture of l-naphthylamine-6-and-7-sulfonic acids 12 b) sulphanilic acid c D) 2-naphthylamine-6-sulfonic acid e) methanilic acid f) p-toluenesulfonic acid g) naphthalene-2-sulfonic acid.

Example 7

A mixture of 3 parts of a rosin-treated calcium tonic of 1- (2'-sulfo-41-methylphenylazo) -2-naphthol-3-10 carboxylic acid, 1.5 parts of the product of Example 1 and 5.5 parts of a petroleum fraction boiling at 100-120 ° C is ball milled for 16 hours to form a liquid, finely divided and well-flocculated dispersion of the pigment.

Similar dispersions are obtained when the pigment above is replaced by the barium tonic agent of 1- (2'-sulfo-4'-methyl-5'-chloro-phenylazo) -2-naphthol-3-carboxylic acid or when the product of Example 1 is replaced by the product from Example 3 or 4.

Example 8

A mixture of 3 parts of the β-form of copper phthalocyanine, 0.2 20 parts of copper phthalocyanine trisulfonic acid, 1.3 parts of the product of Examples 1 and 5.5 parts of a petroleum fraction boiling at 100-120 ° C, is ball milled for 16 hours to form a liquid, finely divided and well-flocculated dispersion of the pigment suitable for use in paint media where there is little or no tendency for the pigment to flocculate.

Example 9

A mixture of 0.2 parts of copper phthalocyanine disulfonic acid, 1.3 parts of the product of Examples 1 and 5.5 parts of a petroleum fraction boiling at 100-120 ° C is ball milled for 16 hours, at which point a clear , blue solution. 3 parts 13 of the β-form of copper phthalocyanine are added and the milling is continued for 2 hours. A liquid, finely divided and well-flocculated dispersion of the pigment is obtained.

Similar results are obtained if 0.2 parts of the above disulfonic acid is replaced by 0.2 parts of the condensation product of 1 mole of phosgene and 2 moles of 41-amino-4-hydroxy-3-methyllazobenzene-5-carboxylic acid or with 0 , 2 parts of the free acid form of CI "Yellow R" (C.I. 40000), and / or when 3 parts of the pigment above is replaced by 3 parts of the pigment obtained by coupling tetrazotated 10,3,3-dichlorobenzidine with 2 moles of acetoacetanilide.

Example 10

A mixture of 3 parts of copper polychlorophthalocyanine, 1.5 parts of the product of Examples 2 and 5.5 parts of a petroleum fraction boiling at 100-120 ° C, is ball milled for 16 hours to form a finely divided, well-flocculated dispersion of the pigment .

A similar dispersion is obtained when the pigment above is replaced with a rosin-treated calcium toner of 1- (2'-sulfo-4'-methylphenylazo) -2-naphthol-3-carboxylic acid.

Example 11 A mixture of 0.39 parts of p-dodecylaniline salt of a copper phthalocyanine disulfonic acid, 1.11 parts of the product of Example 1 and 5.5 parts of a petroleum fraction boiling at 100-120 ° C is stirred for 30 minutes. at 20 ° C. To the resulting blue solution is added 3 parts of the β-form of copper phthalocyanine, 25 and the mixture is ball-milled for 16 hours to give a liquid, finely divided and well-flocculated dispersion of the pigment.

Example 12

A mixture of 1600 parts of polyester A and 204 parts of 3-dimethylaminopropylamine is stirred for 30 minutes at 160 ° C under a reflux condenser and in a stream of nitrogen. The temperature of the mixture is high.

Claims (1)

146824 is then heated to 190 ° C over 30 minutes, the water formed by the reaction being distilled off and the temperature then maintained at 190-200 ° C for 2/3/4 hour. The resulting slightly amber viscous liquid solidifies to a wax upon cooling. The product has an equivalent of titration with perchloric acid of 1008 and the acid number is 4.0 mg KOH / g. Example 13 A mixture of 0.32 parts of an aluminum salt of a copper phthalocyanine trisulfonic acid containing 1.1% aluminum, 1.18 parts of the product of Example 12, 5.5 parts of a petroleum fraction boiling at 100-120 ° C, and o, o 3 parts of water are stirred for 1 hour at 20 ° C. To the resulting blue solution is added 3 parts of the β-form of copper phthalocyanine and the mixture is spherical for 15 hours, giving a liquid, finely divided and well flocculated dispersion of the pigment. The aluminum salt used in this example was itself obtained by dissolving 50 parts of a commercially available sodium salt of copper phthalocyanine trisulfonic acid in 2000 parts of water 20 at 100 ° C, adding 23.6 parts of a concentrated aqueous solution of hydrochloric acid, followed by a solution of 50 parts of aluminum sulfate in water, filter off the solid, wash with water and dry the solid. Claims. Dispersant, characterized in that it has the formula R-A-B- (OC-X-O) -H y or R - A - B - (OC - X - O) x - CO - T