Improvements in or relating to suspension agents for use in lacquers or other film-forming suspensions

GERMAN #fM PATENT OFFICE

DECLARATION DeutscheKl .: 22 g-10/01

Number: 1237 244

Reference number: B 59630IV c / 221

J 237 244 Date of filing: 3 October 1960

Auslegetag: March 23, 1967

In German Patents 1,157,326 and

1,157,327 and British Patent 924,693 have proposed suspending agents for preventing settling of pigments and fillers in paints and other film-forming suspensions consisting of salts of organic lower and higher molecular bases with inorganic or organic acids or acidic compounds. These salts are derived, except for phosphoric acids and their derivatives, especially of acidic di- and polyesters whose alcoholic components are preferably polyglycols of various molecular weights, diols and polyalcohols.

It has become known from German Patent 717 502 already suspending agents for preventing the settling of oil and paint colors whose active ingredients are amine salts of fatty and resin acids. Also known from the Austrian Patent 204149 in paints, the discontinuation of pigments inhibiting effect of the amine salts of acidic diesters in which polyglycols are esterified on the one hand with unsaturated fatty acids and on the other hand with polybasic carboxylic acids. Unfortunately, however, it has been found that these hitherto known suspending agents are not yet satisfactory in their anti-settling action. Further, when paints containing the above-mentioned suspending agents are applied to a wet metal substrate, the resulting paint films exhibit adverse properties.

These disadvantages are now avoided under an improved effect by the suspended matter according to the invention.

These suspending agents in the form of solutions in organic solvents for preventing the settling of pigments and fillers in enamel paints and other film-forming suspensions based on amine salts of acidic dicarboxylic acid esters are characterized by a content of amine salts of acidic esters

2 moles of ricinoleic acid and 1 mole of an unsaturated dicarboxylic acid, preferably maleic acid, have been prepared as the active ingredient.

For the inventive suspending come as unsaturated dicarboxylic acid z. For example, maleic acid, citraconic acid, itaconic acid, butadiene dicarboxylic acid and phthalic acid and their derivatives for use, but maleic acid is preferred. The esterification of ricinoleic acid with the unsaturated dicarboxylic acids makes it possible to produce substances having at least three unsaturated centers in the molecule and thus other interesting reactions in the form of a solution in organic solvents to prevent settling of pigments and fillers in paint colors and other film-forming suspensions

applicant:

B YK-GULDEN Lomberg, Chemical Factory G. mb H., Constance (Lake Constance)

Named as inventor:

Dr. Emil Dreher, Überlingen;

Erich Schneider, Constance

are accessible, for. B. hydrogenation, epoxidation, addition polymerization. Furthermore, one of the two carboxyl groups can be esterified with a polyalcohol, which additionally provides further reaction possibilities in the sense of forming paint-like bodies.

In the suspending agent according to the invention, the amine salts of the acidic dicarboxylic acid esters are present. Monoamines, polyamines and oxyamines of saturated and unsaturated character and, in particular, polyamidoamines of various basicity and molecular size, as used, for example, as amine components. B. by reaction of ricinic acid or tall oil fatty acid with dipropylenetriamine or diethylenetriamine. The salts thus obtained are readily soluble in most organic solvents of polar or nonpolar nature or mixtures thereof, so that their use in paint systems of the various solvent bases is possible. The diester dicarboxylic acids are expediently dissolved in an organic solvent mixture and then reacted with the amines in such an amount that the pH of the salt solutions obtained is in the weakly acidic or weakly basic range, but is preferably neutral.

The salt solutions thus prepared are added to varnishes and lacquer-like substances as well as suspensions and dispersions in amounts of from 0.2 to 1.2%, based on the total amount of these mixtures. They are very effective and permanent suspending agents for pigments and fillers, as well as wetting and dispersing agents. They facilitate the wetting of the

709 520/392

Pigments with binders when pasting and facilitate fine grinding. In addition, the amine salts or their solutions are good wetting agents for paints that are used on damp substrates. Finally, an excellent effect as corrosion and decay inhibitors was also found.

These special advantageous properties of the suspending agents according to the invention are further underlined by the very favorable general behavior in paint systems in that these agents themselves become a constituent part of the paint film due to their relationship with the paint film formers, do not volatilize and contribute to improved adhesion to metallic substrates. They do not delay the drying, but support these especially when even more unsaturated fatty acid esters of oxidative drying nature in the amine salt molecule are included. Finally, the advantageous physical-chemical general behavior finds its expression in the course of the paint film and the surface gloss favorably influencing properties of the amine salts, their incorporation in the paint film, moreover, by no means reduces its water resistance.

Hereinafter, the production of the acidic dicarboxylic acids and their amine salts, for which no protection is desired in the present invention, will be described.

A. Production of suspended matter

1. 596 g of ricinoleic acid (2 mol) are heated with 98 g of maleic anhydride (1 mol) and 0.2 g of boron trioxide as a catalyst in an esterification apparatus consisting of three-necked flask with attached Wasserabschneider and Rückfiußkühler, stirring and passing nitrogen. The temperature is maintained for 1 hour at 200 to 230 ° C, after which deposit 18 g of water. After cooling, a paste-like opaque mass is obtained which consists essentially of the maleic bis-ester of ricinoleic acid.

Acid number 159 (theory 166)

Saponification number 327 (Theory 331)

Iodine number 80 (theory 75)

Molecular weight 683 (theory 676)

The resulting diester dicarboxylic acid is dissolved in a mixture of xylene-butanol in the ratio 3: 1 and the clear solution is neutralized with stirring with amines of various kinds, resulting in clear solutions with 50% active ingredient content. To prepare these solutions, 100 g of diester dicarboxylic acid are used for each of the following batches:

a) 50 g of tributylamine 150 g of xylene-butanol

b) 15 g of monoethanolamine 115 g of xylene-butanol

c) 20 g of diethanolamine 120 g of xylene-butanol

d) 45 g of triethanolamine

145 g xylene-butanol

e) 17.5 g of ethylenediamine 117.5 g of xylene-butanol

f) 10 g of diethylenetriamine 110 g of xylene-butanol

g) 75 g of oleinamine 175 g of xylene-butanol

h) 50 g of oleinediamine 150 g of xylene-butanol

i) 60 g of rosinamine

160 g xylene-butanol k) 15 g cycloaliphatic polyamine

115 g of xylene-butanol 1) 80 g of basic condensation product

2 Moles of ricinene acid with 1 mole of dipropylenetriamine 180 g of xylene-butanol m) 225 g of basic condensation product

from 2 mol of tall oil fatty acid with 1 mol of dipropylene triamine 325 g of xylene-butanol n) 175 g of basic condensation product

2 Moles of tall oil fatty acid with 1 mole of diethylenetriamine

o) 100 g of basic condensation product

1 Mol of tall oil fatty acid with 1 mol of diethylenetriamine 200 g of xylene-butanol.

30

35

40

45

Second 298 g (1 mol) of ricinoleic acid technically pure, 65 g of itaconic acid and 50 ml of xylene as a carrier liquid are added with the addition of 1.0 g of pyrophosphoric acid in a stirred flask with a water separator. Under nitrogen atmosphere, this mixture is heated for 8 hours at 150 to 220 ° C and distilling off the resulting water with xylene azeotrope. The forming diester dicarboxylic acid from 1 mole of itaconic acid and 2 moles of ricinoleic acid, after the xylene and other volatiles were removed in vacuo, represents a pale yellow oil.

Acid number 163 (theory 160)

Saponification number 316 (Theory 320)

Molecular weight 696 (theory 691)

100 g of this compound are correspondingly 1, 1) in a 50 ° /₀Xylene-butanol solution of the salt with the basic condensation product of 2 moles of ricinensic acid with 1 mole of dipropylenetriamine converted.

Third 596 g of ricinoleic acid (2 mol), 148 g of phthalic anhydride (1 mol), 0.8 g of boric acid trioxide and 50 g of xylene are condensed according to 2 10 hours, with the theoretical amount of water is deposited. Subsequent evaporation of the volatiles in vacuo gives a light yellow oil.

Acid number 143 (theory 154)

Saponification number 313.5 (theory 308)

Molecular weight 723 (theory 727)

100 g of this diricinoleic acid phthalate become, according to 1, m), a 50 ° /₀Xylene-butanol solution of the salt with the basic condensation product of 2 moles of tall oil fatty acid with 1 mole of dipropylene triamine converted.

example

The suspended matter solutions prepared as described above are added to various paint systems in amounts of from 0.2 to 1.2% based on the total amount of paint and thus prevent the settling of the pigments in an excellent manner, namely by no or no reaction after 3 months' standing at room temperature at most only minor sediments are formed, which can be stirred up very easily, while the control samples without suspended matter are hard after only a few days, show difficult to stir up sediments.