DE1951129A1 - Alcohol-soluble binders - Google Patents

Abstract

Spirit - soluble condensation products of phenols, formaldehyde, aromatic hydroxycarboxylic acids and/or org. anhydrides are obtained by reacting 1 mole of a (substd.) phenol(s) in aqueous soln. with 0.5-2.5 moles formaldehyde (-releasing cpds.) at elevated temp., at pH 6.5. - 14 followed by further reaction with 0.01-3 moles of an aromatic hydroxycarboxylic acid and/or 0.01-3 moles of an org. acid anhydride at 30-100 degrees C, and pH 7.5 to -1 and opt. drying and separating the condensate. Used as binders in the printing industry for the laking of basic printing inks.

Description

Fuel Soluble Binders The invention relates to condensation products from phenols, formaldehyde, aromatic hydroxycarboxylic acids and acid anhydrides, which one of the printing technology as a highly fuel-soluble binding agent for lacquering of basic dyes - e.g. for the production of rubber prints - in advantageous Way can be used. The invention also relates to a method for Manufacture of these condensation products.

It is known that the condensation products customary in tanning technology can be used from phenols, phenol sulfonic acid, phenol carboxylic acids, polyhydric alcohols and Formaldehyde can be used as a laking agent for basic dyes, however the concerns and requirements of printing technology through these leather or textile auxiliaries not fully met.

Printing inks must be clear and haze-free when they dry can also be diluted very well with gasoline, and finally you may after Do not bleed the printout with water.

These requirements are more imperfect with the previous Hiifsitt-a1n: IflXUr Way has been fulfilled.

There were now condensation products of phenols, formaldehyde, aromatic Hydroxycarboxylic acids and / or organic acid anhydrides found by reacting from one mole of an optionally substituted phenol or various phenols in aqueous solution with 0.5 to 2.5 mol of formaldehyde or formaldehyde-releasing Compounds at elevated temperature in a pH range from about 6.5 to 14, preferably-from 7 to 11, and subsequent further reaction with 0.01 to 3 mol of an aromatic Hydroxycarboxylic acid and / or 0, oil to 5 mol an organic acid anhydride at temperatures of 55 to 1000C in a pH range of about 7.5 to -1, preferably from 5 to 0 and optionally subsequent drying and isolation of the condensation products can be obtained. The reaction can also be carried out under pressure.

The phenols to be used are optionally substituted one or polynuclear phenols. The following may be mentioned in detail: phenol, 4,4'-dioxydiphenylpropane (2.2) and alkylphenols, the alkyl groups of which contain 2 to 20 carbon atoms. The alkyl groups can be branched or straight-chain and carry further substituents. as further substituents of the phenols come with.

for example, halogens or nitrogen-containing groups can also be considered.

The formaldehyde used can be in free form, preferably as aqueous Solution or in the form of formaldehyde-releasing compounds, such as para-formaldehyde, Trioxane or urotropine can be added.

The hydroxycarboxylic acids are e.g. salicylic acid or gallic acid, as acid anhydrides, uniform and / or mixed anhydrides, such as the anhydrides the maleic, vinegar, phthalic, tetrachlorophthalic, amber, o-sulfobenzoe and / or Tartaric acid into consideration.

The properties of the condensates can be particular to the individual Cases of differently high demands on haze-free it drying on the Printing inks whose fuel solubility and bleeding resistance are better matched as a result be that - especially in the second reaction section - additional substances, such as Urea, substituted ureas or urea derivatives, urethanes, acid amides, Xanthates, alcohols, cyanuric acid, polycarboxylic acids such as malonic acid, hydroxycarboxylic acids, such as malic acid, aminocarboxylic acids, melamines, dicyandiamide, barbituric acid, hydantoins or guanine in amounts from 0.001 to 1 mole based on 1 mole of phenol added and condensed under the reaction conditions mentioned.

Also through the use of mixtures of the condensates according to the invention and / or the additional substances mentioned in the previous section are in many cases equally suitable or even advantageous modifications are possible.

For the preparation of the new binders, it is expedient to proceed in detail so before that one or more, preferably 2 to 4 different phenols with Formaldehyde in a pH range of approx.

6.5 to 14 converts. This area can be made alkaline by suitable active compounds, e.g. alkali metal hydroxides such as sodium and potassium hydroxide, Ammonia or primary, secondary or tertiary amines, e.g. ethylamine, diethylamine, Triethylamine, diethanolamine and triethanolamine are adjusted and controlled. The reaction temperature should not be kept too high, in particular not above 100.degree will. It has proven particularly useful at condensation temperatures between 40 and 80 ° C., preferably with a gradual increase in temperature in the pH range of 7 to 11 work. The reaction can also be carried out under pressure, preferably under a pressure of 3 to 10 atmospheres inert gas, e.g. nitrogen or noble gases. the Acid condensation is expediently in a pH range from about 7.5 to -1, preferably from 5 to 0 and at temperatures between 50 and 1000C. Serve here as proton-releasing substances, among other things, the acids themselves to be condensed, or customary inorganic or organic acids, such as dilute sulfuric acid, are used or phosphoric acid. The acids are usually condensed in an amount of 0.01 to 3 moles, preferably 0.5 to 1.5 moles, based on 1 mole of the phenol.

Also the organic acid anhydrides are usually used in an amount from 0.01 to 3 mol, preferably 0.05 to 0.5 mol, based on 1 mol of the phenol, condensed. This reaction step can also be carried out under pressure in an inert gas atmosphere preferably be carried out at 2 to 10 atmospheres. If necessary, between these two reaction steps described, an aqueous phase that forms are separated off, and then 0.001 to 0.6 mol of formaldehyde can be added will. The end of The easiest way to recognize a reaction is to that a reaction sample of the product prepared according to the invention is brittle and how glass breaks.

The new condensation products dissolve in aqueous alkali, are, however, practically insoluble in water and acids, so that they are composed of acidic 6der neutral aqueous medium can be easily separated. To further Working up, the process products can be washed with water and then under dry at about 600C under reduced pressure and then isolate.

For many purposes, however, it is also sufficient to put the products on easy to separate from the bulk of the aqueous phase and to dry, e.g. on a roller in a drying pan or in a spray dryer. The new Condensation products not only dissolve in alkalis and other basic liquids, but also in many organic solvents, especially in ethanol, acetone and a mixture of ethanol and ethyl glycol.

Depending on their composition, the products have an acid number between 5 and 25, are partly colorless, partly slightly colored and odorless up to 130 ° C. Because of Due to their great brittleness, they can be easily crushed. Except as typographical You will find aids in the paint, textile and paper industries, e.g. as dispersants, Use.

The condensation products find a particularly important application as a laking agent for basic dyes, i.e. for the production of so-called Color lacquers. Auramine dyes, rhodamine dyes, Victoria blue dyes, methyl violet, Crystal violet and malachite green are mentioned as examples of basic dyes.

The colored lacquers are water-laudable and excellent despite their salt character lipophilic, so that they can be used for coloring organic masses, e.g. for the production of carbon paper waxes, lithograph compounds or ballpoint pen pastes. Furthermore, the condensation products can be used as lacquer components in rubber printing (Flexography) serve. The color varnishes made with the new products as well the prints and dyeings obtained therewith have very good properties, for example excellent adhesion to metal surfaces.

The parts and percentages given in the examples relate to the weight.

The test for water fastness in the following examples was done in the manner described below ("Rhodamine test"): 15 g Rhodamine FB (Color Index Edition II Vol 1. (1956) No. 45 170) and 30 g of laking agent are included 55 g of a mixture of 9 parts of ethanol and 1 part of ethylene glycol for 12 hours shaken. It is allowed to stand for 4 to 6 hours. Then a film of 10 µ applied to both glassine and cellulose paper. One leaves 24 Air dry for hours. The color swatches are between damp filter paper placed and pressed between two glass plates for 24 hours. Then the water fastness becomes ("Bleeding") checked.

The rating scale ranges from 1 to 5. No bleeding whatsoever Rated 5, increasing color depth on the filter paper results in decreasing color Rating scale from 4 to 1 (visual rating).

In another test ("Victoria Blue Test"). will the solubility ' and the freedom from haze tested: 7.5 g of laking agent are in 35 g of a mixture dissolved from 9 parts of ethyl alcohol and 1 part of ethylene glycol. 7.5 g of Victoria blue are added FB (Color Index Edition II VolWI I (1956) No. 44 045) and shake for 4 hours. The mixture must give clear solutions; no sediment may be present.

1 part dye solution and 2 parts 96 percent ethylene alcohol mixed and applied to a cellulose acetate film.

The product must dry up free of haze.

1 part dye solution and 2 parts 80 percent ethyl alcohol mixed and applied to a cellulose acetate film.

The product should dry up without leaving a haze.

Example 1 A mixture of 1 mole of 4,41-Dioxidiphenylpropane (2.2), 2 moles of formaldehyde (in the form of a 30 percent aqueous solution) and t 0 millimoles Sodium hydroxide solution is heated to 90 ° C. for 5 hours while stirring. Thereupon 1 mole Salicy acid and 0.1 mol of phthalic anhydride were added and a further 4 hours Heated to 1000C. The product is evaporated to dryness and pulverized.

The pale yellow powder becomes a flexographic ink as follows processed: 40 parts of the product are in 90 parts of ethanol (96 Xig) and 10 Parts of ethylene glycol dissolved. 30 parts of a styrene-maleic acid ester copolymer are added to this solution and 7 parts of Rhodamin FB (Color Index Edition II Vol.I (1956) No. 45 170).

One with this flexographic printing ink on a rotary varnishing machine lacquered aluminum foil had completely haze-free lacquer according to the test method DIN 16 524 the excellent water fastness 4 - 5.

Example 2 It is consumed as described in Example 1, used but instead of 1 mole of 4,4'-dioxydiphenylpropane (2.2), 1 mole of p-tertiary butylphenol. Water fastness: 5.

Example 3 A mixture of 0.7 moles of dodecylphenol, 0.3 moles of 4,4l-dioxydi.

aphenylpropane (2.2), 2 moles of formaldehyde in the form of a 30 point aqueous The solution and 0.01 mol of sodium hydroxide solution are heated to 90 ° C. for 5 hours. Thereupon 1 mole Salicylic acid and 0.1 mol of phthalic anhydride were added and a further 4 hours 10,000 heated with stirring. Then the water is evaporated and the product pulverized. Water fastness: 5.

Example 4 A mixture of 0.8 moles of dodecylphenol, 0.2 moles of 4,4'-dioxydiphenylpropane (2.2), 2 mol of formaldehyde in the form of a 30 denier aqueous solution and 0.01 mol of sodium hydroxide solution is heated to 80 ° C. for 4 hours with stirring. Then 1 mole of salicylic acid and 0.1 mol of phthalic anhydride was added and the mixture was heated to 100 ° C. for a further 4 hours. To as the water evaporates, the product is pulverized. Water fastness: 5.

Example 5 The procedure given in Example 2 is used However, as a phenol component, a mixture of 0.8 mol p. -tertiary butylphenol and 0.2 moles of 4,4'-dioxydiphenylpropane (2.2). The water fastness is 5.

Example 6 0.8 mol of dodecylphenol and 0.2 mol of 4,41-dioxydiphenylpropane are charged (2.2), 2 mol of formaldehyde in the form of the 3Q show aqueous solution and 0.01 mol of sodium hydroxide solution in an autoclave, heats to 90 ° C and presses nitrogen to 5 atmospheres. After 2.5 The reaction mixture is allowed to cool to room temperature for hours, the pressure is released and the reaction mixture is poured into a flask, mixed with 1 mol of salicylic acid and 0.1 mol of phthalic anhydride and heated to 1000C for a further 4 hours while stirring. After the water has evaporated the product is pulverized. Water fastness: 4 - 50 Example 7 The procedure is followed the details of Example 6; However, it becomes after the addition of 1 mol of salicylic acid and 0.1 mol of phthalic anhydride heated again to 1000C for 2 hours under 5 atmospheric pressure.

The product obtained in this way shows a water fastness of 5.

Example 8 A mixture of 1 mole of p.-tertiary-butylphenol, 2 moles Formaldehyde as a 30% aqueous solution and 0.01 mol of sodium hydroxide solution is 5 hours stirred at 90 ° C. After adding 0.8 moles of maleic anhydride, the mixture is heated further 4 hours with stirring at 950C.

After the water has evaporated, the product obtained is pulverized. Water fastness: 5.

Example 9 The procedure described in Example 8 is repeated, but continues instead of 0.8 mol of maleic anhydride a mixture of 0.5 mol of acetic anhydride, 0.2 mol of succinic anhydride and 0.2 mol of tetrachlorophthalic anhydride. Water fastness: 4 - 5.

Example 10 The procedure described in Example 8 is repeated, but continues the acid anhydride is a mixture of 0.3 mol of tetrachlorophthalic anhydride, 0.3 mol o-sulfobenzoic anhydride, 0.2 mole pyrocartaric anhydride and 0.1 mole phthalic anhydride to. Water fastness: 5.

Example 11 A mixture of 1 mole of dodecylphenol, 1.9 moles of formaldehyde in the form of the 30% aqueous solution and 0.01 mol of sodium hydroxide solution is 6 hours 800C, then 1 mol of salicylic acid and 0.1 mol of maleic anhydride were added and stirred for a further 4 1/2 hours at 950C. After the water has been evaporated, the product can be pulverized. Water fastness: 5.

Example 12 A mixture of 1 mole of p.-tertiary-butylphenol, 2 moles Formaldehyde (30% in aqueous solution) and 0.01 mol of sodium hydroxide solution is 5 hours stirred at 90 ° C. After cooling down the will forming aqueous Phase separated. 0.2 mol of formaldehyde are added to the organic phase as well 1 mole salicylic acid and 0.1 mole phthalic anhydride. The reaction mixture is 2 Stirred for hours at 90.degree. C. and 4 hours at 1000.degree. That cooled and pulverized Product shows a water fastness of 5.

Claims (9)

Claims 1. Fuel-soluble condensation products from phenols, formaldehyde, aromatic hydroxycarboxylic acids and / or organic acid anhydrides by reacting one mole of an optionally substituted phenol or several Phenols in aqueous solution with 0.5 to 2.5 mol of formaldehyde or formaldehyde-releasing Compounds at elevated temperature in a pH range of approx * 6.5 to 14 and subsequent further reaction with 0.01 to 3 mol of an aromatic hydroxycarboxylic acid and / or 0.01 to 3 mol of an organic acid anhydride at 30 to 1000C and in a pH range of about 7.5 to --1 and, if necessary, subsequent drying and isolating the condensation product. 2. Process for the production of fuel-soluble condensation products from phenols, formaldehyde, aromatic oxycarboxylic acids and / or acid anhydrides according to claim 1, characterized in that, in aqueous solution 1 mole of one optionally substituted phenol or various phenols with 0.5 to 2.5 Moles of formaldehyde or formaldehyde-releasing compounds at elevated temperature in a pH range of about 6.5 to 14 and then with 0.01 mol of one aromatic hydroxycarboxylic acid and / or 0.01 to 3 mol of an organic acid anhydride at 30 to 1000C and in a pH range of about 7.5 to -1 further converts, if necessary dries and the condensation product is then isolated. 3. The method according to claim 2, characterized in that one is a Mixture of up to 4 different phenols used. 4. Process according to Claims 2 and 3, characterized in that the entire reaction is carried out under excess pressure. 5. The method according to claims 2, 3 and 4, characterized in that the implementation, which takes place in a pH range of approx. 6.5 to 14 is carried out, carried out under excess pressure. 6. Process according to Claims 2 to 5, characterized in that one in the part of the implementation; which is carried out in a pH range of 7.5 to -1 is a mixture of 2 to 4 different acid anhydrides in an amount of 0.01 up to 3 moles. 7. Process according to Claims 2 to 6, characterized in that one uses phenols with a side chain of 2 to 20 carbon atoms. 8. Process according to Claims 2 to 7, characterized in that the aqueous phase formed after the condensation of phenols and formaldehyde separated and then before the addition of hydroxycarboxylic acid and acid anhydride 1 to 0.5 moles of formaldehyde are added. 9. Use of the fuel-soluble condensation products according to claim 1 for the production of printing inks.