CS256854B1 - Offset and printing ink - Google Patents

Description

The present invention relates to offset and letterpress inks based on rosin esters and polyhydric alcohols which may contain alpha, beta-unsaturated dicarboxylic acid and are modified with phenol-formaldehyde resins.

The two-step preparation of these resins is known from A.O. No. 227,794, which also describes their use in the formulation of paints. It is also known that offset and intaglio inks are made from resins, which are formed by the simultaneous condensation of rosin, polyhydric alcohols, or. alpha, beta-dicarboxylic acids and phenolic resins. As shown in A.O. No. 227,794, during the preparation of these resins, a series of parallel reactions takes place, which, according to the reaction conditions, contribute to the resulting properties of the resins to an uneven extent. For this reason, the preparation of these resins is difficult to reproduce and the utility properties of the products vary from batch to batch. This results in deterioration and variability in ink quality when formulating inks. These include, in particular, tackiness, color drying rate and gloss, and optical density of the printed ink film.

These disadvantages are overcome by the invention. SUMMARY OF THE INVENTION The present invention provides an offset and letterpress ink based on rosin esters and polyhydric alcohols modified with phenol-formaldehyde resins, alkyd resins, organic solvents and pigments containing, based on the color as a whole, 13.5 to 36% by weight of hard resins having an acid number of 10 to 40 mg. KOH / g and a softening temperature of 140 to 180 ° C, prepared by first preparing at 250 ° C to 300 ° C, an ester of a natural resin with pentaerythritol, wherein the ratio of carboxyl to hydroxyl groups is 1 to 0.8 to 1.5 and natural resin it may be replaced by an equivalent amount of maleic acid or its anhydride, up to 40% of the total sum of the carboxyl groups, after which the ester formed is condensed at a temperature of 220 to 260 ° C with a phenol-formaldehyde resin of 5 to 40% by weight. of the total hard resin charge.

The inks prepared according to the invention are perfectly reproducible in terms of viscosity, tackiness, solvent compatibility and a very narrow range of technical parameters, excellent wettability of pigments and hence high optical values of the printed lacquer film.

The nature of these effects will be illustrated by examples of formulations and properties of inks, to which the invention is not limited in any way.

Example A (comparative - not subject of the invention)

In a 6 liter siilphonation flask equipped with an electric stirrer and transducer, there were 3,578 g of rosin (acid number 166.52; carboxyl equivalent 336.96), i.e. 10.62 equivalents,

27.1 g of maleic anhydride i.e. 0.55 equivalents and 366.9 g of pentaerythrite i.e. 10.79 equivalents condensed with 1020 g of p-tert-butylphenol-based phenol-formaldehyde resin at 255 ° C for 10.20 hours. The total sum of carboxyl equivalents is 11.17, of which 4.92% equivalents are replaced by maleic anhydride. The ratio of hydroxyl groups to carboxyl groups is 0.966.

At the end of the condensation, 4,631 g of a resin with an acid number of 11.96 mg KOH / g, a softening point of 154 ° C and a cloud point in the kerosene fraction PKWF 6/9 38 ° C and 209.6 g of distillate were obtained.

Four batches of this resin were prepared in the same manner and exhibited the properties listed in Table 1 under the designation

5 samples of color labeled A 1 _v (Table 3) were prepared from the resin A 1 g according to the following recipe:

Phthalocyanine blue 17.5 wt Resin 13.8 Alkyd resin mod. 65 » linen oils 18.0 Linseed oil 10.0 Mineral oil (b.p. 280- -310 ' ³ C) 31.7 Wax paste 7.0 Cobalt naphthenate solution 10 i 1.0 Manganese naphthenate solution 5% 1.0

Example B (comparative - not subject of the invention)

As in Example 1, 3,578 g of rosin (10.62 equivalents), 242 g of maleic anhydride (4.94 equivalents), 621 g of pentaerythrite (18.26 equivalents) and 320 g of phenol-formaldehyde were welded at 255 ° C for 18.45 hours. resin. The total sum of carboxylic equivalents is 15.56, of which 31.7% is maleic anhydride. The ratio of hydroxyl and carboxyl groups is 1.17. 360 g of water and terpenes were distilled to obtain 4220 g of resin having an acid number of 11.55 mg KOH / g, a softening point of 156 ° C and a cloud point in the kerosene fraction PKWF 4/7 86 ° C.

Four batches of this resin were prepared in the same manner and their properties are listed in Table 2 under the designation B ^ -5 *.

5 samples of colors marked (Table 4) according to the following recipe were prepared from resin B ^, -:

Phthalocyanine blue 17.0 wt. d.

Resin B 35.8

Isophthalic alkyd mod. 72% linseed oil 3.0

Mineral oil (b.p. 240-270 ° C) 39.0

Aluminum chelate 1,2

Wax Paste 4.0

100.0

Example 1

According to the method protected by A.O. No. 227,794, the same amounts of rosin, maleic anhydride, and pentaerythrite as in Comparative Example A were esterified at 285 ° C for 3.2 hours to an acid number of 11.02 mg KOH / g. 4,071 g of rosin pentaester were obtained, to which, after cooling to 240 ° C, 1,020 g of phenol-formaldehyde resin, i.e. 20% of the total weight, were added and condensed at 240 ° C for one hour. 4.736 g of a resin with an acid number of 18.26 mg KOH / g, a softening point of 165 ° C and a haze temperature in the kerosene fraction PKWF 6/9 34.5 ° C (Resin 1a) were obtained.

The other four batches prepared in a similar manner exhibited the properties listed in Tab. No. 1 under the designation

A resin prepared according to the recipe color samples in Example A, and the colors indicated _in LI (Tab. No. 3).

Example 2

According to a method of preparing a protected A.O. No. 227,794, the same amounts of rosin, maleic anhydride and pentaerythrite were esterified at 255 ° C for 3.30 hours to an acid number of 10.55 mg KOH / g. 4 165 g of rosin pentaester were obtained, to which 320 g of phenol-formaldehyde resin, i.e. 7.13% of the total weight, was added at 245 ° C and condensed for one hour at

AND

245 ° C. 4.398 g of resin having an acid number of 17.55 mg KOH / g, a softening point of 165 [deg.] C. and a cloud point in the kerosene fraction PKWP 4/7 110 [deg.] C. were obtained (Resin 2a).

Prepared in the same manner as 4 batches, whose properties are shown in Table 2 under the designation _J _ _C 2j. The colors of these resins were prepared according to Example B and have the designation 2 _{T- V} (Table 4).

Table 1

Resin designation C. acid Softening point Turbidity temperature mg KOH / g ° C ° C

^A 1 11.96 154.0 38 AND 12.05 150.0 25 ^A 3 11.66 152.5 31 ^A 4 11.58 161.0 39 ^A 5 11.85 165.5 41 1 a 18.26 165.0 34.5 1 b 17.93 164.0 35.0 1 c 18.54 165.5 33.5 2 d 17.85 164.5 35.0 1 e 18.35 165.0 35.5

Table 2 Designation resin C. kys. Softening temperature Turbidity temperature mg KOH / g Noc: 2 ° C ° c ^B 1 11.55 156 86 * 2 11.75 161 91 ^B 3 12.01 155 73 ^B 4 11.05 162 95 ^B 5 12.10 157 81 2 a 17.55 165 110 2 b 18.35 164.5 109 2 c 17.20 163.5 108 2 d 17.95 166 111 2 e 18.20 164 108

Table3 Marking the color sample Gloss% Optical density Drying

^A I 19.6 1.87 4 229 ^And li 21.2 1.98 6 193 ^A III 20.1 . 1.95 3 244 ^A xv 22.7 2.00 5 198 20.5 1.90 5 227 aritmet. Avg. 20.8 1.94 4.6 218 variance (s) 3.1 0.13 3.0 36 ^ZX I 20.8 2.03 5.0 200 ^X II 20.6 2.02 4.0 181 ^X 1XI 20.4 1.99 4.0 178 ^X IV 21.4 1.98 3.0 181

continuation of Table 3

Color Sample Label Gloss% Optical density Drying Stickiness l _at 21.5 2.04 5.0 174 aritmet. Avg. 20.9 2.01 4.2 183 scattering (s, 1.1 0.06 2,0 26 Drying grade 1 - fastest 7 - slowest

Table Sample identification 4 colors Gloss% Optical density Drying Stickiness ^B I 20.4 2.01 3 225 ^B II 24.9 2.08 4 212 ^B III 21.5 1.93 3 249 ^B IV 22.6 1.96 3 227 ^B v 19.1 1.92 2 233 aritmet. Avg. 21.7 1.98 3 229 variance (s) 5.8 0.16 2 37 ² I 27.7 2.09 3 224 ² II 27.2 2.07 3 225 ² III 29.1 2.11 2 214 ² IV 29.3 2.13 3 230 ² v 28.2 2.06 2 209 aritmet. Avg. 28.3 2.09 2.6 220 scattering (S) 2.1 0.07 1 21

Drying grade 1 - fastest 7 - slowest

Example 3

A color was prepared from resin 1-a and 2-a according to the following recipe:

Phthalocyanine blue 16.5 mass, d.

Resin 1-a 11.3

Resin 2-a 13.5

Alkyd resin mod. 72% linseed oil 9.4

Linseed oil 18,2

Mineral oil (bp 260-290 ° C) 24.8

Wax paste 5.0

Aluminum chelate 0.8

Cobalt naphthenate solution 0,5

100.0

The color proof showed the following properties:

gloss 26,5% optical density 2,04 drying 4 tack 205

Example 4

602 g of rosin (acid no. 166.59, esterification equivalent of 336.81), i. 10.69 carboxylic equivalents, 387 g of pentaerythrite, i.e. 11.38 hydroxyl equivalents, were esterified at 295 ° C to an acid number of 12.78 mg KOH / g.

Thus the ratio of hydroxyl to carboxyl group in the batch was 1.06. Esterification yielded 3 705 g of product and 198 g of distillate. 600 g of the ester thus obtained were heated to 220 ° C and 400 g of phenolic resin, i.e. 40% by weight, were added and condensed at the same temperature for one hour. The product was a resin with an acid number of 39.5 mg KOH / g, a softening point of 152 ° C and a cloud point in the kerosene fraction PKWF 6/9 64 ° C. Resin prepared according to recipe A, which showed the following properties:

gloss 20.4%, optical density 1.98, drying 5.0 and tack 1.97,

Example 5

The same amount of rosin as in Example 4, ie 3,602 grams of rosin (10.69 carboxyl equivalents) was esterified in a similar manner at 255 ° C with 541.6 grams of pentaerythrite (15.93 equivalents). Thus, the ratio of hydroxyl to carboxyl groups was 1.49. 3,907 g of an ester with an acid number of 6.25 mg KOH / g and 205 g of an aqueous distillate were obtained.

900 g of product condensed with 100 g of phenolic resin at 257 ° C for 30 minutes.

825 g of the product had an acid number of 12.39 mg KOH / g, a softening point of 152 ° C and a cloud point in the PKWF fraction of 4/7 89 ° C.

The color prepared according to recipe B showed the following characteristics:

gloss 27.1%, optical density 2.08, drying 3, tack 228.

Example 6

696 g of rosin (8 equivalents) and 250.4 g of maleic anhydride (5.11 equivalents - i.e. 39% carboxyl equivalents) were esterified with 534.9 g (15.73 equivalents) of pentaerythritol. Thus, the ratio of hydroxyl to carboxyl groups was 1.2. The reaction was conducted at 295 ° C and discontinued at an acid number of 17.25 mg KOH / g.

3 076 g of ester and 295,4 g of distillate were obtained.

950 g of product condensed with 50 g of phenolic resin (5 wt%) at 240 ° C for one hour.

739 g of the final product showed the following properties:

the acid number 15.25 mg KOH / g, the softening point 178 ° C and the cloud point in the PKWF 4/7 fraction was 141 ° C.

The color prepared according to recipe B showed a gloss of 22.6%, an optical density of 1.98, a drying of 2, a tack of 174,

Example 7

578 g of rosin (ie 10.62 equivalents), 57.8 g of maleic anhydride (1.18 equivalents, ie 10% equivalents) esterified at 265 ° C with 321 g of pentaerythritol (9.44 equivalents) to an acid number of 16.25 mg KOH / g. The ratio of hydroxyl and carboxyl groups was 0.8. The ester yield was 3,687 g and 198 g of condensate.

900 g of ester condensed with 100 g of phenol-formaldehyde resin for 1 hour at 245 ° C. 870 g of a resin with an acid number of 17.65 mg KOH / g, a softening point of 158 ° C and a cloud point in the kerosene fraction PKWF 4/7 69 ° C were obtained.

The color prepared according to recipe B showed a gloss of 27.2%, an optical density of 2.03, a drying of 3, a tack of 225. ·

Claims (1)

Offset and letterpress ink based on rosin esters and polyhydric alcohols modified with phenol-formaldehyde resins, alkyd resins, organic solvents and pigments, characterized in that, based on the color as a whole, it contains 13,5 to 36% by weight of hard resins with an acid number of 10 to 40 mg KOH / g and a softening point of 140 to 180 ° C, obtainable by first preparing at 250 to 300 ° C, an ester of a natural resin with pentaerythritol, wherein the ratio of carboxyl to hydroxyl groups is 1 to 0.8 to 1.5, and natural the resin may be replaced by an equivalent amount of maleic acid or its anhydride of up to 40% of the total sum of the carboxyl groups, after which the ester formed is condensed at 220 to 260 ° C with phenol-formaldehyde resin amounting to 5 to 40% by weight .