NL8007104A - PRINT INK COMPOSITIONS AND METHOD FOR PREPARING THEM. - Google Patents

Description

4 ». 37 N.O. 29.7 ^ 0 -1- *

Printing ink compositions as well as a method of preparing them.

The invention relates to improved printing ink compositions as well as a method of preparing them. In particular, the invention relates to printing ink compositions suitable for high speed printing methods.

The dispersion of finely divided pigments, ie ink dye, into organic ink carriers to form a material suitable as a printing ink is extremely complex.

The type of surface to be printed on, the printing press used, the speed of the process and the time for drying are all basic factors, which determine the quality properties with regard to processing in a satisfactory ink.

The greatly increased circulation of modern newspapers has involved the development and use of high-speed presses in the printing industry. This makes it necessary to have printing inks that dry quickly. Resin-based systems that can be dried using water, steam or hot air gradually replace conventional drying oils. Modern high-speed printing presses require inks that dry in seconds rather than minutes.

20 For high speed printing, inks should maintain an appropriate balance of adhesion, penetration and consistency control. Excessive adhesion can cause the paper to tear or the ink to form mist at high printing speeds. Ink with insufficient adhesion will not be suitably transferred on printing. If the ink penetration is too great, the print will be visible on the other side of the paper, or blurring of shapes will occur. Poorly controlled penetration can stain after the ink is assumed to be dry. An ink must have consistency to prevent the ink from being released by centrifugal forces at high printing speeds. On the other hand, an excessively viscous ink will not flow adequately from the reservoirs to the rollers.

It is necessary for the ink industry to rely on a wide variety of formulations because of these necessary conditions and variations. U.S. Pat. No. 2,750,296 discloses a printing ink containing dye dispersed in a carrier containing an oil-soluble resinous binder containing 8007104 dissolved petroleum containing an aliphatic amine long chain bentonite containing. 3 ^ carbon atoms in the aliphatic chain. On the other hand, U.S. Pat. No. 2,751,219 describes the formation of a non-fog forming printing ink, which is prepared by adding to an ink, the main carrier component of which is a hydrocarbon containing an aromatic component, a finely divided organic derivative of to add montmorillonite, wherein the organic component comprises a chain of at least 12 carbon atoms. U.S. Patent No. 10 2,739,067 describes a printing ink containing a modified clay which forms a gel in the organic carrier and has a substantial gel character therein. However, the known compounds all suffer from various drawbacks. For example, some of them require the undesirable use of polar dispersion additives, which can react with the other components of the ink formulation, thereby eliminating important properties of the ink, while others require numerous shearing operations in the roll chair to form a viscosity. stable material, the storage viscosity of which does not increase with the associated high personnel costs and production cessation.

In contrast to these prior art techniques, US Patent 4,193,806 describes the preparation of a storage stable printing ink containing an organic ink vehicle and an organophilic clay gelling agent comprising the reaction product of a clay of the smectite type with an exchange capacity for cations of at least 75 milliequivalents per 100 g of clay and a methylbenzyldialkylammonium compound or a dibenzyldialkylamonium compound, in which the alkyl groups contain 1 to 22 carbon atoms. According to this US patent, the printing inks are at full viscosity levels. achievable once run through a three-roll device, which is in contrast to known comparable gelling agents that continue to increase in viscosity. Although the printing ink of this patent has brought the state of the art to a new level, further progress and improvement is necessary to eliminate the pre-processing using high shear to obtain acceptable viscosity levels.

Surprisingly, a printing ink composition containing an additive which increases the viscosity has been found, this kO printing ink composition having an organic ink vehicle containing an ink dye dispersed therein and an organophilic clay gelling agent, which is the reaction product of a clay of the smectite type with an exchange capacity for cations of at least 75 milliequivalents per 100 g of clay and containing a material, such as a quaternary compound containing methyl trialkyl and / or benzyl trialkyl group, such as an ammonium and / or phosphonium compound, in which the alkyl groups are straight or branched and contain 12-22 carbon atoms, and the amount of this quaternary compound reacted with this clay is 100-150 milliequivalents per 100 g clay, based on 100 # ac-. 10 clay, inclusive.

The clays used to prepare the organophilic clay gelling agents of the invention are of the smectite type and have a cation exchange capacity of at least 75 milliequivalents per 100 g of clay. Particularly suitable clays are the naturally occurring "Wyoming" varieties of swelling bentonites and similar clays, and hectorite, a swelling magnesium-lithium-silicate-containing clay.

The clays, especially the bento-non clays, are preferably converted to the sodium form unless they are already in this form. This can be conveniently done by preparing an aqueous clay slurry and passing the slurry through a bed of resin to exchange cations to yield the sodium form. Alternatively, the clay can be mixed with water and a soluble sodium compound, such as sodium carbonate, sodium hydroxide and the like, and applied to the mixture using a clay kneader or extruder / shear.

Clays of the smectite type, which occur naturally or are synthetically prepared by a pneumatic or preferably a hydrothermal synthesis method, can also be used to prepare the organophilic clays suitable according to the invention. Examples of such clays are montmorillonite, bentonite, beidelite, hectorite, saponite and stevensite. These clays can be synthesized hydrothermally by forming an aqueous reaction mixture in the form of a suspension, which mixed water-containing oxides or hydroxides of the desired metals with or without sodium, or other interchangeable, depending on the conditions. cation or a mixture thereof) containing fluoride in the amounts desired for the intended synthetic smectite. The slurry is then autoclaved, and heated for 8007104 * * -4 for a period sufficient to form the desired product under autogenous pressure at a temperature in the range of about 100 - 325 ° C »at preferably 27k - 300 ° C,

The cation exchange capacity of the smectite-type clay soils can be determined by the known ammonium acetate method.

The quaternary material, i.e., the ammonium and phosphonium compounds reacted with the smectite type clays, is a methyltrialkylammonium salt, a methyltrialkylphosphonophonium salt, a benzyltrialkylphosphonium salt, a benzyltrialkylphosphonium salt, or a mixture thereof the same or different alkyl groups are linear or branched and contain from 12 to 22 carbon atoms and are saturated or unsaturated. The alkyl groups preferably contain 16-18 carbon atoms, and most preferably 20-35% of the alkyl groups contain 16 carbon atoms and 60-75% 18 carbon atoms. The salt anion is preferably chloride and / or bromide and preferably chloride, although other anions such as acetate, hydroxide, nitrite, etc. may be present in the quaternary salt to neutralize the quaternary cation. These quaternary salts can be represented by the formula of the formula sheet, wherein X represents a nitrogen and / or phosphorus atom, a CH 2 or C 8 H 2 CH 2 group, R 2, R 2 and R 2 long alkyl groups of 12-22 represent carbon atoms, and wherein M "represents chloride, bromide, nitrite, hydroxyl, acetate, and / or methyl sulfate.

The long chain alkyl groups can come from naturally occurring oils including various vegetable oils, such as corn oil, coconut oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils or fats such as tallow oil. The alkyl groups may also originate from petrochemical materials, such as from α-olefinically unsaturated compounds. Other examples are stearyl and oleyl groups.

The quaternary ammonium salts are preferably benzyl and / or methyl groups containing triple hydrogenated tallow ammonium chlorides. Commercially prepared hydrogenated tallow has the following analysis in particular: 2.0% alkyl groups with 1 carbon atoms, 0.5 # alkyl groups with 15 carbon atoms, 20.0 # alkyl groups with 16 carbon atoms, 1.5 # alkyl groups with 17 carbon atoms 66.0 # alkyl groups with 18 carbon atoms and 1.0 # alkyl groups with 20 carbon atoms.

4-0 The organophilic clays of the invention can be prepared 8007104-5 by mixing the clay, quaternary compound and water, preferably at a temperature in the range of 20 - 80 ° C, in particular of 60 - 75 ° C C. for a period of time long enough to obtain a coating of the organic quaternary compound on the clay particles, after which it is filtered, washed, dried and ground. When the organophilic clays are used in emulsions, drying and mowing can be omitted. When the clay, quaternary compound and water are mixed in such concentrations that no slurry is formed, filtration and washing can be omitted.

The clay is preferably dispersed in water at a concentration of about 1-80 wt.%, Preferably 2-7 wt.%, The suspension is optionally centrifuged to remove non-clay-like impurities containing about 10 wt. # to about 15 to 50 weight percent of the clay composition used as the starting material; the suspension is stirred and heated to a temperature in the range of 60-77 ° C; the quaternary ammonium or phosphonium salt is added in the desired milliequivalent ratio, preferably in liquid form in isopropanol or dispersed in water; 20 and stirring is continued to effect the conversion.

The amount of quaternary compound added to the clay according to the invention must be sufficient to impart the desired improved dispersion properties to the clay. The milliequivalent ratio is defined as the number of milliequivalent quaternary compound in the organophilic clay per 100g clay, based on 100 # active material. The organophilic clays of the invention have a milliequivalent ratio of 100-130. At lower milliquivalent ratio values, the organophilic clays are ineffective gelling agents, although they may be effective gelling agents when dispersed conventionally with a polar additive. At higher values of the milliequivalent ratio, the organophilic clays are poor gelling agents. However, the preferred milliequivalent ratio in the range of 100-130 will depend on the properties of the organic system to be gelled by the organophilic clay.

The printing ink is prepared economically and practically by simply incorporating the organophilic clay gelling agents into a base ink composition containing an ink dye and an organic ink vehicle.

8007104 -6- w *

The ink compositions prepared with the compositions of the invention achieve a high viscosity level by stirring only in the ink formulation and do not need to be passed through a three-roll device or similar systems need not be used to increase the obtain viscosity.

The product can be easily dispersed as a rheological additive to obtain a maximum viscosity created by conventional dispersants without the use of a three-roll device. The organophilic clays of the invention provide an ink composition which, when suitably dispersed, has a particle size so fine that it is not necessary to filter or grind to prepare a useful formulation.

Although a three-roll device can be used to assist in dispersing the ink dyes or pigments so that the ink can be used satisfactorily in a printing device usually requiring this process, such no processing required to increase the viscosity.

Passing through a three-roll device will in some cases be necessary in ink systems where oxidation takes place, so that the air trapped during dispersion will not cause the formation of small hard ink particles.

Thus, the invention can be practiced by adding the organophilic clay gelling agent to a previously prepared finished printing ink. These inks can be prepared by any conventional method, such as with colloid mills, roller seats, ball mills, etc., in which the ink pigment material is well dispersed Hn 50 the organic ink vehicle by the high shear applied during the process. The pigment dispersion in the carrier forms a normal ink and tends to mist as usual.

The organophilic clay gelling agent is used in amounts sufficient to obtain the desired viscosity value and tack in the printing ink. If necessary, the viscosity can be further controlled by adding a viscosity reducing agent, for example naphthenic oil or solvent.

Generally, an amount of 0.1-10 wt.% Of the printing ink is sufficient to greatly reduce the tendency to mist the ink bO when it is used for printing with 8007104

* V

Fitting of high speed presses, preferably using an amount of 0.5 wt.%, And in particular an amount of 1-3 wt.%. When the gelling agent is used at a concentration of less than 0.1 wt% or more than 10 5 wt% of the printing ink, the consistency, flow, and other properties affecting the critical characteristic of the ink become severe adversely affected, i.e. the desired increase in viscosity and tack is not achieved.

The printing inks according to the invention may contain the ink additives customary for such printing inks. For example, oil-soluble organic dyes can be used to counteract the brownish tint of petroleum, and gas-carbon black pigment, as well as small amounts of wax or fat, can be used to impart special properties to the printing ink.

Non-limiting examples of printing inks that can be used with the gelling agents of the present invention are; ink that dries using heat or ink for newspaper printing, ink that dries using water or steam, or lithographic printing ink.

Newspaper inks dry mainly by permeation and absorption, although some heat is used to accelerate drying and prevent stains. By suitably controlling the viscosity, tack, and yield strength of such inks, the organophilic clays of the present invention effectively accomplish suitable penetration without centrifugal shedding or misting.

When the organic clays of the invention are used with other typographic inks that dry by application of heat, such as, for example, excellent quality inks for magazines, containing additives such as binders and solvents, the inks are extremely flexible and the inks stain not and press well and dry quickly at high temperature.

The use of the gelling agent in inks drying by the application of steam or water seriously affects the viscosity and tack because it causes a characteristic deficiency of the ink.

Lithographic printing inks, on the other hand, are very similar in composition to typographic inks, except that the consistency is somewhat higher and the concentration of pigment is somewhat higher. The advantages of using the above-mentioned organophilic clays also apply here.

The following examples further illustrate the invention.

In the examples, the following test protocols were used:

Dispersion.

The test ink was drawn from a "NPIHI G-1 Grindometer" in both channels and examined for fineness of grinding (small particles) and scratching. The meter scale is from “10” to “0.” A reading of 10 corresponds to a depth of 0.025 mm and a reading of 0 means a depth of 0. Samples were taken to make a minimum of four individual readings. were taken and averaged A perfect value for a sample to be tested would be "0" 15 for both grinding and scratching fineness.

Viscosity.

Viscosity was measured using a "Thwing-Al-bert" drop bar viscometer at a block temperature of 26 ° C. Air was removed from the ink by simple spatulation and then a rod was completely coated with the ink sample.

Three weights were used to obtain fall time values: 700 g, 500 g and 200 g. The tests with these weights were repeated and the values were processed using a "Hewlett-Packard" computer to obtain the predicted "Bingham" viscosity in poise at 1000 sec. . The viscosity value chosen for the tables was obtained using the values containing the least effective deviation from a straight line, which is calculated from the "Bingham" equation

Vt-dbmb 30 which forms the intercept on the axis of the shear load when the shear rate is zero. f is the value obtained

iJ

T is the shear load Dc is the shear rate 35 M „is the viscosity.

D

Example I.

A "web offset" suitable blue ink formulation on a heat drying base was prepared with the elements listed in Table A and passed once over a three-roll mill to obtain a fine ink dispersion. Then 8007104 ° -9-, the rheological additive was slowly added to the base ink with minimal agitation to avoid wastage. A dispersion was obtained at 3000 revolutions per minute using a 0.3 H.P. Premier Dispersator Unit ”using a“ Cowles ”vane. The appropriate speed was maintained for 15 minutes. After a dispersion was obtained, viscosity measurements were made after 24 hours and one week.

Individual ink samples were treated with various organophilic clay derivatives and comparative material in an amount of 2% by weight.

Comparative Run A did not use a rheological additive, while Comparative Run B used finely divided silica with the trade name "Aerosil fi-972" (DeGussa Ine.).

Runs 1-3 of the invention used a reaction product of Wyoming bentonite and methyl triple hydrogenated tallow ammonium chloride and benzyl triple hydrogenated tallow ammonium chloride at the indicated milliequivalent ratios.

The results are shown in Table B. The results show that the comparative rheological additive exhibits poorer grinding fineness and less effective gelling properties than the formulations of the invention (see Tables A and B). Example II,

A "web offset" suitable red ink formulation on a heat drying base was prepared with the ingredients shown in Table C and passed over a three roll mill to obtain a fine ink dispersion. Then the rheological additives were added in the indicated amount and dispersed by simple mixing with a spatula (spatulation) for 5 minutes. The results are shown in Table G.

The quaternary compounds were prepared in the manner described in Example III.

Comparative Run C did not use a rheological additive, while Comparative Run D used finely divided silica as in Run B. In comparative test E 35, the rheological additive used in U.S. Pat. No. 4,193,806 was used, namely a methylbenzyl-two-hydrogenated tallow-ammonium bentonite with a milliequivalent ratio of 112. The values show that with the material of the invention, prepared from the quaternary compound according to the invention obtained, a good dispersion and efficiency Under conditions 8007104 -10- with gentle mixing, without any significant increase in viscosity.

(see tables C and D).

Example III.

The procedure of Example II was repeated with the same ink base of Table C, except that "after the rheological additives were added to the base" a dispersion was obtained at a rate of 1000 revolutions per minute and 3000 revolutions per minute used for the dispersion. minute using a ”0.5 HP 10 Premier Dispersator Unit "using a" Cowles "blade. Results are shown in Table E (1000 revolutions per minute) and Table F (3000 revolutions per minute).

In order to further investigate rheological additives of the test using 3000 revolutions per minute, the ink samples were passed once under a pressure of 35 kg / cm over a three-roll mill. Viscosity measurements were then made and repeated after 2b hours. The results are shown in Table F.

(see tables E and F).

Example IV.

The procedure of Example II was repeated with the same ink base of Table C. This procedure used 6 g of additive (2 wt. $), Which was added to 29b g of base ink in an open container ("pint friction top can") under low shear using a laboratory grade "0.5 HP Cowles Disperser" with the blade just above the bottom of the container. After the additive was completely taken up by mixing, the mixing speed was brought to 3000 rpm and the ink was then mixed at 5 minute intervals and samples were taken and examined for the fineness of grinding and scratching. The temperature and dispersion were monitored at 5 minute intervals. Mixing was especially interrupted when a good dispersion was obtained or after a maximum mixing time of 20 minutes. The blank test was mixed for 15 minutes to make the course of the test approximately the same as for the other samples.

The results are shown in Table G.

The values show that the materials used for the comparative tests exhibited poor grinding fineness, brackets, difficulties when dispersed at high mixing speed, and viscosity stability problems. after aging in the ink. However, the formulations of the invention exhibited good grinding fineness and highly stable viscosity values without the need to pass through a three-roll mill or the need for similar shearing equipment.

(see table G).

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Claims (12)

A printing ink composition containing an organic ink vehicle with an ink dye dispersed therein and an organophilic clay gelling agent, characterized in that said organophilic clay gelling agent is the reaction product of a smectite type clay with an exchange capacity for at least cations 75 milliequivalent per 100 g of clay and a material such as methyl trialkyl quaternary compound and / or benzyl trialkyl quaternary compound, said quaternary compound being an ammonium and / or phosphonium compound and the alkyl group containing 12 to 22 carbon atoms, and the amount of this quaternary compound reacted with the clay is 100-130 milliequivalent per 100 g clay, 100 # active clay base. Printing ink composition according to claim 1, characterized in that the clay is hectorite and / or sodium bentonite. Printing ink composition according to claim 1 or 2, characterized in that the alkyl group contains 16 or 18 carbon atoms. Printing ink composition according to one or more of the preceding claims, characterized in that the organophilic clay gelling agent comprises 0.1-10% by weight of the printing ink composition. Printing ink composition according to claim 4, characterized in that the organophilic clay gelling agent comprises 1.0-3.0 wt.% Of the printing ink composition. A printing ink composition containing an organic ink vehicle with an ink dye dispersed therein and an organophilic clay gelling agent, characterized in that this organophilic clay gelling agent is the reaction product of a hectorite or sodium bentonite clay with a capacity for exchanging cations of at least 75 milliequivalents per 100 g of clay and a quaternary compound of the formula of the formula sheet, wherein X represents a nitrogen or phosphorus atom, the group is CH 2 or C 8 H 2 Cl 2 and R 1, R 1 and R alkyl groups of 12-22 carbon atoms and M represents a chloride, bromide, nitrite, hydroxide, acetate, and / or methyl sulfate, and wherein the amount of the quaternary compound reacted with this clay is 100-130 milliequivalents per TOO g clay, 100 # active clay base. A printing ink composition according to claim 6, characterized in that the organophilic clay comprises the reaction product of a sodium bentonite and raethyl triple hydrogenated tallow ammonium chloride and / or benzyl triple hydrogenated tallow ammonium chloride 8007104 -20 ride. Printing ink composition according to claim 6 or 7, characterized in that the organophilic clay gelling agent comprises 0.1-10% by weight of the printing ink composition. A method of preparing a printing ink composition, characterized in that (a) a dispersion of an ink dye with an organic ink vehicle is formed; (b) prepare an organophilic clay gelling agent comprising the reaction product of a smectite type clay having a capacity of exchanging cations of at least 75 milliequivalents per 100 g clay and a material such as methyltrialkyl quaternary compound and / or benzyltrialkyl-quaternary compound, said quaternary compound being an ammonium and / or phosphorium compound and the alkyl group containing 12-22 carbon atoms, the amount of this clay-reacted ammonium compound being 100-130 milliequivalents per 100 g clay, 100 # active clay base is} and (c) disperses this mixture to prepare a viscous printing ink composition. Process according to Claim 9i, characterized in that the clay used is hectorite or sodium bentonite. 11. Process according to claim 9 or 10, characterized in that the organophilic clay gelling agent is used in an amount of 0.1 - 10% by weight, based on the printing ink composition. 12. Substrate, printed with the printing ink composition according to claims 1-8, respectively obtained by using the method according to claims 9-11 «8007104" ί * ο "Ί + β I" RZ-f "R3 8007104