JPH0693220A - Printing ink - Google Patents

Abstract

PURPOSE:To obtain oxidation polymerization type printing ink containing few or no ink solvent of a mineral oil fraction, free from problem of volatile solvents and problem of stability in printing, having quick dryness after printing and further capable of printing also on materials to be printed, made of synthetic resins. CONSTITUTION:This printing ink containing a coloring agent and an oxidation polymerization type resin varnish is characterized in that the oxidation polymerization type resin varnish contains 18-50C aliphatic compound having one or more unsaturated groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink, and more specifically, it is an object of the present invention to provide a printing ink free from the problem of volatilized solvent and excellent in drying property and on-machine stability.

[0002]

2. Description of the Related Art Conventionally, printing inks, particularly oxidative polymerization type printing inks, are composed of a colorant which is a pigment, a resin varnish which is a vehicle, an ink solvent of a mineral oil fraction, and additives such as a drying aid. It is mainly used for printing liquid-absorbent paper. As the varnish resin for these conventional oxidative polymerization type printing inks, natural or synthetic oxidative polymerization type resins are used, and ink solvents of various mineral oil fractions are used to control the viscosity, tack, flow, etc. of the ink. It is used in a proportion of 10 to 50% by weight of the total amount. In addition to adjusting the viscosity, the ink solvent absorbs the solvent into the paper after printing and contributes to the acceleration of the drying of the printing ink by improving the concentration of the coating film formed on the paper.

[0003]

[Problems to be solved by the invention] However,
When printing with the above conventional printing ink, the solvent in the ink is volatilized into the working atmosphere during drying, which eventually causes air pollution.Therefore, the printing factory is required to have equipment to prevent the solvent from being released into the atmosphere. It came to be like. This equipment burden is unbearable in small and medium-sized printing plants. Further, in the case of a printing ink containing an ink solvent of a mineral oil fraction, if the printing is interrupted, the ink solvent in the printing ink remaining on the printing plate will evaporate and various problems will occur when printing is restarted. There is a problem that it occurs and lacks on-board stability.

In addition, the oxidation polymerization type ink tends to be used even for a printing material having a low liquid absorbing property such as a synthetic paper or a plastic film (sheet) made of a synthetic resin as a printing material. In the case of a material, there is a problem that the material to be printed is corrugated during or after printing due to its low liquid absorbability, swelling of the synthetic resin due to liquid absorption, etc., which makes subsequent handling difficult. Therefore, an object of the present invention is a printing ink containing little or no ink solvent of a mineral oil fraction, which is free from the problem of volatilized solvent and the problem of on-machine stability, is quick-drying after printing, and is further synthesized. An object of the present invention is to provide an oxidative polymerization type printing ink which can be printed on a resin-made printing material.

[0005]

The above object can be achieved by the present invention described below. That is, the present invention is a printing ink containing a colorant and a resin varnish, wherein the resin varnish is
A printing ink comprising an aliphatic compound having at least one unsaturated group and having 18 to 50 carbon atoms.

[0006]

By using a specific compound capable of forming a film itself as a solvent for dissolving the varnish resin of the printing ink, it becomes unnecessary to use the ink solvent of the conventional mineral oil fraction almost or at all, Therefore, it is possible to provide an oxidative polymerization type printing ink which does not have a problem of a volatilized solvent and a problem of on-machine stability, is quick-drying after printing, and can be printed on a synthetic resin printing material.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. As the resin varnish used in the present invention, conventionally known natural or synthetic drying oils or semi-drying oils can be used. For example, natural oils and fats conventionally used in printing inks include linseed oil, large Soybean oil,
Safflower oil, cinnamon oil, Japanese kiri oil, sunflower oil,
Eno oil, hemp oil, tall oil, sesame oil, wheat germ oil, corn oil, rapeseed oil, rice bran oil, dehydrated castor oil,
Examples thereof include cottonseed oil, squid oil, sardine oil, swordfish oil, cod oil, and other fish oils, whale oil, and various modified products thereof. Examples of synthetic varnish resins include petroleum resins (aromatic and aliphatic). System, aromatic / aliphatic copolymer system), rosin ester, phenol-modified rosin, phenol resin, octylphenol, nonylphenol, and other resole-type or novolac-type resins.

The present invention is characterized in that the resin varnish contains, as a part thereof, an aliphatic compound having at least one unsaturated group and having 18 to 50 carbon atoms. The compound may be commercially available, such as tall oil fatty acid, or can be synthesized by any method. As a preferable synthetic method, the following several methods can be mentioned. A method of esterifying an unsaturated fatty acid with a mono- or dialcohol. A method of alcoholizing a drying oil with a mono- or dialcohol. A method of esterifying an unsaturated aliphatic alcohol with a suitable acid. A method for alcoholizing a drying oil with an unsaturated mono- or dialcohol.

The above method is carried out by using an unsaturated fatty acid having a suitable carbon number such as tall oil fatty acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoleic acid,
Products obtained by reacting linoleic acid, arachidonic acid, bucanic acid, parinaric acid, etc. with an aliphatic saturated or unsaturated monoalcohol having a suitable carbon number or a saturated or unsaturated dialcohol such as ethylene glycol Of 18 to 50 carbon atoms and one or more unsaturated groups. Examples of the saturated aliphatic alcohol used in this method include methanol, ethanol, n- or is
o-propanol, n, sec or tert-butanol, heptinol, 2-ethylhexanol, hexanol, octanol, decanol, dodecanol and the like can be mentioned. Examples of the unsaturated aliphatic alcohol include:
Examples thereof include oleyl alcohol, dodecenol, fuseteri alcohol, sommaryl alcohol, oleyl alcohol, gadreyl alcohol, 11-icosenol, 11-docosenol, and 15-tetooracocenol.
Examples of the glycol (dialcohol) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentamethylene glycol, dipentamethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene. Glycol, butanediol, hexadecane-1,2-diol, octadecane-1,2-diol, icosane-1,2-diol, docosane-1,2-diol, tricosane-1,2.
-Diol, tetracosane-1,2-diol, octadecane-1,3-diol and the like.

In the above method, the drying oil as described above is subjected to alcoholysis with a suitable saturated or unsaturated alcohol or saturated or unsaturated glycol as described above to obtain a product having 18 to 50 carbon atoms, and 1 unsaturated group
It is a method of making more than one piece. Further, the above method is carried out by reacting an unsaturated aliphatic alcohol having an appropriate carbon number as described above with a saturated or unsaturated low to medium-grade fatty acid or polycarboxylic acid having an appropriate carbon number. The resulting product has 18 to 50 carbon atoms and one or more unsaturated groups. Further, the above method is a method in which the unsaturated oil is subjected to alcoholysis with the above-mentioned unsaturated alcohol or unsaturated glycol, and the resulting product has 18 to 50 carbon atoms and at least one unsaturated group. .

Examples of the esterification reaction or alcoholysis reaction as described above include a method of heating both under normal pressure or under pressure in the absence of a catalyst, preferably an acid catalyst or an alkali catalyst, but other methods may be used. It may be. In the present invention, the number of carbon atoms having at least one unsaturated group is particularly preferably 1
The aliphatic compounds 8 to 50 are tall oil fatty acid, its ester, ester of oleic acid and oleyl alcohol, and alcoholysis product of the drying oil. In the present invention, the number of carbon atoms having at least one unsaturated group is 18 to 18
The aliphatic compound of 50 is preferably used in a ratio of about 5 to 90 parts by weight per 100 parts by weight of the varnish resin. When the amount of the C18-C50 aliphatic compound having one or more unsaturated groups is less than 5 parts by weight, the viscosity of the printing ink formed is too high, which makes printing difficult. If the amount of the aliphatic compound having 18 to 50 carbon atoms and having at least one of the above is more than about 90 parts by weight, the quick drying property of the resin varnish is unsatisfactory and the strength and luster of the ink coating become insufficient.

The colorant is a pigment used in conventional printing inks, and any conventionally known pigment can be used as it is as a colorant for the printing ink of the present invention. The amount of the ink used may be the same as that of the conventionally known printing ink, for example, about 1 part by weight in 100 parts by weight of the printing ink.
A proportion of 0 to 40 parts by weight is common. As the dryer, naphthenic acid, octylic acid, resin acid of polyvalent metal such as cobalt, manganese, cerium, zirconium, lead, iron, zinc, copper, vanadium, barium and calcium,
An oil-soluble carboxylic acid such as tall oil fatty acid, a salt of a resin acid, or the like, and these dryers are generally used in a ratio of about 0.005 to 0.5% by weight as a metal in 100 parts by weight of the printing ink. Target.

In the present invention, when the varnish used has a high degree of unsaturation, the dryer may be used alone, but when the varnish used has a low degree of unsaturation (for example, in the present invention). When the compound to be used is a mixture of 1 to 2 unsaturated groups), the drying time after printing is shortened by using a drying auxiliary together in a ratio of 10 to 100 parts by weight per 100 parts by weight of the dryer. This is preferable because it can be performed. The printing ink of the present invention is the above colorant,
In addition to the oxidative polymerization type resin and the drier, some amount of ink solvent, leveling improver, thickening agent, anti-skinning agent, and other conventionally known additives may be contained within a range not hindering the achievement of the object of the present invention. The manufacturing method itself of the printing ink of the present invention as described above may be a conventionally known method.

[0014]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, parts and% are based on weight unless otherwise specified. Example 1 500 parts of Neopolymer # 150 (manufactured by Japan Synthetic Resin) and 400 parts of tall oil fatty acid were heated and melted at 220 ° C. to obtain a varnish. 70 parts of this varnish and phthalocyanine blue 1
8 parts and 3 parts are mixed and kneaded with a triple roll, and the manganese content is 8%
Was mixed with 1.0 part of manganese octylate and 10 parts of linseed oil to obtain an offset printing ink of the present invention having a tack value (value of 400 rpm, 1 minute) of 9.0 by an incometer.

Example 2 100 parts of phenol-modified rosin (softening point 154 ° C.) and 100 parts of tall oil fatty acid octyl alcohol ester were heated and dissolved at 220 ° C. to obtain a varnish. This varnish 70
Part and Carmine 6B18 part are mixed and kneaded with a triple roll,
0.4 parts of cobalt naphthenate with a cobalt content of 8% and 8 parts of soybean oil were mixed, and the tack value (40
An offset printing ink of the present invention having a value of 0 rpm for 1 minute) of 8.7 was obtained. Example 3 100 parts of phenol-modified rosin (softening point 157 ° C.) and 110 parts of tall oil fatty acid oleyl alcohol ester were heated and dissolved at 200 ° C. to obtain a varnish. This varnish 70
Parts and 18 parts of carbon black MA-11 (manufactured by Mitsubishi Kasei) are mixed and kneaded with a triple roll, and 1.0 part of manganese octylate having a manganese content of 8%, 1.0 part of 1,10-phenanthroline and flaxseed. 7 parts of the oil was mixed to obtain an offset printing ink of the present invention having a tack value (400 rpm, 1 minute value) of 9.2 by an incometer.

Example 4 21 parts of 100 parts of phenol-modified rosin (softening point 156 ° C.) and 105 parts of oleic oleyl alcohol ester were added.
It melt | dissolved by heating at 0 degreeC and it was set as the varnish. 70 parts of this varnish and 18 parts of Carmine 6B were mixed and kneaded with a three-roll mill, and 0.5 part of manganese octylate having a manganese content of 8%, 1,1
0.5 parts of 0-phenanthroline and 10 parts of linseed oil were mixed to obtain an offset printing ink of the present invention having an incometer tack value (400 rpm, 1 minute value) of 9.0. Example 5 100 parts of phenol-modified rosin (softening point 156 ° C.) and 110 parts of linseed oil fatty acid methyl ester obtained by alcoholysis of linseed oil with methanol were heated and dissolved at 230 ° C. to obtain a varnish. 70 parts of this varnish and 18 parts of phthalocyanine blue were mixed and kneaded with a three-roll mill, and 0.5 part of manganese octylate having a manganese content of 8% and 2,6-di-t were used.
0.5 parts of butylphenol, 5 parts of varnish and 6 parts of linseed oil fatty acid methyl ester were mixed to obtain an offset printing ink of the present invention having an incometer tack value (400 rpm, 1 minute value) of 8.7.

Example 6 100 parts of phenol-modified rosin (softening point of 152 ° C.) and 100 parts of linseed oil fatty acid ethylene glycol ester composition obtained by alcoholysis of linseed oil with ethylene glycol in a molar ratio of 2: 1 at 200 ° C. It was heated and melted to obtain a varnish. 70 parts of this varnish and 18 parts of Carmine 6B were mixed and kneaded with a three-roll mill to form 0.5 part of manganese octylate having a manganese content of 8%, 0.5 part of 2,6-di-t-butylphenol and 5 parts of varnish. Parts and 7 parts of linseed oil are mixed, and tack value of incometer (400 rpm, 1 minute value) 7.
9 offset printing inks of the invention were obtained. Comparative Example 1 500 parts of Neopolymer # 150 (manufactured by Japan Synthetic Resin) and 500 parts of linseed oil were heated and melted at 220 ° C. to obtain a varnish. 70 parts of this varnish and 18 parts of phthalocyanine blue were mixed and kneaded with a triple roll, and 0.5 part of manganese octylate having a manganese content of 8% and 10 parts of linseed oil were mixed,
Incomer tack value (400 rpm, 1 minute value)
The offset printing ink of the comparative example of 9.4 was obtained.

Comparative Example 2 100 parts of phenol-modified rosin (softening point 156 ° C.), 50 parts of Nisseki # 5 solvent and linseed oil 50 were mixed at 220 ° C.
It was heated and melted in a varnish. 70 parts of this varnish and 18 parts of phthalocyanine blue are mixed and kneaded with a triple roll,
0.4 parts of cobalt naphthenate with a cobalt content of 8% and 10 parts of soybean oil were mixed, and the tack value (4
The offset printing ink of the present invention having a value of 00 rpm for 1 minute) of 8.8 was obtained. Comparative Example 3 Phenol-modified rosin (softening point 156 ° C.) 100 parts, Nisseki # 5 solvent 50 parts and linseed oil 50 220 ° C.
It was heated and melted in a varnish. 70 parts of this varnish and 18 parts of phthalocyanine blue are mixed and kneaded with a triple roll,
0.5 parts of manganese octylate with a manganese content of 8%,
0.5 parts of 2,6-di-t-butylphenol and 10 parts of linseed oil were mixed, and the tack value (400
An offset printing ink of a comparative example having an rpm of 1 minute (value of 9.0) was obtained.

The drying properties of the thick inks of the printing inks of the present invention and the comparative example, the drying time and the volatile matter of the printed matter were measured under the following conditions, and the results shown in Table 1 below were obtained. (1) Drying time for thick ink: 10 g in a can with an inner diameter of 4 cm
The printing ink was taken and allowed to stand at 25 ° C., and the time until the ink did not stick to the high-quality paper was measured (this indicates on-machine stability). (2) Drying time of printed matter: J
It measured at 25 degreeC according to IS method. (3) Volatile content: Measured according to ASTM-D2369.

[0020]

[Table 1]

Examples 7 to 16 The printing inks of the present invention were obtained in the same manner as in Examples 1 to 6 except that the fatty acid ester and the dryer in Examples 1 to 6 were replaced with the esters and dryers in Table 2 below. ,
It evaluated similarly and obtained the result of the following Table 2. Comparative Examples 4 to 7 The compounds shown in Table 2 below were used instead of the fatty acid ester and the dryer in Examples 1 to 6, and the printing inks of the present invention were obtained in the same manner as in Examples 1 to 6 except for the same. It evaluated and obtained the result of the following Table 2. In addition, red, black and indigo in parentheses after the examples in the table represent the corresponding relationship with the above examples 1 to 6.

[0022]

[Table 2]

[0023]

[Effects] According to the present invention as described above, by using a specific compound having a film-forming ability by itself as a solvent for dissolving a varnish resin of a printing ink, a conventional ink solvent for a mineral oil fraction can be almost used. Or, there is no need to use it at all, and therefore there is no problem of volatilized solvent and on-machine stability, quick-drying after printing, and an oxidation polymerization type printing ink that can print on synthetic resin printing materials. You can do it.

Front page continued (72) Inventor Masafumi Nakano 3950-3 Kashiwayama, Moriya-cho, Mizukaido City, Ibaraki Prefecture Taniguchi Ink Mfg. Co., Ltd.

Claims (8)

[Claims] 1. A printing ink containing a colorant and a resin varnish, wherein the resin varnish contains an aliphatic compound having at least one unsaturated group and having 18 to 50 carbon atoms. 2. A carbon number of 18 to 18 having at least one unsaturated group.
The printing ink according to claim 1, wherein 50 aliphatic compounds are esters of unsaturated fatty acid mono- or dialcohols. 3. A carbon number of 18 to 18 having at least one unsaturated group.
The printing ink according to claim 1, wherein the aliphatic compound of 50 is an alcoholysis product of a drying oil with a mono- or dialcohol. 4. A carbon number of 18 to 1 having at least one unsaturated group.
The printing ink according to claim 1, wherein the aliphatic compound of 50 is tall oil fatty acid and / or its ester. 5. A carbon number of 18 to 18 having at least one unsaturated group.
The printing ink according to claim 1, wherein the aliphatic compound of 50 is an ester of oleic acid and oleyl alcohol. 6. The printing ink according to claim 1, wherein the dryer in the ink is selected from the group consisting of metal salts of unsaturated fatty acids, 1,10-phenanthroline and 1,1′-dipyridyl. 7. When the unsaturated degree of the varnish is low,
The printing ink according to claim 1, wherein a metal salt of unsaturated fatty acid is used as a drier, and 1,10-phenanthroline and / or 1,1'-dipyridyl are used as a drying aid. 8. The printing ink according to claim 1, which is substantially free of an ink solvent of a mineral oil fraction.