JP3061694B2 - Oxidation polymerization type printing ink - Google Patents

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, to provide an oxidative polymerization type printing ink which has no problem of a volatile solvent and is excellent in drying property and on-machine stability.

[0002]

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

[0003]

[Problems to be solved by the invention]
When printing with the above-mentioned conventional printing ink, the solvent in the ink is volatilized in the working atmosphere during drying and eventually causes air pollution.Therefore, printing plants are required to have facilities to prevent the solvent from being released into the atmosphere. It has come to be. This equipment burden is unbearable in small and medium-sized printing plants. Furthermore, in the case of printing ink containing an ink solvent of a mineral oil fraction, when printing is interrupted, the ink solvent in the printing ink remaining on the printing plate evaporates, and various problems occur when printing is resumed. There is a problem that it occurs and lacks on-machine stability.

[0004] Oxidation polymerization type inks also tend to be used for printing materials having low liquid absorbing properties, such as synthetic paper made of synthetic resin and plastic films (sheets) as printing materials. In the case of a material, there is a problem that the material to be printed undulates during or after printing due to low liquid absorbing property, swelling of the synthetic resin due to the liquid absorbing, and the like, which makes later handling difficult. Accordingly, it is an object of the present invention to provide a printing ink containing little or no ink solvent of a mineral oil fraction, free from the problem of volatile solvents and the problem of on-machine stability, and fast-drying after printing, and 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 is achieved by the present invention described below. That is, the present invention is seen containing a pigment and a resin varnish, containing a substantially mineral oil fractions of ink solvent
In no printing ink, the resin varnish, hydrin
Roxyl-free unsaturated fatty acids and their monoalcohols
At least one unsaturated group selected from
An oxidative polymerization printing ink comprising an aliphatic compound having 18 or more carbon atoms and having 18 to 50 carbon atoms.

[0006]

By using a specific compound capable of forming a film by itself to dissolve the varnish resin of the printing ink, it becomes unnecessary to use the ink solvent of the conventional mineral oil fraction with little or no use. Therefore, it is possible to provide an oxidative polymerization type printing ink which is free from the problem of a volatile solvent and the problem of on-machine stability, is fast drying after printing, and can be printed on a synthetic resin printing material.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to 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, Soybean oil,
Safflower oil, cinnamon oil, Japanese drill 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 include fish oil such as cottonseed oil, squid oil, sardine oil, sword fish oil, cod oil, etc., whale oil, and various modified products thereof. Examples of synthetic varnish resins include petroleum resins (aromatic and aliphatic). Resins, aromatic / aliphatic copolymers), rosin esters, phenol-modified rosins, phenolic resins, resol type or novolak type resins such as octylphenol and nonylphenol.

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 obtained from the market, such as tall oil fatty acid, or may be synthesized by any method. Preferred synthesis methods include the following several methods. How to esters of unsaturated fatty acids in mode Noah alcohol. How to alcoholysis by mode Noah alcohol drying oil.
A method of esterifying an unsaturated aliphatic monoalcohol with a suitable acid. How to alcoholysis by unsaturated mode Noah alcohol drying oil.

The above process comprises the steps of using unsaturated fatty acids having a suitable number of carbon atoms, such as tall oil fatty acids, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoleic acid,
Linolenic acid, arachidonic acid, Bukani acid, and the like parinaric acid, is reacted with an appropriate aliphatic saturated or unsaturated monocarboxylic alcohol of which having a number of carbon, the carbon number of the product obtained and 18 to 50 and unsaturated In this method, one or more groups are used. As the aliphatic saturated monoalcohol used in this method, for example, methanol, ethanol, n- or i
So-propanol, n, sec or tert-butanol, heptinol, 2-ethylhexanol, hexanol, octanol, decanol, dodecanol and the like, and examples of unsaturated aliphatic monoalcohols include oleyl alcohol, dodecenol, fuseteri Alcohol, somaryl alcohol, oleyl alcohol, gadoleyl alcohol, 11-icosenol, 11
-Docosenol, 15-tetooracosenol and the like.

[0010] Also, the above method the such drying oils by alcoholysis of Te <br/> by a suitable saturated or unsaturated mono alcohol such as the above, the product obtained carbon number 18
To 50 and one or more unsaturated groups.
Further, the above method comprises reacting an unsaturated aliphatic monoalcohol 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. To obtain a product having 18 to 50 carbon atoms.
And one or more unsaturated groups. Further, the above method is to alcoholysis the nondrying oil in the aforementioned such unsaturated monoalkoxy <br/> Lumpur, of products obtained carbon number 1
In this method, the number of unsaturated groups is 8 to 50 and the number of unsaturated groups is one or more.

The esterification reaction or alcoholysis reaction as described above includes, for example, a method in which both are heated at normal pressure or under pressure in the absence of a catalyst, preferably in the presence of an acid catalyst or an alkali catalyst. There may be. Particularly preferred in the present invention are those having 1 or more carbon atoms having at least one unsaturated group.
Aliphatic compounds 8 to 50, the tall oil fatty acids, the motor
Alcohol esters, esters of oleic acid and oleyl alcohol and alcoholic products of the drying oils. In the present invention, the aliphatic compound having 18 to 50 carbon atoms having one or more unsaturated groups is preferably used at a ratio of about 5 to 90 parts by weight per 100 parts by weight of the varnish resin. 1 carbon atom having at least one unsaturated group
When the amount of the aliphatic compound of 8 to 50 is less than 5 parts by weight, the printing ink formed has too high a viscosity to make printing difficult, and on the other hand, has 18 to more carbon atoms having one or more unsaturated groups.
If the amount of 50 aliphatic compounds exceeds about 90 parts by weight, the quick drying property of the resin varnish is unsatisfactory, and the strength and gloss of the ink film become insufficient.

The coloring agent is a pigment used in conventional printing inks, and any conventionally known pigment can be used as it is as a coloring agent for the printing ink of the present invention. The amount of the ink used may be the same as that of a conventionally known printing ink.
The proportion occupying 0 to 40 parts by weight is generally used. Examples of the dryer include cobalt, manganese, cerium, zirconium, lead, iron, zinc, copper, vanadium, barium, calcium, and other polyvalent metals such as naphthenic acid, octylic acid, and resin acid.
Oil-soluble carboxylic acids such as tall oil fatty acids, salts of resin acids, and the like. These dryers are generally used in a proportion of about 0.005 to 0.5% by weight as a metal in 100 parts by weight of printing ink. It is a target.

In particular, in the present invention, when the degree of unsaturation of the varnish to be used is high, the above-mentioned dryer may be used alone, but when the degree of unsaturation of the varnish to be used is low (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 aid in a proportion of 10 to 100 parts by weight per 100 parts by weight of the above-mentioned dryer. It is preferable because it can be performed. The printing ink of the present invention is the above colorant,
In addition to the oxidative polymerization resin and the dryer, the ink may contain a small amount of ink solvent, leveling improver, thickener, anti-skinning agent, and other conventionally known additives in a range that does not hinder the achievement of the object of the present invention. The method for producing the printing ink of the present invention as described above may be a conventionally known method.

[0014]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, parts and% are based on weight unless otherwise specified. Example 1 A varnish was prepared by heating and dissolving 500 parts of Neopolymer # 150 (manufactured by Nippon Synthetic Resin) and 400 parts of tall oil fatty acid at 220 ° C. 70 parts of this varnish and phthalocyanine blue 1
8 parts and mixed and kneaded with 3 rolls, manganese content 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 of 9.0 (400 rpm, 1 minute value) of 9.0.

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 melted at 220 ° C. to form a varnish. This varnish 70
Part and carmine 6B18 part are mixed and kneaded with three rolls,
0.4 part of cobalt naphthenate having a cobalt content of 8% and 8 parts of soybean oil were mixed, and the tack value of an incometer (40
An offset printing ink of the present invention having a value of 8.7 (0 rpm, 1 minute value) of 8.7 was obtained. Example 3 A varnish was prepared by heating and dissolving 100 parts of phenol-modified rosin (softening point: 157 ° C.) and 110 parts of tall oil fatty acid oleyl alcohol ester at 200 ° C. This varnish 70
And 18 parts of carbon black MA-11 (manufactured by Mitsubishi Kasei) were 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 7 parts of oil was mixed to obtain an offset printing ink of the present invention having an incometer tack value (400 rpm, 1 minute value) of 9.2.

Example 4 100 parts of phenol-modified rosin (softening point: 156 ° C.) and 105 parts of oleyl alcohol oleate were mixed in 21 parts.
A varnish was obtained by heating and dissolving at 0 ° C. 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% was added.
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 a tack value of an incometer (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 form a varnish. 70 parts of this varnish and 18 parts of phthalocyanine blue were mixed and kneaded with three rolls, and 0.5 part of manganese octylate having a manganese content of 8%, 2,6-di-t
-0.5 parts of butylphenol, 5 parts of varnish and 6 parts of linseed oil fatty acid methyl were mixed to obtain an offset printing ink of the present invention having a tack value of an incometer (400 rpm, 1 minute value) of 8.7.

Comparative Example 1 A varnish was prepared by heating and dissolving 500 parts of Neopolymer # 150 (manufactured by Nippon Synthetic Resin) and 500 parts of linseed oil at 220 ° C. 70 parts of this varnish and 18 parts of phthalocyanine blue were mixed and kneaded with three rolls, and 0.5 part of manganese octylate having a manganese content of 8% and 10 parts of linseed oil were mixed.
Incomometer tack value (400 rpm, 1 minute value)
An offset printing ink of Comparative Example 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 heated to 220 ° C.
And heat-melted to obtain a varnish. 70 parts of this varnish and 18 parts of phthalocyanine blue were mixed and kneaded with three rolls,
0.4 parts of cobalt naphthenate having a cobalt content of 8% and 10 parts of soybean oil were mixed, and the tack value of the incometer (4
An offset printing ink of the present invention having a value of 8.8 (00 rpm, 1 minute value) of 8.8 was obtained. Comparative Example 3 100 parts of phenol-modified rosin (softening point: 156 ° C.), 50 parts of Nisseki # 5 solvent and linseed oil 50 at 220 ° C.
And heat-melted to obtain a varnish. 70 parts of this varnish and 18 parts of phthalocyanine blue were mixed and kneaded with three rolls,
0.5 parts of manganese octylate having a manganese content of 8%,
0.5 part of 2,6-di-t-butylphenol and 10 parts of linseed oil were mixed, and the tack value of an incometer (400
rpm (1 minute value) 9.0 was obtained as an offset printing ink of Comparative Example.

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

[0020]

[Table 1]

Examples 6 to 15 The printing inks of the present invention were obtained in the same manner as in Examples 1 to 5 , except that the esters and dryers shown in Table 2 below were used instead of the fatty acid esters and the dryer in Examples 1 to 5. ,
Evaluation was performed in the same manner, and the results in Table 2 below were obtained. Comparative Example 4-7 in place of the fatty esters and dryers in Example 1-5 using the compounds and dryer in the following Table 2, others give printing ink of the present invention in the same manner as in Example 1 to 5 as well The results are shown in Table 2 below. In addition, red, black, and indigo in parentheses after the examples in the table represent the correspondence with the above-described Examples 1 to 5 .

[0022]

[Table 2]

[0023]

According to the present invention as described above, by using a specific compound capable of forming a film by itself to dissolve the varnish resin of the printing ink, the ink solvent of the conventional mineral oil fraction can be almost completely dissolved. The present invention provides an oxidative polymerization type printing ink which eliminates the need for use at all and therefore has no problems of volatile solvents and on-machine stability, is fast drying after printing, and can be printed on a synthetic resin printing material. You can do it.

Continuation of front page (72) Inventor Masafumi Nakano 3950-3 Kashiwayama, Moriyacho, Mizukaido, Ibaraki Pref. Taniguchi Ink Manufacturing Co., Ltd. (56) References JP-A-62-22872 (JP, A) JP-A-62- 46681 (JP, A) JP-A-52-101111 (JP, A) JP-A-5-1253 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11 / 20

Claims (6)

(57) [Claims] 1. A saw contains a pigment and a resin varnish, substantially mineral
In a printing ink that does not contain an ink solvent for an oil fraction , the resin varnish is not saturated with hydroxyl groups.
Selected from sum fatty acids and their monoalcohol esters
18 carbon atoms having at least one unsaturated group
Oxidation heavy , characterized in that it contains up to 50 aliphatic compounds.
Mold printing ink. 2. The method of claim 1, wherein said monoalcohol ester comprises a drying oil.
2. An alcoholysis product of a monoalcohol.
2. The oxidative polymerization type printing ink according to item 1. 3. The oxidative polymerization printing ink according to claim 1, wherein the aliphatic compound is a tall oil fatty acid and / or a monoalcohol ester thereof. Wherein said aliphatic compound is an acid of claim 1 which is an ester of oleic acid and oleyl alcohol
Polymerization printing ink. 5. A drier in the ink is a metal salt of an unsaturated fatty acid, 1,10-phenanthroline and 2,2 '- oxidation of claim 1 selected from the group consisting of dipyridyl
Polymerized printing ink. 6. When the degree of unsaturation of the varnish is low,
Using a metal salt of unsaturated fatty acid as a dryer, and 1,10-phenanthroline and / or as a drying aid
2. The oxidation according to claim 1, wherein 2,2'-dipyridyl is used.
Polymerized printing ink.