JP2555488B2 - Complex, drying aid and 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 complex, a drying aid for a printing ink, and a printing ink. More specifically, it is an object of the invention to provide a printing ink having excellent stability with time in drying property.

[0002]

2. Description of the Related Art Conventionally, various printing inks have been known in order to give a pattern to various materials to be printed. For example, for printing non-liquid-absorbent materials such as plastic films, metals, and glass, solvent-evaporation-type printing in which the solvent contained is evaporated and dried by polymerization reactions such as oxidative polymerization, polycondensation, and addition polymerization. Ink is used, and for a liquid-absorbent printing material typified by paper, a printing ink in which a solvent contained is absorbed and dried by oxidative polymerization, for example, lithographic printing ink, intaglio printing ink, letterpress printing. Inks and silk screen printing inks are known. Each of the various printing inks as described above, ink is applied to the surface of the printing plate according to the respective printing format, the applied ink is transferred to the printing material, solvent evaporation, solvent absorption, varnish The printing ink is fixed by being dried by oxidative polymerization or the like. Therefore, these printing inks are preferably dried immediately after transfer. Conventionally, as a method for increasing the drying speed of printing ink, particularly oxidation polymerization type printing ink, for example,
The most widely used method is to add a metal salt of a fatty acid, which is generally called a drier (drying aid).

[0003]

[Problems to be solved by the invention] However,
In order to enhance the drying property of the printing ink by the above conventional method, a large amount of a dryer is added, the varnish is strongly colored due to the dryer, and as a result, the vividness of the color of the printing ink and the print is impaired, and, In offset printing, the balance between the printing ink and the dampening water is lost, and stains are likely to occur, so it is impossible to use more than a certain amount,
There is a limit to the improvement of the drying speed. Further, in the case of the conventional dryer, there is a problem that the performance of the dryer is lowered and the drying property is lowered according to the storage period of the printing ink. Therefore, an object of the present invention is to provide a drying aid for a printing ink, which gives excellent drying properties even when added in a small amount, does not change with time in the printing ink, and exhibits sufficient performance even after long-term storage, and a printing containing the same. It is to provide ink.

[0004]

The above object can be achieved by the present invention described below. That is, the present invention is a complex of 1,10-phenanthroline, a polyvalent metal, and a carboxylic acid represented by the following general formula, use of the complex in a printing ink, and a printing ink containing the complex.

Embedded image (However, M in the formula is selected from cobalt, iron and manganese.
At least one metal that, R represents the residue of a carboxylic acid. )

[0005]

The complex is a novel substance, and the complex has excellent performance as a drying aid for promoting the oxidative polymerization of oxidative polymerization type varnish, and does not change with time in the printing ink.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The complex of the present invention is 1,10
It is easily formed by dissolving phenanthroline in a suitable solvent such as alcohol and adding to the solution 2 to 5 mol of 1,10-phenanthroline to 2 to 5 mol of a metal salt of a fatty acid. It is presumed by the analysis such as infrared absorption spectrum, elemental analysis, and X-ray crystal analysis that the complex thus formed is represented by the above structural formula.

The preferred metal in the above complex is cobal
And at least one metal selected from iron and manganese , and preferable R is, for example, a residue such as naphthenic acid, octylic acid, resin acid, and oil-soluble carboxylic acid such as tall oil fatty acid. . The printing ink of the present invention contains a colorant, an oxidative polymerization type varnish and the complex as a main component, and the colorant is a pigment or dye used in a conventional printing ink, which is a conventionally known pigment or dye. Can be used as they are 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, and for example, a ratio of about 10 to 40 parts by weight in 100 parts by weight of the printing ink is general.

As the varnish, any conventionally known oxidation-polymerization type resin can be used in the present invention. The amount of the oxidative polymerization type resin used is the same as that of the conventional printing ink, and is, for example, a ratio of 50 to 80 parts by weight in 100 parts by weight of the printing ink. The printing ink of the present invention may contain an ink solvent, a leveling improver, a thickener, an anti-skinning agent, and other conventionally known additives in addition to the colorant and the oxidative polymerization type resin described above. For example, the ink solvent is added to correct the viscosity, consistency, flow, etc. of the ink, and various organic solvents conventionally used for printing inks such as light oil, spindle oil and various ink solvents. , Machine oil, etc. can be used. The amount used is generally such that it accounts for about 5 to 80 parts by weight in 100 parts by weight of printing ink. The complex of the present invention is generally used as a dryer in an amount of about 0.005 to 0.5% by weight as a metal in 100 parts by weight of the printing ink. If the amount used is less than the above range,
The effect of accelerating the oxidative polymerization of the printing ink after printing is insufficient. On the other hand, when it exceeds the above range, the oxidative polymerization is too fast, and the stability of the printing ink on the printing machine decreases. The manufacturing method itself of the printing ink of the present invention as described above may be a conventionally known method.

[0009]

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 Manganese acetate tetrahydrate (Kanto Chemical Co., Inc. special grade reagent) 2.4
Dissolve 5 g (0.01 mol) in 60 ml of ethanol.
1,10-phenanthroline (Kanto Chemical, special grade reagent)
As soon as 1.98 g (0.01 mol) of powder was added to the above ethanol solution, the color of the solution changed to yellow and a yellowish white precipitate was gradually formed. The precipitate was washed with ethanol and ether in this order and dried in a desiccator to obtain a white powder of the complex of the present invention. This complex was readily soluble in water and insoluble in acetone and chloroform, and the elemental analysis values were as follows. Analytical value (%) C: 49.19, H: 3.95,
N: 6.26 Calculated value (%) C: 49.16, H: 3.90,
N: 6.37 The infrared absorption spectrum of the above complex was as shown in FIG.

Example 2 Mn 6% octylate (manufactured by San Nopco) 10 g (0.011 mol as Mn) and xylene 5 g were heated to 100
After raising the temperature to ˜120 ° C., 3 g (0.015 mol) of 1,10-phenanthroline (Kanto Chemical Co., Inc. special grade reagent) is added and reacted for 10 minutes while stirring. Then, after cooling to room temperature, the crystals were separated by filtration and purified according to a conventional method * to obtain a yellow-white powder crystal complex of the present invention. The elemental analysis value of the complex was in good agreement with the calculated value, and the infrared absorption spectrum was also the same as the spectrum in FIG. Example 3 Mn 6% naphthenic acid according to Example 1 (manufactured by San Nopco)
The same operation was carried out using to obtain a complex of the present invention as a yellow powder crystal. The elemental analysis value of the complex was in good agreement with the calculated value, and the infrared absorption spectrum was also the same as the spectrum in FIG.

Example 4 Example 1 using 6% tall oil Mn (manufactured by San Nopco)
In the same manner as described above, a yellow-white powder crystal complex of the present invention was obtained. The elemental analysis value of the complex was in good agreement with the calculated value, and the infrared absorption spectrum was also the same as the spectrum in FIG. Example 5 10 g of Fe 6% naphthenate (manufactured by San Nopco Ltd.) (0.011 mol as Fe) was added together with 5 g of xylene to 100 to 1
After heating to 20 ° C., 3 g of 1,10-phenanthroline
Is added, the mixture is stirred, then allowed to cool and filtered. The crystal was purified according to a conventional method * to obtain a brown powder crystal of the complex of the present invention. The elemental analysis value of the complex was in good agreement with the calculated value, and the infrared absorption spectrum was also the same as the spectrum in FIG.

Example 6 Co 12% neodecanoate (manufactured by San Nopco) 5 g (Co
0.010 mol) as a mixture with 10 g of xylene, and
After heating to 00 to 120 ° C., 3 g of 1,10-phenanthroline was added, and the mixture was reacted as it was, allowed to cool, and filtered. After purification according to a conventional method *, an off-white powder crystal complex of the present invention was obtained. The elemental analysis value of the complex was in good agreement with the calculated value, and the infrared absorption spectrum was also the same as the spectrum in FIG. The same complex of the present invention can be obtained by previously mixing the fatty acid metal salt, xylene and 1,10-phenanthroline in the reactions of Examples 1 to 5 and stirring with heating. * Conventional method:
The obtained complex is used as a suitable organic solvent (here, ethanol).
After being dissolved in water, the filtrate was filtered to remove impurities, and the filtrate was dropped into water little by little to forcibly precipitate crystals.

Example 7 3,070 parts of linseed oil and 490 parts of tall oil fatty acid were heated to give Gardner viscosity (25 ° C.) X and acid value (KOHm).
g / g) 34.2 of acid-modified oil was obtained. This acid-modified oil 1,
600 parts and 94 parts of epoxy resin (R-140) were heated in the coexistence of xylene to distill 7 parts of water to obtain an epoxy-modified oxidative polymerization type resin having a Gardner viscosity G and an acid value of 9.0. 300 parts of this oxidation-polymerizable resin, 300 parts of phenol-modified rosin having a softening point of 163 ° C. and an acid value of 22.6, and 300 parts of Nisseki # 5 solvent were heated and dissolved at 260 ° C. for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of Disazo Yellow were mixed and kneaded with a three-roll mill, and 5 parts of the complex of Example 1, 150 parts of Nisseki # 5 solvent and 30 parts of ethyl cellosolve were mixed, and the tack value of the incometer ( 40
0 rpm. ) 9.8 inventive offset printing inks were obtained.

Example 8 3,070 parts of linseed oil and 490 parts of tall oil fatty acid were heated to give Gardner viscosity (25 ° C.) X and acid value (KOHm).
g / g) 34.2 of acid-modified oil was obtained. This acid-modified oil 1,
600 parts and 94 parts of epoxy resin (R-140) were heated in the coexistence of xylene to distill 7 parts of water to obtain an epoxy-modified oxidative polymerization type resin having a Gardner viscosity G and an acid value of 9.0. 300 parts of this oxidation-polymerizable resin, 300 parts of phenol-modified rosin having a softening point of 163 ° C. and an acid value of 22.6, and 300 parts of Nisseki # 5 solvent were heated and dissolved at 200 ° C. for 1 hour to obtain a varnish. Example 2 of 700 parts of this varnish and 200 parts of phthalocyanine blue were mixed and kneaded with a three-roll mill.
5 parts of the complex of No. 5, Niseki # 5 solvent of 150 parts and ethyl cellosolve of 30 parts were mixed to obtain an offset printing ink of the present invention having an incometer tack value (400 rpm.) Of 9.8.

Example 9 3,000 parts of linseed oil and 120 parts of tall oil fatty acid were heated to give Gardner viscosity (25 ° C.) X and acid value (KOHm).
g / g) 13.5 acid modified oil was obtained. This acid-modified oil 2,
080 parts and 80 parts of an epoxy resin (R-301) were heated in the coexistence of xylene to distill 14 parts of water to obtain an epoxy-modified oxidative polymerization type resin having a Gardner viscosity E and an acid value of 7.7. 300 parts of this oxidation-polymerizable resin, 300 parts of phenol-modified rosin having a softening point of 163 ° C. and an acid value of 22.6, and 250 parts of Nisseki # 5 solvent were heated and dissolved at 200 ° C. for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of carbon black were mixed and kneaded with a three-roll mill, 5 parts of the complex of Example 3, 100 parts of Nisseki # 5 solvent and 10 parts of cellosolve acetate were mixed, and the tack value of the incometer ( 400 rpm.) 9.6 offset printing ink of the present invention was obtained.

Example 10 3,000 parts of linseed oil and 120 parts of tall oil fatty acid were heated to give Gardner viscosity (25 ° C.) X and acid value (KOHm).
g / g) 13.5 acid modified oil was obtained. This acid-modified oil 1,
640 parts and 387 parts of epoxy resin (R-307) were heated in the coexistence of xylene to distill 12 parts of water to obtain an epoxy-modified oxidative polymerization type resin having a Gardner viscosity W and an acid value of 8.6. 300 parts of this oxidative polymerization type resin, softening point 163 ° C.
And 300 parts of a phenol-modified rosin having an acid value of 22.6 and 280 parts of Nisseki # 5 solvent were heated and dissolved at 230 ° C. for 1 hour, and 20 parts of butyl carbitol was added to obtain a varnish. 700 parts of this varnish and 200 parts of Disazo Yellow are mixed and kneaded with a three-roll mill, 5 parts of the complex of Example 4 and 220 parts of Nisseki # 5 solvent are mixed, and the tack value (400 rpm) of an incometer is 9.8. The offset printing ink of the present invention was obtained.

Example 11 94 parts of epoxy resin (R-140) and tung oil fatty acid 480
And 6 parts of water are distilled off, 3,070 parts of linseed oil are added and heated to remove xylene to remove Gardner viscosity (25 ° C.) Y and acid value of 7.2. An epoxy-modified oxidative polymerization type resin was obtained. This oxidation polymerization type resin 3
00 parts, 300 parts of phenol-modified rosin having a softening point of 168 ° C. and an acid value of 23.2 and 300 parts of Nisseki # 5 solvent were heated and dissolved at 220 ° C. for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of Brilliant Carmine 6B were mixed and kneaded with a three-roll mill to form 5 parts of the complex of Example 5, Nisseki # 5.
Mix 180 parts solvent and 10 parts castor oil fatty acid,
An offset printing ink of the present invention having an incometer tack value (400 rpm.) Of 9.6 was obtained.

Example 12 80 parts of epoxy resin (R-304) and linseed oil fatty acid 1
20 parts are heated in the presence of xylene, 12 parts of water is distilled off, 3,000 parts of linseed oil are added and heated to remove xylene, and Gardner viscosity (25 ° C.) X and acid value of 6.5.
To obtain an epoxy-modified oxidative polymerization type resin. 300 parts of this oxidation-polymerizable resin, 350 parts of phenol-modified rosin having a softening point of 165 ° C. and an acid value of 23.6, and Nisseki # 5 solvent 35.
0 part and 0 part were heated and dissolved at 260 ° C. for 1 hour to obtain a varnish. 700 parts of this varnish and 200 parts of phthalocyanine blue were mixed and kneaded with a triple roll, and 5 parts of the complex of Example 6 and Nisseki #
120 parts of 5 solvent and 10 parts of ethylene oxide adduct of nonylphenol were mixed to obtain an offset printing ink of the present invention having an incometer tack value (400 rpm) of 9.8.

Comparative Example 1 A printing ink of Comparative Example was obtained in the same manner as in Example 8 except that 5 parts of manganese octylate having a manganese content of 8% was used in place of the complex used in Example 2. Comparative Example 2 A printing ink of Comparative Example was obtained in the same manner as in Example 9 except that 5 parts of 6% manganese naphthenate was used instead of the complex in Example 3. Comparative Example 3 Instead of the complex in Example 2, 5 parts of 6% manganese naphthenate and 10 parts of an alcohol solution of 15% 1,10-phenanthroline were used, and the printing ink of Comparative Example was prepared in the same manner as in Example 9. Obtained.

Comparison of changes with time About the inks of the above-mentioned Examples and Comparative Examples, immediately after production, 1
The drying time after 30 days and 6 months after the JIS method (J
When measured according to ISK-5701), the following results were obtained.

[Table 1]

[0021]

[Effect] According to the present invention as described above, the complex is a novel substance, and the complex has an excellent performance as a drying aid for promoting the oxidative polymerization of the oxidative polymerization type varnish, and in the printing ink. It does not change over time.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of a complex obtained in Example 1.

Claims (4)

(57) [Claims] 1. A complex of 1,10-phenanthroline represented by the following general formula, a polyvalent metal and a carboxylic acid. Embedded image (In the formula, M represents at least one metal selected from cobalt, iron and manganese, and R represents a carboxylic acid residue.) 2. R is naphthenic acid, octylic acid, resin acid,
The complex according to claim 1, which is a residue of an oil-soluble carboxylic acid such as tall oil fatty acid. 3. A printing ink drying aid comprising the complex of claim 1. 4. A printing ink comprising a colorant and an oxidative polymerization varnish, the printing ink comprising the drying aid according to claim 3 .