JP2016017171A - Composition for lithographic printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic printing ink having improved suitability for emulsification and suitability for fast printing such as stability in a printing machine while maintaining ink deposition property, glossiness and drying property as well as decreasing misting, and to provide a production method of a resol (A) having an average number of nuclei of 1.5 to 3.0 to be used for the ink.SOLUTION: A composition for a lithographic printing ink is provided, which uses a varnish containing a rosin-modified phenolic resin using a resol as a part of a raw material. The resol is resol (A) having an average number of nuclei of 1.5 to 3.0. The rosin-modified phenolic resin shows a cloud point of 100 to 210°C by AF-6 solvent.SELECTED DRAWING: None

Description

  The present invention is a lithographic printing ink composition using a varnish containing a rosin-modified phenolic resin using resole as part of a raw material, wherein the resole has a specific average number of nuclei and the rosin-modified The present invention relates to a lithographic printing ink composition in which the cloud point of a phenol resin is a specific temperature.

In recent years, offset printing has increased printing speed for the purpose of improving productivity, and printing conditions have led to increased ink tack. On the other hand, reuse of used paper and increased import paper have caused a reduction in paper strength. There is a problem.
Due to these problems, imperfections due to peeling of paper are likely to be induced, so the ink tack value cannot be set high, and the ink misting amount from the exit of the roller nip as the printing speed increases. And the pollution of the work environment has been promoted.

  In addition, simply adding petroleum solvent or vegetable oil to reduce the tack value of the ink also reduces the viscosity of the ink, causing printing troubles such as background smudges, blanket remaining on the blanket, and dirt on the water supply roller. There is also an adverse effect on print quality due to an increase in dot gain and the like. In order to maintain stain resistance such as background stains while maintaining inking properties, it is important how to reduce the tack value and maintain the viscosity high in the ink formulation design.

  Patent Document 1 discloses an environmentally conscious ink for waterless printing that reduces the content of volatile organic compounds by using vegetable oil as a main component of a solvent component and does not discharge dampening water as an object of the invention. And a rosin-modified phenol having a certain range of softening point, weight average molecular weight, and solubility in a lithographic printing ink composition containing a binder resin, a vegetable oil, a paraffinic raw material oil, and a pigment. A waterless ink characterized by having good scumming suitability and low volatile organic compound components by using a resin and a paraffinic raw material oil having a boiling point in a certain range, and a binder The resin has a softening point of 160 to 200 ° C., a weight average molecular weight of 50,000 to 200,000, and a normal paraffin cloud temperature of 110 to 180 ° C. Paraffinic feedstock is described the provision of what is boiling range 280 to 700 ° C..

  Patent Document 2 relates to an improvement in printing quality and a printing work environment as an object of the invention, and further provides an ink that has excellent inking properties and gloss and can reduce misting; and As a solution, in a lithographic printing ink composition containing a pigment, calcium carbonate, binder resin, petroleum solvent, vegetable oil, calcium carbonate has a primary particle size of 0.02 to 0.10 μm, a surface treatment of rosin acid and The provision of a lithographic printing ink characterized in that the fatty acid and the binder resin have a weight average molecular weight of 20,000 to 100,000 and a normal paraffin turbidity temperature of 40 to 110 ° C is described.

JP 2012-46586 A JP 2013-139551 A

Although the conventional technology is effective in improving the inking property and gloss, or reducing misting, the temperature dependency of the ink is large, and the drying property, emulsification suitability and on-machine stability are insufficient. It was unsuitable for high-speed printing. Therefore, while maintaining the fillability, gloss, and drying properties, while reducing misting, the change in ink viscoelasticity accompanying the increase in the roller temperature of the printing press is reduced, and the excess ink and ink tack value increase due to overemulsification. Accordingly, it is difficult to provide ink that is less likely to cause imperfection and has improved high-speed printability.
Accordingly, an object of the present invention is to provide a lithographic printing ink having improved high-speed printing suitability such as emulsification suitability and on-machine stability while reducing the misting while maintaining the inking property, glossiness and drying property. To do.
Furthermore, the manufacturing method of the resole (A) of 1.5-3.0 average nuclei used for the said ink is also provided.

  As a result of earnestly examining the provision of a lithographic printing ink that solves the above problems, the present inventors have developed a lithographic printing ink composition using a varnish containing a rosin-modified phenolic resin using resole as a part of the raw material. It has been found that the above-mentioned problems can be solved by a lithographic printing ink composition in which the resol has a specific average number of nuclei and the cloud point of the rosin-modified phenol resin is a specific temperature.

That is, the present invention is a lithographic printing ink composition using a varnish containing a rosin modified phenolic resin using resole as a part of a raw material,
The lithographic printing characterized in that the resol is a resole (A) having an average number of nuclei of 1.5 to 3.0, and the rosin-modified phenol resin has an AF-6 solvent cloud point of 100 to 210 ° C. The above-described problems are solved by providing an ink composition.

  According to the present invention, it is possible to provide a lithographic printing ink having improved high-speed printing suitability such as temperature dependency, emulsification suitability and on-machine stability while reducing misting while maintaining fillability, gloss and drying properties. It becomes possible.

The present invention includes the following items.
1. A lithographic printing ink composition using a varnish containing a rosin-modified phenolic resin using resole as part of a raw material,
The lithographic printing characterized in that the resol is a resole (A) having an average number of nuclei of 1.5 to 3.0, and the rosin-modified phenol resin has an AF-6 solvent cloud point of 100 to 210 ° C. Ink composition,
2. 1. In the resol (A), 1 to 15% by mass of a resol having an average number of nuclei of 2 or more is contained in the lithographic printing ink. The composition for lithographic printing inks according to
3.1. Or 2. Printed matter obtained by printing using the lithographic printing ink composition as described in
4). In the method for producing resole (A) having an average number of nuclei of 1.5 to 3.0 obtained by reacting mononuclear resole (B),
After the reaction, the method for producing resole (A), comprising a step of holding the product at a temperature of 80 to 180 ° C. for 20 minutes to 2 hours,
5.4. 1. Using resole (A) obtained by the production method described in 1. Or 2. The composition for lithographic printing inks according to
6.5. Printed matter obtained by printing using the lithographic printing ink composition described in 1 above as a base material.

(Rosin modified phenolic resin)
The rosin-modified phenol resin used in the present invention is made of resole as a part of the raw material, the resole is resole (A) having an average number of nuclei of 1.5 to 3.0, and the rosin-modified phenol resin It is characterized in that the AF-6 solvent cloud point is 100 to 210 ° C.

The resole used in the present invention is a resole (A) having an average number of nuclei of 1.5 to 3.0.
Here, the average number of nuclei indicates the average number of benzene rings bonded to the resole (A). If the average number of nuclei is less than 1.5, the ink tends to be over-emulsified. In addition, it is not preferable because the temperature dependency increases, the drying property decreases, and the misting deteriorates due to the decrease in viscosity due to the increase in solubility, and if it exceeds 3.0, the compatibility with the solvent decreases due to the decrease in solubility. However, it is not preferable because the on-machine stability is lowered.

Production of those having an average number of nuclei of 1.5 or more and 3.0 or less can be carried out, for example, by a known and commonly used method.
That is, it can be obtained by reacting formaldehyde or paraform with phenols.
It is important to carry out the reaction step at 100 ° C or higher, preferably 120 ° C or higher, more preferably 130 ° C or higher. During the process, the resol generated from the reaction of formaldehyde or paraform with phenols undergoes thermal condensation, increasing the number of mononuclear or low-nuclear number of resoles, resulting in an average of 2 or more nuclei. In order to cause the number of nuclei to actively react to 2 or more, it is important to keep the temperature at 100 ° C. or higher, preferably 120 ° C. or higher for 20 minutes or longer.

  In the present invention, after completion of the resol reaction, the temperature is kept at 100 ° C. or higher for 20 minutes or longer, preferably 30 to 60 minutes, so that the number of nuclei is 2 or more. In particular, since the reaction becomes active at 120 ° C. or higher, it is particularly preferable to keep the temperature at 120 ° C. or higher for 20 to 60 minutes.

Further, in the resole (A) used in the present invention, when the resole having 2 or more nuclei is contained in the lithographic printing ink in an amount of 1 to 15% by mass, a better effect is exhibited.
If it is less than 1% by mass, the molecular weight of the rosin-modified phenolic resin is small, so the temperature dependency is large, and the emulsification suitability and misting deteriorate. Since it falls, it is not preferable.
The rosin-modified phenolic resin of the present invention is characterized in that AF-6 solvent cloud point is 100 to 210 ° C. When the temperature is lower than 100 ° C., the drying property is decreased, which is not preferable. When the temperature is higher than 210 ° C., the on-machine stability is decreased, which is not preferable.

(Vegetable oil)
In the lithographic printing ink composition of the present invention, vegetable oil can be added to the extent that the effect of the invention is not reduced.

  Examples of vegetable oil components used in the present invention include oils such as soybean oil, linseed oil, rice oil, giraffe oil, castor oil, dehydrated castor oil, corn oil, safflower oil, Nanyang oil paulownia oil, canol oil, and thermal polymerization thereof. There are oil and oxidative polymerization oil. As vegetable oil fatty acid ester, linseed oil fatty acid methyl ester, linseed oil fatty acid ethyl ester, linseed oil fatty acid propyl ester, linseed oil fatty acid butyl ester, soybean oil fatty acid methyl ester, soybean oil fatty acid ethyl ester, soybean oil fatty acid propyl ester, large Bean oil fatty acid butyl ester, palm oil fatty acid methyl ester, palm oil fatty acid ethyl ester, palm oil fatty acid propyl ester, palm oil fatty acid butyl ester, castor oil fatty acid methyl ester, castor oil fatty acid ethyl ester, castor oil fatty acid propyl ester, castor oil fatty acid butyl ester, southern ocean Oil tung oil esters and the like can be used as well. Further, as ethers made from vegetable oil, di-n-octyl ether, di-nonyl ether, dihexyl ether, nonyl hexyl ether, nonyl butyl ether, diheptyl ether, didecyl ether, nonyl octyl ether and the like can be used as well. Can be mentioned.

The vegetable oil component can be used even if it is a regenerated vegetable oil.
Regenerated vegetable oil is vegetable oil that has been recovered and regenerated. The regenerated vegetable oil is preferably an oil regenerated with a water content of 0.3% by mass or less, an iodine value of 90 or more, and an acid value of 3 or less, more preferably an iodine value of 100 or more. By making the water content 0.3% by mass or less, it becomes possible to remove impurities that affect the emulsification behavior of the ink, such as salt contained in moisture, and by regenerating with an iodine value of 90 or more, drying characteristics That is, it becomes possible to make it good in oxidative polymerizability, and it becomes possible to suppress over-emulsification of ink by selecting and regenerating vegetable oil having an acid value of 3 or less. Examples of the method for regenerating the recovered vegetable oil include, but are not limited to, filtration, removal of precipitates by standing, and decolorization by activated clay.

(Calcium carbonate)
In the lithographic printing ink composition of the present invention, calcium carbonate can be added to the extent that the effects of the invention are not reduced. Examples of the calcium carbonate used in the present invention include known and commonly used calcium carbonate.

(Organic solvent)
In the lithographic printing ink composition of the present invention, an organic solvent can be added to the extent that the effects of the invention are not reduced. Examples of the organic solvent used in the present invention include known conventional solvents used in inks. For example, AF Solvent No. 4, No. 5, No. 6, No. 7, No. 0 Solvent L manufactured by JX Nippon Oil & Energy , M, H, ISU Chemical Co., Ltd. LTD DSOL240, 260SP, 260C, 280, 300, Idemitsu Kosan's linearlen 10, 12, 14, 16, 18, 124, 148, 168, Supersol LA-25, 30, FP-25, 30, 38, etc. . A naphthenic base oil may be used in combination to such an extent that the drying property does not extremely decrease.

(Other ingredients)
Other components mainly include pigments, binder resins other than rosin-modified phenolic resins, waxes, auxiliaries and the like.
Arbitrary inorganic and organic pigments can be used as the pigment used in the present invention. Examples of inorganic pigments include chrome yellow, zinc yellow, bitumen, magnesium carbonate, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, ultramarine blue, carbon black, graphite, aluminum powder, and organic pigments. As such, pigments used in offset inks such as azo, phthalocyanine, quinacridone, anthraquinone, and dioxazine are equivalent.

  Regarding organic pigments, for example, copper phthalocyanine pigments (CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, CI Pigment Green 7, 36) Monoazo pigments (CI Pigment Red 3, 4, 5, 23, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 53: 1, 57: 1 ), Disazo pigments (CI Pigment Yellow 12, 13, 14, 17, 83), anthraquinone pigments (CI Pigment Red 177), quinacridone pigments (CI Pigment Red 122, C.I.). CI Pigment Violet 19), dioxazine pigments (CI Pigment Violet 23), and the like. Not intended to be. Examples of the binder resin excluding the rosin-modified phenol resin include petroleum resins, alkyd resins, rosin-modified alkyd resins, petroleum resin-modified alkyd resins, and rosin esters. As the wax, a general wax used in printing ink can be used. For example, carnauba wax, beeswax, paraffin wax, microcrystalline wax, polyethylene wax, fatty acid amide, polytetrafluoroethylene and the like. A small amount of a known surfactant may be added as an auxiliary agent for the purpose of finely adjusting emulsification suitability. These components can be appropriately used in a ratio within a range that does not reduce the effect of the present invention.

(Printing ink)
In the printing ink of the present invention, raw materials having the following composition are kneaded by a known method, and in the kneading degree test described in JIS K5701-1, the groove depth at the kneading position A is 7 .5 μm or less (3 or less on the scale).

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Further, “part” is part by mass.

(Production Example 1-1) Synthesis of resol-type phenolic resin In a pressurized reaction kettle equipped with a stirrer and a thermometer, 1000 parts of para-tertiary butylphenol was charged and heated and dissolved at 120 degrees, 434 parts of 92% paraformaldehyde, water 8 parts of calcium oxide was added, and the temperature was raised to 130 ° C. and reacted for 2 hours while maintaining the same temperature. Then, the pressure was released, and the mixture was further stirred at the same temperature for 20 minutes to take out the resol type phenol resin A. As a result of measuring the weight average molecular weight of the resol type phenol resin A, the average number of nuclei was 2.2.

(Production Example 1-2) Synthesis of rosin-modified phenolic resin In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introducing device, 1000 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride The mixture was heated to 180 ° C., 110 parts of pentaerythritol and 2 parts of zinc oxide were added, the temperature was raised to 250 ° C., and the reaction was continued until the acid value reached 20 mgKOH / g or less. Thereafter, the temperature was lowered to 180 ° C., and resol A was added step by step while maintaining the same temperature. When the Gardner viscosity of the 50% toluene solution became F to G, the addition was stopped, and after 30 minutes, the resin was taken out, and rosin Modified phenol resin B was obtained. The amount of resole A charged was 515 parts. The weight average molecular weight of the rosin-modified phenolic resin B was 100,000, and the AF-6 solvent (JX Nippon Mining & Energy Corporation) had a chemotronic cloud point of 180 degrees. The AF-6 solvent cloud point is the lower cloudy minimum temperature when 180 parts of AF-6 (JX Nippon Mining & Energy Co., Ltd.) and 20 parts of resin are heated and mixed using NOBOMATICS automatic cloud point measuring device CHEMOTORONIC II. is there.

(Production Example 2-1) Synthesis of resol-type phenol resin In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introducing device, 1000 parts of paratertiary butylphenol, 326 parts of 92% paraformaldehyde, xylene After adding 1000 parts and 10 parts of 50% sodium hydroxide and raising the temperature to 95 ° C. and reacting for 6 hours while maintaining the same temperature, 300 parts of water and 13 parts of hydrochloric acid were added and neutralized, and then water 1000 The supernatant was taken out in the same apparatus as described above, heated to 120 ° C. and stirred for 20 minutes to obtain a resol type phenol resin D having a solid content of 57%. As a result of measuring the weight average molecular weight of the resol type phenol resin D, the average number of nuclei was 2.2.

(Production Example 2-2) Synthesis of rosin-modified phenolic resin In the same apparatus as in Production Example 1-2, 1000 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged, and the temperature was raised to 180 ° C. 110 parts of erythritol and 2 parts of zinc oxide were added, and the reaction was continued until the acid value reached 20 mgKOH / g or less while maintaining the same temperature by raising the temperature to 250 degrees. Thereafter, the temperature was lowered to 180 ° C., and while maintaining the same temperature, the resol type phenol resin D was added dropwise at a dropping rate of 2.5 parts / minute using a dropping funnel, and the Gardner viscosity of the 50% toluene solution became FG. The dropping was stopped at the time, and the resin was taken out after 30 minutes to obtain a modified phenolic resin E. The dripped resol type phenol resin D was 680 parts. The weight average molecular weight of the rosin-modified phenol resin E was 80000, and AF-6 Solvent (JX Nippon Mining & Energy Co., Ltd.) had a chemotronic cloud point of 120 degrees.

(Production Example 3-1) Synthesis of resol-type phenol resin In the same apparatus as in Production Example 2-1, 1000 parts of para-tert-butylphenol, 370 parts of 92% paraformaldehyde, 1000 parts of xylene, and 10 parts of 50% sodium hydroxide were charged. The mixture was heated to 95 ° C., reacted for 6 hours while maintaining the same temperature, mixed with 300 parts of water and 13 parts of hydrochloric acid, neutralized, added with 1000 parts of water, and the supernatant was put in the same apparatus as above. The mixture was taken out, heated to 120 ° C., stirred for 30 minutes, and the supernatant was taken out to obtain a resol type phenol resin G having a solid content of 57%. As a result of measuring the weight average molecular weight of the resol type phenol resin G, the average number of nuclei was 1.7.

(Production Example 3-2) Synthesis of rosin-modified phenol resin 1000 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged in the same apparatus as in Production Example 1-2, and the temperature was raised to 180 ° C. 110 parts and 2 parts of zinc oxide were added, and the reaction was continued until the acid value reached 20 mgKOH / g or less while maintaining the same temperature by raising the temperature to 250 degrees. Thereafter, the temperature was lowered to 180 ° C., and while maintaining the same temperature, the resol type phenol resin G was dropped using a dropping funnel at a dropping rate of 2.5 parts / minute, and the 25 ° C. Gardner viscosity of the 50% toluene solution was changed to FG. At that time, dropping was stopped, and after 30 minutes, the resin was taken out to obtain rosin-modified phenolic resin H. The dripped resol type phenol resin G was 570 parts. The weight average molecular weight of the rosin-modified phenol resin H was 60000, and the clouding point of AF-6 Solvent (JX Nippon Mining & Energy Corporation) was 105 degrees.

(Production Example 4-1) Synthesis of Resol Type Phenolic Resin In a device similar to Production Example 1-1, 1000 parts of para-tert-butylphenol was charged and heated and dissolved at 120 degrees, and 280 parts of 92% paraformaldehyde, calcium hydroxide. 8 parts were added, and the temperature was raised to 130 ° C. and reacted for 2 hours while maintaining the same temperature. Then, the pressure was released, and the mixture was further stirred at the same temperature for 20 minutes, and the resol type phenol resin J was taken out. As a result of measuring the weight average molecular weight of the resol type phenol resin J, the average number of nuclei was 3.0.

(Production Example 4-2) Synthesis of rosin-modified phenolic resin In the same apparatus as in Production Example 1-2, 1000 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged, and the temperature was raised to 180 ° C. 110 parts of erythritol and 2 parts of zinc oxide were added, and the reaction was continued until the acid value reached 20 mgKOH / g or less while maintaining the same temperature by raising the temperature to 250 degrees. Thereafter, the temperature was lowered to 180 ° C., and Resol J was added step by step while maintaining the same temperature. When the Gardner viscosity of the 50% toluene solution became FG, the addition was stopped, and after 30 minutes, the resin was taken out, and rosin A modified phenolic resin K was obtained. The amount of resole J charged was 700 parts. The weight average molecular weight of the rosin-modified phenol resin K was 150,000, and the clouding point of AF-6 Solvent (JX Nippon Mining & Energy Corporation) was 200 degrees.

(Production Example 5-1) Synthesis of resol type phenolic resin The same apparatus as in Production Example 2-1 was charged with 1000 parts of paratertiary butylphenol, 434 parts of 92% paraformaldehyde, 1000 parts of xylene and 10 parts of 50% sodium hydroxide. The mixture was heated to 95 ° C., reacted for 6 hours while maintaining the same temperature, mixed with 300 parts of water and 13 parts of hydrochloric acid, neutralized, added with 1000 parts of water, the supernatant was taken out, and the solid content was 58. % Resol type phenol resin M was obtained. As a result of measuring the weight average molecular weight of the resol type phenol resin M, the average number of nuclei was 1.0.

(Production Example 5-2) Synthesis of Rosin Modified Phenolic Resin 1000 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged in the same apparatus as in Production Example 1-2, and the temperature was raised to 180 ° C., pentaerythritol 110 parts and 2 parts of zinc oxide were added, and the reaction was continued until the acid value reached 20 mgKOH / g or less while maintaining the same temperature by raising the temperature to 250 degrees. Thereafter, the temperature was lowered to 180 ° C., and while maintaining the same temperature, the resol type phenol resin M was dropped at a dropping rate of 2.5 parts / minute using a dropping funnel, and the 25 ° C. Gardner viscosity of the 50% toluene solution was changed to FG. At that time, the dropping was stopped, and after 30 minutes, the resin was taken out to obtain rosin-modified phenolic resin N. The dripped resol type phenol resin M was 460 parts. The weight average molecular weight of the rosin-modified phenol resin N was 50,000, and the clouding point of AF-6 Solvent (JX Nippon Mining & Energy Corporation) was 50 degrees.

(Production Example 6-1) Synthesis of resol-type phenol resin In the same apparatus as in Production Example 2-1, 1000 parts of para-tert-butylphenol, 290 parts of 92% paraformaldehyde, 1000 parts of xylene, and 10 parts of 50% sodium hydroxide were charged. The mixture was heated to 95 ° C., reacted for 6 hours while maintaining the same temperature, mixed with 300 parts of water and 13 parts of hydrochloric acid, neutralized, added with 1000 parts of water, and the supernatant was put in the same apparatus as above. The mixture was taken out, heated to 120 ° C., stirred for 140 minutes, and the supernatant was taken out to obtain a resol type phenol resin P having a solid content of 56%. As a result of measuring the weight average molecular weight of the resol type phenol resin P, the average number of nuclei was 3.8.

(Production Example 6-2) Synthesis of rosin-modified phenolic resin In the same apparatus as in Production Example 1-2, 1000 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged, and the temperature was raised to 180 ° C. 110 parts of erythritol and 2 parts of zinc oxide were added, and the reaction was continued until the acid value reached 20 mgKOH / g or less while maintaining the same temperature by raising the temperature to 250 degrees. Thereafter, the temperature was lowered to 180 ° C., and while maintaining the same temperature, the resol type phenolic resin P was dropped at a dropping rate of 2.5 parts / minute using a dropping funnel, and the Gardner viscosity of the 50% toluene solution became FG. The dropping was stopped at the time, and after 30 minutes, the resin was taken out to obtain rosin-modified phenol resin Q. The dripped resol type phenolic resin P was 1400 parts. The weight average molecular weight of the rosin-modified phenol resin Q was 200000, and the clouding point of AF-6 Solvent (JX Nippon Mining & Energy Corporation) was 220 degrees.

(Adjustment of resin varnish for printing ink)
Using the rosin modified phenolic resins of Production Examples 1-2, 2-2, 3-2, 4-2, 5-2, and 6-2, resin varnishes were obtained by the following method.
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introducing device was charged with 450 parts of rosin-modified phenolic resin and 340 parts of AF-7 Solvent (JX Nippon Mining & Energy Corporation), 180 The mixture was stirred with heating for 1 hour. Then, 200 parts of soybean oil was added, the temperature was lowered to 160 ° C., 10 parts of ethyl acetoacetate aluminum dinormal butyrate was added, and the same temperature was maintained for 1 hour to obtain a resin varnish for printing ink. A comparison table of rosin-modified phenolic resin and resin varnish obtained from the resin is as follows.

  Table 2 below summarizes the results of the resin part blending and varnish part blending produced above.

(Preparation of printing ink)
Printing inks of Examples 1-4 and Comparative Examples 1-2 were prepared using the resin varnishes C, F, I, L, O, and R, respectively. Phthalocyanine blue is FASTOGENBlue FA5375 manufactured by DIC Corporation. Further, as the calcium carbonate, white gloss flower O manufactured by Shiroishi Kogyo Co., Ltd. was used.

  The mixture ratio shown in Table 3 was used to knead using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the groove depth at kneading position A was 7.5 μm or less (on the scale). 3 or less), and the L-type viscosity value of the ink at 25 ° C. was adjusted to 18 to 19 (Pa.s). The L-type viscosity was measured by a method using an L-type viscometer described in JIS K5701-1. The tack (TV) value was measured in a room air-conditioned at 25 ° C. using the rotary tack meter described in 4.2 Adhesiveness of JIS K5701-1 (lithographic ink test method). Set the controller temperature of the tack meter to 32 ° C and stabilize for 30 minutes or more, then apply 1.31 mL of ink on the roller of the tack meter using a pipette, and set the value for 1 minute at a roller rotation speed of 400 rpm. TV value was used.

(Evaluation of wearability and gloss)
The printing inks of Examples 1 to 4 and Comparative Examples 1 to 2 were printed using a Prüfbau multipurpose printing aptitude tester (MZ-II, prufbau, Dr-Ing H. Durner GmbH) with a printing pressure of 400 N and a printing speed of 8 m / Under the condition of seconds, the color was developed on OK top coat paper (manufactured by Oji Paper Co., Ltd.) so that the color density was 1.6 ± 0.2. And it was left to dry for 10 second in the dryer of atmospheric temperature 100 degreeC, and was dried. The ink color of the color-extended product after drying was confirmed visually. X when there are many white spots where no ink is attached. ○ which has almost no white spots. Although it is confirmed a little, the one with a good degree is marked with Δ.
The concentration was measured using SpectroEye (manufactured by Gretagmacbeth) with a light source D50, an observation field of view 2 °, a concentration standard Status T, a built-in filter Pol, and a paper white and white standard (Paper).

Further, for the measurement of gloss, the developed product used for the evaluation of the inking property was used as it was, and the 60 ° gloss was measured. The gloss value is preferably 50 or more. The Prüfbau printability tester is widely used for evaluating printing ink compositions.
(Evaluation of dryness)
The color was applied to OK Kanto single-sided art paper (manufactured by Oji Paper Co., Ltd.) under the same conditions as the evaluation of the inking property. Immediately after the color development, a conveyor type dryer maintained at 200 ° C. was passed for 5 seconds. Then, the stickiness of the exhibition color was evaluated by finger touch. Evaluation was made sticky → heat set property “poor”, not sticky → heat set property “excellent”.

(Evaluation of misting)
For evaluation of misting, the rotary tack meter described in 4.2 Adhesion section of JIS K5701-1 (lithographic ink test method) in which 1.3 mL of ink was placed in an air-conditioned room at 25 ° C. had a temperature of 42 It is operated for 10 minutes under the conditions of ℃ and the rotational speed of the roller is 1200 rpm. During rotation, place a blank paper at a distance of 10 cm from the roller. Misted ink is scattered and transferred to and adhered to white paper. The degree of contamination of this blank paper is determined visually. The evaluation is a five-level evaluation, with 1 being the worst and 5 being the best. 3 or more is preferable.

(Evaluation of onboard stability)
For the on-machine stability test, the rotary tack meter described in the stickiness section of JIS K5701-1 (lithographic ink test method) 4.2 is used. Whether the surface temperature of the roller is 42 ° C. or not and the TV value increases with the evaporation of the solvent in the ink at a roller rotation speed of 1200 rpm is judged as superior or inferior. Elapsed time (minutes) is plotted on the horizontal axis, and tack values are plotted on the vertical axis. Linear linear approximation is performed within a range where the tack value rises linearly. An ink having a large slope of a straight line obtained as a result of the linear approximation has poor on-machine stability, and a small ink is good. More preferably, the inclination is 1.5 or less. Furthermore, in order to print on paper with weak paper surface strength, the inclination is more preferably 1.0 or less.

(Evaluation of temperature dependence)
Evaluation of temperature dependence was performed by taking the loss tangent (tan δ) from 15 ° C. to 45 ° C. in the linear region as the vertical axis, the horizontal axis as the measurement temperature, and the difference between tan δ at 45 ° C. and 15 ° C. as Δtan δ. An ink having a small Δtan δ has little change in viscoelasticity of the ink due to a temperature rise on the printing press roller during high-speed printing, and has good ink transfer between the printing press rollers during high-speed printing. A more preferable range of the value of Δtanδ is 0 to 2.0.

(Emulsification suitability evaluation)
The emulsification suitability of the ink was measured under the following conditions using a lithotronic high-speed emulsification tester manufactured by Novomatics.
Conditioning time (preliminary stirring time without adding water) ... 300 sec.
Stirring speed ... 1200rpm
Amount of ink sample: 25g
Temperature ... 40 ± 2 ℃
Amount of water dripping 2 mL / min,
Propeller: Propeller angle 10 °, thickness 1.5mm
Distance between propeller and cup bottom: 1mm
Liquid temperature: 22 ± 2 ° C

Distilled water is used as water. When dripping water, the water injection needle is brought into contact with the cup wall surface so that the water gently enters the ink, and the torque curve noise due to water drops is minimized.
EC (Emulsification Capacity: unit%) is defined by the following equation.

In this testing machine, the torque (unit mN · m) is measured twice / second. When water is dripped into the varnish or ink of the sample placed in the cup while stirring, the initial torque decreases and shows the minimum torque value (Tmin). Thereafter, the torque value increases with an increase in the amount of dripping water, and shows a maximum torque value (Tmax). If dripping is further continued, a part of the water is separated from the sample, causing a sharp decrease in torque and an unstable torque curve. EC value is defined as ECmax when the standard deviation of the latest 10 measured values of the torque value exceeds 100 when the torque starts to fluctuate unstablely. Printing ink having an ECmax of 80% or more is liable to cause entanglement and water rod entanglement in a printing test.
Table 3 below shows the ink evaluation results.

  The ink composition of the present invention can be used as a lithographic ink, heat set (off-wheel) ink, newspaper ink, sheet-fed ink, and the like.

Claims (6)

A lithographic printing ink composition using a varnish containing a rosin-modified phenolic resin using resole as part of a raw material,
The lithographic printing characterized in that the resol is a resole (A) having an average number of nuclei of 1.5 to 3.0, and the rosin-modified phenol resin has an AF-6 solvent cloud point of 100 to 210 ° C. Ink composition. The lithographic printing ink composition according to claim 1, wherein in the resol (A), 1 to 15% by mass of a resol having an average number of nuclei of 2 or more is contained in the lithographic printing ink. A printed matter obtained by printing using the lithographic printing ink composition according to claim 1 or 2 as a base material. In the method for producing resole (A) having an average number of nuclei of 1.5 to 3.0 obtained by reacting mononuclear resole (B),
A method for producing resole (A), comprising a step of holding the product at a temperature of 80 to 180 ° C. for 20 minutes to 2 hours after the reaction. The lithographic printing ink composition according to claim 1 or 2, wherein the resol (A) obtained by the production method according to claim 4 is used. A printed matter obtained by printing using the lithographic printing ink composition according to claim 5 as a base material.