JP2011144315A - Offset ink composition and printed matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an offset ink composition which is excellent in flowability of ink, stability with the lapse of time, drying property during printing, and stability on a printing machine, and to provide a printed matter. <P>SOLUTION: In the offset ink composition containing a binder resin, a pigment, and specific vegetable oils as solvent components, the vegetable oils contain compounds represented by general formula (1) in an amount of 50-100 wt.% to the total weight of the vegetable oils. In the general formula (1), R1, R2 and R3 each represent a 14-18C saturated hydrocarbon group or a 14-18C unsaturated hydrocarbon group having no triple bond, with the proviso that, to total moles of (R1+R2+R3), the molar ratio of the 16C saturated hydrocarbon group is 30-50%, the molar ratio of the 18C unsaturated hydrocarbon group having two double bonds is 5-15%, and the molar ratio of the 18C unsaturated hydrocarbon group having three double bonds is ≤1.0%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an offset ink composition used for printing books, books, leaflets, catalogs, and the like, and more specifically, the flowability and temporal stability of ink and the drying property during printing and on the printing press. The present invention relates to an oxidation polymerization type offset ink composition having excellent stability and low environmental load.

  Conventional offset inks include synthetic resins such as rosin-modified phenolic resin, rosin-modified alkyd resin, petroleum resin-modified phenolic resin, vegetable oil such as linseed oil, tung oil, soybean oil, mineral oil, synthetic oil, and ink as required. In order to give flexibility and softness to the dry film, it consists of additives such as plasticizers and wax compounds, colorants and solvents for pigments and dyes, and the solvents used in these inks Aromatic solvents have been mainly used from the standpoint of solubility and dispersibility and printability (Patent Documents 1 and 2).

  However, in recent years, inks mainly composed of oils such as the above-described mineral oils and aromatic solvents have a problem that odors of volatile vapors such as residual solvents are strong during production and printing and in printed materials. Therefore, from the viewpoint of environmental hygiene such as work environment and air pollution, the odor of volatile vapor is extremely low, and it is replaced with ink mainly composed of vegetable oil and non-aromatic solvents that have less environmental load such as work environment and air pollution. (Patent Documents 1 and 2).

  In other words, Patent Document 3 and Patent Document 4 propose a printing ink composition that uses rosin-modified phenolic resin and vegetable oil ester as solvent main components, significantly reduces VOC components compared with conventional inks, and has high-speed setting properties. However, the drying property is insufficient.

In Patent Document 5, rosin-modified phenolic resin, rice bran oil and fatty acid monoester are used as main raw materials, and VOC components are greatly reduced compared to conventional inks. Printing inks with stability have been proposed, but this is also insufficient with respect to drying properties.

In patent document 6, although the offset ink using the rice bran oil which adjusted the iodine value to 100 or more is proposed, dryness and on-machine stability are inadequate.
Furthermore, in recent years, crops such as soybean oil have been diverted to bioethanol raw materials, and there are concerns that the price of soybean oil will rise and that a stable supply amount will be secured. On the other hand, with the rapid movement of CO ₂ emission reduction on a global scale, the idea of eliminating decalcified materials and VOCs from ink components has been spreading. Moreover, the same concept applies to transportation fuel.

From the perspective of reducing CO ₂ emissions by shortening the distance between production / manufacturing sites and consumption areas of raw materials and products, such as transportation mileage, procurement of ink raw materials in close proximity to the ink manufacturing area This can contribute to the reduction of CO ₂ emissions.

  However, soybean oil used as a vegetable oil component is mainly imported from overseas harvested soybeans harvested in North and South America, and transport mileage is poor, which is undesirable for the environment.

JP 2006-249385 A JP 2005-290084 A JP 2002-69354 A JP 2002-155227 A JP 2005-330317 A JP 2003-96375 A

  The present invention provides an offset ink composition excellent in the fluidity and temporal stability of ink, the drying property during printing, and the stability on the printing press while taking into consideration the global environment, and a printed matter using the same. It is.

  As a result of sincere research to solve the above-mentioned problems, in the offset ink composition containing a binder resin, a vegetable oil and a pigment, the offset ink composition containing a specific vegetable oil has a fluidity and stability over time as well as during printing. The present inventors have found that it is excellent in drying property and stability on a printing press, and completed the present invention.

That is, the present invention relates to an oxidation polymerization type offset printing ink composition containing vegetable oil as a binder resin, a pigment and a solvent component, wherein the vegetable oil is 50 to 100% by weight based on the whole vegetable oil. It is related with the oxidation polymerization type offset ink composition characterized by containing the compound represented by this.

General formula (1)

  Furthermore, this invention relates to said oxidation polymerization type offset ink composition characterized by the iodine value of the compound represented by General formula (1) being 30-100 (mg / 100 mg).

一般式（３）

一般式（４）

Moreover, this invention relates to said oxidation polymerization type offset ink composition characterized by further containing the compound represented by General formula (2)-(4).

General formula (2)

General formula (3)

General formula (4)

The present invention further comprises the oxidation polymerization type offset ink composition described above, further comprising 0.01 to 1.0% by weight of the compound represented by the general formula (5) based on the total weight of the ink. It is about things.

General formula (5)

Moreover, this invention reacts the compound represented by General formula (2)-(5) with the compound represented by General formula (1), and the compound represented by General formula (6) in an alkali catalyst. The present invention relates to an oxidation polymerization type offset ink composition as described above.

General formula (6)

Furthermore, in the present invention, the binder resin is
The acid value is 5-30 (mg KOH / g),
Softening point by ring-and-ball method is 120-300 ° C
And a weight average molecular weight of 10,000 to 100,000
The oxidative polymerization type offset ink composition is characterized by being a rosin-modified phenol resin.

The present invention further includes
Aniline point 75-95 ° C
And boiling point 260-350 ° C
It is related with said oxidation polymerization type offset ink composition characterized by containing the petroleum solvent which is.

  Furthermore, this invention relates to the printed matter formed by printing said oxidation polymerization type offset ink composition on a base material.

  The oxidative polymerization type offset ink composition provided by the present invention is excellent in fluidity and aging stability of ink, drying property at the time of printing and stability on a printing press in printing of books, books, leaflets, catalogs, etc. Excellent and less environmental impact.

  Next, the present invention will be described more specifically with reference to preferred embodiments.

  In the compound represented by the general formula (1) used in the present invention, the molar ratio of the unsaturated hydrocarbon group having 18 carbon atoms having two double bonds is 5 to 15% with respect to the total amount of (R1 + R2 + R3). 10 to 15% is preferable. Furthermore, the molar ratio of the C18 unsaturated hydrocarbon group having three double bonds is more preferably 1.0% or less, preferably 0.7% or less, and more preferably 0.5% or less. It is desirable that it should not be included if possible. That is, the compound represented by the general formula (1) preferably has a specific double bond ratio.

  Further, the content of the compound represented by the general formula (1) is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and preferably 80 to 100% by weight with respect to the whole vegetable oil. . Furthermore, it is desirable to contain 10 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 20 to 30% by weight with respect to the total amount of the oxidation polymerization type offset ink composition. If the content of the compound represented by the general formula (1) is less than 10% by weight based on the total amount of the oxidation polymerization offset ink composition, the stability of the ink on the printing press is inferior, and the ink is thickened. , Leading to a decrease in fluidity. When the content of the compound represented by the general formula (1) is more than 50% by weight with respect to the total amount of the oxidation polymerization offset ink composition, the drying property is inferior, and after rubbing on the printing press or binding on the printing paper surface. This results in blocking and results in poor quality as a printed matter.

  In addition, if the ratio of the unsaturated hydrocarbon group having 18 carbon atoms having two double bonds is less than 5%, the printed matter after ink drying is inferior in friction resistance and gloss. Ink is not preferable because the ink is not stable over time. In addition, when an unsaturated hydrocarbon group having 18 carbon atoms having one triple bond is present, the stability over time of the ink in the storage container is remarkably inferior, so it is not preferable to reduce it as much as possible (preferably the content is 0% by weight). .)

  In the present invention, the vegetable oils include vegetable oils and compounds derived from vegetable oils. As the compound, for example, in a triglyceride of glycerin and a fatty acid, at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond. Examples include fatty acid monoesters obtained by ester reaction of triglycerides with saturated or unsaturated alcohols from these triglycerides, fatty acid monoesters obtained by direct ester reaction of fatty acids of vegetable oils and monoalcohols, and ethers.

  A method of typically obtaining the compound represented by the general formula (1) used in the present invention may be obtained as palm oil, but other vegetable oils and the like are purified to become the general formula (1). May be processed.

  In the present invention, as required, for example, cane seed oil, linseed oil, eno oil, prickly oil, olive oil, cacao oil, kapok oil, kayak oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil , Sesame oil, safflower oil, radish seed oil, soybean oil, daikon oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine Oils derived from vegetable oils such as seed oil, cottonseed oil, coconut oil, peanut oil, dehydrated castor oil, thermal polymerized oils, oxygen-blown polymerized oils, etc. can be used in combination, or these can be used alone or in combination of two or more. However, the content is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total amount of the offset ink composition. When used in an amount of 10% by weight or more, it is not preferable because the temporal stability of the ink in the storage container is poor.

  In the present invention, when a suitable vegetable oil represented by the general formula (1) is given, a vegetable oil having an iodine value of 30 to 100 (mg / 100 mg) is preferable, and an iodine value of 40 to 100 ( mg / 100 mg) of vegetable oil is more preferred. By limiting the range of the iodine value, it is possible to increase the drying property by oxidative polymerization of the ink film, which is particularly effective for a sheet-fed printing method that does not use a hot air dryer.

  In the present invention, the fatty acid ester of the general formulas (2) to (5) is preferably composed of a saturated or unsaturated fatty acid having 14 to 18 carbon atoms and a linear or branched monoalcohol having 1 to 8 carbon atoms. Examples of fatty acid esters derived from animal and vegetable oils include palm oil methyl ester, palm oil butyl ester, palm oil isohexyl ester, soybean oil methyl ester, soybean oil butyl ester, soybean oil isohexyl ester, and the like. Fatty acid esters composed of saturated or unsaturated fatty acids having less than 14 carbon atoms are too high in solubility, and there are concerns about adverse effects on printing materials such as blankets and rubber rollers, and saturated or unsaturated fatty acids or carbon numbers having more than 18 carbon atoms. A fatty acid ester composed of 9 or more monoalcohols has insufficient solubility.

  Examples of binder resins that can be used in the present invention include phenolic resins (phenolic resins, rosins, cured rosins, rosin-modified phenolic resins using polymerized rosins, etc.), maleic acid resins (rosin-modified maleic acid, etc.). Resin, rosin ester resin and the like), alkyd resin or modified alkyd resin, petroleum resin and the like, and these can be used alone or in combination of two or more.

In particular, the binder resin preferably used in the present invention has an acid value of 5 to 30 (mg KOH / g), a weight average molecular weight of 10,000 to 100,000, preferably 20,000 to 80,000, and a softening point by a ring and ball method of 120 to 120. A rosin-modified phenolic resin having a temperature of 300 ° C., preferably 120 to 280 ° C. is desirable.
When the weight average molecular weight is 10,000 or less, the viscoelasticity of the ink is lowered, and when it is 100,000 or more, the fluidity and gloss of the ink are inferior.

The rosin-modified phenolic resin in the present invention is obtained by reacting rosin which is a resin acid, resole which is a condensate of alkylphenol and formalin, and a polyhydric alcohol, and a third component such as maleic acid is added as necessary. Sometimes. The blending ratio of rosin and resole is one of the important factors controlling the physical properties of the resin. The blending ratio of rosin in the rosin-modified phenolic resin according to the present invention is desirably 60% by weight or more and 70% by weight or less, and preferably 62% by weight or more and 67% by weight or less. If the ratio is less than 60% by weight, the resole has excessive alkyl groups. As a result, the solubility of the resin in the solvent becomes excessive, making it difficult to achieve the desired high viscosity of the ink. Since the alkyl group of the resole is reduced and the solubility of the resin in the solvent is too bad, the solvent may be separated from the ink.

  The petroleum solvent used in the present invention is a crude oil-derived solvent (petroleum solvent) having an aromatic hydrocarbon content of 1% by weight or less, and has a boiling point of 260 to 350 ° C, preferably 280 to 340 ° C. The thing in the range of ° C is good. When the boiling point of petroleum-based solvents is less than 260 ° C, the solvent evaporation of the ink on the printing machine increases, and the transferability of the ink to rollers, blankets, plates, etc. deteriorates due to the deterioration of the fluidity of the ink. It is not preferable. Further, when the boiling point of the petroleum solvent used in combination exceeds 350 ° C., the drying property of the ink is inferior. The petroleum solvent used in the present invention is desirably contained in an amount of 5 to 20% by weight, preferably 7 to 18% by weight, based on the total amount of the ink, if necessary.

  Further, an aniline point of 75 ° C to 95 ° C is suitable for the petroleum solvent. When the aniline point is less than 75 ° C., the ability to dissolve the resin is too high, the ink viscosity becomes too low, and the stain resistance is not sufficient. Also, if the aniline point exceeds 95 ° C, the ability to dissolve the resin is too low, the ink viscosity becomes too high, the ink fluidity is poor, and ink tends to accumulate on the rollers, plates, and blankets. Therefore, it is not preferable.

Moreover, 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, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, and organic pigments. As such, pigments used for offset inks such as azo, phthalocyanine, quinacridone, anthraquinone, and dioxazine are equivalent. As for organic pigments, for example, copper phthalocyanine pigments (CI Pig)
ment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, C.I. I. 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, CI Pigment Violet 19), dioxazine pigments (CI Pigment Violet 23), and the like, but are not limited thereto.

Furthermore, the offset ink composition of the present invention includes a gelling agent, a pigment dispersant, a metal dryer, a drying inhibitor, an antioxidant, a friction improver, an anti-set-off agent, and a nonionic sea surface activity as required. An additive such as an agent and a polyhydric alcohol can be conveniently used.
In the present invention, the dryer is an oxidative polymerization catalyst that promotes oxidative polymerization, and includes acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethylbutyric acid, naphthenic acid, octylic acid, nonanoic acid, decanoic acid, 2 -Ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, secanoic acid, tall oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, dimethylhexano Known metal salts of organic carboxylic acids such as ic acid, 3,5,5, -trimethylhexanoic acid, dimethyloctanoic acid, such as calcium, cobalt, lead, iron, manganese, zinc, zirconium, salt, etc. Official compounds can be used to promote printing ink surface and internal curing In addition, a plurality of these can be used in combination as appropriate.

  The antioxidant is a polymerization inhibitor having an inhibitory effect on the oxidative polymerization reaction, and hydroquinone derivatives represented by hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, etc. -Denotes phenolic compounds typified by tert-butyl-4-hydroxytoluene and the like, vitamin compounds having an antioxidant action typified by ascorbic acid, tocopherol, etc., and these are arbitrarily used alone or in combination of two or more. Can be used.

  As auxiliary agents, anti-friction agents, anti-blocking agents, slip agents, pigment dispersants, carnauba wax, beeswax, lanolin wax, montan wax, paraffin wax, microcrystalline wax, natural wax, Fischer-Tropsch synthetic wax, Synthetic waxes such as polyethylene wax, polypropylene wax, polytetrafluoroethylene wax and polyamide wax, silicone additives, leveling agents and the like can be used as appropriate.

  In the offset ink composition, the proportion of each component is 5 to 30% by weight for pigment, 20 to 50% by weight for binder resin, 20 to 50% by weight for vegetable oils, 0 to 20% by weight for petroleum solvents, It is preferable that 0 to 3% by weight, antioxidant is 0 to 4% by weight, other additives are 0 to 10% by weight, and the total amount is 100% by weight.

  The offset ink composition of the present invention preferably has a viscosity of 100.0 Pa · s or less, more preferably 1.0 Pa · s to 90.0 Pa · s at 25 ° C. and a shear rate of 100 / s with a cone plate viscometer. If the viscosity is greater than the above values, the fluidity and transferability will decrease, so the stability of the ink supplied to the roller will be poor, and the printing workability will be hindered, and the leveling property of the ink transferred to the paper will be reduced. It is not preferable because it deteriorates and causes quality problems such as gloss deterioration. In addition, the tack value of the ink increases with the viscosity, so that paper peeling or paper separation failure is likely to occur, and paper dust accumulates on the blanket, which is not preferable because stable printing workability such as transfer failure cannot be secured.

  The offset ink composition of the present invention is used for lithographic printing, but can be applied to coating methods such as roll coaters and knife coaters, or printing methods such as gravure printing, letterpress printing, and silk screen printing, as long as they do not depart from the idea. Is also applicable.

In the present invention, the weight average molecular weight was measured by gel permeation chromatography (HLC-8020, hereinafter referred to as GPC) manufactured by Tosoh Corporation. A calibration curve was prepared with a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.
Furthermore, in the present invention, “molecular weight” means a weight average molecular weight unless otherwise specified.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited by these Examples. In the present invention, “part” represents “part by weight” and “%” represents “% by weight”.

(Phenolic resin production example 1)
P-octylphenol 1000 parts, 35% formalin 850 parts, 93% sodium hydroxide 60 parts and toluene 1000 parts were added to a four-necked flask equipped with a stirrer, cooler and thermometer, and reacted at 90 ° C. for 6 hours. It is dripping. Thereafter, 125 parts of 6N hydrochloric acid and 1000 parts of tap water were added, stirred and allowed to stand, and the upper layer part was taken out to obtain 2000 parts of a toluene solution of a resol type phenol resin having a nonvolatile content of 49%. Y.

(Production Example 1 of rosin-modified phenolic resin)
A four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer was charged with 1000 parts of gum rosin, dissolved at 200 ° C. while blowing nitrogen gas, and 1360 parts of resole liquid Y was added to remove toluene. Then, after reacting at 230 ° C. for 4 hours, 100 parts of glycerin was added and esterified at 250 to 260 ° C. until the acid value was 25 or less, and a rosin having a weight average molecular weight of 28000, an acid value of 21.7 and a softening point of 170 ° C. A modified phenolic resin A (hereinafter referred to as “resin A”) was obtained.

(Production Example 2 of rosin-modified phenolic resin)
A four-necked flask equipped with a stirrer, a condenser with a water separator and a thermometer was charged with 1000 parts of gum rosin, dissolved at 200 ° C. while blowing nitrogen gas, and 1490 parts of resole liquid Y was added to remove toluene. Then, after reacting at 230 ° C. for 4 hours, 115 parts of glycerin was charged and esterified at 250 to 260 ° C. until an acid value of 25 or less, and a rosin having a weight average molecular weight of 60000, an acid value of 19.5 and a softening point of 180 ° C. Modified phenol resin B (hereinafter referred to as resin B) was obtained.

(Production Example 3 of rosin-modified phenolic resin)
A four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer was charged with 1000 parts of gum rosin, dissolved at 200 ° C. while blowing nitrogen gas, and 1370 parts of resole liquid Y was added to remove toluene. Then, after reacting at 230 ° C. for 4 hours, 130 parts of glycerin was charged and esterified at 250 to 260 ° C. until the acid value was 25 or less, and a rosin having a weight average molecular weight of 140000, an acid value of 18.5 and a softening point of 190 ° C. A modified phenolic resin C (hereinafter referred to as “resin C”) was obtained.

(Varnish production example 1)
A stirrer, Liebig condenser, four-neck flask with thermometer, 43 parts of resin A (weight average molecular weight 28000, acid value 21.7, softening point 170 ° C.), vegetable oil D (compound represented by general formula (1) The molar ratio of the saturated hydrocarbon group having 16 carbon atoms is 30 to 50% with respect to the total amount of (R1 + R2 + R3) in the compound represented by the general formula (1) of 98% by weight, and a double bond The molar ratio of unsaturated hydrocarbons having 18 carbon atoms having 2 carbon atoms is 5 to 15%, and the molar ratio of unsaturated hydrocarbons having 18 carbon atoms having 3 double bonds is 1.0% or less) 56 parts and 1 part of ALCH (Kawaken Fine Chemical Co., Ltd. gelling agent) were charged, heated to 190 ° C., stirred at the same temperature for 1 hour, and then allowed to cool to obtain varnish 1.

(Varnish production examples 2 to 213, Comparative example varnish production examples 1 to 7)
Based on the compositions in Tables 1 to 7, varnishes 2 to 213 were obtained by the same varnish production method as in Varnish Production Example 1. Moreover, C14-C18 in Tables 1-7 shows the content rate of the compound represented by General formula (1). C18: 2 represents a molar ratio of an unsaturated hydrocarbon having 18 carbon atoms having two double bonds with respect to the total amount of (R1 + R2 + R3) in the compound represented by the general formula (1), and C18: 3 represents the molar ratio of an unsaturated hydrocarbon having 18 carbon atoms having 3 double bonds.
In the table, AF Solvent No. 5 is manufactured by Nippon Oil Corporation.

(Base ink and ink manufacturing)
17 parts of LIONOL BLUE FG7330 (manufactured by Toyo Ink Manufacturing Co., Ltd.), 70 parts of varnish 1 and 87 parts in total were placed on 3 rolls and kneaded twice with 3 rolls at 60 ° C. Dispersed to 7.5 μm or less to obtain base ink 1.
Then, for base ink 1, 6.3 parts of AF solvent No. 5, 5 parts of wax compound (new friction-resistant compound manufactured by Toyo Ink Manufacturing Co., Ltd.), metal dryer (MK dryer manufactured by Toyo Ink Manufacturing Co., Ltd.) 5 parts and 0.2 part of a drying inhibitor (Drying inhibitor CP manufactured by Toyo Ink Manufacturing Co., Ltd.) were added to obtain about 100 parts by weight of the ink of Example 1.

  Using the same base ink preparation method as described above, base inks were prepared with the formulations shown in Tables 8 to 13, and AF solvent No. 5, vegetable oil D, wax compound, metal dryer, and drying inhibitor shown in the table were added. As a result, about 100 parts of inks of Examples 2 to 213 and Comparative Examples 1 to 7 were obtained.

(Evaluation results)
In the sheet-fed inks of Examples 1 to 213 and Comparative Examples 1 to 7, the fluidity, drying property, on-machine stability, and stability over time were evaluated, and the results are shown in Tables 8 to 13, respectively.

<Measurement method of fluidity>
After setting 2.1 cc of ink in a hemispherical container and allowing it to stand at 40 ° C. for 1 hour, the ink was dropped on an inclined plate inclined at 60 °, and the length of flow for 10 minutes was measured. Evaluation was performed based on the following evaluation criteria.
(Evaluation criteria)
◎: 80 mm or more ○: 70 mm or more, less than 80 mm Δ: 50 mm or more, less than 70 mm ×: less than 50 mm

<Method of measuring dryness>
The ink was developed on coated paper by using an RI tester (manufactured by Meiko Seisakusho Co., Ltd.), and sulfuric acid paper was superimposed on the developed surface, and the drying time was measured using a Chaoyang drying tester. The drying time was the time when the ink no longer adhered to the sulfuric acid paper, and the evaluation was performed based on the following evaluation criteria.
(Evaluation criteria)
◎: Less than 6 hours ○: 6 hours or more, less than 8 hours △: 8 hours or more, less than 10 hours ×: 10 hours or more

<Measurement method of on-board stability>
After the ink was developed on a glass plate with a 75 μm applicator, the drying time was examined by finger touch every 30 minutes under conditions of 40 ° C. and humidity of 52%. The drying time was the time when the ink no longer adhered to the finger, and the evaluation was performed based on the following evaluation criteria.
(Evaluation criteria)
◎: 12 hours or more ○: 10 hours or more, less than 12 hours △: 6 hours or more, less than 10 hours ×: Less than 6 hours

<Measurement method of stability over time>
The ink viscosity (Pa · s) at 25 ° C. and a share rate of 117 / s was measured by HAAKE Rheopress 600 (manufactured by Thermo ELECTRON CORPORATION). Then, it put into the airtight container, purged with nitrogen, closed the lid | cover, and stored in 90 degreeC oven for 1 week. After one week, the ink was removed from the oven and the ink viscosity was measured again. The difference in ink viscosity before and after oven storage was determined and evaluated based on the following evaluation criteria. The smaller the amount of change in viscosity, the better the stability over time.
(Evaluation criteria)
◎: Less than 10 Pa · s ○: 10 Pa · s or more, less than 15 Pa · s Δ: 15 Pa · s or more, less than 20 Pa · s ×: 20 Pa · s or more

From the results of Tables 8 to 13, it was found that the fluidity, drying property, on-machine stability, and stability over time were all well balanced and excellent.
In addition, as a result of performing a printing test of the offset ink composition of the example under the following conditions using a Lithlon 426 sheet-fed printing press (manufactured by Komori Corporation), printing was possible without problems and good printed matter was obtained.

(Printing conditions)
Version: CTP plate for flat plate HP-F (Fuji Film Graphic Systems Co., Ltd.)
Dampening water: AQUAUNITY C 2.0% (Toyo Ink Manufacturing Co., Ltd.)
Paper: Art paper (Mitsubishi Paper)
Printing speed: 8000 sheets / hour

Claims (8)

In the offset printing ink composition containing vegetable oils as binder resin, pigment and solvent component,
The oxidative polymerization type offset ink composition, wherein the vegetable oil contains 50 to 100% by weight of the compound represented by the general formula (1) with respect to the whole vegetable oil.

General formula (1)

  2. The oxidation polymerization type offset ink composition according to claim 1, wherein the compound represented by the general formula (1) has an iodine value of 30 to 100 (mg / 100 mg). The oxidation polymerization type offset ink composition according to claim 1 or 2, further comprising one or more compounds represented by the general formulas (2) to (4).

General formula (2)

R1-OCO-R4

General formula (3)

R2-OCO-R4

General formula (4)

R3-OCO-R4
(In General Formulas (2) to (4), R4 represents a linear saturated hydrocarbon group or branched saturated hydrocarbon group having 1 to 8 carbon atoms.)
The oxidation polymerization type according to any one of claims 1 to 3, further comprising 0.01 to 1.0% by weight of the compound represented by the general formula (5) based on the total weight of the ink. Offset ink composition.

General formula (5)

CH ₂ -OCOR1
｜
CH-OH
｜
CH ₂ -OH
(In general formula (5), R1 represents a C14-C18 saturated hydrocarbon group or an unsaturated hydrocarbon group having no triple bond.)
The compound represented by the general formulas (2) to (5) is obtained by reacting the compound represented by the general formula (1) and the compound represented by the general formula (6) in an alkali catalyst. The oxidation polymerization type offset ink composition according to any one of claims 1 to 4.

General formula (6)

R4-OH
(In General formula (6), R4 represents a C1-C8 linear saturated hydrocarbon group or branched saturated hydrocarbon group.)
Binder resin
Acid value 5-30 (mgKOH / g),
Softening point 120-300 ° C by ring and ball method
And a weight average molecular weight of 10,000 to 100,000
The oxidative polymerization type offset ink composition according to claim 1, which is a rosin-modified phenolic resin. further,
Aniline point 75-95 ° C
And boiling point 260-350 ° C
The oxidative polymerization type offset ink composition according to any one of claims 1 to 6, comprising a petroleum solvent.   The printed matter formed by printing the oxidation polymerization type offset ink composition in any one of Claims 1-7 on a base material.