JP2017149877A - Lithographic Printing Ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve problems in the prior arts, particularly, to improve printing quality and printing workability, in particular, to suppress roller stripping.SOLUTION: A lithographic printing ink composition is provided, which comprises an acid- or acid derivative-modified vegetable oil, a binder resin, and vegetable oil. The acid- or acid derivative-modified vegetable oil is included in the whole amount of a non-volatile content of the lithographic printing ink composition. A printed matter is obtained by printing a base material with the above lithographic printing ink.SELECTED DRAWING: None

Description

  The present invention relates to a lithographic printing ink (hereinafter abbreviated as “ink”) used for offset printing for printing books, flyers, catalogs, posters, etc., and in particular, the emulsification ability is improved by an additive. It relates to ink, and more specifically, to reduce printing troubles related to dampening water generated in printing with water, improve the quality of printing paper, improve printing work efficiency, and improve the printing work environment It relates to ink.

  In printing with offset water, ink is supplied from the ink fountain to the plate surface via a plurality of rollers, and dampening water is supplied from the water boat to the plate surface via a plurality of rollers. Since the image area on the printing plate is oleophilic, ink is accepted, and since the non-image area on the printing plate is hydrophilic, an image is formed on the paper surface by coating with dampening water. If the amount of ink supplied and the amount of dampening water supplied are imbalanced, printing trouble may occur. For example, if dampening water is insufficient in the non-image area of the printing plate, a piling phenomenon generally referred to as non-image area remains. Further, when dampening water is supplied excessively, serious printing troubles such as water rod entanglement, water eyes, density fluctuation, flying, remaining roller, and roller peeling are induced. In order to prevent these printing troubles and to reproduce an excellent printing paper surface, the emulsification state of the ink and the dampening water on the printing machine is controlled, and the water width (the dampening water is applied to the printing machine or the paper surface). It is necessary to design a prescription for printing ink that expands the range of the amount of rising water that does not cause trouble. In recent years, with the progress of high-speed printing accompanying the improvement in the performance of offset printing presses, the ratio of waste paper used for printing paper has increased, so the supply and demand balance of ink and fountain solution has changed, and an optimal and stable emulsification state It is difficult to hold.

  In particular, in printing with a small number of patterns, the amount of dampening water supplied tends to be excessive with respect to the amount of ink supplied. It appears on the surface of the ink as water and inhibits smooth transfer of the ink between the rollers. In such a case, it is necessary to design an ink that can receive a large amount of fountain solution. By selecting a resin constant of the rosin-modified phenolic resin and using a surfactant, the target ink emulsification rate can be achieved. However, when an ink with a high emulsification rate on the resin surface is made, soiling is induced in the non-image area of the plate, and generally a low surface tension cationic surfactant / anionic surfactant / amphoteric surfactant. If a nonionic surfactant is used, the ink surface tension is remarkably lowered and the ink is easily scattered in the fountain solution, causing troubles such as scumming and metering (Patent Documents 1 to 3). .

 On the other hand, in Patent Document 4, the addition of a nonionic surfactant suppresses water eyes and roller peeling under the condition that dampening water is supplied excessively, but dampening water is supplied excessively. In this case, since the emulsification rate is greatly increased, troubles such as poor drying and low gloss are induced.

JP 2007-31477 A JP 2007-169465 A JP 11-349880 A JP 2010-229299 A

  The present invention has been made to solve such problems in the prior art, and the problem is that the printing quality is improved and the printing workability is improved, especially the dampening water is supplied in excess. The present invention relates to a lithographic printing ink that provides stable printing workability and density stability even under the printing conditions, and reduces the occurrence of roller peeling and provides a high-gloss printed matter.

  A lithographic printing ink composition containing a binder resin and a vegetable oil contains a certain amount of acid or acid derivative-modified vegetable oil having a certain range of modification rate, and is stable even under printing conditions in which dampening water is supplied in excess. The present inventors have invented a lithographic printing ink that provides printing workability and density stability, reduces the occurrence of roller peeling, and provides high-gloss printed matter.

 That is, the present invention relates to a lithographic printing ink comprising an acid or acid derivative-modified vegetable oil, a vegetable oil (excluding an acid or acid derivative-modified vegetable oil), and a binder resin.

The present invention also relates to the above lithographic printing ink, wherein the modification rate of the acid or acid derivative-modified vegetable oil is 30 mmol% to 300 mmol% / [vegetable oil 1 g].
However, the modification rate is the molar amount of the acid or acid derivative to be modified with 1 g of vegetable oil.

 In the lithographic printing ink according to the present invention, the acid or acid derivative in the acid or acid derivative-modified vegetable oil may be in an amount of 0.5 to 15 mmol% / [ink 1 g] in terms of monomer. The present invention relates to the above lithographic printing ink comprising an acid derivative-modified vegetable oil.

 Moreover, this invention relates to the printed matter provided with the base material and the printing layer formed from the said lithographic printing ink.

  Conventionally, by adding a surfactant, the emulsification rate of the ink is increased and the roller peeling and the water droplets are suppressed. However, when the fountain solution is supplied excessively, the emulsification rate of the ink is greatly increased. However, there was a tendency that poor drying and a decrease in gloss were induced. According to the present invention, even in a situation where fountain solution is excessively supplied, the water and the roller are not peeled off, and further, the emulsification rate of the ink is not significantly increased. It became possible to provide.

The binder resin used in the present invention is a rosin-modified phenol resin, a rosin-modified maleic resin, an alkyd resin, a polyester resin, a petroleum resin, or the like, which can be used alone or in combination of two or more, preferably It is desirable to use a rosin modified phenolic resin.
The rosin-modified phenolic resin preferably has a mass average molecular weight of 20,000 to 200,000, more preferably 25,000 to 160,000, and even more preferably 30,000 to 120,000. When the mass average molecular weight is 20,000 or more, it becomes easy to appropriately adjust the elasticity. Further, when the mass average molecular weight is 200,000 or less, the fluidity and the inking property are further improved. The term “thickness” refers to the adhesion of the ink to the substrate.

The rosin-modified phenolic resin preferably has a normal paraffin cloudiness temperature of 40 to 160 ° C, more preferably 50 to 130 ° C. When the normal paraffin white turbidity temperature is 40 ° C. or higher, it becomes easy to suppress the tackiness of the ink, and it becomes easy to prevent blocking. Further, when the normal paraffin white turbidity temperature is 160 ° C. or lower, it becomes difficult to separate the solvent from the ink, so that the viscosity stability of the ink with time is improved. The normal paraffin white turbidity temperature refers to a temperature at which the white turbidity of the solution disappears by heating a white turbid solution in which 10% by mass of resin and 90% by mass of normal paraffin having 14 to 16 carbon atoms are mixed at 25 ° C.
The binder resin can be used alone or in combination of two or more.

 The binder resin is preferably contained in the ink in an amount of 18 to 40% by mass, and more preferably 20 to 30% by mass. By being 18% by mass or more, the viscosity stability and fluidity of the ink with time are further improved. By making it 40% by mass or less, an increase in tack can be further suppressed.

  The above-mentioned binder resin can be prepared by adding vegetable oils, petroleum-based solvents, and gelling agents as needed, and dissolving them by heating to produce a gel varnish for lithographic printing ink.

  Examples of the gelling agent include various known materials such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, and aluminum triacetyl acetate. Can be used.

The vegetable oil used in the present invention is a vegetable oil itself and a compound (modified vegetable oil) using the vegetable oil as a raw material.
Vegetable oil is, for example, soybean oil, regenerated soybean oil, rapeseed oil, coconut oil, olive oil, flaxseed oil, linseed oil, eno oil, prickly oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyounin oil, tung oil, Kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, Japanese radish seed 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 seed oil, cottonseed oil, coconut oil, peanut oil, dehydrated castor oil, Jatropha oil and the like.
These include oils obtained by thermally polymerizing these vegetable oils and oils obtained by polymerizing oxygen by blowing into vegetable oils (these are referred to as polymerized vegetable oils), and these are modified vegetable oils.

 Vegetable oil generally refers to triesters of glycerin and fatty acids. A monoalcohol is added to this vegetable oil, and a fatty acid monoester obtained by transesterification is also included in the modified vegetable oil. Further, fatty acid monoesters obtained by ester reaction of fatty acids and monoalcohols, ethers derived from fatty acids, and acid or acid derivative-modified vegetable oils in the present invention described later are also included in the modified vegetable oils.

The monoalcohol is, for example, a saturated alcohol such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, heptynol, 2-ethylhexanol, hexanol, octanol, decanol, dodecanol;
Examples thereof include unsaturated alcohols such as oleyl alcohol, dodecenol, husetelli alcohol, somaryl alcohol, gadrelyl alcohol, 11-icosenol, 11-docosenol, and 15-tetracosenol.

  Examples of the ether include di-n-octyl ether, dinonyl ether, diheptyl ether, dihexyl ether, didecyl ether, nonyl hexyl ether, nonyl heptyl ether, nonyl octyl ether and the like.

 The vegetable oil is preferably contained in the ink in an amount of 7 to 30% by mass, and more preferably 10 to 20% by mass. When it is 7% by mass or more, the setting property and the inking property are further improved. Moreover, drying property improves more by becoming 30 mass% or less. Particularly in the heat set printing method, the content is preferably in the range of 10 to 20%.

 The acid or acid derivative-modified vegetable oil in the present invention is a copolymer of an acid or acid derivative and a vegetable oil.

The former acid or acid derivative refers to an α, β-unsaturated fatty acid derivative, which may be any of carboxylic acid, ester, amide, acid anhydride, lactone, etc., but considering the high reactivity Carboxylic acid and acid anhydride are preferred. Further, in consideration of offset printing suitability, it is most preferable to select an acid anhydride rather than a highly hydrophilic carboxylic acid. Moreover, when carboxylic acid is used, since a highly hydrophilic carboxyl group is present in the copolymer with the vegetable oil, there is a risk of causing soiling. Specific examples of the acid or acid derivative include acrylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid, cinnamic acid, 2,4-hexadienic acid and the like. However, maleic anhydride is most preferable in view of reactivity with vegetable oil and emulsification suitability of offset ink.

 The latter vegetable oil is preferably selected from species having conjugated double bonds such as eleostearic acid, parinaric acid, conjugated linoleic acid, and conjugated linolenic acid as fatty acids constituting the vegetable oil in consideration of high reactivity. These are often classified as dry oils. In particular, tung oil contains a lot of α-eleostearic acid having a conjugated double bond, so that the addition reaction of acid or acid derivative and Diels Alder type proceeds easily only with heat, and high modification rate by acid or acid derivative is high. Most preferable in that it can be achieved. In addition, spinach seed oil contains a large amount of parinaric acid, which is also preferable in that an acid or an acid derivative and a Diels-Alder type addition reaction proceed easily only by heat. Bittern oil, pomegranate oil, and cowpea oil contain conjugated linolenic acid and are likewise preferred. On the other hand, linseed oil, safflower oil, corn oil, sunflower oil, and cottonseed oil contain linoleic acid and linolenic acid that are not conjugated to a double bond. Since it becomes an acid, since the same reaction is easy to advance, it is preferable.

 As the acid or acid derivative of the acid or acid derivative-modified vegetable oil in the present invention, it is preferable to use an acid or acid derivative modified at a rate of 30 mmol% to 300 mmol% of 1 g of vegetable oil. In the present invention, the weight ratio of the acid or acid derivative to 1 g of this vegetable oil is called the modification rate and expressed as mmol% / [vegetable oil 1 g]. In the present invention, the modification rate is more preferably 100 to 300 mmol% / [vegetable oil 1 g], and further preferably 200 to 300 mmol% / [vegetable oil 1 g]. When the modification rate is 30 mmol% / [vegetable oil 1 g] or more, it is possible to reduce roller peeling while maintaining the drying property and viscoelasticity of the ink. On the other hand, at 300 mmol% / [vegetable oil 1 g] or less, an excessive amount of unreacted acid or acid derivative does not remain, and a small amount of acid or acid derivative-modified vegetable oil can efficiently suppress troubles such as roller peeling. From these points, the acid or acid derivative-modified vegetable oil in the present invention is made from maleic anhydride and tung oil, which are the most reactive as acid or acid derivative and vegetable oil, respectively, and maleic tung oil is most preferred, with a maximum of 300 mmol% / [vegetable oil It can be modified with a modification rate of 1 g].

 The acid or acid derivative-modified vegetable oil in the present invention is preferably included in the total ink composition in an amount of 0.5 to 10% by mass, and more preferably 1 to 5% by mass. More preferably, the acid or acid derivative-modified vegetable oil is preferably added so that the mol% of the acid or acid derivative alone in the acid or acid derivative-modified vegetable oil is 0.5 to 15 mmol% in the total ink composition. When the acid or acid derivative alone is in the range of 0.5 mmol% or more, the effect of improving emulsification suitability such as suppression of roller peeling is sufficiently obtained. On the other hand, troubles such as scumming do not occur in the range of 15 mmol% or less, and appropriate emulsification suitability can be imparted to the ink.

 The acid or acid derivative-modified vegetable oil in the present invention can be used as it is, but it may be used by dispersing it in an ink varnish and a solvent and compounding it in advance.

 In the present invention, a wax can optionally be used in combination. Wax is also referred to as an anti-friction agent, and imparts a property to suppress rubbing of the printing surface by adding to the lithographic printing ink.

  Waxes are mainly classified into dispersion waxes and melt waxes. Examples of the first dispersion wax include polyethylene (PE) and polytetrafluoroethylene (PTFE), which are fine particles of 1 to 10 μm. Dispersed wax is a printing surface in which some of the fine particles protrude from the printing surface and the contacted material comes into contact with the smooth surface to give the printing surface slipperiness, and the printing surface comes into direct contact with the contacted material. Prevent scratches.

  As the second molten wax, generally, a molten hydrocarbon wax having a melting point of less than 100 ° C. such as paraffin or microcrystalline is often used as a surface coating on a printing surface. When the sheet-fed printing method is used, the wax particles adhere to the printing surface without being melted or exist in a state of protruding from the printing surface. Protect.

  Hydrocarbon waxes having a melting point of less than 100 ° C, such as paraffin and microcrystalline, are also used in the heat-set offset type off-wheel printing method with hot air drying, and the melted wax passes through a dryer where the paper surface temperature reaches 100 ° C or more. Covers the printed surface, cools it with a cooling roller, and re-solidifies it, thereby showing the effect of reducing the cooling of the ink.

  The above-mentioned anti-friction agent can be used as a powder or dispersion as it is, but it is also possible to use a compound that has been previously dispersed in an ink varnish and a solvent.

 The wax is preferably contained in the lithographic printing ink in an amount of 0.1 to 6% by mass, and more preferably 0.5 to 5% by mass. When the content is 0.1% by mass or more, the friction resistance is further improved. Moreover, the printed matter which maintained high gloss by being 6 mass% or less is obtained.

  Moreover, you may add a leveling agent, surfactant, an antifoamer, etc. as other additives in lithographic printing ink.

A pigment can be used for the lithographic printing ink of the present invention. If no pigment is used, it can be used as a clear ink.
Examples of the pigment used in the present invention include general inorganic pigments and organic pigments. Examples of inorganic pigments include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, dial, alumina white, calcium carbonate, ultramarine, carbon black, graphite, and aluminum powder. Organic pigments include azo pigments, soluble azo pigments such as C-based (β-naphthol-based), 2B-based and 6B-based (β-oxynaphthoic), β-naphthol-based, β-oxynaphthoic acid anilide-based, monoazo yellow-based, disazo Insoluble azo pigments such as yellow and pyrazolone, condensed azo pigments such as acetoacetate allylide, phthalocyanine, copper phthalocyanine (α blue, β blue, ε blue), halogenated copper phthalocyanine such as chlorine and bromine, metal Examples of free phthalocyanine pigments and polycyclic pigments include perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, and quinophthalone pigments. The addition amount of the pigment is 0 to 30% by weight with respect to the total amount of the printing ink.

The ink of the present invention may further contain a petroleum solvent. The petroleum solvent preferably has an aromatic hydrocarbon content of 1% by mass or less. The petroleum solvent preferably has an aniline point of 60 to 130 ° C and a boiling point of 230 to 400 ° C, more preferably an aniline point of 80 to 100 ° C and a boiling point of 240 to 310 ° C. An aniline point of 60 to 130 ° C. is preferable because the solubility in the binder resin is further improved, so that the ink setting property and the inking property are further improved, and the gloss of the printed matter is further improved.
Petroleum solvents are commercially available products such as AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6 and AF Solvent No. 7, which are mainly composed of naphthene, manufactured by JX Nippon Oil & Energy Corporation, n- Examples include No. 0 solvent mainly composed of paraffin.

 The petroleum solvent is preferably contained in the ink in an amount of 0.1 to 45% by mass, and more preferably 30 to 45% by mass of the petroleum solvent is added particularly in the heat set printing ink. When it is contained at a content of 45% by mass or less, it becomes easy to be certified as an environmentally friendly ink.

  The ink of the present invention can be produced by a known production method. To explain an example of the production method, a binder resin, a petroleum solvent, and vegetable oil are added and a varnish is prepared by stirring at 190 ° C. for about 1 hour. Next, a pigment, petroleum-based solvent, vegetable oil, and a dispersant are added to the varnish for dispersion treatment to produce an ink base. The dispersion treatment is preferably a bead mill, three rolls or the like. An ink is obtained by adding an acid or acid derivative-modified vegetable oil, petroleum-based solvent, vegetable oil, or other additives to the obtained ink base to adjust the viscosity to a predetermined level. The use of the ink is applicable to gravure printing, lithographic printing, silk screen printing, etc., and lithographic printing is preferred. Examples of lithographic printing include ink for rotary offset printing presses, ink for newspaper printing presses, and ink for sheet-fed printing presses.

 As the method for adding the acid or acid derivative-modified vegetable oil in the present invention, it can be added at any step in the conventional printing ink production process. That is, the pigment, acid or acid derivative-modified vegetable oil both dispersed in the varnish and kneaded may be converted into ink, or the dispersion or kneaded step may be mixed with the acid or acid derivative-modified vegetable oil to be converted into ink. The latter is preferable in order to exert the maximum effect of the acid oil or acid derivative-modified vegetable oil. The same effect can be obtained by mixing acid or acid derivative-modified vegetable oil with the printing ink that has become a product.

The printed matter of the present invention includes a base material and an ink layer formed from the ink.
As the substrate, a known substrate for printed matter can be used. Examples of the substrate include a paper substrate and a film substrate. In the present invention, a paper base material is preferred. Examples of the paper base material include coated paper, finely coated paper, non-coated paper, and reprinted paper.
The paper substrate generally in coated papers ^{60~200g / m 2, 30~80g / m} 2 in Binurikoshi-uncoated paper, which is 30 to 50 g / m ² approximately in bleached.

A known lithographic printing machine is used to form the ink layer.
The thickness of the ink layer is usually about 0.3 to 5 μm.

  Applications of printed materials include posters, flyers, magazines, comics, books, newspapers, and the like.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples do not limit the scope of rights of the present invention in any way. In the examples, “part” represents “part by mass” and “%” represents “mass%”.

<Mass average molecular weight>
The mass average molecular weight was measured by gel permeation chromatography (HLC-8020 manufactured by Tosoh Corporation). A calibration curve was prepared with a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgelSuperHM-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, the mass average molecular weight may be simply referred to as “molecular weight”.

(Synthesis example 1 of resol type phenol resin)
To a four-necked flask equipped with a stirrer, a cooler, and a thermometer, add 1000 parts of octylphenol, 480 parts of paraformaldehyde with a purity of 92%, 10 parts of calcium hydroxide with a purity of 98%, and 530 parts of xylene. Let react for hours. Thereafter, 430 parts of xylene and 250 parts of water were added to the flask, and 10 parts of 98% sulfuric acid was added dropwise with stirring. After completion of stirring, the mixture was allowed to stand. Subsequently, the upper layer part (water) of the solution was removed, and the solution of the lower layer part was obtained as a resol type phenol resin solution (hereinafter, resin solution A) having a nonvolatile content of 60%.

(Synthesis 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 440 parts of gum rosin and dissolved at 200 ° C. while blowing nitrogen gas. Subsequently, 870 parts of obtained resin solution A was dripped at 200 degreeC over 2 hours to the flask. Thereafter, the internal temperature was raised to 250 ° C. while removing xylene, and 40 parts of glycerin and 0.22 part of p-toluenesulfonic acid were charged at 250 ° C. and reacted for 14 hours. After completion of the reaction, the mixture was cooled to obtain a rosin-modified phenol resin having a weight average molecular weight (Mw) of 60,000 and an acid value of 26.

(Production example of gel varnish)
44 parts of rosin-modified phenolic resin obtained in a 4-neck flask with a stirrer, Liebig condenser, thermometer, 35 parts of soybean oil, 20 parts of AF solvent 7 (manufactured by JX Nippon Oil & Energy Corporation) as a petroleum solvent, As a gelling agent, 1 part of ALCH (ethyl acetoacetate aluminum diisopropoxide manufactured by Kawaken Fine Chemical Co., Ltd.) was charged, and the internal temperature was raised to 190 ° C. After stirring at 190 ° C. for 60 minutes, the ink gel varnish 1 was obtained by cooling.

The acids or acid derivatives used in the present invention are as follows.
・ Maleic anhydride (Tokyo Chemical Industry Co., Ltd.)
・ Acrylic acid (Tokyo Chemical Industry Co., Ltd.)
・ Fumaric acid (Tokyo Chemical Industry Co., Ltd.)

(Synthesis example of vegetable oil A modified with acid or acid derivative)
A four-necked flask equipped with a stirrer, a Liebig condenser, and a thermometer was charged with 100 parts by weight of Tung oil (iodine number 190) and 28 parts by weight of maleic anhydride (Tokyo Chemical Industry Co., Ltd.) and stirred at 120 ° C. for 2 hours. As a result, an acid or acid derivative-modified vegetable oil A was obtained.

 By the same reaction, as shown in Table 1, the vegetable oil and the acid or acid derivative were changed to obtain acid or acid derivative-modified vegetable oils A to J.

Table 1

(Heat set type offset printing ink composition Example 1)
Lionol Red 6B No. 2 as a red pigment on a 2.5 L flasher. While adding 818 parts (solid content 28%) of press cake of 4214SP (made by Toyocolor Co., Ltd.) and stirring, 500 parts of the gel varnish 1 for ink was used for flushing to replace the pigment in the varnish. Then discard the water, add 431 parts of gel varnish for ink, dehydrate under reduced pressure at 120 ° C. until the moisture content in the base ink is 0.5% or less, knead with 3 rolls and paste the base α (pigment content 19.7% by weight) was obtained. 80.2 parts by weight of the obtained base α, 12.8 parts by weight of gel varnish 1 for ink, 5.0 parts by weight of AF solvent 7 (manufactured by JX Nippon Oil & Energy Corporation) as a petroleum solvent, 2.0 parts by weight of modified vegetable oil A Parts were mixed using a homodisper (manufactured by PRIMIX Co., Ltd.) to obtain a red ink of Example 1.

(Heat set type offset printing ink composition Example 14)
Rionol Blue No. 2 as an indigo pigment on a 2.5 L flasher. While charging 571 parts (solid content 49%) of 7334P (Toyocolor Co., Ltd.) press cake and stirring, 500 parts of the above gel varnish was used for flushing to replace the pigment in the varnish. Then discard the water, add 520 parts of gel varnish for ink, dehydrate under reduced pressure at 120 ° C. until the water content in the base ink is 0.5% or less, knead with 3 rolls and paste the base β (pigment content 21.5% by weight) was obtained. 93.0 parts by weight of the obtained base β, 5.0 parts by weight of AF solvent 7 (manufactured by JX Nippon Oil & Energy Corporation) as a petroleum solvent, and 2.0 parts by weight of modified vegetable oil B were made by homodisper (manufactured by Primics Co., Ltd.). ) To obtain an indigo ink of Example 14.

(Heat Set Offset Printing Ink Composition Example 15)
Carbon black (Mitsubishi Chemical Corporation, DBP oil absorption 72 ml / 100 g, BET specific surface area 99 m ² / g) 20 parts by weight, gel varnish 70 parts by weight, F Solvent No. 7 (manufactured by JX Nippon Mining & Energy Corporation) 2 parts by weight In accordance with a conventional method, the mixture was kneaded using a three roll to obtain a kneaded meat base γ (pigment content 21.8% by weight). 91.7 parts by weight of the base obtained, 1.3 parts by weight of gel varnish 1 for ink, 5.0 parts by weight of AF solvent 7 (manufactured by JX Nippon Oil & Energy Corporation) as a petroleum solvent, 2.0 parts by weight of modified vegetable oil B The parts were mixed using a homodisper (manufactured by PRIMIX Co., Ltd.) to obtain a black ink of Example 15.

  In the same manner as in Example 1, Examples 2 to 13 and Comparative Example 1 were blended in the proportions shown in Table 1, Comparative Example 2 was blended in Example 1 in the same manner as in Example 14, and Comparative Example 2 was blended in Example 15. Comparative Example 3 was obtained in the same manner at the blending ratio shown in Table 1.

The roller peeling and dirt recovery tests, which are performance evaluation tests, were performed on the center of the solid chart / printing direction with a 20cm wide non-image area using LITHOPIABT2-800NEO (Mitsubishi Heavy Industries, Ltd.) as a heatset offset printing press. Based on the following evaluation criteria, visually check the degree of ink fountain roller peeling when the water dial is raised +15 points from the lower limit. A 35-point relative evaluation was performed.

Paper: Pearl coat N (65.5 g / m ² ) (Mitsubishi Paper Corporation)
(Colorimetric values: L ^* : 97.43, a ^* : 0.07, b ^* : -2.14)
Printing speed: 600rpm
Paper surface temperature after passing through the dryer: 105 ° C
Version: CTP version (Fuji Film Co., Ltd.)
Number of printed copies: 20,000 fountain solutions: AQUAUNITY WKK 20KG GN 2% (Toyo Ink Co., Ltd.)
IPA 1%

<Performance evaluation test Roller peeling>
1: Roller peeling has occurred.
2: Slight roller peeling has occurred.
3: No roller peeling has occurred.
In this test, IPA was added, and the water level was higher than that during normal printing, so 2 and 3 are practical levels.

<Performance evaluation test (2) Dirt recovery>
The water dial that can completely remove the dirt on the paper surface is within +10 points with respect to Comparative Example 1 within the practical range. In the case of +10 points or more, the amount of water rising is large, and it becomes a level that hinders dryness.
The performance evaluation test results are shown in Table 2.

Table 2

 In Examples 1 to 15 to which an acid or acid derivative-modified vegetable oil was added, the evaluation items for roller peeling are all within the practical range. In particular, in Examples 1 to 12, 14, and 15, in which maleic anhydride derived from an acid or an acid derivative-modified vegetable oil or the like is in a range of 0.5 mmol / [ink 1 g] or more, roller peeling was a good result. On the other hand, the lower limit dial value of water at which the stain recovers in Examples 1 to 10 and 12 to 15 in which the acid or acid derivative-modified vegetable oil-derived maleic anhydride is 15 mmol / [ink 1 g] or less is a comparative example. On the other hand, good results were obtained within +10 points.

 From the above, even in the situation where fountain solution was supplied excessively, water and roller peeling did not occur, and further, without significantly increasing the emulsification rate of the ink, drying defects were suppressed, and high-gloss prints were produced. Could be provided.

Claims (4)

   A lithographic printing ink comprising an acid or acid derivative-modified vegetable oil, a vegetable oil (excluding an acid or acid derivative-modified vegetable oil) and a binder resin. The lithographic printing ink according to claim 1, wherein the acid or acid derivative-modified vegetable oil has a modification rate of 30 mmol% to 300 mmol% / [vegetable oil 1 g].
However, the modification rate is the molar amount of the acid or acid derivative to be modified with 1 g of vegetable oil.   The lithographic printing ink contains an acid or acid derivative-modified vegetable oil such that the acid or acid derivative in the acid or acid derivative-modified vegetable oil is in the range of 0.5 to 15 mmol% / [ink 1 g] in terms of monomer. The lithographic printing ink according to claim 1 or 2.   The printed matter provided with the base material and the printing layer formed from the lithographic printing ink of any one of Claims 1-3.