JP6243502B2 - Printing ink composition - Google Patents

Description

  The present invention relates to a printing ink composition which is used for lithographic offset printing using a fountain solution and hardly causes printing stains.

The basic principle of lithographic offset printing uses the repulsion phenomenon of water and oil, and it consists of an oleophilic part (image area) where printing ink adheres and a part (non-image area) where printing ink does not adhere (non-image area). Use to print. In printing, dampening water is supplied to the plate surface in advance to prevent printing ink from adhering to the non-image area of the plate surface.
The fountain solution is made by adding a concentrated fountain solution composition (also called an etchant) at a concentration of 1 to 5% with respect to raw water such as tap water and groundwater. Etch solution components include ethylene glycol and propylene glycol solvents, surfactants as emulsifiers for printing inks, water-soluble resins as plate surface protectors, phosphoric acids and their salts, citric acid and their salts, etc. include.

  However, printing ink may adhere to the non-image area as printing progresses. If the printing ink adheres to the non-image area, the printed matter is smudged and loses its value as a product or product, resulting in a waste paper. When printing ink adheres to the non-image area, the generation of stains can be suppressed by increasing the amount of water supplied to the plate surface, but on the other hand it induces over-emulsification of the ink. Over-emulsified ink loses its fluidity on the rollers of the printing press and scatters and causes the surroundings of the printing press to become dirty.

  Therefore, in order to prevent the printing ink from adhering to the non-image area, phosphoric acids or salts thereof have been added to the lithographic offset printing ink as a leveling aid. The leveling means that the non-image area is cleaned to prevent the printing ink from adhering. However, even if such a leveling aid is added, the effect may not be exhibited. As a result of intensive studies on the cause, the present inventors have found the configuration of the present invention.

Patent Documents 1 and 2 describe that an aqueous solution containing an inorganic acid such as metaphosphoric acid or a salt thereof is added to the printing ink in order to impart a leveling effect. Ink transfer failure due to a decrease in fluidity due to emulsification may occur on the printing press, so printing inks contain calcium carbonate, carbonic acid for the purpose of adjusting emulsification, viscosity, fluidity, and reducing misting. Magnesium and barium sulfate are often added. When the contents described in Patent Documents 1 and 2 are carried out, sodium phosphate contained in the added aqueous solution reacts with calcium carbonate in the printing ink to generate calcium phosphate, and before using the ink in the printing press The sodium phosphate having a surface-adjusting effect disappears. Therefore, there is a possibility that the surface-smoothing effect cannot be fully exhibited.

  In Patent Document 3, as a conventional technique, a material such as phosphoric acid or metaphosphoric acid is sometimes added to the printing ink in order to clean the printing plate and prevent printing stains. It is described that this has not been prevented.

Patent Document 4 describes that, in an offset printing ink containing a metal soap dryer, the printing stain can be improved by adding phosphoric acid, citric acid and / or a salt thereof.
Since metaphosphate and sodium citrate described as an example are crystalline substances, it is considered that coarse crystals remain in the printing ink as they are simply added to the base ink composition and stirred. Since coarse crystals are larger than the printing ink film thickness on the paper surface at the time of printing, many portions where the printing ink is not transferred appear on the paper surface, resulting in broken paper. Moreover, since the surface-adjusting effect is weak with coarse particles, it is necessary to add a large amount.

Japanese Patent Application No. 53-18223 Japanese Patent Application No. 58-179310 JP-A-9-12952 Japanese Patent Application No. 2008-556087

  SUMMARY OF THE INVENTION An object of the present invention is to provide a printing ink composition having a leveling effect for preventing non-image area stains, a method for producing the same, and a printed matter printed using the printing ink composition.

  As a result of earnest research to solve the above problems, phosphoric acid, ammonium salt of phosphoric acid, for lithographic offset printing ink composition containing one or more selected from calcium carbonate, magnesium carbonate and barium sulfate, One or more selected from the group consisting of alkali metal phosphate, alkaline earth metal dihydrogen phosphate, citric acid, ammonium salt of citric acid, alkali metal citric acid, magnesium salt of citric acid The present invention has been completed by finding that this problem can be solved by adding under the condition that coarse particles are not contained and reducing the water content in the printing ink.

(1) That is, the present invention is a printing ink composition that satisfies all of the following (a) to (d).
(A) One or more selected from the following group A is contained.
(B) An extender pigment containing at least one selected from the group consisting of calcium carbonate, magnesium carbonate and barium sulfate.
(C) The water content is 0.5% by mass or less.
(D) The depth of the groove at the position A measured by the method described in the kneading degree test of JIS K5701-1 is 7.5 μm or less.
(Group A)
Phosphoric acid, ammonium salt of phosphoric acid, alkali metal salt of phosphoric acid, alkaline earth metal dihydrogen salt of phosphoric acid, citric acid, ammonium salt of citric acid, alkali metal salt of citric acid, magnesium salt of citric acid.
(2) Further, the present invention relates to the above-mentioned group A,
Phosphoric acid, phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexapolyphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid And one or more selected from the group consisting of hexametaphosphoric acid,
The ammonium salt of phosphoric acid is at least one selected from the group consisting of triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and sodium ammonium hydrogen phosphate;
The alkali metal salt of phosphoric acid is lithium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium pyrophosphate , Disodium dihydrogen pyrophosphate, potassium pyrophosphate, potassium hydrogen pyrophosphate, potassium polyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, potassium metaphosphate, sodium metaphosphate, sodium trimetaphosphate, sodium hexametaphosphate, One or more selected from the group consisting of sodium phosphite and sodium hypophosphite,
The alkaline earth metal dihydrogen salt of phosphoric acid is one or more selected from the group consisting of calcium dihydrogen phosphate, barium dihydrogen phosphate and magnesium dihydrogen phosphate;
The ammonium salt of citric acid is one or more selected from the group consisting of diammonium hydrogen citrate and triammonium citrate;
The alkali metal salt of citric acid is trisodium citrate, disodium citrate, monosodium citrate, tripotassium citrate, dipotassium citrate, monopotassium citrate, sodium dihydrogen citrate, potassium dihydrogen citrate and The printing ink composition according to (1), wherein the printing ink composition is one or more selected from the group consisting of disodium hydrogen citrate.
(3) Furthermore, this invention is a manufacturing method of the printing ink composition as described in said (1) using the compound which satisfies all the following (e)-(g) as one of the raw materials.
(E) containing one or more selected from the group A.
(F) The water content is 0.5% by mass or less.
(G) The depth of the groove at the position A measured by the method described in the kneading degree test described in JIS K5701-1 is 7.5 μm or less.
(4) Furthermore, the present invention is a printed matter prepared using the printing ink composition according to either (1) or (2).

  According to the present invention, the leveling effect for preventing the non-image area from being stained is improved. As a result, it is effective in reducing printing stains, reducing waste paper, and reducing the cleaning work time of the printing press.

Hereinafter, embodiments for carrying out the present invention will be described in detail. % And parts are based on mass unless otherwise specified.
(Main ingredients and water content of printing ink)
Printing ink compositions generally comprise pigments, vehicles and auxiliaries, as are the printing ink compositions of the present invention. Hereinafter, main components of the printing ink composition of the present invention will be described.

The printing ink composition of the present invention contains an organic pigment or an inorganic colored pigment as a pigment, and an extender pigment, and contains one or more selected from calcium carbonate, magnesium carbonate, and barium sulfate as the extender pigment.
As the auxiliary agent, wax, dryer, drying inhibitor, surfactant and the like are used. In particular, the printing ink composition of the present invention contains one or more selected from the following group A as an auxiliary agent.
Those belonging to Group A are referred to as leveling aids.
(Group A)
Phosphoric acid, ammonium salt of phosphoric acid, alkali metal salt of phosphoric acid, alkaline earth metal dihydrogen salt of phosphoric acid, citric acid, ammonium salt of citric acid, alkali metal salt of citric acid, magnesium salt of citric acid.
Furthermore, the water content in the printing ink composition is 0.5% by mass or less.

  As the vehicle, resin varnish, petroleum solvent, vegetable oil, mineral oil, vegetable oil ether, vegetable oil fatty acid ester and the like are appropriately used.

(Explanation of moisture content)
The water content is the percentage of water contained in the ink composition expressed in mass%, and is usually measured by the Karl Fischer method. However, in the moisture measurement by the Karl Fischer method, when the ink composition material contains water containing crystal water, the water content including the crystal water is measured. Crystallized water is not included in the water content of the ink composition in the present invention.
Therefore, when a raw material containing crystal water is contained in the ink composition, the raw material is heated to a constant weight at 105 ° C. using a heat-drying moisture meter, and the reduced weight is added to the ink in the present invention. Include in moisture.

As a calculation example, the moisture content of an ink composition 1000 g containing only 100 g of pigment A and containing 100 g of pigment A will be described.
Moisture content of pigment (100 g) by Karl Fischer method: 0.5 g
Moisture amount of pigment (100 g) by the above-mentioned heat drying type moisture meter. 0.3 g
Moisture amount of the ink composition by Karl Fischer method 3g
Since 3 g of this contains 0.2 g (= 0.5-0.3) of water of crystallization of Pigment A, the water content in the ink composition is 2.8 g by subtracting it. Is 0.28% by mass.
In order to determine how much crystal water is contained in the raw material containing crystal water, in addition to the method of using the moisture measurement by the heat-drying moisture meter and the Karl Fischer method as described above, a method of calculating based on the chemical formula Alternatively, it is possible to use a method of obtaining and calculating information on the content of crystallization water and the desorption temperature from technical literature.

The reason why the moisture content should be below a certain ratio is as follows.
As described above, phosphoric acids and salts thereof, citric acid and salts thereof are generally added to the printing ink as a leveling aid.
In addition, calcium carbonate, magnesium carbonate, and barium sulfate are often added to the printing ink for the purpose of adjusting the fluidity, viscosity, emulsification amount, etc. of the printing ink. In the presence of water, barium gradually reacts with phosphoric acid, citric acid, and the like added as a leveling aid to produce calcium phosphate, calcium citrate, magnesium phosphate, and barium phosphate.
When these salts are used, the surface-adjusting effect of phosphoric acid or citric acid is lost, and therefore stains are likely to occur during printing.

  In order to maintain the leveling effect of the printing ink, it is preferable to reduce the water content in the printing ink to 0.5% or less, and to prevent the leveling aid from changing to a salt during ink storage. . If the generation of salt can be suppressed, a state with a high leveling effect is maintained, so that it is possible to prevent the occurrence of smudges during printing. In addition, if the leveling effect of the ink is high, the dampening water supplied at the time of printing will also be reduced, and the printing trouble due to the excessive emulsification of the ink will also be reduced.

(Method of reducing the water content of the printing ink composition)
The water in the printing ink composition is almost entirely derived from the water in the pigment.
Examples of the pigment include a powder pigment that has been powdered through a drying process and a slurry pigment that is dispersed in water.
The moisture content of the powder pigment is adjusted by adjusting the drying temperature and drying time and drying at a high temperature for a long time within the limits that do not affect the pigment quality.
A solid material obtained by filtering and dewatering the slurry pigment to reduce the water content is called a wet cake pigment. When wet cake pigments are used, varnish and wet cake pigments are put into a dispersing kneader such as a kneader in a process called flushing during printing ink production, and kneading, dispersing, and heat dehydration are performed. In order to lower the water content of the printing ink composition produced through flushing, the temperature during dehydration is increased in the flushing process, or the time of the dehydration process is increased.

(Smoothing aid)
The printing ink composition of the present invention contains one or more selected from the group A as an essential component as an auxiliary agent for obtaining a leveling effect.
0.01-0.5 mass% is preferable, and, as for the total content of the leveling adjuvant in the printing ink composition of this invention, More preferably, it is 0.01-0.2 mass%.
If it is less than 0.01% by mass, the antifouling effect may not be sufficient. On the other hand, if the amount exceeds 0.5% by mass, roller flaking and printing ink imperfection will occur, and good printing will be difficult.

(Examples of those preferably used for the leveling aid belonging to Group A)
Examples of those preferably used for the group A surface-adjusting aid are as follows:
Phosphoric acid, phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexapolyphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid And one or more selected from the group consisting of hexametaphosphoric acid,
The ammonium salt of phosphoric acid is at least one selected from the group consisting of triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and sodium ammonium hydrogen phosphate;
The alkali metal salt of phosphoric acid is lithium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium pyrophosphate , Disodium dihydrogen pyrophosphate, potassium pyrophosphate, potassium hydrogen pyrophosphate, potassium polyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, potassium metaphosphate, sodium metaphosphate, sodium trimetaphosphate, sodium hexametaphosphate, One or more selected from the group consisting of sodium phosphite and sodium hypophosphite,
The alkaline earth metal dihydrogen salt of phosphoric acid is one or more selected from the group consisting of calcium dihydrogen phosphate, barium dihydrogen phosphate and magnesium dihydrogen phosphate;
The ammonium salt of citric acid is one or more selected from the group consisting of diammonium hydrogen citrate and triammonium citrate;
The alkali metal salt of citric acid is trisodium citrate, disodium citrate, monosodium citrate, tripotassium citrate, dipotassium citrate, monopotassium citrate, sodium dihydrogen citrate, potassium dihydrogen citrate and One or more selected from the group consisting of disodium hydrogen citrate.

(Composition of printing ink composition)
The preferable content of the main components in the printing ink composition of the present invention is as follows.
1) Organic pigment and / or inorganic colored pigment: 5 to 40% by mass.
2) An extender pigment containing at least one selected from calcium carbonate, magnesium carbonate, and barium sulfate: 0.1 to 20% by mass.
3) Resin varnish: 25 to 35% by mass.
4) Petroleum solvent having a boiling point of 160 to 330 ° C.—zero to 45% by mass.
5) Total of vegetable oil, vegetable oil ester, vegetable oil ether: 7 to 40% by mass.
6) Total of drying inhibitors such as BHT, HQ, TBHQ, etc., desiccants such as wax, metal dryer, and other additives, etc .: Zero to 8% by mass.
7) Leveling aid: 0.01 to 0.5% by mass in total.
Examples of the other additives include surfactants and dispersants such as DEMO, Poise, Emulgen, Rhedol, Homogenol manufactured by Kao Corporation, Epan, Charol, Haitenol, Neugen manufactured by Daiichi Kogyo Seiyaku Co., Ltd. The
BHT represents dibutylhydroxytoluene, HQ represents hydroquinone, and TBHQ represents t-butylhydroquinone.

(Organic pigment)
Examples of the organic pigment used in the present invention include textile printing pigments, azo pigments, phthalocyanine pigments, condensed polycyclic pigments, nitro pigments, nitroso pigments, and fluorescent pigments. Examples of the azo group include soluble azo and insoluble azo, and examples of the soluble azo pigment include carmine 6B and lake red C. Insoluble azo pigments include monoazo yellow, monoazo red, disazo yellow, and disazo orange. Other examples of the azo group include nickel azo yellow, permanent orange, nickel azo yellow, chromophthal yellow, and chromophthal scarlet. Examples of printing pigments include rhodamine lake, methyl violet lake, quinoline yellow lake, alizarin lake and the like. Examples of the phthalocyanine pigment include copper phthalocyanine blue (α type, β type, ε type), copper phthalocyanine green (chlorinated, brominated), cobalt phthalocyanine blue, and the like. Others, unsubstituted quinacridone, dimethylquinacridone, anthraquinonyl red, polyazo yellow, benzimidazolone yellow, naphthol yellow, pigment green, dioxane violet, naphthol yellow, pigment green, alkali blue, aniline black, luminogen yellow, signal red, etc. Is given.

(Inorganic colored pigment)
Examples of the inorganic colored pigment used in the present invention include titanium dioxide, zinc oxide, zinc sulfide, chromium oxide, chromium hydroxide, black oxide (iron black), cobalt blue, ferrocyanide (bitumen), manganese violet, and carbon black. , Lead white, ultramarine, yellow lead, lead molybdate chromate (molybdate orange), zinc chromate, strontium chromate, yellow iron oxide (yellow iron), red iron oxide (bengal), viridian, potassium titanate, barium titanate Molybdenum disulfide, antimony trioxide, silicon nitride, silicon carbide, and the like.

(External pigment containing at least one selected from calcium carbonate, magnesium carbonate, and barium sulfate)
Calcium carbonate, magnesium carbonate, and barium sulfate used in the present invention are called extender pigments. In the dry state, the appearance is almost white and the refractive index is small. When dispersed in varnish, the hiding power is low. The extender pigment is used for adjusting the fluidity, viscosity, emulsification amount and the like of the ink.
Examples of calcium carbonate used in the present invention include calcium carbonate chemically synthesized from limestone and heavy calcium carbonate obtained by pulverizing natural limestone. Chemically synthesized calcium carbonate that is easy to disperse the kneaded meat and has less ink transparency and gloss reduction is preferred. Among them, colloidal calcium carbonate that can produce finer particles having a cubic shape and can be surface-treated is particularly preferable.

Examples of magnesium carbonate used in the present invention include basic magnesium carbonate.
Examples of the barium sulfate used in the present invention include a pulverized product called barite powder obtained by pulverizing barite and precipitated barium sulfate produced by a chemical reaction. Precipitating barium sulfate, which can obtain fine particles, is more preferable because the decrease in gloss is small.
As extender pigments used in the present invention, white carbon, talc, aluminum hydroxide, magnesium hydroxide, alumina white, silica stone powder, diatomaceous earth, synthetic silica used as extender pigments as well as calcium carbonate, magnesium carbonate and barium sulfate. Calcium silicate, attapulgite, sericite, mica, hydrotalcite, bentonite, zeolite, kaolin clay, pyrophyllite and the like can be used in combination.

  These extender pigments are added in a proportion of 0.1 to 20% by mass with respect to the total weight of the printing ink composition. Furthermore, the present invention is particularly applicable to a printing ink composition containing at least 0.1 (temporary) mass% of one or more selected from calcium carbonate, magnesium carbonate, and barium sulfate with respect to the total weight of the printing ink composition. Demonstrate the effect.

(Resin varnish)
The resin varnish includes a resin, a vegetable oil, a vegetable oil ester, a vegetable oil ether, a solvent, a thickener, an antioxidant, and the like. Resins used in the resin varnish used in the present invention are rosin-modified phenol resin, petroleum resin, petroleum resin-modified rosin-modified phenol resin, alkyd resin, rosin ester, vegetable oil-modified rosin-modified phenol resin, vegetable oil-modified rosin ester, polyester, There are acrylic resins.
The resin varnish is a viscous liquid, and includes vegetable oil, vegetable oil ester, vegetable oil ether, antioxidant, solvent, thickener and the like in order to adjust the viscosity and printability of the printing ink. Antioxidants are added to prevent oxidation of resins and vegetable oils in the varnish.

  Examples of the thickener used in the resin varnish used in the present invention include an organoaluminum compound, an organotitanate compound, an organozinc compound, and an organometallic lucium compound. Among these, an organoaluminum compound is preferable. For example, aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum dipropoxide monoacetylacetonate, aluminum tributoxide, aluminum dibutoxide monoethylacetoacetate, aluminum triacetylacetate, aluminum oxide octate, aluminum oxide Examples include stearate, aluminum ethyl acetoacetate diisopropylate, and ethyl acetoacetate aluminum dinormal butyrate. The amount used is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin varnish, and more preferably in the range of 0.2 to 3 parts by mass.

  As the antioxidant used in the resin varnish used in the present invention, BHT (dibutylhydroxytoluene), HQ (hydroquinone), MHQ (methylhydroquinone), TBHQ (t-butylhydroquinone) and the like can be used.

(Petroleum solvent)
The boiling point of the petroleum solvent used in the present invention is preferably 160 to 330 ° C, more preferably 230 to 330 ° C. Examples of the solvent include AF Solvent No. 4, No. 5, No. 6, No. 7, No. 0 Solvent L, M, H, ISU Chemical Co., manufactured by JX Nippon Oil & Energy Corporation. Examples include DSOL 240, 260C, and 280 manufactured by LTD.

(Vegetable oil)
As vegetable oils used in the present invention, soybean oil, linseed oil, rice bran oil, kiri oil, castor oil, dehydrated castor oil, corn oil, safflower oil, south sea oil tung oil, regenerated vegetable oil, canol oil, rapeseed oil, tung oil, peanut oil, cottonseed oil Oils such as sesame oil, sunflower oil, olive oil, palm oil, palm kernel oil, coconut oil, and the like, and thermal polymerization oils and oxidation polymerization oils thereof.

(Vegetable oil ester)
Vegetable oil esters used in the present invention include 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 Esters, soybean 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 Esters, rice bran oil fatty acid methyl ester, rice bran oil fatty acid ethyl ester, rice bran oil fatty acid propyl ester, rice bran oil fatty acid butyl ester, esters of regenerated vegetable oil Esters of South Sea oil tung oil and the like.

(Vegetable oil ether)
Examples of ethers made from vegetable oil used in the present invention include di-n-octyl ether, di-nonyl ether, dihexyl ether, nonyl hexyl ether, nonyl butyl ether, diheptyl ether, didecyl ether, nonyl of the above vegetable oil. And acryl ether.

(Various additives)
If necessary, the printing ink composition of the present invention may contain various additives for printing ink such as wax, dryer, antioxidant, and antifouling agent. Examples of the wax include polyethylene wax, PTFE wax, and sazol wax.
The dryer is a salt of a metal such as cobalt, manganese, lead, zinc, iron, calcium, cerium, or rare earth with a carboxylic acid such as octyl acid, naphthenic acid, neodecanoic acid, tung oil, linseed oil, or resin acid. Examples include certain metal soaps and borates with the above metals.
Examples of the antioxidant include BHT (dibutylhydroxytoluene), HQ (hydroquinone), MHQ (methylhydroquinone), TBHQ (t-butylhydroquinone) and the like.

(Other forms)
The present invention can be applied to an active energy ray-curable lithographic printing ink composition widely used in the printing field such as paper containers because of the convenience of instantaneous curing characteristics.

  The active energy ray described in the present invention refers to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition of the present invention to improve curability. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α ray, β ray, and γ ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no need to add a photosensitizer. In the printing field, ultraviolet rays and electron beams are often used, and in particular, ultraviolet rays are widely used. An ultraviolet lamp light source that emits ultraviolet rays is installed inside the printing press, and ink printed on the printing paper passes immediately below the lamp and is instantaneously cured by being irradiated with ultraviolet energy. The present invention can be used with or without a photopolymerization initiator or a photosensitizer.

(Formulation of active energy ray-curable printing ink composition)
Preferable content of the main components in the active energy ray-curable printing ink composition of the present invention is as follows.
1) Organic pigment and / or inorganic colored pigment: 5 to 50% by mass.
2) An extender pigment containing at least one selected from calcium carbonate, magnesium carbonate, and barium sulfate: 0.1 to 30% by mass.
3) Polymerizable acrylate monomer: 10 to 50% by mass
4) Binder resin: 5 to 40% by mass.
5) Photopolymerization initiator: 0 to 20% by mass.
6) Auxiliaries such as waxes, dispersants, polymerization inhibitors, ... 0 to 10% by mass.
7) Leveling aid: 0.01 to 0.5% by mass in total.

  Organic pigments and / or inorganic colored pigments, extender pigments containing at least one selected from calcium carbonate, magnesium carbonate, barium sulfate, auxiliary agents such as waxes, dispersants, polymerization inhibitors, and leveling auxiliary agents are those described above. Can be used. Moreover, a conventionally well-known thing can be used for a polymerizable acrylate monomer and a photoinitiator, and there is no restriction | limiting in particular. As the binder resin, epoxy acrylate, urethane acrylate, polyester acrylate, etc., which are oligomers having a polymerizable group such as acrylate group, or diallyl phthalate resin, polyester resin, etc., which are non-polymerizable resins, are used. Such a binder resin is highly hydrophilic and easily emulsified, and it is preferable to perform printing while reducing the amount of water supplied to the plate surface. Since the active energy ray-curable printing ink composition of the present invention has a high leveling effect, printing stains can be suppressed even if the amount of water supplied to the plate surface is reduced.

(Manufacture of printing ink composition)
In order to produce the printing ink composition of the present invention, it is possible to produce the printing ink composition by adding the above leveling aid in the step of mixing the pigment, vehicle, auxiliary agent and the like and dispersing the kneaded meat according to a conventional method. .
In the step of kneading and dispersing, a three-roll mill, a bead mill, or the like is used, and a step of finely pulverizing and dispersing particles contained in the pigment, auxiliary agent, and the like is always performed. Thereby, the surface-adjusting aid used in the present invention can be finely dispersed in the printing ink so that coarse particles are not included.

(Kneading degree of printing ink composition)
In order to add a leveling aid to the printing ink composition of the present invention, the meat is dispersed by a three roll mill or the like. In that case, in the kneading degree test described in JIS K5701-1, it is preferable to knead the meat so that the depth of the groove at the kneading position A is 7.5 μm or less (3 or less on the scale).

The degree of kneading refers to the degree to which particulate materials such as pigments and auxiliaries are finely dispersed in ink, and the evaluation is based on JIS K5701-1 (established on January 20, 2000). 4.3 Use the method specified in the degree of kneading.
According to JIS regulations, the sample is placed in the groove on the grindometer gauge plate where the groove depth varies linearly from 25 μm to 0 μm, and the sample is placed in the groove using a scraper. Make a membrane. A scale corresponding to the depth of the groove is generally marked on the gauge board from 0 to 10. For example, 10 is written as a scale at a position of 25 μm depth, 4 is written as a scale at a position of 10 μm depth, and 3 is written as a scale at a position of 7.5 μm depth.
When particles are present in the sample, the particles are scraped off and moved by a scraper, and a line is formed in a groove shallower than the size (diameter, etc.) of the particles. The line is observed, and a scale position where three or more continuous lines appear for 10 mm or more appear in one groove is A, and a scale position where 10 or more lines appear is B.

In the present invention, the depth of the groove at the position A is preferably 7.5 μm or less. This corresponds to position 3 on the scale.
If the particles are finely dispersed so that the degree of kneading is equal to or finer than that, that is, the depth of the groove at position A is 7.5 μm or less, the printing ink can be used without any problem in normal printing. Transcribed above. If the depth of the groove at position A is larger than 7.5 μm, a large number of coarse particles having a diameter etc. larger than 7.5 μm are included, and white spots where printing ink is not transferred to the paper are likely to occur. Become.

(Manufacturing method using compound)
In order to add a leveling aid to the printing ink composition of the present invention, in addition to the method of kneading and dispersing with a three-roll mill or the like, a leveling aid, vehicle and other additives and auxiliary agents are contained. The compound to be produced can be separately produced and used as one of raw materials for producing the printing ink composition of the present invention. The compound said here satisfies all of the following (e), (f) and (g).
(E) containing one or more selected from the group A.
(F) The water content is 0.5% by mass or less.
(G) The depth of the groove at the position A measured by the method described in the kneading degree test described in JIS K5701-1 is 7.5 μm or less.
In addition, as for the leveling aid belonging to the group A, those preferably used are as exemplified above.

The water content of the printing ink composition of the present invention is measured by Karl Fischer. An example of the measurement method is given below.
As the solvent of the Karl Fischer main body, a mixed solvent of toluene: Aquamicron GEX (manufactured by API Corporation) = 2: 1 (volume ratio) is used.
Use a mixed solvent in the moisture meter to measure the moisture content after making it into an anhydrous normal state.
THF (tetrahydrofuran) is used as a solvent for dissolving the sample. A solution of 2 g of sample dissolved in 8 g of THF is used for Karl Fischer titration.
The moisture content of the sample dissolved solution and the THF for sample dissolution are measured with a Karl Fischer moisture meter, respectively, and the moisture content in the sample is calculated.

As an example of obtaining the water content, a case where the red pigment Carmine 6B (CI Pigment Red 57: 1) is used will be described. For printing ink, β-type Carmine 6B is usually used.
In the case of β-type carmine 6B, referring to documents such as the crystal transition of carmine 6B (1st report) (Color Material Association Journal, Color Material Association, 1984, 249-254), It can be seen that one molecule of crystal water is contained. Since this crystal water is desorbed at around 200 ° C., it is not included in the water content.
Since the molecular weight of β-type carmine 6B is 442, 0.04 parts by mass of water is contained in 1 part by mass of β-type carmine 6B.
When the water content of a printing ink composition containing only 20% of β-type carmine 6B as a raw material having crystal water was measured with a Karl Fischer moisture meter, and a value of 1.25% by mass was obtained, The derived moisture is 0.8% by mass (= 20 × 0.04). The water content in the present invention is 0.45% by mass (= 1.25-0.8), which satisfies the water content of 0.5% by mass or less for obtaining the effect as the printing ink composition of the present invention.

Hereinafter, the present invention will be described in detail by way of examples.
(Preparation of resin varnish for printing ink (A))
As rosin-modified phenolic resin, 44 parts by mass of Beccasite F-8305 (weight average molecular weight 45,000, manufactured by DIC Corporation) and 15 parts by mass of soybean white oil (Nisshin Oilio Group Co., Ltd.) were charged, and a nitrogen stream After heating to 220 ° C. and stirring for 1.5 hours, 39.7 parts by mass of AF Solvent No. 7 (petroleum solvent: JX Nippon Mining & Energy Co., Ltd.) was added and stirred for 30 minutes. And cooled to 140 ° C.
After cooling, 1.0 part by mass of aluminum ethyl acetoacetate diisopropylate solution diluted 50% with AF Solvent 7 was added, the temperature was raised to 160 ° C., heated and stirred for 1.0 hour, cooled to 140 ° C., and cooled to BHT ( After charging 0.3 parts by mass of Honshu Chemical Co., Ltd. and stirring, varnish (A) was obtained.

(Preparation of sodium hexametaphosphate compound base (B))
Sodium hexametaphosphate manufactured by Taiyo Chemical Co., Ltd. was used. The following compounding proportions (total 100 parts by mass of 1 to 3) are kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished compound base The scale of A was adjusted to 3 or less (the groove depth of the scale 3 was 7.5 μm).
1) Resin varnish for printing ink (A) 73 parts 2) Sodium hexametaphosphate 20 parts 3) AF solvent 7 7 Part

(Preparation of diammonium hydrogen citrate compound base (C))
The diammonium hydrogen citrate used was made by Komatsuya Co., Ltd. The following compounding proportions (total 100 parts by mass of 1 to 3) are kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished compound base The scale of A was adjusted to 3 or less.
1) Resin varnish for printing ink (A) 73 parts 2) Diammonium hydrogen citrate 20 parts 3) AF solvent No. 7・ 7 copies

(Preparation of printing ink of Example 1)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. Moreover, NEOLIGHT SA-300 made by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... -5 parts 4) Sodium hexametaphosphate-0.2 part 5) AF solvent No. 7-13.8 parts The water content of the printing ink is 0.14% Was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Example 2)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. As magnesium carbonate, basic magnesium carbonate TT manufactured by Naikai Shigyo Co., Ltd. was used. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Magnesium carbonate ... 5 parts 4) Sodium hexametaphosphate ... 0.2 parts 5) AF solvent No. 7 ... 13.8 parts The water content of the printing ink is 0.14%. This was confirmed with a Karl Fischer moisture meter.

(Printing ink adjustment of Example 3)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. As barium sulfate, sedimentary barium sulfate SS-50 manufactured by Sakai Chemical Industry Co., Ltd. was used. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) 65 parts 2) Phthalocyanine blue 16 parts 3) Barium sulfate ... 5 parts 4) Sodium hexametaphosphate 5 0.2 parts AF solvent 7 13.8 parts The water content of the printing ink is 0.14% This was confirmed with a Karl Fischer moisture meter.

(Printing ink adjustment of Example 4)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. As sodium pyrophosphate, tetrasodium pyrophosphate (anhydrous) manufactured by Taiyo Chemical Co., Ltd. was used.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... · 5 parts 4) Sodium pyrophosphate ········ 0.2 parts 5) AF solvent 7 ··················· 13.8 parts It was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Example 5)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less. Thereafter, 0.3 parts by mass of distilled water was added to the printing ink and mixed and dispersed.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... · 5 parts 4) Sodium hexametaphosphate ··· 0.2 parts 5) AF solvent No. 7 ······· 13.8 parts 6) Distilled water ········· ..... It was confirmed with a Karl Fischer moisture meter that the water content of 0.3 parts printing ink was 0.44%.

(Preparation of printing inks of Examples 6 and 7)
The following blending proportions (total of each of Examples 6 and 7 are 100 parts by mass) are kneaded using a three-roll mill, and the finished printing ink is kneaded by the kneading degree test described in JIS K5701-1. Adjustment was made so that the scale of the position A of the sum was 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate.
1) The above-mentioned resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... ... 5 parts 4) Sodium hexametaphosphate compound base (B) 1 part (Example 6)
Diammonium hydrogen citrate compound base (C) 1 part (Example 7)
5) AF Solvent No. 7 ··················· A 13-part printing ink was confirmed to have a moisture content of 0.14% with a Karl Fischer moisture meter.

(Preparation of printing ink of Example 8)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. Moreover, Wako Pure Chemical Industries, Ltd. reagent special grade phosphoric acid was used as 85% phosphoric acid.
1) Resin varnish for printing ink (A) ··· 64.96 parts 2) Phthalocyanine blue ··· 16 parts 3) Calcium carbonate ··· 5 parts 4) 85% phosphoric acid ... 0.24 parts 5) AF solvent 7 ... 13 It was confirmed with a Karl Fischer moisture meter that the water content of 8 parts printing ink was 0.18%.

(Preparation of printing ink of Example 9)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. Further, anhydrous citric acid manufactured by Komatsuya Co., Ltd. was used as citric acid.
1) Resin varnish for printing ink (A) 65 parts 2) Phthalocyanine blue 16 parts 3) Calcium carbonate ... 5 parts 4) Citric acid ... 0.2 parts 5) AF solvent No. 7 ... 13.8 parts of printing ink It was confirmed with a Karl Fischer moisture meter that the water content was 0.14%.

(Preparation of printing ink of Example 10)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. As the calcium carbonate, Shiroishi Hana T-DD manufactured by Shiroishi Kogyo Co., Ltd. was used. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) The above-mentioned resin varnish for printing ink (A) 69.2 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... 0 8 parts 4) Sodium hexametaphosphate 0.2 part 5) AF solvent No. 7 13.8 parts The water content of the printing ink is 0.14% Was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Example 11)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. As the calcium carbonate, Shiroishi Hana T-DD manufactured by Shiroishi Kogyo Co., Ltd. was used. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... -5 parts 4) Sodium hexametaphosphate-0.2 part 5) AF solvent No. 7-13.8 parts The water content of the printing ink is 0.14% Was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Example 12)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. As the calcium carbonate, Shiroishi Hana T-DD manufactured by Shiroishi Kogyo Co., Ltd. was used. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) The resin varnish for printing ink (A) 60 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... 10 parts 4) Sodium hexametaphosphate .... 0.2 parts 5) AF solvent No. 7 .... 13.8 parts The water content of the printing ink is 0.14%. This was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Example 13)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. As the calcium carbonate, Shiroishi Hana T-DD manufactured by Shiroishi Kogyo Co., Ltd. was used. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) The above-mentioned resin varnish for printing ink (A) 52 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... 18 parts 4) Sodium hexametaphosphate .... 0.2 parts 5) AF solvent 7 .... 13.8 parts The water content of the printing ink is 0.14%. This was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Example 14)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. Moreover, NEOLIGHT SA-300 made by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) 65.17 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... 5 parts 4) Sodium hexametaphosphate 0.03 parts 5) AF solvent No. 7 13.8 parts The water content of the printing ink is 0.14% It was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Example 15)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. Moreover, NEOLIGHT SA-300 made by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) 62.1 parts 2) Phthalocyanine blue 16 parts 3) Calcium carbonate ··· 5 parts 4) Sodium hexametaphosphate ······ 0.1 parts 5) AF solvent No. 7 ·········· 13.8 parts The water content of the printing ink is 0. It was confirmed with a Karl Fischer moisture meter that it was 14%.

(Preparation of printing ink of Comparative Example 1)
In the following blending ratio, the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the scale of position A of the kneading degree of the finished printing ink is 3 or less. It was adjusted.
The phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC Corporation. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... 5 parts 4) AF solvent No. 7 ... 14 parts It was confirmed with a Karl Fischer moisture meter that the water content of the printing ink was 0.14%.

(Preparation of printing ink of Comparative Example 2)
The ingredients of the following 1) to 4) are blended, kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the scale of position A of the kneading degree of the finished printing ink. Was adjusted to 3 or less.
Thereafter, sodium hexametaphosphate of 5) was added. In addition, the meat after addition is not performed. The scale of the position A of the kneading degree of the printing ink after addition of sodium hexametaphosphate was 8 or more.
The phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC Corporation. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... 5 parts 4) AF solvent No. 7 ... 13.8 parts 5) Sodium hexametaphosphate ... 0.2 parts The water content of the printing ink is 0.14% Was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Comparative Example 3)
The ingredients of the following 1) to 4) are blended, kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the scale of position A of the kneading degree of the finished printing ink. Was adjusted to 3 or less.
Thereafter, 5) diammonium hydrogen citrate was added. In addition, the meat after addition is not performed. The scale at position A of the kneading degree of the printing ink after addition of diammonium hydrogen citrate was 8 or more.
The phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC Corporation. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. In addition, diammonium hydrogen citrate was manufactured by Komatsuya Co., Ltd.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... 5 parts 4) AF Solvent No. 7 ... 13.8 parts 5) Diammonium hydrogen citrate ... 0.2 parts Water content of printing ink is 0.14% It was confirmed with a Karl Fischer moisture meter.

(Preparation of printing ink of Comparative Example 4)
The following raw materials 1) to 5) were blended and kneaded using a three-roll mill. In the kneading degree test described in JIS K5701-1, the scale of position A of the kneading degree of the finished printing ink was adjusted to 3 or less. Thereafter, 0.5 parts by mass of distilled water was added to the printing ink and mixed and dispersed.
The phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC Corporation. In addition, NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3) Calcium carbonate ... · 5 parts 4) Sodium hexametaphosphate ··· 0.2 parts 5) AF solvent No. 7 ······· 13.3 parts 6) Distilled water ········· ..... 0.5 parts It was confirmed with a Karl Fischer moisture meter that the water content of the printing ink was 0.64%.

(Preparation of printing inks of Comparative Examples 5 and 6)
The following raw materials 1) to 5) were blended and kneaded using a three-roll mill. In the kneading degree test described in JIS K5701-1, the scale of position A of the kneading degree of the finished printing ink was adjusted to 3 or less. Thereafter, 0.5 parts by mass of distilled water was added to the printing ink and mixed and dispersed.
The phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC Corporation. Moreover, NEOLIGHT SA-300 made by Takehara Chemical Industry Co., Ltd. was used as the calcium carbonate.
1) The above-mentioned resin varnish for printing ink (A) ... 65 parts 2) Phthalocyanine blue ... 16 parts 3 ) Calcium carbonate ... 5 parts 4) Sodium hexametaphosphate compound base (B) ... 1 part (Comparative Example 5)
Ammonium hydrogen citrate compound base (C) ... 1 part (Comparative Example 6)
5) AF Solvent No. 7 ... 12.5 parts 6) Distilled water ... ... It was confirmed with a Karl Fischer moisture meter that the water content of 0.5 part printing ink was 0.64%.

(Preparation of printing ink of Comparative Example 7)
In the following blending ratio (total 100 parts by mass of 1 to 5), the mixture is kneaded using a three-roll mill, and in the kneading degree test described in JIS K5701-1, the position of the kneading degree of the finished printing ink The scale of A was adjusted to 3 or less.
As phthalocyanine blue, FASTOGEN Blue FA5375 manufactured by DIC Corporation was used. As the calcium carbonate, Shiroishi Hana T-DD manufactured by Shiroishi Kogyo Co., Ltd. was used. In addition, sodium hexametaphosphate manufactured by Taiyo Chemical Industry Co., Ltd. was used.
1) Resin varnish for printing ink (A) 70 parts 2) Phthalocyanine blue ... 16 parts 3) Sodium hexametaphosphate 0.2 parts 4) AF Solvent No. 7 ························ 13.8 parts The water content of the printing ink was confirmed to be 0.14% with a Karl Fischer moisture meter.

  The printing inks of Examples 1 to 15 and Comparative Examples 1 to 7 prepared by the above-described blending were subjected to the following stain resistance test and paper quality confirmation test. The results are shown in Tables 1-3.

(Stain resistance test)
The stain resistance test was evaluated using a Roland 704 printer manufactured by Man Roland. Printing was performed with the dampening water supply dial at the start of printing fixed, and the determination was made based on whether the printing paper surface was smudged. In the test, a plate comprising 35% of the image area 90%, 35% of the 20% area, and 30% of the non-image area was used.
The criteria for evaluation are as follows.
When the image area is 90%, 20%, and the non-image area is not stained ...
When the image area is 20% and the non-image area is not stained ...
When the non-image area was not stained, but the 20% area of the image area was partially stained ... △,
If the non-image area is dirty, ×.

The conditions when the printing test was conducted are as follows.
Printing machine: Roland 704 printing machine (separate continuous water supply system) (man Roland)
Dampening solution: Presert SD100 (manufactured by DIC Graphics) concentration 1.5%
Printing speed: 8,000 sheets / hour Room temperature 25 ° C, Humidity 55%
Printing paper / OK Top Coat N (Oji Paper Co., Ltd.)

(Paper quality confirmation test)
0.125 cc of ink was developed on OK Kanto single-sided art paper (manufactured by Oji Paper Co., Ltd.) with a RI tester (manufactured by Meiko Seisakusho) using a two-part roll. Then, it was left to heat for 20 seconds in a dryer having an atmospheric temperature of 100 ° C., and the state of the printing paper surface was visually confirmed. The case where a large number of portions where the ink was not transferred was recognized was evaluated as x, and the case where there were almost no portions where the ink was not transferred was evaluated as ◯.

(Missing test)
In a room conditioned at 25 ° C., using the rotary tack meter described in 4.2 Adhesion section of JIS K5701-1 (lithographic ink test method), the ink amount is 1.32 ml, the roller temperature is 42 ° C., The operation was performed for 10 minutes under the condition of 1200 rpm. Prior to the start of operation, a blank paper was placed at a distance of 10 cm from the roller, ink scattered during the operation was collected, and the degree of contamination of this blank paper was visually determined. The evaluation criteria are as follows.
Very little scattering ... 5
Less than usual ... 4,
Spattering amount is normal level ... 3
More than usual ... 2,
The amount of scattering is extremely large ... 1.

(Fluidity test)
In a room controlled at 25 ° C. ± 2 ° C., the fluidity was evaluated by the spread meter method described in 4.1 of JIS K5701-1. The D value (mm) corresponding to the spread diameter after 60 seconds was measured. In order to improve the transferability of the ink on the printing press, the D value is preferably 38 or more. However, if the D value is too large, the emulsification amount increases or misting deteriorates, so the D value is 42 or less. It is preferable.

As shown in Examples 1 to 15, good stain resistance was obtained by adding sodium hexametaphosphate or diammonium hydrogen citrate to reduce the water content in the printing ink to less than 0.5%. . Similar results were obtained when the addition was made on a compound basis in Examples 6 and 7 and the water content in the printing ink was less than 0.5%.
In Comparative Examples 2 and 3 in which sodium hexametaphosphate or diammonium hydrogen citrate was added and the meat was not kneaded, the added material remained as a foreign material, and the result was x in the foreign material confirmation test. In Comparative Example 7 in which the extender pigment was not added, the amount was higher than that of normal misting.

  According to the present invention, the leveling effect for preventing the non-image area from being soiled is enhanced, and the cleaning time and waste paper of the printing press due to the soil are greatly reduced.

Claims (6)

It consists of phosphoric acid, ammonium salt of phosphoric acid, alkali metal salt of phosphoric acid, alkaline earth metal dihydrogen salt of phosphoric acid, citric acid, ammonium salt of citric acid, alkali metal salt of citric acid, magnesium salt of citric acid At least one leveling aid selected from the group;
At least one extender pigment selected from the group consisting of calcium carbonate, magnesium carbonate and barium sulfate;
Including water,
The groove depth at position A measured by the method described in the kneading degree test of JIS K5701-1 is 7.5 μm or less,
The content of the leveling aid is 0.01 to 0.5% by mass,
The content of the extender pigment is 0.1 to 30% by mass,
An active energy ray-curable lithographic printing ink composition, wherein the water content excluding crystallization water is 0.5% by mass or less. The phosphoric acid is phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexapolyphosphoric acid, trimetaphosphoric acid, tetrametalin One or more selected from the group consisting of acid and hexametaphosphoric acid,
The ammonium salt of phosphoric acid is at least one selected from the group consisting of triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and sodium ammonium hydrogen phosphate;
The alkali metal salt of phosphoric acid is lithium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, pyrophosphoric acid Sodium, disodium dihydrogen pyrophosphate, potassium pyrophosphate, potassium hydrogen pyrophosphate, potassium polyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, potassium metaphosphate, sodium metaphosphate, sodium trimetaphosphate, sodium hexametaphosphate One or more selected from the group consisting of sodium phosphite and sodium hypophosphite,
The alkaline earth metal dihydrogen salt of phosphoric acid is one or more selected from the group consisting of calcium dihydrogen phosphate, barium dihydrogen phosphate and magnesium dihydrogen phosphate;
The ammonium salt of citric acid is one or more selected from the group consisting of diammonium hydrogen citrate and triammonium citrate;
The alkali metal salt of citric acid is trisodium citrate, disodium citrate, monosodium citrate, tripotassium citrate, dipotassium citrate, monopotassium citrate, sodium dihydrogen citrate, potassium dihydrogen citrate And at least one selected from the group consisting of disodium hydrogen citrate and the active energy ray-curable lithographic printing ink composition according to claim 1. 3. The active energy ray-curable lithographic printing ink composition according to claim 1, wherein the water content is 0.18% by mass or less. At least one extender pigment selected from the group consisting of calcium carbonate, magnesium carbonate and barium sulfate, phosphoric acid, ammonium phosphate, phosphoric acid alkali metal salt, phosphoric acid alkaline earth metal dihydrogen salt, citric acid , An ammonium salt of citric acid, an alkali metal salt of citric acid, a magnesium salt of citric acid, and water, and a content of the extender pigment is 0.1. Active energy ray in which the content of the surface-adjusting aid is 0.01 to 0.5% by mass and the water content excluding crystallization water is 0.5% by mass or less. A curable lithographic printing ink composition comprising:
It consists of phosphoric acid, ammonium salt of phosphoric acid, alkali metal salt of phosphoric acid, alkaline earth metal dihydrogen salt of phosphoric acid, citric acid, ammonium salt of citric acid, alkali metal salt of citric acid, magnesium salt of citric acid Including at least one leveling aid selected from the group ,
The groove depth at position A measured by the method described in the kneading degree test of JIS K5701-1 is 7.5 μm or less,
An active energy ray-curable lithographic printing ink composition using a compound as one of raw materials, wherein the water content excluding crystallization water is 0.5% by mass or less. The phosphoric acid is phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexapolyphosphoric acid, trimetaphosphoric acid, tetrametalin One or more selected from the group consisting of acid and hexametaphosphoric acid,
The ammonium salt of phosphoric acid is one or more selected from the group consisting of triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and sodium ammonium hydrogen phosphate;
The alkali metal salt of phosphoric acid is lithium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, pyrophosphoric acid Sodium, disodium dihydrogen pyrophosphate, potassium pyrophosphate, potassium hydrogen pyrophosphate, potassium polyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, potassium metaphosphate, sodium metaphosphate, sodium trimetaphosphate, sodium hexametaphosphate One or more selected from the group consisting of sodium phosphite and sodium hypophosphite,
The alkaline earth metal dihydrogen salt of phosphoric acid is one or more selected from the group consisting of calcium dihydrogen phosphate, barium dihydrogen phosphate and magnesium dihydrogen phosphate,
The ammonium salt of citric acid is one or more selected from the group consisting of diammonium hydrogen citrate and triammonium citrate;
The alkali metal salt of citric acid is trisodium citrate, disodium citrate, monosodium citrate, tripotassium citrate, dipotassium citrate, monopotassium citrate, sodium dihydrogen citrate, potassium dihydrogen citrate And at least one selected from the group consisting of disodium hydrogen citrate and the active energy ray-curable lithographic printing ink composition according to claim 4 . A printed matter produced using the lithographic printing ink composition according to any one of claims 1 to 5 .