TW201604249A - Printing ink composition - Google Patents

Abstract

In order to prevent contamination of a non-image part, i.e., to impart surface conditioning effects in lithographic offset printing, an aqueous solution including an inorganic acid such as metaphosphoric acid or a salt thereof is added to printing ink in the present invention. The present invention addresses the problem of providing a printing ink composition whereby the aforementioned inorganic acid or the like exhibits adequate surface conditioning effects, a method for manufacturing the printing ink composition, and a printed article printed using the printing ink composition. A printing ink composition in which at least one species selected from the group consisting of phosphoric acid, an ammonium salt of phosphoric acid, an alkali metal salt of phosphoric acid, an alkaline earth metal dihydrogen salt of phosphoric acid, citric acid, an ammonium salt of citric acid, an alkali metal salt of citric acid, and a magnesium salt of citric acid is added under conditions of not including coarse particles to a lithographic offset printing ink composition containing an extender pigment including at least one species selected from calcium carbonate, magnesium carbonate, and barium sulfate, and the moisture content of the printing ink is reduced.

Description

Printing ink composition

This invention relates to a printing ink composition for lithographic printing using dampening water with less production of printed stains.

The basic principle of lithography is to use a repellency phenomenon of water and oil, and use a plate containing a lipophilic portion (line portion) to which printing ink is attached and a portion (non-line portion) to which no printing ink is attached. At the time of printing, in order to prevent the printing ink from adhering to the non-line portion of the layout, the dampening water is supplied to the layout in advance.

The dampening water system is prepared by adding a concentrated dampening water composition (also referred to as an erosive liquid) to a raw water such as tap water or ground water at a concentration of 1 to 5%. The component of the etching solution contains a glycol-based or propylene glycol-based solvent, a surfactant as an emulsifying agent for printing ink, a water-soluble resin as a plate protecting agent, a phosphoric acid or a salt thereof, citric acid or a salt thereof.

However, as the printing progresses, there is a case where the printing ink is attached to the non-line portion. When the printing ink is attached to the non-line portion, stains are generated on the printed matter, and the value of the product or the product is lost, resulting in damage to the paper. In the case where the printing ink is attached to the non-line portion, the generation of the stain can be suppressed by suppressing the supply amount of water on the plate surface, but on the other hand, excessive emulsification of the ink is induced. The excessively emulsified ink loses fluidity on the rollers of the printing press, causing splashing and contaminating the periphery of the printing press.

Therefore, in order to prevent adhesion of the printing ink to the non-line portion, phosphoric acid or a salt thereof is added to the lithographic ink as a whole surface auxiliary. The so-called full surface means that the non-line portion is cleaned and the printing ink is prevented from adhering. However, even if such a whole-surface additive is added, there is no In the case where the effect was exerted, the inventors of the present invention conducted an effort to study the cause, and as a result, found out the constitution of the present invention.

In Patent Documents 1 and 2, 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 full-surface effect. Since the printing machine may have poor ink transfer failure due to a decrease in fluidity due to emulsification, calcium carbonate is often added to the printing ink for the purpose of emulsification, viscosity, fluidity adjustment, and reduction of ink mist. Magnesium carbonate, barium sulfate. In the case of carrying out the contents described in Patent Documents 1 and 2, the sodium phosphate contained in the added aqueous solution reacts with calcium carbonate in the printing ink to form calcium phosphate, resulting in a sodium phosphate having a full-surface effect. Disappears before using ink in the press. Therefore, there is a possibility that the full-face effect cannot be fully exerted.

In Patent Document 3, as a prior art, a case where phosphoric acid or a substance such as phosphoric acid is added to the printing ink in order to prevent the printing stain from being cleaned is described, but it is not sufficient to completely prevent the stain.

Patent Document 4 discloses that in the lithographic printing ink containing a metal soap-type desiccant, the printing stain is improved by containing phosphoric acid or citric acid and/or a salt of the acid.

The metaphosphate or sodium citrate described as an example is a crystalline substance, and therefore it is considered that the coarse crystal is directly left in the printing ink by merely adding it to the base ink composition and stirring it. Since the coarse crystal is larger than the thickness of the printing ink on the paper surface during printing, a large portion of the printing surface on which the printing ink is not transferred may occur, resulting in damage to the paper. Moreover, in the state of coarse particles, the whole surface effect is weak, and thus a large amount of addition is required.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application No. Sho 53-18223

[Patent Document 2] Japanese Patent Application No. Sho 58-179310

[Patent Document 3] Japanese Patent Laid-Open Publication No. 9-12952

[Patent Document 4] Japanese Patent Application No. 2008-556087

An object of the present invention is to provide a printing ink composition having a full-surface effect of preventing stains on a non-line portion, a method for producing the same, and a printed matter printed using the printing ink composition.

In order to solve the above problems, an effort has been made to solve the above problems. As a result, it has been found that a lithographic ink composition containing at least one selected from the group consisting of calcium carbonate, magnesium carbonate, and barium sulfate is added to the group selected from the group consisting of phosphoric acid without containing coarse particles. And one or more of the group consisting of an ammonium phosphate salt, an alkali metal salt of phosphoric acid, an alkaline earth metal dihydrogen salt of phosphoric acid, an ammonium salt of citric acid, citric acid, an alkali metal salt of citric acid, and a magnesium salt of citric acid. Further, the present invention can be accomplished by reducing the moisture in the printing ink and solving the problem.

(1) That is, the present invention is a printing ink composition which satisfies all of the following (a) to (d).

(a) Containing one or more selected from the group A below.

(b) containing an extender pigment containing one or more 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 training and degree test of JIS K5701-1 is 7.5 μm or less.

(Group A)

Phosphoric acid, ammonium phosphate, phosphoric acid alkali metal salt, phosphoric acid alkaline earth metal dihydrogen salt, citric acid, ammonium citrate salt, alkali metal salt of citric acid, magnesium salt of citric acid.

(2) The printing ink composition according to the above (1), wherein in the group A, the phosphoric acid is selected from the group consisting of phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, and phosphorous One or more of the group consisting of acid, hypophosphorous acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexaphosphoric acid, trimellitic acid, tetrametaphosphoric acid and hexametaphosphoric acid, and the ammonium phosphate is selected from the group consisting of phosphoric acid One or more of the group consisting of ammonium, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and sodium hydrogen phosphate. The alkali metal salt of phosphoric acid is selected from the group consisting of lithium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and 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, four One or more of a group consisting of sodium polyphosphate, potassium metaphosphate, sodium metaphosphate, sodium trimetaphosphate, sodium hexametaphosphate, sodium phosphite and sodium hypophosphite, the alkaline earth metal dihydrogen salt of phosphoric acid is selected from the group consisting of phosphoric acid One or more of the group consisting of calcium hydride, bismuth dihydrogen phosphate and magnesium dihydrogen phosphate, and the ammonium salt of citric acid is one or more selected from the group consisting of diammonium hydrogen citrate and triammonium citrate, citric acid The alkali metal salt is selected from the group consisting of trisodium citrate and citric acid. Sodium, sodium citrate, tripotassium citrate, dipotassium citrate, a citrate group consisting of potassium, sodium dihydrogen citrate, disodium hydrogen citrate, potassium dihydrogen citrate and the one or more.

(3) The present invention is a method for producing a printing ink composition according to the above (1), which uses one of the following composites (e) to (g) as a raw material.

(e) containing one or more selected from the group A above.

(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 training and strength test described in JIS K5701-1 is 7.5 μm or less.

(4) Further, the present invention is a printed matter produced by using the printing ink composition of the above (1) or (2).

According to the present invention, the effect of preventing the entire surface of the stain of the non-line portion is improved. In this way, in India It is effective in reducing the stains, reducing the amount of paper, and reducing the cleaning time of the printing press.

Hereinafter, the form for carrying out the invention will be described in detail. In addition, % and parts are quality standards unless otherwise specified.

(Main material and moisture content of printing ink)

The printing ink composition generally comprises a pigment, a vehicle and an auxiliary agent, and the printing ink composition of the present invention is also the same. Hereinafter, the 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, and an extender pigment as a pigment, and contains at least one selected from the group consisting of calcium carbonate, magnesium carbonate, and barium sulfate as an extender pigment.

As the auxiliary agent, a wax, a desiccant, a drying inhibitor, a surfactant, or the like is used. In particular, the printing ink composition of the present invention contains one or more selected from the group A below as an auxiliary agent.

Those belonging to group A are referred to as whole-surface auxiliaries.

(Group A)

Phosphoric acid, ammonium phosphate, phosphoric acid alkali metal salt, phosphoric acid alkaline earth metal dihydrogen salt, citric acid, ammonium citrate salt, alkali metal salt of citric acid, magnesium salt of citric acid.

Further, the water content in the printing ink composition is 0.5% by mass or less.

As the above-mentioned vehicle, a resin varnish, a petroleum solvent, a vegetable oil, a mineral oil, a vegetable oil ether, a vegetable oil fatty acid ester or the like is suitably used.

(Description of water content)

The water content is expressed by mass% of the ratio of the moisture contained in the ink composition. It is usually measured by the Karlsfeld method. In the case of the moisture measurement by the Karl Fischer method, in the case where the raw material of the ink composition contains crystal water, the amount of water including the crystal water is measured. The moisture of the ink composition of the present invention does not include crystal water.

Therefore, when the ink composition contains a raw material containing crystal water, the raw material is heated to a constant amount at 105 ° C using a heat-drying moisture meter, and the reduced weight is included in the moisture in the ink of the present invention. .

As a calculation example, the water content of the ink composition containing only the pigment A and the ink composition containing 100 g of the pigment A is 1000 g.

The amount of water measured by the Karlscher method for pigment (100g) 0.5g

The amount of water measured by the above-mentioned heat-drying moisture meter of pigment (100g) 0.3g

The total amount of water in the ink composition is measured by the Karl Fischer method.

Since 0.2 g (= 0.5 - 0.3) of the crystal water containing the pigment A in the 3 g was subtracted from 0.2 g, the water content in the ink composition was 2.8 g, and the water content was 0.28% by mass.

In order to determine to what extent the crystal water is contained in the raw material containing the crystal water, in addition to the method of measuring the moisture by the Karl Fischer method using the heat drying type moisture meter as described above, calculation based on the chemical formula may be used. The method or the method for calculating the content of the crystallization water and the dehydration temperature from the technical literature and calculating the method.

Furthermore, the reason why the water content should be below a certain ratio is as follows.

As described above, phosphoric acid or a salt thereof, citric acid or a salt thereof is usually added as a surface builder in the printing ink.

Further, in order to adjust the fluidity, viscosity, emulsification amount, and the like of the printing ink, calcium carbonate, magnesium carbonate, and barium sulfate are often added to the printing ink, and calcium carbonate, magnesium carbonate, and barium sulfate in the printing ink are used in water. In the presence of a phosphoric acid, citric acid or the like added as a whole-surface auxiliary agent, it is slowly reacted to form calcium phosphate, calcium citrate, magnesium phosphate, and strontium phosphate.

When these salts are formed, the entire surface effect of phosphoric acid or citric acid disappears, so that it is easy to cause stains during printing.

In order to maintain the overall surface effect of the printing ink, it is preferred to reduce the moisture content in the printing ink to 0.5% or less, and to suppress the conversion of the entire surface additive into salt during the ink preservation process. If the formation of salt is suppressed, the state in which the entire surface effect is maintained is maintained, so that stains can be prevented from occurring in the middle of printing. Moreover, if the effect of the entire surface of the ink is high, the dampening water supplied at the time of printing is reduced, and the printing trouble caused by excessive emulsification of the ink is also reduced.

(Method of reducing the moisture content of the printing ink composition)

The moisture in the printing ink composition is almost entirely derived from the moisture in the pigment.

Among the pigments, there are a powder pigment which is pulverized by a drying step, and a slurry pigment which is dispersed in water.

The adjustment of the moisture content of the powder pigment is carried out by drying at a high temperature for a long period of time by adjusting the drying temperature and the drying time without affecting the quality of the pigment.

The solid matter which is subjected to filtration and dehydration of the slurry pigment to lower the moisture content is called a tidal cake pigment. In the case of using a tidal cake pigment, in the step called flashing in the production of printing ink, the varnish and the tidal cake pigment are placed in a dispersion squeezing machine such as a kneader, and kneaded, dispersed, and heated and dehydrated. In order to reduce the moisture content of the printing ink composition produced by flashing, it is carried out by increasing the temperature at the time of dehydration in the flashing step or by prolonging the time of the dehydration step.

(Whole auxiliaries)

The printing ink composition of the present invention contains one or more selected from the above group A as an auxiliary component for obtaining a full-surface effect as an essential component.

The total content of the whole-surface auxiliary agent in the printing ink composition of the present invention is preferably from 0.01 to 0.5% by mass, more preferably from 0.01 to 0.2% by mass.

When the content is less than 0.01% by mass, there is a case where the effect of preventing stains is insufficiently exhibited. On the other hand, when it exceeds 0.5 mass %, roll peeling or printing ink adhesion failure may occur, and it becomes difficult to perform favorable printing.

(Illustration of a preferred user for the whole surface additive belonging to Group A)

Regarding the above-mentioned group A, the phosphoric acid is selected from the group consisting of phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, tetramerization. One or more of the group consisting of phosphoric acid, pentaphosphoric acid, hexaphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid and hexametaphosphoric acid, the ammonium phosphate salt is selected from the group consisting of triammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate And one or more of the group consisting of sodium hydrogen phosphate, the alkali metal salt of phosphoric acid is selected from the group consisting of lithium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, phosphoric acid. Dihydrogen potassium, sodium pyrophosphate, disodium dihydrogen pyrophosphate, potassium pyrophosphate, potassium hydrogen pyrophosphate, potassium polyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, potassium metaphosphate, sodium metaphosphate One or more of the group consisting of sodium trimetaphosphate, sodium hexametaphosphate, sodium phosphite and sodium hypophosphite. The alkaline earth metal dihydrogen salt of phosphoric acid is selected from the group consisting of calcium dihydrogen phosphate, dihydrogen phosphate and dihydrogen phosphate. One or more of the group consisting of magnesium, ammonium citrate The salt is one or more selected from the group consisting of diammonium hydrogen citrate and triammonium citrate. The alkali metal salt of citric acid is selected from the group consisting of trisodium citrate, disodium citrate, monosodium citrate and citric acid. One or more of the group consisting of potassium, dipotassium citrate, monopotassium citrate, sodium dihydrogen citrate, potassium dihydrogen citrate and disodium hydrogen citrate.

(mixing of printing ink compositions)

The preferred content of the main components in the printing ink composition of the present invention is as follows.

1) Organic pigments and/or inorganic pigments 5 to 40% by mass.

2) 0.1 to 20% by mass of an extender pigment containing at least one selected from the group consisting of calcium carbonate, magnesium carbonate and barium sulfate.

3) Resin varnish 25~35 mass%.

4) Petroleum solvent having a boiling point of 160 to 330 ° C 0 to 45 mass%.

5) The total of vegetable oil, vegetable oil ester and vegetable oil ether is 7 to 40% by mass.

6) A total of 0 to 8 mass% of a desiccant such as a drying inhibitor such as BHT, HQ or TBHQ, a wax, a metal desiccant, or the like.

7) The total amount of additives on the whole surface is 0.01 to 0.5% by mass.

As the other additives, Demol, Poiz, Emulgen, Rheodol, Homogenol manufactured by Kao Co., Ltd., and surfactants or dispersants such as Epan, Shallol, Hytenol, and Noigen manufactured by Daiichi Kogyo Co., Ltd. can be exemplified.

Further, BHT represents dibutylhydroxytoluene, HQ represents hydroquinone, and TBHQ represents tert-butylhydroquinone.

(organic pigment)

The organic pigment used in the present invention includes a dye for printing, an azo pigment, a phthalocyanine pigment, a condensed polycyclic pigment, a nitro pigment, a nitroso pigment, and a fluorescent pigment. Examples of the azo system include soluble azo and insoluble azo. As the soluble azo pigment, there are carmine red 6B and lake red C. Further, examples of the insoluble azo pigment include monoazo yellow, monoazo red, disazo yellow, and disazo orange. Examples of the other azo system include nickel azo yellow, permanent orange, nickel azo yellow, chrome-containing phthalocyanine yellow, and chrome-containing phthalocyanine. As the dyes for printing, there are rhodamine lakes, methyl violet lakes, quinoline yellow lakes, alizarin lakes and the like. Examples of the phthalocyanine pigment include copper phthalocyanine blue (α type, β type, ε type), copper phthalocyanine green (chlorinated, brominated), and cobalt phthalocyanine blue. Further, examples thereof include unsubstituted quinacridone, dimethyl quinacridone, eosin, polyazo yellow, benzimidazolone yellow, naphthol yellow, pigment green, and Alkanel violet, naphthol yellow, pigment green, basic blue, nigrosine, Lumogen yellow, signal red, and the like.

(inorganic colored pigment)

As the inorganic colored pigment used in the present invention, there are titanium dioxide, zinc oxide, zinc sulfide, chromium oxide, chromium hydroxide, black oxide (iron black), cobalt blue, ferrocyanide (iron blue), manganese violet, carbon. Black, lead white, ultramarine, chrome yellow, lead chromate molybdate (molybdenum orange), zinc chrome yellow, strontium chromate, yellow iron oxide (yellow iron), red iron oxide (red iron oxide), green pigment (veridian) , potassium titanate, barium titanate, molybdenum disulfide, antimony trioxide, antimony nitride, antimony carbide, and the like.

(containing one or more body pigments selected from the group consisting of calcium carbonate, magnesium carbonate, and barium sulfate)

The calcium carbonate, magnesium carbonate, and barium sulfate used in the present invention are referred to as body pigments, and in a dry state, the appearance is substantially white and the refractive index is small, and the hiding power is reduced when dispersed in the varnish. The body pigment is used to adjust the fluidity, viscosity, emulsification, and the like of the ink.

Examples of the calcium carbonate used in the present invention include calcium carbonate chemically synthesized using limestone as a raw material or heavy calcium carbonate obtained by pulverizing natural limestone. It is preferable that the transparency of the ink and the decrease in gloss are small, and the chemically synthesized calcium carbonate which is easy to perform ink dispersion dispersion is easily obtained. Further, among them, it is particularly preferable to produce a finer particle in the form of a cube, and to carry out the entire surface of the colloidal calcium carbonate.

As the magnesium carbonate used in the present invention, basic magnesium carbonate can be mentioned.

The barium sulfate used in the present invention includes a ground product called barite powder obtained by pulverizing barite, and precipitated barium sulfate produced by a chemical reaction. The precipitated barium sulfate which can obtain fine particles is more preferable because the decrease in gloss is small.

As the extender pigment used in the present invention, white carbon, talc, aluminum hydroxide, magnesium hydroxide, alumina white, vermiculite powder, which is used as an extender pigment in the same manner as calcium carbonate, magnesium carbonate or barium sulfate may be used in combination. Diatomaceous earth, synthetic cerium oxide, calcium silicate, erbium, sericite, mica, hydrotalcite, bentonite, zeolite, kaolin clay, pyrophyllite, and the like.

These extender pigments are added in a ratio of 0.1 to 20% by mass based on the total weight of the printing ink composition. Furthermore, the present invention exerts an effect particularly in a printing ink composition containing at least one selected from the group consisting of calcium carbonate, magnesium carbonate, and barium sulfate in an amount of 0.1 (presumed) or more by mass based on the total weight of the printing ink composition.

(resin varnish)

The resin varnish contains a resin, a vegetable oil, a vegetable oil ester, a vegetable oil ether, a solvent, a tackifier, an antioxidant, and the like. The resin used in the resin varnish used in the invention is 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 modification Rosin ester, polyester, acrylic Resin or the like.

The resin varnish is a viscous liquid, and contains vegetable oil, vegetable oil ester, vegetable oil ether, antioxidant, solvent, tackifier, etc. in order to adjust the viscosity or printability of the printing ink. The antioxidant is added to prevent oxidation of the resin or vegetable oil in the varnish.

Examples of the tackifier used in the resin varnish used in the present invention include an organoaluminum compound, an organic titanate compound, an organic zinc compound, and an organic calcium compound. Among these, an organoaluminum compound is preferred. For example, aluminum octoate, aluminum stearate, aluminum triisopropoxide, aluminum diisopropoxide, aluminum tributoxide, aluminum tributoxide, aluminum dibutoxide, and tris(ethylene hydride) Acetic acid) aluminum, octenoic acid aluminum oxide, aluminum stearate oxide, ethyl acetoacetate aluminum diisopropoxide, ethyl acetoacetate di-n-butoxide aluminum, and the like. The amount of use of the tackifier is preferably in the range of 0.1 to 5 parts by mass, more preferably in the range of 0.2 to 3 parts by mass, based on 100 parts by mass of the resin varnish.

As the antioxidant used in the resin varnish used in the present invention, BHT (dibutylhydroxytoluene), HQ (hydroquinone), MHQ (methyl hydroquinone), TBHQ (third butyl group) can be used. Hydroquinone).

(Petroleum solvent)

The petroleum solvent used in the present invention preferably has a boiling point of 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, and ISU Chemical Co. LTD manufactured by JX Nippon Mining & Energy Co., Ltd. , 260C, 280, etc.

(vegetable oil)

Examples of the vegetable oil used in the present invention include soybean oil, linseed oil, rice bran oil, lignan oil, castor oil, dehydrated castor oil, corn oil, safflower oil, Nanyang oil tung oil, regenerated vegetable oil, and canola oil (canola). Oil), colza oil, tung oil, peanut oil, cottonseed oil, sesame oil, sunflower oil, olive oil, palm oil, palm kernel oil, coconut oil and other oils and such thermal polymer oils, oxidized polymer oils .

(vegetable oil ester)

As the vegetable oil ester used in the present invention, linseed oil fatty acid methyl ester, linseed oil fatty acid ethyl ester, linseed oil fatty acid propyl ester, linseed oil fatty acid butyl ester, soybean oil fatty acid methyl ester, soybean oil fatty acid ethyl Ester, soybean oil fatty acid propyl ester, 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, 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, regenerated vegetable oil ester, Nanyang oil tung oil ester and the like.

(plant oil ether)

Examples of the ether of the vegetable oil used in the present invention as a raw material include di-n-octyl ether, dinonyl ether, dihexyl ether, nonylhexyl ether, mercaptobutyl ether, and diheptyl group of the above vegetable oil. Ether, dimercapto ether, mercaptooctyl ether, and the like.

(various additives)

The printing ink composition of the present invention may optionally contain various additives for printing inks such as waxes, desiccants, antioxidants, and antifouling agents. Examples of the wax include polyethylene wax, PTFE (polytetrafluoroethylene) wax, and sasol wax.

Examples of the desiccant include metals such as cobalt, manganese, lead, zinc, iron, calcium, barium, and rare earth elements, and octanoic acid, naphthenic acid, neodecanoic acid, tung oil, linseed oleic acid, and resin acid. The acid salt is a metal soap or a borate such as the above metal.

Examples of the antioxidant include BHT (dibutylhydroxytoluene), HQ (hydroquinone), MHQ (methyl hydroquinone), and TBHQ (tert-butylhydroquinone).

(other forms)

The present invention can be developed into an active energy ray-curable lithographic ink composition widely used in the printing field due to the convenience of the characteristics of the instant hardening.

The active energy ray in the present invention refers to ultraviolet rays, electron beams, alpha rays, beta rays, Free radiation such as gamma rays. When the ultraviolet ray is used as the active energy ray to form a cured coating film, it is preferred to add a photopolymerization initiator to the active energy ray-curable composition of the present invention to improve the hardenability. Further, a photosensitizer may be added as needed to improve the hardenability. On the other hand, in the case of using free radiation such as electron beam, alpha ray, beta ray, or gamma ray, it can be quickly hardened without using a photopolymerization initiator or a photosensitizer, so that it is especially unnecessary to add Photopolymerization initiator or photo sensitizer. In the field of printing, ultraviolet rays and electron beams are frequently used, and ultraviolet rays are widely used. The ultraviolet light source that emits ultraviolet light is placed inside the printing machine, and the ink printed on the printing paper passes through the light directly under the lamp, and is irradiated with ultraviolet energy, thereby being instantly hardened. The present invention can be utilized regardless of whether a photopolymerization initiator or a photosensitizer is used.

(Adaptation of active energy ray-curable printing ink composition)

The preferred content of the main component in the active energy ray-curable printing ink composition of the present invention is as follows.

1) Organic pigments and/or inorganic pigments 5 to 50% by mass.

2) 0.1 to 30% by mass of an extender pigment containing at least one selected from the group consisting of calcium carbonate, magnesium carbonate and barium sulfate.

3) Polymerizable acrylate monomer 10~50% by mass

4) Adhesive resin 5 to 40% by mass.

5) Photopolymerization initiator 0 to 20% by mass.

6) Auxiliary agents such as waxes, dispersants, and polymerization inhibitors are 0 to 10% by mass.

7) The total amount of additives on the whole surface is 0.01 to 0.5% by mass.

An organic pigment and/or an inorganic colored pigment, an auxiliary agent containing at least one selected from the group consisting of calcium carbonate, magnesium carbonate, and barium sulfate, an auxiliary agent such as a wax, a dispersing agent, and a polymerization inhibitor, and a whole surface auxiliary agent can be used. Further, the polymerizable acrylate monomer and the photopolymerization initiator can be used as previously known, and are not particularly limited. As the binder resin, epoxy acrylate, urethane acrylate, or polycondensate which is an oligomer having a polymerizable group such as an acrylate group can be used. An ester acrylate or the like, or a diallyl phthalate resin or a polyester resin which is a non-polymerizable resin. Such a binder resin is high in hydrophilicity and tends to be excessively emulsified, and it is preferred to reduce the amount of water supplied to the plate to perform printing. Since the active energy ray-curable printing ink composition of the present invention has a high overall surface effect, it is possible to suppress printing stains even if the supply amount of water to the stencil is reduced.

(Manufacture of printing ink composition)

In order to produce the printing ink composition of the present invention, a pigment, a vehicle, an auxiliary agent, and the like may be mixed according to a usual method, and the above-mentioned full-surface auxiliary agent may be added in the step of dispersing the ink to be produced.

In the step of dispersing the ink, a three-roll mill or a bead mill or the like is used, and a step of finely pulverizing and dispersing the particles contained in the pigment or the auxiliary agent is necessary. Thereby, the entire surface builder used in the present invention is finely dispersed into the printing ink, and it is possible to try to contain no coarse particles.

(the degree of training of the printing ink composition)

In order to add a coplanar auxiliary to the printing ink composition of the present invention, ink dispersion is carried out by a three-roll mill or the like. In this case, the depth of the groove at the position A of the degree of training in the training degree test described in JIS K5701-1 is preferably 7.5 μm or less (3 or less on a scale).

The degree of training refers to the degree of fineness of the particulate material such as a pigment or an auxiliary agent dispersed in the ink. The evaluation is based on the 4.3 degree of training in JIS K5701-1 (established on January 20, 2000). The method.

According to the JIS regulations, the sample is placed at the deepest point on the instrument panel on the instrument panel of the grind meter which has a linear change from 25 μm to 0 μm, and a film of the sample is prepared in the tank using a squeegee. On the dashboard, the scale corresponding to the depth of the groove is usually 0 to 10. For example, at a depth of 25 μm, the scale is 10, and at a depth of 10 μm, the scale is 4, and the scale is 7.5 μm, and the scale is 3.

If particles are present in the sample, the particles are scraped off by the squeegee and moved, thereby creating a line in a groove shallower than the size (diameter, etc.) of the particles. Observe the line and it will appear in a slot 3 The position of the scale at the line above 10 mm for the strip is set to A, and the position where the scale of 10 or more points is set to B.

In the present invention, it is preferable that the depth of the groove at the position A is 7.5 μm or less. This corresponds to a position of 3 on a scale.

If the depth is equal to or less than the degree of training, that is, the depth of the groove at the position A is 7.5 μm or less, the printing ink is transferred to the paper without any problem in normal printing. . When the depth of the groove of the position A is more than 7.5 μm, coarse particles having a diameter of more than 7.5 μm are formed in a large amount, and it becomes easy to be generated in the white portion of the untransferred printing ink on the paper.

(Manufacturing method using composite)

In order to add the whole-surface auxiliary agent to the printing ink composition of the present invention, in addition to the method of performing ink-dispersion dispersion by the above-described three-roll mill or the like, a whole-surface auxiliary agent, a vehicle, and other additives or auxiliary agents may be separately prepared in advance. The composite is used as one of the raw materials for the production of the printing ink composition of the present invention. Here, the composite satisfies all of the following (e), (f), and (g).

(e) containing one or more selected from the group A above.

(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 training and strength test described in JIS K5701-1 is 7.5 μm or less.

Further, as for the whole-surface auxiliary belonging to Group A, the user is preferably as described above.

The measurement of the water content of the printing ink composition of the present invention is carried out by the Karlsfeld method. Hereinafter, an example of the measurement method will be listed.

The solvent of the Karlscher's method itself is a mixed solvent containing toluene: Aquamicron GEX (manufactured by API Co., Ltd.) = 2:1 (capacity ratio).

The mixed solvent was placed in a moisture meter to be in a water-free state, and then used for measurement of moisture content.

The solvent used for the dissolution of the sample was THF (tetrahydrofuran). A solution obtained by dissolving 2 g of the sample in 8 g of THF was used for the titration of the Karlsfeld method.

The water content of the solution in which the sample was dissolved and the THF in which the sample was dissolved was measured by a Karl Fischer moisture meter, and the water content in the sample was calculated.

As an example of determining the water content, the case of using the red pigment carmine 6B (C.I. Pigment Red 57:1) will be described. Beta type carmine 6B is commonly used for printing ink applications.

In the case of β-type carmine 6B, if you refer to the crystal transformation of Carmine 6B (No. 1) (Color Materials Association, Color Materials Association, 1984, 249-254), etc., it is known that relative to one molecule The β-carmine 6B contains one molecule of crystal water. Since the crystal water is detached at around 200 ° C, it is not included in the water content.

Since the molecular weight of the β-carmine 6B is 442, the moisture content of the β-carmine 6B is 0.04 parts by mass.

When the moisture content of the printing ink composition containing only 20% β carmine 6B as a raw material of crystal water is measured by a Karl Fischer moisture meter, and a value of 1.25 mass% is obtained, the moisture from the inner crystal water becomes 0.8 mass. %(=20×0.04). The water content of the present invention is 0.45 mass% (= 1.25 - 0.8), which satisfies the water content of 0.5% by mass or less for obtaining the effect of the printing ink composition of the present invention.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples.

(Preparation of resin varnish (A) for printing ink)

44 parts by mass of Beckacite F-8305 (weight average molecular weight: 45,000, manufactured by DIC Co., Ltd.) and 15 parts by mass of soybean refined oil (manufactured by Nisshin OilliO Co., Ltd.) were added as rosin-modified phenol resin, and the temperature was raised to 220 under a nitrogen stream. After heating and stirring for 1.5 hours at ° C, 39.7 parts by mass of AF solvent No. 7 (petroleum solvent: manufactured by JX Nippon Mining & Energy Co., Ltd.) was added, and the mixture was stirred for 30 minutes, and then cooled to 140 °C.

After cooling, 1.0 part by mass of an ethyl acetoacetic acid aluminum diisopropylate solution diluted with 50% of the AF solvent was added, and the mixture was heated to 160 ° C and heated and stirred for 1.0 hour, and then cooled to 140 ° C to add BHT (Honzhou Chemical ( After the 0.3 part by mass of the company was manufactured and stirred, a varnish (A) was obtained.

(Preparation of sodium hexametaphosphate composite matrix (B))

Sodium hexametaphosphate is manufactured by Taiyang Chemical Industry Co., Ltd. The following blending ratio (100 parts by mass in total of 1 to 3) was used to carry out ink rolling using a three-roll mill, and the blending degree test described in JIS K5701-1 was used to form a composite matrix. The scale of the position A is adjusted to be 3 or less (the depth of the groove of the scale 3 is 7.5 μm).

(Preparation of diammonium hydrogen citrate complex matrix (C))

The diammonium hydrogen citrate system is manufactured by Komatsuya (shares). The following blending ratio (100 parts by mass in total of 1 to 3) was used to carry out ink rolling using a three-roll mill, and the blending degree test described in JIS K5701-1 was used to form a composite matrix. The scale of the position A is adjusted to be 3 or less.

(Preparation of printing ink of Example 1)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. also, Sodium hexametaphosphate is manufactured by Taiyang Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 2)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, magnesium carbonate is a basic magnesium carbonate TT manufactured by Naikai Salt Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 3)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, barium sulfate is a precipitated barium sulfate SS-50 manufactured by Nippon Chemical Industry Co., Ltd. also, Sodium hexametaphosphate is manufactured by Taiyang Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 4)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. Further, sodium pyrophosphate is tetrasodium pyrophosphate (anhydrous) manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 5)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less. Thereafter, 0.3 parts by mass of distilled water was added to the printing ink to carry out mixing and dispersion.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.44% by a Karl Fischer moisture meter.

(Preparation of printing inks of Examples 6 and 7)

The following blending ratio (100 parts by mass of each of Examples 6 and 7) was used to carry out ink rolling using a three-roll mill, and the printing ink was prepared by the strength test described in JIS K5701-1. The scale of the position A of the training level is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, the calcium carbonate is NEOLIGHTSA-300 manufactured by Takehara Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 8)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. In addition, 85% of the phosphoric acid is a reagent grade phosphoric acid manufactured by Wako Pure Chemical Industries, Ltd.

The water content of the printing ink was confirmed to be 0.18% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 9)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. Further, the citric acid is anhydrous citric acid manufactured by Komatsuya (stock).

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 10)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, calcium carbonate is a calcene T-DD manufactured by Shiraishi Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 11)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, calcium carbonate is a colloidal calcium carbonate T-DD manufactured by Shiraishi Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 12)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, calcium carbonate is a colloidal calcium carbonate T-DD manufactured by Shiraishi Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 13)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, calcium carbonate is a colloidal calcium carbonate T-DD manufactured by Shiraishi Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 14)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Example 15)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Comparative Example 1)

The ink was pulverized by a three-roll mill at the following blending ratio, and the degree of the position A of the degree of the degree of the degree of the degree of the printing ink produced was 3 or less by the strength test described in JIS K5701-1. Adjustment.

Further, phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC (Stock). Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Comparative Example 2)

The raw materials of the following 1) to 4) were prepared, and the ink was rolled using a three-roll mill, and the degree of the degree of the degree of the degree of the degree of the printing ink produced was measured by the strength test described in JIS K5701-1. Adjust to be 3 or less.

Thereafter, 5) sodium hexametaphosphate was added. Furthermore, the ink after the addition was not performed. The scale of the position A of the printing ink after the addition of sodium hexametaphosphate is 8 or more.

Further, phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC (Stock). Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Comparative Example 3)

The raw materials of the following 1) to 4) were prepared, and the ink was rolled using a three-roll mill, and the degree of the degree of the degree of the degree of the degree of the printing ink produced was measured by the strength test described in JIS K5701-1. Adjust to be 3 or less.

Thereafter, 5) of diammonium hydrogen citrate was added. Furthermore, the ink after the addition was not performed. The scale of the position A of the printing ink after the addition of diammonium hydrogen citrate is 8 or more.

Further, phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC (Stock). Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. Further, diammonium hydrogen citrate is manufactured by Komatsuya (shares).

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

(Preparation of printing ink of Comparative Example 4)

The raw materials of the following 1) to 5) were prepared, and the ink was rolled using a three-roll mill. According to the training and strength test described in JIS K5701-1, the scale of the position A of the degree of training of the produced printing ink is adjusted to be 3 or less. Thereafter, 0.5 part by mass of distilled water was added to the printing ink to carry out mixing and dispersion.

Further, phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC (Stock). Further, the calcium carbonate is NEOLIGHT SA-300 manufactured by Takehara Chemical Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.64% by a Karl Fischer moisture meter.

(Preparation of printing inks of Comparative Examples 5 and 6)

The raw materials of the following 1) to 5) were prepared, and the ink was rolled using a three-roll mill. According to the training and strength test described in JIS K5701-1, the scale of the position A of the degree of training of the produced printing ink is adjusted to be 3 or less. Thereafter, 0.5 part by mass of distilled water was added to the printing ink to carry out mixing and dispersion.

Further, phthalocyanine blue is FASTOGEN Blue FA5375 manufactured by DIC (Stock). Further, the calcium carbonate is NEOLIGHTSA-300 manufactured by Takehara Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.64% by a Karl Fischer moisture meter.

(Comparison of printing ink of Comparative Example 7)

The following blending ratio (100 parts by mass in total of 1 to 5) was used to carry out ink rolling using a three-roll mill, and the degree of training of the prepared printing ink was carried out by the strength test described in JIS K5701-1. The scale of the position A is adjusted to be 3 or less.

Further, the phthalocyanine blue system uses FASTOGEN Blue FA5375 manufactured by DIC Corporation. Further, calcium carbonate is a colloidal calcium carbonate T-DD manufactured by Shiraishi Industry Co., Ltd. Further, sodium hexametaphosphate is manufactured by Taiyo Chemical Industry Co., Ltd.

The water content of the printing ink was confirmed to be 0.14% by a Karl Fischer moisture meter.

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

(Stain resistance test)

The stain resistance test was evaluated using a Roland 704 printer manufactured by Manroland. The printing is performed in a state where the dampening water supply dial at the time of starting printing is fixed, and the determination is made based on whether or not stains are generated on the printing paper surface. The test system uses 35% of the area of the drawn line, 35% of the part of the drawn line area, and 35% of the non-lined part.

The basis of the evaluation is as follows.

90% of the line area, 20% of the line area and no stains in the non-line part ◎, 20% of the line area and no stains in the non-line part ○, no stain on the line, but painting A part of the line area of 20% has stains △, and the non-line part also has stains ×.

The conditions for carrying out the printing test are as follows.

Printing machine: Roland 704 printing machine (separate continuous water supply method) (manuland company)

Dampening water: Presarto SD100 (made by DIC GRAPHICS (share)) 1.5% concentration

Printing speed: 8,000 sheets / hour

Room temperature 25 ° C, humidity 55%

Printing paper: OK Top Coat N (made by Oji Paper (share))

(paper quality confirmation test)

Using a double separation roll, 0.125 cc of ink was spread on OK Golden Rattan single-sided coated paper (manufactured by Oji Paper Co., Ltd.) in RI Tester (manufactured by Akira Seisakusho Co., Ltd.). Thereafter, it was placed in a dryer at an ambient temperature of 100 ° C for 20 seconds to be heat set and visually observed. Confirm the status of the printed paper. The case where a large amount of the portion where the ink was not transferred was set to x, and the case where the portion where the ink was not transferred was set to ○.

(Ink test)

In a room where the air is adjusted to 25 ° C, the rotational viscometer described in the item 4.2 of the adhesion of JIS K5701-1 (lithographic ink test method) is used, the ink amount is 1.32 ml, the roll temperature is 42 ° C, and the number of rotations of the rolls is 1200 rpm. Run for 10 minutes under conditions. Before the start of the operation, the white paper was fixedly placed at a position 10 cm away from the roller, and the ink scattered during the operation was captured, and the stain of the white paper was judged by visual inspection. The evaluation criteria are as follows.

The amount of scattering is extremely small. 5. The amount of scattering is less than usual. 4. The amount of scattering is the normal level. 3 The amount of scattering is more than usual. 2. The amount of scattering is extremely large.

(liquidity test)

The fluidity was evaluated by a method using a parallel plate viscometer as described in 4.1 of JIS K5701-1 in a room managed at 25 ° C ± 2 ° C. The D value (mm) corresponding to the stretch diameter after 60 seconds was measured. In order to improve the transferability of the ink on the printing machine, the D value is preferably 38 or more. When the D value is too large, the emulsification amount is increased or the ink mist is deteriorated. Therefore, it is preferably 42 or less.

As shown in Examples 1 to 15, good stain resistance was obtained by adding sodium hexametaphosphate or diammonium hydrogen citrate and making the water content in the printing ink less than 0.5%. In Examples 6 and 7, the same results were obtained in the case of adding in the form of a composite matrix and making the moisture content in the printing ink less than 0.5%.

In Comparative Examples 2 and 3 in which sodium hexametaphosphate or diammonium hydrogen citrate was added and the ink was not pulverized, the added one remained as a foreign matter, and in the foreign matter confirmation test, it became ×. In Comparative Example 7 in which the extender pigment was not added, the ink mist was higher than usual.

[Industrial availability]

According to the present invention, the entire surface effect of the stain of the non-line portion is prevented from being improved, and the cleaning time and the paper loss of the printing machine caused by the stain are greatly reduced.

Claims (4)

A printing ink composition which satisfies all of the following (a) to (d): (a) contains one or more selected from the group A below; and (b) contains a material selected from the group consisting of calcium carbonate, magnesium carbonate and barium sulfate. One or more of the constituent pigments in the group; (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 training and hardness test of JIS K5701-1 7.5 μm or less; (Group A) phosphoric acid, ammonium phosphate, alkali metal phosphate, alkaline earth metal dihydrogen phosphate, citric acid, ammonium citrate, alkali metal citrate, magnesium citrate salt. The printing ink composition of claim 1, wherein in the above group A, the phosphoric acid is selected from the group consisting of phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, tetrapolyphosphoric acid, One or more of the group consisting of pentaphosphoric acid, hexaphosphoric acid, trimellitic acid, tetrametaphosphoric acid and hexametaphosphoric acid, the ammonium phosphate salt is selected from the group consisting of triammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate and phosphoric acid. One or more of the group consisting of sodium hydrogen hydride, the alkali metal phosphate is selected from the group consisting of lithium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, dihydrogen phosphate Potassium, sodium pyrophosphate, disodium dihydrogen pyrophosphate, potassium pyrophosphate, potassium hydrogen pyrophosphate, potassium polyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, potassium metaphosphate, sodium metaphosphate, three One or more of the group consisting of sodium metaphosphate, sodium hexametaphosphate, sodium phosphite and sodium hypophosphite, the alkaline earth metal dihydrogen salt of phosphoric acid is selected from the group consisting of calcium dihydrogen phosphate, dihydrogen phosphate and magnesium dihydrogen phosphate. One or more of the group, ammonium citrate Is selected from the group consisting of diammonium hydrogen citrate and ammonium citrate composed of One or more of the group, the alkali metal salt of citric acid is selected from the group consisting of trisodium citrate, disodium citrate, monosodium citrate, tripotassium citrate, dipotassium citrate, monopotassium citrate, sodium dihydrogen citrate And one or more of the group consisting of potassium dihydrogen citrate and disodium hydrogen citrate. A method for producing a printing ink composition according to claim 1, wherein a composite material satisfying all of the following (e) to (g) is used as one of 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 training and strength test described in JIS K5701-1 is 7.5 μm or less. A printed matter produced by using the printing ink composition of claim 1 or 2.