JP7161434B2 - Plasma-curable ink composition, additive for plasma-curable ink composition, method for producing printed matter, and method for printing - Google Patents

Description

The present invention provides a plasma-curable ink composition containing a "photocatalyst compound" and/or a "composite of a metal component and a photocatalyst compound", a "photocatalyst compound" and/or a "composite of a metal component and a photocatalyst compound". The present invention relates to an additive for a plasma-curable ink composition containing the plasma-curable ink composition, a method for producing a printed matter using the plasma-curable ink composition, and a printing method using the plasma-curable ink composition.

Typical printing methods currently used include offset printing, gravure printing, flexographic printing, screen printing, and inkjet printing. Among these, the offset printing method is mainly used when printing a large amount of printed matter quickly.
Offset printing is a printing method that utilizes the property of oil-based offset printing ink to repel water, and is a printing method that uses a printing plate without unevenness. This printing plate has lipophilic image areas and hydrophilic non-image areas instead of unevenness, and in printing, the non-image areas are first wetted with dampening water supplied to the printing plate. When the offset printing ink is supplied to the printing plate, it does not repel and adhere to the non-image areas that are moistened with dampening water and adheres only to the oleophilic image areas. Thus, an image is formed by offset printing ink on the surface of the printing plate, and printing is performed by sequentially transferring the image to a blanket and a substrate (paper is often selected as the substrate).

In addition to offset printing using dampening water as described above, a waterless offset printing method using a printing plate having a non-image portion formed with a silicone resin has also been put to practical use. In this method, the silicone resin repels the offset printing ink and forms a non-image area. Except for these points, waterless offset printing is also a printing method common to offset printing using dampening water. In this specification, the term "offset printing" may be used as a concept including a printing method using dampening water and a waterless printing method.
The printed matter obtained by printing must be in a state in which the ink composition adhering to the surface is sufficiently dried and cured. If the ink is not sufficiently dried and hardened and fixed, set-off may occur when printed matter is piled up, or ink may adhere when the printed matter is touched with a finger. In such a case, it cannot be sent to a post-process or distributed as a product. Therefore, after printing, a step of drying and curing the ink composition adhering to the surface of the printed matter to fix it on the surface of the base material is required.

As means for drying and curing the ink coating adhered to the surface of the printed material to fix it on the surface of the base material, one of the four methods of evaporation, permeation, oxidative polymerization, and photopolymerization is mainly used. For example, in the offset printing method, the method of drying and curing and fixing the ink coating film is the penetration drying method typified by newspaper printing, the oxidative polymerization method typified by sheet-fed printing, the light curing method using ultraviolet (UV), etc. An evaporative drying method typified by off-wheel printing is the mainstream. In addition, new drying and curing methods such as an LED curing method and an energy beam (EB) curing method have been developed as an application of the ultraviolet curing method in order to save energy and deal with environmental loads.
The method of drying and curing the ink film by evaporation uses mineral oil, which is a volatile component, as a solvent component, and has relatively high productivity. However, since many raw materials derived from minerals are used, the degree of biomass is low, the environmental load due to the release of VOCs (volatile organic compounds) into the atmosphere is large, and there are concerns about safety.
The method of drying, hardening, and fixing the ink film by permeation is a method in which the oil component contained in the ink film adhering to the surface of the printed matter permeates into the interior of the printed matter to dry the surface. Although the drying and hardening state can be obtained relatively quickly, the solvent must quickly permeate the paper, so the paper is limited to rough paper, etc., and it is not suitable for printing that requires high cosmetic properties. . In addition, since the ink coating spreads on the surface of the printed matter, halftone dots tend to be thickened.

From this point of view, there is a tendency to adopt a method of drying and curing an ink coating film by oxidative polymerization or photopolymerization to fix it when obtaining a printed matter that requires high cosmetic properties.
For example, the ink composition used in the method of drying and curing the ink film by oxidation polymerization uses plant-derived unsaturated oil with a high iodine value such as linseed oil as the oil component, and the oxygen contained in the air Oxidative polymerization of unsaturated oils results in the formation of non-sticky (that is, dry) coatings. This ink composition uses a large amount of plant-derived raw materials to increase the degree of biomass, and the oil component penetrates into the interior of the printed matter to suppress the release of VOC components into the atmosphere. It can be obtained with low environmental impact. According to the method of drying the ink film by oxidative polymerization, there is no process of permeating the oil component inside the printed matter or releasing VOC into the atmosphere, so it is possible to produce printed matter with high aesthetics and low environmental impact. can be obtained with
However, the chemical reaction for oxidative polymerization of the unsaturated oil requires a relatively long time, resulting in poor quick-drying properties and possibly causing problems due to poor fixation due to insufficient drying and hardening of the ink film.

In view of the above background, printing by a photopolymerization method, in which the printed matter is dried and fixed by irradiating the printed matter with light such as ultraviolet rays, has been actively performed in recent years. A main ink composition used in this method contains a monomer or oligomer having an ethylenically unsaturated bond and a photopolymerization initiator that generates radicals upon irradiation with active energy rays such as ultraviolet rays. By irradiating active energy rays after printing, radical polymerization occurs instantaneously to form a non-sticky (that is, dry) coating film, which does not release a large amount of VOCs into the atmosphere. In recent years, ink compositions that employ such a drying method have been proposed with various compositions (see, for example, Patent Documents 1 and 2).
However, the ink composition used in the active energy ray irradiation method cannot increase the degree of biomass, and there are concerns about environmental load and safety, such as the possibility that monomers may remain in printed matter. Due to environmental and safety regulations that will become increasingly strict in the future, regulations on the use of monomers and the use of photopolymerization initiators are expected in the future.

The method of irradiating plasma after printing to dry/harden and fix the ink film is a new method. It is excellent in that it can suppress separation of from the printed matter. The drying and curing of the ink coating film of this method is achieved by causing the components in the ink composition to react with the energy of the plasma to increase the molecular weight. The plasma used at this time is classified into a direct type and a remote type according to the generation method. Plasma is formed by ionizing the gas present in the discharge space by causing discharge between electrodes, and the object to be irradiated with plasma (printed matter in the present invention) is directly sent into this discharge space to perform plasma irradiation. The method is direct type. The remote type is a method in which the raw material gas of the plasma is circulated from the outside to the inside of the discharge space, and the plasmified gas is circulated outside the discharge space to irradiate the plasma irradiation target (same as above).
The direct type is advantageous in terms of drying the ink composition, since the object to be irradiated can be irradiated with highly reactive plasma immediately after generation. However, a printing substrate such as paper can be damaged by passing through the discharge space. In addition, considering that the entrance and exit of the discharge space isolated from the outside are narrow, there is a possibility that the base material may clog due to fluttering in the vertical direction during the process of conveying the base material.
The remote type does not have the same problems as the direct type. However, the drying of the ink composition on the substrate may be insufficient due to effects such as a decrease in plasma reactivity accompanying movement of the plasma gas from the discharge space, diffusion of the plasma gas, and the like.

Patent Document 3 describes oxygen radical cross-linking polymerization of non-volatile sheet-fed offset ink used for sheet-fed offset printing by generating ions with atmospheric pressure plasma as a new drying and fixing method for oxidative polymerization type oil-based ink. It is proposed to promote the drying and fixing time to shorten the drying time. In the examples, TK Hi-Echo NV100 manufactured by Toyo Ink Mfg. Co., Ltd. is used as an oxidative polymerization oil-based ink containing no volatile organic compounds, and negative ions generated by plasma are brought into contact with the oxidative polymerization ink. It is However, since it takes several minutes for drying and fixing, there is a problem in terms of quick drying, and it is difficult to apply it to a method for printing in large quantities quickly.
Patent Document 4 discloses an image fixing method comprising a step of fixing an image on a recording medium using a recording agent containing a component that is cured by plasma treatment, by applying plasma treatment to the image. A method is proposed. Examples include offset inks containing carbon black, rosin modified phenolic resin, linseed oil, high boiling petroleum solvents and dryers, or dyes, styrene-acrylic acid-ethyl acrylate copolymers, glycerin, ethylene glycol and surfactants. It discloses forming a printed image with an inkjet ink containing an agent and applying plasma irradiation to fix the image.
U.S. Pat. No. 5,300,000 describes curing in a plasma discharge chamber various printing inks, which may contain oxidatively drying alkyd systems. It is not clear if there are any.
US Pat. No. 6,200,400 discloses coating a steel plate with a radiation curable composition comprising a urea-urethane oligomer, an acrylic compound and a photoinitiator and curing with a 0.6 second exposure to continuous light from an argon eddy current plasma arc. is described, but the biomass degree is low.
In Patent Document 7, a printing ink that contains at least a nonvolatile organic compound having a carboxyl group and does not contain a photopolymerization initiator is subjected to discharge between electrodes near atmospheric pressure (by irradiating plasma). An ink fixing method is described that includes an ink fixing step for fixing to the material, but the biomass content is low.
Patent Document 8 discloses a composition containing at least one of a polymerization initiator and a chain transfer agent, at least one radically polymerizable compound, and an ink containing at least one colorant, which is coated on a substrate. and plasma irradiation of the composition to form an image comprising a plasma-polymerized film is described, but has a low biomass content.
Patent Document 9 discloses an ink fixing method including at least an ink fixing step of fixing ink on a base material to a base material using discharge between electrodes near atmospheric pressure, wherein the ink contains at least polyvinylpyrrolidone. is described, but the biomass degree is low.
Patent Document 10 discloses a printed matter obtained by printing printing ink on printing paper and further surface-treating the printed surface, wherein (1) the printing ink contains a rosin resin, (2) the surface treatment is corona treatment, and flame It is a treatment or a plasma treatment, and the printed matter after the treatment has a specific surface resistance value of a specific value or less is described. However, in the examples, it is only described that the printed matter obtained by printing with the ink containing the organic solvent and stored for 24 hours is subjected to the plasma treatment. Therefore, it cannot be said that plasma processing (plasma irradiation) is performed.
None of the aforementioned Patent Documents 1 to 10 discloses the use of a "photocatalyst compound" and/or a "composite of a metal component and a photocatalyst compound" as components of the ink composition.

JP 2012-102217 A Japanese Patent No. 4649952 JP 2007-054987 A JP 2008-012919 A Japanese Patent Publication No. 2005-523803 JP-A-51-052494 JP 2007-106105 A JP 2013-10933 A JP 2008-297506 A JP 2015-140390 A

An object of the present invention is to obtain a plasma-curable ink composition which can shorten the drying and curing start time and which is excellent in the drying and curability of the ink composition coating film.
An object of the present invention is to obtain an additive for a plasma-curable ink composition that can shorten the drying and curing start time of the plasma-curable ink composition and improve the drying and curability of the ink composition coating film. and
The present invention provides a plasma-curable ink composition having high reactivity with respect to plasma, capable of obtaining a sufficiently dry state even when plasma generated by a remote-type plasma generator is used. , and a method for producing a printed matter and a method for printing using the same.
An object of the present invention is to construct a printing system that does not need to contain a volatile organic solvent (VOC) or the like, has a small environmental load, is excellent in safety, and has a high degree of biomass.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found that a plasma-curable ink composition containing a "photocatalyst compound" and/or a "composite of a metal component and a photocatalyst compound" can be applied for printing. It has been found that when the film is irradiated with plasma, the drying and curing start time is shortened and the drying and curing property of the ink composition coating film is improved.
In particular, even if the plasma-curing ink composition contains an animal or plant oil and/or an animal or plant oil derivative or is of the oxidation polymerization type, the "photocatalyst compound" and/or the "composite of the metal component and the photocatalyst compound By including the "body", the drying and curing start time is shortened, and the drying and curing properties of the coating film are further improved. As a result, the present inventors have found that a printing system using a plasma-curable ink composition that does not emit volatile organic solvents, has a small environmental burden, is excellent in safety, and has a high degree of biomass content can be constructed.
The present invention has been completed based on these findings, and specifically, it is as follows.
[1] A plasma-curable ink composition containing a photocatalyst compound and/or a composite of a metal component and a photocatalyst compound.
[2] The plasma-curable ink composition of [1], wherein the photocatalyst compound contains titanium oxide and/or zinc oxide.
[3] The plasma-curable ink composition of [1] or [2], wherein the metal component is at least one selected from metals, metal oxides and metal soaps.
[4] The plasma-curable ink composition of [1] to [3], further comprising a binder.
[5] The plasma-curing ink of [1] to [4], further comprising at least one selected from the group consisting of animal and plant oils and/or animal and plant oil derivatives, and liquid compounds having ethylenically unsaturated bonds. Composition.
[6] The plasma-curing ink composition of [5], wherein the animal or plant oil and/or animal or plant oil derivative is an animal or plant oil and/or animal or plant oil derivative having an iodine value of 80 or more.
[7] The animal or plant oil and/or animal or plant oil derivative is at least one selected from the group consisting of soybean oil, tung oil, linseed oil, castor oil, and modified products thereof, [5] or [6 ] plasma-curable ink composition.
[8] An additive for a plasma-curable ink composition, containing a photocatalyst compound and/or a composite of a metal component and a photocatalyst compound.
[9] A printing step of printing on a substrate using the plasma-curable ink composition of [1] to [7]; and a plasma irradiation step of fixing the ink composition by curing.
[10] The method for producing a printed matter according to [9], wherein the plasma is generated by a remote plasma generator.
[11] The plasma is generated by passing air, oxygen gas, nitrogen gas, carbon dioxide gas, or a mixed gas containing two or more selected from these, between electrodes during discharge. ] or the manufacturing method of the printed matter of [10].
[12] The ink composition for plasma curing of [1] to [7] is used for printing on a substrate, and then the surface of the printed ink composition is irradiated with plasma to cure the ink composition. A printing method that is fixed to a base material.

According to the present invention, when plasma irradiation is used as a means for drying and curing the ink composition, the drying and curing start time can be shortened, and the drying and curing properties of the ink composition coating film are further improved. A plasma curable ink composition with reactivity is provided.
According to the present invention, for a plasma-curable ink composition that uses plasma irradiation as a means for drying and curing the ink composition, the drying and curing start time when plasma is irradiated can be shortened, and the ink composition coating film can be formed. Provided is an additive for a plasma-curable ink composition that can further improve dry curability.
According to the present invention, a plasma-curable ink having high reactivity with respect to plasma can be obtained in a sufficiently dry state even when plasma generated by a remote-type plasma generator is used. A composition, and a method for producing and printing a printed matter using the composition are provided.
ADVANTAGE OF THE INVENTION According to this invention, the printing system using the ink composition for plasma hardening which does not discharge a volatile organic solvent, has a small environmental burden, is excellent in safety, and has a high degree of biomass can be constructed.

Hereinafter, the plasma-curable ink composition, the additive for the plasma-curable ink composition, the method for producing a printed matter, and the printing method of the present invention will be described. It should be noted that the present invention is not limited to the following embodiments and modes, and can be implemented with appropriate modifications within the scope of the present invention.
The plasma-curable ink composition of the present invention contains a "photocatalyst compound" and/or a "composite of a metal component and a photocatalyst compound". In addition, it may contain binders, animal and plant oils and/or animal and plant oil derivatives and/or conjugated polyene compounds, and may further contain other components such as liquid components and various additives.
The additive for the plasma-curable ink composition of the present invention includes a "photocatalyst compound" and/or a "composite of a metal component and a photocatalyst compound". In addition, it may contain binders, animal and plant oils and/or animal and plant oil derivatives and/or conjugated polyene compounds, and may further contain other components such as liquid components and various additives.
The plasma-curable ink composition of the present invention and the additive for the plasma-curable ink composition are described in detail below.

[Photocatalyst compound]
The photocatalyst compound contained in the plasma-curable ink composition of the present invention and/or the additive for the plasma-curable ink composition of the present invention is irradiated with light such as ultraviolet light or visible light and has a bandgap energy higher than that of the bandgap energy. Any semiconductor or the like can be used as long as it becomes an excited state by absorbing light energy and exhibits a photocatalytic action. According to studies by the present inventors, it has an unexpected property of promoting the polymerization reaction of the ink composition during plasma irradiation.
The reason why the "photocatalyst compound" and/or the "composite of the metal component and the photocatalyst compound" improves the curability of the ink composition during plasma irradiation is not necessarily clear. It is presumed that highly active chemical species such as radicals and superoxide anions are generated, and that such chemical species assist the drying and curing (polymerization, etc.) of the components contained in the plasma-curable ink composition.

The photocatalyst compound includes semiconductors such as various metal oxides, nitrides, sulfides, oxynitrides, oxysulfides, oxyfluorides, oxyfluorides, and oxynitride fluorides that exhibit photocatalytic activity. , for example, titanium oxide, titanium peroxide, tungsten oxide, niobium oxide, bismuth oxide, zinc oxide, tin oxide, iron oxide, copper oxide, vanadium oxide, gallium oxide, lithium titanate, strontium titanate. Not limited.
Titanium oxide is classified into rutile type and anatase type according to its crystal form. An anatase type titanium oxide is preferably used in the present invention. According to studies by the present inventors, anatase-type titanium oxide has a higher effect of accelerating the polymerization reaction during plasma irradiation than rutile-type titanium oxide.
Metal elements such as gold, silver, copper, platinum, rhodium, palladium, ruthenium, iridium, chromium, niobium, manganese, cobalt, vanadium, iron, and nickel; It may be doped with one or more halogens (lattice substitution), but is not limited to these. You may use a photocatalyst compound in combination of 1 type or 2 or more types.

The photocatalyst compound used in the present invention is preferably powdery. The photocatalyst compound may be kneaded with varnish to form a paste and added to the ink composition, or may be added and kneaded together with other pigment components during the production of the ink composition.
The average particle size of the photocatalyst compound is not particularly limited, but is usually 0.001 to 100 μm, preferably 0.01 to 50 μm, more preferably 0.05 to 5 μm in consideration of dispersion stability, fluidity, etc. be done.
The photocatalyst compound used in the present invention preferably has a small particle size. A photocatalyst compound with a small particle size has a large surface area and accelerates the curing reaction during plasma irradiation. An example of such a particle size is an average particle size of about 5 to 30 nm, more preferably about 5 to 20 nm, as determined by X-ray scattering, but is not particularly limited.
If the average particle size is less than 0.001 μm, it is difficult to produce, and problems may arise in terms of fluidity, dispersion stability, and the like. Moreover, when the average particle size is larger than 100 μm, problems may occur in terms of dispersion stability and the like.

The content of the photocatalyst compound is usually 0.001 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total plasma-curable ink composition. .
The content of the photocatalyst compound is usually 0.001 to 100% by mass, preferably 0.05 to 100% by mass, more preferably 0.1 to 100% by mass, based on the total amount of additives for the plasma-curable ink composition. 100% by mass.

[Composite of metal component and photocatalyst compound]
The composite of the metal component and the photocatalyst compound contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention is a composite of the metal component and the photocatalyst compound. be.

Any metal component can be used as long as it is a metal or a substance containing a metal component. Preferably, an elemental metal, a metal oxide, a metal nitride, a metal sulfide, a metal oxynitride, a metal oxysulfide, a metal nitrofluoride, a metal oxyfluoride, a metal oxynitride fluoride, an inorganic acid metal salt, an organic It is one or more selected from acid metal salts and organometallic compounds. One or more of metal elements, metal oxides, inorganic acid metal salts, and organic acid metal salts are particularly preferred. Moreover, the form may be any form such as particle, dispersion, solution, melt, precursor, gas, and the like.

Examples of metals include metals or semimetals of Groups 1 to 15 of the periodic table, such as alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (magnesium, calcium, strontium, barium, etc.), Transition metals (scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, iridium, platinum, gold ), zinc, cadmium, aluminum, gallium, indium, silicon, germanium, tin, lead, antimony, bismuth, tellurium, and astatine. Preferably, one or more of magnesium, titanium, vanadium, iron, nickel, copper, palladium, silver, platinum, gold, zinc, aluminum and tin are mentioned, and particularly preferably iron, nickel, copper, silver, zinc, One or more kinds of aluminum can be mentioned.

The simple metal is preferably one or more of iron, nickel, copper, silver, zinc and aluminum.
The metal oxide is preferably one or more of titanium oxide, zinc oxide, tungsten oxide, copper oxide, cuprous oxide, iron oxide, calcium oxide, silicon oxide and aluminum oxide.
The inorganic acid metal salt is one or more of the above metals, hydrogen halide (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide), carbonic acid, sulfuric acid, nitric acid, phosphoric acid, silicic acid, titanic acid, vanadic acid , with one or more inorganic acids such as molybdic acid. One or more of copper chloride, copper bromide, iron chloride, calcium carbonate, calcium phosphate (various apatites), copper nitrate, iron nitrate and iron sulfate are preferred.
Organic acid metal salts are salts of one or more of the above metals and one or more of organic acids such as carboxylic acid, sulfonic acid and phosphonic acid. One or more carboxylic acid metal salts are preferred, and one or more metal soaps are particularly preferred.
Any metal soap that is commonly used in ink compositions for printing may be used. A salt of one or more fatty acids having 8 or more carbon atoms and a metal is used. Fatty acids with 8 or more carbon atoms include, for example, nonanoic acid, decanoic acid, octylic acid (2-ethylhexanoic acid), naphthenic acid, neodecanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, isooctanoic acid, Tall oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, tung oil fatty acid, dimethylhexanoic acid, 3,5,5-trimethylhexanoic acid, dimethyloctanoic acid, resin acid and the like.

Metal soaps are composed of transition metals such as cobalt, manganese, copper, iron and zirconium, alkaline earth metals such as magnesium, calcium and barium, rare earth metals such as cerium, and metals such as zinc, lead and lithium. be done. preferably one or more of naphthenic acid, neodecanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, isooctanoic acid, tall oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, and tung oil fatty acid; and cobalt , manganese, zirconium, copper, iron, zinc, calcium, barium or lead. More preferably, one or more of naphthenic acid, neodecanoic acid, lauric acid, stearic acid, tall oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, and tung oil fatty acid, and cobalt, manganese, zirconium, copper, and iron. or one or more metals of zinc and one or more salts thereof are used. These metal soaps may be used alone or in combination of two or more.

As the photocatalyst compound constituting the composite of the metal component and the photocatalyst compound, one or more of the photocatalyst compounds described in the above [Photocatalyst compound] can be used without limitation.
The average particle size of the composite of the metal component and the photocatalyst compound is not particularly limited, but is usually 0.001 to 100 μm, preferably 0.01 to 50 μm, more preferably 0.01 to 50 μm, in consideration of dispersion stability, fluidity, etc. is 0.05 to 5 μm. If the average particle size is less than 0.001, it is difficult to produce, and problems may arise in terms of fluidity, dispersion stability, and the like. Moreover, when the average particle size is larger than 100 μm, problems may arise in terms of dispersion stability and the like.

The content of the metal component in the composite of the metal component and the photocatalyst compound is usually 0.1 to 99.9% by mass, preferably 1 to 99% by mass, based on the entire composite of the metal component and the photocatalyst compound. , more preferably 5 to 95% by mass, most preferably 10 to 90% by mass. If the content of the metal component is less than 0.1% by mass, the effect of the metal component will not be exhibited. If the content of the metal component is more than 99.9% by mass, light will not reach the photocatalyst compound, and the photocatalyst activity will be inhibited. Therefore, in any case, when the printed coating film of the plasma-curable ink composition is irradiated with plasma, it may be difficult to shorten the drying and curing start time and to improve the drying and curing properties of the coating film. be.
The content of the composite of the metal component and the photocatalyst compound is usually 0.001 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.05% to 5% by mass, relative to the entire plasma-curable ink composition. It is 1 to 3% by mass.
The content of the composite of the metal component and the photocatalyst compound is usually 0.001 to 100% by mass, preferably 0.05 to 100% by mass, based on the total amount of additives for the plasma-curable ink composition. More preferably, it is 0.1 to 100% by mass.

In addition, the amount of metal derived from the metal component contained in the composite of the metal component and the photocatalyst compound (metal pure content) is usually 0.0005 to 0.2% by mass with respect to the entire plasma-curable ink composition. , preferably 0.001 to 0.1% by mass, more preferably 0.001 to 0.05% by mass. When the amount of metal derived from the metal component contained in the composite of the metal component and the photocatalyst compound relative to the entire plasma-curable ink composition is outside the above range, the printed coating film of the plasma-curable ink composition is irradiated with plasma. In this case, it may be difficult to shorten the drying and curing start time and to improve the drying and curing properties of the coating film.

A composite of a metal component and a photocatalyst compound can be produced by a known method.
For example, (1) a method in which a metal component is attached, coated, adsorbed, reacted, etc. on the surface of a photocatalyst compound to form a composite, (2) a photocatalyst compound is attached, coated, adsorbed, etc. on the surface of a metal component, etc. (3) A method of mixing and compositing a metal component and a photocatalyst compound under conditions such as heat treatment and/or pressure treatment if necessary; (4) A metal component and a photocatalyst compound. After mixing with, a method of combining by heat treatment and / or pressure treatment if necessary, (5) after mixing the metal component and / or its precursor with the photocatalyst compound and / or its precursor, the metal component (6) a metal component and a photocatalyst compound in an ink composition or an additive for an ink composition; A method of adding and mixing a metal component and/or a precursor thereof and a photocatalyst compound and/or a precursor thereof to an ink composition or an additive for an ink composition so as to form a composite of is given.

The above methods (1) and (2) are carried out by mixing the metal component and the photocatalyst compound using known or commonly used stirring and dispersing means.
In the methods (3) and (4) above, the heat treatment may be treatment at a temperature at which the metal component and/or the photocatalyst compound melts or vaporizes, and the pressure treatment may be pressurization or pressure reduction treatment. good.
The metal component precursor used in the method (5) above can form a metal component by heat treatment or the like, and the photocatalyst compound precursor can form a photocatalyst compound by heat treatment or the like. . Examples of these include alkoxide compounds, hydroxides, carbonates, organometallic compounds and complexes of metals such as titanium, silicon, aluminum, zinc, germanium, gallium and iron.
In the method (6) above, the metal component and/or its precursor and the photocatalyst compound and/or its precursor are added to the ink composition or additive, and stirred and dispersed by means of stirring and dispersing means so as to form a composite. A complex is formed in the ink composition or the additive by mixing with the like.

When compositing by the above methods (1) to (6), the metal component and/or its precursor and the photocatalyst compound and/or its precursor are mixed using known or conventional stirring and dispersing means, Can be compounded. For mixing, for example, mixers such as paint shakers, butterfly mixers, planetary mixers, pony mixers, dissolvers, tank mixers, homomixers, homodispers, attritors, roll mills, sand mills, ball mills, bead mills, line mills, ultrasonic mills, Various mixing and dispersing devices such as mills such as dyno mills and shot mills, kneaders, mixer kneaders, and high-pressure impingement dispersers may be used, or such mixing and dispersing devices may not be used. Further, one type of mixing and dispersing device may be used to perform the stirring and dispersing treatment once or multiple times, or two or more types of mixing and dispersing devices may be used in combination to perform the stirring and dispersion treatment multiple times. If necessary, liquid components and various additive components may be further added and stirred and dispersed using the above mixing and dispersing device when performing the stirring and dispersing treatment a plurality of times.
The form of the metal component and/or its precursor at the time of compositing is not particularly limited. A solution state or a gas state is preferred. In addition, the form of the photocatalyst compound and/or its precursor at the time of compositing is not particularly limited. It is preferably in a solution state or a gas state.

[binder]
The binder that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention is a component that functions as a binder that fixes the pigment component on the surface of the printing paper. It is also a component used to disperse the pigment component in the ink composition. Resins and curable compounds having an ethylenically unsaturated bond, which are used as binders and binders in the field of ink compositions, can be used without particular limitation, and one or a mixture of two or more of these can be used. .
Examples of binders include acrylic resins, polyester resins, styrene resins, polyolefin resins, epoxy resins, polyurethane resins, phenol resins, rosin resins, block polymers, graft polymers (core-shell polymers), and acrylic-modified phenols. resin, rosin-modified phenolic resin, rosin-modified maleic acid resin, rosin-modified alkyd resin, rosin-modified petroleum-based resin, rosin ester-based resin, petroleum-based resin-modified phenolic resin, alkyd-based resin, vegetable oil-modified alkyd-based resin , petroleum-based resins, and hydrocarbon-based resins (polybutene, polybutadiene, etc.), having a weight average molecular weight of 500 to 300,000.
These resins are preferably acrylic resins, polyester resins, polyolefin resins, polyurethane resins, phenolic resins, rosin resins, acrylic-modified phenolic resins, rosin-modified phenolic resins, and rosin-modified maleic resins. , rosin-modified alkyd-based resin, rosin-modified petroleum-based resin, rosin ester-based resin, petroleum-based resin-modified phenol-based resin, alkyd-based resin, and vegetable oil-modified alkyd-based resin. Particularly preferably, one or more selected from the group consisting of rosin-modified phenol-based resins, rosin-modified maleic acid-based resins, rosin-modified alkyd-based resins, rosin ester-based resins, alkyd-based resins, and vegetable oil-modified alkyd-based resins are used. . Moreover, from the viewpoint of quick drying during plasma irradiation, the resin preferably has an acid value of 10 mgKOH/g or more.

Among these resins, the group consisting of rosin-modified phenolic resins and rosin-modified maleic resins having a weight average molecular weight of 10,000 to 150,000 from the viewpoint of pigment dispersibility, print quality, and stable printability over a long period of time. It is preferable to use at least one selected. It is also preferable to use these resins together with an alkyd resin in order to improve the dispersibility of the pigment component and to improve the reactivity during plasma irradiation. In this case, it is preferable to use about 3 to 10 parts by mass of the alkyd resin with respect to a total of 100 parts by mass of the rosin-modified phenolic resin and the rosin-modified maleic acid resin.

A fatty acid-modified rosin-based resin can also be used as a preferred binder. A fatty acid-modified rosin-based resin is obtained by mixing and reacting a fatty acid-modified material and a rosin-based resin.
Fatty acid-modified materials used in the production of fatty acid-modified rosin resins include, for example, decanoic acid, lauric acid, myristic acid, octanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and eleostearin. Acid, acetic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, citraconic anhydride, acrylic acid, methacrylic acid, and other natural or synthetic fatty acids having about 2 to 30 carbon atoms; , linseed oil, castor oil, sunflower oil, safflower oil, corn oil, cottonseed oil, rice bran oil, rapeseed oil, canola oil, perilla oil, sesame oil, camellia oil, olive oil, peanut oil, grapeseed oil, coconut oil , tall oil, palm oil, palm kernel oil, beef tallow, horse oil, lard, chicken oil, fish oils such as sardines and saury, whale oil, shark oil, lanolin, mink oil, beeswax and other animal and plant oils; Derivatives (modified products of animal and plant oils such as oxidized polymerized oil (boil oil), heat polymerized oil (stand oil), dehydrated products and esterified products); and one or more of these can be used. .

Here, the esterified animal and plant oils are generally obtained by transesterification of animal and plant oils, which are triglycerides of fatty acids, with alcohols, and are preferably stearic acid, isostearic acid, and hydroxystearic acid. Animal and plant oils composed of C14-30 saturated or unsaturated fatty acids such as acids, oleic acid, linoleic acid, linolenic acid, and eleostearic acid, and C1-10 linear or branched monoalcohols It is a fatty acid ester derived from

Such modified animal and plant oils include, for example, polymerized soybean oil, polymerized linseed oil, polymerized castor oil, polymerized tung oil, dehydrated castor oil, polymerized dehydrated castor oil, and the like. ) Heat polymerized oil (stand oil), dehydrated product; soybean oil methyl ester, soybean oil ethyl ester, soybean oil butyl ester, soybean oil isohexyl ester, linseed oil methyl ester, linseed oil ethyl ester, linseed oil butyl ester, linseed Oil isohexyl ester, tung oil methyl ester, tung oil ethyl ester, tung oil butyl ester, tung oil isohexyl ester, palm oil methyl ester, palm oil ethyl ester, palm oil butyl ester, palm oil isohexyl ester, etc. fatty acid ester;
The fatty acid-modified material is preferably coconut oil or one having an iodine value of 80 or more, and particularly preferably coconut oil, tung oil, soybean oil, tall oil, linseed oil, castor oil, safflower oil, perilla oil, polymerized oil. At least one of soybean oil, polymerized linseed oil, polymerized castor oil, polymerized tung oil, polymerized dehydrated castor oil, dehydrated castor oil, soybean oil butyl ester, linseed oil butyl ester, and tung oil butyl ester is used.

Rosin-based resins used in the production of fatty acid-modified rosin-based resins include, for example, unmodified rosins such as wood rosin, gum rosin and tall oil rosin, and modification of these unmodified rosins by polymerization, disproportionation, stabilization, hydrogenation, etc. Polymerized rosin, disproportionated rosin, stabilized rosin, hydrogenated rosin, rosin chemically modified by introducing various functional groups, rosin ester resin, rosin alcohol resin, rosin resin metal salt, etc. can be used, and one or a mixture of two or more thereof can be used. Among these, one or more of unmodified rosin, polymerized rosin ester, rosin ester, disproportionated rosin, and rosin-based resin metal salt are preferred, and unmodified rosin, polymerized rosin ester, and rosin-based resin are particularly preferred. one or more metal salts.

The weight average molecular weight of the rosin-based resin is usually in the range of 1,000 to 200,000, preferably 10,000 to 150,000, particularly preferably 15,000 to 100,000.
The amount of fatty acid modification (amount of fatty acid introduced) in the fatty acid-modified rosin resin is generally 5 to 50% by mass, preferably 10 to 40% by mass, particularly preferably 10 to 20% by mass. If it is less than 5% by mass, the effect of fatty acid modification may be insufficient and the curability of the coating film may be lowered.

As a binder, an oligomer and/or polymer having an ethylenically unsaturated bond may be used. Oligomers having ethylenically unsaturated bonds are epoxy-modified (meth)acrylates exemplified by esters of hydroxyl groups and (meth)acrylic acid generated after the epoxy groups contained in epoxy compounds such as epoxy resins are ring-opened with acids or bases. ) acrylates, rosin-modified epoxy acrylates, polyester-modified (meth)acrylates exemplified by esters of (meth)acrylic acid and terminal hydroxyl groups of polycondensates of dibasic acids and diols, terminal hydroxyl groups of polyether compounds and (meth) ) Polyether-modified (meth)acrylates exemplified by esters with acrylic acid, urethane-modified (meth)acrylates exemplified by esters of terminal hydroxyl groups and (meth)acrylic acid in condensates of polyisocyanate compounds and polyol compounds etc. can be given. Such oligomers are commercially available, for example, Ebecryl series from Daicel Cytec, CN, SR series from Sartomer, Aronix M-6000 series, 7000 series, 8000 series from Toagosei, Aronix M -1100, Aronix M-1200, Aronix M-1600, NK Oligo manufactured by Shin-Nakamura Chemical Co., Ltd., and the like. These oligomers can be used alone or in combination of two or more.
Examples of polymers or oligomers having ethylenically unsaturated bonds include polydiallyl phthalate, acrylic resins having unreacted unsaturated groups, acrylic-modified phenolic resins, and the like. Among these, polydiallyl phthalate can be preferably used. In this specification, "(meth)acrylate" means "acrylate and/or methacrylate", and "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid".

The curable compound having an ethylenically unsaturated bond is a monomer capable of curing the ink composition by being polymerized by plasma irradiation, and may be a monofunctional monomer having one ethylenically unsaturated bond in the molecule, or , bifunctional or higher monomers having two or more ethylenically unsaturated bonds in the molecule.
Di- or higher-functional monomers can crosslink molecules when the ink composition is cured, and are therefore useful for increasing the curing speed and forming a strong coating film. Although the monomer does not have the above-mentioned cross-linking ability, it is useful for reducing curing shrinkage due to cross-linking. One or two or more of the above monomers can be used in arbitrary combination.

Any conventionally known monofunctional monomer can be used without limitation. For example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, t-butyl acrylate, amyl (meth)acrylate, isoamyl (meth) acrylate, isooctyl (meth) acrylate, isostearyl (meth) acrylate, isodecyl (meth) acrylate, isobutyl acrylate, isomyristyl (meth) acrylate, octadecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, di Cyclopentenyl (meth)acrylate, stearyl (meth)acrylate, decyl (meth)acrylate, tridecyl (meth)acrylate, nonyl (meth)acrylate, norbornyl (meth)acrylate, propyl (meth)acrylate, hexadecyl (meth)acrylate, myristyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylcyclohexyl acrylate, 4 - (cyclo)alkyl (meth)acrylates such as t-butylcyclohexyl (meth)acrylate; (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleimide, unsaturated carboxylic acids such as maleic acid or salts thereof; meth)acrylate ethylene oxide adduct, (meth)acrylate propylene oxide adduct, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate Acrylate, polypropylene glycol mono (meth) acrylate, 2-ethylhexyl EO-modified (meth) acrylate, o-phenylphenol EO-modified acrylate, p-cumylphenol EO-modified (meth) acrylate, nonylphenol EO-modified (meth) acrylate ( Poly) alkylene glycol-modified (meth) acrylates;

phenoxydiethylene glycol (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate, hexaethylene glycol monophenyl ether mono(meth)acrylate, ethoxydiethylene glycol (meth)acrylate, diethylene glycol monobutyl ether acrylate, dipropylene glycol monomethyl ether (meth)acrylate, Methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (Meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, ethoxyethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxyethyl (meth)acrylates, alkoxylated 2-phenoxyethyl (meth)acrylate, alkoxylated nonylphenyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, ethoxylated 2-phenoxyethyl (meth)acrylate, ethoxylated (4) nonylphenol Acrylates, nonylphenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, propoxylated 2-phenoxyethyl (meth)acrylate, methylphenoxyethyl acrylate, ethoxylated succinic acid acrylate, ethoxy Alkoxy and/or phenoxy (meth)acrylates such as tribromophenyl acrylate, ethoxylated nonylphenyl (meth)acrylate; (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl ( meth)acrylate, 1-(meth)acryloylpiperidin-2-one, 2-(meth)acrylic acid-1,4-dioxaspiro[4,5]dec-2-ylmethyl, N-(meth)acryloyloxyethyl hexahydro phthalimide, N-(meth)acryloylmorpholine, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-butyrolactone (meth)acrylate, caprolact heterocycle-containing (meth)acrylates such as n-modified tetrahydrofurfuryl acrylate and imide acrylate;

(meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, diacetoneacrylamide, diethylacrylamide, dimethyl (meth)acrylamide, (Meth)acrylamides such as dimethylaminopropyl (meth)acrylamide; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-methoxy Propyl (meth)acrylate, glycerin mono(meth)acrylate, acryloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, tricyclodecane monomethylol (meth) acrylate, β-carboxyethyl (meth) acrylate, (meth) acrylic acid dimer, ω-carboxypolycaprolactone mono (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-( meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-ethylhexyl-diglycol (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N- Dimethylaminopropyl (meth)acrylate, aminoethyl (meth)acrylate, ethyl carbitol acrylate, ethyl diglycol acrylate, dimethylaminoethyl acrylate benzyl chloride quaternary salt, trifluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate , tribromophenyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, (meth)acrylonitrile, cresol acrylate, dicyclopentenyloxyethyl (meth)acrylate, trimethylolpropane formal (meth)acrylate, Neopentyl glycol (meth)acrylate benzoate, Ben various monofunctional monomers such as dilu (meth)acrylate, vinyl acetate, styrene, vinyl toluene, N-vinyl-2-caprolactam, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylcarbazole; However, it is not particularly limited.

Any conventionally known bifunctional monomer can be used without limitation. For example, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1, 2-hexadecanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-dimethyl-2,4-pentanediol di(meth)acrylate Acrylates, 1,4-butanediol di(meth)acrylate, 1,5-dimethyl-2,5-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 1,5-pentanediol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,4-diethyl-1 ,5-pentanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 2, methyl-1,3-butylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2-butyl-2 -ethyl-1,3-propanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, 2-methyl -2-propyl-1,3-propanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, glycerin di(meth)acrylate, diethylene glycol di(meth)acrylate (meth)acrylates, cyclohexane di Methanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, dipropylene glycol di(meth)acrylate, dimethyloloctane di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, dimethylolpropane di(meth)acrylate (meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tri propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, tricyclodecanedimethylol dicaprolactonate di(meth)acrylate,

Bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, butylene glycol di(meth)acrylate, propylene glycol Di(meth)acrylate, hexanediol diacrylate, pentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, hydrogenated bisphenol A diacrylate (Meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, diethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, dipropylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane divinyl ether, butanediol divinyl ether, propylene glycol Divinyl ether, hexanediol divinyl ether, trimethylolpropane diallyl ether, vinyloxyalkyl (meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, polypropylene glycol monovinyl ether (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate Acrylate, N,N'-methylenebisacrylamide and the like can be mentioned, but are not particularly limited. Bisphenol A tetraethylene oxide adduct di(meth)acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, bisphenol F tetraethylene oxide adduct di(meth)acrylate, bisphenol F tetraethylene oxide Adduct dicaprolactonate di(meth)acrylate, bisphenol S tetraethylene oxide adduct di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, hydrogenated bisphenol A tetraethylene oxide adduct Di(meth)acrylate, hydrogenated bisphenol F tetraethylene oxide adduct di(meth)acrylate and other alkoxylated products such as ethoxylated, propoxylated and butoxylated bifunctional monomers; alkylene oxide modifications such as ethylene oxide and propylene oxide; However, it is not particularly limited.

Any conventionally known trifunctional monomer can be used without limitation. For example, glycerin tri(meth)acrylate, tetramethylolmethane triacrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylol Examples include propane tri(meth)acrylate, trimethylolpropane trivinyl ether, trimethylolhexane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol triallyl ether, and pentaerythritol trivinyl ether, but are not particularly limited.
As the tetrafunctional or higher functional monomer, conventionally known monomers can be used without limitation. For example, diglycerin tetra(meth)acrylate, ditrimethylolethane tetra(meth)acrylate, ditrimethyloloctane tetra(meth)acrylate, ditrimethylolbutane tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate. Caprolactonate tetra(meth)acrylate, ditrimethylolhexane tetra(meth)acrylate, trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetraallyl ether, pentaerythritol tetracaprolactonate tetra (Meth)acrylates, pentaerythritol tetravinyl ether, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol poly Alkylene oxide hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate and the like can be mentioned, but are not particularly limited. In addition, alkoxylated products such as ethoxylated, propoxylated and butoxylated trifunctional monomers such as glycerin propoxy tri(meth)acrylate, trimethylolpropane tricaprolactonate tri(meth)acrylate, or tetrafunctional or higher monomers, ethylene oxide , alkylene oxide-modified products such as propylene oxide, and caprolactone-modified products, but are not particularly limited.

These monomers are alkyl acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid , (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid propylene oxide adduct, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, hexanediol diacrylate (HDDA; bifunctional), trimethylolpropane triacrylate ( TMPTA; trifunctional), glycerin propoxytriacrylate (GPTA; trifunctional), ditrimethylolpropane tetraacrylate (DITMPTA; tetrafunctional), dipentaerythritol hexaacrylate (DPHA; hexafunctional) and the like are preferred.

When a binder is used in the plasma-curable ink composition of the present invention and/or an additive for the plasma-curable ink composition, the binder is usually 0 to 70% by mass in the plasma-curable ink composition of the present invention. , preferably 0 to 50% by mass, particularly preferably 15 to 30% by mass.
The binder is melted by being heated together with the liquid component described later, and is used in the form of a varnish. When preparing the varnish, a gelatinized varnish may be obtained by adding a gelling agent such as a metal chelate compound or metallic soap to the dissolved varnish obtained by dissolving the binder. It is preferable to prepare a gelled varnish from a binder and use it for preparation of an ink composition because it is possible to impart appropriate viscoelasticity to the ink composition.
When a binder is used as an additive for the plasma-curable ink composition of the present invention, the binder is appropriately set in the range of 0 to 99% by mass with respect to the total additive for the plasma-curable ink composition. be done.

[Animal and plant oils and/or animal and plant oil derivatives]
The plasma-curable ink composition and/or additives for the plasma-curable ink composition of the present invention may include animal and plant oils and/or animal and plant oil derivatives.
Animal and vegetable oils that may be contained in the plasma-curing ink composition and/or additives for the plasma-curing ink composition of the present invention include, for example, tung oil, soybean oil, linseed oil, castor oil, and sunflower oil. , safflower oil, corn oil, cottonseed oil, rice oil (rice bran oil), rapeseed oil, canola oil, perilla oil, sesame oil, camellia oil, olive oil, peanut oil, grapeseed oil, coconut oil, tall oil, palm oil, palm kernel oil, beef tallow, horse oil, lard, chicken oil, fish oil such as sardine and saury, whale oil, shark oil, lanolin, mink oil, animal and vegetable oils such as beeswax, and mixtures of two or more of these. Among these, those having an iodine value of 80 or more are preferred, and one or more of tung oil, soybean oil, linseed oil, castor oil, safflower oil and perilla oil are particularly preferred, and tung oil and soybean oil are most preferred. , castor oil, and linseed oil.

Animal and plant oil derivatives that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention include the above modified animal and plant oils.
Here, as the modified animal or plant oil, one or more of oxidatively polymerized oil (boil oil), heat polymerized oil (stand oil), dehydrated product, esterified product, etc. of the animal and plant oil can be used. .
The animal and plant oil esters are generally obtained by transesterifying animal and plant oils, which are triglycerides of fatty acids, with alcohol, and are preferably stearic acid, isostearic acid, hydroxystearic acid, olein. Acids, saturated or unsaturated fatty acids with 14 to 30 carbon atoms such as linoleic acid, linolenic acid and eleostearic acid, and fatty acids derived from animal and plant oils composed of linear or branched monoalcohols with 1 to 10 carbon atoms. is an ester.

Such modified animal and plant oils include, for example, polymerized soybean oil, polymerized linseed oil, polymerized castor oil, polymerized tung oil, dehydrated castor oil, polymerized dehydrated castor oil, and the like. ) Heat polymerized oil (stand oil), dehydrated product; soybean oil methyl ester, soybean oil ethyl ester, soybean oil butyl ester, soybean oil isohexyl ester, linseed oil methyl ester, linseed oil ethyl ester, linseed oil butyl ester, linseed Oil isohexyl ester, tung oil methyl ester, tung oil ethyl ester, tung oil butyl ester, tung oil isohexyl ester, palm oil methyl ester, palm oil ethyl ester, palm oil butyl ester, palm oil isohexyl ester, etc. fatty acid ester; Among these, those having an iodine value of 80 or more are preferred, and polymerized soybean oil, polymerized linseed oil, polymerized castor oil, polymerized tung oil, polymerized dehydrated castor oil, dehydrated castor oil, soybean oil butyl ester, and linseed oil are particularly preferred. At least one of oil butyl ester and tung oil butyl ester is used.

As the animal and plant oils and/or animal and plant oil derivatives, one or a mixture of two or more of the animal and plant oils and/or animal and plant oil derivatives is used. Among these vegetable oils and/or animal and plant oil derivatives, those selected from the group consisting of soybean oil, tung oil, linseed oil, castor oil, and modified products thereof from the viewpoint of improving curability during plasma irradiation. At least one is preferably used.
When the animal or plant oil and/or the animal or plant oil derivative is used in the plasma-curing ink composition of the present invention, the animal or plant oil and/or the animal or plant oil derivative is usually 0% in the plasma-curing ink composition of the present invention. It is blended in an amount of up to 70% by mass, preferably 20-70% by mass, particularly preferably 40-60% by mass.
When the animal or plant oil and/or the animal or plant oil derivative is used as an additive for the plasma-curing ink composition of the present invention, the animal or plant oil and/or the animal or plant oil derivative is used for the plasma-curing ink composition. It is appropriately set in the range of 0 to 99% by mass based on the total amount of the additive. By adding the polymerized oil to the ink composition, the curability of the ink composition upon plasma irradiation is significantly improved. The upper limit of the polymerized oil content in the ink composition is preferably 30% by mass, more preferably 20% by mass, and still more preferably 10% by mass. The lower limit of the polymerized oil content in the ink composition is preferably 0.5% by mass, more preferably 2.5% by mass, and even more preferably 5% by mass.

[Conjugated polyene compound]
The conjugated polyene compound that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention has alternating carbon-carbon double bonds and carbon-carbon single bonds. It is a compound having a so-called conjugated double bond, which is a structure connected to and has two or more carbon-carbon double bonds. It may be a conjugated diene having a structure in which two carbon-carbon double bonds and one carbon-carbon single bond are alternately connected, or three carbon-carbon double bonds and two carbons. - It may be a conjugated triene having a structure in which carbon single bonds are alternately connected, or a conjugated polyene having a structure in which a greater number of carbon-carbon double bonds and carbon-carbon single bonds are alternately connected. It may be a system compound. In addition, a plurality of pairs of the above conjugated double bonds consisting of two or more carbon-carbon double bonds may be present in one molecule without being conjugated with each other. For example, compounds having three conjugated trienes in the same molecule, such as tung oil, are also included in the conjugated polyene compounds of the present invention.

Furthermore, in addition to the above conjugated double bonds consisting of two or more carbon-carbon double bonds, other functional groups such as carboxyl groups and salts thereof, hydroxyl groups, ester groups, carbonyl groups, ether groups, amino groups, imino groups , amide group, cyano group, diazo group, nitro group, sulfone group, sulfoxide group, sulfide group, thiol group, sulfonic acid group and its salts, phosphoric acid group and its salts, phenyl group, halogen atom, double bond, triple It may have various functional groups such as bonds. Such functional groups may be attached directly to the carbon atom in the conjugated double bond or attached at a position remote from the conjugated double bond. Therefore, the multiple bond in the functional group may be at a position that allows conjugation with the conjugated double bond. For example, 1-phenylbutadiene having a phenyl group and sorbic acid having a carboxyl group are also included in the conjugated polyene compounds of the present invention.

Among conjugated polyene compounds, conjugated dienes having a conjugated structure with two carbon-carbon double bonds include, for example, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3- butadiene, 2-t-butyl-1,3-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl- 1,3-pentadiene, 3-ethyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3- hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4-hexadiene, 1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-phenyl-1,3-butadiene, 1,4-diphenyl-1,3-butadiene, 1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene, 1-ethoxy-1,3-butadiene, 2-ethoxy-1,3- butadiene, 2-nitro-1,3-butadiene, chloroprene, 1-chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 2-bromo-1,3-butadiene, fulvene, tropone, ocimene, Phellandrene, myrcene, farnesene, cembrene, sorbic acid, sorbate, sorbate, abietic acid, conjugated linoleic acid and the like.

Among conjugated polyene compounds, conjugated triene compounds having a conjugated structure with three carbon-carbon double bonds include, for example, 1,3,5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, cholecalciferol and the like. Among conjugated polyene compounds, conjugated polyene compounds having a conjugated structure with 4 or more carbon-carbon double bonds include cyclooctatetraene, 2,4,6,8-decatetraene-1-carboxylic acid, retinol, and retinoic acid. , parinaric acid, balsamic seed oil, and carotenes.

As these conjugated polyene compounds, animal and plant oils, eleostearic acid, etc. are preferred, and dehydrated castor oil, tung oil and eleostearic acid are particularly preferred. As the conjugated polyene compound, one or a mixture of two or more of the conjugated diene compound and/or the conjugated triene compound and/or the conjugated polyene compound is used.
When a conjugated polyene-based compound is used in the plasma-curable ink composition of the present invention, the conjugated polyene-based compound is usually 0 to 70% by mass, preferably 0 to 50% by mass, in the plasma-curable ink composition of the present invention. , and more preferably in an amount of 5 to 30% by mass.
When a conjugated polyene-based compound is used as an additive for the plasma-curable ink composition of the present invention, the conjugated polyene-based compound is 0 to 99 masses with respect to the total additive for the plasma-curable ink composition. It is set appropriately within the range of %.

[Other ingredients]
The plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention further contains various components depending on the target biomass degree, environmental performance, safety performance, color tone, etc. be able to. Such components include liquid components, colorants (colored pigments, bright pigments, dyes, fluorescent pigments, colored resin particles, etc.), extender pigments, dispersants, surfactants, stabilizers, antifoaming agents, polymerization initiators, Anti-friction agents (waxes), gelling agents, viscosity modifiers, plasticizers, polymerization inhibitors, antioxidants, pH adjusters, bactericidal/antifungal agents, silane coupling agents, etc. are commonly used in the field of ink compositions. Additives that are In addition, drying and curing accelerators other than the above-mentioned "photocatalyst compound" and/or "composite of metal component and photocatalyst compound" are also included.
When the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention contains other components, the dry curability of the plasma-curable ink composition is usually not affected. The content is within the range. However, if the plasma curing ink composition contains components that affect the drying curability, such as the drying curing accelerator, conjugated polyene compound, polymerization initiator, polymerization inhibitor, and rosin-treated particles, The amount may be within a range that does not affect the drying curability of the plasma-curing ink composition, or within a range that affects it.

(liquid component)
The liquid component that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention dissolves the resin into a varnish and adjusts the viscosity of the ink composition. It is used to The liquid component is a liquid component other than the liquid among the binder, animal and plant oils, animal and plant oil derivatives, and conjugated polyene compounds. Such a liquid component exhibits a liquid state at the printing temperature (usually 10° C. to 40° C.), and examples thereof include liquid compounds such as organic solvents, mineral oils, and water.

Examples of organic solvents to be used include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol and tert-butanol; chlorinated solvents such as methylene; aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-hexane, n-pentane and cyclohexane; petroleum hydrocarbon solvents such as mineral spirits; Ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether and tripropylene glycol monomethyl ether; and organic solvents such as cyclic ester solvents such as 2-methylpyrrolidone, 2-pyrrolidone, and amide solvents such as dimethylacetamide. One or more of these can be used.

Mineral oils include, for example, light mineral oils and heavy mineral oils, and from the viewpoint of adapting to OSHA standards in the United States and EU standards, the content of condensed polycyclic aromatic components is suppressed. is preferably Light mineral oils have been classified as non-aromatic petroleum solvents with a boiling point of 160°C or higher, preferably 200°C or higher, while heavy mineral oils have been classified as spindle oils, machine oils, dynamo oils, cylinder oils, etc. Various lubricating oils can be exemplified, specifically, JX Nikko Nisseki Energy Co., Ltd. No. 0 solvent, AF solvent No. 5, AF solvent No. 6, AF solvent No. 7, ink oil H8, ink oil H35, Sankyo oil SNH8, SNH46, SNH220 and SNH540 manufactured by Kakogyo Co., Ltd. are exemplified.
Such a liquid component is preferably about 0 to 33% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 33% by mass relative to the entire additive for the plasma-curable ink composition of the present invention. About 99% by mass of each is contained, but is not particularly limited.

(coloring agent)
The colorant that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention imparts coloring strength that has been used in the preparation of ink compositions. Any component can be used as long as it is a component. Examples thereof include inorganic coloring pigments, organic coloring pigments, luster pigments, dyes, fluorescent pigments, and colored resin particles. may be mixed and used. Among these, particles such as pigments and colored resin particles may be surface-treated with a surface treatment agent such as a rosin compound, a silane coupling agent, a resin, a pigment derivative, or may be untreated. good.

Coloring pigments include inorganic and/or organic coloring pigments of various colors such as red, blue, yellow, green, purple, black, white, orange, and brown, which have been conventionally used in ink compositions. In order to obtain a desired color tone, two or more kinds of inorganic coloring pigments and/or organic coloring pigments may be mixed and used. Inorganic coloring pigments include carbon black, iron black, titanium oxide, zinc oxide, lead white, yellow lead, zinc yellow, cadmium yellow, red iron oxide, cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, composite oxides (nickel・ Titanium-based, chromium-titanium-based, bismuth-vanadium-based, cobalt-aluminum-based, cobalt-aluminum-chromium-based, ultramarine blue, etc. can be used.
Organic coloring pigments include phthalocyanine pigments, threne pigments, azo pigments, quinacridone pigments, anthraquinone pigments, dioxane pigments, indigo pigments, thioindigo pigments, perinone pigments, perylene pigments, indoline pigments, and azomethine. pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, polycyclic pigments, benzimidazolone pigments, anthrapyrimidine pigments, Nitro-based pigments, nitroso-based pigments, aniline black, etc. can be used.

Metal powder such as aluminum, metal foil, oxide-coated mica such as titanium dioxide-coated mica, oxide-coated glass flakes, fish scale foil, bismuth oxychloride, and other pigments with pearl luster or interference luster can be used as luster pigments. be.
Dyes include water-soluble dyes, oil-soluble dyes and disperse dyes of various colors such as red, blue, yellow, green, purple, black, white, orange and brown, which have been conventionally used in ink compositions. These may be acid dyes, substantive dyes, basic dyes, reactive dyes, food dyes.

The fluorescent pigment uses light of a specific wavelength such as ultraviolet light or infrared light as excitation energy, and a pigment that emits light in a wavelength range different from the above wavelength can be used.
The colored resin particles are fine particles of a mixture of the above-mentioned coloring pigment, luster pigment, dye, fluorescent pigment and resin, and the resin can be polyolefin, polystyrene, acrylic resin, urethane resin, or the like.
The pigment may be a self-dispersing pigment in which at least one hydrophilic group or lipophilic group is bonded directly or through various atomic groups to the surface of the pigment. The self-dispersion pigment is preferably ionic, and particularly preferably anionically charged.

Preferred coloring pigments include disazo yellow (Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 17, Pigment Yellow 1), yellow pigments such as Hansa yellow, magenta pigments such as brilliant carmine 6B, lake red C, and watching red, and phthalocyanine blue. , phthalocyanine green, cyan pigments such as alkali blue, black pigments such as carbon black, and white pigments such as titanium oxide and zinc oxide.
From the viewpoint of weather resistance and plasma resistance, it is preferable to use a coloring agent that is not a dye.

It is also preferable to use rosin-treated particles. The rosin-treated particles are obtained by treating one or more kinds of particles such as the above-mentioned color pigments, luster pigments, fluorescent pigments and colored resin particles with a rosin compound. Rosin-based compounds used to obtain rosin-treated particles include unmodified rosins such as wood rosin, gum rosin and tall oil rosin; polymerized rosins modified by polymerization, disproportionation, stabilization, hydrogenation, etc. , disproportionated rosin, stabilized rosin, hydrogenated rosin; maleated rosin, fumarated rosin, rosin ester, rosin amine, rosin amide, and other chemically modified rosins and rosin derivatives introduced with various functional groups; rosin-modified ester resins , rosin-modified acrylic resins, rosin-modified alkyd resins, rosin-modified maleic acid resins, rosin-modified phenolic resins, rosin-modified polyester resins, rosin-modified polyamide resins, rosin-modified fumaric acid resins, etc. metal salts of these various rosin-based compounds can be used, and one or a mixture of two or more thereof can be used. As the rosin-based compound, rosin acid contained in natural rosin can be used, and the rosin acid referred to herein is abietic acid, abietic acid, dihydroabietic acid, dihydroabietic acid, neoabietic acid, neoabietic acid. acid, dehydroabietic acid, dehydroabietic acid, tetrahydroabietic acid, tetrahydroabietic acid, parastric acid, parastric acid, levopimaric acid, levopimarate, pimaric acid, pimarate, isopimaric acid, isopimarate, citronel A compound or mixture comprising at least one selected from acids and citronellates, which may be extracted from natural rosin or synthesized. The salt contained in rosin acid is preferably a metal salt, more preferably an alkaline earth metal salt, particularly a calcium salt.

These particles have an average particle diameter of 0.001 to 100 μm, preferably 0.01 to 50 μm, more preferably 0.05 to 5 μm, taking into account dispersion stability, fluidity, etc. Those having a BET specific surface area of 1 to 350 m ² /g, preferably 10 to 70 m ² /g, more preferably 20 to 50 m ² /g are used.
Methods for preparing such rosin-treated particles include, for example, a method of adding a rosin compound to a pigment paste and mixing, a method of adding a powdered rosin compound to dry pigment particles and mixing, and an aqueous slurry of pigment. and a rosin soap (or an alkaline aqueous solution of rosin), and then adding an alkaline earth metal salt, acid, etc., and depositing the rosin sparingly soluble salt or rosin free acid on the surface of the pigment, the dye before lake formation Alkali metal salt and rosin soap (or alkaline aqueous solution of rosin) are mixed, alkaline earth metal salt etc. are added to make the dye into a lake, and rosin is precipitated on the surface at the same time. Coupling dye and metal A method of mixing a mixture with a salt with a mixture of a coupling component and a rosin soap (or an alkaline aqueous solution of rosin), followed by coupling to form a lake, rosin treatment, and the like.

The content of rosin in the rosin-treated particles is usually 0.1 to 50 parts by mass, preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the rosin-treated particles, taking into account dispersion stability, fluidity, etc. , more preferably 1 to 20 parts by mass. In the case of rosin-treated particles, the rosin present on the particle surface serves as a starting point for the curing reaction by plasma, and it is presumed that the curing of the ink coating film by plasma is accelerated.
The colorant is preferably about 0 to 33% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 99% by mass relative to the entire additive for the plasma-curable ink composition of the present invention. degree, respectively, but not particularly limited. When preparing ink compositions using color pigments, it is possible to use pigments of other colors as complementary colors, or to add ink compositions of other colors.

(Extender pigment)
The extender pigment that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention may be any one that has been used in the preparation of ink compositions. It may be used in the form of a powder, may be in the form of a dispersion in an appropriate solvent, or may be used alone or in combination of two or more. Examples thereof include talc, mica, barium sulfate, clay, calcium carbonate, kaolinite (kaolin), silicon oxide, bentonite, ground calcium carbonate, barium carbonate, zirconia, and alumina.
The average particle diameter of the extender pigment is 0.001 to 100 μm, preferably 0.01 to 50 μm, more preferably 0.05 to 5 μm, and the BET specific surface area is 1 to 350 m ² /g, preferably 10 -70 m ² /g, more preferably 20-50 m ² /g are used.

It is also preferable to use rosin-treated particles. The rosin-treated particles are obtained by treating particles of one or more of the above extender pigments with a rosin-based compound. As the rosin-based compound, the rosin-based compound used for forming the rosin-treated colorant can be used.
These particles have an average particle diameter of 0.001 to 100 μm, preferably 0.01 to 50 μm, and more preferably 0.05 to 5 μm, in consideration of dispersion stability and fluidity. Those having a BET specific surface area of 1 to 350 m ² /g, preferably 10 to 70 m ² /g, more preferably 20 to 50 m ² /g are used.
The rosin-treated particles obtained by treating an extender with a rosin-based compound may be commercially available products or may be prepared by a known method. Commercially available products include, for example, Neolite (rosin-treated calcium carbonate manufactured by Takehara Chemical Industry Co., Ltd.), Shiraenka (rosin-treated calcium carbonate manufactured by Shiraishi Calcium Co., Ltd.), and the like.
Methods for preparing rosin-treated particles include, for example, a method of adding rosin to a pigment paste and mixing, a method of adding powdery rosin to dry pigment particles and mixing, a method of adding an aqueous slurry of pigment and rosin soap ( or an alkaline aqueous solution of rosin), and then adding an alkaline earth metal salt, an acid, or the like to deposit a sparingly soluble rosin salt or rosin free acid on the surface of the pigment.
The content of rosin in the rosin-treated particles is usually 0.1 to 50 parts by mass, preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the rosin-treated particles, taking into account dispersion stability, fluidity, etc. , more preferably 1 to 20 parts by mass.
In the case of rosin-treated particles, the rosin present on the particle surface serves as a starting point for the curing reaction by plasma, and it is presumed that the curing of the ink coating film by plasma is accelerated.
The extender pigment is preferably about 0 to 33% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 99% by mass relative to the entire additive for the plasma-curable ink composition of the present invention. degree, respectively, but not particularly limited.

(dispersant)
Dispersants that may be contained in the plasma-curable ink composition and/or additives for the plasma-curable ink composition of the present invention include, for example, anionic dispersants, cationic dispersants, amphoteric dispersants and Any of nonionic dispersants may be used, and any of high molecular weight compounds, low molecular weight compounds (surfactants) and pigment derivatives may be used. For example, polyvinyl alcohol-based compounds, polyvinylpyrrolidone-based compounds, hydroxyl group-containing carboxylic acid esters, high molecular weight polycarboxylates, naphthalenesulfonic acid formalin condensate salts, polyoxyethylene alkyl phosphate esters, long-chain polyaminoamide-high molecular weight acid esters salts, long-chain polyaminoamide-polar acid ester salts, polyester polyamines, stearylamine acetate, high-molecular-weight unsaturated acid esters, polyoxyethylene nonylphenyl ethers, urethanes such as modified polyurethanes, polyester amines, fatty acid amines, polycarboxylic acids, Polyesteramine salts, polychain nonionic polymers, (modified) acrylic resins (salts) such as acrylic acid-acrylate copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, Styrene-acrylic resin (salt ), styrene-maleic acid copolymer (salt), styrene-maleic anhydride copolymer (salt), vinylnaphthalene-acrylic acid copolymer (salt), polyethyleneimine-based compound, polyallylamine-based compound, polyoxyethylene Alkyl ether compounds, polyoxyethylene diester compounds, polyether phosphate compounds, polyester phosphate compounds, sorbitan aliphatic ester compounds, and the like can be used.

Commercially available products of the dispersant include trade name Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), trade name Disperbyk (manufactured by BYK-Chemie), trade name EFKA (manufactured by BASF), trade name SOLSPERSE (manufactured by Nippon Lubrizol Co., Ltd.), trade name TEGO (Evonik), trade name Demol (manufactured by Kao Corporation), trade name Homogenol (manufactured by Kao Corporation), trade name Disparon (manufactured by Kusumoto Kasei Co., Ltd.), trade name Discol (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), trade name Hypermer (manufactured by Croda Japan). These dispersants can be used singly or in combination of two or more.
The amount of the dispersant to be added may be an amount capable of dispersing various particles such as the pigment in the plasma-curable ink composition of the present invention or the additive for the plasma-curable ink composition. The amount of the dispersant is 10 to 500 parts by mass with respect to 100 parts by mass of the dispersion.
In addition, such a dispersant is preferably about 0 to 33% by mass with respect to the entire plasma-curable ink composition of the present invention, and with respect to the entire additive for the plasma-curable ink composition of the present invention. Each is contained in an amount of about 0 to 99% by mass, but is not particularly limited.

(Surfactant)
Surfactants that may be contained in the plasma-curable ink composition and/or additives for the plasma-curable ink composition of the present invention include, for example, dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts. Anionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, nonionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers, alkylamine salts, Cationic surfactants such as quaternary ammonium salts, amphoteric surfactants such as compounds having an acid structure (anion portion) and quaternary ammonium (cation portion) structure as hydrophilic groups in the molecule, organic fluoro compounds, etc. Silicone surfactants such as fluorine-based surfactants and polysiloxane compounds can be mentioned.
Such a surfactant is preferably about 0 to 33% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to the entire additive for the plasma-curable ink composition of the present invention. Although each is contained in an amount of about to 99% by mass, it is not particularly limited.

(Drying curing accelerator)
The plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention includes a dry curing accelerator other than the above-mentioned "photocatalyst compound" and/or "a composite of a metal component and a photocatalyst compound". agents may be included. A metal dryer etc. are mention|raise|lifted as a drying hardening accelerator.
As the metal drier, any substance that has been used in the preparation of ink compositions can be used as long as it is a substance that promotes oxidative polymerization of the ink composition for plasma curing. may be used, or two or more may be used in combination. For example, cobalt, manganese, lead, iron, zinc, calcium, zirconium, transition metals such as copper, alkaline earth metals such as calcium, rare earth metals such as cerium, acetic acid, propionic acid, butyric acid, isopentanoic acid, Hexanoic acid, 2-ethylbutyric acid, naphthenic acid, octylic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, secanoic acid, tall oil fatty acid, dimethylhexanoic acid, 3,5,5-trimethylhexanoic acid, dimethyloctanoic acid, resin acid, tung oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, etc. Metal salts of carboxylic acids (metal soaps), borates, and the like can be mentioned. Moreover, a peroxide may be added in order to further improve the drying property.
Such a drying curing accelerator is preferably about 0 to 10% by mass with respect to the entire plasma-curable ink composition of the present invention, and with respect to the entire additives for the plasma-curable ink composition of the present invention. Each is contained in an amount of about 0 to 99% by mass, but is not particularly limited.

(Anti-friction agent)
The anti-friction agent that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention is any one that has been used in the preparation of ink compositions. can be used, and one type may be used alone, or two or more types may be used in combination. For example, plant waxes such as carnauba and Japan wax, animal waxes such as spermaceti and lanolin, petroleum waxes such as montan, polyethylene (PE) wax, polypropylene (PP) wax, polytetrafluoroethylene (PTFE) wax, and polystyrene. and hard fine particles such as polystyrene rubber, natural or synthetic waxes such as synthetic waxes such as paraffin wax, carnauba wax, beeswax, microcrystalline wax, polyethylene oxide wax and amide wax.
Such an anti-friction agent is preferably about 0 to 10% by mass relative to the total plasma-curable ink composition of the present invention, and 0% relative to the total additives for the plasma-curable ink composition of the present invention. Although each is contained in an amount of about to 99% by mass, it is not particularly limited.
In general ink compositions, paraffin wax and PTFE wax are used for the purpose of suppressing scratches on printed matter. The amount can be 0% by weight. This is because, according to the findings of the present inventors, if the ink composition contains wax, the curability of the ink composition when exposed to plasma may decrease. Although the reason for this is not necessarily clear, it is believed that the wax component contained in the ink composition floats on the surface of the coating film of the ink composition after printing. This is thought to be for the purpose of inhibiting the entry of plasma into the coating film of the ink composition.

(Gelling agent)
The gelling agent that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention is any one that has been used in the preparation of ink compositions. can be used, and one type may be used alone, or two or more types may be used in combination. Examples thereof include gelling agents such as metal chelate compounds, organic acid metal salts (metal soaps), and metal soap oligomers. For example, metal salts such as lithium, sodium, potassium, aluminum, calcium, cobalt, iron, manganese, magnesium, lead, zinc, and zirconium of organic acids such as stearic acid, lauric acid, ricinoleic acid, octylic acid, and naphthenic acid ( Specifically, manganese naphthenate, aluminum octylate, zinc stearate, aluminum stearate, etc.), aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetylacetate, aluminum diisopropoxide monoethylacetoacetate , aluminum dibutoxide monoacetylacetate and aluminum triacetylacetate; titanium-based chelating agents such as tetraisopropoxytitanium, tetrabutoxytitanium and dipropoxybis(acetylacetonato)titanium; zirconium such as tetrabutoxyzirconium system chelating agent; polyisocyanates such as tolylene diisocyanate, diphenyl diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and isophorone diisocyanate, etc., and two or more thereof may be mixed and used.
It is preferable to prepare a gelled varnish using a gelling agent and use it in preparation of an ink composition because it is possible to impart appropriate viscoelasticity to the ink composition.
The amount of the gelling agent is preferably about 0 to 5% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 99% by mass relative to the entire additive for the plasma-curable ink composition of the present invention. %, respectively, but is not particularly limited.

(Viscosity modifier)
The viscosity modifier that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention is any one that has been used in the preparation of ink compositions. can be used, and one type may be used alone, or two or more types may be used in combination. For example, the animal and plant oils and/or animal and plant oil derivatives, the liquid components, celluloses, polyvinyl alcohol, cellulose derivatives such as carboxymethyl cellulose (salt) and methyl cellulose, polyamines, polyimine, starch glycolates and starch phosphates starches such as salts, alginates, propylene glycol alginate, glycerin fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyacrylic acid (salts), alkylene glycol fatty acid esters, and the like.
The viscosity modifier is preferably about 0 to 5% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 99% by mass relative to the entire additive for the plasma-curable ink composition of the present invention. %, respectively, but is not particularly limited.

(polymerization inhibitor)
When the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention contains a polymerizable compound having an ethylenically unsaturated double bond, it contains a polymerization inhibitor. This can impart storage stability, viscosity stability over time, and the like to the ink composition. Any polymerization inhibitor that has hitherto been used in the preparation of ink compositions can be used, and one type can be used alone, or two or more types can be used in combination. For example, hydroquinone, methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, trimethylhydroquinone, phenolic compounds such as methoxyhydroquinone, 4-methoxyphenol, butylhydroxytoluene, p-benzoquinone, 2,5-di-t-butylbenzoquinone and naphthoquinone; nitrosamine compounds such as tocopherol acetate and N-nitrosophenylhydroxylamine salts; Examples include benzotriazole, phenothiazine-based compounds, hindered amine-based compounds, phosphorus-based compounds, and N-oxyl-based compounds.
The polymerization inhibitor is preferably about 0 to 5% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 99% by mass relative to the entire additive for the plasma-curable ink composition of the present invention. %, respectively, but is not particularly limited.

(Antioxidant)
The antioxidant that may be contained in the plasma-curable ink composition of the present invention and/or the additive for the plasma-curable ink composition is any one that has been used in the preparation of ink compositions. can be used, and one type may be used alone, or two or more types may be used in combination. Examples thereof include phenol antioxidants, amine antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
The antioxidant is preferably about 0 to 5% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 99% by mass relative to the entire additive for the plasma-curable ink composition of the present invention. %, respectively, but is not particularly limited.

(Sterilization/antifungal agent)
The bactericidal/antifungal agent that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention may be any can also be used, and one type may be used alone, or two or more types may be used in combination.
Examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof.
The amount of the bactericidal/antifungal agent is preferably about 0 to 3% by mass with respect to the entire plasma-curable ink composition of the present invention, About 99% by mass of each is contained, but is not particularly limited.

(Silane coupling agent)
The silane coupling agent that may be contained in the plasma-curable ink composition and/or the additive for the plasma-curable ink composition of the present invention includes, for example, (methacryloxypropyltrimethoxysilane) ) acrylic silane coupling agents, vinyl silane coupling agents such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, vinyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β -(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyl Epoxy silane coupling agents such as trimethoxysilane and γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxy Silane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl- At least one of amino silane coupling agents such as γ-aminopropyltriethoxysilane, mercapto silanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, and imidazole silane can be used.
The amount of the silane coupling agent is preferably about 0 to 10% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 99% relative to the entire additive for the plasma-curable ink composition of the present invention. They are each contained in an amount of about % by mass, but are not particularly limited.

[Method for producing plasma-curable ink composition and additive for plasma-curable ink composition]
Conventionally known methods can be used to produce the plasma-curable ink composition and the additive for the plasma-curable ink composition of the present invention using the components described above.
For example, it includes a method of mixing all or part of the components constituting the plasma-curable ink composition or the additive for the plasma-curable ink composition using known or conventional stirring and dispersing means. For mixing, for example, mixers such as paint shakers, butterfly mixers, planetary mixers, pony mixers, dissolvers, tank mixers, homomixers, homodispers, attritors, roll mills, sand mills, ball mills, bead mills, line mills, ultrasonic mills, Various mixing and dispersing devices such as mills such as dyno mills and shot mills, kneaders, mixer kneaders, and high-pressure collision dispersers may or may not be used. Further, one type of mixing and dispersing device may be used to perform the stirring and dispersing treatment once or multiple times, or two or more types of mixing and dispersing devices may be used in combination to perform the stirring and dispersion treatment multiple times. If necessary, liquid components and various additive components may be further added and stirred and dispersed using the above mixing and dispersing device when performing the stirring and dispersing treatment a plurality of times.

The plasma-curable ink composition and/or the additive for the plasma-curable ink composition may be produced by heating or cooling, or at room temperature, as required. As for the manufacturing atmosphere, it may be carried out under an atmosphere such as an inert gas atmosphere, or it may not be carried out under various gas atmospheres.
Further, the plasma-curable ink composition of the present invention can be prepared, for example, by charging the raw materials into a container, using any of the above mixing and dispersing devices if necessary, heating and cooling if necessary, and Under a specific atmosphere, premixing is performed to prepare a varnish, and then the required amount of varnish and the ink raw materials are mixed, and the mixture is sufficiently stirred and dispersed to achieve the present invention. can obtain a plasma-curable ink composition.
In the present invention, the "photocatalyst compound" and/or the "composite of the metal component and the photocatalyst compound" may be added in the premixing stage or in the subsequent ink composition manufacturing stage.
After mixing the above components and kneading with a bead mill or three-roll mill to disperse the pigment components, oil components and additives (antioxidants, alcohols, etc.) are added as necessary. It can be exemplified by stirring well and further adjusting the viscosity. In ordinary offset printing ink compositions, a drier comprising a metal complex is added in order to promote drying by oxidation. In the plasma-curable ink composition of the present invention, a drier comprising such a metal complex is also added. By doing so, curing during plasma irradiation is accelerated.

[Substrate to which plasma-curing ink composition is applied]
The substrate to which the plasma-curable ink composition of the present invention is applied is not particularly limited. For example, fine paper, coated paper, art paper, imitation paper, thin paper, thick paper, polyester such as PET and polylactic acid, (meth)acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, etc. polyolefin, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, polyamide, polycarbonate resin film or sheet, cellophane, aluminum foil metal such as glass, wood, Inorganic materials such as gypsum board, composite materials composed of two or more of these materials, and other various substrates used as printing substrates can be mentioned.

[Plasma-curable ink composition to which additive for plasma-curable ink composition is added]
The plasma-curable ink composition to which the additive for the plasma-curable ink composition of the present invention is added is not particularly limited as long as it is an ink composition that dries and cures a printed coating film using plasma. For example, the binder, animal and plant oils and/or animal and plant oil derivatives and/or conjugated polyene compounds that may be contained in the plasma-curing ink composition of the present invention may be included, and liquid components and Other components such as various additives may be included.

[Printing method that can be used for plasma-curing ink composition]
The plasma-curable ink composition of the present invention can be used without limitation in various printing methods, such as offset printing using dampening water, waterless offset printing not using dampening water, gravure printing, It is used in various printing methods such as flexographic printing, screen printing, pad printing, electrophotographic printing, and inkjet printing.

[Plasma/plasma irradiation device]
The plasma-curable ink composition of the present invention is applicable to the various printing methods described above, and has the ability to dry and cure upon exposure to plasma, which is an ionized gas. More specifically, the curable components and the like contained in the ink composition are polymerized when exposed to plasma irradiation, and the coating film of the plasma-curable ink composition formed by printing dries and cures. When plasma is applied to the ink composition which is sticky on the surface of the printed matter immediately after printing, the ink composition instantly hardens and becomes a dry (tack-free) state.
Plasma generated under various conditions can be used for the plasma used in the present invention. Among these, atmospheric pressure plasma is preferable because it is easy to handle and is advantageous in terms of equipment and cost. An atmospheric pressure plasma is a plasma generated under substantially atmospheric pressure. The term "substantially atmospheric pressure" means a pressure state in which neither extreme pressurization nor extreme decompression is performed in addition to atmospheric pressure. It refers to a pressure range ranging from 7 to 1.5 atmospheres. The temperature at which the plasma is generated is not particularly limited, but it is preferable to set the temperature to about 50° C. or less in consideration of handling properties and the like. When plasma is generated, there is no need to reduce the pressure (no need to form a vacuum system), so equipment costs and processing costs can be reduced. It does not impair the shape and characteristics of
The plasma temperature in atmospheric pressure plasma can be any temperature from high temperature to low temperature, and it is more preferable to use atmospheric pressure plasma controlled to a temperature suitable for reaction or the like. For example, atmospheric pressure low temperature plasma is preferable in consideration of damage to the base material. The plasma temperature is not particularly limited as long as it is suitable for reaction or the like, but is preferably about 100° C. or less, particularly preferably 0° C. to 100° C., in consideration of handleability and the like. For controlling the temperature of the atmospheric pressure plasma, the means described in Japanese Patent No. 4611409, for example, can be used.

The plasma used for curing the plasma-curing ink composition of the present invention is generated by ionizing a discharge gas present in an electric field, and has high energy capable of causing a chemical reaction. Any material that cures (polymerizes) the fatty acid-modified rosin-based resin contained in the product or various components such as liquid components and the like may be used.
Plasma is generally generated by a discharge in which a current flows between electrodes separated from each other, but the plasma used in the present invention is not limited to that generated by a discharge in which a current flows between electrodes separated from each other, It may be produced in a variety of ways, and any scientifically defined plasma can be used without limitation, and is a gas containing charged particles produced by ionization and having an equal or approximately equal number of ions and electrons. It is sufficient that they have the same number and are in an electrically neutral or nearly neutral state.

In the present invention, the discharge gas used for plasma generation is gas such as air, oxygen, carbon dioxide, nitrogen, rare gas (argon, helium, neon, etc.), hydrogen, halogen (fluorine, chlorine), water vapor, or A mixed gas containing two or more selected from these groups is used, but is not particularly limited. Air, oxygen, nitrogen, carbon dioxide, or a mixed gas containing two or more selected from these groups are preferred, and air, oxygen, nitrogen, or two or more selected from these groups are particularly preferred. It is a mixed gas. Further, as described in Patent Document 6, when plasma irradiation and ultraviolet irradiation are used in combination, a large discharge gas such as argon, krypton, or xenon is used as the discharge gas used when generating atmospheric pressure plasma. It is also possible to mix a small amount of a gas that easily emits ultraviolet rays when generating atmospheric pressure plasma with the discharge gas.

The plasma irradiation device is connected to a high-frequency power source and is placed in a discharge state by passing a current through electrodes separated from each other, and the discharge gas is introduced between the electrodes and passed (actively flows between the electrodes) to generate plasma. It is preferable to use such a mechanism, which is readily available and capable of being released toward an irradiation target. Such an apparatus includes a direct type, a remote type, and a combined type of both according to the plasma irradiation mode.

In the direct type, the printed substrate is passed between electrodes to which a voltage is applied (i.e., within the discharge space) to perform plasma irradiation, and high reactivity is expected from the plasma immediately after generation. It is. In the present invention, each condition is not particularly limited when a direct type plasma irradiation apparatus is used.
The treatment voltage is arbitrarily set based on the gas type of the discharge gas, the treatment current, the treatment frequency, the distance between the electrodes, the substrate treatment speed, the discharge gas flow rate, the irradiation distance, etc., and is, for example, 10 to 1000 V, preferably 20 to 1000 V. 600 V, more preferably 100 to 500 V, but not particularly limited.
The treatment current is arbitrarily set based on the gas type of the discharge gas, treatment voltage, treatment frequency, distance between electrodes, substrate treatment speed, discharge gas flow rate, irradiation distance, etc., for example, 0.001 to 1000 A, preferably 0.01 to 500 A, more preferably 0.1 to 100 A, but not particularly limited.

The treatment frequency is arbitrarily set based on the gas type of the discharge gas, treatment voltage, treatment current, distance between electrodes, substrate treatment speed, discharge gas flow rate, irradiation distance, etc., for example, 0.001 to 1000 kHz, preferably 0.01 to 500 kHz, more preferably 0.05 to 100 kHz, but not particularly limited.
The distance between the electrodes is arbitrarily set based on the type of discharge gas, treatment voltage, treatment current, treatment frequency, substrate treatment speed, discharge gas flow rate, irradiation distance, etc., and is, for example, 0.1 to 50 mm, preferably 0.5 to 25 mm, more preferably 0.5 to 10 mm, but not particularly limited.
The substrate processing speed (substrate passing speed) is arbitrarily set based on the type of discharge gas, processing voltage, processing current, processing frequency, distance between electrodes, discharge gas flow rate, irradiation distance, etc. For example, 0.01 7000 mm/sec, preferably 0.1 to 3000 mm/sec, more preferably 1 to 2000 mm/sec, but not particularly limited.
The discharge gas flow rate is arbitrarily set based on the type of discharge gas, treatment voltage, treatment current, treatment frequency, distance between electrodes, base material treatment speed, irradiation distance, etc. For example, 0.01 to 100 liters/minute It is preferably 0.1 to 30 liters/minute, more preferably 0.1 to 20 liters/minute, but is not particularly limited.

The remote type irradiates the plasma by transporting the plasma generated in a place other than the processing target to the processing target in a stream of plasma gas, which causes great damage to the substrate. Plasma irradiation can be performed without In the present invention, each condition is not particularly limited when using the remote type plasma irradiation apparatus.
The treatment voltage is arbitrarily set based on the gas type of the discharge gas, the treatment current, the treatment frequency, the distance between the electrodes, the substrate treatment speed, the discharge gas flow rate, the irradiation distance, etc., and is, for example, 10 to 1000 V, preferably 20 to 1000 V. 600 V, more preferably 100 to 500 V, but not particularly limited.
The treatment current is arbitrarily set based on the gas type of the discharge gas, treatment voltage, treatment frequency, distance between electrodes, substrate treatment speed, discharge gas flow rate, irradiation distance, etc., for example, 0.001 to 1000 A, preferably 0.01 to 500 A, more preferably 0.1 to 100 A, but not particularly limited.

The treatment frequency is arbitrarily set based on the gas type of the discharge gas, treatment voltage, treatment current, distance between electrodes, substrate treatment speed, discharge gas flow rate, irradiation distance, etc., for example, 0.001 to 1000 kHz, preferably 0.01 to 500 kHz, more preferably 0.05 to 100 kHz, but not particularly limited.
The distance between the electrodes is arbitrarily set based on the gas type of the discharge gas, treatment voltage, treatment current, treatment frequency, substrate treatment speed, discharge gas flow rate, irradiation distance, etc., for example, 0.1 to 50 mm, preferably, 0.5 to 25 mm, more preferably 0.5 to 10 mm, but not particularly limited.
The substrate processing speed (substrate passing speed) is arbitrarily set based on the type of discharge gas, processing voltage, processing current, processing frequency, distance between electrodes, discharge gas flow rate, irradiation distance, etc. For example, 0.01 7000 mm/sec, preferably 0.1 to 3000 mm/sec, more preferably 1 to 2000 mm/sec, but not particularly limited.
The discharge gas flow rate is arbitrarily set based on the gas type of the discharge gas, treatment voltage, treatment current, treatment frequency, distance between electrodes, substrate treatment speed, irradiation distance, etc. It is preferably 5 to 300 liters/minute, more preferably 5 to 100 liters/minute, but is not particularly limited.
The irradiation distance (the distance between the substrate and the irradiation port) is arbitrarily set based on the gas type of the discharge gas, the processing voltage, the processing current, the processing frequency, the distance between the electrodes, the processing speed of the substrate, the flow rate of the discharge gas, and the like. , 0.1 to 10000 mm, preferably 0.3 to 5000 mm, more preferably 1 to 2000 mm, but not particularly limited.

In the case of direct type and/or remote type plasma processing, if the irradiation distance (the distance between the substrate and the irradiation port) is short (gas type of discharge gas, processing voltage, processing current, processing frequency, distance between electrodes, Although it varies depending on the substrate processing speed, the discharge gas flow rate, etc., in the case of less than 100 mm, the drying is mainly due to the reaction promoting action of the plasma-modified gas emitted from the plasma irradiation port by the light emitting part (excitation light part). It is assumed that curing occurs. Here, the light-emitting portion is a portion that can be visually observed as a flame-like light-emitting portion from the irradiation port under the condition that light is shielded, and is a portion that contains relatively highly active radicals and the like.
When the irradiation distance (the distance between the base material and the irradiation port) is long in the case of performing plasma processing by direct type and / or remote type (gas type of discharge gas, processing voltage, processing current, processing frequency, distance between electrodes, Although it varies depending on the substrate processing speed, the discharge gas flow rate, etc., in the case of 100 mm or more, drying and curing occurs mainly due to the reaction promotion effect of the quenching part of the plasma-modified gas ejected from the plasma irradiation port. guessed. Here, the quenching portion refers to a region downstream of the light-emitting portion in the plasma-denatured gas stream. or radicals contained in ambient gas (such as air) activated by the light-emitting portion and/or the light-quenching portion. Here, when the irradiation distance is long, usually, a part having a desired shape, such as a cylindrical member or a plate-like member, is provided at a desired position of the plasma irradiation device to converge and converge the gas modified by the plasma. Condensed and collected, the plasma-denatured gas can be jetted (plasma irradiation) to the base material. In general, the shorter the irradiation distance (the distance between the base material and the irradiation port after printing), the more dominant the drying and curing of the ink composition coating film is in many cases.

The plasma-curable ink composition of the present invention exhibits high reactivity when irradiated with plasma, and is highly reactive when using direct-type plasma and/or remote-type plasma. In either case, the drying and curing initiation time of the ink composition coating film is shortened and good drying and curing properties are exhibited.

<Printing Method Using Ink Composition for Plasma Curing>
A printing method using the plasma-curable ink composition of the present invention comprises a printing step of printing the plasma-curable ink composition on a substrate, and a plasma-curable ink composition present on the surface of the substrate after the printing step. and a plasma irradiation step of irradiating the coating film of the ink composition with plasma to dry and cure the coating film of the ink composition for plasma curing and fix it.

The printing step is a step of printing on a substrate using the plasma-curable ink composition of the present invention. The base material on which printing is performed may be of any shape such as sheet or three-dimensional, and may be of any material such as paper, plastic, metal, glass, ceramics, or wood. Paper, plastic film, metal plate, glass and the like are preferable. As the printing means, conventionally known various printing means can be used without limitation. For example, offset printing using dampening water, waterless offset printing without using dampening water, gravure printing, Various printing means such as printing, screen printing, pad printing, electrophotographic printing, and inkjet printing are used, and offset printing, screen printing, and inkjet printing are preferably used. In particular, when offset printing is used, sheet-fed printing, offset rotary printing, or the like is used as an example. When performing offset printing, in addition to normal offset printing using dampening water, waterless offset printing may be employed. After the printing process, the substrate is imaged with the undried ink composition, and the substrate is subjected to the plasma irradiation process.

In the plasma irradiation step, the substrate that has undergone the printing step is irradiated with plasma to cure and fix the ink composition present on the surface of the substrate. Plasma generated under various conditions can be used. Among these, atmospheric pressure plasma is preferable because it is easy to handle and is advantageous in terms of equipment and cost. A direct type plasma irradiation apparatus, a remote type plasma irradiation apparatus, and a combination type plasma irradiation apparatus can be used.
Here, the plasma and the plasma irradiation device can be those described in the above [plasma/plasma irradiation device]. Since the ink composition of the present invention has high reactivity to plasma irradiation, it can be sufficiently cured even by plasma generated from a remote plasma generator. Therefore, from the viewpoint of suppressing damage to the substrate and suppressing clogging of the substrate due to fluttering in the vertical direction that occurs when the substrate is conveyed, in this process, plasma is generated from a remote plasma generator. It is preferable to use a plasma with a

When plasma generated from a direct-type and/or remote-type plasma generator is used to cure an ink coating film, the plasma irradiation port (plasma gas jet port) is arranged in a line along the width direction of the substrate. is preferred. A plurality of point-shaped irradiation ports (plasma gas outlets) may be arranged in a row along the width direction of the substrate, or linear irradiation ports (plasma gas outlets) may be arranged along the width direction of the substrate. It may be arranged in the same way. Moreover, in order to adjust the curability of the ink composition, the temperature of the plasma with which the ink composition is irradiated may be adjusted, for example, by using a technique such as that described in Japanese Patent No. 4611409.
The discharge gas used for plasma generation is the same as that described in the above [Plasma/Plasma Irradiation Apparatus]. The discharge gas is turned into plasma by passing between electrodes connected to a high-frequency power source and in a discharging state, and is discharged from the discharge port toward the surface of the substrate.

[Use of ink composition for plasma curing]
When the plasma-curable ink composition of the present invention contains a coloring component, for example, images and characters are printed. ), etc., it is used for printing in various printing methods. It is useful for various types of printing such as ordinary printed materials for information transmission and appreciation, package printing, marking printing, and printing on three-dimensional objects.
The plasma-curable ink composition of the present invention can be applied to offset printing as a plasma-curable offset printing ink composition, and has the ability to be cured by being irradiated with plasma, which is an ionized gas. More specifically, components such as a binder and a liquid component contained in the ink composition are polymerized when exposed to plasma to increase the molecular weight, thereby curing the coating film of the ink composition formed by printing. . Therefore, when the ink film that is sticky on the surface of the printed matter is irradiated with plasma immediately after printing, the ink film instantly hardens and becomes dry (tack-free). The ink composition of the present invention can be applied not only to offset printing using dampening water, but also to waterless offset printing that does not use dampening water.

The ink composition and/or the additive for the ink composition of the present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[Preparation of varnish 1]
40.5 parts by mass of rosin-modified phenolic resin, 52.7 parts by mass of soybean oil, and 5.2 parts by mass of alkyd resin are charged into a reaction vessel, heated and stirred, and aluminum ethylacetoacetate diisopropylate (ALCH; gelling agent). Varnish 1 was prepared by charging 0.6 parts by mass into a reaction vessel and heating and stirring.

[Preparation of varnish 2]
A 4-necked flask equipped with a condenser, a thermometer and a stirrer was charged with 40.5 parts of a rosin-modified phenolic resin having a weight average molecular weight of 50,000 to 60,000 (Hariphenol P-160 manufactured by Harima Chemicals Co., Ltd.) and 58 parts of soybean oil. After charging 9 parts, the temperature was raised to 210° C., and the temperature was maintained for 40 minutes to dissolve the resin, and then aluminum ethyl acetoacetate diisopropylate (manufactured by Kawaken Fine Chemicals Co., Ltd., ALCH) was added in an amount of 0.6. A varnish was obtained by charging in parts and then heating and holding at 170° C. for 50 minutes.

[Ingredients used in Tables 1-14]
Titanium oxide 1: anatase-type titanium oxide, purity 98.9%, average particle size 9 nm, specific surface area 309.8 m ² /g
Zinc oxide 1: purity 99.60%, average particle size 100 nm
Zinc oxide 2: purity 98.50%, average particle size 70 nm
Titanium oxide 2: Anatase titanium oxide, purity 98.9%, average particle size 12 nm, specific surface area 159.5 m ² /g
Titanium oxide 3: Anatase-type titanium oxide, purity 85.1%, average particle size 10 nm, specific surface area 100 m ² /g (surface treated with silica and alumina)
Titanium oxide 4: rutile type titanium oxide, purity 97.5%, average particle size 16 nm, specific surface area 100 m ² /g
Copper oxide 1: purity 96.70%, D10 = 18.5 µm, specific surface area 21.5 m ² /g
Copper oxide 2: Purity 96%, D10 = 0.5 µm, specific surface area 28.6 m ² /g
Cuprous oxide 1: Purity 98.50%, D10 = 1.3 µm, specific surface area 0.8 m ² /g
Cuprous oxide 2: Purity 95.4%, specific surface area 36 m ² /g
Copper bromide: Cu:Br=44.4%:55%
Aluminum oxide 1: particle diameter 0.7 µm, specific surface area 7.5 m ² /g, amorphous silica ≤ 0.2 wt%, aluminum oxide ≥ 99.5 wt%, iron oxide ≤ 0.3 wt%
Aluminum oxide 2: particle diameter 10 µm, specific surface area 1.5 m ² /g, amorphous silica ≤ 0.2 wt%, aluminum oxide ≥ 99.5 wt%, iron oxide ≤ 0.3 wt%
Copper oxide catalyst 1: specific surface area 85 m ² /g, CuO 48 wt%, CaO 15 wt%, SiO ₂ 35 wt%
Copper oxide catalyst 2: specific surface area 134 m ² /g, CuO 56 wt%, SiO ₂ 4 wt%, ZrO ₂ 39 wt%
Copper oxide catalyst 3: specific surface area 85 m ² /g, CuO 48 wt%, CaO 15 wt%, SiO ₂ 35 wt%, Fe ₂ O ₃ 30 wt%, Al ₂ O ₃ 7 wt%
Nickel powder: specific surface area 222 m ² /g
Color pigment: phthalocyanine titanium oxide 5: anatase type titanium oxide, average particle size 15 nm, specific surface area 100 m ² /g
Oligomer: chlorinated polyester acrylate (manufactured by Sartomer, product name CN736)
Monomer: trimethylolpropane triacrylate (TMPTA)

(Examples 1 to 18; Comparative Example 1)
[Preparation of ink composition and evaluation of curability]
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), and the photocatalyst compound shown in Table 1 as the amount of the photocatalyst compound in the ink composition. Ink compositions of Examples 1 to 18 were prepared by blending and mixing equal amounts of each.
An ink composition of Comparative Example 1 was prepared by mixing 55 parts by mass of Varnish 1, 25 parts by mass of soybean oil, and 17 parts by mass of a coloring pigment (indigo pigment).
For the ink compositions of Examples 1 to 18 and Comparative Example 1, evaluation of curability upon plasma irradiation is also shown in Table 1.

For evaluation of curability, 0.1 cc of each ink composition was spread on a polypropylene film (manufactured by Sekisui Seisei Co., Ltd., Polytheme PC-8162) using an RI spreader, and the spread surface was measured using a remote plasma generator. was irradiated with plasma under the following irradiation conditions.
(Plasma irradiation conditions)
Gas type: Air Flow rate: 5 liters/min Irradiation aperture: 1 mm
Irradiation distance: 4mm
The color development surface of each ink composition is irradiated with plasma for 1 to 10 seconds at intervals of 1 second, and in each case, the color development surface is rubbed with absorbent cotton to wipe off uncured ink composition, and plasma curing is started. The time and diameter of the cured circular cured film at the plasma cure onset time were measured. Since the reactivity of the plasma is higher at the irradiation center and lower at the periphery, the reactivity of the ink composition to the plasma can be evaluated based on the cured diameter.

(Examples 19-36; Comparative Examples 2-7)
[Preparation of ink composition and evaluation of curability]
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), and the photocatalyst compounds (titanium oxides 1 to 3) listed in Table 2 as photocatalyst compound amounts in the ink composition. Ink compositions of Examples 19 to 36 were prepared by blending and mixing amounts corresponding to parts by weight shown in Table 2.
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), and titanium oxide 4 in an amount of parts by mass shown in Table 2 as the photocatalyst compound amount in the ink composition, respectively. By blending and mixing, ink compositions of Comparative Examples 2-7 were prepared.
For the ink compositions of Examples 19 to 36 and Comparative Examples 2 to 7, evaluation of curability upon plasma irradiation is also shown in Table 2.
Curability was evaluated under the same plasma irradiation conditions and the same measurement method as in Examples 1-18.

(Examples 37 to 70; Comparative Example 8)
[Preparation of ink composition and evaluation of curability]
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), a composite of the metal compound described in Table 3 and the titanium oxide 1, the metal in the ink composition Ink compositions of Examples 37 to 70 were prepared by blending and mixing the amounts of the compound and titanium oxide (photocatalyst compound) shown in Table 3, respectively. The composites of the metal compounds listed in Table 3 and the titanium oxide 1 were each formed by dry-mixing the metal compounds listed in Table 3 and the titanium oxide 1.
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, and 17 parts by mass of a coloring pigment (indigo pigment) were blended and mixed to prepare an ink composition of Comparative Example 8 (ink composition of Comparative Example 1 It is the same thing as a thing.).
For the ink compositions of Examples 37 to 70 and Comparative Example 8, evaluation of curability upon plasma irradiation is also shown in Table 3.
Curability was evaluated under the same plasma irradiation conditions and the same measurement method as in Examples 1-18.

(Examples 71-95, Comparative Examples 9-32)
[Preparation of ink composition and evaluation of curability]
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), a composite of a metal soap and a photocatalyst compound (a composite of a metal naphthenate and the titanium oxide 1) were mixed in the amount of the metal soap-derived metal (pure metal amount) and the amount of the photocatalyst compound shown in Table 4, respectively, and mixed to prepare the ink compositions of Examples 71 to 95. did. The composites of metal soap and titanium oxide 1 were formed by mixing melted metal soaps listed in Table 4 with titanium oxide 1, respectively.
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), and a metal naphthenate metal salt as a metal soap in the ink composition. were mixed in amounts corresponding to parts by mass shown in Table 5, and ink compositions of Comparative Examples 9 to 32 were prepared.
For the ink compositions of Examples 71 to 95 and Comparative Examples 9 to 32, Tables 4 and 5 also show the evaluation of curability when exposed to plasma.
Curability was evaluated under the same plasma irradiation conditions and the same measurement method as in Examples 1-18.

(Examples 96-118)
[Preparation of ink composition and evaluation of curability]
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), a composite of a metal soap and a photocatalyst compound (a composite of a metal naphthenate and the titanium oxide 1) were mixed in the amount of the metal soap-derived metal (metal pure content) and the amount of the photocatalyst compound shown in Table 6, respectively, and mixed to prepare the ink compositions of Examples 96 to 118. did. The composites of metal soap and titanium oxide 1 were prepared by mixing melted metal soaps shown in Table 6 with titanium oxide 1 . For the ink compositions of Examples 96 to 118, evaluation of curability upon plasma irradiation is also shown in Table 6.

For evaluation of curability, 0.1 cc of each ink composition was spread on a polypropylene film (manufactured by Sekisui Seisei Co., Ltd., Polytheme PC-8162) using an RI spreader, and the spread surface was measured using a remote plasma generator. was irradiated with plasma under the following irradiation conditions.
(Plasma irradiation conditions)
Gas type: Air Flow rate: 5 liters/min Irradiation aperture: 1 mm
Irradiation distance: 7mm
The color development surface of each ink composition is irradiated with plasma for 1 to 20 seconds at intervals of 1 second, and in each case, the color development surface is rubbed with absorbent cotton to wipe off the uncured ink composition, and plasma curing is started. The time and diameter of the cured circular cured film at the plasma cure onset time were measured. In Examples 96 to 118, the irradiation distance was set to 7 mm, thereby intentionally lowering the plasma processing ability in order to clarify the order of coating curability.

(Examples 119-142, Comparative Examples 33-56)
[Preparation of ink composition and evaluation of curability]
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), a composite of a copper metal soap and a photocatalyst compound (a composite of copper naphthenate and the titanium oxide 1) The amount of metal soap-derived metal (pure metal content; pure copper content) and the amount of photocatalyst compound (photocatalyst titanium oxide) in the ink composition, which are shown in Table 7, are each blended and mixed. 119-125 were prepared. The composite of the copper metal soap and the titanium oxide 1 was formed by mixing the melt of the copper metal soap and the titanium oxide 1, respectively.
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), and an amount of photocatalytic titanium oxide, which is a photocatalyst compound, as shown in Table 7. An ink composition according to Example 126 was prepared.
An ink composition according to Comparative Example 33 was prepared by mixing 55 parts by mass of Varnish 1, 25 parts by mass of soybean oil, and 17 parts by mass of a coloring pigment (indigo pigment).
55 parts by mass of the varnish 1, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), and copper naphthenate as a metal soap in the ink composition. Ink compositions according to Comparative Examples 34 to 40 were prepared by blending and mixing the amounts corresponding to parts by mass shown in Table 7 (pure amount).
Table 7 also shows the evaluation of the curability when irradiated with plasma for the ink compositions according to Examples 119 to 126 and Comparative Examples 33 to 40.

Ink compositions according to Examples 127 to 134 and Comparative Examples 41 to 48 were prepared in the same manner as in Examples 119 to 126 and Comparative Examples 33 to 40, except that soybean oil was changed to tung oil. The evaluation of curability upon preparation and plasma irradiation is also described.
Ink compositions according to Examples 135 to 142 and Comparative Examples 49 to 56 were prepared in the same manner as in Examples 119 to 126 and Comparative Examples 33 to 40 except that castor oil was used instead of soybean oil. was prepared, and the evaluation of curability upon plasma irradiation was also described.
The curability was evaluated under the same plasma irradiation conditions and the same measurement method as in Examples 96-118.

(Examples 143-179; Comparative Examples 57-61)
[Preparation of ink composition and evaluation of curability]
Ink compositions of Examples 143 to 171 and Comparative Examples 57 to 60 were prepared by mixing various materials according to the formulations shown in Tables 10 to 13 and kneading the mixture using a triple roll. The amount of each component shown in Tables 10 to 13 is parts by mass.
Ink compositions of Examples 172 to 179 and Comparative Example 61 were prepared by mixing various materials according to the formulations shown in Table 14 and kneading the mixture using a triple roll. The blending amount of each component shown in Table 14 is parts by mass.

For evaluation of curability, 0.1 cc of a sample of the ink composition was taken and a PP (polypropylene) film (manufactured by Sekisui Seisaku Kogyo Co., Ltd., product name: Polytheme PC) was used with an RI color development machine (2-split roll, manufactured by Akira Seisakusho Co., Ltd.). -8162), and plasma was irradiated onto the surface of the display using a damage-free multi-gas plasma jet (remote plasma generator) manufactured by Plasma Concept Tokyo Co., Ltd. At that time, the plasma gas was air (flow rate 5 L/min), the plasma irradiation diameter was 1 mm, and the irradiation distance was 4 mm.
For each ink composition, irradiation was performed while changing the plasma irradiation time from 0.5 seconds to 10 seconds at intervals of 0.5 or 1 second. Wipe off and measure the diameter of the cured circular film. Then, the number of seconds required for irradiation to start curing and the diameter of the cured coating film at an irradiation time of 6 seconds were used for evaluation.
The results are shown in the "hardening start" and "hardening diameter" columns of Tables 10 to 13. The shorter the time to start curing, the higher the reactivity of the ink composition to plasma. In addition, since the reactivity of the plasma is higher at the irradiation center and lower at the periphery, an ink composition having a larger curing diameter is an ink composition with higher plasma reactivity.

As shown in Tables 1 to 14, by using a "photocatalyst compound" and/or a "composite of a metal component and a photocatalyst compound" as a constituent component of a plasma-curable ink composition, the drying and curing start time can be shortened. can be done. In addition, the dry curability can be improved (the diameter of the dried and cured coating film can be increased).
As shown in Tables 1, 2, and 10 to 14, by using a photocatalyst compound as a constituent component of a plasma-curable ink composition, when a compound (rutile-type titanium oxide) that is not a photocatalyst compound is used, or the photocatalyst component The drying and hardening start time can be significantly shortened compared to the case where is not used. In addition, the dry curability can be improved (the diameter of the dried and cured coating film can be increased).
As shown in Tables 3 to 9, by using the composite of the metal component and the photocatalyst compound as a constituent component of the plasma-curable ink composition, when only the metal component is used, or when neither the metal component nor the photocatalyst compound is used. Compared to the case, the drying and hardening start time can be greatly shortened. In addition, the dry curability can be improved (the diameter of the dried and cured coating film can be increased).
In particular, in a soybean oil-based ink composition, which has the lowest curability, by using a "photocatalyst compound" and/or a "composite of a metal component and a photocatalyst compound" as a curing accelerator, the drying curing start time and drying It can be seen that the effect of improving the curability (increasing the diameter of the dried and cured coating film) is remarkably exhibited.
As shown in Table 14, it can be seen that ink compositions prepared using binders (oligomers) and monomers having ethylenically unsaturated bonds exhibit the same tendency as above.

Claims (12)

A plasma-curable ink composition comprising a photocatalyst compound and/or a composite of a metal component and a photocatalyst compound. 2. The plasma-curable ink composition according to claim 1, wherein said photocatalyst compound comprises titanium oxide and/or zinc oxide. 3. The plasma-curable ink composition according to claim 1, wherein said metal component is at least one selected from metals, metal oxides and metal soaps. 4. The plasma-curable ink composition according to any one of claims 1 to 3, further comprising a binder. 5. The plasma-curing ink according to any one of claims 1 to 4, further comprising at least one selected from the group consisting of animal and plant oils and/or animal and plant oil derivatives, and liquid compounds having ethylenically unsaturated bonds. Composition. 6. The plasma-curing ink composition according to claim 5, wherein the animal or plant oil and/or animal or plant oil derivative is an animal or plant oil and/or animal or plant oil derivative having an iodine value of 80 or more. 7. The plasma according to claim 5 or 6, wherein the animal or plant oil and/or animal or plant oil derivative is at least one selected from the group consisting of soybean oil, tung oil, linseed oil, castor oil, and modified products thereof. A curable ink composition. An additive for a plasma-curable ink composition comprising a photocatalytic compound and/or a composite of a metal component and a photocatalytic compound. A printing step of printing on a substrate using the plasma-curable ink composition according to any one of claims 1 to 7; and a plasma irradiation step in which an existing ink composition is fixed by curing. 10. The method of manufacturing printed matter according to claim 9, wherein the plasma is generated by a remote plasma generator. 11. The plasma is generated by passing air, oxygen gas, nitrogen gas, carbon dioxide gas, or a mixed gas containing two or more selected from these between electrodes during discharge. A method for producing the described printed matter. Printing is performed on a substrate using the plasma-curable ink composition according to any one of claims 1 to 7, and then the surface of the printed ink composition is irradiated with plasma to obtain the ink composition. A printing method in which the is fixed to a substrate.