JP7139196B2 - Plasma-curable ink composition and additive for plasma-curable ink composition - Google Patents

Description

The present invention provides a plasma-curable ink composition containing at least one selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond. and one or more selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond. for additives.

Typical printing methods currently in use include offset printing, gravure printing, flexographic printing, screen printing, and inkjet printing. Among these, the offset printing method is used when printing a large amount of printed matter quickly. Mainly used.
Unless the ink composition adhering to the surface of the printed material is sufficiently dried and hardened to fix the printed material, set-off may occur when the printed materials are stacked, or the printed material may be touched with a finger. Since the ink adheres to the product when it is pressed, it cannot be sent to the 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 material to fix it on the surface of the substrate is required.

Here, as means for drying and curing the ink composition adhering to the surface of the printed matter to fix it on the surface of the substrate, there are mainly four methods of evaporation, permeation, oxidative polymerization, and photopolymerization, depending on the ink composition. It is known to use For example, systems that dry and harden and fix the coating film of ink in offset printing include the penetration drying type typified by newspaper printing, the oxidative polymerization type typified by sheet-fed printing, and the light-curing type using ultraviolet (UV) rays. In addition, the evaporation drying method represented by off-wheel printing is the mainstream, and from the viewpoint of energy saving and environmental load, new applications of UV curing such as LED curing and energy ray (EB) curing are being introduced. Dry cure systems have also been developed.

The method of drying, hardening and fixing the ink composition by evaporation uses mineral oil, which is a volatile component, as a solvent component, and although it has relatively high productivity, it uses many mineral-derived raw materials. The biomass content is low, the environmental load is large due to the release of VOCs (volatile organic compounds) into the atmosphere, and there are concerns about safety.
The method of drying and fixing the ink composition by permeation is a method in which the oil component contained in the ink composition adhering to the surface of the printed matter penetrates into the interior of the printed matter to dry the surface, and the drying state is relatively fast. However, it is not suitable for printing where the paper is limited to raw paper or the like and high cosmetic properties are required because the solvent needs to permeate the paper quickly.

From this point of view, there is a tendency to adopt a method of drying and fixing the ink composition by oxidative polymerization or photopolymerization 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 composition by oxidative 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 These unsaturated oils are oxidatively polymerized to form non-sticky (that is, dry) films. Since this ink composition can use many plant-derived raw materials, it is possible to increase the degree of biomass. It is possible to obtain printed matter with a low environmental impact.
However, the chemical reaction for oxidative polymerization of the unsaturated oil requires a relatively long time, resulting in poor quick-drying properties, which may cause problems due to poor drying and fixation of the ink composition.

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. The main ink composition used in this method contains a monomer or oligomer with an ethylenically unsaturated bond and a photopolymerization initiator that generates radicals when irradiated with active energy rays such as ultraviolet rays. By irradiating them with radiation, they instantly radically polymerize to form a non-sticky (i.e. dry) film without releasing large amounts of VOCs into the atmosphere.
However, the ink composition used in the photopolymerization method cannot have a high degree of biomass, and there are concerns about environmental impact and safety, such as the possibility that monomers may remain in printed matter. Due to regulations and safety regulations, regulations on the use of monomers and the use of photopolymerization initiators are expected in the future.

Under such circumstances, various proposals have been made so far.
Japanese Patent Application Laid-Open No. 2007-54987 (Patent Document 1) describes a new drying and fixing method for oxidative polymerization type oil-based ink, in which ions are generated by atmospheric pressure plasma to produce a non-volatile ink that is used in sheet-fed offset printing. It has been proposed to shorten the drying and fixing time by promoting the oxygen radical cross-linking polymerization of sheet-fed offset ink. In the examples, TK Hi-Echo NV100 manufactured by Toyo Ink Mfg. Co., Ltd. was used as an oxidative polymerization type oil ink containing no volatile organic compounds, and anions generated by plasma were brought into contact with the oxidative polymerization type ink. is disclosed.
However, an ink composition containing one or more selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond is not described. . In addition, there is a problem in terms of quick-drying because it takes several minutes to dry and fix, and it is difficult to apply it to a large-scale printing method.

In Japanese Patent Application Laid-Open No. 2008-12919 (Patent Document 2), an image recorded on a recording medium using a recording agent containing a component that is cured by plasma treatment is subjected to the plasma treatment, thereby converting the image into the above-described image. An image fixing method has been proposed that includes a step of fixing an image onto a recording medium.
Although the detailed description of the invention describes the use of an ink composition that may contain various alcohols as the recording agent, the examples describe carbon black, rosin-modified phenolic resin, linseed oil, A printed image is formed with an offset ink containing a high-boiling petroleum solvent and a drier, or an inkjet ink containing a dye, styrene-acrylic acid-ethyl acrylate copolymer, glycerin, ethylene glycol and a surfactant, followed by plasma irradiation. It is only disclosed that the image is fixed by means of
Further, there is no description of an ink composition containing at least one selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond. .

Japanese Patent Application Publication No. 2005-523803 (Patent Document 3) describes curing various printing inks in a plasma discharge chamber, which may contain an oxidatively drying alkyd system. It is not clear what kind of ink to use.

Japanese Patent Application Laid-Open No. 51-52494 (Patent Document 4) discloses that a steel plate is coated with a radiation-curable composition containing a urea-urethane oligomer, an acrylic compound and a photoinitiator, and exposed to a continuous beam of light from an argon swirl plasma arc. It is described to be cured by exposing for 0.6 seconds, but the degree of biomass is low, and monohydric alcohols, dihydric alcohols with 4 or more carbon atoms having two primary hydroxyl groups and 2 having ether bonds There is no description of ink compositions containing at least one selected from the group consisting of functional alcohols.

Japanese Patent Application Laid-Open No. 2007-106105 (Patent Document 5) discloses that a printing ink containing at least a non-volatile organic compound having a carboxyl group and containing no photopolymerization initiator is produced by inter-electrode discharge at near atmospheric pressure. A method of fixing an ink is described that includes an ink fixing step for fixing to a substrate by means of an ink-fixing step.
However, this printing ink (ink composition) has a low biomass content, and although printing inks (ink compositions) containing glycerin, 1,3-BD or castor oil have been described, monovalent An ink composition containing one or more selected from the group consisting of alcohols, dihydric alcohols having 4 or more carbon atoms having two primary hydroxyl groups, and dihydric alcohols having an ether bond is not described.

Japanese Patent Application Laid-Open No. 2013-10933 (Patent Document 6) discloses an ink containing at least one of a polymerization initiator and a chain transfer agent, at least one radically polymerizable compound, and at least one coloring material. on the surface of a substrate in an imagewise manner, and plasma-irradiating said composition to form an image comprising a plasma-polymerized film. ing.
However, although the detailed description of the invention describes that an ink composition that may contain various alcohols is used as a composition for forming an image, in the examples, a monohydric alcohol , the use of an ink composition containing one or more selected from the group consisting of dihydric alcohols having 4 or more carbon atoms having two primary hydroxyl groups and dihydric alcohols having an ether bond is not described.

Japanese Patent Application Laid-Open No. 2008-297506 (Patent Document 7) discloses an ink fixing method including at least an ink fixing step of fixing ink on a substrate to a substrate using discharge between electrodes near atmospheric pressure, wherein the ink is , describes an ink fixing method containing at least polyvinylpyrrolidone and glycerin, but has a low biomass degree, a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and an ether bond. An ink composition containing one or more selected from the group consisting of dihydric alcohols is not described.

Japanese Patent Application Laid-Open No. 2015-140390 (Patent Document 8) describes a printed matter obtained by printing printing ink on printing paper and further surface-treating the printed surface, wherein the surface treatment is corona treatment, flame treatment or plasma treatment. , printed matter having a specific surface resistivity value of a specific value or less after treatment is described.
In the detailed description of the invention, it is described that an ink composition that may contain various alcohols is used as the printing ink (ink composition). There is no description of using an ink composition containing at least one selected from the group consisting of dihydric alcohols having 4 or more carbon atoms and having two hydroxyl groups and dihydric alcohols having an ether bond.
Moreover, in the examples, it is only described that the printed material 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.

JP-A-2007-54987 JP 2008-12919 A Japanese Patent Publication No. 2005-523803 JP-A-51-52494 JP 2007-106105 A JP 2013-10933 A JP 2008-297506 A JP 2015-140390 A

The present invention has been made in view of the above circumstances, and 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 curing properties of the ink composition film. do.
It is another object of the present invention 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 film. aim.
Another 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 present inventors have made intensive studies to solve the above problems, and found that from a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond It has been found that when a printed film of a plasma-curable ink composition containing one or more selected from the group is irradiated with plasma, the drying and curing start time is shortened and the drying and curability of the ink composition film is improved. rice field.

In particular, even if the plasma-curing ink composition contains an animal or vegetable oil and/or a derivative thereof or is of the oxidation polymerization type, By containing one or more selected from the group consisting of dihydric alcohols and dihydric alcohols having an ether bond, the drying and curing start time is shortened, and the drying and curing properties of the 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 one or more selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond.
(2) The plasma-curable ink composition of (1), further comprising a binder.
(3) The plasma-curable ink composition of (1) or (2), further comprising an animal or plant oil and/or an animal or plant oil derivative.
(4) The plasma-curing ink composition according to (3) above, 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.
(5) A plasma-curable ink composition containing at least one selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond. Additive for.

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 film are further improved, resulting in a high reaction rate. A plasma curable ink composition with properties is provided.
Further, according to the present invention, with respect to 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 film can be formed. Provided is an additive for a plasma-curable ink composition that can further improve the dry curability of the ink composition.
As a result, it is possible to construct a printing system using a plasma-curable ink composition that does not emit a volatile organic solvent, has a small environmental load, is excellent in safety, and has a high degree of biomass.

An embodiment of the plasma-curable ink composition and the additive for the plasma-curable ink composition of the present invention will be described below. 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 at least one selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond. In addition, it may contain binders, animal and plant oils and / or animal and plant oil derivatives and / or conjugated polyene compounds, and other components such as liquid components and various additives You can
The additive for the plasma-curable ink composition of the present invention is selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond. It contains one or more types, and in addition, it may contain a binder, an animal and plant oil and / or an animal and plant oil derivative and / or a conjugated polyene compound, and further liquid components, other additives such as various additives may contain components of

The present inventors investigated various hydroxyl group-containing compounds to be added to the plasma-curable ink composition, and found that the addition of a trihydric or higher alcohol (e.g., glycerin or pentaerythritol) resulted in a plasma-curable ink composition. It was discovered that the drying and curing by plasma irradiation was inhibited. On the other hand, if one or more selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond is particularly selected and added, plasma curing can be achieved. It has been found that drying and curing of an ink composition for ink composition by plasma irradiation is accelerated (especially, drying and curing start time is shortened).
Based on these findings, the plasma-curable ink composition of the present invention and the additive for the plasma-curable ink composition of the present invention are a monohydric alcohol and a primary hydroxyl group having 4 or more carbon atoms having two primary hydroxyl groups. and one or more selected from the group consisting of dihydric alcohols and dihydric alcohols having an ether bond.
The plasma-curable ink composition of the present invention and the additive for the plasma-curable ink composition are described in detail below.

[Monohydric alcohol]
The monohydric alcohol 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 has a structure in which one hydroxyl group is bonded to an organic group having 1 to 30 carbon atoms. have Examples of the organic group include saturated hydrocarbon groups and unsaturated hydrocarbon groups, which may be linear or branched and may have a ring structure. Monohydric alcohols may be primary alcohols, secondary alcohols or tertiary alcohols.

Monohydric alcohols that are primary alcohols include, for example, methanol, ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-methyl-1-butanol, 3-methyl -1-butanol, 4-methyl-1-butanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, undecan-1-ol, dodecane-1-ol (lauryl alcohol), tridecane -1-ol, tetradecane-1-ol (myristyl alcohol), pentadecane-1-ol, hexadecan-1-ol (cetyl alcohol), heptadecane-1-ol, octadecan-1-ol (stearyl alcohol), isostearyl alcohol , nonadecan-1-ol, icosan-1-ol, heneicosan-1-ol, docosan-1-ol (behenyl alcohol), tricosan-1-ol, tetracosan-1-ol, pentacosan-1-ol, hexacosan-1-ol ol, heptacosan-1-ol, octacosan-1-ol, nonacosan-1-ol, triacontan-1-ol, allyl alcohol, oleyl alcohol, linolyl alcohol, 3-buten-1-ol, crotyl alcohol, 4 -Penten-1-ol, 3-penten-1-ol, cinnamyl alcohol, benzyl alcohol and the like, but not limited thereto.

Monohydric alcohols that are secondary alcohols include, for example, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, 2-hexanol, 3-hexanol, 3- methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 4-methyl-3-pentanol, 2-2-ol, 2-heptanol, 3-heptanol, 4- Heptanol, 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, cyclopropanol, cyclo One or more of butanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, 4-penten-2-ol, 3-penten-2-ol and the like, but particularly Not limited.

Monohydric alcohols that are tertiary alcohols include, for example, 2-methyl-2-propanol (t-butyl alcohol), 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3 -pentanol, 2-methyl-2-hexanol, 3-methyl-3-hexanol, 3-ethyl-3-pentanol, 2-methyl-2-heptanol, 3-methyl-3-heptanol, 4-methyl-4 -heptanol, 3-methyl-3-octanol, 2-methyl-3-buten-2-ol, 2-hydroxy-2,5-dimethyl-5-hexene and the like, but not limited thereto.

Among these, preferably methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cinnamyl alcohol, isostearyl alcohol, benzyl alcohol, allyl alcohol, oleyl alcohol, 2-propanol, 2-butanol, 2-pentanol, cyclohexanol, 4-penten-2-ol, 3-penten-2-ol, 2-methyl-2-propanol one or more selected from the group consisting of (t-butyl alcohol), 2-methyl-2-butanol, 2-methyl-3-buten-2-ol, and 2-hydroxy-2,5-dimethyl-5-hexene can give. More preferably, one or more selected from the group consisting of 1-butanol, 1-hexanol, 2-butanol and 2-methyl-2-propanol (t-butyl alcohol).

[Dihydric alcohol having 4 or more carbon atoms and two primary hydroxyl groups]
The dihydric alcohol having 4 or more carbon atoms and having two primary hydroxyl groups 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 has 1 carbon atom. It is a dihydric alcohol having a structure in which two primary hydroxyl groups are bonded to ~30 organic groups. Examples of the organic group include saturated hydrocarbon groups and unsaturated hydrocarbon groups, which may be linear or branched and may have a ring structure.

Examples of dihydric alcohols having 4 or more carbon atoms and having two primary hydroxyl groups include 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 2,2- Dimethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 1,6-hexanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-ethyl-1,4- butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tride candiol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, etc. One or more types can be used, but there is no particular limitation.
Among these, preferably 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1 ,4-butanediol and 1,6-hexanediol. More preferably, one or more selected from the group consisting of 1,4-butanediol, 2-methyl-1,3-propanediol, and 1,6-hexanediol.

[Dihydric alcohol having an ether bond]
The dihydric alcohol having an ether bond 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 represented by the following general formula (1) or (2)
HO—(—R ¹ —O—) _n —R ² —OH (1)
R ³ —OR ⁴ —(OH) ₂ (2)
(Wherein, R ¹ , R ² and R ⁴ are divalent organic groups having 1 to 30 carbon atoms which may be the same or different, and R ³ is a monovalent organic group having 1 to 30 carbon atoms. , n is an integer of 1 or more.When n is 2 or more, two or more R1 may be the same or different.)
It is a compound represented by Examples of the organic group include saturated hydrocarbon groups and unsaturated hydrocarbon groups, which may be linear or branched and have two or more cyclic structures or ether bonds. good too.

Examples of dihydric alcohols having an ether bond include di-, tri-, tetra- and polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and polypropylene glycol. One or more of the compounds of the system are included, but not particularly limited.
Among these, one or more selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, and tripropylene glycol are preferred. More preferably, one or more selected from the group consisting of diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.

At least one selected from the group consisting of the monohydric alcohol, the dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and the dihydric alcohol having an ether bond contained in the plasma-curable ink composition of the present invention. The content of is usually 0.001 to 20% by mass, preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total plasma-curable ink composition.
At least one selected from the group consisting of the monohydric alcohol, the dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and the dihydric alcohol having an ether bond contained in the plasma-curable ink composition of the present invention. is outside the above range, it may be difficult to shorten the drying and curing start time and to improve the drying and curing properties of the film when the printed film of the plasma-curable ink composition is irradiated with plasma. .
from the group consisting of the monohydric alcohol, the dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and the dihydric alcohol having an ether bond contained in the additive for the plasma-curable ink composition of the present invention; The content of the selected one or more is appropriately set in the range of 0.001 to 100% by mass with respect to the total additives for the plasma-curable ink composition.
from the group consisting of the monohydric alcohol, the dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and the dihydric alcohol having an ether bond contained in the additive for the plasma-curable ink composition of the present invention; If one or more selected are out of the above range, it may be difficult to prepare the composition of the plasma-curable ink composition when blending it into the plasma-curable ink composition.
The plasma-curable ink composition of the present invention and/or the additive for the plasma-curable ink composition of the present invention may or may not contain a trihydric or higher alcohol.
When it contains a trihydric or higher alcohol, it contains one or more selected from the group consisting of the monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond. It is contained in an amount within a range that does not hinder the curing obtained by curing.

[binder]
Binders that may be contained in the plasma-curable ink composition and/or additives for the plasma-curable ink composition of the present invention include resins used as binders and binders in the field of ink compositions, A curable compound having an ethylenically unsaturated bond can be used without particular limitation, and one or a mixture of two or more thereof 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), acrylic modified Phenolic resin, rosin-modified phenol-based resin, rosin-modified maleic acid-based resin, rosin-modified alkyd-based resin, rosin-modified petroleum-based resin, rosin ester-based resin, petroleum-based resin-modified phenol-based resin, alkyd-based resin, vegetable oil-modified alkyd-based At least one resin selected from the group consisting of resins, petroleum-based resins, and hydrocarbon-based resins (polybutene, polybutadiene, etc.) and 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.

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, eleo Natural or synthetic fatty acids having about 2 to 30 carbon atoms such as stearic acid, acetic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, citraconic anhydride, acrylic acid, and methacrylic acid; Soybean oil, 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, animal and plant oils such as beeswax; (boil oil), heat-polymerized oil (stand oil), dehydrated products, esterified products and other modified products of animal and plant oils); can be done.

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. Acid, saturated or unsaturated fatty acid with 14 to 30 carbon atoms such as oleic acid, linoleic acid, linolenic acid and eleostearic acid, and linear or branched monohydric alcohol with 1 to 10 carbon atoms. It is an oil-derived fatty acid ester.

Examples of such modified animal and plant oils include, for example, polymerized soybean oil, polymerized linseed oil, polymerized castor oil, polymerized paulownia oil, dehydrated castor oil, polymerized dehydrated castor oil, and the like. boiled oil), 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 esters derived from animal and plant oils;
Preferred examples of fatty acid-modified materials include coconut oil and those having an iodine value of 80 or more, and particularly preferred are coconut oil, paulownia oil, soybean oil, tall oil, linseed oil, castor oil, safflower oil, perilla oil, At least one of polymerized soybean oil, polymerized linseed oil, polymerized castor oil, polymerized paulownia 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; Modified polymerized rosin, disproportionated rosin, stabilized rosin, hydrogenated rosin, chemically modified rosin by introducing various functional groups, rosin ester resin, rosin alcohol resin, rosin resin metal salt, etc. can be used, and a mixture of one or more of these 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 include epoxy-modified esters (meth)acrylic acid and hydroxyl groups generated after the epoxy groups contained in epoxy compounds such as epoxy resins are ring-opened with acids or bases. meth) acrylates, rosin-modified epoxy acrylates, polyester-modified (meth) acrylates exemplified by esters of terminal hydroxyl groups of polycondensation products of dibasic acids and diols and (meth) acrylic acid, terminal hydroxyl groups of polyether compounds and ( Polyether-modified (meth)acrylates exemplified by esters with meth)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 Acrylate and the like can be mentioned. Such oligomers are commercially available and include, for example, the Ebecryl series from Daicel Cytec, CN, SR series from Sartomer, Aronix M-6000 series, 7000 series, 8000 series from Toagosei Co., Ltd. It is available under trade names such as Aronix M-1100, Aronix M-1200, Aronix M-1600, and NK Oligo manufactured by Shin-Nakamura Chemical Co., Ltd. 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.

The curable compound having an ethylenically unsaturated bond is a monofunctional monomer having one ethylenically unsaturated bond in the molecule, which is capable of curing the ink composition by being polymerized by irradiation with plasma. and 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, so they are useful for increasing the curing speed and forming a strong film. Although the monomer does not have the above-mentioned cross-linking ability, it is useful for reducing curing shrinkage due to cross-linking. 1 or 2 or more of the monomers can be used in any 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)acryloyloxyethylhexahydrophthalimide , N-(meth)acryloylmorpholine, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-butyrolactone (meth)acrylate, caprolactone Heterocycle-containing (meth)acrylates such as 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.

As the bifunctional monomer, any conventionally known one 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,

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 modified 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 more 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 include 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, the binder is usually 0 to 70% by mass, preferably 0 to 50% by mass, particularly preferably 15 to 70% by mass, in the plasma-curable ink composition of the present invention. It is blended in an amount of 30% by mass.
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, paulownia oil, soybean oil, linseed oil, castor oil, 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 plant 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 paulownia oil, soybean oil, linseed oil, castor oil, safflower oil and perilla oil are particularly preferred. One or more of soybean oil, castor oil and linseed oil are used.

Examples of the 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 modified products of the animal and plant oils described above.
Here, as the modified animal and plant oils, one or more of oxidatively polymerized oils (boiled oils), thermally polymerized oils (stand oils), dehydrated products, esterified products, etc. of the above animal and plant oils can be used. can.
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, eleostearic acid, and linear or branched monohydric alcohols with 1 to 10 carbon atoms derived from animal and plant oils It is a fatty acid ester.

Such modified animal and plant oils include, for example, polymerized soybean oil, polymerized linseed oil, polymerized castor oil, polymerized paulownia oil, dehydrated castor oil, polymerized dehydrated castor oil, and other oxidatively polymerized oils ( boiled oil), 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 esters derived from animal and plant oils;
Among these, those having an iodine value of 80 or more are preferred, and particularly preferred are polymerized soybean oil, polymerized linseed oil, polymerized castor oil, polymerized paulownia oil, polymerized dehydrated castor oil, dehydrated castor oil, soybean oil butyl ester, At least one of linseed oil butyl ester and paulownia 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.
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 to 70% by mass, particularly preferably 40 to 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.

[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, conjugated polyene compounds, colorants (coloring pigments, brightening pigments, dyes, fluorescent pigments, colored resin particles, etc.), extender pigments, dispersants, surfactants, stabilizers, antifoaming agents, agent, polymerization initiator, anti-friction agent (wax), gelling agent, viscosity modifier, plasticizer, polymerization inhibitor, antioxidant, pH adjuster, sterilization/antifungal agent, silane coupling agent, etc. Additives commonly used in the field of products can be mentioned. In addition, drying curing accelerators that are not "one or more selected from the group consisting of monohydric alcohols, dihydric alcohols having 4 or more carbon atoms having two primary hydroxyl groups, and dihydric alcohols having an ether bond" are mentioned. be done.
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-curable 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 includes liquid components that have been used in the preparation of ink compositions. It is used for dissolving a resin to make a varnish or for adjusting the viscosity of an ink composition, and the above-mentioned monohydric alcohol and carbon number 4 or more having two primary hydroxyl groups A liquid component other than a liquid one or more selected from the group consisting of a dihydric alcohol and a dihydric alcohol having an ether bond, a liquid component other than a liquid binder among the binders, the animal and plant oils and It is a liquid component other than the liquid one among the animal and plant oil derivatives. Examples of such liquid components include liquid compounds such as organic solvents, mineral oils, and water, which exhibit a liquid state at the printing temperature (usually 10° C. to 40° C.).

Examples of the organic solvent 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; chloroform; Chlorine-based solvents such as methylene chloride, aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon-based solvents such as n-hexane, n-pentane, and cyclohexane, and petroleum-based hydrocarbon-based 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; Organic solvents such as cyclic ester solvents such as butyrolactone and amide solvents such as 2-methylpyrrolidone, 2-pyrrolidone and dimethylacetamide can be used, and one or more of these can be used.

Mineral oils include, for example, light mineral oils and heavy mineral oils, and the content of condensed polycyclic aromatic components has been suppressed from the viewpoint of conforming to OSHA standards in the United States and EU standards. It is preferable to be Light mineral oils are classified into non-aromatic petroleum solvents having a boiling point of 160°C or higher, preferably 200°C or higher, and heavy mineral oils are classified as spindle oils, machine oils, dynamo oils, cylinder oils, and the like. Specific examples include JX Nippon Oil & Energy Corporation's No. 0 Solvent, AF Solvent No. 5, AF Solvent No. 6, AF Solvent No. 7, Ink Oil H8, and Ink Oil H35. , SNH8, SNH46, SNH220 and SNH540 manufactured by Sankyo Yuka Kogyo 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.

(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 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 paulownia 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, examples of conjugated dienes having a conjugated structure with two carbon-carbon double bonds include 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, examples of conjugated triene compounds having a conjugated structure of three carbon-carbon double bonds include 1,3,5-hexatriene and 2,4,6-octatriene-1-carboxylic acid. , eleostearic acid, paulownia oil, cholecalciferol, and the like.
Among conjugated polyene compounds, examples of conjugated polyene compounds having a conjugated structure having 4 or more carbon-carbon double bonds include cyclooctatetraene, 2,4,6,8-decatetraene-1-carboxylic acid, retinol, and retinoin. acid, parinaric acid, balsamic seed oil, carotenes, and the like.

As these conjugated polyene compounds, animal and plant oils, eleostearic acid, etc. are preferred, and dehydrated castor oil, paulownia 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.
Such a conjugated polyene compound is preferably contained in an amount of 0 to 70% by mass, preferably 0 to 50% by mass, more preferably 5 to 30% by mass, based on the total plasma-curable ink composition of the present invention. Also, the conjugated polyene compound is contained in an amount of about 0 to 99% by mass relative to the total amount of additives for the plasma-curable ink composition of the present invention, but is not particularly limited.

(coloring agent)
As the coloring 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, coloring power that has been used in the preparation of ink compositions so far can be used. Any component can be used as long as it is a component to be imparted, and examples thereof include inorganic coloring pigments, organic coloring pigments, luster pigments, dyes, fluorescent pigments, colored resin particles, and the like. may be particles or a dispersion liquid, and two or more kinds of colorants may be mixed and used to obtain a desired color tone.
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.

Examples of the coloring pigment 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, chromium-titanium, bismuth-vanadium, cobalt-aluminum, cobalt-aluminum-chromium, ultramarine blue) and the like can be used.

Examples of 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, 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, and the like 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. is.
Dyes include water-soluble dyes of various colors such as red, blue, yellow, green, purple, black, white, orange and brown, oil-soluble dyes and disperse dyes, which have been conventionally used in ink compositions. These may be acid dyes, substantive dyes, basic dyes, reactive dyes, food dyes.

As the fluorescent pigment, a pigment that emits light in a wavelength range different from the above-mentioned wavelength using light of a specific wavelength such as ultraviolet light or infrared light as excitation energy 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 resins such as polyolefin, polystyrene, acrylic resin and urethane resin can be used.
Further, as the pigment, a self-dispersing pigment may be used in which at least one hydrophilic group or lipophilic group is bonded directly or through various atomic groups to the surface of the pigment. As the self-dispersion pigment, an ionic one is preferable, and an anionically charged one is particularly preferable.

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; Rosin, 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 esters 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. Resins; metal salts of these various rosin-based compounds and the like 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. Neoabietic acid, dehydroabietic acid, dehydroabietic acid, tetrahydroabietic acid, tetrahydroabietic acid, palastric acid, parastrate, levopimaric acid, levopimarate, pimaric acid, pimarate, isopimaric acid, isopimarate , citronellic acid, and citronellate, 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 size of 0.001 to 100 μm, preferably 0.01 to 50 μm, 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.
Methods for preparing such rosin-treated particles include, for example, a method of adding a rosin-based compound to a pigment paste and mixing, a method of adding a powdered rosin-based compound to dry pigment particles and mixing, a method of A method of mixing a slurry and a rosin soap (or an alkaline aqueous solution of rosin) and then adding an alkaline earth metal salt, an acid, or the like to precipitate a rosin sparingly soluble salt or a rosin free acid on the surface of a pigment; A method of mixing an alkali metal salt of a dye and a rosin soap (or an alkaline aqueous solution of rosin), adding an alkaline earth metal salt or the like to form a lake of the dye, and depositing rosin on the surface at the same time; For example, a mixture with a metal salt is mixed with a mixture of a coupling component and a rosin soap (or an alkaline aqueous solution of rosin), coupled to form a lake, and treated with rosin.

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 such rosin-treated particles, it is presumed that the rosin present on the particle surface serves as a starting point for the curing reaction by plasma, thereby accelerating the curing of the ink film by plasma.
Such a colorant is preferably about 0 to 33% by mass relative to the entire plasma-curable ink composition of the present invention, and 0 to 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.

(Extender pigment)
Extender pigments that may be contained in the plasma-curable ink composition and/or additives for the plasma-curable ink composition of the present invention include extender pigments that have been used in the preparation of ink compositions. Any one can be used as long as it exists, and it may be in the form of a powder or a dispersion in an appropriate solvent, and may be used singly 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 size 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 size of 0.001 to 100 μm, preferably 0.01 to 50 μm, 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.), Shiroenka (rosin-treated calcium carbonate manufactured by Shiraishi Calcium Co., Ltd.), and the like.
Examples of methods for preparing rosin-treated particles include a method of adding rosin to a pigment paste and mixing, a method of adding powdery rosin to dry pigment particles and mixing, and a method of adding 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 poorly 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 such rosin-treated particles, it is presumed that the rosin present on the particle surface serves as a starting point for the curing reaction by plasma, thereby accelerating the curing of the ink film by plasma.
Such an 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 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.

(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, and amphoteric dispersants. and nonionic dispersants, and any of high-molecular-weight compounds, low-molecular-weight compounds (surfactants), and pigment derivatives may be used.
Dispersants include, for example, polyvinyl alcohol-based compounds, polyvinylpyrrolidone-based compounds, hydroxyl group-containing carboxylic acid esters, high molecular weight polycarboxylic acid salts, naphthalenesulfonic acid formalin condensate salts, polyoxyethylene alkyl phosphate esters, and long-chain polyaminoamides. - high molecular weight acid ester salts, long-chain polyaminoamides - polar acid ester salts, polyester polyamines, stearylamine acetate, high molecular weight unsaturated acid esters, polyoxyethylene nonylphenyl ether, urethanes such as modified polyurethanes, polyester amines, fatty acid amines , polycarboxylic acid, polyesteramine salt, polychain nonionic polymer, (modified) acrylic resin (salt) such as acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic Styrenes such as acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymers, etc. 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-based compound, polyoxyethylene diester-based compound, polyether phosphate-based compound, polyester phosphate-based compound, sorbitan aliphatic ester-based compound, and the like can be used.

Commercially available dispersing agents include Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), EFKA (manufactured by BASF), SOLSPERSE (manufactured by Lubrizol Japan), Name TEGO (Evonik), trade name Demol (manufactured by Kao Corporation), trade name Homogenol (manufactured by Kao Corporation), trade name Disparon (manufactured by Kusumoto Chemicals Co., Ltd.), trade name Discol (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), trade name Hypermer (manufactured by Croda Japan) can be mentioned.
These dispersants can be used singly or in combination of two or more.
The amount of the dispersant to be added may be any amount that allows the various particles such as the pigment to be dispersed in the plasma-curable ink composition of the present invention or the additive for the plasma-curable ink composition. is an amount of 10 to 500 parts by mass of the dispersant per 100 parts by mass of the substance to be dispersed.
Further, 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. They are each contained in an amount of about 0 to 99% by mass, but are not particularly limited.

(Surfactant)
Surfactants that may be contained in the plasma-curable ink composition of the present invention and/or additives for the plasma-curable ink composition include, for example, dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acids. Anionic surfactants such as salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylallyl 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 a quaternary ammonium (cation portion) structure as hydrophilic groups in the molecule, organic fluoro compounds, etc. and silicone surfactants such as polysiloxane compounds.
The surfactant is preferably contained in an amount of about 0 to 33% by mass based on the total amount of the plasma-curable ink composition or the additive for the plasma-curable ink composition of the present invention.
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 the above-mentioned "monohydric alcohol, dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups and One or more selected from the group consisting of dihydric alcohols having an ether bond may also contain a dry curing accelerator. Examples of such drying and curing accelerators include metal dryers, photocatalyst compounds, composites of metal components and photocatalyst compounds, and the like. Moreover, a peroxide may be added in order to further improve the drying property.
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 accelerates the 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. carboxylic acid metal salts (metal soaps) and borates.

As the photocatalyst compound, any semiconductor can be used as long as it is irradiated with light such as ultraviolet light or visible light and absorbs light energy equal to or greater than the band gap energy to enter an excited state and exhibit photocatalytic action. .

Examples of the photocatalyst compound include semiconductors such as oxides, nitrides, sulfides, oxynitrides, oxysulfides, nitride fluorides, oxyfluorides, and oxynitride fluorides of various metals that exhibit photocatalytic activity. Examples include (anatase type) titanium oxide, titanium peroxide, tungsten oxide, niobium oxide, bismuth oxide, zinc oxide, tin oxide, iron oxide, copper oxide, vanadium oxide, gallium oxide, lithium titanate, and strontium titanate. include but are not limited to.
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. The photocatalyst compound may be used singly or in combination of two or more.

The average particle size of the photocatalyst compound is not particularly limited, but it 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 and fluidity. be done. 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 occur in terms of dispersion stability and the like.

As the composite of the metal component and the photocatalyst compound, any composite can be used as long as the metal component and the photocatalyst compound are combined.
for example,
(1) Composites made by attaching, covering, adsorbing, or reacting metal components on the surface of a photocatalyst compound, etc.
(2) A compound obtained by attaching, covering, adsorbing, or reacting a photocatalyst compound on the surface of a metal component, etc.
(3) A composite obtained by mixing a metal component and a photocatalyst compound under conditions such as heat treatment and/or pressure treatment if necessary,
(4) After mixing a metal component and a photocatalyst compound, a compound obtained by heat treatment and/or pressure treatment as necessary,
(5) After mixing the metal component and/or its precursor with the photocatalyst compound and/or its precursor, the metal component precursor is used as the metal component and/or the photocatalyst compound precursor is used as the photocatalyst compound. compounded,
(6) the metal component and/or its precursor and the photocatalyst compound and/or its precursor such that a complex of the metal component and the photocatalyst compound is formed in the ink composition or an additive for the ink composition; A composite obtained by adding a precursor to an ink composition or an additive for an ink composition and mixing or the like,
is given.

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 particles, dispersion, solution, melt, precursor, gas, and the like.
Examples of metals include metals and 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.

As an elemental metal, one or more of iron, nickel, copper, silver, zinc and aluminum are preferably used.
As metal oxides, one or more of titanium oxide, zinc oxide, tungsten oxide, copper oxide, cuprous oxide, iron oxide, calcium oxide, silicon oxide, and aluminum oxide are preferred.
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 , molybdic acid, etc., preferably one of copper chloride, copper bromide, iron chloride, calcium carbonate, calcium phosphate (various apatites), copper nitrate, iron nitrate and iron sulfate. More than seeds can be given.
The organic acid metal salt is a salt of one or more of the above metals and one or more of organic acids such as carboxylic acid, sulfonic acid and phosphonic acid, preferably one or more of carboxylic acid metal salts. and particularly preferably one or more metal soaps.
Any metal soap that is commonly used in ink compositions for printing may be used, and a salt of one or more fatty acids having 8 or more carbon atoms and a metal is used.
Examples of fatty acids having 8 or more carbon atoms include nonanoic acid, decanoic acid, octylic acid (2-ethylhexanoic acid), naphthenic acid, neodecanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and 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.

Metals constituting the metal soap include 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. can give.
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; One or more salts of a metal that is one or more of cobalt, manganese, zirconium, copper, iron, zinc, calcium, barium or lead are used.
More preferably, a fatty acid that is 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 chili oil fatty acid, and cobalt, manganese, zirconium, copper, One or more salts of a metal that is one or more of iron or zinc 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 above photocatalyst compounds 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 occur 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 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 film.
The content of the composite of the metal component and the photocatalyst compound is generally 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.
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 was outside the above range, the printed film of the plasma-curable ink composition was 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 film.

A composite of a metal component and a photocatalyst compound can be produced by a known method.
for example,
(1) A method of forming a composite by attaching, covering, adsorbing, or reacting a metal component to the surface of a photocatalyst compound, etc.
(2) A method of forming a composite by attaching, coating, adsorbing, or reacting a photocatalyst compound on the surface of a metal component, etc.
(3) A method of mixing a metal component and a photocatalyst compound under conditions such as heat treatment and/or pressure treatment if necessary,
(4) After mixing the metal component and the photocatalyst compound, 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 precursor is used as the metal component and/or the photocatalyst compound precursor is used as the photocatalyst compound. how to compound,
(6) the metal component and/or its precursor and the photocatalyst compound and/or its precursor such that a complex of the metal component and the photocatalyst compound is formed in the ink composition or an additive for the ink composition; A method of adding and mixing a precursor to an ink composition or an additive for an ink composition,
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. may
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 an additive for the ink composition so as to form a composite. A complex is formed in the ink composition or the additive for the ink composition by mixing with stirring/dispersing means or 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 preferable. In addition, the form of the photocatalyst compound and/or its precursor at the time of compositing is not particularly limited. A dissolved solution state or a gas state is preferred.

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 when irradiated with plasma is not necessarily clear, but the photocatalyst compound is excited by the plasma light emission to cause hydroxyl radicals and It is speculated that highly active species such as superoxide anions are generated and that such species aid in the drying and curing (polymerization, etc.) of the components contained in the ink composition.
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)
As 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, any anti-friction agent that has hitherto been used in the preparation of an ink composition can be used. Any one of them may be used alone, or two or more of them 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 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.

(Gelling agent)
As the gelling agent that may be contained in the plasma-curable ink composition of the present invention and/or the additive for the plasma-curable ink composition, any Any one of them may be used alone, or two or more of them 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.
Examples of the gelling agent include organic acids such as stearic acid, lauric acid, ricinoleic acid, octylic acid, naphthenic acid, lithium, sodium, potassium, aluminum, calcium, cobalt, iron, manganese, magnesium, lead, zinc, Metal salts such as zirconium (specifically, manganese naphthenate, aluminum octylate, zinc stearate, aluminum stearate, etc.), aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dipropoxide aluminum-based chelating agents such as isopropoxide monoethylacetoacetate, aluminum dibutoxide monoacetylacetate and aluminum triacetylacetate; titanium-based chelating agents such as tetraisopropoxytitanium, tetrabutoxytitanium and dipropoxybis(acetylacetonato)titanium zirconium-based chelating agents such as tetrabutoxyzirconium; and polyisocyanates such as tolylene diisocyanate, diphenyl diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and isophorone diisocyanate.

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.
Such a gelling agent is preferably about 0 to 5% by mass relative to the entire 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.

(Viscosity modifier)
As 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, any viscosity modifier that has hitherto been used in the preparation of an ink composition can be used. Any one of them may be used alone, or two or more of them may be used in combination.
Viscosity modifiers include, for example, the animal and plant oils and/or animal and plant oil derivatives, the liquid component, celluloses, polyvinyl alcohol, cellulose derivatives such as carboxymethyl cellulose (salt) and methyl cellulose, polyamines, polyimine, and starch glycolic acid. Examples include starches such as salts and starch phosphate 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.
Such a viscosity modifier is preferably about 0 to 5% by mass relative to the entire plasma-curable ink composition of the present invention, and 0% relative 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.

(Polymerization inhibitor)
When the plasma-curable ink composition of the present invention and/or the additive for the plasma-curable ink composition 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. As such a polymerization inhibitor, any one that has hitherto been used in the preparation of ink compositions can be used. good too.
Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t- Phenolic compounds such as butylhydroquinone, trimethylhydroquinone, methoxyhydroquinone, 4-methoxyphenol, butylhydroxytoluene, p-benzoquinone, 2,5-di-t-butylbenzoquinone, naphthoquinone, tocopherol acetate, N-nitrosophenylhydroxylamine salts nitrosamine-based compounds, benzotriazole, phenothiazine-based compounds, hindered amine-based compounds, phosphorus-based compounds, N-oxyl-based compounds, and the like.
Such a polymerization inhibitor is preferably about 0 to 5% 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.

(Antioxidant)
As 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, any Any one of them may be used alone, or two or more of them may be used in combination.
Examples thereof include phenol antioxidants, amine antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
Such an antioxidant is preferably about 0 to 5% 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, there is no particular limitation.

(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 has been used in the preparation of ink compositions. Any one can be used, and one type may be used alone, or two or more types may be used in combination.
Examples thereof include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof.
Such a bactericidal/antifungal agent is preferably about 0 to 3% by mass with respect to the entire plasma-curable ink composition of the present invention, and with respect to the total additives for the plasma-curable ink composition of the present invention. 0 to 99% by mass, respectively, but is not particularly limited.

(Silane coupling agent)
Examples of 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 include (meth)acryloxypropyltrimethoxysilane and the like. 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-glycidoxypropyltri Epoxy silane coupling agents such as methoxysilane and γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane , N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ Amino-based silane coupling agents such as -aminopropyltriethoxysilane, mercapto-based silanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, and imidazole silane.
Such a silane coupling agent 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 total additives for the plasma-curable ink composition of the present invention. They are each contained in an amount of about 0 to 99% 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.
As such a method, for example, all or part of the components constituting the plasma-curable ink composition or the additive for the plasma-curable ink composition are mixed using a known or commonly used stirring/dispersing means. including how to
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 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 performed under an atmosphere such as an inert gas atmosphere, or it may not be performed under various gas atmospheres.

In addition, 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 mixing and dispersing devices described above if necessary, heating and cooling if necessary, and Under a specific atmosphere, premixing is performed to prepare a varnish, and then the necessary 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, at least one selected from the group consisting of the monohydric alcohol, the dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and the dihydric alcohol having an ether bond is added in the premixing step. Alternatively, it may be added in the subsequent stage of manufacturing the ink composition.

[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 film using plasma. For example, the binder, animal or plant oil and/or animal or plant oil derivative that may be contained in the plasma-curing ink composition of the present invention may be contained, and other liquid components, various additives, etc. may contain ingredients.

[Printing Method Usable 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 components and the like contained in the ink composition are polymerized when exposed to plasma irradiation, and the film of the plasma-curable ink composition formed by printing is dried and cured immediately after printing. When the ink composition that is sticky on the surface of the printed matter is irradiated with plasma, the ink composition instantly cures and becomes dry (tack-free).
Plasma generated under various conditions can be used as 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 the reaction or the like, but is preferably about 100° C. or less, particularly preferably 0° C. to 100° C., in consideration of handling properties 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 includes gases such as air, oxygen, carbon dioxide, nitrogen, rare gases (argon, helium, neon, etc.), hydrogen, halogens (fluorine, chlorine), water vapor, etc. , 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.

As a plasma irradiation apparatus, a current is applied to electrodes separated from each other and connected to a high-frequency power supply to create a discharge state, and the discharge gas is introduced between the electrodes and passed (actively flows between the electrodes). It is preferable to use the one with the mechanism of plasmatization and discharge toward the irradiation target, which is easily available. As such an apparatus, there are a direct type, a remote type, and a combined type of both depending on 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 a thing.
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 type of discharge gas, treatment current, treatment frequency, distance between electrodes, substrate treatment speed, discharge gas flow rate, irradiation distance, etc. For example, 10 to 1000 V, preferably 20 ~600 V, more preferably 100 to 500 V, but not particularly limited.
The treatment current is arbitrarily set based on the type of discharge gas, treatment voltage, treatment frequency, distance between electrodes, base material 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 is not particularly limited.

The treatment frequency is arbitrarily set based on the type of discharge gas, treatment voltage, treatment current, distance between electrodes, base material treatment speed, discharge gas flow rate, irradiation distance, etc. For example, 0.001 to 1000 kHz, preferably , 0.01 to 500 kHz, and more preferably 0.05 to 100 kHz, but are 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. For example, 0.1 to 50 mm, preferably , 0.5 to 25 mm, more preferably 0.5 to 10 mm, but is 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, and the like. 01 to 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. , preferably 0.1 to 30 liters/minute, more preferably 0.1 to 20 liters/minute, but not particularly limited.

The remote type irradiates the plasma by transporting the plasma, which is generated in a place other than the processing target, to the processing target in a stream of plasma gas, without damaging the substrate. Plasma irradiation can be performed.
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 type of discharge gas, treatment current, treatment frequency, distance between electrodes, substrate treatment speed, discharge gas flow rate, irradiation distance, etc. For example, 10 to 1000 V, preferably 20 ~600 V, more preferably 100 to 500 V, but not particularly limited.
The treatment current is arbitrarily set based on the type of discharge gas, treatment voltage, treatment frequency, distance between electrodes, base material 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 is not particularly limited.

The treatment frequency is arbitrarily set based on the type of discharge gas, treatment voltage, treatment current, distance between electrodes, base material 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 is 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. For example, 0.1 to 50 mm, preferably , 0.5 to 25 mm, more preferably 0.5 to 10 mm, but is 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, and the like. 01 to 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 1000 liters/minute. , preferably 5 to 300 liters/minute, more preferably 5 to 100 liters/minute, but 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 substrate processing speed, the discharge gas flow rate, etc. For example, it is 0.1 to 10000 mm, preferably 0.3 to 5000 mm, more preferably 1 to 2000 mm, but is 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 plasma-curable ink composition]
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 film of the ink composition with plasma to dry and cure and fix the film of the ink composition for plasma curing.

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. Preferable examples include paper, plastic film, metal plate, and glass.
As the printing means, conventionally known various printing means can be used without limitation. Examples include offset printing using dampening water, waterless offset printing not using dampening water, gravure printing, Various printing means such as flexographic 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 offset printing is performed, 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 as the plasma. Among these, atmospheric pressure plasma is preferable because it is easy to handle and is advantageous in terms of equipment and cost. As the plasma irradiation apparatus to be used, a direct type plasma irradiation apparatus, a remote type plasma irradiation apparatus, and a combination type plasma irradiation apparatus of both 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 for curing the ink composition, the plasma irradiation port (plasma gas jet port) is arranged in a line along the width direction of the substrate. preferably. Such an irradiation port (plasma gas jet port) may be formed by arranging a plurality of point-type irradiation ports (plasma gas jet port) in a row along the width direction of the substrate, or may be a linear irradiation port. (Plasma gas ejection port) may be arranged along the width direction of the substrate. 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 using a method such as that described in Japanese Patent No. 4611409, for example.

As the discharge gas used for plasma generation, the same ones as those described in the above [Plasma/Plasma Irradiation Apparatus] can be mentioned.
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 jet outlet toward the surface of the substrate.

[Use of ink composition for plasma curing]
The plasma-curable ink composition of the present invention can be used, for example, for printing images and characters by various printing methods when it contains a coloring component, and when it does not contain a coloring component, it can be used, for example, for clear printing. It can be used for applications such as coating and security printing (transparent printing). .

EXAMPLES 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.

(Examples 1 to 16, Comparative Examples 1 to 5)
[Preparation of varnish]
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 were charged into a reaction vessel, heated and stirred, and 0.6 parts by mass of aluminum ethylacetoacetate diisopropylate was reacted. A varnish was prepared by charging into a container and heating and stirring.

[Preparation of ink composition and evaluation of curability]
55 parts by mass of the varnish, 25 parts by mass of soybean oil, 17 parts by mass of a coloring pigment (indigo pigment), a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, or an ether bond The parts by weight shown in Table 1 of dihydric alcohols were blended and mixed to prepare ink compositions of Examples 1 to 16 and Comparative Examples 1 to 5.

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 condition 1 (treatment by plasma emission unit) or irradiation condition 2 (treatment by plasma modified gas).
Plasma is applied to the color development surface of each ink composition for 1 to 15 seconds, and the uncured ink composition is wiped off by rubbing the color development surface with absorbent cotton. The diameter of the cured coating was 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.

(Plasma irradiation condition 1: treatment by plasma light emitting unit)
Gas type: Air flow rate: 5 liters/minute Irradiation aperture: 1 mm
Irradiation distance: 4mm

(Plasma irradiation condition 2: treatment with plasma modified gas)
Gas type: Air flow rate: 5 liters/minute Irradiation aperture: 1 mm
Irradiation distance: 200 mm (A cylindrical member is attached to the plasma irradiation port and converged by the cylindrical member)

As shown in Table 1, one or more selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond is used as a plasma-curable ink composition. By using it as a constituent component, the curing start time can be shortened compared to the case where they are not included (Comparative Example 1) or the case where a trihydric or higher alcohol is used as a constituent component (Comparative Examples 2 to 5). It is possible to improve the dry curability (increase the diameter of the cured coating film).

From Table 1, it can be seen that glycerin, which is a trihydric alcohol, and pentaerythritol, which is a tetrahydric alcohol, exhibit a drying and curing inhibitory effect when treatment is performed using a plasma light emitting unit (irradiation distance of 4 mm) as a plasma irradiation condition. Recognize. On the other hand, one or more selected from the group consisting of monohydric alcohols, dihydric alcohols having 4 or more carbon atoms having two primary hydroxyl groups, and dihydric alcohols having an ether bond are found to shorten the drying and curing start time. , In particular, when using a monohydric primary alcohol, a monohydric secondary alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond be.

It can be seen that glycerin, which is a trihydric alcohol, and pentaerythritol, which is a tetrahydric alcohol, exhibit a dry-hardening inhibitory effect when treatment with a plasma-denatured gas (irradiation distance of 200 mm) is performed as a plasma irradiation condition. On the other hand, one or more selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond is found to significantly shorten the curing start time. It is also found that the drying curability is good.

From these, one or more selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond is used selectively to create a plasma curing ink. By forming an additive for the composition and/or the ink composition for plasma curing, when the ink composition for plasma curing is subjected to plasma treatment, the drying and curing start time can be shortened and the ink composition film can be formed. can be made excellent in drying curability.

Claims (4)

one or more selected from the group consisting of a monohydric alcohol, a dihydric alcohol having 4 or more carbon atoms having two primary hydroxyl groups, and a dihydric alcohol having an ether bond ;
A plasma-curable ink composition comprising an animal or vegetable oil and/or an animal or vegetable oil derivative . 2. The plasma-curing ink composition according to claim 1 , wherein the animal or plant oil and/or the animal or plant oil derivative has an iodine value of 80 or more. 3. The plasma-curable ink composition according to claim 1, further comprising a binder. Animal and plant oils and/or animal and plant oil derivatives containing one or more selected from the group consisting of monohydric alcohols, dihydric alcohols having 4 or more carbon atoms having two primary hydroxyl groups, and dihydric alcohols having an ether bond. An additive for a plasma-curable ink composition containing