JP7139193B2 - Ink composition for plasma curing - Google Patents

Description

TECHNICAL FIELD The present invention relates to a plasma-curable ink composition containing a fatty acid-modified rosin resin.

Typical printing methods currently in use include offset printing, gravure printing, screen printing, and inkjet printing. Among these, the offset printing method, which enables the rapid printing of a wide variety of printed matter in large quantities, is the main method. used.
Unless the ink composition adhering to the surface of the printed matter is sufficiently dried and hardened to fix the printed matter, set-off may occur when the printed matter is piled up, or the printed matter may be touched with a finger. Since the ink adheres when printing, it cannot be sent to the post-process or distributed as a product. A process of fixing to the surface of the material 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 raw materials derived from minerals. 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 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 a printed matter having aesthetic properties with a low environmental load.
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 Laying-Open No. 2007-54987 (Patent Document 1) describes a new drying and fixing method for oxidative polymerization type oil-based ink, in which oxygen anions O ₂ ⁻ generated by atmospheric pressure plasma are brought into contact with the printing surface, It has been proposed to carry out oxygen radical crosslinking polymerization of non-volatile sheet-fed offset inks used in sheet-fed offset printing.
In the examples, TK Hi-Echo NV100 manufactured by Toyo Ink Mfg. Co., Ltd. was used as an oxidative polymerization type oil ink that does not contain volatile organic compounds, and negative ions were generated by turning the gas into a plasma state by bipolar corona discharge, It is disclosed that the printing surface is dried and cured by contacting the ink with anions in the stagnant gas.
However, as shown in FIG. 5, it takes several minutes for drying and fixing, and there is a problem in terms of quick-drying, and it is difficult to apply it to a large-volume 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 characterized by comprising a step of fixing to a recording medium has been proposed, and in Examples, an offset ink containing carbon black, a rosin-modified phenolic resin, linseed oil, a high boiling point petroleum solvent and a dryer, Alternatively, it is merely disclosed to form a printed image with an inkjet ink containing a dye, a styrene-acrylic acid-ethyl acrylate copolymer, glycerin, ethylene glycol and a surfactant, and apply plasma irradiation to fix the image. It has a low biomass content, and there is a concern that substances that are suspected to be harmful such as phenols and formaldehyde due to rosin-modified phenolic resin will be generated, so there are problems in terms of safety and environmental load. There is no mention of using a rosin-based resin.

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 describes curing by exposure for 0.6 seconds, but the biomass degree is low, and the use of a fatty acid-modified rosin resin is not described.

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. Although an ink-fixing method including an ink-fixing step of fixing to a base material is described, the biomass degree is low and the use of a fatty acid-modified rosin-based resin 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 subjecting the composition to plasma irradiation to form an image comprising a plasma polymerized film. However, there is no mention of using a low biomass content or a fatty acid-modified rosin resin.

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, but does not describe the low biomass content and the use of a fatty acid-modified rosin resin.

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 printing surface, wherein (1) the printing ink contains a rosin resin, ( 2) The printed matter is surface-treated by corona treatment, flame treatment or plasma treatment, and the surface resistivity of the treated printed matter is below a specific value. However, it is only described that the printed matter obtained by printing using the method and storing it for 24 hours is subjected to plasma treatment.・There is no mention of plasma irradiation for fixation.

Japanese Patent Application Laid-Open No. 8-253723 (Patent Document 9) describes (1) a pigment, a rosin ester mainly composed of vegetable oil, an unsaturated polyester resin having a free carboxylic acid group, a cross-linking agent comprising an organic metal salt, a reducing a first material containing a liquid lithographic printing ink composition containing an organic hydroperoxide or organic peroxide; and a second material containing an organic hydroperoxide or a dampening solution containing an organic peroxide. Lithographic printing ink material, (2) pigment, rosin ester mainly composed of vegetable oil, unsaturated polyester resin having free carboxylic acid group, cross-linking agent comprising organic metal salt, and organic hydroperoxide or organic peroxide. A thermosetting lithographic printing ink material is described comprising a first material containing a liquid lithographic printing ink composition containing However, since it contains a volatile organic solvent, there is a problem in terms of environmental impact, and there is no description of fixing the ink composition by drying and curing with plasma.

Japanese Patent Application Laid-Open No. 2005-290084 (Patent Document 10) discloses a lithographic printing ink composition containing an α-olefin polymer and not containing a rosin-modified phenol resin, wherein rosin and/or polymerization are used as raw materials for the binder resin. A lithographic printing ink composition containing a polyester resin obtained by reacting a rosin and/or petroleum resin, an unsaturated carboxylic acid or its anhydride, an aliphatic polybasic acid, and an alcohol, and a vegetable oil as a solvent component is disclosed. However, it is not described that the ink composition has a low biomass degree and that the ink composition is dried and cured by plasma to be fixed.

Japanese Patent Application Laid-Open No. 2011-225827 (Patent Document 11) discloses a resin composition obtained by subjecting specific rosins, fatty acids, specific amines, and metal compounds to a salt-forming reaction in an alicyclic organic solvent. Although a binder for publication gravure printing ink is described in the above, the degree of biomass is low, and fixing by drying and curing printing ink using such a binder with plasma is not described.

Japanese Patent Application Laid-Open No. 2011-38023 (Patent Document 12) describes a printing ink containing 3 to 60% by mass of non-edible vegetable oil. It is also not described that the ink is dried and cured by plasma to be fixed.

Japanese Patent Application Laid-Open No. 2003-20431 (Patent Document 13) describes a printing ink comprising an ester resin containing phenol-free rosins or petroleum resins, and a vegetable oil or a fatty acid ester thereof. No, it is not described that such printing ink is dried and cured by plasma to be fixed.

Japanese Patent Application Laid-Open No. 2005-307132 (Patent Document 14) discloses polymerized rosin (a), vegetable oil, polymerized vegetable oil, vegetable oil fatty acid, at least one or more of other higher fatty acids (b), rubber (c), unsaturated Although an ink containing a resin for offset ink obtained by reacting a dibasic acid (d) and a polyhydric alcohol (e) is described, the synthesis reaction of the resin is complicated, and such a printing ink is used in plasma. It is not described that it is dried and cured to fix it.

Japanese Patent Application Laid-Open No. 2001-288394 (Patent Document 15) discloses that the varnish contains a rosin-modified phenolic resin having an average weight average molecular weight of 30,000 or more and a vegetable oil and/or vegetable oil fatty acid ester that dissolves the resin, (b) Although a printing ink composition containing a volatile organic solvent content of 3% by weight or less is described, it contains substances suspected of being harmful, such as phenols and formaldehyde derived from rosin-modified phenolic resins. Moreover, there is no description of drying and curing such a printing ink composition by plasma to fix it.

JP 2007-054987 A JP 2008-012919 A Japanese Patent Publication No. 2005-523803 JP-A-51-052494 JP 2007-106105 A JP 2013-010933 A JP 2008-297506 A JP 2015-140390 A JP-A-08-253723 JP 2005-290084 A JP 2011-225827 A JP 2011-038023 A Japanese Patent Application Laid-Open No. 2003-020431 Japanese Patent Application Laid-Open No. 2005-307132 JP-A-2001-288394

The present invention has been made in view of the above circumstances, and does not contain substances suspected of being harmful such as phenols and formaldehyde, or volatile organic solvents (VOC), so it is excellent in environment and safety, and dries quickly. It is an object of the present invention to obtain an ink composition with which a printing system having excellent biomass content can be constructed.

The present inventors have made intensive studies to solve the above problems, and found that when a printed film of an ink composition containing a fatty acid-modified rosin resin is irradiated with plasma, a drying and curing reaction occurs rapidly. Since modified rosin-based resin is used, it does not contain substances suspected of being harmful such as phenols and formaldehyde, and does not contain volatile organic solvents. The inventors have found that a high-performance printing system can be constructed, and have completed the present invention. Specifically, the present invention is as follows.

(1) A plasma-curable ink composition containing a fatty acid-modified rosin resin.
(2) The plasma-curable ink composition according to (1) above, wherein the fatty acid-modified rosin-based resin is an animal or plant-based oil-modified rosin-based resin.
(3) The plasma-curable ink composition according to (2) above, wherein the animal or plant oil used to obtain the animal or plant oil-modified rosin resin is an animal or plant oil having an iodine value of 80 or more.
(4) The plasma according to any one of (1) to (3) above, wherein the rosin resin is one or more of unmodified rosin, polymerized rosin ester, rosin ester, disproportionated rosin, and rosin resin metal salt. A curable ink composition.
(5) The plasma-curable ink composition according to any one of (1) to (4), further comprising an animal or plant oil and/or an animal or plant oil derivative.
(6) The plasma-curing ink composition according to (5) above, wherein the animal or plant oil and/or animal or plant oil derivative is one or more of paulownia oil, soybean oil, linseed oil and castor oil.

According to the present invention, a plasma-curable ink having high reactivity to plasma can be obtained in a sufficiently dry state even when plasma generated by a remote-type plasma generator is used. A composition, and a method for producing and printing a printed matter using the composition are provided.

An embodiment of the plasma-curable ink composition of the present invention is 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.

<Ink composition for plasma curing>
The plasma-curable ink composition of the present invention may contain an animal or vegetable oil and/or an animal or vegetable oil derivative in addition to the fatty acid-modified rosin resin. Moreover, it may contain a conjugated polyene-based compound, and may further contain other components such as a resin other than the fatty acid-modified rosin-based resin, other liquid components, and various additives.
The components contained in the plasma-curable ink composition of the present invention are described in detail below.

[Fatty acid modified rosin resin]
The fatty acid-modified rosin-based resin contained in the plasma-curable ink composition of the present invention 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 with 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, methacrylic acid; 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, grape seed oil, coconut oil, Animal and plant oils such as 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, and beeswax; (Oxidation-polymerized oil (boil oil), heat-polymerized oil (stand oil), modified products of animal and plant oils such as dehydrated products and esterified products); can.

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.

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;
As the fatty acid-modified material, animal and plant oils are preferably used, more preferably coconut oil and those having an iodine value of 80 or more are used, and particularly preferably coconut oil, paulownia oil, soybean oil, tall oil, and linseed oil. Oil, castor oil, safflower oil, perilla oil, 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, tung oil butyl ester One or more of 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.
The fatty acid-modified rosin resin is blended in an amount of usually 10 to 70% by mass, preferably 15 to 50% by mass, particularly preferably 15 to 30% by mass, in the plasma-curable ink composition.

[Animal and plant oils and/or animal and plant oil derivatives]
The plasma-curable ink composition of the present invention may contain an animal or vegetable oil and/or an animal or vegetable oil derivative.
Animal and vegetable oils that may be contained in the plasma-curable 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, grape seed 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, and animal and plant oils such as beeswax can be mentioned, and the plasma of the present invention can be obtained by using one or a mixture of two or more of these as animal and plant oils. A curable ink composition can be constructed.
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-curing ink composition of the present invention include modified products of the above animal and plant oils.
Here, the modified animal and plant oils include oxidatively polymerized oils (boil oils), heat-polymerized oils (stand oils), dehydrated products, esterified products, etc. of the above animal and plant oils, and one or two of them. The above mixture can be used as the animal or vegetable oil derivative to constitute the plasma-curable ink composition of the present invention.
Animal and vegetable oil derivatives include, for example, polymerized soybean oil, polymerized linseed oil, polymerized castor oil, polymerized paulownia oil, polymerized dehydrated castor oil, and dehydrated castor oil.

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 having 14 to 30 carbon atoms such as linoleic acid, linolenic acid and eleostearic acid, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, tert-butyl alcohol, It is a fatty acid ester derived from animal and plant oils, composed of linear or branched alcohols having 1 to 10 carbon atoms such as 2-ethylhexyl alcohol.

Examples of such modified animal and plant oils include, for example, polymerized soybean oil, polymerized linseed oil, polymerized castor oil, dehydrated castor oil, polymerized dehydrated castor oil, and the like. Thermally 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 iso Hexyl 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. derived fatty acid ester;
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 or plant oil and/or the animal or plant oil derivative, one or a mixture of two or more of the animal or plant oil and/or the animal or plant oil derivative is used. % by weight, preferably 20 to 70% by weight, particularly preferably 40 to 60% by weight.

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

As these conjugated polyene compounds, animal and plant oils, eleostearic acid, etc. are preferred, and dehydrated castor oil, paulownia oil, eleostearic acid, etc. 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, and usually 0 to 70% by mass in the plasma-curable ink composition. , preferably 5 to 50% by mass, particularly preferably 5 to 30% by mass.

[Other ingredients]
The plasma-curable ink composition of the present invention can contain various components depending on the desired biomass content, environmental performance, safety performance, color tone, and the like.
Such components include binders other than fatty acid-modified rosin-based resins, liquid components, coloring agents (coloring pigments, bright pigments, dyes, fluorescent pigments, colored resin particles, etc.), extender pigments, dispersants, surfactants, stabilizers, agent, antifoaming agent, drying curing accelerator, polymerization initiator, anti-friction agent (wax), gelling agent, viscosity modifier, plasticizer, polymerization inhibitor, antioxidant, pH adjuster, sterilization/antifungal agent , silane coupling agents, and other additives commonly used in the field of ink compositions.
When the plasma-curable ink composition of the present invention contains other components, the content is usually within a range that does not affect the drying curability of the plasma-curable ink composition. However, when the plasma curing ink composition contains components that affect the drying curability, such as drying curing accelerators, polymerization initiators, polymerization inhibitors, and rosin-treated particles, their content is It may be in a range in which the drying curability of the ink composition is not affected or in a range in which it is affected.

(Binder other than fatty acid-modified rosin-based resin)
Binders other than the fatty acid-modified rosin-based resin that may be contained in the plasma-curable ink composition of the present invention include resins used as binders and binders in the field of ink compositions, and resins having an ethylenically unsaturated bond. Any curable compound can be used without any particular limitation, and one or a mixture of two or more thereof can be used.
Examples of resins include acrylic resins, polyester resins, styrene resins, polyolefin resins, epoxy resins, polyurethane resins, phenol resins, rosin resins, block polymers, graft polymers (core-shell polymers), and acrylic modified resins. 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 selected from the group consisting of resins, petroleum-based resins, and hydrocarbon-based resins (polybutene, polybutadiene, etc.) is used. The weight average molecular weight of the resin is about 500-300,000. From the viewpoint of quick drying during plasma irradiation, the resin preferably has an acid value of 10 mgKOH/g or more.

As the resin, 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 having ethylenically unsaturated bonds include polydiallyl phthalate, acrylic resins having unreacted unsaturated groups, and acrylic-modified phenolic resins. Among these, polydiallyl phthalate can be preferably used.

The curable compound having an ethylenically unsaturated bond is a monomer capable of curing the ink composition by being polymerized by plasma irradiation, and is a monofunctional monomer having one ethylenically unsaturated bond in the molecule. 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)acryloyloxyethyl hexahydro phthalimide, N-(meth)acryloylmorpholine, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-butyrolactone (meth)acrylate, caprolact heterocycle-containing (meth)acrylates such as n-modified tetrahydrofurfuryl acrylate and imide acrylate;

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

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 Examples include acrylate, N,N'-methylenebisacrylamide, and the like, but are not particularly limited.
Bisphenol A tetraethylene oxide adduct di(meth)acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, bisphenol F tetraethylene oxide adduct di(meth)acrylate, bisphenol F tetraethylene oxide Adduct dicaprolactonate di(meth)acrylate, bisphenol S tetraethylene oxide adduct di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, hydrogenated bisphenol A tetraethylene oxide adduct Di(meth)acrylate, hydrogenated bisphenol F tetraethylene oxide adduct di(meth)acrylate and other alkoxylated products such as ethoxylated, propoxylated and butoxylated bifunctional monomers; alkylene oxide modifications such as ethylene oxide and propylene oxide; but 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 other than a fatty acid-modified rosin resin 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, in the plasma-curable ink composition of the present invention. %, particularly preferably 15 to 30 mass %.
When a binder other than the fatty acid-modified rosin-based resin is used in the plasma-curable ink composition of the present invention, the binder other than the fatty acid-modified rosin-based resin is usually 0 to 70% by mass, preferably 0% by mass, in the plasma-curable ink composition. It is blended in an amount of up to 50% by mass, particularly preferably 0 to 30% by mass.

(liquid component)
Examples of the liquid component that may be contained in the plasma-curable ink composition of the present invention include liquid components that have been used in the preparation of ink compositions so far, such as dissolving a resin to form a varnish or forming an ink composition. It is used to adjust the viscosity of a substance, and is a liquid component other than the animal or plant oil and the animal or plant oil derivative, or a liquid component other than the liquid conjugated polyene compound. . Such a liquid component exhibits a liquid state at the printing temperature (usually 10° C. to 40° C.), and examples thereof include liquid compounds such as organic solvents, mineral oils, and water.

Examples of 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 contained in an amount of about 0 to 33% by mass with respect to the entire plasma-curable ink composition of the present invention, but is not particularly limited.

(coloring agent)
As the colorant that may be contained in the plasma-curable ink composition of the present invention, any component that imparts coloring power that has been used in the preparation of ink compositions can be used. Such pigments include, for example, inorganic coloring pigments, organic coloring pigments, luster pigments, dyes, fluorescent pigments, colored resin particles, and the like. To achieve this, two or more colorants may be mixed and used.
Among these, powders such as pigments and colored resin particles may be surface-treated with a surface treatment agent such as rosin, organic compounds, silane coupling agents, resins, pigment derivatives, or may be untreated. good too.

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 pigments, bright pigments, dyes, fluorescent pigments and resins, and resins such as polyolefins, polystyrenes, acrylic resins and urethane resins 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 to the surface of the pigment or via various atomic groups. As the self-dispersion pigment, an ionic one is preferable, and an anionically charged one is particularly preferable.

As the colorant, it is preferable to use a pigment rather than a dye from the viewpoint of weather resistance and plasma resistance.
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 diameter of 0.001 to 100 μm, preferably 0.01 to 50 μm, and more preferably 0.05 to 5 μm, in consideration of dispersion stability and fluidity. Those having a BET specific surface area of 1 to 350 m ² /g, preferably 10 to 70 m ² /g, more preferably 20 to 50 m ² /g are used.
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 coloring agent is preferably contained in an amount of about 0 to 33% by mass with respect to the entire plasma-curable ink composition of the present invention, but is not particularly limited.

(Extender pigment)
As the extender pigment that may be contained in the plasma-curable ink composition of the present invention, any extender pigment that has hitherto been used in the preparation of ink compositions can be used. You may mix and use 2 or more types.
Examples thereof include talc, mica, barium sulfate, clay, calcium carbonate, kaolinite (kaolin), silicon oxide, bentonite, ground calcium carbonate, barium carbonate, zirconia, and alumina.
The average particle diameter of the extender pigment is 0.001 to 100 μm, preferably 0.01 to 50 μm, more preferably 0.05 to 5 μm, and the BET specific surface area is 1 to 350 m ² /g, preferably 10 -70 m ² /g, more preferably 20-50 m ² /g are used.

It is also preferable to use rosin-treated particles.
The rosin-treated particles are obtained by treating particles of one or more of the above extender pigments with a rosin-based compound. As the rosin-based compound, the rosin-based compound used for forming the rosin-treated colorant can be used.
These particles have an average particle diameter of 0.001 to 100 μm, preferably 0.01 to 50 μm, and more preferably 0.05 to 5 μm, in consideration of dispersion stability and fluidity. Those having a BET specific surface area of 1 to 350 m ² /g, preferably 10 to 70 m ² /g, more preferably 20 to 50 m ² /g are used.
The rosin-treated particles obtained by treating an extender with a rosin-based compound may be commercially available products or may be prepared by a known method.
Commercially available products include, for example, Neolite (rosin-treated calcium carbonate manufactured by Takehara Chemical Industry Co., Ltd.), Shiraenka (rosin-treated calcium carbonate manufactured by Shiraishi Calcium Co., Ltd.), and the like.
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 precipitate a sparingly soluble rosin salt or rosin free acid on the surface of the pigment.

The content of rosin in the rosin-treated particles is usually 0.1 to 50 parts by mass, preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the rosin-treated particles, taking into account dispersion stability, fluidity, etc. , more preferably 1 to 20 parts by mass.
In 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 contained in an amount of about 0 to 33% by mass with respect to the entire plasma-curable ink composition of the present invention, but is not particularly limited.

(dispersant)
Dispersants that may be contained in the plasma-curable ink composition of the present invention include, for example, anionic dispersants, cationic dispersants, amphoteric dispersants, and nonionic dispersants. , high-molecular-weight compounds, low-molecular-weight compounds (surfactants), and pigment derivatives.
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. The amount of the agent is 10 to 500 parts by mass.
Moreover, the dispersant is preferably contained in an amount of about 0 to 33% by mass with respect to the entire plasma-curable ink composition, but is not particularly limited.

(Surfactant)
Examples of surfactants that may be contained in the plasma-curable ink composition of the present invention include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts, and polyoxyethylene alkyl ethers. nonionic surfactants such as polyoxyethylene alkylallyl ethers, acetylene glycols, polyoxyethylene/polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, molecules Amphoteric surfactants such as compounds having an acid structure (anion portion) and a quaternary ammonium (cation portion) structure as hydrophilic groups inside, fluorine-based surfactants such as organic fluoro compounds, silicone-based surfactants such as polysiloxane compounds A surfactant can be mentioned.
The surfactant is preferably contained in an amount of about 0 to 33% by mass with respect to the entire plasma-curable ink composition, but is not particularly limited.

(Drying curing accelerator)
Examples of the drying and curing accelerator that may be contained in the plasma-curable ink composition of the present invention 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 promotes 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 is usually 0.001 to 100 μm, preferably 0.01 to 50 μm, more preferably 0.05 to 5 μm in consideration of dispersion stability, fluidity, etc. be done. 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) adding the metal component and/or its precursor and the photocatalyst compound and/or its precursor to the ink composition so that a composite of the metal component and the photocatalyst compound is formed in the ink composition; In addition, compounded by mixing, etc.
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 particle, 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 arise in terms of dispersion stability and the like.

The content of the metal component in the composite of the metal component and the photocatalyst compound is usually 0.1 to 99.9% by mass, preferably 1 to 99% by mass, based on the entire composite of the metal component and the photocatalyst compound. , more preferably 5 to 95% by mass, most preferably 10 to 90% by mass.
If the content of the metal component is less than 0.1% by mass, the effect of the metal component will not be exhibited. If the content of the metal component is more than 99.9% by mass, light will not reach the photocatalyst compound and the photocatalyst activity will be inhibited. Therefore, in any case, when the printed 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 usually 0.001 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.05% to 5% by mass, relative to the entire plasma-curable ink composition. It is 1 to 3% by mass.
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% by mass to 0.2% with respect to the entire plasma-curable ink composition. % by mass, 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, if necessary, a method of heat treatment and/or pressure treatment to form a composite,
(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) adding the metal component and/or its precursor and the photocatalyst compound and/or its precursor to the ink composition so that a composite of the metal component and the photocatalyst compound is formed in the ink composition; A method of adding and mixing, etc.
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, and a stirring/dispersing means or the like is used so as to form a composite. By mixing or the like, a complex is formed in the ink composition.
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. It is preferably in a solution state or a gas state. 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 preferable.

The reason why the photocatalyst compound and/or the composite of the metal component and the photocatalyst compound improves the curability of the ink composition during plasma irradiation is not necessarily clear. It is speculated that highly active chemical species, such as superoxide anions, are generated and that such chemical species aid in the drying and curing (polymerization, etc.) of the components contained in the ink composition.
The drying curing accelerator is preferably contained in an amount of about 0 to 10% by mass with respect to the entire plasma curing ink composition of the present invention, but is not particularly limited.

(Anti-friction agent)
As the anti-friction agent that may be contained in the plasma-curable ink composition of the present invention, any anti-friction agent that has hitherto been used in the preparation of ink compositions can be used. may be used, or two or more 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.
The anti-friction agent is preferably contained in an amount of about 0 to 10% by mass with respect to the entire plasma-curable ink composition, but is not particularly limited.

(Gelling agent)
As the gelling agent that may be contained in the plasma-curing ink composition of the present invention, any gelling agent that has hitherto been used in the preparation of ink compositions can be used. may be used, or two or more 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.
The gelling agent is preferably contained in an amount of about 0 to 5% by mass with respect to the entire plasma-curable ink composition, but is not particularly limited.

(Viscosity modifier)
As the viscosity modifier that may be contained in the plasma-curable ink composition of the present invention, any viscosity modifier that has hitherto been used in the preparation of ink compositions can be used. may be used, or two or more 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.
The viscosity modifier is preferably contained in an amount of about 0 to 5% by mass with respect to the entire plasma-curable ink composition, but is not particularly limited.

(polymerization inhibitor)
When the plasma-curable ink composition of the present invention contains a polymerizable compound having an ethylenically unsaturated double bond, it may contain a polymerization inhibitor, thereby improving the storage stability of the ink composition. and viscosity stability over time can be imparted. 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.
The polymerization inhibitor is preferably contained in an amount of about 0 to 5% by mass with respect to the entire plasma-curable ink composition, but is not particularly limited.

(Antioxidant)
As the antioxidant that may be contained in the plasma-curable ink composition of the present invention, any antioxidant that has hitherto been used in the preparation of ink compositions can be used. may be used, or two or more may be used in combination.
Examples thereof include phenol antioxidants, amine antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
The antioxidant is preferably contained in an amount of about 0 to 5% by mass with respect to the entire plasma-curable ink composition, but is not particularly limited.

(Sterilization/antifungal agent)
As the bactericidal/antifungal agent, any agent that has hitherto been used in the preparation of ink compositions can be used. good.
Examples thereof include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof.
The bactericidal/antifungal agent is preferably contained in an amount of about 0 to 3% by mass with respect to the entire plasma-curing ink composition, but is not particularly limited.

(Silane coupling agent)
Silane coupling agents that may be contained in the plasma-curable ink composition of the present invention include (meth)acrylic silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, and vinyltris(β-methoxyethoxy). Vinyl silane coupling agents such as silane, vinylethoxysilane, vinyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β -(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, etc. Epoxy silane coupling agents, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldisilane amino-silane coupling agents such as ethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane; , mercapto-based silanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, and imidazole silane.
The silane coupling agent is preferably contained in an amount of about 0 to 10% by mass with respect to the entire plasma-curable ink composition, but is not particularly limited.

<Method for Producing Plasma Curing Ink Composition>
Conventionally known methods can be used to produce 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 can be mixed by a known or commonly used mixing method. , mixers such as planetary mixer, pony mixer, dissolver, tank mixer, homomixer, homodisper, mills such as attritor, roll mill, sand mill, ball mill, bead mill, line mill, ultrasonic mill, dyno mill, shot mill, kneader, etc. Stir and disperse using various mixing and dispersing devices such as a mixing kneader and a high-pressure collision dispersing device, and if necessary, add liquid components and various additive components and stir and disperse using the mixing and dispersing device. The method can be exemplified.
In the case of stirring and dispersing, the mixing and dispersing device may not be used, and one type of mixing and dispersing device may be used to stir and disperse once or multiple times. You may stir and disperse|distribute several times using an apparatus together.

The plasma-curable printing ink composition of the present invention can be produced by a known method using the raw materials described above. For example, to the fatty acid-modified rosin-based resin, animal and plant oils and/or animal and plant-based oil derivatives and/or conjugated polyene-based compounds, resins other than fatty acid-modified rosin-based resins, gelling agents, etc., are added as necessary. If there is any, premixing is performed by thoroughly mixing using any of the above mixing and dispersing devices to prepare a varnish, and then the required amount of varnish, animal and plant oils and / or animal and plant oil derivatives, colorants, etc. The plasma-curable printing ink composition of the present invention can be obtained by adding the other components and sufficiently stirring and mixing.

<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. , (meth) acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyolefins such as polyethylene and polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, polyamide , resin films or sheets such as polycarbonate, metals such as cellophane and aluminum foil, inorganic materials such as glass, wood, gypsum board, composite materials consisting of two or more of these, and other various bases used as printing substrates I can give you the materials.

<Printing method that can use the ink composition for plasma curing>
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, when the fatty acid-modified rosin resin or the like contained in the ink composition is subjected to plasma irradiation, its molecular weight increases, and the film of the plasma-curable ink composition formed by printing dries and cures. When plasma is applied to the ink composition that is sticky on the surface of the printed matter immediately after printing, the ink composition instantly hardens 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 in the case of using a direct plasma irradiation apparatus is not particularly limited.
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 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 generated in a place other than the processing target to the processing target in a stream of plasma gas, which causes great damage to the substrate. Plasma irradiation can be performed without
In the present invention, each condition is not particularly limited when using the remote type plasma irradiation apparatus.
The treatment voltage is arbitrarily set based on the 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 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 injected (plasma irradiation) onto the base material.
In general, the shorter the irradiation distance (the distance between the base material and the irradiation port after printing), the more dominant the drying and curing of the ink composition coating film is in many cases.

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

<Printing Method Using Ink Composition for Plasma Curing>
A printing method using the plasma-curable ink composition of the present invention comprises a printing step of printing the plasma-curable ink composition on a substrate, and a plasma-curable ink composition present on the surface of the substrate after the printing step. and a plasma irradiation step of irradiating the 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 types can be used.
Here, the plasma and the plasma irradiation apparatus can be those described in the above <plasma/plasma irradiation apparatus>.
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 used.
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 letters 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), and is useful for various types of printing such as ordinary printed materials for information transmission and viewing, package printing, marking printing, and printing on three-dimensional objects. .

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.

[Preparation of fatty acid-modified rosin-based resin]
Fatty acid-modified rosin-based resins 1 to 6 were prepared by mixing and reacting the fatty acid-modified material and rosin-based resin in the amounts shown in Table 1. Table 1 also shows the fatty acid introduction ratio, acid value and weight average molecular weight of the resulting fatty acid-modified rosin resin. Table 1 also shows the acid value and weight average molecular weight of the rosin-modified phyllenol resin (Resin 7) used as a comparative example.

[Preparation of varnish]
Using resins 1 to 7 as resins, as described in Table 2, 40.5 parts by mass of resin, 53.7 parts by mass of soybean oil, and 5.2 parts by mass of alkyd resin were charged in a container, heated and stirred, and aluminum ethylacetate was added. Acetate diisopropylate (ALCH; gelling agent) of 0.6 parts by mass was introduced into a container, and heated and stirred to prepare a varnish.

[Preparation of ink composition and evaluation of curability]
Using the varnishes 1 to 7 as varnishes, as described in Tables 3 and 4, 55 parts by mass of varnish, 25 parts by mass of various vegetable oils, and 17 parts by mass of indigo pigment are taken, charged in a container, and kneaded. , Examples 1-24, and Comparative Examples-4 were prepared.
The ink compositions of Examples 1 to 24 and Comparative Examples 1 to 4 were evaluated for curability when exposed to plasma, and the results are shown in Tables 3 and 4.

In addition, evaluation about curability was performed as follows.
A 0.1 cc sample of the ink composition was taken and spread on a polypropylene film (manufactured by Sekisui Seisei Co., Ltd., product name: Polytheme PC-8162) using an RI spreader, and then spread using a remote plasma generator. The colored surface was irradiated with plasma under the following irradiation conditions.
(Plasma irradiation conditions)
Gas type: Air Flow rate: 5 liters/min Irradiation aperture: 1 mm
Irradiation distance: 4mm

Plasma is applied to the color development surface of each ink composition for 1 to 15 seconds at intervals of 1 second, and in each case, the uncured ink composition is wiped off with absorbent cotton, and the plasma curing start time and plasma curing start time are determined. Circular cured film diameter in hours was measured.
In addition, since the reactivity of the plasma is higher toward the center of the irradiation and lower toward the periphery, an ink composition having a larger curing diameter is an ink composition having a higher reactivity to the plasma.

As shown in Tables 3 and 4, the plasma-curable ink composition containing a fatty acid-modified rosin resin can shorten the curing initiation time compared to, for example, an ink composition containing a rosin-modified phenolic resin. The dry curability can be the same or improved (increase the cured coating diameter).
Comparing Examples 1 to 6 with Comparative Example 1, when soybean oil was used in preparing the ink composition, compared with the ink composition of Comparative Example 7, which contained a rosin-modified phenolic resin, The ink compositions of Examples 1 to 6, which contain fatty acid-modified rosin-based resins, have a shortened or the same plasma curing start time, and a large or the same diameter of the cured coating film when cured in a circular shape. .
Similarly, when linseed oil was used to prepare the ink compositions of Examples 7 to 12 and Comparative Example 2, tung oil was used to prepare the ink compositions of Examples 13 to 18 and Comparative Example 3. When castor oil was used in preparing the ink compositions of Examples 19 to 24 and Comparative Example 4, the ink compositions of Comparative Examples 2 to 4 containing the rosin-modified phenolic resin Compared to the ink compositions of Examples 7 to 24, which contain a fatty acid-modified rosin resin, the plasma curing initiation time is shortened or equivalent, and the diameter of the cured coating film that is cured in a circular shape is increased. or equivalent.
Therefore, it does not contain substances suspected of being harmful such as phenols and formaldehyde, nor does it contain volatile organic solvents (VOCs). It is environmentally friendly and safe, has excellent quick-drying properties, and builds a printing system with a high degree of biomass. It can be seen that an ink composition capable of

Claims (5)

A plasma-curable ink composition containing an animal or plant-based oil- modified rosin-based resin. 2. The plasma-curable ink composition according to claim 1 , wherein the animal or vegetable oil used to obtain the animal or vegetable oil-modified rosin resin is an animal or vegetable oil having an iodine value of 80 or more. 3. The plasma-curable ink composition according to claim 1 , wherein the rosin-based resin is one or more of unmodified rosin, polymerized rosin ester, rosin ester, disproportionated rosin, and rosin-based resin metal salt. 4. The plasma-curing ink composition according to any one of claims 1 to 3 , further comprising an animal or vegetable oil and/or an animal or vegetable oil derivative. 5. The plasma-curable ink composition according to claim 4 , wherein the animal or plant oil and/or animal or plant oil derivative is one or more of paulownia oil, soybean oil, linseed oil and castor oil.