JP7267085B2 - Active energy ray-curable flexographic printing ink composition - Google Patents

Description

The present invention relates to an active energy ray-curable flexographic printing ink composition.

With the goal of preserving the global environment, activities to reduce the environmental load are being carried out in various industries and industries, and activities are being carried out to encourage the reduction of the environmental load from various viewpoints. For example, volatile organic compounds (VOC) contained in paints, inks, etc. are chemical substances that lead to global warming. there is
From the viewpoint of reducing VOCs, the use of active energy ray-curable printing ink compositions that are cured by active energy rays such as ultraviolet rays and electron beams has been studied. The active energy ray-curable flexographic printing ink composition contains a polymerizable compound that polymerizes upon irradiation with an active energy ray, and optionally a polymerization initiator that exhibits a polymerization initiation function upon irradiation with an active energy ray.
The active energy ray-curable printing ink composition can reduce the use of VOCs and the volatilization amount of VOCs can be reduced to zero or less, so that it is possible to reduce the environmental load. Furthermore, since it cures rapidly (has quick-drying properties), it is possible to save energy and improve productivity, and it has been actually used as a paint or ink.
In the printing industry, if the ink on the surface of the printed matter printed by various methods does not dry sufficiently, set-off occurs when the printed matter is piled up, and ink adheres when the printed matter is touched. It cannot be distributed as a commodity. For this reason, active energy ray-curable inks that can instantly cure (dry) the ink on the surface of printed matter by irradiating the printed matter immediately after printing with an active energy ray have become widespread.
Such active energy ray-curable inks are widely known, for example, as disclosed in Patent Document 1 and Patent Document 2.

Furthermore, various efforts have been made to reduce the environmental impact of active energy ray-curable printing ink compositions. For example, development of products that can be cured (dried) with less active energy radiation, high-pressure mercury lamps that consume a large amount of power and cause ozone generation due to short-wave ultraviolet rays, and energy-saving UV LED lamps that generate less ozone. Replacement with low output ultraviolet lamps, etc. are being carried out.
In recent years, as an activity to reduce environmental impact, by replacing raw materials derived from fossil resources with raw materials derived from biomass, which is a renewable resource, biomass products that do not increase _CO2 in the environment (carbon-neutral) emit greenhouse gases. Reductions are being made.
For example, in the printing ink industry, a new ink green mark (IG mark) system has been established, and the environmental response level is ranked in three stages according to the ratio of biomass-derived components in the printing ink constituents to reduce environmental impact. activities are being carried out to encourage
However, conventional active energy ray-curable inks use a large amount of polymerizable compounds, which are raw materials derived from fossil resources, and it has been difficult to meet the certification criteria for the IG mark. Moreover, it has been difficult to easily obtain a large amount of polymerizable compounds derived from biomass.
Furthermore, recently, the use of non-edible biomass components (non-edible biomass components, especially biomass components obtained from non-edible substances) has been considered as a biomass-derived component in consideration of competition with food production. ing.
For example, in Patent Document 3, it is possible to use a UV-curable composition based on urethane acrylate synthesized from natural renewable resources such as cardanol contained in cashew nut shell liquid or their derivatives as a printing ink. It is stated that there is. However, it is considered difficult to obtain such urethane acrylates easily and in large quantities.
Also, when a large amount of polyfunctional acrylate compound is blended, the viscosity increases, which may make handling difficult.

JP 2017-137369 A JP 2015-081264 A Japanese Patent No. 5335436

The present invention has been made in view of the above circumstances, and while using more biomass-derived components, basic properties such as low viscosity, curability, adhesion, abrasion resistance, and scratch resistance are maintained. An object of the present invention is to provide an active energy ray-curable flexographic printing ink composition.
In addition, by increasing the ratio of raw materials derived from biomass and using non-edible biomass, it does not compete with food production, and it is possible to prevent starvation and food problems. Another object of the present invention is to provide an active energy ray-curable flexographic printing ink composition that can greatly contribute to the formation of a sustainable recycling society.

The present inventors have found that the above problems can be solved by using the following active energy ray-curable flexographic printing ink composition, and have completed the present invention.
That is, the present invention
1. An active energy ray-curable flexographic printing ink composition containing a polyfunctional polyester oligomer, a plasticizer and a photopolymerizable compound, and having a viscosity of 300 to 2000 mPa·s.
2. 1. The activation energy according to 1, wherein the sp value (solubility parameter) of the plasticizer is 9.0 (cal/cm ³ ) ^{1/2 or} more and less than 11.0 (cal/cm ³ ) ^1/2 by turbidity point titration. A line-curable flexographic printing ink composition.
3. The total content of the polyfunctional polyester oligomer and the plasticizer is 20.0 to 75.0% by mass in the ink composition, and the ratio of the plasticizer to the polyfunctional polyester oligomer on a mass basis is the plasticizer/polyfunctional polyester oligomer. = 1.0 to 30.0% by mass, the active energy ray-curable flexographic printing ink composition according to 1 or 2.
4. 4. The active energy ray-curable flexographic printing ink composition according to any one of 1 to 3, wherein the polyfunctional polyester oligomer is a vegetable oil-modified polyfunctional polyester oligomer and/or the plasticizer is a plasticizer containing a vegetable oil component.
5. 5. The active energy ray-curable flexographic printing ink composition according to 4, wherein the vegetable oil used for modifying the vegetable oil-modified polyfunctional polyester oligomer is a non-edible vegetable oil.
6. 5. The active energy ray-curable flexographic printing ink composition according to 4, wherein the vegetable oil used in the plasticizer having a vegetable oil component is a non-edible vegetable oil.
7. 7. The active energy ray-curable flexographic printing ink composition according to any one of 1 to 6, which contains 1.0 to 5.0% by mass of wax having an average particle size of 8.0 μm or less.
8. 8. The active energy ray-curable flexographic printing ink composition according to any one of 1 to 7, which contains 0.01 to 1.00% by mass of a surface control agent in the ink composition.
9. 9. The active energy ray-curable flexographic printing ink composition according to any one of 1 to 8, which contains a coloring agent.
According to the present invention, it is possible to obtain an active energy ray-curable flexographic printing ink composition in which curability, adhesion, scratch resistance, abrasion resistance, etc. are maintained, and the ratio of raw materials derived from biomass can be increased. It becomes possible.

The active energy ray-curable flexographic printing ink composition of the present invention is used for printing labels and the like. This composition will be described in detail below.
(coloring agent)
The active energy ray-curable flexographic printing ink composition of the present invention can also contain a colorant of each hue to obtain an active energy ray-curable flexographic printing ink composition of each color. Also, a colorless clear composition or a colored clear composition can be prepared by not containing a coloring agent or by reducing the content thereof.
As the colorant used in the active energy ray-curable flexographic printing ink composition of the present invention, known pigments and dyes used in flexographic ink compositions can be used without limitation. Pigments such as pigments or inorganic pigments are preferred.
Specifically, inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, iron black, chromium oxide green, carbon black, and graphite (achromatic colors such as white and black). (including coloring pigments), and extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc. In addition, as organic pigments, dye lake pigments, azo-based, benzimidazolone-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo-based, thioindico-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, isoindo Examples include linone, nitro, nitroso, anthraquinone, flavanthrone, quinophthalone, pyranthrone, and indanthrone pigments.
When the active energy ray-curable flexographic printing ink composition of each color is formed by containing the colorant of each hue, the concentration of the colorant in the active energy ray-curable flexographic printing ink composition is 1 to 60% by mass. is preferably

(Pigment Dispersant/Pigment Dispersion Resin)
When the active energy ray-curable flexographic printing ink composition of the present invention employs a pigment as a colorant, a pigment dispersant and/or a pigment dispersing resin can be blended.
As the pigment dispersant, one or more selected from the group consisting of known nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants can be used.
Examples of these surfactants include silicone surfactants (e.g., polyether-modified silicone oil, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, etc.), fluorine-based surfactants, and oxyalkylene ether-based surfactants. One or more selected from the group consisting of active agents, acetylene glycol-based surfactants, phosphoric acid-based surfactants, sulfonic acid-based surfactants, and the like can be used.
In addition, as a pigment dispersion resin, a polymer dispersant (e.g., carbodiimide, polyester, polyamine, polyesteramine, polyurethane, fatty acid amine, polyacrylate, polycaprolactone, polysiloxane, polychain At least one selected from the group consisting of polymeric nonionic dispersants, polymeric ionic dispersants, etc.) can be used.
When the active energy ray-curable flexographic printing ink composition contains a pigment dispersant or a pigment dispersing resin, the content is preferably 1 to 200 parts by mass based on 100 parts by mass of the total pigment used. .

<Polyfunctional polyester oligomer and plasticizer>
In consideration of the environment, a vegetable oil-modified polyfunctional polyester oligomer can be employed as the polyfunctional polyester oligomer and/or a vegetable oil component can be used as a plasticizer so that the ink composition has a biomass content of 10% or more. A plasticizer can be employed.

(Polyfunctional polyester oligomer)
As the polyfunctional polyester oligomer, polyfunctional polyester oligomers conventionally used in active energy ray-curable flexographic printing ink compositions can be used.
The content of the polyfunctional polyester oligomer in the active energy ray-curable flexographic printing ink composition is preferably 15.0 to 65.0% by mass, more preferably 20.0 to 50.0% by mass, even more preferably 28.0 to 45.0% by mass.
Above all, when the active energy ray-curable flexographic printing ink composition of the present invention is not clear, the polyfunctional polyester oligomer is preferably added to the active energy ray-curable flexographic printing ink composition of the present invention in an amount of 15.0 to 55.0. It can be blended so as to be 0% by mass, more preferably 20.0 to 50.0% by mass, more preferably 25.0 to 45.0% by mass.
Furthermore, when the active energy ray-curable flexographic printing ink composition of the present invention is clear, the polyfunctional polyester oligomer is preferably added to the active energy ray-curable flexographic printing ink composition of the present invention at a ratio of 15.0 to 65.0. It can be blended so as to be 0% by mass, more preferably 20.0 to 55.0% by mass, more preferably 25.0 to 50.0% by mass.
In a clear ink composition, the substrate can be seen through the printed surface. Curability with active energy rays and scratch resistance deteriorate when the polyfunctional polyester oligomer is not blended.

(Vegetable oil-modified polyfunctional polyester oligomer)
In the present invention, it is preferable to use a vegetable oil-modified polyfunctional polyester oligomer as the polyfunctional polyester oligomer. As the vegetable oil-modified polyfunctional polyester oligomer, any bifunctional, tetrafunctional or hexafunctional polyfunctional polyester oligomer having two or more (meth)acrylate groups in the molecule and modified with vegetable oil can be used without limitation. be able to. This is preferable because the biomass degree of the active energy ray-curable flexographic printing ink composition can be increased.
When the vegetable oil-modified polyfunctional polyester oligomer is not blended, curability with active energy rays and scratch resistance deteriorate.
The vegetable oil used for modification is a concept that includes various fatty acid esters contained in vegetable oils, fatty acids obtained by hydrolyzing the various fatty acid esters, and the like. Vegetable oils include edible oils such as soybean oil, rapeseed oil, sunflower oil, tall oil, corn oil, castor oil, coconut oil, palm kernel oil, unsaturated animal and vegetable oils, epoxidized fatty acids thereof, and hardened castor. Non-edible vegetable oils such as oil, polymerized castor oil, cashew nut shell liquid, polymers of cashew nut shell liquid, and modified derivatives of cashew nut shell liquid, or modifications thereof can be used. Among them, non-edible vegetable oils or modified products thereof are preferred, and tall oil is more preferred.
Among polyfunctional polyester oligomers, hexafunctional plant-derived modified (polyester) oligomers are preferred, and for example, one or more selected from the group consisting of EBECRYL 450, AgiSyn 716 and the like is preferably used.

(Plasticizer)
Plasticizers include dimethyl phthalate, dibutyl phthalate, dioctyl adipate, dioctyl sebacate, castor oil, coconut oil, palm kernel oil, unsaturated animal and vegetable oils and their fatty acid epoxides, hardened castor oil, and polymerized castor oil. , cashew nut shell liquid, polymers of cashew nut shell liquid, modified derivatives of cashew nut shell liquid, acetyltributyl citrate, and the like.
In the present invention, it is preferable to use a plasticizer containing a vegetable oil component as the plasticizer.
As the plasticizer containing a vegetable oil component, a non-edible vegetable oil component is preferred.
Plasticizers having non-edible vegetable oil components include, specifically, castor oil, coconut oil, palm kernel oil, unsaturated animal and vegetable oils and epoxidized fatty acids thereof, hydrogenated castor oil, polymerized castor oil, and cashew nuts. Shell liquids, polymers of cashew nut shell liquids, modified derivatives of cashew nut shell liquids, dioctyl sebacate, acetyltributyl citrate and the like can be exemplified.
Among the plasticizers, the sp value (solubility parameter) by the turbidity point titration method is 9.0 (cal/cm ³ ) ^1/2 or more and 11.0 from the viewpoint of compatibility with the active energy ray-curable flexographic printing ink composition. It is preferably less than (cal/cm ³ ) ^1/2 .
The sp value by turbidity point titration is determined according to the following K.I. W. SUH, J. M. It is a value calculated according to the CORBETT formula. For calculation of the sp value by this method, see J. Am. Appl. Polym. Sci. 1968, 12, 2359 can be referred to. The same applies to the sp value.
Formula sp value = (Vml ^1/2 · δH + Vmh ^1/2 · δD) / (Vml ^1/2 + Vmh ^1/2 )
In the turbidity point titration, 0.5 g of the sample is dissolved in 10 mL of toluene or trimethylolpropane triacrylate (TMPTA), which is a good solvent, and n-hexane, which is a low sp value poor solvent, is added to titrate at the turbid point. Read the amount H (mL), similarly read the titration amount D (mL) at the turbid point when ethanol, a poor solvent with a high sp value, is added to the toluene solution, apply these to the following formula, Vml, Vmh, δH and δD may be calculated and substituted into the above equation.
The molecular volume and sp value of each solvent used in the above turbid point titration are as follows.
Molecular volume of good solvent φ0 toluene: 106.28 mL/mol
TMPTA: 279.55 mL/mol
Molecular volume of low sp value poor solvent φl n-hexane: 131.61 mL/mol
Molecular volume of high sp value poor solvent φh ethanol: 58.39 mL/mol
sp value of each solvent toluene: 9.14, TMPTA: 9.88
n-hexane: 7.28, ethanol: 12.58
Vml=(φ0・φl)/{(1−VH)・φl+VH・φ0}
Vmh=(φ0・φh)/{(1−VD)・φh+VD・φ0}
VH=H/(M+H)
VD=D/(M+D)
δH=(δ0・M)/(M+H)+(δl・H)/(M+H)
δD=(δ0・M)/(M+D)+(δl・D)/(M+D)
δ0: sp value of good solvent δl: sp value of low sp value poor solvent δh: sp value of high sp value poor solvent H: titration volume (mL) of low sp value poor solvent
D: Titration volume of high sp value poor solvent (mL)
M: amount of good solvent (mL)
VH: volume fraction (%) of low sp value antisolvent titer
VD: volume fraction (%) of high sp value antisolvent titer

By containing a plasticizer, the viscosity of the ink can be lowered while various physical properties are maintained favorable. Since the present invention is an ink composition containing a polyfunctional polyester oligomer in particular, the absence of a plasticizer results in increased viscosity and reduced adhesion.
Regardless of whether the active energy ray-curable flexographic printing ink composition of the present invention is clear or not, the plasticizer is preferably added to the active energy ray-curable flexographic printing ink composition of the present invention in an amount of 0.5 to 15%. 0% by mass, preferably 1.0 to 10.0% by mass, more preferably 1.0 to 9.0% by mass.
Also, the total content of the polyfunctional polyester oligomer and the plasticizer may be 20.0 to 75.0% by mass in the ink composition.
Among them, when making a non-clear active energy ray-curable flexographic printing ink composition, it is preferably 20.0 to 60.0% by mass to make a clear active energy ray-curable flexographic printing ink composition. In some cases, it is preferably 25.0 to 70.0% by mass.
The ratio of the polyfunctional polyester oligomer and the plasticizer to be used is preferably such that the weight-based ratio of the plasticizer to the polyfunctional polyester oligomer is plasticizer/polyfunctional polyester oligomer=1.0 to 30.0% by mass.
As a result, the active energy ray-curable flexographic printing ink composition can obtain an ink that is excellent in curability, adhesion, abrasion resistance, and scratch resistance.

(wax)
Specifically, animal and plant waxes such as beeswax, lanolin wax, spermaceti, candelilla wax, carnauba wax, rice wax, Japanese wax, jojoba oil, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, petrolatum, etc. minerals, petroleum waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene wax, polyethylene oxide wax, polypropylene oxide wax, modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, hardened castor oil , hydrogenated waxes such as hydrogenated castor oil derivatives, polytetrafluoroethylene wax (PTFE), and the like.
As such a wax, a wax having an average particle size of 8.0 μm or less can be selected and used in order to improve the scratch resistance, preferably 6.0 μm or less, more preferably 4.0 μm or less, and even more preferably 4.0 μm or less. 2.0 μm or less can be used. When the average particle size is 2.0 μm or less, the abrasion resistance (scratch resistance) becomes better.
Moreover, the average particle size of the wax to be used may be appropriately selected according to the viscosity of the active energy ray-curable flexographic printing ink composition and the line number of the anilox of the flexographic printing machine.
When wax is contained, the content in the active energy ray-curable flexographic printing ink composition is preferably 0.5 to 5.0% by mass, more preferably 1.5 to 4.5% by mass. 0 to 4.0% by mass is more preferable.
If the wax content is less than 0.5% by mass, the abrasion resistance (scratch resistance) tends to decrease. There is a tendency.

(Surface conditioner)
The active energy ray-curable flexographic printing ink composition may contain a known surface modifier for improving leveling properties and slipping properties.
As the surface conditioner, for example, one or more selected from the group consisting of silicon surface conditioners, fluorine surface conditioners, acrylic surface conditioners, acetylene glycol surface conditioners and the like can be used.
As a specific example of the surface conditioner, one or more selected from the group consisting of the BYK series manufactured by BYK Chemie, the TEGO series manufactured by Evonik Japan, the Polyflow series manufactured by Kyoeisha Kagaku, and the like can be used.
When the active energy ray-curable flexographic printing ink composition contains a surface control agent, the content thereof can be 0.01 to 1.0% by mass.

(Photoinitiator)
The active energy ray-curable flexographic printing ink composition may contain a known photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it generates active species such as radicals upon irradiation with an active energy ray and initiates photopolymerization of the active energy ray-curable flexographic printing ink composition. One or more selected from the group consisting of redox initiators, thermal polymerization initiators, photopolymerization initiators and the like can be used. When the active energy ray-curable flexographic printing ink composition of the present invention is cured with an electron beam, it is not necessary to contain a photopolymerization initiator.
A redox initiator exhibits a polymerization initiation function through a redox reaction under mild conditions by combining a peroxide and a reducing agent.
Thermal polymerization initiators and photopolymerization initiators each generate radicals upon irradiation with active energy rays (infrared rays, ultraviolet rays, LEDs, electron beams, etc.) to exhibit a polymerization initiation function.
The polymerization initiator is appropriately selected according to the application, purpose, etc. Usually, it is preferable to use a photopolymerization initiator, but if toxicity needs to be examined, a thermal polymerization initiator with high potential toxicity Redox initiators, which are relatively less toxic than photoinitiators, can also be used.
Among these, from the point of being able to improve the curability to ultraviolet light using a light emitting diode (LED) as a light source, it has light absorption characteristics over a wavelength of 450 to 300 nm, and a curing reaction ( It is preferable to use a radical photopolymerization initiator capable of exhibiting the initiator function for radical polymerization.
Examples of photoradical polymerization initiators include acylphosphine oxide-based compounds, triazine-based compounds, aromatic ketone-based compounds, aromatic onium salt-based compounds, organic peroxides, thioxanthone-based compounds, thiophenyl-based compounds, and anthracene-based compounds. , hexaarylbisimidazole-based compounds, ketoxime ester-based compounds, borate-based compounds, azinium-based compounds, metallocene-based compounds, active ester-based compounds, halogenated hydrocarbon-based compounds and alkylamine-based compounds, iodonium salt-based compounds and sulfonium salts It is possible to use one or more selected from the group consisting of system compounds and the like.
Examples of acylphosphine oxide compounds include 1 selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. More than one species can be used.
Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-pipenyl-4,6-bis(trichloromethyl)-s-triazine , 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy- Naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine and 2,4-trichloromethyl(4′-methoxystyryl)- One or more selected from the group consisting of 6-triazine and the like can be used.
Further, for example, benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropan-1-one, 4-benzoyl-4′-methyldiphenylsulfide, 1-chloro-4-propoxy thioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- methyl-1-propan-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butane- One or more selected from the group consisting of 1-one and the like can be used.
Examples of such a photopolymerization initiator include Irgacure 907, 369, 184, 379, 819 from BASF, TPO, DETX from Lamberti, and TAZ-204 from Midori Kagaku.
The content of the photopolymerization initiator in the ink composition can be appropriately determined according to the components of the active energy ray-curable flexographic printing ink composition. It can be 0.1 to 25.0% by mass, preferably 0.1 to 15.0% by mass, more preferably 1.0 to 15.0% by mass.
When the content of the photopolymerization initiator in the ink composition is within the above range, it is possible to achieve both sufficient curability of the ink composition and good internal curability and cost, which is preferable.

(Photopolymerizable compound)
In the active energy ray-curable flexographic printing ink composition of the present invention, known monomers, oligomers and resins having ethylenically unsaturated bonds can be used as polymerizable compounds other than those described above.
(Compound with one ethylenically unsaturated bond)
The active energy ray-curable flexographic printing ink composition of the present invention can use a known compound having one ethylenically unsaturated bond.
Examples of such compounds include the following compounds.

- Acrylamide Derivatives -
Depending on the color of the active energy ray-curable flexographic printing ink composition, it is preferable to incorporate an acrylamide derivative in order to improve curability. For example, (meth)acrylamide, N-methylol (meth)acrylamide, diacetone (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, ( One or more selected from the group consisting of meth)acryloylmorpholine (ACMO), N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide and the like can be used.
The content of the acrylamide derivative in the active energy ray-curable flexographic printing ink composition is 45.0% by mass or less. And it is preferably 35.0% by mass or less.
If the content of the acrylamide derivative exceeds 45.0% by mass, the abrasion resistance, scratch resistance, etc. may deteriorate.

-Unsaturated carboxylic acid-based compound-
Examples of unsaturated carboxylic acid compounds include unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, fumaric acid and maleic acid, salts thereof and acid anhydrides thereof. be done.

- Alkyl (meth)acrylate compounds -
Examples of alkyl (meth)acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) Acrylate, t-butyl acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate , isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, isodecyl (meth)acrylate, isomyristyl (meth)acrylate, octadecyl (meth)acrylate, dicyclopentanyl ( meth)acrylate, tridecyl (meth)acrylate, nonyl (meth)acrylate, hexadecyl (meth)acrylate, myristyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl ( meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, 3,5,5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc. mentioned.

-Hydroxyl Group-Containing (Meth)acrylate Compound-
Examples of hydroxyl group-containing (meth)acrylate compounds include 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-methoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, tri Ethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, glycerin mono(meth)acrylate Acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, (meth)acrylic acid-2- Hydroxy-3-allyloxypropyl, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-ethylhexyl EO-modified (meth) acrylate, o-phenylphenol EO-modified acrylate, p-cumylphenol EO-modified (meth) ) acrylates, (poly)alkylene glycol-modified (meth)acrylates such as nonylphenol EO-modified (meth)acrylates, and the like.

-Halogen-containing (meth)acrylate-based compound-
Examples of halogen-containing (meth)acrylate compounds include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate. , 1H-hexafluoroisopropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,2H,2H-heptadecafluorodecyl (meth)acrylate, 2,6-dibromo-4- Butylphenyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, 2,4,6-tribromophenol-3EO (ethylene oxide) addition (meth)acrylate and the like.

- Ether Group-Containing (Meth)acrylate Compound -
Examples of ether group-containing (meth)acrylate compounds include 1,3-butylene glycol methyl ether (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol ( meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cresyl polyethylene glycol ( meth) acrylate, 2-(vinyloxyethoxy) ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, p-nonylphenoxyethyl (meth) acrylate, p-nonylphenoxy polyethylene glycol (meth) acrylate, glycidyl (meth) ) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate, hexaethylene glycol monophenyl ether mono (meth) acrylate, diethylene glycol monobutyl ether acrylate, dipropylene glycol monomethyl ether (meth) acrylate, 3-methoxybutyl (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate (EO repeating unit number 400, 700, etc.), 2-(2-ethoxyethoxy) ethyl (meth) Acrylates, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, ethoxyethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, alkoxylated 2-phenoxy Ethyl (meth)acrylate (ethoxylated 2-phenoxyethyl (meth)acrylate, propoxylated 2-phenoxyethyl (meth)acrylate, etc.), alkoxylated nonylphenyl (meth)acrylate (ethoxylated (4) nonylphenol acrylate, etc.), 2 - phenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, methylphenoxyethyl acrylate, ethoxylated succinic acid (meth)acrylate, ethoxylated tribromophenyl acrylate, ethoxylated nonylphenyl (meth)acrylate, etc. Alkoxy and/or phenoxy (meth)acrylates and the like are included.

-Carboxyl Group-Containing (Meth)acrylate Compound-
Carboxyl group-containing (meth)acrylate compounds include, for example, β-carboxyethyl (meth)acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrogen phthalate, 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate and the like.

-Vinyl ether group-containing (meth)acrylate compound-
Vinyl ether group-containing (meth)acrylate compounds include, for example, 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate , (meth) 2-methyl-3-vinyloxypropyl acrylate, 3-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, ( meth)3-vinyloxybutyl acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate, 2-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, (meth)acrylate 5-vinyloxypentyl acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, 3-vinyloxymethylcyclohexylmethyl (meth)acrylate, ( 2-vinyloxymethylcyclohexylmethyl meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, m-vinyloxymethylphenylmethyl (meth)acrylate, o-vinyl(meth)acrylate Roxymethylphenylmethyl, 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxy)isopropyl (meth)acrylate , (meth)acrylate-2-(vinyloxyisopropoxy)propyl, (meth)acrylate-2-(vinyloxyisopropoxy)isopropyl, (meth)acrylate-2-(vinyloxyethoxyethoxy)ethyl, ( 2-(vinyloxyethoxyisopropoxy)ethyl meth)acrylate, 2-(vinyloxyisopropoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)ethyl (meth)acrylate etc.

-Other (meth)acrylate compounds-
Other (meth)acrylate compounds include, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, morpholinoethyl (meth)acrylate, trimethylsiloxyethyl (meth) Acrylates, diphenyl-2-(meth)acryloyloxyethyl phosphate, 2-(meth)acryloyloxyethyl acid phosphate, caprolactone-modified 2-(meth)acryloyloxyethyl acid phosphate, 2-hydroxy-1-(meth)acryloxy- 3-methacryloxypropane, acryloxyethyl phthalate, 2-(meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth) acryloyloxypropyl phthalate, tricyclodecane monomethylol (meth) acrylate, (meth) ) acrylic acid dimer, diethylaminoethyl (meth) acrylate, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-ethylhexyl-diglycol (meth) acrylate, amino Ethyl (meth) acrylate, ethyl carbitol acrylate, ethyl diglycol acrylate, dimethylaminoethyl acrylate benzyl chloride quaternary salt, tribromophenyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, cresol (meth) ) acrylate, trimethylolpropane formal (meth)acrylate, neopentyl glycol (meth)acrylic acid benzoate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-(meth)acryloylpiperidin-2-one, 2-(meth)acrylic acid-1,4-dioxaspiro[4,5]dec-2-ylmethyl, N-(meth)acryloyloxyethylhexahydrophthalimide, γ- butyrolactone (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, imide acrylate, vinyl (meth)acrylate, maleimide and the like.

- Styrene-based compounds -
Styrenic compounds include, for example, styrene, vinyltoluene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxy carbonylstyrene, pt-butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene, divinylbenzene and the like.
-N-vinyl compound-
Examples of N-vinyl compounds include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-2-caprolactam, and N-vinylcarbazole.
-Arylate compounds-
Examples of arylate compounds include allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, and isocyanuric acid triallylate.

- Other compounds with one ethylenically unsaturated bond -
As the compound having one ethylenically unsaturated bond, "another compound having one ethylenically unsaturated bond" other than the above compounds can be used.
Examples of such compounds include vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl crotonate, vinyl 2-ethylhexanoate, and three-membered ring compounds. (e.g., vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes, 2-phenyl-3-vinyloxiranes, 2,3-divinyloxiranes, etc.), cyclic ketene acetals (e.g., 2-methylene -1,3-dioxepane, dioxolanes, 2-methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, 5,6-benzo-2-methylene- 1,3-dioxepane, etc.).

(Compound with two ethylenically unsaturated bonds (excluding vegetable oil-modified polyfunctional polyester oligomer))
The active energy ray-curable flexographic printing ink composition of the present invention can use a known compound having two ethylenically unsaturated bonds.
As such a compound having two ethylenically unsaturated bonds, known compounds can be used without limitation. (meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polyethylene glycol (100) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (700) di (meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, cyclohexanedi Methanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, dimethyloloctane di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, dimethylolpropane di(meth)acrylate, tetraethylene glycol di(meth)acrylate (Meth)acrylates, triethylene glycol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, neopentylglycol hydroxypivalate di(meth) Acrylates, polytetramethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-dimethyl-2,4-pentanediol di(meth)acrylate, 1,4-butanediol di( meth)acrylate, 1,5-dimethyl-2,5-hexanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, pentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate , hydroxypivalyl hydroxypivalate di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate ) acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate , 1,2-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1 , 12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16 -hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate ) acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3 -propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethyloloctane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate (Meth)acrylates, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2,4-diethyl-1,5-pentane Diol di(meth)acrylate, 2-methyl-1,3-butylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecanedimethylol Dicaprolactonate di(meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, 1,6-hexanediol bis(2-hydroxy-3-(meth)acryloyloxypropyl) ether, bis(4-(meth) ) Acryloxypolyethoxyphenyl)propane, pentaerythritol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, pentaerythritol di(meth)acrylate monobenzoate, glycerin di(meth)acrylate, 2-hydroxy-1 , 3-di(meth)acryloxypropane, 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, hexane Diol divinyl ether, trimethylolpropane diallyl ether, vinyloxyalkyl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate, N,N'-methylenebisacrylamide, bisphenol A di(meth)acrylate, bisphenol F di(meth) ) acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate and the like.
The ethylenically unsaturated bond may also be, for example, ethoxylated 1,6-hexanediol di(meth)acrylate, ethoxylated neopentylglycol di(meth)acrylate, or propoxylated neopentylglycol di(meth)acrylate. and alkoxylated compounds (eg, ethoxylated, propoxylated, butoxylated compounds, etc.) and the like.
Further, for example, ethylene oxide (EO)-modified bisphenol A di(meth)acrylate, propylene oxide (PO)-modified bisphenol A di(meth)acrylate, EO-modified hydrogenated bisphenol A di(meth)acrylate, PO-modified hydrogenated bisphenol A Di(meth)acrylate, EO-modified bisphenol F di(meth)acrylate, PO-modified bisphenol F di(meth)acrylate, EO-modified tetrabromobisphenol A di(meth)acrylate, bisphenol A tetraethylene oxide adduct di(meth)acrylate , bisphenol F tetraethylene oxide adduct di(meth)acrylate, bisphenol S tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol F tetraethylene oxide adduct di(meth)acrylate, EO-modified neopentyl glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, polypropylene glycol monovinyl ether (meth)acrylate, neo A compound having two ethylenically unsaturated bonds, which may be one or more selected from the group consisting of pentyl glycol PO (propylene oxide)-modified di(meth)acrylate and isocyanuric acid EO-modified di(meth)acrylate. One or more modified alkylene oxides (eg, ethylene oxide, propylene oxide, etc.) can be used.
Further, for example, bisphenol A tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, Caprolactone-modified compounds having two ethylenically unsaturated bonds, which may be one or more selected from the group consisting of meth)acrylates, caprolactone adducts of neopentylglycol hydroxypivalate and di(meth)acrylates One or more of can be used.

(Compound with three ethylenically unsaturated bonds (excluding vegetable oil-modified polyfunctional polyester oligomer))
The active energy ray-curable flexographic printing ink composition of the present invention can contain a known compound having three ethylenically unsaturated bonds.
As such a compound having three ethylenically unsaturated bonds, known compounds can be used without limitation. ) acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane trivinyl ether , trimethylolhexane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol triallyl ether, pentaerythritol trivinyl ether, 1,3,5-tri(meth)acryloylhexahydro-s-triazine, dipentaerythritol tri(meth)acrylate tripropionate, isocyanuric acid tri(meth)acrylate, tris(acryloyloxy)phosphate and the like.
In addition, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, trimethylolpropane tricaprolactonate tri(meth)acrylate, glycerin PO-modified tri( meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, isocyanurate EO-modified ε-caprolactone-modified tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, etc. alkoxylated products such as ethoxylated, propoxylated and butoxylated trifunctional monomers; alkylene oxide modified products such as ethylene oxide and propylene oxide; and caprolactone modified products.

(Compounds with 4 or more ethylenically unsaturated bonds (excluding vegetable oil-modified polyfunctional polyester oligomers))
For the active energy ray-curable flexographic printing ink composition of the present invention, a known compound having four or more ethylenically unsaturated bonds can be used.
As such compounds having four or more ethylenically unsaturated bonds, known compounds can be used without limitation. For example, compounds having four ethylenically unsaturated bonds, ethylenically unsaturated bonds A compound with five ethylenically unsaturated bonds, a compound with six ethylenically unsaturated bonds, and a compound with seven or more ethylenically unsaturated bonds are included.
Compounds having four or more ethylenically unsaturated bonds include, for example, diglycerin tetra(meth)acrylate, ditrimethylolethane tetra(meth)acrylate, ditrimethyloloctane tetra(meth)acrylate, ditrimethylolbutane tetra(meth) Acrylates, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetracaprolactonate tetra(meth)acrylate, ditrimethylolhexane tetra(meth)acrylate, trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate , pentaerythritol tetraallyl ether, pentaerythritol tetracaprolactonate tetra(meth)acrylate, pentaerythritol tetravinyl ether, dipentaerythritol tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, oligoester tetra(meth)acrylate , dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol polyalkylene oxide hepta(meth)acrylate, tri pentaerythritol octa(meth)acrylate and the like.
In addition, alkoxylated products such as ethoxylated, propoxylated and butoxylated monomers having four or more functional groups such as ethylene oxide-modified pentaerythritol tetra(meth)acrylate and ethoxylated pentaerythritol tetra(meth)acrylate, ethylene oxide, propylene oxide, etc. alkylene oxide-modified products, caprolactone-modified products, and the like.

<Epoxidized vegetable oil (meth)acrylate compound>
The active energy ray-curable flexographic printing ink composition of the present invention can also contain a known epoxidized vegetable oil (meth)acrylate compound. Since the epoxidized vegetable oil (meth)acrylate is derived from vegetable oil, it is possible to increase the amount of the biomass component in the active energy ray-curable flexographic printing ink composition.
The epoxidized vegetable oil (meth)acrylate compound is obtained by (meth)acryl-modifying an epoxidized vegetable oil. Examples include compounds obtained by ring-opening addition polymerization of (meth)acrylic acid to the epoxy group of epoxidized vegetable oil epoxidized by.

(Oligomers or polymers (excluding vegetable oil-modified polyfunctional polyester oligomers))
The active energy ray-curable flexographic printing ink composition of the present invention can contain a known polymer or oligomer having an ethylenically unsaturated bond.
Examples of polymers or oligomers having ethylenically unsaturated bonds include those having one or more ethylenically unsaturated bonds selected from the group consisting of (meth)acryloyl groups, vinyl groups, and the like.
Polymers or oligomers having ethylenically unsaturated bonds include, for example, polydiallyl phthalate, neopentyl glycol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate. ) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, rosin modified epoxy (meth) acrylate, unsaturated polyester, Examples include polyether (meth)acrylate, acrylic resins having unreacted unsaturated groups, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, acrylic-modified phenolic resins, oligomers of acrylated amine compounds, and the like.

(Commercial goods)
Examples of commercially available compounds having an ethylenically unsaturated bond other than the above compounds include, for example, Kyoeisha Chemical Co., Ltd.'s "light acrylate", "light ester", "epoxy ester", "urethane acrylate" and "high function Oligomer" series, "NK Ester" and "NK Oligo" series manufactured by Shin-Nakamura Chemical Co., Ltd., "Funkryl" series manufactured by Hitachi Chemical Co., Ltd., "Aronix" series manufactured by Toagosei Chemical Co., Ltd., Daihachi Chemical Industry "Functional Monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd. "Special Acrylic Monomer" series manufactured by Mitsubishi Rayon Co., Ltd. "Acryester" and "Diabeam Oligomer" series manufactured by Mitsubishi Rayon Co., Ltd. "Kayarad" manufactured by Nippon Kayaku Co., Ltd. and "Kayamer" series, Nippon Shokubai Co., Ltd.'s "(Meth)acrylic acid / methacrylic acid ester monomer" series, Nippon Synthetic Chemical Industry Co., Ltd.'s "NICHIGO-UV Shiko Urethane Acrylate Rigomer" series, Nippon Acetate Poval Co., Ltd. "Carboxylic Acid Vinyl Ester Monomer" Series, Kohjin Film & Chemicals "Functional Monomer" Series, Daicel Allnex "EBECRYL", "ACA", "KRM", "IRR", "RDX" and "OTA" series, Arkema's "CN" and "SR" series, BASF's "Laromer" series, IGM Resins'"Photomer" series, Neagari Kogyo Co., Ltd.'s "Artresin" series, Japan "Blemmer" series manufactured by Yusha, "New Frontier" series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Miramer" series manufactured by MIWON, and "AgiSyn" series manufactured by DSM.
The compound having an ethylenically unsaturated bond can be contained in the active energy ray-curable flexographic printing ink composition in an amount of 0 to 80.0% by mass, preferably 45.0% by mass or less.

(Resins without other ethylenically unsaturated bonds)
Other resins not having an ethylenically unsaturated bond include properties to be imparted to the active energy ray-curable flexographic printing ink composition, particularly suitable viscoelastic properties and printing properties at the time of forming the ink composition. , known ones can be used without particular limitation as long as the performance is not lowered.
Examples of other resins that do not have ethylenically unsaturated bonds include acrylic resins, polyester resins, styrene resins, polyolefin resins, epoxy resins, polyurethane resins, phenol resins, rosin resins, block Polymers, graft polymers (core-shell polymers), acrylic-modified phenolic resins, rosin-modified phenolic resins, rosin-modified alkyd-based resins, rosin-modified petroleum-based resins, rosin-modified maleic acid resins, rosin-ester-based resins, fatty acid-modified rosin-based resins, Group consisting of petroleum-based resin-modified phenol-based resins, alkyd-based resins, vegetable oil-modified alkyd-based resins, petroleum-based resins, hydrocarbon-based resins (polybutene, polybutadiene, etc.), fluorine resins (tetrafluoroethylene (PTFE) resin wax, etc.), etc. One or more selected from can be used.
Particularly preferably, acrylic resins (acrylic ester-styrene copolymer resins, etc.), styrene resins (styrene-acrylate copolymer resins, etc.), rosin-modified phenolic resins, rosin-modified alkyd resins, rosin-modified One or more selected from the group consisting of maleic acid resins, rosin ester-based resins, fatty acid-modified rosin-based resins, alkyd-based resins, and vegetable oil-modified alkyd-based resins can be used.
Such a resin preferably has a weight average molecular weight of 500 to 300,000. Also, from the viewpoint of quick drying when irradiated with active energy rays, etc., the acid value is preferably 1 to 100 mgKOH/g.
When the active energy ray-curable flexographic printing ink composition contains the above resin component, the content of the resin component in the active energy ray-curable flexographic printing ink composition is 0 to 30.0% by mass, preferably 0 It can be up to 20.0% by mass.

<Other ingredients>
The active energy ray-curable flexographic printing ink composition of the present invention may contain other components.
As such "other components", known components that can impart desired functions and properties to the composition can be used without limitation. Stabilizers, antifoaming agents, ultraviolet absorbers, infrared absorbers, thickeners (thixotropic agents), antibacterial/antifungal agents, and the like.

(Polymerization inhibitor)
The active energy ray-curable flexographic printing ink composition may contain a known polymerization inhibitor for the purpose of preventing polymerization during storage.
Examples of polymerization inhibitors include phenolic compounds such as p-methoxyphenol, catechol, tert-butylcatechol, and butylhydroxytoluene, hydroquinone, alkyl-substituted hydroquinone, phenothiazine, tocopherol acetate, nitrosamine, benzotriazole, hindered amine, and the like. .
When the active energy ray-curable flexographic printing ink composition contains a polymerization inhibitor, its content can be 0.01 to 1.0% by mass.

(solvent)
The active energy ray-curable flexographic printing ink composition may contain a known solvent in order to lower the viscosity and improve the spreadability on the substrate.
Examples of solvents include water, glycol monoacetates, glycol diacetates, glycol ethers, lactic acid esters and the like. Among these, water, tetraethylene glycol dialkyl ether, ethylene glycol monobutyl ether acetate, and diethyl diglycol are preferred.
When the active energy ray-curable flexographic printing ink composition contains a solvent, the content thereof can be 0 to 50.0% by mass.

[Production method]
The method for producing the active energy ray-curable flexographic printing ink composition of the present invention is not particularly limited, and known methods can be used.
For example, it can be prepared by adding all of the above components and mixing them with a bead mill, a three-roll mill, or the like.
In addition, after obtaining a concrete base in advance by mixing a pigment, a pigment dispersant and various active energy ray-curable compounds, an active energy ray-curable compound, a polymerization initiator, and, if necessary, an active energy ray-curable compound to obtain a desired composition. It can also be prepared by adding additives such as surfactants to the conch base.
In addition, after mixing each of the above components and kneading with a bead mill or a three-roll mill to disperse the pigment (that is, the coloring component and the extender pigment), if necessary, additives (polymerization initiator, polymerization inhibitor , other additives such as wax, etc.) may be added, and the viscosity may be adjusted by adding other components.
The viscosity of the active energy ray-curable flexographic printing ink composition of the present invention is 300 to 2000 mPa·s, and can be appropriately adjusted depending on the application. It is also preferably 500 to 1500 mPa·s, more preferably 1000 to 1500 mPa·s, still more preferably 1200 to 1500 mPa·s. This viscosity is a value obtained by measuring viscosity (unit: mPa·s) at 25° C. and 60 rpm using a Brookfield viscometer.
Substrates to be printed with the active energy ray-curable flexographic printing ink composition of the present invention include plastics, paper, carton, etc., and composite substrates such as laminates composed of a plurality of these substrates. There may be.
Among these, examples of plastic substrates to be printed with the active energy ray-curable flexographic printing ink composition of the present invention include polyester-based polymers (e.g., polyethylene terephthalate (PET), polyethylene naphthalate, etc.) and cellulose-based polymers. (e.g., diacetyl cellulose, triacetyl cellulose (TAC), etc.), polycarbonate-based polymers, polyacrylic polymers (e.g., polymethyl methacrylate, etc.), vinyl chloride-based polymers, polyolefin-based polymers (e.g., polyethylene, polypropylene, cyclic or norbornene) Structured polyolefin polymer, ethylene-propylene copolymer polymer, etc.), polyamide-based polymer (e.g., nylon, aromatic polyamide polymer, etc.), polystyrene-based polymer (e.g., polystyrene, acrylonitrile-styrene copolymer polymer, etc.), polyimide polysulfone-based polymer, polyethersulfone-based polymer, polyetherketone-based polymer, polyphenylsulfide-based polymer, polyvinyl alcohol-based polymer, polyvinylidene chloride-based polymer, polyvinyl butyral-based polymer, polyarylate-based polymer, polyoxymethylene-based polymer At least one selected from the group consisting of polymers, polyepoxy-based polymers, blends of these polymers, and the like can be used.
In order to use the active energy ray-curable flexographic printing ink composition of the present invention, for example, the active energy ray-curable flexographic printing ink composition is applied onto a substrate using a known flexographic printing machine using an anilox roll. It is printed and then irradiated with active energy rays such as ultraviolet rays. As a result, the active energy ray-curable flexographic printing ink composition on the substrate (printing medium) is rapidly cured.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited only to these Examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "mass parts". In addition, the number of the amount of each material in the table is also "mass part". The unit of acid value is mgKOH/g.

(Active energy ray-curable flexographic printing ink composition)
・Pigment carbon black PB15:4
・ Pigment dispersant PB822 (Ajisper manufactured by Ajinomoto Fine-Techno Co., Ltd.)
・Vegetable oil-modified polyfunctional polyester oligomer AgiSyn716 renewable material 30%
・Acrylamide derivative Acryloylmorpholine (ACMO)
・Other photopolymerizable compounds Dipropylene glycol diacrylate (DPGDA)
dipentaerythritol pentaacrylate
(Product name: SR399, manufactured by Sartomer)
Rosin-modified epoxy acrylate (trade name: UV22C, manufactured by Harima Chemicals)
・Plasticizer with vegetable oil component Dioctyl sebacate (vegetable oil component (non-edible) 39%)
Acetyl tributyl citrate (vegetable oil component (non-edible) 50%)
Castor oil (vegetable oil component (non-edible) 100%)
EO modified cardanol (vegetable oil component (non-edible) 91%)
・PTFE wax Average particle size 1 μm or more and less than 2 μm Product name: SST-1MG (manufactured by SHAMROCK)
Average particle size 2 μm or more and less than 4 μm Product name: Fluo HT (manufactured by Micro Powders)
Average particle size 4 μm or more and less than 6 μm Product name: Ceridust 9202F (manufactured by Clariant)
・Initiator TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxa
ido Ir184 (1-hydroxycyclohexyl-phenylketone)
Ir369 (2-benzyl-2-dimethylamino-4-morpholinobtyropheno
hmm)
Ir907 (2-methyl-1-[4-methylthiophenyl]-2-morpholinopro
pan-1-on)
BMS (4-benzoyl-4'-methyldiphenylsulfide)
EMK (Ethyl Michler's Ketone)
・Antifoaming agent Product name: AIREX920 (manufactured by Evonik)
・Polymerization inhibitor Product name: IN510 (nitrosamine) (manufactured by Daido Kasei Co., Ltd.)
・Surface conditioner Product name: 1000J, PDMS (polydimethylsiloxane) (manufactured by Momentive)

(Preparation of active energy ray-curable flexographic printing ink composition)
A mixture containing a pigment, a dispersant, a photopolymerizable component, etc. (rosin-modified epoxy acrylate, PDMS, PTFE wax, ACMO (20 parts by mass)) is processed using an Eiger mill (using zirconia beads with a diameter of 0.5 mm as media). to obtain a pigment dispersion base composition.
To the obtained pigment dispersion base composition, other components were blended so as to have the blending composition (% by mass) shown in Tables 1 and 2, mixed with stirring, and active energy rays of Examples and Comparative Examples. A curable flexographic printing ink composition was obtained.

(Evaluation method)
Ink Viscosity Viscosity (unit: mPa·s) was measured at 25° C. and 60 rpm using a Brookfield viscometer.

<UV curing>
・Curability Use a hand proofer of 800 lpi on the base material (synthetic paper YUPO 80) and apply UV light (light source is a metal halide lamp) so that the irradiation intensity per pass (1 pass) is 120 W and 80 mJ. irradiated. Then, the number of times of irradiation until curing was evaluated. After the irradiation, when the coating film was rubbed with a cotton swab, it was determined that the ink was not adhered to the cured film.

・Adhesion The base material (PET and YUPO 80) is developed using a hand proofer of 800 lpi, and UV light (light source is a metal halide lamp) is applied so that the irradiation intensity per pass (1 pass) is 120 W and 80 mJ. irradiated. Cellotape (registered trademark) manufactured by Nichiban Co., Ltd. was adhered to the obtained coating film, rubbed three times with a finger from the adhered surface, and then peeled off. The degree of removal of the coating film after peeling was visually observed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: No peeling of the cured film
△: There was peeling of the cured film, but the peeled area was less than 20% ×: The peeled area of the cured film was 20% or more

・Scratch resistance Use a hand proofer of 800 lpi on the base material (YUPO 80) to develop the color, and irradiate UV light (light source is a metal halide lamp) so that the irradiation intensity per pass (1 pass) is 120 W and 80 mJ. bottom. The coating film thus obtained was rubbed with the tip of a fingernail, and peeling off of the coating film was visually observed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
〇: No flaking 〇～△: A little flaking, but a little flaking △: Some flaking, but the base material cannot be seen ×: Some flaking, but the base material can be seen

・Abrasion resistance Use a hand proofer of 800 lpi on the base material (Yupo 80) to develop the color, and irradiate UV light (light source is a metal halide lamp) so that the irradiation intensity per pass (1 pass) is 120 W and 80 mJ. bottom. When the resulting coating film was rubbed against a pressing cloth with Kanakin No. 3 200 g × 1000 times using a Gakushin rubbing fastness tester, the degree of removal of the cured film from the base sheet was visually observed. It was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: There was no scratch on the surface of the cured film ○ ~ △: There was a slight scratch on the surface of the cured film △: There was a scratch on the surface of the cured film ×: The cured film was removed and the sheet was visible

<Electron beam curing>
A base material (PET, synthetic paper) was developed using a hand proofer of 800 lpi, and cured with an EB irradiation apparatus at an acceleration voltage of 90 kV and an irradiation dose of 30 kGy per pass (per pass) to form a cured film. . Evaluation was made in the same manner as in the case of curing with UV light.

According to the examples according to the present invention, it was possible to obtain an ink composition having an appropriate viscosity range, and to obtain a printed surface having excellent curability, adhesion, scratch resistance, and abrasion resistance.
On the other hand, according to Comparative Example 1 in which no plasticizer was added, the ink composition had a high viscosity and was difficult to print, resulting in poor adhesion. According to Comparative Example 2 containing dipentaerythritol pentaacrylate without containing a polyfunctional polyester oligomer, the adhesion was poor.

Claims (8)

It contains a polyfunctional polyester oligomer, a plasticizer and a photopolymerizable compound, and has a viscosity of 300 to 2000 mPa s,
The polyfunctional polyester oligomer comprises a vegetable oil-modified polyfunctional polyester oligomer,
The mass-based ratio of the plasticizer to the polyfunctional polyester oligomer is plasticizer/polyfunctional polyester oligomer = 1.0 to 30.0%.
An active energy ray-curable flexographic printing ink composition. The active energy ray-curable flexographic printing ink composition according to claim 1 , wherein the total content of the polyfunctional polyester oligomer and the plasticizer is 20.0 to 75.0% by mass in the ink composition. The active energy ray-curable flexographic printing ink composition according to claim 1 or 2 , wherein the plasticizer has a vegetable oil component. 2. The active energy ray-curable flexographic printing ink composition according to claim 1 , wherein the vegetable oil used for modifying the vegetable oil-modified polyfunctional polyester oligomer is a non-edible vegetable oil. 4. The active energy ray-curable flexographic printing ink composition according to claim 3 , wherein the vegetable oil used in the plasticizer having a vegetable oil component is a non-edible vegetable oil. The active energy ray-curable flexographic printing ink composition according to any one of claims 1 to 5 , which contains 1.0 to 5.0% by mass of wax having an average particle size of 8.0 µm or less. 7. The active energy ray-curable flexographic printing ink composition according to any one of claims 1 to 6, which contains 0.01 to 1.00% by mass of a surface control agent in the ink composition. The active energy ray-curable flexographic printing ink composition according to any one of claims 1 to 7 , which contains a coloring agent.