JP2020169266A - Active energy ray-curable flexographic printing ink composition - Google Patents

Abstract

To provide an active energy ray-curable flexographic printing ink composition which has low viscosity and maintains the basic characteristics such as adhesiveness, scratch resistance, and abrasion resistance, while using more components that are derived from biomass.SOLUTION: An active energy ray-curable flexographic printing ink composition contains a vegetable oil-modified polyfunctional (polyester) oligomer, a rosin-modified maleic acid resin and a photopolymerizable compound, and has a viscosity of 300-2000 mPa s.SELECTED DRAWING: None

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 environmental impact are being carried out in various industries and industries, and activities are being carried out to promote reduction of environmental impact from various perspectives. For example, volatile organic compounds (VOCs) contained in paints and inks are chemical substances that lead to global warming, so they are subject to activities to reduce the environmental burden by self-regulating and reducing the use of VOCs. There is.
From the viewpoint of reducing VOCs, utilization of an active energy ray-curable printing ink composition that cures with active energy rays such as ultraviolet rays and electron beams is being studied. The active energy ray-curable flexographic printing ink composition contains a polymerizable compound that polymerizes by irradiation with active energy rays, a polymerization initiator that exhibits a polymerization initiation function by irradiation with active energy rays, and the like, if necessary.
Since the active energy ray-curable printing ink composition can suppress the use of VOC and reduce the amount of VOC volatile to zero or less, 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 printed matter printed by various methods is not sufficiently dried, set-off when the printed matter is stacked and ink adhesion occurs when the printed matter is touched, so it is necessary to proceed to the subsequent process. It cannot be distributed as a product. Therefore, 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 active energy rays have become widespread.
Such active energy ray-curable inks are widely known, for example, as described in Patent Document 1 and Patent Document 2.

Further, with respect to the active energy ray-curable printing ink composition, various measures are taken with the aim of reducing the environmental load. For example, from the development of products that can be cured (dried) with less active energy ray irradiation, high-pressure mercury lamps that consume a lot of power and cause ozone to be generated by ultraviolet rays of short wavelengths, and ultraviolet LED lamps that save power and generate less ozone. It has been replaced with a low-power ultraviolet lamp.

In recent years, as an activity to reduce the environmental load, greenhouse gas emissions have been achieved as a biomass product that does not increase CO ₂ in the environment (carbon neutral) by substituting raw materials derived from fossil resources with raw materials derived from biomass, which is a renewable resource. The amount is being reduced.
For example, in the printing ink industry, a new ink green mark (IG mark) system has been established, and environmentally friendly levels are ranked in three levels according to the ratio of biomass-derived components in printing ink components to reduce environmental impact. There are activities to encourage people to do so.

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 IG mark certification criteria. Moreover, it has been difficult to easily and in large quantities a polymerizable compound 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 studied as biomass-derived components in consideration of competition with food production. ing.
For example, in Patent Document 3, it is possible to use an ultraviolet curable composition based on a natural renewable resource such as cardanol contained in cashew nut shell liquid or a urethane acrylate synthesized from a derivative thereof as a printing ink. It is stated that there is. However, it is considered difficult to easily and in large quantities such urethane acrylates.
Further, if a large amount of the polyfunctional acrylate compound is blended, the viscosity may increase, which may make handling difficult.

JP-A-2017-137369 JP-A-2015-081264 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, scratch resistance, and scratch resistance are maintained. An object of the present invention is to prepare an active energy ray-curable flexographic printing ink composition.
Moreover, since the ratio of raw materials derived from biomass is increased and non-edible biomass is used, it does not compete with food production and can suppress the problems of hunger and food. An 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-oriented 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 come to solve the present invention.
That is, the present invention
1. 1. An active energy ray-curable flexographic printing ink composition containing a vegetable oil-modified polyfunctional (polyester) oligomer, a rosin-modified maleic acid resin, and a photopolymerizable compound and having a viscosity of 300 to 2000 mPa · s.
2. The total content of the vegetable oil-modified polyfunctional (polyester) oligomer and the rosin-modified maleic acid resin is 20.0 to 75.0% by mass in the ink composition, and the rosin-modified maleic acid resin with respect to the vegetable oil-modified polyfunctional (polyester) oligomer is The active energy ray-curable flexo printing ink composition according to 1, wherein the mass-based ratio of rosin-modified maleic acid / vegetable oil-modified polyfunctional (polyester) oligomer = 1.0 to 50.0% by mass.
3. 3. The active energy ray-curable flexographic printing ink composition according to 1 or 2, which contains 1.0 to 5.0% by mass of wax having an average particle size of 8.0 μm or less in the ink composition.
4. The active energy ray-curable flexographic printing ink composition according to any one of 1 to 3, which contains 0.01 to 1.00% by mass of a surface conditioner in the ink composition.
5. The active energy ray-curable flexographic printing ink composition according to any one of 1 to 4, which contains a colorant.

According to the present invention, it is possible to obtain an active energy ray-curable flexographic printing ink composition in which basic properties such as curability, adhesion, and scratch resistance are maintained, and it is also possible to increase the ratio of raw materials derived from biomass. It will be possible.

The active energy ray-curable flexographic printing ink composition of the present invention is printed on a label or the like. Hereinafter, this composition will be described in detail.
(Colorant)
The active energy ray-curable flexographic printing ink composition of the present invention may contain a colorant of each hue to obtain an active energy ray-curable flexographic printing ink composition of each color. Further, the composition can be made colorless clear or colored clear by not containing a colorant or reducing the content.
As the colorant used in the active energy ray-curable flexographic printing ink composition of the present invention, known pigments and dyes used in the flexo ink composition can be used without limitation, but from the viewpoint of light resistance, they are organic. Pigments such as pigments or inorganic pigments are preferred.
Specifically, as inorganic pigments, colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, dark blue, ultramarine blue, iron black, chromium oxide green, carbon black, and graphite (achromatic colors such as white and black). Color pigments are also included), and extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc can be mentioned. In addition, as organic pigments, dye lake pigments, azo pigments, benzoimidazolone-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo-based, thioindico-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and isoind Examples thereof include linone-based, nitro-based, nitroso-based, anthraquinone-based, flavanthron-based, quinophthalone-based, pyranthron-based, and indanthron-based pigments.
When a colorant of each hue is contained to prepare an active energy ray-curable flexo printing ink composition of each color, the concentration of the colorant in the active energy ray-curable flexo printing ink composition is 1 to 60% by mass. Is preferable.

(Pigment dispersant / resin for pigment dispersion)
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 dispersion 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 silicon-based surfactants (for example, 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 activators, acetylene glycol-based surfactants, phosphoric acid-based surfactants, sulfonic acid-based surfactants, and the like can be used.
Further, as the resin for pigment dispersion, a polymer dispersant (for example, carbodiimide-based, polyester-based, polyamine-based, polyesteramine-based, polyurethane-based, fatty acid amine-based, polyacrylate-based, polycaprolactone-based, polysiloxane-based, multi-chain type) One or more selected from the group consisting of polymer nonionic, polymer ionic dispersants, etc.) can be used.
When the active energy ray-curable flexographic printing ink composition contains a pigment dispersant or a pigment dispersion resin, it is preferably contained in an amount of 1 to 200% by mass when the total amount of pigments used is 100% by mass. ..

(Vegetable oil-modified polyfunctional (polyester) oligomer)
The vegetable oil-modified polyfunctional (polyester) oligomer is limited as long as it has two or more (meth) acrylate groups in the molecule and is a bifunctional, tetrafunctional or hexafunctional polyfunctional polyester oligomer modified with vegetable oil. Can be used without. This is preferable because the degree of biomass of the active energy ray-curable flexographic printing ink composition can be increased.
When the vegetable oil-modified polyfunctional (polyester) oligomer is not blended, the curability and scratch resistance due to the active energy rays deteriorate.
The vegetable oil used for modification is a concept that includes various fatty acid esters contained in the vegetable oil, fatty acids obtained by hydrolyzing the various fatty acid esters, and the like. As the vegetable oil, soybean oil, rapeseed oil, sunflower oil, tall oil, corn oil and the like can be used. Above all, it is preferable to use non-edible tall oil as a vegetable oil for denaturation.
Among the polyfunctional (polyester) oligomers, a hexafunctional plant-derived modified (polyester) oligomer is preferable, and for example, one or more selected from the group consisting of EBECRYL 450, AgiSyn 716 and the like is preferably used.
The content of the vegetable oil-modified polyfunctional (polyester) oligomer in the active energy ray-curable flexographic printing ink composition is preferably 14.0 to 65% by mass, more preferably 15.0 to 65% by mass, and 16.0. It is more preferably ~ 40.0% by mass, most preferably 18.0 to 35% by mass, and extremely preferably 20.0 to 30% by mass.
Above all, when the active energy ray-curable flexographic printing ink composition of the present invention is not clear, a vegetable oil-modified polyfunctional (polyester) oligomer is preferably used in the active energy ray-curable flexographic printing ink composition of the present invention. It can be blended so as to be 0 to 55.0 mass%, more preferably 15.0 to 40 mass%, and more preferably 16.0 to 30.0 mass%. ..
Further, when the active energy ray-curable flexographic printing ink composition of the present invention is clear, a vegetable oil-modified polyfunctional (polyester) oligomer is preferably contained in the active energy ray-curable flexographic printing ink composition of the present invention. It can be blended so as to be 0 to 65.0 mass%, more preferably 18.0 to 40 mass%, and more preferably 20.0 to 30.0 mass%. ..
In the clear ink composition, the base can be confirmed through the printed surface.

(Rosin-modified maleic acid resin)
In the present invention, it contains a rosin-modified maleic acid-based resin.
By containing this resin, the viscosity of the ink can be lowered while keeping various physical properties good, and if it is not contained, the adhesion is inferior.
Regardless of whether the active energy ray-curable flexographic printing ink composition of the present invention is clear or not, a rosin-modified maleic acid-based resin is preferably 0 in the active energy ray-curable flexographic printing ink composition of the present invention. It can be blended so as to be 5 to 20.0 mass%, more preferably 0.8 to 15.0 mass%, and more preferably 1.0 to 10.0 mass%. Can be blended with.
Moreover, the total content of the vegetable oil-modified polyfunctional (polyester) oligomer and the rosin-modified maleic acid resin may be 20.0 to 75.0% by mass in the ink composition.
When making a non-clear active energy ray-curable flexographic printing ink composition, it is preferably 20.0 to 60.0% by mass, and when making a clear active energy ray-curable flexographic printing ink composition. Is preferably 25.0 to 70.0% by mass.
The ratio of the vegetable oil-modified polyfunctional (polyester) oligomer to the rosin-modified maleic acid resin is the mass ratio. The vegetable oil-modified polyfunctional (polyester) oligomer: rosin-modified maleic acid resin = 100: 1 to 100: 50 (vegetable oil-modified polyfunctional (polyester) The mass-based ratio of the rosin-modified maleic acid resin to the polyester) oligomer is preferably rosin-modified maleic acid resin / vegetable oil-modified polyfunctional (polyester) oligomer = 1.0 to 50.0% by mass), and more preferably. It is preferably 100: 2 to 100: 45, more preferably 100: 15 to 100:45.
As a result, the active energy ray-curable flexographic printing ink composition can obtain an ink having excellent curability, adhesion, scratch resistance, scratch resistance, and a high degree of biomass.

(wax)
As the wax, a wax having an average particle size of 8.0 μm or less can be selected and used in order to improve scratchability.
Specifically, animal and plant waxes such as beeswax, lanolin wax, whale wax, candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, montan wax, ozokelite, selecin, paraffin wax, microcrystallin wax, petrolatum, etc. Minerals, petroleum wax, Fisher Tropsch wax, polyethylene wax, polyethylene oxide wax, synthetic hydrocarbon wax such as polypropylene oxide wax, monttan wax derivative, paraffin wax derivative, modified wax such as microcrystallin wax derivative, hardened castor oil The average particle size of hydride wax such as hardened castor oil derivative, polytetrafluoroethylene wax (PTFE), etc. is 8.0 μm or less, preferably 6.0 μm or less, more preferably 4.0 μm or less, still more preferably 2. Those of 0.0 μm or less can be used. When the average particle size is 2.0 μm or less, the scratch resistance becomes better.
Further, 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 number of lines of Anilox of the flexographic printing machine.

When wax is contained, the content in the active energy ray-curable flexographic printing ink composition is preferably in the range of 0.5 to 5.0% by mass, more preferably in the range of 1.5 to 4.5% by mass. preferable.
If the wax content is less than 0.5% by mass, the scratch resistance (scratch resistance) tends to be lowered, while if it is more than 5.0% by mass, the turn roll is soiled and the workability is lowered. There is a tendency.

(Surface conditioner)
The active energy ray-curable flexographic printing ink composition may contain a known surface conditioner for improving leveling property and slipping property.
As the surface conditioner, for example, one or more selected from the group consisting of a silicon-based surface conditioner, a fluorine-based surface conditioner, an acrylic surface conditioner, an acetylene glycol-based surface conditioner, and the like can be used.
As a specific example of the surface conditioner, one or more selected from the group consisting of BYK series manufactured by Big Chemie, TEGO series manufactured by Evonik Japan, Polyflow series manufactured by Kyoei Kagaku Co., Ltd., and the like can be used.
When the active energy ray-curable flexographic printing ink composition contains a surface conditioner, the content thereof can be 0.01 to 1% by mass.

(Photopolymerization initiator)
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 is irradiated with active energy rays to generate active species such as radicals and initiates polymerization of the active energy ray-curable flexographic printing ink composition. For example, Redox. One or more selected from the group consisting of an initiator, a thermal polymerization initiator, a photopolymerization initiator and the like can be used. When the active energy ray-curable flexographic printing ink composition of the present invention is cured by an electron beam, it is not necessary to contain a photopolymerization initiator.

The redox initiator exerts a polymerization initiation function by a redox reaction under mild conditions by combining a peroxide and a reducing agent.
Each of the thermal polymerization initiator and the photopolymerization initiator exerts a polymerization initiation function by generating radicals by being irradiated with active energy rays (infrared rays, ultraviolet rays, LEDs, electron beams, etc.).
The polymerization initiator is appropriately selected according to the application, purpose, etc., and it is usually preferable to use a photopolymerization initiator. However, when toxicity needs to be investigated, a thermal polymerization initiator having high potential toxicity is used. And redox initiators, which are relatively less toxic than photopolymerization initiators, can also be used.
Among these, since it is possible to improve the curability against ultraviolet rays 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 (curing reaction (curing reaction) by light having a wavelength in that range. It is preferable to use a photoradical polymerization initiator capable of exhibiting the initiator function of (radical polymerization).

Examples of the photoradical polymerization initiator include acylphosphine oxide compounds, triazine compounds, aromatic ketone compounds, aromatic onium salt compounds, organic peroxides, thioxanthone compounds, thiophenyl compounds, and anthracene compounds. , Hexaarylbisimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, halogenated hydrocarbon compounds and alkylamine compounds, iodonium salt compounds and sulfonium salts One or more selected from the group consisting of system compounds and the like can be used.
The acylphosphine oxide-based compound is selected from the group consisting of, for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like1 More than a seed can be used.

Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 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- Naft-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-on and the like can be used.
As such a photopolymerization initiator, for example, BASF's Irgacure 907, 369, 184, 379, 819 and the like, Lamberti's TPO, DETX and the like, Midori Chemical's TAZ-204 and the like can be used.

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, for example, in 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, and 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 preferable because sufficient curability of the ink composition and good internal curability and cost can be achieved at the same time.

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

-Acrylamide derivative-
Although it depends on the color of the active energy ray-curable flexographic printing ink composition, it is preferable to contain an acrylamide derivative in order to improve the 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 meta) 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 scratch resistance, scratch resistance, etc. may decrease.

-Unsaturated carboxylic acid compounds-
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 the alkyl (meth) acrylate-based compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and 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 ( Meta) acrylate, tridecyl (meth) acrylate, nonyl (meth) acrylate, hexadecyl (meth) acrylate, myristyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl ( Meta) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, 3,5,5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

-Hydroxy group-containing (meth) acrylate compound-
Examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 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, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, -2-hydroxy (meth) acrylate Hydroxy-3-allyloxypropyl, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, 2-ethylhexyl EO modified (meth) acrylate, o-phenylphenol EO modified acrylate, p-cumylphenol EO modified (meth) ) (Poly) alkylene glycol-modified (meth) acrylates such as acrylate and nonylphenol EO-modified (meth) acrylate.

-Halogen-containing (meth) acrylate compounds-
Examples of the halogen-containing (meth) acrylate-based compound 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- Examples thereof include butylphenyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, and 2,4,6-tribromophenol 3EO (ethylene oxide) -added (meth) acrylate.

-Ether group-containing (meth) acrylate compound-
Examples of the ether group-containing (meth) acrylate-based compound include 1,3-butylene glycol methyl ether (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, and methoxytripropylene glycol ( Meta) 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) Meta) acrylate, -2- (vinyloxyethoxy) ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, p-nonylphenoxyethyl (meth) acrylate, p-nonylphenoxypolyethylene 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 (Meta) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate (EO repetition unit number 400, 700, etc.), 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, 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 G, ethoxylated succinic acid (meth) acrylate, ethoxylated tribromophenyl acrylate, ethoxylated nonylphenyl (meth) acrylate, and other alkoxy and / or phenoxy-based (meth) acrylates.

-Carboxylic group-containing (meth) acrylate compound-
Examples of the carboxyl group-containing (meth) acrylate compound include β-carboxyethyl (meth) acrylate, monoacryloyloxyethyl succinate ester, ω-carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyl. Examples thereof include hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyl oxypropyl hexahydrohydrogen phthalate, and 2- (meth) acryloyl oxypropyl tetrahydrohydrogen phthalate.

-Vinyl ether group-containing (meth) acrylate compound-
Examples of the vinyl ether group-containing (meth) acrylate compound include (meth) acrylate-2-vinyloxyethyl, (meth) acrylate-3-vinyloxypropyl, (meth) acrylate-1-methyl-2-vinyloxyethyl, and the like. (Meta) -2-vinyloxypropyl acrylate, (meth) -4-vinyloxybutyl acrylate, -1-methyl-3-vinyloxypropyl (meth) acrylate, -1-vinyloxymethylpropyl (meth) acrylate , (Meta) Acrylic Acid-2-Methyl-3-Biniroxypropyl, (Meta) Acrylic Acid-3-Methyl-3-Biniroxypropyl, (Meta) Acrylic Acid-1,1-dimethyl-2-Biniroxyethyl, ( -3-Vinyloxybutyl (meth) acrylate, -1-methyl-2-vinyloxypropyl (meth) acrylate, -2-vinyloxybutyl (meth) acrylate, -4-vinyloxycyclohexyl (meth) acrylate, (meth) Acrylic acid-5-vinyloxypentyl, (meth) acrylic acid-6-vinyloxyhexyl, (meth) acrylic acid-4-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid-3-vinyloxymethylcyclohexylmethyl, ( Meta) Acrylic acid-2-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid-p-vinyloxymethylphenylmethyl, (meth) acrylic acid-m-vinyloxymethylphenylmethyl, (meth) acrylic acid-o-bini Loxymethylphenylmethyl, -2- (vinyloxyisopropoxy) ethyl (meth) acrylate, -2- (vinyloxyethoxy) propyl (meth) acrylate, -2- (vinyloxyethoxy) isopropyl (meth) acrylate , (Meta) Acrylic Acid-2- (Vinyloxyisopropoxy) propyl, (Meta) Acrylic Acid-2- (Vinyloxyisopropoxy) isopropyl, (Meta) Acrylic Acid-2- (Vinyloxyethoxyethoxy) Ethyl, ( -2- (Vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, -2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, -2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate And so on.

-Other (meth) acrylate compounds-
Examples of other (meth) acrylate-based compounds include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, morpholinoethyl (meth) acrylate, and trimethylsiloxyethyl (meth). Acrylate, diphenyl-2- (meth) acryloyloxyethyl phosphate, 2- (meth) acryloyloxyethyl acid phosphate, caprolactone-modified -2- (meth) acryloyloxyethyl acid phosphate, 2-hydroxy-1- (meth) acryloxy- 3-methacryloxypropane, acryloxyethylphthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalate, 2- (meth) acryloyloxypropylphthalate, tricyclodecanemonomethylol (meth) acrylate, (meth) ) Acrylate dimer, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 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, Trimethylol Propaneformal (meth) Acrylate, Neopentyl Glycol (Meta) Acrylic Acid Acrylate, (2-Methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl (Meta) Acrylate, 1- (meth) acryloyl piperidine-2-one, 2- (meth) acrylic acid-1,4-dioxaspiro [4,5] deci-2-ylmethyl, N- (meth) acryloyloxyethyl hexahydrophthalimide, γ- Examples thereof include butyrolactone (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, imide acrylate, vinyl (meth) acrylate, maleimide and the like.

-Styrene compounds-
Examples of styrene-based compounds include styrene, vinyl toluene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, and pt-butoxy. Examples thereof include carbonyl styrene, pt-butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene, and divinylbenzene.

-N-Vinyl compound-
Examples of the N-vinyl compound include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-2-caprolactam, N-vinylcarbazole and the like.

-Alilate compounds-
Examples of the allylate compound include allyl glycidyl ether, diallyl phthalate, triallyl trimerite, and isocyanuric acid trialilate.

-Compounds with one other ethylenically unsaturated bond-
As the compound having one ethylenically unsaturated bond, a "compound having one other ethylenically unsaturated bond" other than the above compound can be used.
Examples of such compounds include vinyl acetate, monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl crotonate, vinyl 2-ethylhexanate, and three-membered ring compounds. (For example, vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes, 2-phenyl-3-vinyloxylanes, 2,3-divinyloxylanes, etc.), cyclic ketene acetals (for example, 2-methylene). -1,3-dioxepan, dioxolanes, 2-methylene-4-phenyl-1,3-dioxepan, 4,7-dimethyl-2-methylene-1,3-dioxepan, 5,6-benzo-2-methylene- 1,3-Dioxepan, etc.) and the like.

(Compounds having two ethylenically unsaturated bonds (excluding vegetable oil-modified polyfunctional (polyester) oligomers))
In the active energy ray-curable flexographic printing ink composition of the present invention, a compound having two known ethylenically unsaturated bonds can be used.

As the compound having two such ethylenically unsaturated bonds, known compounds can be used without limitation, and for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di. (Meta) 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 (Meta) 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, dimethylol octane di (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, dimethylol propandi (meth) acrylate, tetraethylene glycol di (Meta) acrylate, triethylene glycol di (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, neopentyl glycol di (meth) hydroxypivalate Acrylate, 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 ( Meta) 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 To,

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-pentanedioldi (meth) acrylate, 2-methyl-2-propyl-1,3-propanedioldi (meth) acrylate, 2,4- Dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanedioldi (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) ) Acrylate, dimethylol octane (meth) acrylate,

2-Ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol 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, dimethylol dicyclopentane di (meth) acrylate, 1,6-hexanediol bis (2-hydroxy-3- (meth) acryloyl) Oxypropyl) 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, cyclohexanedi Methanol Divinyl Ether, Dipropylene Glycol Divinyl Ether, Triethylene Glycol Divinyl Ether, Trimethylol Propane Divinyl Ether, Butanediol Divinyl Ether, Propropylene Glycol Divinyl Ether, Hexadiol Divinyl Ether, Trimethylol Propane Dialyl Ether, Vinyloxy Acrylate (meth) Alkyl, vinyloxyethoxyethyl (meth) acrylate, N, N'-methylenebisacrylamide, bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, hydroxypivalyl hydroxypivalate di (meth) acrylate, hydrogenated Examples thereof include bisphenol A di (meth) acrylate and hydrogenated bisphenol F di (meth) acrylate.

Further, for example, the ethylenically unsaturated bond may be ethoxylated 1,6-hexanediol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, or propoxylated neopentyl glycol di (meth) acrylate. Examples thereof include an alkoxide of a compound comprising two of the above (for example, ethoxylation, propoxylation, butoxylation, etc.).

Further, for example, ethylene oxide (EO) -modified bisphenol A di (meth) acrylate, propylene oxide (PO) -modified bisphenol A di (meth) acrylate, EO-modified hydride bisphenol A di (meth) acrylate, PO-modified hydride bisphenol A di. (Meta) 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, (meth) polyethylene glycol monovinyl ether acrylate, (meth) polypropylene glycol monovinyl ether acrylate, neopentyl The alkylene of a compound having two ethylenically unsaturated bonds, which may be one or more selected from the group consisting of glycol PO (propylene oxide) -modified di (meth) acrylate and isocyanuric acid EO-modified di (meth) acrylate. One or more kinds of oxide modified products (for example, 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 adduct of meta) acrylate and hydroxypivalate neopentyl glycol ester A caprolactone adduct of a compound having two ethylenically unsaturated bonds, which may be one or more selected from the group consisting of di (meth) acrylate. One or more of can be used.

(Compounds having three ethylenically unsaturated bonds (excluding vegetable oil-modified polyfunctional (polyester) oligomers))
The active energy ray-curable flexographic printing ink composition of the present invention can contain a compound having three known ethylenically unsaturated bonds.
As the compound having three such ethylenically unsaturated bonds, known compounds can be used without limitation, and for example, glycerintri (meth) acrylate, tetramethylolmethanetriacrylate, and tetramethylolpropanetri (meth) can be used. ) Acrylate, Tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, Trimethylolethanetri (meth) acrylate, Trimethyloloctanetri (meth) acrylate, Trimethylolpropanetri (meth) acrylate, Trimethylolpropanetrivinyl ether , Trimethylolhexanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol triallyl ether, pentaerythritol trivinyl ether, 1,3,5-tri (meth) acryloylhexahydro-s-triazine, dipentaerythritol Examples thereof include tri (meth) acrylate tripropionate, tri (meth) acrylate of isocyanurate, and trimethylolpropane phosphate.

In addition, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, glycerin propoxytri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, and glycerin PO-modified tri (meth) acrylate. Meta) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, isocyanuric acid EO-modified ε-caprolactone-modified tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, etc. Examples thereof include ethoxylated, propoxylated, butoxylated alkoxylates of the trifunctional monomer, alkylene oxide modified products such as ethylene oxide and propylene oxide, and caprolactone modified products.

(Compounds having four or more ethylenically unsaturated bonds (excluding vegetable oil-modified polyfunctional (polyester) oligomers)
In the active energy ray-curable flexographic printing ink composition of the present invention, a compound having four or more known ethylenically unsaturated bonds can be used.
As the compound having four or more such ethylenically unsaturated bonds, known compounds can be used without limitation. For example, a compound having four ethylenically unsaturated bonds and an ethylenically unsaturated bond can be used. Examples thereof include a compound having five, a compound having six ethylenically unsaturated bonds, and a compound having seven or more ethylenically unsaturated bonds.

Examples of the compound having four or more ethylenically unsaturated bonds include diglycerin tetra (meth) acrylate, ditrimethylolethanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, and ditrimethylolbutanetetra (meth). Aacrylate, trimethylolpropane tetra (meth) acrylate, dimethylolpropanetetracaprolactonate tetra (meth) acrylate, trimethylolhexanetetra (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, tetramethylolmethanetetra (meth) acrylate, oligoestertetra (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. Examples thereof include pentaerythritol octa (meth) acrylate.

Further, ethoxylation, propoxylation, butoxylation and the like of the above-mentioned tetrafunctional or higher functional monomers such as ethylene oxide-modified pentaerythritol tetra (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate, ethylene oxide, propylene oxide and the like. Examples thereof include alkylene oxide-modified products and caprolactone-modified products.

<Epoxy vegetable oil (meth) acrylate compound>
The active energy ray-curable flexographic printing ink composition of the present invention may 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 biomass components in the active energy ray-curable flexographic printing ink composition.
The epoxidized vegetable oil (meth) acrylate compound is obtained by (meth) acrylic modification of the epoxidized vegetable oil. For example, a double bond of an unsaturated vegetable oil is formed by an oxidizing agent such as peracetic acid or perbenzoic acid. Examples thereof include a compound obtained by ring-opening addition polymerization of (meth) acrylic acid on the epoxy group of the 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 polymer or oligomer having a known ethylenically unsaturated bond.
Examples of the polymer or oligomer having an ethylenically unsaturated bond include those having one or more ethylenically unsaturated bonds selected from the group consisting of (meth) acryloyl group, vinyl group and the like.

Examples of the polymer or oligomer having an ethylenically unsaturated bond include polydiallyl phthalate, neopentyl glycol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, and 1,6-hexanediol oligo (meth). ) 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 thereof include polyether (meth) acrylates, acrylic resins having unreacted unsaturated groups, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, acrylic-modified phenolic resins, and oligomers of acrylicized amine compounds.

(Commercial goods)
Commercially available products of compounds having an ethylenically unsaturated bond other than the above compounds include, for example, "light acrylate", "light ester", "epoxy ester", "urethane acrylate" and "high performance" manufactured by Kyoeisha Chemical Co., Ltd. "Sex Monomer" series, "NK ester" and "NK oligo" series manufactured by Shin-Nakamura Chemical Co., Ltd., "Funkril" series manufactured by Hitachi Kasei Kogyo Co., Ltd., "Aronix" series manufactured by Toa Synthetic Chemical Co., Ltd., Daihachi Chemical Industry Co., Ltd. "Functional Monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Special Acrylic Monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam Oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., "Kayarad" manufactured by Nippon Kayaku Co., Ltd. "Kayamer" series, "(meth) acrylic acid / methacrylate ester monomer" series manufactured by Nippon Catalyst Co., Ltd., "NICHIGO-UV purple light urethane acrylate ligomer" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., manufactured by Nippon Vinegar Bi-Poval Co., Ltd. "Carbonate Vinyl Ester Monomer" Series, "Functional Monomer" Series manufactured by Kojin Film & Chemicals, "EBECRYL", "ACA", "KRM", "IRR", "RDX" and manufactured by Daicel Ornex. "OTA" series, "CN" and "SR" series manufactured by Alchema, "Laromer" series manufactured by BASF, "Photomer" series manufactured by IGM Resins, "Art Resin" series manufactured by Negami Kogyo Co., Ltd., manufactured by Nichiyu Kagaku Co., Ltd. "Blemmer" series, "New Frontier" series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Miramer" series manufactured by MIWON, "AgiSyn" series manufactured by DSM, and the like.

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.

(Other resins that do not have ethylenically unsaturated bonds)
Other resins are known as long as the performance does not deteriorate depending on the characteristics imparted to the active energy ray-curable flexographic printing ink composition, particularly the appropriate viscoelasticity characteristics and the printing characteristics when the ink composition is formed. Those can be used without particular limitation.
Other resins that do not have an ethylenically unsaturated bond include, for example, acrylic resin, polyester resin, styrene resin, polyolefin resin, epoxy resin, polyurethane resin, phenol resin, rosin resin, and block. Polymers, graft polymers (core-shell polymers), acrylic-modified phenolic resins, rosin-modified phenolic resins, rosin-modified alkyd resins, rosin-modified petroleum-based resins, rosin ester-based resins, fatty acid-modified rosin-based resins, petroleum-based resin-modified phenolic resins One or more selected from the group consisting of resins, alkido-based resins, vegetable oil-modified alkyd-based resins, petroleum-based resins, hydrocarbon-based resins (polybutene, polybutadiene, etc.), fluororesins (tetrafluoroethylene (PTFE) resin wax, etc.), etc. Can be used.

Particularly preferably, acrylic resin (acrylic acid ester-styrene copolymer system resin, etc.), styrene resin (styrene-acrylic acid ester copolymer system resin, etc.), rosin-modified phenolic resin, rosin-modified alkyd resin, rosin ester. One or more selected from the group consisting of styrene 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. Further, from the viewpoint of quick-drying when irradiated with active energy rays, the acid value is preferably 1 to 100 mgKOH / g.

When the active energy ray-curable flexographic printing ink composition contains the above resin components, the content of the resin components in the active energy ray-curable flexographic printing ink composition is 0 to 30.0% by mass, preferably 0. It can be ~ 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, and for example, a polymerization inhibitor, a solvent, an anti-blocking agent, and light can be used. Examples thereof include stabilizers, antifoaming agents, ultraviolet absorbers, infrared absorbers, thickeners (thixotropy 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 the polymerization inhibitor include phenol compounds such as p-methoxyphenol, catechol, tert-butylcatechol, and butylhydroxytoluene, hydroquinone, alkyl-substituted hydroquinone, phenothiazine, tocopherol acetate, nitrosoamine, benzotriazole, and hindered amine. ..
When the active energy ray-curable flexographic printing ink composition contains a polymerization inhibitor, the content thereof 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 reduce the viscosity and improve the wettability and spreadability to a substrate.
Examples of the solvent include water, glycol monoacetates, glycol diacetates, glycol ethers, lactic acid esters and the like. Of these, water, tetraethylene glycol dialkyl ether, ethylene glycol monobutyl ether acetate, and diethyl diglycol are preferable.
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 a known method can be used.
For example, all of the above components can be added and mixed with a bead mill, a three-roll mill, or the like to prepare the mixture.
Further, after obtaining a conch 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, a desired composition can be obtained. It can also be prepared by adding an additive such as a surfactant to the conch base.

Further, after mixing each of the above components, the mixture is kneaded with a bead mill, a three-roll mill, or the like to disperse the pigment (that is, the coloring component and the extender pigment), and then, if necessary, an additive (polymerization initiator, polymerization inhibitor). , Other additives such as wax, etc.), and the viscosity can 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 according to the application and the like. Further, it is preferably 500 to 1500 mPa · s.

The base material for printing the active energy ray-curable flexographic printing ink composition of the present invention is plastic, paper, carton, etc., and is a composite base material such as a laminate composed of a plurality of these base materials. There may be.

Among these, as the plastic base material for printing the active energy ray-curable flexo printing ink composition of the present invention, for example, a polyester polymer (for example, polyethylene terephthalate (PET), polyethylene naphthalate, etc.), a cellulose polymer (for example, polyethylene naphthalate, etc.) and a cellulose polymer ( For example, diacetyl cellulose, triacetyl cellulose (TAC), etc.), polycarbonate polymer, polyacrylic polymer (eg, polymethyl methacrylate, etc.), vinyl chloride polymer, polyolefin polymer (eg, polyethylene, polypropylene, cyclic or norbornene structure). Polyethylene polymer, ethylene / propylene copolymer polymer, etc.), polyamide-based polymer (eg, nylon, aromatic polyamide polymer, etc.), polystyrene-based polymer (eg, polystyrene, acrylonitrile / styrene copolymer polymer, etc.), polyimide-based Polymers, polysulfone-based polymers, polyethersulfone-based polymers, polyetherketone-based polymers, polyphenylsulfide-based polymers, polyvinyl alcohol-based polymers, polyvinylidene chloride-based polymers, polyvinylbutyral-based polymers, polyarylate-based polymers, polyoxymethylene-based polymers , And one or more selected from the group consisting of 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 placed on a substrate by using a known flexographic printing machine and using 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.

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

(Active energy ray-curable flexographic printing ink composition)
・ Pigment Carbon Black PB15: 4
-Pigment dispersant PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.)
-Vegetable oil-modified polyfunctional polyester oligomer AgiSyn716 renewable material 30%
・ Acrylamide derivative acryloyl morpholine (ACMO)
-Other photopolymerizable compounds Dipropylene glycol diacrylate (DPGDA)
Dipentaeristol pentaacrylate
(Product name: SR399, Product name: Made by Sartmer)
Rosin-modified epoxy acrylate (trade name: UV22C, manufactured by Harima Chemicals, Inc.)
-Non-polymerizable resin Product name: Tesspor 1107 Rosin-modified maleic acid (manufactured by Arakawa Chemical Co., Ltd.)
Product Name: Tamanor 803L Terpene Phenol (manufactured by Arakawa Chemical Co., Ltd.)
-PTFE wax average particle size 1-2 μm Product name: SST-1MG (manufactured by SHAMROCK)
Average particle size 2-4 μm Product name: Fluo HT (manufactured by Micro Powders)
Average particle size 4-6 μm Product name: Ceridust 9202F (manufactured by Clariant)
-Initiator TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxa
Id Ir184 (1-Hydroxycyclohexyl-phenylketon)
Ir369 (2-benzyl-2-dimethylamino-4-morpholinobtyropheno)
N)
Ir907 (2-Methyl-1- [4-Methylthiophenyl] -2-morpholinopro
Pan-1-on)
BMS (4-benzoyl-4'-methyldiphenylsulfide)
EMK (Ethyl Michelers Ketone)
・ Antifoaming agent Product name: AIREX920 (manufactured by Evonik Industries)
-Polymerization inhibitor Product name: IN510 (nitrosamine, manufactured by Daido Kasei Co., Ltd.)
・ Surface conditioner product system: 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)) was prepared using an Eiger mill (using zirconia beads having a diameter of 0.5 mm as a medium). To obtain a pigment dispersion-based composition.
Each of the other components is blended with the obtained pigment dispersion base composition so as to have the blending composition (mass%) shown in Table 1, stirred and mixed, and the active energy ray-curable flexo of Examples and Comparative Examples is used. A printing ink composition was obtained.

(Evaluation method)
-Ink Viscosity Using a B-type viscometer, the viscosity (unit: mPa · s) was measured at 25 ° C. under the condition of 60 rpm.

<UV curing>
-Use 800 lpi hand proofer on a curable base material (synthetic paper YUPO 80) and apply UV light (light source is a metal halide lamp) so that the irradiation intensity per one time (1 pass) is 120 W, 80 mJ. Irradiated. Then, the number of irradiations until curing was evaluated. After the irradiation, when the coating film was rubbed with a cotton swab, it was judged that the state in which the ink did not adhere was cured.

-Adhesion Using an 800 lpi hand proofer on the base material (PET and YUPO 80), UV light (light source is a metal halide lamp) so that the irradiation intensity per one time (1 pass) is 120 W, 80 mJ. Irradiated. Nichiban cellophane tape (registered trademark) was attached to the obtained coating film, and the coating film was rubbed three times with a finger 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)
〇: No peeling of the cured film Δ: The cured film was peeled but the peeled area was less than 20% ×: The peeled area of the cured film was 20% or more

-Scratch resistance Using an 800 lpi hand proofer on the base material (Yupo 80), irradiate UV light (light source is a metal halide lamp) so that the irradiation intensity per one time (1 pass) is 120 W, 80 mJ. did. The obtained coating film was rubbed with the tip of a nail, and the removal of the coating film was visually observed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
〇: No dropout 〇 △: Dropped but only a little △: Dropped but the base material is not visible ×: Dropped and the base material is visible

-Abrasion resistant base material (YUPO 80) is irradiated with UV light (light source is a metal halide lamp) so that the irradiation intensity per one time (1 pass) is 120 W, 80 mJ using a hand proofer of 800 lpi. did. When the obtained coating film was rubbed against a patch cloth with Kanakin No. 3 200 g × 1000 times with a Gakushin type abrasion resistance fastness tester, the degree of removal of the cured film from the base sheet was visually observed. Evaluation was made according to the following evaluation criteria.
(Evaluation criteria)
〇: There was no scratch on the surface of the cured film Δ: 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 hardened film was formed by developing a color on a base material (PET, synthetic paper) using an 800 lpi hand proofer and curing it with an EB irradiation device under an accelerating voltage of 90 kV and an irradiation dose of 30 kGy per pass. .. The evaluation was carried out in the same manner as in the case of curing with the above UV light.

According to each of the examples according to the present invention, it is possible to obtain a printed portion having a low viscosity and excellent curability, adhesion, scratch resistance and scratch resistance. However, according to Comparative Example 1 containing no rosin-modified maleic acid resin, the result was that the adhesion was inferior. Further, according to Comparative Example 2 containing no vegetable oil-modified polyfunctional (polyester) oligomer, the result was that the viscosity was high and the adhesion and scratch resistance were inferior.

Claims (5)

An active energy ray-curable flexographic printing ink composition containing a vegetable oil-modified polyfunctional (polyester) oligomer, a rosin-modified maleic acid resin, and a photopolymerizable compound and having a viscosity of 300 to 2000 mPa · s. The total content of the vegetable oil-modified polyfunctional (polyester) oligomer and the rosin-modified maleic acid resin is 20.0 to 75.0% by mass in the ink composition, and the rosin-modified maleic acid resin with respect to the vegetable oil-modified polyfunctional (polyester) oligomer is The active energy ray-curable flexo printing ink composition according to claim 1, wherein the mass-based ratio of rosin-modified maleic acid resin / vegetable oil-modified polyfunctional (polyester) oligomer = 1.0 to 50.0% by mass. .. The active energy ray-curable flexographic printing ink composition according to claim 1 or 2, wherein the ink composition contains 1.0 to 5.0% by mass of wax having an average particle size of 8.0 μm or less. The active energy ray-curable flexographic printing ink composition according to any one of claims 1 to 3, wherein the surface conditioner is contained in the ink composition in an amount of 0.01 to 1.00% by mass. The active energy ray-curable flexographic printing ink composition according to any one of claims 1 to 4, which contains a colorant.