Active energy ray curable printing ink composition, cured product, and printed product

Abstract

To provide an active energy ray-curable ink composition for printing that ensures superior pigment dispersion, provides a coating layer with superior gloss and coating resistance, and increases the biomass component ratio within the resin constituting the ink composition.SOLUTION: An active energy ray-curable ink composition for printing includes at least a pigment, an epoxy (meth) acrylate resin, and a monomer. The epoxy (meth) acrylate resin includes a cardanol skeleton, a bisphenol skeleton, and a (meth) acrylate site.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray curable printing ink composition, a cured product, and a printed product. [Background technology]

[0002] Epoxy acrylates containing a bisphenol skeleton are among the most commonly used industrial materials in active energy ray curing resins.

[0003] In the field of printing inks and coatings, it is widely used because of the hardness, flexibility, toughness, and chemical resistance it exhibits, derived from its bisphenol skeleton.

[0004] For example, Patent Document 1 discloses that bisphenol A type epoxy resin is mainly used as a base resin for paint varnishes, a base resin for film molding, and is added to epoxy resin varnishes to adjust fluidity, improve toughness and adhesion of the cured product. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2021 / 187180 [Overview of the project] [Problems that the invention aims to solve]

[0006] When conventional epoxy acrylates containing a bisphenol skeleton were used in printing inks and paints, the dispersibility of pigments was insufficient, requiring the addition of pigment dispersants or use in combination with other resins.

[0007] Furthermore, while many epoxy acrylates containing a common bisphenol skeleton are synthesized from petroleum-derived materials, there has been a growing demand in recent years for active energy ray-curable resins made from biomass materials. [Means for solving the problem]

[0008] Therefore, the present invention aims to provide an active energy ray curable printing ink composition that exhibits excellent pigment dispersibility, can impart excellent gloss and coating film resistance to the coating film, and can increase the biomass component ratio of the resin constituting the ink composition.

[0009] The present inventors have found that by providing at least a pigment, an epoxy (meth)acrylate resin, and a monomer, and by providing the epoxy (meth)acrylate resin with a cardanol skeleton, a bisphenol skeleton, and a (meth)acrylate moiety, all of the above-mentioned problems can be solved.

[0010] In other words, the present invention is an active energy ray curable printing ink composition containing at least a pigment, an epoxy (meth)acrylate resin, and a monomer, wherein the epoxy (meth)acrylate resin contains a cardanol skeleton, a bisphenol skeleton, and a (meth)acrylate moiety.

[0011] The active energy ray curable printing ink composition of the present invention preferably has a biomass component ratio of 20% or more of the resin component. Furthermore, it is preferable that the cardanol skeleton contained in the epoxy (meth)acrylate resin is a polymerized cardanol skeleton. Furthermore, the bisphenol skeleton contained in the epoxy (meth)acrylate resin is preferably a bisphenol A skeleton. Furthermore, it is preferable that the epoxy (meth)acrylate resin described above be obtained by the reaction of polymerized cardanol, an epoxy resin containing a bisphenol skeleton, and (meth)acrylic acid. Furthermore, it is preferable that the epoxy (meth)acrylate resin is present in an amount of 15 to 40% by mass relative to the total mass of the active energy ray curable printing ink composition. Furthermore, the present invention is also a cured product obtained by curing the active energy ray curable printing ink composition of the present invention. The present invention is also a printed matter having a printed layer formed from the active energy ray-curable ink composition of the present invention.

Effects of the Invention

[0012] The present invention provides an active energy ray-curable ink composition for printing, which is excellent in the dispersibility of pigments, can impart excellent gloss and coating film resistance to a coating film, and can increase the biomass component ratio of the resin constituting the ink composition.

Modes for Carrying Out the Invention

[0013] The active energy ray-curable ink composition for printing of the present invention contains at least a pigment, an epoxy (meth) acrylate resin, and a monomer, and the epoxy (meth) acrylate resin contains a cardanol skeleton, a bisphenol skeleton, and a (meth) acrylate moiety.

[0014] In the present specification, “(meth) acrylate” means “acrylate and / or methacrylate”.

[0015] Hereinafter, each component of the active energy ray-curable ink composition for printing of the present invention (simply referred to as an ink composition) will be described in detail.

[0016] (Pigment) The ink composition of the present invention contains a pigment.

[0017] The pigment is not particularly limited, and may be an organic pigment or an inorganic pigment.

[0018] Examples of the above organic pigments include dye lake pigments, azo-based, benzimidazolone-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo-based, thioindigo-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, isoindolinone-based, nitro-based, nitroso-based, anthraquinone-based, flavanthrone-based, quinophthalone-based, pyranthrone-based, indanthrone-based pigments, etc.

[0019] Examples of the above inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, ultramarine, dark blue, iron black, chromium oxide green, carbon black, graphite, etc. (including achromatic colored pigments such as white and black), and extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, talc, etc.

[0020] Specific examples of pigments for each hue are as follows.

[0021] Examples of yellow pigments include C.I.Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 42, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 108, 109, 114, 120, 128, 129, 138, 139, 150, 151, 155, 166, 180, 184, 185, 213, etc.

[0022] Examples of magenta pigments include C.I.Pigment Red 5, 7, 12, 19, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1, 57, 57:1, 63:1, 101, 102, 112, 122, 123, 144, 146, 149, 168, 177, 178, 179, 180, 184, 185, 190, 202, 209, 224, 242, 254, 255, 270, C.I.Pigment Violet 19, etc.

[0023] Examples of cyan pigments include CIPigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 22, 27, 29, and 60, with CIPigment Blue 15:4 being a notable example.

[0024] Examples of black pigments include carbon black (CIPigment Black 7).

[0025] Examples of white pigments include titanium dioxide and aluminum oxide. The titanium oxide mentioned above may be surface-treated with various materials such as alumina and silica.

[0026] The content of the above-mentioned pigment is not particularly limited, but when using a white pigment, it is preferably 1 to 20% by mass relative to the total mass of the ink composition. Furthermore, if a pigment other than white pigment is used, it is preferable that it be 0.5 to 15% by mass of the total mass of the ink composition.

[0027] (Epoxy (meth)acrylate resin) The ink composition of the present invention contains an epoxy (meth)acrylate resin. The above epoxy (meth)acrylate resin contains a cardanol skeleton, a bisphenol skeleton, and a (meth)acrylate moiety.

[0028] The epoxy (meth)acrylate resin, by containing a cardanol skeleton, a bisphenol skeleton, and a (meth)acrylate moiety, can impart excellent pigment dispersibility to the ink composition, excellent gloss and coating film resistance to the coating film, and increase the biomass component ratio of the resin constituting the ink composition.

[0029] The cardanol skeleton contained in the epoxy (meth)acrylate resin described above is preferably a polymerized cardanol skeleton.

[0030] Examples of the polymerized cardanol skeleton include the structure shown in formula (1) below.

[0031] [ka] (In formula (1), R 1 (where l is an integer between 2 and 10, and l is a hydrocarbon group with 15 carbon atoms and 25-31 hydrogen atoms.)

[0032] In equation (1) above, l represents the number of constituent units expressed in parentheses in equation (1). In formula (1) above, l is an integer between 2 and 10. The constituent units represented in parentheses in formula (1) above may be present in a continuous (block) manner in the epoxy (meth)acrylate resin, or they may be present randomly.

[0033] Examples of bisphenol skeletons contained in the epoxy (meth)acrylate resin mentioned above include bisphenol A skeleton, bisphenol F skeleton, bisphenol P skeleton, and bisphenol Z skeleton. In particular, a bisphenol A skeleton is preferred from the viewpoint of the availability of the corresponding epoxy resin.

[0034] The epoxy (meth)acrylate resin described above preferably has a weight-average molecular weight (Mw) of 3,000 to 20,000, and more preferably 6,000 to 10,000. The weight-average molecular weight mentioned above is measured, for example, as a polystyrene-converted value using gel permeation chromatography (GPC).

[0035] The epoxy (meth)acrylate resin content is preferably 15 to 40% by mass relative to the total mass of the ink composition. With the above-mentioned content, the dispersibility of the pigment, the gloss of the coating film, and the durability of the coating film can be suitably expressed. Furthermore, while providing the above-mentioned performance, it is also possible to increase the proportion of biomass components in the ink composition.

[0036] The epoxy (meth)acrylate resin described above is preferably obtained by the reaction of polymerized cardanol, an epoxy resin containing a bisphenol skeleton, and (meth)acrylic acid. The following describes an example of a method for producing the epoxy (meth)acrylate resin mentioned above.

[0037] In the above method for producing epoxy (meth)acrylate resin, polymerized cardanol represented by the following formula (2) is synthesized.

[0038] [ka] (In formula (2), R 1 (where m is an integer between 2 and 20, where m is a hydrocarbon group with 15 carbon atoms and 25-31 hydrogen atoms.)

[0039] Polymerized cardanol represented by formula (2) above may be purchased commercially or synthesized by the following method.

[0040] One method for synthesizing the cardanol compound represented by formula (2) above is to react the cardanol compound represented by formula (3) below in the presence of an acid catalyst.

[0041] [ka] (In formula (3), R 2 (It is a hydrocarbon group with 15 carbon atoms and 25-31 hydrogen atoms.)

[0042] As the acid catalyst mentioned above, known ones can be used, such as inorganic acids like sulfuric acid, hydrochloric acid, and nitric acid, or organic acids like acetic acid, citric acid, propionic acid, oxalic acid, and p-toluenesulfonic acid. In particular, from the viewpoint of catalytic activity and solubility in solution, it is preferable to use p-toluenesulfonic acid. The amount of the above acid catalyst used is approximately 0.1 to 10 parts by mass per 100 parts by mass of the cardanol compound represented by formula (3) above.

[0043] The reaction temperature for the cardanol compound represented by formula (3) above, when reacted in the presence of an acid catalyst, is, for example, around 120 to 200°C. The reaction time is, for example, around 1 to 10 hours. Furthermore, the acquisition of the target compound represented by formula (2) can be confirmed, for example, by using gel permeation chromatography (GPC) to observe the decrease in the peak derived from formula (3) and the distillation of a new component.

[0044] Furthermore, the equipment used during the above reaction (stirring device, reflux device, etc.) can be appropriately selected from known sources. After the above reaction, the product may be purified by a known method, or it may not be purified. Purification by a known method is more preferable.

[0045] In the above example of a method for producing epoxy (meth)acrylate resin, polymerized cardanol represented by formula (2) is reacted with a compound containing a bisphenol skeleton represented by formula (4) below.

[0046] [ka]

[0047] In the above formula (4), O 1 The O may be in the ortho, meta, or para position relative to the central hydrocarbon group in formula (4) above. 2 The hydrocarbon group in the center of formula (4) may be in the ortho, meta, or para position, but from the viewpoint of availability, O 1 and O 2 It is preferable that each of these is in the para position relative to the central hydrocarbon group of formula (4) above.

[0048] In addition, although the above formula (4) uses an epoxy resin containing a bisphenol A skeleton, it may also contain a bisphenol F skeleton, a bisphenol P skeleton, a bisphenol Z skeleton, or the like.

[0049] The reaction between the polymerized cardanol represented by formula (2) and the compound containing the bisphenol skeleton represented by formula (4) is preferably carried out under basic conditions.

[0050] The base used in the reaction between polymerized cardanol represented by formula (2) and a compound containing a bisphenol skeleton represented by formula (4) is not particularly limited, but examples include alkali metal hydrides, alkaline earth metal hydrides, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal fluorides, amines, organophosphorus compounds, and the like. The amount of the above-mentioned base used varies depending on the type of base, but for example, it is about 0.1 to 2.0 parts by mass per 100 parts by mass of polymerized cardanol represented by formula (2) above.

[0051] A solvent may be used in the reaction between the polymerized cardanol represented by formula (2) and the compound containing the bisphenol skeleton represented by formula (4).

[0052] The above solvents are not particularly limited, but preferred examples include water, alcohols such as methanol, ethanol, and 2-propanol, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, methylene chloride, and dimethylformamide, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, chloroform, and carbon tetrachloride, but are not limited to these. The above solvents may be used individually or in combination of multiple types. The amount of the above solvent used is, for example, about 30 parts by mass or less per 100 parts by mass of polymerized cardanol represented by formula (2) above.

[0053] The reaction temperature when reacting polymerized cardanol represented by formula (2) with a compound containing a bisphenol skeleton represented by formula (4) is, for example, around 60 to 120°C. The reaction time is, for example, around 1 to 24 hours. Furthermore, the acquisition of the target epoxy resin can be confirmed, for example, by using gel permeation chromatography (GPC) to observe a decrease in the peak originating from the raw material (e.g., polymerized cardanol represented by formula (2) above) and the distillation of new components.

[0054] The apparatus (stirring device, reflux device, etc.) used in the reaction between polymerized cardanol represented by formula (2) and a compound containing a bisphenol skeleton represented by formula (4) can be appropriately selected from known equipment. After the above reaction, the product may be purified by a known method, or it may not be purified. Purification by a known method is more preferable.

[0055] The epoxy resin obtained by the reaction of polymerized cardanol represented by formula (2) above with a compound containing a bisphenol skeleton represented by formula (4) above has a structure represented by formula (1) above and a structure represented by formula (5) below. The epoxy resin described above has relatively low viscosity and contains a sufficient number of epoxy groups in its molecule, allowing it to undergo the (meth)acrylate reaction described later.

[0056] [ka] (In formula (5), R 1 (where n is a hydrocarbon group with 15 carbon atoms and 25-31 hydrogen atoms, and n is an integer between 1 and 10.)

[0057] In equation (5) above, n represents the number of constituent units expressed in the parentheses in equation (5). In equation (5) above, n is an integer between 1 and 10. The constituent units represented in parentheses in equation (5) above may be present in a continuous (block) manner in the epoxy (meth)acrylate resin, or they may be present randomly.

[0058] The epoxy (meth)acrylate resin can be obtained by (meth)acrylateing the epoxy group of the structure represented by formula (5) above. The above (meth)acrylate formation can be carried out by reacting an epoxy group having the structure represented by formula (5) with acrylic acid and / or methacrylic acid in the presence of a base catalyst.

[0059] The above-mentioned acrylic acid and methacrylic acid are preferably in amounts of about 5 to 20 parts by mass per 100 parts by mass of the epoxy resin.

[0060] As the above-mentioned base catalyst, any known one can be appropriately selected. Furthermore, a solvent may be used, and the solvent described above can be appropriately selected in the step of reacting the polymerized cardanol represented by formula (2) with the compound containing the bisphenol skeleton represented by formula (4). Furthermore, known additives such as polymerization inhibitors and antioxidants may be added as needed. The above-mentioned base catalyst is preferably present in an amount of about 0.1 to 4 parts by mass per 100 parts by mass of the epoxy resin. The amount of the above additive used is preferably about 0.01 to 3 parts by mass per 100 parts by mass of the epoxy resin.

[0061] The reaction to convert the epoxy resin to (meth)acrylate is preferably carried out under a nitrogen atmosphere. The reaction temperature is, for example, around 60 to 120°C. The reaction time is, for example, around 1 to 10 hours. Furthermore, to confirm that the desired epoxy (meth)acrylate has been obtained, for example, by measuring the acid value of the reactants to confirm the consumption of (meth)acrylic acid, and by measuring the infrared absorption spectrum to confirm that the epoxy groups in the structure represented by formula (5) above have decreased and that (meth)acrylic acid has been introduced.

[0062] Furthermore, the equipment used during the above reaction (stirring device, reflux device, etc.) can be appropriately selected from known sources. After the above reaction, the product may be purified by a known method, or it may not be purified. Purification by a known method is more preferable.

[0063] (monomer) The ink composition of the present invention contains a monomer.

[0064] The above monomer may be a monofunctional monomer, a polyfunctional monomer, or a combination of both.

[0065] Examples of the above monofunctional monomers include benzyl methacrylate, butyl (meth)acrylate, ethyl carbitol (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, caprolactone (meth)acrylate, methoxytripropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, EO (ethylene oxide) modified succinic acid (meth)acrylate, and other monofunctional (meth)acrylates, as well as acryloyl morpholine, acrylonitrile, acrylamide, diethylacrylamide, vinylmethyloxazolidinone, styrene, and (meth)acrylic acid.

[0066] Examples of the above polyfunctional monomers include (poly)alkylene glycol di(meth)acrylates such as vinyl oxyethoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, neopentyl glycol di(meth)acrylate, polytetramethylene glycol diacrylate, trimethylolpropane tri(meth)acrylate and its ethylene oxide modified products, and pentaerythritol Examples include litol tri(meth)acrylate, ditrimethylolpropanetetraacrylate, pentaerythritol tetra(meth)acrylate and its ethylene oxide modified product, dipentaerythritol penta(meth)acrylate and its ethylene oxide modified product, dipentaerythritol hexa(meth)acrylate and its ethylene oxide modified product, urethane(meth)acrylate, epoxy(meth)acrylate, polyester(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, caprolactam-modified dipentaerythritol hexa(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and alkoxylated tetrahydrofurfuryl(meth)acrylate.

[0067] Polyfunctional monomers are preferred as the above monomers, and among them, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate and its ethylene oxide modified products, and ditrimethylolpropane tetra(meth)acrylate are more preferred from the viewpoint of curability.

[0068] From the viewpoint of ink viscosity, the monomer content is preferably 20 to 50% by mass relative to the total mass of the ink composition.

[0069] (others) The ink composition of the present invention may optionally contain polymerization initiators, polymerization inhibitors, waxes, resins, sensitizers, surface modifiers, solvents, plasticizers, ultraviolet absorbers, and the like.

[0070] Examples of the polymerization initiators mentioned above include azo initiators such as azobisisobutyronitrile and dimethyl 2,2'-azobisisobutyrate; peroxide initiators such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and benzoyl peroxides; acetophenone-based initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 1-hydroxycyclohexylphenyl ketone; benzoin-based initiators such as benzoin and benzoin ethyl ether; benzophenone-based initiators such as benzophenone; phosphorus-based initiators such as acylphosphine oxide; sulfur-based initiators such as thioxanthone; and benzyl-based photopolymerization initiators such as benzyl and 9,10-phenanthrenequinone. The polymerization initiators described above may be used individually or in combination of two or more.

[0071] The content of the polymerization initiator is preferably 0.1 to 10% by mass relative to the total mass of the ink composition.

[0072] Examples of polymerization inhibitors include hydroquinone, dibutylhydroxytoluene, hydroquinone monomethyl ether, and phenothiazine. The polymerization inhibitors described above may be used individually or in combination of two or more. The amount of polymerization inhibitor used is, for example, about 0.1 to 2.0% by mass relative to the total mass of the ink composition.

[0073] The waxes mentioned above are not particularly limited, and either natural waxes, synthetic waxes, or both may be used. The above waxes may be used individually or in combination of two or more types.

[0074] The wax content is, for example, about 0.1 to 10% by mass relative to the total mass of the ink composition.

[0075] Examples of the above-mentioned resins include polyvinyl chloride, poly(meth)acrylic acid esters, epoxy resins, polyurethane resins, cellulose derivatives (e.g., ethylcellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, butadiene-acrylonitrile copolymers, acrylic resins, styrene-acrylic resins, styrene-maleic acid resins, rosin resins, rosin ester resins, ethylene-vinyl acetate resins, petroleum resins, coumarone-indene resins, terpene phenolic resins, phenolic resins, urethane resins, melamine resins, urea resins, epoxy resins, cellulose resins, vinyl chloride-vinyl acetate resins, xylene resins, alkyd resins, aliphatic hydrocarbon resins, butyral resins, silicone resins, maleic acid resins, fumaric acid resins, and the like. The above resins may be used individually or in combination of two or more types.

[0076] The resin content is, for example, about 0.1 to 10% by mass relative to the total mass of the ink composition.

[0077] For the sensitizers, surface modifiers, solvents, plasticizers, ultraviolet absorbers, etc. mentioned above, known materials used in the field of ink compositions may be appropriately selected. These components are present in amounts of approximately 0.1 to 10% by mass, relative to the total mass of the ink composition.

[0078] (Ink composition) The ink composition of the present invention contains at least a pigment, an epoxy (meth)acrylate resin, and a monomer. The ink composition of the present invention may optionally contain other materials as described above.

[0079] The method for producing the ink composition of the present invention is not particularly limited, and it may be prepared by dispersion and mixing using known dispersants such as wet circulation mills, bead mills, ball mills, sand mills, attritors, roll mills, DCP mills, agitators, Henschel mixers, colloid mills, ultrasonic homogenizers, high-pressure homogenizers (microfluidizers, nanomizers, ultimateizers, Genus PY, DeBEE2000, etc.), and pearl mills.

[0080] (Physical properties of the ink composition) The ink composition of the present invention preferably has a biomass component ratio of 20% or more of the resin component, and more preferably 30% or more. The above biomass component ratio of 20% or more allows for a favorable contribution to the construction of a circular economy. The above biomass component ratio refers to the proportion of biomass-derived components contained in the epoxy (meth)acrylate resin and other resins described above, and is expressed by the following formula. Biomass component ratio (%) = {Mass of biomass-derived components / [Mass of epoxy (meth)acrylate resin mentioned above + Mass of other resins]} × 100

[0081] The ink composition of the present invention exhibits excellent pigment dispersibility. The dispersibility of the above pigments can be determined, for example, by measuring the flow value of the ink composition using a spread meter and examining the fluidity as a flow slope value. The flow gradient value is calculated by subtracting the spread diameter measured in millimeters after 10 seconds from the spread diameter measured in millimeters after 100 seconds using a spread meter. A larger value indicates better fluidity (pigment dispersibility).

[0082] If the above fluidity is 8 mm or more, it can be judged that the pigment has excellent dispersibility. The above flow rate is preferably 8.5 mm or more, more preferably 9 mm or more, even more preferably 9.5 mm or more, and particularly preferably 10 mm or more.

[0083] The ink composition of the present invention has excellent gloss of the coating film. For example, the gloss of the coating film is obtained by spreading 0.1 cc of the ink composition on coated paper (Aurora Coat, manufactured by Nippon Paper Industries Co., Ltd.) using a RI color spreading machine (two-division roll, manufactured by Meisei Seisakusho Co., Ltd.), and then irradiating the spread material with ultraviolet rays of 80 mJ / cm 2 at an output of 120 W / cm using a metal halide lamp to cure it, and measuring the 60° specular gloss value of the spread surface using a Murakami-type digital gloss meter (manufactured by Murakami Color Research Laboratory).

[0084] If the 60° specular gloss value is 35 or more, it can be determined that the gloss is excellent. The 60° specular gloss value is preferably 40 or more, and more preferably 45 or more.

[0085] The ink composition of the present invention has excellent abrasion resistance of the coating film. For example, the abrasion resistance of the coating film is obtained by using a hand proofing machine to spread the ink composition on Aurora Coat paper (manufactured by Nippon Paper Industries Co., Ltd.) as a test piece, and then irradiating the test piece with ultraviolet rays of 80 mJ / cm 2 at an output of 120 W / cm using a metal halide lamp to cure the ink composition and form a coated surface. Thereafter, the abrasion resistance of each of the obtained test pieces is evaluated by a Gakushin-type friction fastness tester. In addition, the conditions for evaluating the abrasion resistance are such that a friction of 20 reciprocations is applied with a 1 kg weight through a rubbing cloth (Kanakin No. 3), and the state of the coating film immediately after applying this friction is visually observed.

[0086] In the above test method, it is preferable that the coated surface does not peel even when a friction of 9 reciprocations is applied, more preferably that the coated surface does not peel even when a friction of 15 reciprocations is applied, and still more preferably that the coated surface does not peel even when a friction of 20 reciprocations is applied.

[0087] <Cured product and printed matter> A cured product obtained by curing the ink composition of the present invention is also included in the present invention. Furthermore, printed materials having a printed layer formed from the ink composition of the present invention are also included in the present invention. By printing and curing the ink composition of the present invention, cured products and printed materials of the present invention can be manufactured.

[0088] The method for printing and curing the ink composition of the present invention is not particularly limited. For example, one method of printing and curing involves ejecting an ink composition onto a substrate using an inkjet head, and then exposing the ink composition coating that has landed on the substrate to light to cure it. For printing images onto a substrate, the ink composition is supplied to a low-viscosity compatible printer head of an inkjet recording printer, and then ejected from the printer head so that the film thickness on the substrate is 1 to 60 μm. Furthermore, light exposure and curing (image curing) can be performed by irradiating the coating film of the ink composition applied to the substrate as an image with light. The coating film formed on the above substrate is also called the printed layer.

[0089] The inkjet recording printer device may be a conventional inkjet recording printer device. Furthermore, the light source for curing the coating film may be ultraviolet light (UV lamp), ultraviolet light (LED), electron beam, visible light, etc.

[0090] The above-mentioned base material may be metal, paper, or plastic. Furthermore, examples of the printed materials mentioned above include various packaging materials such as beverage cans, beverage containers, food containers, and pharmaceutical packaging. [Examples]

[0091] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass%" and "parts" means "parts by mass".

[0092] (Preparation of epoxy acrylate resin 1) [Synthesis of polymerized cardanol represented by formula (2) above] A reaction solution was prepared by weighing 100 parts by mass of purified cardanol into a flask equipped with a stirrer, reflux condenser, and stirring device, while purging with nitrogen, and adding 0.8 parts by mass of p-toluenesulfonic acid monohydrate. The reaction solution was then heated to 150°C and stirred for 3 hours. The reaction temperature was returned to room temperature, and the mixture was neutralized with an aqueous sodium hydroxide solution. The aqueous layer was extracted three times with ethyl acetate, and then the organic layer was dehydrated with sodium sulfate. Afterward, the sodium sulfate was removed by filtration, and the solvent was removed by distillation using an evaporator. The obtained crude product is heated to 300°C and stirred under reduced pressure for 3 hours to remove the distillate components, thereby obtaining polymerized cardanol represented by formula (2) above (wherein formula (2), R 1 This is a hydrocarbon group with 15 carbon atoms and 25-31 hydrogen atoms. Gel permeation chromatography (GPC) confirmed the decrease in the peak derived from cardanol and the distillation of a new high molecular weight component, confirming that polymerized cardanol represented by formula (2) above was obtained.

[0093] [Synthesis of epoxy resins] In a flask equipped with a stirrer, reflux condenser, and stirring device, 100 parts by mass of polymerized cardanol represented by formula (2) above were weighed out while purging with nitrogen, and 112 parts by mass of bisphenol A type epoxy resin jer-828 (manufactured by Mitsubishi Chemical Corporation), 0.6 parts by mass of sodium hydroxide, 18 parts by mass of methanol, and 5 parts by mass of water were added to prepare a reaction solution. The reaction solution was then heated to 75°C and stirred under reflux for 3 hours. The reaction temperature was returned to room temperature, the aqueous layer was extracted three times with toluene, and then the organic layer was dehydrated with sodium sulfate. Afterward, the sodium sulfate is removed by filtration, and the solvent is removed by distillation using an evaporator to obtain the structure represented by the above formula (1) (wherein formula (1), R 1R is a hydrocarbon group having 15 carbon atoms and 25 to 31 hydrogen atoms. ) and the structure represented by the above formula (5) (in formula (5), R 1 An epoxy resin containing (which is a hydrocarbon group with 15 carbon atoms and 25-31 hydrogen atoms) was obtained. Gel permeation chromatography (GPC) confirmed the decrease in the peak originating from the bisphenol A type epoxy resin and the distillation of a new high molecular weight component, thus confirming that epoxy resin was obtained.

[0094] [Synthesis of epoxy acrylate resin 1] A reaction solution was prepared by weighing 100 parts by mass of the epoxy resin into a flask equipped with a stirrer, reflux condenser, and stirring device, while purging with nitrogen, and adding 0.4 parts by mass of triphenylphosphine, 0.1 parts by mass of hydroquinone, and 11 parts by mass of acrylic acid. Next, the reaction solution was heated to 110°C and stirred under reflux for 5 hours to obtain the target epoxy acrylate resin 1. The consumption of acrylic acid was confirmed by measuring the acid value of the reactants, and the decrease in epoxy groups and the introduction of acrylic acid were confirmed by measuring the infrared absorption spectrum, thus confirming that epoxy acrylate resin 1 was obtained. The biomass component ratio of epoxy acrylate resin 1 was 42.2%.

[0095] Other materials besides the epoxy acrylate resin mentioned above are as follows: (Pigment) BHS (Pigment Yellow 13, product name "BHS", manufactured by Clariant Chemicals) T-DD (Calcium carbonate, product name "Hakuenka DD", primary particle size 80nm, manufactured by Shiraishi Calcium Co., Ltd.) (resin) PE210 (Bisphenol A type epoxy acrylate, trade name "MIRAMER PE210", manufactured by MIWON) EBECRYL600 (Bisphenol A type epoxy acrylate, trade name "EBECRYL600", manufactured by Daicel Ornex Co., Ltd.) EBECRYL3700 (Bisphenol A type epoxy acrylate, trade name "EBECRYL3700", manufactured by Daicel Ornex Co., Ltd.) CN104 (Bisphenol A type epoxy acrylate, trade name "CN104", manufactured by Sartomer) A-DAP varnish (30 parts by mass of "A-DAP" (diallyl phthalate resin) manufactured by Osaka Soda Co., Ltd., dissolved in 70 parts by mass of Di-TMPTA) (monomer) DPHA (Dipentaerythritol Hexaacrylate) 3EO-TMPTA: Ethylene oxide modified trimethylolpropane triacrylate Di-TMPTA Ditrimethylolpropanetetraacrylate (Polymerization inhibitor) BHT (Dibutylhydroxytoluene) (Polymerization initiator) EMK (4,4'-bis(diethylamino)benzophenone, trade name "Omnirad EMK", manufactured by IGM Resins BV) 379(2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butanone, trade name "Omnirad379", manufactured by IGM Resins BV) (wax) NJ-100 (Polyethylene wax, product name "NJ-100", manufactured by Morimura Chemical Co., Ltd.)

[0096] (Examples 1-6, Comparative Examples 1-4) Based on the information in Table 1, each material was dispersed and mixed using a three-roll mill at a roll temperature of 40°C to prepare the ink composition.

[0097] <Biomass component ratio> The biomass component ratio of the resin component contained in the ink compositions prepared in the examples and comparative examples was calculated using the following formula. Biomass component ratio (%) = {Mass of biomass-derived components / [Mass of epoxy acrylate resin 1 + Mass of other resins (PE210, EBECRYL600, EBECRYL3700, CN104, resin components contained in A-DAP varnish)]} × 100

[0098] <Liquidity> The flow rate of the ink compositions prepared in the examples and comparative examples was measured using a spread meter, and the fluidity was investigated as the flow slope value. The flow gradient value is calculated by subtracting the spread diameter measured in millimeters after 10 seconds from the spread diameter measured in millimeters after 100 seconds using a spread meter. A larger value indicates better fluidity (pigment dispersibility).

[0099] <Glossy> 0.1 cc each of the ink compositions prepared in the examples and comparative examples was spread onto coated paper (Nippon Paper Industries Ltd., Aurora Coat) using an RI spreading machine (2-roll type, manufactured by Akira Seisakusho Co., Ltd.), and then 80 mJ / cm² was applied to the spread material using a metal halide lamp at an output of 120 W / cm². 2 The material was cured by irradiating it with ultraviolet light, and the 60° reflected gloss value of the colored surface was measured using a Murakami-type digital gloss meter (manufactured by Murakami Color Research Institute).

[0100] <Abrasion resistance> The ink compositions prepared in the examples and comparative examples were spread onto aurora-coated paper (manufactured by Nippon Paper Industries Co., Ltd.) using a hand proofer to create test specimens. Subsequently, 80 mJ / cm³ of the test specimens were tested using a metal halide lamp at an output of 120 W / cm³. 2 The ink composition was cured by irradiation with ultraviolet light to form a coated surface. Subsequently, the abrasion resistance of each obtained test specimen was evaluated using a JSPS-type abrasion fastness tester according to the following criteria. The abrasion resistance evaluation will be conducted by applying friction with a 1kg weight 20 times back and forth through a backing cloth (Kanakin No. 3), and the condition of the coating immediately after this friction will be observed visually. Even after applying friction back and forth for 5:20 seconds, the coated surface could not be removed. The coating surface was removed due to friction from 4:10 to 4:19. The coating surface was removed due to friction from 3:5 to 9 back-and-forth movements. The coating surface was removed due to friction from 2:2 to 4 back-and-forth movements. The coating surface was removed due to 1:1 reciprocating friction.

[0101] [Table 1]

[0102] The results from the examples confirmed that the ink composition of the present invention has excellent pigment dispersibility, can impart excellent gloss and coating film durability to the coating film, and can increase the biomass component ratio of the resin constituting the ink composition.

[0103] This specification discloses the following:

[0104] (1) The present disclosure is an active energy ray curable printing ink composition containing at least a pigment, an epoxy (meth)acrylate resin, and a monomer, wherein the epoxy (meth)acrylate resin contains a cardanol skeleton, a bisphenol skeleton, and a (meth)acrylate moiety. Disclosure (2) is the active energy ray curable printing ink composition described in Disclosure (1), wherein the biomass component ratio of the resin component is 20% or more. Disclosure (3) is an active energy ray curable printing ink composition according to Disclosure (1) or (2), wherein the cardanol skeleton contained in the epoxy (meth)acrylate resin is a polymerized cardanol skeleton. Disclosure (4) is an active energy ray curable printing ink composition according to any one of Disclosures (1) to (3), wherein the bisphenol skeleton contained in the epoxy (meth)acrylate resin is a bisphenol A skeleton. Disclosure (5) is an active energy ray curable printing ink composition according to any one of Disclosures (1) to (4) above, wherein the epoxy (meth)acrylate resin is obtained by the reaction of polymerized cardanol, an epoxy resin containing a bisphenol skeleton, and (meth)acrylic acid. Disclosure (6) is an active energy ray-curable printing ink composition according to any one of Disclosures (1) to (5), wherein the epoxy (meth)acrylate resin is present in an amount of 15 to 40% by mass relative to the total mass of the active energy ray-curable printing ink composition. Disclosure (7) is a cured product obtained by curing an active energy ray curable printing ink composition described in any of Disclosures (1) to (5). Disclosure (8) is a printed material having a printed layer formed on a substrate from an active energy ray curable printing ink composition described in any of Disclosures (1) to (5). [Industrial applicability]

[0105] The present invention provides an active energy ray curable printing ink composition that exhibits excellent pigment dispersibility, can impart excellent gloss and coating film resistance to the coating film, and can increase the biomass component ratio of the resin constituting the ink composition.

Claims

1. It contains at least a pigment, an epoxy (meth)acrylate resin, and a monomer. The epoxy (meth)acrylate resin contains a cardanol skeleton, a bisphenol skeleton, and a (meth)acrylate moiety. Active energy ray curing type printing ink composition.

2. The active energy ray curable printing ink composition according to claim 1, wherein the biomass component ratio of the resin component is 20% or more.

3. The active energy ray curable printing ink composition according to claim 1 or 2, wherein the cardanol skeleton contained in the epoxy (meth)acrylate resin is a polymerized cardanol skeleton.

4. The active energy ray curable printing ink composition according to claim 1 or 2, wherein the bisphenol skeleton contained in the epoxy (meth)acrylate resin is a bisphenol A skeleton.

5. The epoxy (meth)acrylate resin is obtained by the reaction of polymerized cardanol, an epoxy resin containing a bisphenol skeleton, and (meth)acrylic acid, according to claim 1 or 2.

6. The active energy ray-curable printing ink composition according to claim 1 or 2, wherein the epoxy (meth)acrylate resin is present in an amount of 15 to 40% by mass relative to the total mass of the active energy ray-curable printing ink composition.

7. A cured product obtained by curing the active energy ray curable printing ink composition according to claim 1 or 2.

8. A printed article having a printed layer formed on a substrate from the active energy ray curable printing ink composition described in claim 1 or 2.

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