Active energy ray-curable composition, active energy ray-curable ink, and method for producing printed matter

Abstract

The present invention addresses the problem of providing an active energy ray-curable composition which can exhibit sufficient adhesion even to a film that does not have a highly adhesive layer. The present invention is an active energy ray-curable composition containing (A) a 1-4 functional (meth) acrylate having a tertiary amino group, and (B) a compound having a carboxyl group and having a weight-average molecular weight of 3000-100,000, the ratio nc (B) / na (A) of the number of moles nc (B) of the carboxyl group derived from the compound (B) to the number of moles na (A) of the tertiary amino group derived from the (meth) acrylate (A) being 0.01-0.50.

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable composition, an active energy ray-curable ink, and a method for producing a printed matter. Background Art

[0002] With the increase in population around the world, it is predicted that the demand for flexible packaging used in the packaging of food and daily necessities will also expand in the future. At present, according to gravure printing, which has become the mainstream in flexible packaging printing, printed materials with bright appearance can be obtained. On the other hand, gravure printing uses ink containing a large amount of solvent, so a large amount of energy is required in the drying of the ink solvent and the treatment of waste gas, which has a large environmental load. In addition, in recent years, in order to cope with environmental problems and carbon neutrality, there is a demand to reduce the volatile components contained in the ink.

[0003] Therefore, the use of active energy ray curing methods that do not contain volatile components and are instantly cured by irradiation with active energy rays is being promoted in offset printing, flexographic printing, and online anchor coating and overcoating related to these printings (Patent Documents 1 and 2). In flexible packaging printing, printing is performed in a roll-to-roll method, so the quick drying properties of ink and coating agents are important. In addition to the environmental advantages, the active energy ray curing method shortens the drying process without using heat energy, thereby saving energy and having high productivity.

[0004] However, generally, the main raw material of the active energy ray curable composition is acrylates, and therefore the cured product obtained by free radical polymerization, i.e., poly(meth)acrylate, has low adhesion to major films such as polyolefins, polyesters, and polyamides (nylons). Therefore, the cured film of the active energy ray curable composition has problems such as peeling off during subsequent processing and insufficient strength of the product.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-104180

[0008] Patent Document 2: Japanese Patent Application Publication No. 2019-198970

[0009] Patent Document 3: Japanese Patent Application Publication No. 2021-98773 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Therefore, research has been conducted to improve the adhesion to the film by providing an easy-adhesion layer on the film side, as in Patent Document 3. However, this inevitably increases the cost and limits the films that can be used, so the invention described in Patent Document 3 has problems in terms of versatility.

[0012] Therefore, an object of the present invention is to provide an active energy ray-curable composition that can exhibit sufficient adhesion even to a film having no easy-adhesion layer.

[0013] Means for solving problems

[0014] The present invention is an active energy ray-curable composition comprising a monofunctional to tetrafunctional (meth)acrylate (A) having a tertiary amino group and a compound (B) having a carboxyl group and having a weight average molecular weight of 3,000 to 100,000, wherein the number of moles of the carboxyl group derived from (B) is n c (B) and the number of moles of amino groups derived from (A) a (A) ratio n c (B) / n a (A) is 0.01 or more and 0.50 or less.

[0015] The present invention also provides an active energy ray-curable ink obtained by further adding a pigment to the active energy ray-curable composition of the present invention.

[0016] The present invention is also a method for producing a printed article, comprising the steps of transferring the active energy ray-curable composition of the present invention or the active energy ray-curable ink of the present invention onto a film, and then irradiating the film with active energy rays.

[0017] Effects of the Invention

[0018] The active energy ray-curable composition or active energy ray-curable ink according to the present invention can exhibit sufficient adhesion even to a film having no easily adhesive layer. DETAILED DESCRIPTION

[0019] The present invention is described in detail below. It should be noted that, in the present invention, the so-called "above" means the same as or greater than the numerical value shown here. In addition, the so-called "below" means the same as or less than the numerical value shown here. In addition, the so-called "(meth)acrylate" is a general term including acrylate and methacrylate, and the so-called "(meth)acryloyl" is a general term including acryloyl and methacryloyl. In addition, the so-called "n-functional (meth)acrylate" and "(meth)acrylate is n-functional" mean that the number of (meth)acryloyl groups possessed by the (meth)acrylate is n.

[0020] The active energy ray-curable composition of the present invention contains a 1-4 functional (meth)acrylate having a tertiary amino group. Hereinafter, the (meth)acrylate is also referred to as (meth)acrylate (A). The above-mentioned (meth)acrylate (A) is cured by irradiation with active energy rays to form a thin film, and the tertiary amino group interacts strongly with polar groups such as hydroxyl groups on the surface of the film, especially carboxyl groups, thereby improving the adhesion of the cured film of the active energy ray-curable composition to the film. This is because the adhesion improvement effect is exhibited only when the tertiary amino group and the (meth)acryloyl group are present in the same compound. For example, when a tertiary amine without a (meth)acryloyl group is mixed with a (meth)acrylate and cured using active energy rays, the two compounds are not connected by a covalent bond, and therefore, the interaction between the (meth)acrylate crosslinked product in the cured film and the film surface does not become stronger, and the adhesion does not improve.

[0021] The (meth)acrylate (A) is preferably monofunctional or difunctional. If the (meth)acrylate (A) is pentafunctional or more, the curing shrinkage of the active energy ray-curable composition is large, which impairs the adhesion.

[0022] As the (meth)acrylate (A), a compound represented by the following structural formula (1) is preferred.

[0023]

[0024] Here, R 1 Represents H or methyl, R 2 represents a monovalent organic group having a (meth)acryloyl group, R 3 and R 4 Each independently represents a monovalent hydrocarbon group or a monovalent organic group containing a heteroatom.

[0025] Furthermore, as the (meth)acrylate (A), a compound represented by the following structural formula (2) or (3) is more preferred.

[0026]

[0027] Here, R 1 Represents H or methyl, R 2 It represents a monovalent organic group having a (meth)acryloyl group.

[0028] As the (meth)acrylate (A), a compound represented by the following structural formula (4) is preferred.

[0029]

[0030] Here, X represents a nitrogen atom or a carbon atom, and R 1 Represents H or methyl, R 2represents a monovalent organic group having a (meth)acryloyl group, R 3 and R 4 R each independently represents a monovalent hydrocarbon group or a monovalent organic group containing a heteroatom. 3 and R 4 They are independent of each other or they can be integrated into a cyclic group.

[0031] The amine value of the (meth)acrylate (A) is preferably 80 mgKOH / g or more from the viewpoint of strongly interacting with various carboxyl groups to improve adhesion. In addition, in order to impart compatibility with other compounds, the amine value of the (meth)acrylate (A) is preferably 400 mgKOH / g or less, and more preferably 357 mgKOH / g or less.

[0032] Here, the amine value is represented by the number of mg of potassium hydroxide equivalent to the hydrochloric acid required to neutralize the amino groups contained in 1 g of the sample, and can be measured by a method in accordance with ASTM D2074.

[0033] The above-mentioned (meth)acrylate (A) can be obtained by subjecting primary or secondary amines to Michael addition reaction with multifunctional (meth)acrylate. (Meth)acryloyl is an α-β unsaturated carbonyl compound, so the primary or secondary amines undergo 1,4 conjugated addition to form a 3-aminopropionate structure. In the case where the amino group in the structure after the reaction is a secondary amino group, there is also the possibility of further reaction again and conversion to a tertiary amine. In addition, the reaction is a nucleophilic reaction, and the higher the nucleophilicity, the milder the conditions. In addition, acids and bases serve as catalysts, which can make it proceed at a lower temperature / higher speed.

[0034] Specifically, in the case of performing the Michael addition reaction, it is preferred to react at a temperature below 20 to 100°C. In addition, in the reaction between the polyfunctional (meth)acrylate and the amine, if all the (meth)acryloyl groups in one molecule react with the amine, curing by active energy rays will not be performed, and therefore, the equivalent ratio is preferably that the (meth)acryloyl group is excessive compared to the amino group. On the other hand, in order to increase the amine equivalent, it is also preferred to introduce multiple tertiary amino groups into the polyfunctional (meth)acrylate having three or more functions, preferably four or more functions. In addition, if a polyamine having two or more functions is used as the raw material amine, there is a concern that it will crosslink with the polyfunctional (meth)acrylate and gelate, and therefore, it is not preferred from the viewpoint of reaction control. In addition, in order to easily obtain the desired (meth)acrylate (A), it is preferred to perform improvements such as slowly adding the amine to the polyfunctional (meth)acrylate by dropwise addition during synthesis.

[0035] As the polyfunctional (meth)acrylate used as a raw material for the Michael addition reaction, a polyfunctional (meth)acrylate is used in principle because the (meth)acryloyl group must remain even after the reaction. Monofunctional (meth)acrylate is not suitable because the (meth)acryloyl group disappears when Michael addition is performed.

[0036] Specific examples of the bifunctional (meth)acrylates used as raw materials for the Michael addition reaction include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, bisphenol A di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, diglycerol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene oxide adducts thereof, propylene oxide adducts, tetraethylene oxide adducts, and the like.

[0037] Examples of the trifunctional (meth)acrylate serving as a raw material for the Michael addition reaction include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ethylene oxide adducts, propylene oxide adducts, and tetraethylene oxide adducts thereof.

[0038] Examples of the tetrafunctional (meth)acrylate used as a raw material for the Michael addition reaction include ditrimethylolpropane tetra(meth)acrylate, diglycerol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and ethylene oxide adducts and propylene oxide adducts thereof.

[0039] Examples of the pentafunctional or higher-functional (meth)acrylates used as raw materials for the Michael addition reaction include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide adducts thereof, propylene oxide adducts, etc. In particular, when using a hexafunctional or higher-functional (meth)acrylate, it is preferred to set the equivalent ratio so that the difunctional or higher-functional (meth)acrylate reacts with the amines.

[0040] Specific examples of primary amines used as raw materials for the Michael addition reaction include monoamines such as alkylamines having 1 to 20 carbon atoms, alkanolamines having 1 to 10 carbon atoms, and derivatives thereof. Specific examples of secondary amines include N-alkyl substituted products (having 1 to 20 carbon atoms) of the above monoamines, N-alkanol substituted products (having 1 to 10 carbon atoms) of the above monoamines, cyclic amines such as morpholine, pyrrolidine, and piperidine, derivatives thereof other than N-substituted products, 1H-triazole, 1H-benzotriazole, 1H-benzimidazole, 1H-imidazole, 1H-pyrazole, and derivatives thereof other than 1H-substituted products. Polyamines thereof may also be used, but control is required to suppress gelation.

[0041] Among these primary and secondary amines, amines with little odor are preferred, and octadecylamine and diethanolamine are particularly preferred because they may be raw materials that can be used in regulations related to food packaging such as the Swiss Ordinance.

[0042] In addition, adducts of 1H-azoles having a heterocyclic ring such as 1H-triazole, 1H-benzotriazole, 1H-benzimidazole, and 1H-imidazole are preferred because they have a particularly large effect of improving adhesion.

[0043] Among these primary and secondary amines, highly nucleophilic aliphatic amines undergo Michael addition reaction under relatively mild conditions of 20 to 60° C. On the other hand, the reaction of less nucleophilic aromatic amines proceeds slowly, and the Michael addition reaction is preferably carried out by heating to 80 to 100° C.

[0044] When the (meth)acrylate (A) is synthesized using the particularly preferred diethanolamine listed above, the compound represented by the structural formula (2) is obtained. When the (meth)acrylate (A) is synthesized using octadecylamine, the compound represented by the structural formula (3) is obtained. In addition, when the (meth)acrylate (A) is synthesized using 1H-azoles, the compound represented by the structural formula (4) is obtained.

[0045] As the (meth)acrylate (A), commercially available products can be used, and examples thereof include "EBECRYL" (registered trademark) LEO 10101, "EBECRYL" (registered trademark) LEO 10551, "EBECRYL" (registered trademark) LEO 10552, "EBECRYL" (registered trademark) LEO 10553, "EBECRYL" (registered trademark) LEO 10554, "EBECRYL" (registered trademark) LEO 10555, and "EBECRYL" (registered trademark) LEO 10556. 10553, EBECRYL (registered trademark) 80, EBECRYL (registered trademark) 81, EBECRYL (registered trademark) 83, EBECRYL (registered trademark) 85, EBECRYL (registered trademark) 880, EBECRYL (registered trademark) 7100, ETERCURE (registered trademark) 63922 manufactured by Eternal, CN549NS, CN550, CN551NS manufactured by Sartomer, AgiSyn (registered trademark) 701, AgiSyn (registered trademark) 701P, AgiSyn (registered trademark) 703, AgiSyn (registered trademark) 703TF manufactured by DSM, Miramer (registered trademark) AS1000, Miramer (registered trademark) AS3500, Miramer (registered trademark) LR3600 manufactured by Miwon, Photocryl A104, Photocryl DP143, etc.

[0046] The molecular weight of the (meth)acrylate (A) is preferably 1,000 or less, and more preferably 600 or less, from the viewpoint of improving the curability with respect to active energy rays and suppressing the viscosity increase of the active energy ray-curable composition of the present invention.

[0047] The active energy ray curable composition preferably contains 20% by mass or more and 60% by mass or less of the (meth)acrylate (A). By making the content of the (meth)acrylate (A) 20% by mass or more, more preferably 30% by mass or more, the film adhesion is improved. In addition, by making the content of the (meth)acrylate (A) 60% by mass or less, in the case of containing other functional materials such as colorants according to the purpose, in the case of adding initiators and sensitizers according to the active energy ray source, it is possible to cope with the case of adding resins, oligomers, auxiliary agents, etc. in order to adjust the viscoelasticity of the active energy ray curable composition.

[0048] The active energy ray-curable composition of the present invention contains a compound having a carboxyl group and a weight average molecular weight of 3000 to 100000. Hereinafter, the compound is also referred to as compound (B). The carboxyl group of the compound (B) interacts with the tertiary amino group of the (meth)acrylate (A), thereby improving the film-forming property and film strength of the cured film of the active energy ray-curable composition.

[0049] The compound (B) preferably has a (meth)acryloyl group and / or a vinyl group. The compound (B) also interacts with the (meth)acrylate (A) to crosslink, and therefore, by providing the compound (B) with such a photosensitive group, the curability with respect to active energy rays is improved, and the strength and adhesion of the cured film are also improved.

[0050] In the active energy ray-curable composition of the present invention, the number of moles of the carboxyl groups derived from the compound (B) is n c (B) The number of moles n of the tertiary amino group derived from the above (meth)acrylate (A) a (A) ratio n c (B) / n a (A) is 0.01 or more and 0.50 or less. c (B) / n a (A) is 0.01 or more, which can effectively improve the film-forming property and film strength of the cured film of the active energy ray-curable composition. c (B) / n a (A) is 0.50 or less, more preferably 0.30 or less, and even more preferably 0.15 or less, and improvement in adhesion due to the interaction between the tertiary amino group and the polar group on the film surface can be effectively obtained.

[0051] The active energy ray-curable composition of the present invention preferably further contains a polyfunctional (meth)acrylate having no epoxy group, acid anhydride group, isocyanate group, or amino group. Hereinafter, this (meth)acrylate is also referred to as (meth)acrylate (C).

[0052] The (meth)acrylate (C) is cured by irradiation with active energy rays, which helps film formation. As the (meth)acrylate (C), from the viewpoint of curability, a (meth)acrylate with high reactivity is preferred. In addition, from the viewpoint of safety / environment, low volatility is preferred. Low volatility means that the weight loss rate when heated at 110°C for 1 hour is less than 1% by weight as defined by Method 24 of the U.S. Environmental Protection Agency (EPA).

[0053] Specific examples of such (meth)acrylates (C) include bifunctional (meth)acrylates (C), such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, diglycerol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene oxide adducts, propylene oxide adducts, and tetraethylene oxide adducts thereof.

[0054] Examples of the trifunctional (meth)acrylate (C) include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ethylene oxide adducts, propylene oxide adducts, and tetraethylene oxide adducts thereof.

[0055] Examples of the tetrafunctional (meth)acrylate (C) include ditrimethylolpropane tetra(meth)acrylate, diglycerol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and ethylene oxide adducts and propylene oxide adducts thereof.

[0056] Examples of the pentafunctional or higher-functional (meth)acrylate (C) include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide adducts and propylene oxide adducts thereof.

[0057] The active energy ray-curable composition of the present invention preferably contains a (meth)acrylate (D) having at least one of an epoxy group, an anhydride group and an isocyanate group. In this way, the adhesion of the film is further improved. It is believed that this is because the (meth)acrylate (A) has a tertiary amino group and acts as a catalyst, so that any group of the epoxy group, anhydride group, and isocyanate group in the (meth)acrylate (D) is bonded to polar groups such as hydroxyl groups and carboxyl groups on the surface of the film through condensation or addition reaction under mild conditions.

[0058] Specific examples of the (meth)acrylate (D) include glycidyl (meth)acrylate, glycidyl crotonate, glycidyl isocrotonate, maleic anhydride, (meth)acryloyl isocyanate, (meth)acryloylethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0059] The active energy ray-curable composition of the present invention may contain other components described below in addition to the (meth)acrylate (A), the compound (B), the (meth)acrylate (C) and the (meth)acrylate (D). However, the other components preferably do not have an acidic group. This is because the acidic group interacts with the (meth)acrylate (A) and there is a concern that the adhesion is hindered.

[0060] The active energy ray-curable composition of the present invention preferably contains a colored pigment. In this manner, it can be used as an active energy ray-curable ink.

[0061] Examples of the colored pigments include phthalocyanine pigments, soluble azo pigments, insoluble azo pigments, lake pigments, quinacridone pigments, isoindoline pigments, threne pigments, metal complex pigments, titanium oxide, zinc oxide, alumina white, calcium carbonate, barium sulfate, red iron oxide, cadmium red, chrome yellow, zinc yellow, Prussian blue, ultramarine, oxide-coated glass powder, oxide-coated mica, oxide-coated metal particles, aluminum powder, gold powder, silver powder, copper powder, zinc powder, stainless steel powder, nickel powder, organic bentonite, iron oxide, carbon black, graphite, and the like.

[0062] Furthermore, as the above-mentioned pigment, mica (hydrous potassium aluminum silicate) and talc (magnesium silicate) which are colorless extender pigments may be used, and the active energy ray-curable composition of the present invention may be used as a varnish or an anchor coating agent.

[0063] As the pigment, it is preferable to use a neutral or basic pigment on the surface of which the (meth)acrylate (A) is not adsorbed.

[0064] The active energy ray-curable composition of the present invention may contain a photopolymerization initiator depending on the active energy ray source. Examples of the photopolymerization initiator include α-aminoalkylphenones, thioxanthones, benzyl ketals, and acylphosphine oxides.

[0065] The active energy ray-curable composition of the present invention may contain additives such as wax, a pigment dispersant, a defoaming agent, and a leveling agent as other components.

[0066] In order to adjust the viscosity, a solvent may be used. However, when a solvent is contained, the curability of the active energy ray-curable composition of the present invention with respect to active energy rays decreases.

[0067] The acryloyl equivalent of the active energy ray-curable composition of the present invention is preferably 150 g / eq or more and 500 g / eq or less. By making the above-mentioned acryloyl equivalent 150 g / eq or more, more preferably 200 g / eq or more, and further preferably 250 g / eq or more, the storage stability is improved. In addition, by making the above-mentioned acryloyl equivalent 500 g / eq or less, more preferably 450 g / eq or less, and further preferably 400 g / eq or less, the curability using active energy rays becomes good. It should be noted that in the present invention, the so-called acryloyl equivalent means the number of grams (unit: g / eq) of the active energy ray-curable composition required for the amount of (meth) acryloyl groups contained in the active energy ray-curable composition to become 1 mole.

[0068] The active energy ray-curable composition of the present invention can be used as an anchor coating agent to be transferred to a film and an active energy ray-curable ink can be transferred thereto, or can be used as an overcoat agent to be transferred to a film after an active energy ray-curable ink is transferred in a pattern on a film.

[0069] In addition, the active energy ray-curable composition of the present invention can also be used as an active energy ray-curable ink containing a color pigment. That is, the active energy ray-curable ink of the present invention is obtained by further containing a pigment in the active energy ray-curable composition of the present invention.

[0070] Next, the method for producing the active energy ray-curable composition of the present invention will be described.

[0071] The active energy ray-curable composition of the present invention can be obtained by mixing the (meth)acrylate (A), the compound (B), the (meth)acrylate (C) as needed, and other components at room temperature to 80°C.

[0072] After or during mixing, it is also preferred to perform a degassing operation under vacuum or reduced pressure conditions.

[0073] When a color pigment is added to prepare an ink, it is also preferable to add the pigment during the mixing and then disperse and knead the mixture using an attritor, ball mill, sand mill, three-roll mill, or the like depending on the viscosity.

[0074] The method for producing a printed article of the present invention comprises the steps of transferring the active energy ray-curable composition or active energy ray-curable ink of the present invention onto a film and then irradiating the film with active energy rays.

[0075] Examples of the film used in the present invention include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polylactic acid, polyamides, polyimides, polyalkyl (meth)acrylates, polystyrene, poly-α-methylstyrene, polycarbonates, polyvinyl alcohol, polyvinyl acetal, polyvinyl chloride, and polyvinylidene fluoride.

[0076] In addition, a thin film in which these thin films further have a vapor-deposited thin film layer made of a metal such as aluminum oxide or a metal compound can be used.

[0077] The film is preferably subjected to a corona treatment on its surface in order to increase the number of polar functional groups on the film surface and improve the adhesion with the active energy ray-curable composition or the active energy ray-curable ink.

[0078] The film whose surface is subjected to corona treatment may be a ready-made product or a film obtained by subjecting the film to in-line corona treatment before transferring the active energy ray-curable composition or the active energy ray-curable ink onto the film.

[0079] The film may have an easy-adhesion coating layer, but this will increase the cost. The active energy ray-curable composition or active energy ray-curable ink of the present invention is suitable because it can exhibit sufficient adhesion even to a film without an easy-adhesion layer.

[0080] The film may be in the form of a single sheet or a roll film. When a film for a flexible package is used, it is preferred to use a roll film and perform coating / printing in a roll-to-roll manner.

[0081] Examples of methods for transferring the active energy ray-curable composition or active energy ray-curable ink of the present invention onto a film include flexographic printing, offset printing, gravure printing, screen printing, inkjet printing, varnish coater, bar coater, etc. The transfer method can be selected depending on the viscosity of the active energy ray-curable composition or active energy ray-curable ink and whether patterning is required.

[0082] Specifically, if patterning is required, printing methods such as flexographic printing, offset printing, gravure printing, screen printing, and inkjet printing are preferred. If the entire surface is coated, a varnish coater or a rod coater is preferably used. In addition, from the aspect of viscosity, if it is a high viscosity of more than 5Pa·s and less than 200Pa·s, offset printing and screen printing are preferred, if it is 0.1Pa·s to 5Pa·s, flexographic printing is preferred, and if it is less than 0.1Pa·s, gravure printing and inkjet printing are preferred. If it is within the above-mentioned viscosity range, leveling is usually better in the case of low viscosity, and the appearance of the coating becomes good, so it is preferred.

[0083] By the irradiation with the active energy ray, the (meth)acryloyl group reacts and is cross-linked by covalent bonds, whereby the active energy ray-curable composition or the active energy ray-curable ink is instantly cured.

[0084] Examples of the active energy ray source used in the present invention include ultraviolet rays, electron rays, and gamma rays.

[0085] If ultraviolet rays are used, it is preferred to use ultraviolet irradiation devices such as high-pressure mercury lamps, xenon lamps, metal halide lamps, and light-emitting diodes (LEDs). Among them, LED lamps are preferred because they save power and produce less ozone. As the wavelength of LED, the luminous line of 350 to 420 nm is preferred from the perspective of power saving and low cost.

[0086] If it is an electron beam, the (meth) acryloyl group is directly excited by free radicals, and free radical polymerization is performed in the active energy ray-curable composition to form a film. In addition, the electron beam has high transmittance and can also act on the film. In the case of a polyolefin film, free radicals are easily generated, causing reactions such as crosslinking and decomposition between molecules, and free radical polymerization is performed between the active energy ray-curable composition / film, thereby forming a covalent bond between the active energy ray-curable composition / film, which can present higher adhesion. In particular, from the perspective of not requiring special qualifications when using and easy operation, it is preferred to use electron beams with low acceleration voltage.

[0087] The penetration depth of electron beams is determined by the accelerating voltage, so from the viewpoint of sufficient penetration and damage to the film, the accelerating voltage is preferably 50 kV to 300 kV. In addition, since the amount of free radical species generated in the target substance increases, the damage to the film also increases, so the irradiation dose of electron beams is preferably 10 kGy or more and 100 kGy or less.

[0088] Example

[0089] Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited thereto.

[0090] [Measurement / Evaluation Method]

[0091] (1) Viscosity

[0092] The viscosity of each active energy ray-curable composition was measured at 25° C. and 0.5 rpm using a B-type viscometer (DV-II manufactured by Brookfield) equipped with a cylindrical rotor No. 4. From the viewpoint of coating and printing properties, the viscosity is preferably 100 Pa·s or less, and more preferably 50 Pa·s or less.

[0093] (2) Amine value

[0094] The amine value was measured by the method according to ASTM D2074. An ethanol solution of each (meth)acrylate (A) was prepared, and a potentiometric titration apparatus was used to perform a potentiometric measurement using a 0.2N hydrochloric acid ethanol solution, and the inflection point of the obtained titration curve was taken as the end point. Then, the amount of hydrochloric acid consumed until the inflection point was converted into the equivalent of potassium hydroxide.

[0095] (3) Acryloyl equivalent

[0096] A CDCl3 solution with a concentration of 1% by mass of each active energy ray-curable composition was prepared, 0.05% by mass of tetramethylsilane as an internal standard was added and sealed, and 1 H-NMR measurement: The molar ratio was determined from the integrated ratio of the (meth)acryloyl peak (δ: 5.8 to 6.5) and the methyl peak of tetramethylsilane as an internal standard (δ: -0.05 to +0.05), and the number of moles of acryloyl in the coating agent was calculated to calculate the acryloyl equivalent.

[0097] (4) Coating appearance

[0098] The following evaluation was performed by visual observation on the appearance of the coated material of the active energy ray-curable composition or active energy ray-curable ink obtained in each Example / Comparative Example.

[0099] A: The surface is small and no holes or pits are observed, indicating a good appearance.

[0100] B: Some scattered holes, etc.

[0101] C: The unevenness is large, and pits and the like are observed overall.

[0102] (5) Peel strength

[0103] On the coated article of the active energy ray-curable composition or active energy ray-curable ink obtained in the coating step of each Example / Comparative Example, a coating amount of 3.0 g / m 2 A mixed laminating adhesive ("Takelac" (registered trademark) A626 / "Takenet" (registered trademark) A50 manufactured by Mitsui Chemicals, Inc.) was applied in a manner, and laminated using an unstretched polypropylene film (CPP) with a thickness of 60 μm (ZK-207 manufactured by Toray Film Advanced Processing Co., Ltd.). Then, it was aged at 40°C for 3 days to obtain a laminated sample. The coated portion of the active energy ray-curable composition in the obtained laminated sample was cut into strips with a width of 15 mm, and a peel test was carried out using a TENSILON universal testing machine (RTG-1210 manufactured by Orientec Co., Ltd.), and the peel strength when peeled at 90° at 300 mm / min was measured.

[0104] If the peel strength is less than 1.5 N / 15 mm, the adhesion is judged to be insufficient; if the peel strength is greater than 1.5 N / 15 mm and less than 2.0 N / 15 mm, the adhesion is judged to be good; if the peel strength is greater than 2.0 N / 15 mm and less than 3.0 N / 15 mm, the adhesion is judged to be very good; and if the peel strength is greater than 3.0 N / 15 mm, the adhesion is judged to be extremely good.

[0105] (6) Destruction mode

[0106] In the peel test of (5) above, the peeling behavior (failure mode) was also observed. In a laminated sample having a multilayer structure, the interlayer where failure occurs during peeling corresponds to the weakest adhesion point. The failure mode was evaluated according to the following A to C.

[0107] A: The film was broken.

[0108] B: The active energy ray-curable composition layer undergoes cohesive failure.

[0109] C: Peeling occurred between the film / active energy ray-curable composition layers.

[0110] Here, the "active energy ray-curable composition layer" refers to a layer formed by curing an active energy ray-curable composition or ink. A is most preferred, B is second most preferred, and C is least preferred.

[0111] [(Meth)acrylate (A)]

[0112] The corresponding primary or secondary amine and polyfunctional (meth)acrylate were weighed and mixed with a mechanical stirrer at 60° C. for 4 hours to perform a Michael addition reaction, thereby obtaining an active energy ray-curable composition containing the corresponding (meth)acrylate (A).

[0113] (A)-1: A 2- to 3-functional (meth)acrylate obtained by subjecting pentaerythritol triacrylate (Miramer (registered trademark) M340 manufactured by MIWON) to a Michael addition reaction with diethanolamine (manufactured by Waken Chemical Co., Ltd.) at an equivalent ratio of 5:2. Amine value: 159 mgKOH / g.

[0114] (A)-2: A 2- to 3-functional (meth)acrylate obtained by subjecting ditrimethylolpropane tetraacrylate (Miramer (registered trademark) M410 manufactured by MIWON) to a Michael addition reaction with di(2-ethylhexyl)amine (manufactured by Waken Chemical Co., Ltd.) at an equivalent ratio of 2:1. Amine value: 118 mgKOH / g.

[0115] (A)-3: A bifunctional (meth)acrylate obtained by subjecting EO-modified trimethylolpropane triacrylate (Miramer (registered trademark) M3190 manufactured by MIWON) to a Michael addition reaction with di(2-ethylhexyl)amine (manufactured by Waken Chemical Co., Ltd.) at an equivalent ratio of 2:1. The amine value is 79 mgKOH / g.

[0116] (A)-4: a mono- or di-functional (meth)acrylate obtained by subjecting tricyclodecane dimethanol diacrylate ("EBECRYL" (registered trademark) 130 manufactured by Dicel Ornex) to a Michael addition reaction with octadecylamine (manufactured by TCI Corporation) at an equivalent ratio of 2:1. The amine value is 96 mgKOH / g.

[0117] (A)-5: dimethylaminoethyl methacrylate (manufactured by TCI Corporation). (A)-5 is a monofunctional (meth)acrylate having an amine value of 357 mgKOH / g.

[0118] (A)-6: 4-5 functional (meth)acrylate obtained by Michael addition reaction of dipentaerythritol hexaacrylate (Miramer (registered trademark) M600 manufactured by MIWON) with 1H-benzotriazole (manufactured by Waken Chemical Co., Ltd.) at an equivalent ratio of 3:1. Amine value: 135 mgKOH / g.

[0119] (A)-7: A 2- to 3-functional (meth)acrylate obtained by subjecting ditrimethylolpropane tetraacrylate (Miramer (registered trademark) M410 manufactured by MIWON) to a Michael addition reaction with 1H-benzimidazole (manufactured by Waken Chemical Co., Ltd.) at an equivalent ratio of 4:1. Amine value: 96 mgKOH / g.

[0120] [Compound (B) or its alternative]

[0121] (B)-1: Acrylic resin having a photosensitive group and a carboxylic acid (TWR-1001 manufactured by Toray Industries, Inc.) The molecular weight is 30,000 and the acid value is 105 mgKOH / g.

[0122] (B)-2: Acrylic resin having carboxylic acid (TWR-3001 manufactured by Toray Industries, Inc.) having a molecular weight of 27,000 and an acid value of 200 mgKOH / g.

[0123] (b)-3: Adipic acid (manufactured by Waken Chemical Co., Ltd.), molecular weight: 146.

[0124] [(Meth)acrylate (C)]

[0125] (C)-1: EO-modified trimethylolpropane triacrylate ("Miramer" (registered trademark) M3190 manufactured by MIWON Corporation).

[0126] (C)-2: ditrimethylolpropane tetraacrylate ("Miramer" (registered trademark) M410 manufactured by MIWON Corporation).

[0127] (C)-3: tricyclodecane dimethanol diacrylate ("EBECRYL" (registered trademark) 130 manufactured by Dicel Ornex Corporation).

[0128] [Compound (D)]

[0129] (D)-1: 1,1-(bisacryloyloxymethyl)ethyl isocyanate (“Karenzu” (registered trademark) BEI manufactured by Showa Denko K.K.).

[0130] [Other (meth)acrylates]

[0131] (E)-1: A pentafunctional or higher-functional (meth)acrylate having a tertiary amino group obtained by subjecting dipentaerythritol hexaacrylate (Miramer (registered trademark) M600 manufactured by MIWON) to a Michael addition reaction with di(2-ethylhexyl)amine (manufactured by Waken Chemical Co., Ltd.) at an equivalent ratio of 6:1. The amine value was 66 mgKOH / g.

[0132] [Other added ingredients]

[0133] Pigment 1: Titanium oxide ("Tipec" (registered trademark) CR58-2 manufactured by Ishihara Industry Co., Ltd.)

[0134] Pigment 2: Acidic carbon black ("MOGUL" (registered trademark) E manufactured by CABOT Co., Ltd.)

[0135] Surfactant 1: "EMALEX" (registered trademark) 503 manufactured by Japan Emal Chemical Co., Ltd.

[0136] Surfactant 2: "Disperbyk" (registered trademark) 111 manufactured by Bicchem Co., Ltd.

[0137] Surfactant 3: "Disperbyk" (registered trademark) manufactured by Bicchem Co., Ltd. 2013

[0138] Photopolymerization initiator: bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide ("ILGACURA" (registered trademark) 819 manufactured by BASF Corporation).

[0139] [Active energy ray-curable composition or active energy ray-curable ink]

[0140] (Active Energy Ray Curable Compositions 1 to 16)

[0141] Each material was weighed to the composition shown in Table 1, and dissolved and dispersed using a mixer (manufactured by Shinky Co., Ltd.), thereby obtaining an active energy ray-curable composition.

[0142] [Table 1]

[0143]

[0144] (Active energy ray curing inks 1 to 9, 11 to 13, 16, 17)

[0145] The compositions including pigments, (meth)acrylates, and other additives shown in Table 2 were weighed, kneaded, and dispersed using a three-roll mill (EXAKT (registered trademark) M-80S manufactured by EXAKT) to obtain high-viscosity active energy ray-curable inks 1 to 9, 11 to 13, 16, and 17.

[0146] (Active energy ray curing inks 10, 14, 15)

[0147] The compositions containing pigments, (meth)acrylates, and other additive components shown in Table 2 were weighed and dispersed using a batch sand mill (manufactured by Hayashi Shoten Co., Ltd.) to obtain low-viscosity active energy ray-curable inks 10, 14, and 15.

[0148] [Table 2]

[0149]

[0150] [film]

[0151] Film 1: A PET film having a thickness of 12 μm (E5102 manufactured by Toyobo Co., Ltd.) having a corona treatment layer.

[0152] Film 2: 12 μm thick PET film (FS2000 manufactured by FTAMURA CHEMICAL CO., LTD.), without surface treatment.

[0153] Film 3: A polyamide film (ON manufactured by UNITICA CO., LTD.) having a thickness of 15 μm and a corona-treated layer.

[0154] Film 4: a barrier film / PET film laminate (1011HG SBR2 manufactured by Toray Film Advanced Technology Co., Ltd.) having a thickness of 12 μm and having no corona treatment layer.

[0155] Film 5: OPP film (P2111 manufactured by Toyobo Co., Ltd.) with a thickness of 20 μm and a corona-treated layer.

[0156] Film 6: A PET film having a thickness of 12 μm ("Lumira" (registered trademark) S10 manufactured by Toray Industries, Inc.), without surface treatment.

[0157] [Method for producing coating]

[0158] (Method 1 for producing a coating)

[0159] Various active energy ray-curable compositions or active energy ray-curable inks were transferred to various films. Regarding the transfer method, a No. 5 rod coater was used in the case of an active energy ray-curable composition without a pigment, and an RI tester was used in the case of an active energy ray-curable ink containing a pigment. Then, an electron beam irradiation device (EC250 / 30 / 90LS manufactured by Iwasaki Electric Co., Ltd.) was used to cure the film by electron beam irradiation with an acceleration voltage of 110 kV and an irradiation dose of 30 kGy.

[0160] (Method 2 for producing coating)

[0161] Various active energy ray curing inks were transferred to various films. The transfer method used an RI tester. Then, a light emitting diode ultraviolet irradiation device (UD90 manufactured by Panasonic Debius SUNX Co., Ltd.) was used to irradiate at an intensity of 8 W / cm 2 , and cure it by irradiating with LED-UV at a wavelength of 385nm.

[0162] (Method 3 for producing coating)

[0163] The films were subjected to a corona treatment using a corona treatment apparatus (TEC-4AX manufactured by Kasuga Electric Co., Ltd.) at a discharge level of 200 W·min / m 2 After corona treatment under the conditions of , various active energy ray curing inks were transferred. The transfer method used an RI tester. Then, an electron beam irradiation device (EC250 / 30 / 90LS manufactured by Iwasaki Electric Co., Ltd.) was used to cure the ink by electron beam irradiation at an acceleration voltage of 110 kV and an irradiation dose of 30 kGy.

[0164] [Example 1]

[0165] Using the active energy ray-curable composition 1 as the active energy ray-curable composition and the film 1 as the film, a coating of the active energy ray-curable composition was prepared by the coating preparation method 1. The lamination peel strength was 3.4 N / 15 mm, which was extremely good, the failure mode was also (A), which was good, and the appearance of the coating was also good. The results are shown in Table 3.

[0166] [Examples 2 to 12 and Comparative Examples 1 to 4]

[0167] Using the corresponding active energy ray-curable compositions 2 to 16 as shown in Table 3 and the film 1 as the film, a coating of the active energy ray-curable composition was prepared by the coating preparation method 1. In Examples 2 to 12, the lamination peel strength was good or above. In particular, the ratio n c (B) / n a (A), Examples 6 to 11, in which the acryl equivalent and the amine value were within the preferred range, were extremely good. Among them, Examples 8 to 11, in which the viscosity was not high, also had good appearance of the coating. Comparative Examples 1 to 4 were insufficient in both lamination peel strength and failure mode. The results are shown in Table 3.

[0168] [Examples 13 to 25 and Comparative Examples 5 to 7]

[0169] Using the corresponding active energy ray-curable inks 1 to 16 as shown in Table 4 and the film 1 as the film, a printed material of the active energy ray-curable ink was prepared by the method for preparing a coated material 1. In Examples 13 to 25, the lamination peel strength was good or above. In particular, the ratio n c (B) / n a (A), Examples 13 and 19 to 23, in which the acryl equivalent and the amine value were within the preferred range, were extremely good. Among them, Examples 13 and 21 to 23, in which the viscosity was not high, also had good appearance of the coating. Comparative Examples 5 to 7 were insufficient in both lamination peel strength and failure mode. The results are shown in Table 4.

[0170] [Examples 26 to 30]

[0171] Using active energy ray-curable ink 10 as an active energy ray-curable ink and corresponding films 2 to 6 as described in Table 5 as films, printed materials using active energy ray-curable ink were prepared by the method for preparing a coated article 1. The lamination peel strength was good or above for all films, and was particularly good for the films subjected to corona treatment. The results are shown in Table 5.

[0172] [Examples 31 and 32]

[0173] Active energy ray-curable ink 17 as active energy ray-curable ink and corresponding films 1 and 2 as shown in Table 5 were used as films, and printed materials of active energy ray-curable ink were prepared by UV curing according to the method for preparing a coated article 2. The lamination peel strength was good or above for all films, and was particularly good for the corona-treated film 1.

[0174] [Examples 33 and 34]

[0175] Using active energy ray curable ink 10 as active energy ray curable ink and corresponding films 2 and 4 as shown in Table 5 as films, printed materials using active energy ray curable ink were prepared by coating preparation method 3. Since the corona treatment was performed, the lamination peel strength was extremely good for all the films. The results are shown in Table 5.

[0176] [Table 3]

[0177]

[0178] [Table 4]

[0179]

[0180] [Table 5]

[0181] Table 5

[0182]

Claims

1. An active energy ray-curable composition comprising a monofunctional to tetrafunctional (meth)acrylate (A) having a tertiary amino group and a compound (B) having a carboxyl group and having a weight average molecular weight of 3,000 or more and 100,000 or less, wherein the number of moles of the carboxyl group derived from the compound (B) is n c (B) and the number of moles of the tertiary amine group derived from the (meth)acrylate (A) a (A) ratio n c (B) / n a (A) is 0.01 or more and 0.50 or less.

2. The active energy ray-curable composition according to claim 1, wherein the (meth)acrylate (A) is represented by the structural formula (1): in, R 1 Represents H or methyl, R 2 represents a monovalent organic group having a (meth)acryloyl group, R 3 and R 4 Each independently represents a monovalent hydrocarbon group or a monovalent organic group containing a heteroatom. 3 . The active energy ray-curable composition according to claim 1 , wherein the (meth)acrylate (A) has an amine value of 80 mgKOH / g or more. 4 . The active energy ray-curable composition according to claim 1 , wherein an acryl equivalent of the active energy ray-curable composition is 150 g / eq or more and 500 g / eq or less. 5 . The active energy ray-curable composition according to claim 1 , wherein a content of the (meth)acrylate (A) in the active energy ray-curable composition is 20% by mass or more and 60% by mass or less.

6. The active energy ray-curable composition according to any one of claims 1 to 5, wherein the (meth)acrylate (A) is represented by the structural formula (2) or (3), in, R 1 Represents H or methyl, R 2 It represents a monovalent organic group having a (meth)acryloyl group.

7. The active energy ray-curable composition according to any one of claims 1 to 5, wherein the (meth)acrylate (A) is represented by structural formula (4): in, X represents a nitrogen atom or a carbon atom, R 1 Represents H or methyl, R 2 represents a monovalent organic group having a (meth)acryloyl group, R 3 and R 4 Each independently represents a monovalent hydrocarbon group or a monovalent organic group containing a heteroatom, and R 3 and R 4 They are independent of each other or they can be integrated into a cyclic group. 8 . The active energy ray-curable composition according to claim 1 , wherein the compound (B) has a (meth)acryloyl group and / or a vinyl group. 9 . The active energy ray-curable composition according to claim 1 , comprising a polyfunctional (meth)acrylate (C) having no epoxy group, no acid anhydride group, no isocyanate group, and no amino group. 10 . The active energy ray-curable composition according to claim 1 , comprising a (meth)acrylate (D) having at least one group selected from the group consisting of an epoxy group, an acid anhydride group and an isocyanate group. 11 . The active energy ray-curable composition according to claim 1 , wherein components other than the (meth)acrylate (A), the compound (B), the (meth)acrylate (C) and the (meth)acrylate (D) do not have an acidic group. 12 . An active energy ray-curable ink, comprising the active energy ray-curable composition according to claim 1 further comprising a pigment.

13. A method for producing a printed matter, comprising the following steps: The active energy ray-curable composition according to any one of claims 1 to 11 or the active energy ray-curable ink according to claim 12 is transferred onto a film, and then irradiated with active energy rays. 14 . The method for producing a printed matter according to claim 13 , wherein the surface of the film is subjected to a corona treatment.

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