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

Abstract

To provide an active energy ray-curable composition that has superior curability, and can exhibit sufficient adhesion even to a film without an easy-to-bond layer.SOLUTION: An active energy ray-curable composition includes (A) a primary or secondary amine with a conjugate acid pKa of 6.0 or lower, (B) a polyfunctional (meth)acrylate without amino groups, and (C) a compound including a carboxyl group with a weight average molecular weight of 3000 or more and 100000 or less.SELECTED DRAWING: None

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 technology]

[0002] With the global population increasing, demand for flexible packaging, which is mainly used for packaging food and daily necessities, is expected to continue to grow. Gravure printing, which is currently the mainstream method for printing on flexible packaging, produces prints that look vivid. However, gravure printing uses inks that contain large amounts of solvent, which requires a large amount of energy to dry the ink solvent and treat the exhaust, placing a large burden on the environment. Furthermore, in recent years, there has been a demand to reduce the volatile components contained in ink in response to environmental issues and carbon neutrality.

[0003] For this reason, active energy ray curing methods, which do not contain volatile components and cure instantly when irradiated with active energy rays, are being used in offset printing, flexographic printing, and the in-line anchor coats and overcoats associated with these printing methods (Patent Documents 1 and 2). Since flexible packaging printing is performed using a roll-to-roll method, the quick drying of the ink is important, and in addition to being environmentally advantageous, the active energy ray curing method is energy-saving and highly productive because it shortens the drying process without using thermal energy.

[0004] However, since the main raw material of active energy ray-curable compositions is generally acrylates, the cured products obtained by radical polymerization of these, i.e., poly(meth)acrylates, have low adhesion to major films such as polyolefins, polyesters, polyamides (nylons), etc. Therefore, the cured films of active energy ray-curable compositions have problems such as peeling during post-processing and insufficient strength of the products. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2019-104180 A [Patent Document 2] JP 2019-198970 A [Patent Document 3] Patent Publication No. 2021-98773 Summary of the Invention [Problem to be solved by the invention]

[0006] For this reason, studies have been conducted to improve adhesion to films by providing an easy-adhesion layer on the film side as in Patent Document 3. However, this inevitably increases costs and limits the films that can be used, resulting in poor versatility.

[0007] Therefore, an object of the present invention is to provide an active energy ray-curable composition that has excellent curability and can exhibit sufficient adhesion even to a film that does not have an easy-adhesion layer. [Means for solving the problem]

[0008] The present invention provides an active energy ray-curable composition comprising a primary or secondary amine (A) having a conjugated acid with a pKa of 6.0 or less, a polyfunctional (meth)acrylate (B) having no amino group, and a compound (C) having a carboxyl group and having a weight average molecular weight of 3,000 or more and 100,000 or less.

[0009] The present invention also relates to an active energy ray-curable ink, in which the active energy ray-curable composition of the present invention further contains a pigment.

[0010] The present invention also relates to a method for producing a printed matter, comprising, in this order, a transfer step 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, an irradiation step of curing the active energy ray-curable composition or the active energy ray-curable ink by irradiation with active energy rays, and a heating step of heating the film and a cured product of the active energy ray-curable composition or the active energy ray-curable ink. Effect of the Invention

[0011] The active energy ray-curable composition according to the present invention has excellent curability and can exhibit sufficient adhesion even to a film that does not have an easy-adhesion layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be specifically described below. In the present invention, "or more" means that the value is the same as or larger than the indicated value. Also, "or less" means that the value is the same as or smaller than the indicated value. Also, "(meth)acrylate" is a general term including acrylate and methacrylate, and "(meth)acryloyl group" is a general term including acryloyl group and methacryloyl group.

[0013] The active energy ray curable composition of the present invention contains a primary or secondary amine whose conjugate acid has a pKa of 6.0 or less. Hereinafter, the amine is also referred to as amine (A). The amine (A) can undergo a Michael addition reaction by mixing and heating with a compound having a (meth)acryloyl group. In this reaction, since the (meth)acryloyl group is an α-β unsaturated carbonyl compound, primary or secondary amines undergo 1,4 conjugate addition to form a 3-aminopropionate structure. Furthermore, if the amino group in the structure after the reaction is secondary, it may react again and be converted to a tertiary amine. In addition, since this reaction is a nucleophilic reaction, the higher the nucleophilicity, the milder the conditions under which it proceeds.

[0014] The amine (A) has low nucleophilicity, so that the reaction hardly proceeds when mixed with a compound having a (meth)acryloyl group at room temperature. However, since the reaction does not proceed, the (meth)acryloyl group is not consumed, and the curability of the active energy ray curable composition of the present invention is not reduced. In addition, depending on the type of amine, thickening due to the progress of the reaction is suppressed, and the coatability of the active energy ray curable composition of the present invention is maintained good, and the storage stability during storage is improved.

[0015] On the other hand, after the active energy ray curable composition of the present invention is cured by active energy rays, unreacted (meth)acryloyl groups remain in the cured composition. Therefore, when the cured composition is heated, the Michael addition reaction between the amine (A) and the (meth)acryloyl residue of the radical polymer proceeds, and a radical polymer having a 3-aminopropionate structure is obtained. The amino group of the polymer strongly interacts with polar groups such as hydroxyl groups on the film surface, particularly carboxyl groups, thereby improving the adhesion of the cured film of the active energy ray curable composition to the film.

[0016] This is because the adhesion improving effect is only realized when the amino group and the radical polymer of (meth)acrylate are covalently bonded in the same compound. For example, when amines and (meth)acrylate polymers are simply mixed, the interaction between the crosslinked (meth)acrylates in the cured film and the film surface is not strong because the two compounds are not covalently bonded, and the adhesion is not improved.

[0017] The amine (A) is preferably an aromatic amine.Specific examples include aniline and its derivatives substituted at 1-5 positions, N-1-substituted aniline derivatives, isoquinoline, 1,8-naphthyridine, acridine, 1H-azoles such as 1H-triazole, 1H-benzotriazole, 1H-benzimidazole, 1H-imidazole, and 1H-pyrazole, and derivatives substituted at other than 1H.In particular, 1H-benzotriazole derivatives and 1H-benzimidazole derivatives are preferred because they have a large effect of improving adhesion.

[0018] The amine (A) is preferably low in volatility from the viewpoint of suppressing odor when made into an active energy ray-curable composition, and specifically, is preferably one that is solid at 25° C. and 1 atmospheric pressure.

[0019] As the amine (A), not only monoamines but also polyamines having a plurality of structures in which the pKa of the conjugate acid is 6.0 or less can be used.

[0020] The amine (A) may be used in combination of two or more kinds.

[0021] In the active energy ray curable composition of the present invention, the amine (A) is preferably contained in the active energy ray curable composition in an amount of 5% by mass or more and 30% by mass or less. When the content of the amine (A) is 5% by mass or more, more preferably 10% by mass or more, the film adhesion is further improved. In addition, when the content of the amine (A) is 30% by mass or less, more preferably 20% by mass or less, the curability of the active energy ray curable composition is further improved.

[0022] The active energy ray curable composition of the present invention contains a polyfunctional (meth)acrylate that does not contain an amino group. Hereinafter, the polyfunctional (meth)acrylate is also referred to as (meth)acrylate (B). The (meth)acrylate (B) is cured by irradiation with active energy rays to form a film, and from the viewpoint of curability, it is preferable that it is highly reactive. In addition, since it is a raw material for the Michael addition reaction by heating with the amine (A), a polyfunctional (meth)acrylate having multiple (meth)acryloyl groups is used. Monofunctional (meth)acrylates are generally unsuitable because they have low curability and become a component that can be liberated from the cured film if they remain as an uncured component in the cured film of the active energy ray curable composition.

[0023] From the viewpoints of safety and the environment, the (meth)acrylate (B) preferably has low volatility, which means that the weight loss rate when heated at 110°C for 1 hour is 1% by weight or less, as defined by Method 24 of the U.S. Environmental Protection Agency (EPA).

[0024] Examples of the bifunctional (meth)acrylate (B) 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, and polypropylene glycol di(meth)acrylate. Examples of the acrylates include 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, diglycerin di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and ethylene oxide adducts, propylene oxide adducts, and tetraethylene oxide adducts thereof.

[0025] Examples of the trifunctional (meth)acrylate (B) include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ethylene oxide adducts, propylene oxide adducts, and tetraethylene oxide adducts thereof.

[0026] Examples of the tetrafunctional (meth)acrylate (B) include ditrimethylolpropane tetra(meth)acrylate, diglycerin tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and ethylene oxide and propylene oxide adducts thereof.

[0027] Examples of the penta- or higher functional (meth)acrylate (B) include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide and propylene oxide adducts thereof.

[0028] In particular, when a tetrafunctional or higher (meth)acrylate is used, it is preferable to set the equivalent ratio so that a difunctional or higher compound reacts with the amines.

[0029] The active energy ray curable composition of the present invention contains a compound having a carboxyl group with a weight average molecular weight of 3000 or more and 100000 or less. Hereinafter, this compound is also referred to as compound (C). The amino group of the amine (A) and the carboxyl group of the compound (C) interact with each other to improve the film formability and film strength of the cured film of the active energy ray curable composition. In addition, the compound (C) exhibits catalytic action for the Michael addition reaction between the amine (A) and the (meth)acrylate (B) due to the carboxyl group. The reaction can only proceed by heating the amine (A) in the presence of the compound (C).

[0030] In the active energy ray-curable composition of the present invention, the molar number n of the carboxyl group derived from the compound (C) is c (C) and the number of moles of amino groups derived from the amine (A), n a (A) c (C) / n a It is preferable that (A) is 0.01 or more and 0.50 or less. c (B) / n a When (A) is 0.01 or more, the film-forming property and film strength of the cured film of the active energy ray-curable composition can be effectively improved. c (B) / n a When (A) is 0.50 or less, more preferably 0.30 or less, and further preferably 0.15 or less, improvement in adhesion due to interaction between the amino group and the polar group on the film surface can be effectively obtained.

[0031] In the active energy ray curable composition of the present invention, the compound (C) preferably has a (meth)acryloyl group or a vinyl group. The compound (C) having a photosensitive group such as a (meth)acryloyl group or a vinyl group can form a radical copolymer with other (meth)acrylates such as the (meth)acrylate (B), and the curability against active energy rays is improved, and the strength and adhesion of the cured film are also improved.

[0032] The active energy ray curable composition of the present invention may contain the components described below in addition to the amine (A), the polyfunctional (meth)acrylate (B), and the compound (C). However, it is preferable that the other components do not have an acidic group. This is because the acidic group may interact with the amine (A) and inhibit the improvement of adhesion.

[0033] The active energy ray-curable composition of the present invention preferably contains a colored pigment, so that it can be used as an active energy ray-curable ink.

[0034] 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, yellow lead, zinc yellow, iron 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, and graphite.

[0035] As the pigment, colorless extender pigments such as mica (hydrated potassium aluminum silicate) and talc (magnesium silicate) can also be used, and the active energy ray-curable composition of the present invention can also be used as a varnish or anchor coating agent.

[0036] 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 that can be used include α-aminoalkylphenones, thioxanthones, benzyl ketals, and acylphosphine oxides.

[0037] The active energy ray-curable composition of the present invention may further contain additives such as wax, pigment dispersant, antifoaming agent, and leveling agent.

[0038] A solvent may be used to adjust the viscosity. However, the inclusion of a solvent decreases the curability of the active energy ray-curable composition of the present invention with respect to active energy rays.

[0039] The active energy ray-curable composition of the present invention can be used as an anchor coating agent that is transferred to a film and then an active energy ray-curable ink is transferred thereon, or can be used as an overcoating agent that is transferred to a film after an active energy ray-curable ink is transferred to a film in a pattern shape.

[0040] The active energy ray-curable composition of the present invention can also be used as an active energy ray-curable ink containing a colored pigment. That is, the active energy ray-curable ink of the present invention comprises the active energy ray-curable composition of the present invention further containing a pigment.

[0041] Next, a method for producing the active energy ray-curable composition of the present invention will be described.

[0042] The active energy ray-curable composition of the present invention can be obtained by mixing the amine (A), the polyfunctional (meth)acrylate (B), and the compound (C), and further other components such as a photopolymerization initiator, if necessary, at room temperature to 80°C.

[0043] After or during the mixing, degassing is preferably carried out under vacuum or reduced pressure conditions.

[0044] When a colored pigment is added to prepare an ink, it is also preferable to add the pigment during the above mixing and then disperse and knead the ink using an attritor, ball mill, sand mill, triple roll mill, or the like depending on the viscosity.

[0045] The method for producing a printed matter of the present invention includes, in this order, a transfer step of transferring the active energy ray-curable composition of the present invention or the active energy ray-curable ink of the present invention to a film, an irradiation step of curing the active energy ray-curable composition or the active energy ray-curable ink by irradiation with active energy rays, and a heating step of heating the film and the cured product of the active energy ray-curable composition or the active energy ray-curable ink. Hereinafter, the term "active energy ray-curable composition" may be used as a general term for the active energy ray-curable composition and the active energy ray-curable ink.

[0046] Examples of films that can be used in the present invention include polyesters such as polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, and polylactic acid, polyamide, polyimide, polyalkyl(meth)acrylate, polystyrene, poly-α-methylstyrene, polycarbonate, polyvinyl alcohol, polyvinyl acetal, polyvinyl chloride, and polyvinylidene fluoride.

[0047] These films may also have a vapor-deposited thin film layer of a metal such as alumina or a metal compound.

[0048] The surface of the film is preferably corona-treated, since this increases the polar functional groups on the film surface and improves the adhesion to the active energy ray-curable composition or active energy ray-curable ink.

[0049] The film having a corona-treated surface may be a ready-made product, or may be a film that has been subjected to in-line corona treatment before the active energy ray-curable composition or active energy ray-curable ink is transferred to the film.

[0050] The film may have an easy-adhesion coating layer, but this increases the cost. The active energy ray-curable composition of the present invention is suitable because it can exhibit sufficient adhesion even to a film that does not have an easy-adhesion layer.

[0051] The film may be in the form of either a sheet or a roll film. When a thin film for flexible packaging is used, it is preferable to use a roll film and perform coating and printing by roll-to-roll.

[0052] Methods for transferring the active energy ray-curable composition or active energy ray-curable ink of the present invention to a film include, for example, flexographic printing, offset printing, gravure printing, screen printing, inkjet printing, varnish coater, bar coater, etc. The transfer method is selected depending on the viscosity of the active energy ray-curable composition and whether or not patterning is required.

[0053] Specifically, if patterning is required, printing methods such as flexographic printing, offset printing, gravure printing, screen printing, and inkjet printing are preferred. For full surface coating, it is preferable to use a varnish coater or a bar coater. From the viewpoint of viscosity, if the viscosity is high, 5 Pa·s or more and 200 Pa·s or less, offset printing or screen printing is preferred, if it is 0.1 Pa·s to 5 Pa·s, flexographic printing is preferred, and if it is 0.1 Pa·s or less, gravure printing or inkjet printing is preferred. Within the above viscosity range, a lower viscosity is generally preferred because it has better leveling properties and the appearance of the coated product is better.

[0054] Examples of the active energy ray source used in the irradiation step include ultraviolet rays, electron beams, gamma rays, etc. By irradiation with active energy rays, the (meth)acryloyl group reacts and crosslinks through a covalent bond, so that the active energy ray-curable composition is instantly cured.

[0055] For ultraviolet rays, ultraviolet irradiation devices such as high-pressure mercury lamps, xenon lamps, metal halide lamps, and light-emitting diodes (LEDs) are preferably used. Among them, LED lamps are preferred because they are power-saving and generate less ozone. As for the wavelength of the LED, an emission line of 350 to 420 nm is preferred from the viewpoints of power saving and cost reduction.

[0056] In the case of electron beams, (meth)acryloyl groups are directly radically excited, and radical polymerization proceeds in the active energy ray curable composition to form a film. In addition, electron beams have high permeability and can act on films. When the film is a polyolefin, radicals are easily generated, causing reactions such as intermolecular crosslinking and decomposition, and radical polymerization proceeds between the active energy ray curable composition / film, forming covalent bonds between the active energy ray curable composition / film, thereby enabling higher adhesion to be expressed. In particular, electron beams with low acceleration voltages are preferred because they do not require special qualifications for use and are easy to handle. Since the penetration depth of electron beams is determined by the acceleration voltage, the acceleration voltage is preferably 50 kV to 300 kV from the viewpoint of sufficient permeability and damage to the film. In addition, the irradiation dose of electron beams is preferably 10 kGy to 100 kGy because the amount of radical species generated in the target substance increases while the damage to the film also increases.

[0057] The heating step promotes a Michael addition reaction between the amine (A) and the (meth)acryloyl residue of the polyfunctional (meth)acrylate (B) contained in the active energy ray curable composition cured product of the present invention, thereby improving the adhesion between the active energy ray curable composition cured product and the film. The carboxyl group of the compound (C) acts as a catalyst, and the reaction proceeds by heating at 40°C or higher. By providing this step after the transfer step, it is possible to suppress the decrease in coatability due to thickening caused by the progression of the Michael addition reaction and the decrease in curability due to consumption of the (meth)acryloyl group. Therefore, the curability, coatability, and storage stability of the active energy ray curable composition of the present invention are improved.

[0058] In the heating step, the heating temperature is preferably 40° C. to 120° C., and the heating time is preferably 2 hours or longer.

[0059] The heating temperature is preferably 40° C. or higher, more preferably 60° C. or higher, since the rate of progression of the Michael addition reaction increases. Also, in order to suppress thermal damage to the film, the heating temperature is preferably 120° C. or lower, more preferably 100° C. or lower, and even more preferably 80° C. or lower.

[0060] The heating time is preferably 2 hours or more, more preferably 4 hours or more, and even more preferably 6 hours or more in order to complete the reaction, and is preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 8 hours or less in order to suppress thermal damage to the film.

[0061] Furthermore, the heating step may be carried out before or after post-processing such as lamination, so long as it is after curing by irradiation with active energy rays. EXAMPLES

[0062] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0063] [Measurement and evaluation method] (1) Viscosity A cylinder spindle No. 4 was attached to a Brookfield type viscometer (DV-II manufactured by Brookfield Corporation) and the viscosity of each active energy ray curable composition was measured at 25°C and 0.5 rpm. From the viewpoint of coatability and printability, the viscosity is preferably 100 Pa s or less, and more preferably 50 Pa s or less.

[0064] (2) Curability Each of the active energy ray curable compositions 1 to 10 and 12 to 15 was transferred to the film 1 using an RI tester, and then electron beam irradiation was performed using an electron beam irradiation device (EC250 / 30 / 90LS manufactured by Iwasaki Electric Co., Ltd.) at an acceleration voltage of 90 kV and an exposure dose of 10 to 30 kGy, which was changed in increments of 5 kGy. The minimum exposure dose at which the cured product did not peel off when cellophane adhesive tape ("Cellotape" (registered trademark) No. 405) was adhered to the cured product and then peeled off was determined. When the minimum exposure dose was 25 to 30 kGy, the curability was good, and when the minimum exposure dose was 10 to 20 kGy, the curability was extremely good.

[0065] (3) Coating appearance The appearance of the coating of the active energy ray-curable composition obtained in the coating step of each of the Examples and Comparative Examples was visually evaluated as follows. A: The surface has a good appearance with minimal unevenness and no visible holes. B: Some minor defects were observed. C: The surface was largely uneven, and defects such as voids were observed overall.

[0066] (4) Peel strength A mixed laminating adhesive (Takelac A626 / Takenate A50 manufactured by Mitsui Chemicals, Inc.) was applied to the coating of the active energy ray curable composition obtained in the coating process of each Example and Comparative Example in a coating amount of 3.0 g / m. 2 The coated film was laminated with a 60 μm thick non-oriented polypropylene film (CPP) (ZK-207, manufactured by Toray Film Processing Co., Ltd.). The film was then aged at 40° C. for 3 days to obtain a laminate sample. The coated portion of the active energy ray curable composition in the obtained laminate sample was cut into a 15 mm wide strip, and a peel test was performed using a Tensilon universal testing machine (RTG-1210, manufactured by Orientec Co., Ltd.) to measure the peel strength when peeled at 90° at 300 mm / min.

[0067] When the peel strength was less than 1.5 N / 15 mm, the adhesion was judged to be insufficient, when it was 1.5 N / 15 mm or more but less than 2.0 N / 15 mm, the adhesion was judged to be good, when it was 2.0 N / 15 mm or more but less than 3.0 N / 15 mm, the adhesion was judged to be fairly good, and when it was 3.0 N / 15 mm or more, the adhesion was judged to be extremely good.

[0068] (5) Destruction mode In the peel test (4) above, the state of peeling (fracture mode) was also observed. In the laminate sample having a multi-layer structure, the interlayer where the fracture occurred during peeling corresponds to the location with the weakest adhesion. The fracture mode was evaluated according to the following A to C. A: The film broke. B: The active energy ray-curable composition layer underwent cohesive failure. C: Peeling occurred between the film and active energy ray-curable composition layers. Here, the term "active energy ray-curable composition layer" refers to a layer formed by curing an active energy ray-curable composition or ink. The above A is most preferred, the above B is next preferred, and the above C is least preferred.

[0069] [Amine (A) or its substitute] (A)-1: Indoline (manufactured by Waken Pharmaceutical Co., Ltd.), secondary amine, pKa of conjugate acid: 4.9. Liquid at 25°C and 1 atm. (A)-2: Aniline (manufactured by Waken Pharmaceutical Co., Ltd.), primary amine, pKa of conjugate acid: 4.6. Liquid at 25°C and 1 atm. (a)-3: Octadecylamine (TCI Corporation), primary amine, pKa of conjugate acid: 10.8. Solid at 25°C and 1 atm. (A)-4: 1H-benzotriazole (manufactured by Waken Pharmaceutical Co., Ltd.), primary amine, pKa of conjugate acid: 1.2. Solid at 25°C and 1 atm.

[0070] [(Meth)acrylate (B)] (B)-1: EO-modified trimethylolpropane triacrylate (MIWON Corporation's "Miramer" (registered trademark) M3190) (B)-2: Ditrimethylolpropane tetraacrylate ("Miramer" (registered trademark) M410 manufactured by MIWON) (B)-3: Tricyclodecane dimethanol diacrylate ("EBECRYL" (registered trademark) 130, manufactured by Daicel Allnex Corporation).

[0071] [Compound (C) or its substitute] (C)-1: acrylic resin having a photosensitive group and a carboxylic acid (TWR-1001 manufactured by Toray Industries, Inc.), molecular weight: 30,000, acid value: 105 mgKOH / g. (C)-2: Acrylic resin having carboxylic acid (TWR-3001 manufactured by Toray Industries, Inc.), molecular weight: 27,000, acid value: 200 mg KOH / g. (c)-3: Adipic acid (manufactured by Wakenyaku Co., Ltd.), molecular weight: 146.

[0072] [Other added ingredients] Pigment: Titanium oxide ("Tipaque" (registered trademark) CR58-2, manufactured by Ishihara Sangyo Kaisha, Ltd.) Surfactant 1: ("EMALEX" (registered trademark) 503, manufactured by Nippon Emulsion Co., Ltd.) Surfactant 2: (BYK-Chemie "Disperbyk" (registered trademark) 111) Photopolymerization initiator: bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide (BASF "Irgacure" (registered trademark) 819).

[0073] [Active energy ray curable composition or active energy ray curable ink] Each material was weighed out according to the composition shown in Table 1, and dissolved and dispersed using a hybrid mixer (manufactured by Thinky Corporation). When no pigment was contained (active energy ray-curable composition 7), it was used as it was as an active energy ray-curable composition.

[0074] When the active energy ray curable composition contained a pigment (active energy ray curable inks 1 to 6, 9 to 15), mixing and dispersion were carried out using a triple roll mill "EXAKT" (registered trademark) M-80S (manufactured by EXAKT), and when the viscosity was low (active energy ray curable ink 8), mixing and dispersion were carried out using a batch type sand mill (manufactured by Hayashi Shoten Co., Ltd.).

[0075] [Table 1] [film] Film 1: PET film with a thickness of 12 μm (E5102 manufactured by Toyobo Co., Ltd.), with a corona treatment layer. Film 2: PET film with a thickness of 12 μm (FS2000 manufactured by Futamura Chemical Co., Ltd.), no surface treatment. Film 3: 15 μm thick polyamide film (ON manufactured by Unitika Ltd.), with a corona treatment layer. Film 4: 12 μm thick barrier film / PET film laminate (1011HG SBR2 manufactured by Toray Film Processing Co., Ltd.), without a corona treatment layer. Film 5: OPP film (P2111 manufactured by Toyobo Co., Ltd.) having a thickness of 20 μm, with a corona treatment layer. Film 6: PET film having a thickness of 12 μm ("Lumirror" (registered trademark) S10 manufactured by Toray Industries, Inc.), no surface treatment.

[0076] [Coating preparation method 1] Various active energy ray curable compositions or active energy ray curable inks were transferred onto various films. The transfer method was to use a bar coater No. 5 for active energy ray curable compositions not containing a pigment, and an RI tester for active energy ray curable inks containing a pigment. Then, using an electron beam irradiation device (EC250 / 30 / 90LS manufactured by Iwasaki Electric Co., Ltd.), curing was performed by irradiating with electron beams at an acceleration voltage of 110 kV and an exposure dose of 40 kGy. After that, the film was heated at 80°C for 12 hours.

[0077] [Coating preparation method 2] Various active energy ray curable inks were transferred onto various films. An RI tester was used for the transfer method. A light-emitting diode ultraviolet irradiation device (UD90 manufactured by Panasonic Devices SUNX Co., Ltd.) was used with an irradiation intensity of 8 W / cm. 2 The resin was then cured by irradiating it with LED-UV light with a wavelength of 385 nm, and then heated at 80°C for 12 hours.

[0078] [Coating preparation method 3] For various films, a corona treatment device (Kasuga Electric Co., Ltd., TEC-4AX) was used, and the discharge amount E was 200 W min / m 2 After corona treatment under the above conditions, various active energy ray curable inks were transferred. An RI tester was used for the transfer method. Then, using an electron beam irradiation device (EC250 / 30 / 90LS manufactured by Iwasaki Electric Co., Ltd.), the ink was cured by irradiating it with an electron beam at an acceleration voltage of 110 kV and an exposure dose of 40 kGy. After that, the ink was heated at 80°C for 12 hours.

[0079] [Example 1] A coated product was prepared by coating method 1 using active energy ray curable ink 1 as the active energy ray curable ink and film 1 as the film. The peel strength was 3.7 N / 15 mm, which was extremely good, and there was no peeling at a dose of 20 kGy. The curability was also good, the failure mode was good (A), and the appearance of the coated product was also good. The results are shown in Table 2.

[0080] [Examples 2 to 10 and Comparative Examples 1 to 4] As the active energy ray curable composition, active energy ray curable composition 7, active energy ray curable inks 2 to 6, 8 to 10, 12 to 15, and film 1 were used as the film, and coated products were produced by coating product production method 1. In Examples 2 to 10, the peel strength was good or better, but Examples 2, 5, 7, 8, 9, and 10, which had amine amounts in the preferred range, were very good in both appearance and adhesion. In Comparative Examples 1 to 3, both the peel strength and the fracture mode were insufficient. Comparative Example 4 showed good adhesion, but the Michael addition reaction proceeded at room temperature, the viscosity was high, and the acryloyl group was consumed, resulting in poor curability. The results are shown in Table 2.

[0081] [Examples 11 to 15] A coated product was prepared by coating method 1 using active energy ray curable ink 1 as the active energy ray curable ink and films 2 to 6 as the films corresponding to those shown in Table 3. The peel strength was good or better for all of the films, and was particularly excellent for the corona-treated films. The results are shown in Table 3.

[0082] [Examples 16 and 17] A coated product was prepared by UV curing using active energy ray curable ink 11 as the active energy ray curable ink and films 1 and 2 as the films in accordance with the correspondence in Table 3, according to coating product preparation method 2. The peel strength was good or better for both films, and was particularly excellent for corona-treated film 1.

[0083] [Examples 18 and 19] A coated product was prepared by coating method 3 using active energy ray curable ink 1 as the active energy ray curable ink and films 2 and 4 as the films, as shown in Table 3. By subjecting the film to corona treatment, the peel strength of both films was extremely good. The results are shown in Table 3.

[0084] [Table 2]

[0085] [Table 3]

Claims

1. An active energy ray-curable composition comprising a primary or secondary amine (A) having a pKa of the conjugate acid of 6.0 or less, a polyfunctional (meth)acrylate (B) having no amino group, and a compound (C) having a carboxyl group with a weight average molecular weight of 3000 or more and 100000 or less.

2. The active energy ray-curable composition according to Claim 1, wherein the amine (A) is an aromatic amine.

3. The active energy ray-curable composition according to Claim 1 or 2, wherein the amine is one or more selected from 1H-benzotriazole derivatives and 1H-benzimidazole derivatives.

4. The active energy ray-curable composition according to Claim 1 or 2, wherein the amine (A) is solid at 25 ° C and 1 atm.

5. The number of moles n of the carboxyl group derived from the compound (C) ｃ The number of moles n of the amino group derived from (C) and the amine (A) ａ The ratio n with (A) ｃ (C) / n ａ The active energy ray-curable composition according to claim 1 or 2, wherein (A) is 0.01 or more and 0.50 or less.

6. The active energy ray-curable composition according to Claim 1 or 2, wherein the compound (C) has a meth(acryloyl) group or a vinyl group.

7. The active energy ray-curable composition according to Claim 1 or 2, wherein components other than the amine (A), the (meth)acrylate (B), and the compound (C) do not have an acidic group.

8. An active energy ray-curable ink comprising the active energy ray-curable composition according to Claim 1 further comprising a pigment.

9. A method for producing a printed matter, comprising in this order: a transfer step of transferring the active energy ray-curable composition according to Claim 1 or the active energy ray-curable ink according to Claim 8 onto a film; an irradiation step of curing the active energy ray-curable composition or the active energy ray-curable ink by irradiation with active energy rays; and a heating step of heating the film and the cured product of the active energy ray-curable composition or the active energy ray-curable ink.

10. The method for producing a printed matter according to Claim 9, wherein the surface of the film is corona-treated.

11. The method for producing a printed matter according to Claim 9, wherein in the heating step, the heating temperature is 40 ° C to 120 ° C and the heating time is 2 hours or more.