Active energy ray-curable overprint varnish composition, method for producing printed matter using same, and method for suppressing odor and migration of printed matter

Abstract

To provide an active energy ray-curable overprint varnish composition capable of reducing generation of odor and migration from a formed varnish film while maintaining performance as a varnish composition.SOLUTION: The photosensitive resin composition contains a monomer which is a compound having two or more ethylenically unsaturated bonds and a photopolymerization initiator, wherein the monomer contains a monomer A having four or more ethylenically unsaturated bonds and a monomer B having an alkylene oxide-modified bisphenol A skeleton or the like and having two ethylenically unsaturated bonds. In the varnish composition, the photopolymerization initiator is selected from (A) a compound having a diphenylmethane skeleton, (B) a compound having a morpholine skeleton and a fluorene skeleton, and (C) a compound having a diphenyl ether skeleton, and in the monomer, the proportion of the monomer A is 10 to 55% by mass and the proportion of the monomer B is 10 to 46% by mass.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable overprint varnish composition, a method for producing a printed item using the same, and a method for suppressing odor and migration of printed items. [Background technology]

[0002] After printing on the surface of various substrates, such as films, sheets, and plates, coating them with an overprint varnish (OP varnish) is widely used to protect the substrate itself and the printed surface and impart gloss. When an active energy ray-curable varnish composition is used as the OP varnish for such surface treatments, the varnish composition is applied to the substrate surface and then irradiated with active energy rays such as ultraviolet rays or electron beams, resulting in instantaneous curing and the formation of a glossy cured film. This results in higher productivity than conventional vinyl cladding and other processes. Furthermore, active energy ray-curable varnish compositions are preferable from an environmental perspective because they do not emit VOCs (volatile organic compounds) into the atmosphere, as solvent-based coatings do. Due to these advantages, coating processes using active energy ray-curable varnish compositions are rapidly replacing conventional vinyl cladding and solvent-based coatings. Such surface varnishes are widely applied to not only conventional printed materials such as magazine covers, posters, and calendars, but also packaging applications such as carton prints, making them a familiar part of our daily lives.

[0003] It is known that such active energy ray-curable varnish compositions can be endowed with various functions, such as adhesion to substrates, high gloss, and blocking resistance, by using compounds necessary for curing, such as monomers or oligomers having ethylenically unsaturated bonds, in combination with various other components as necessary (see, for example, Patent Documents 1 to 3, etc.). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-167088 [Patent Document 2] Japanese Patent Application Publication No. 10-17787 [Patent Document 3] Japanese Patent Application Laid-Open No. 2004-315546 Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, surface treatment of printed materials using an active energy ray-curable overprint varnish composition offers significant advantages, such as the ability to form a varnish film with excellent properties in a short time. However, surface treatment using an active energy ray-curable overprint varnish composition is not without its disadvantages, such as the odor and migration of the formed varnish film. A photopolymerization initiator is added to an active energy ray-curable overprint varnish composition to initiate a polymerization reaction for curing when irradiated with active energy rays. When irradiated with active energy rays, this photopolymerization initiator undergoes intramolecular cleavage, generating lower molecular weight radicals. These radicals then polymerize the monomers and oligomers contained in the varnish composition, curing the varnish composition.

[0006] The generated radicals are incorporated into polymers formed by the polymerization of monomers and oligomers. However, low-molecular-weight compounds generated by intramolecular cleavage of the photopolymerization initiator and low-molecular-weight compounds generated from some of the radicals remain in the varnish film and are released into the environment over time as volatile organic compounds. Examples of these low-molecular-weight compounds include aldehyde compounds, which have a distinctive odor. Therefore, printed materials with varnish films formed from active energy ray-curable overprint varnish compositions often have a noticeable odor. This odor can sometimes be a turn-off for consumers.

[0007] Furthermore, low-molecular-weight compounds remaining in the varnish film can migrate from the varnish film present on the surface of the printed material to the interior of the printed material or to other items that come into contact with the varnish film. This migration of low-molecular-weight compounds from the varnish film is called migration, and it can be problematic, along with the odor mentioned above, especially when printed materials are used in food packaging.

[0008] The present invention has been made in consideration of the above circumstances, and aims to provide an active energy ray-curable overprint varnish composition that can reduce the occurrence of odor and migration from the formed varnish film while maintaining the performance of the varnish composition, such as abrasion resistance and scratch resistance. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that the above-mentioned problems can be solved by using a specific photopolymerization initiator and, among monomers that are compounds having two or more ethylenically unsaturated bonds, a monomer having four or more ethylenically unsaturated bonds and a monomer having an alkylene oxide-modified bisphenol A skeleton or an alkylene oxide-modified hydrogenated bisphenol A skeleton and two ethylenically unsaturated bonds, in specific proportions relative to the total monomers. The present invention was made based on this finding and provides the following.

[0010] (1) The present invention provides an active energy ray-curable overprint varnish composition comprising a monomer, which is a compound having two or more ethylenically unsaturated bonds, and a photopolymerization initiator, wherein the monomers include monomer A having four or more ethylenically unsaturated bonds and monomer B having an alkylene oxide-modified bisphenol A skeleton or an alkylene oxide-modified hydrogenated bisphenol A skeleton and having two ethylenically unsaturated bonds, and the photopolymerization initiator is at least one compound selected from the group consisting of (A) compounds having a diphenylmethane skeleton, (B) compounds having a morpholine skeleton and a fluorene skeleton, and (C) compounds having a diphenyl ether skeleton, and the proportion of monomer A relative to the total amount of the monomers is 10 to 55 mass% and the proportion of monomer B is 10 to 46 mass%.

[0011] (2) The present invention also provides the active energy ray-curable overprint varnish composition according to (1), wherein the number of alkylene oxides added to the monomer B is 3 to 30.

[0012] (3) The present invention also provides an active energy ray-curable overprint varnish composition according to item (1) or (2), wherein the alkylene oxide in the monomer B is ethylene oxide.

[0013] (4) The present invention also relates to an active energy ray-curable overprint varnish composition according to any one of items (1) to (3), further comprising a dicarboxylic acid diester compound as a plasticizer, the compound having a carbon number per molecule of 20 or more.

[0014] (5) The present invention also relates to an active energy ray-curable overprint varnish composition according to (4), wherein the diester compound of a dicarboxylic acid is bis(2-ethylhexyl) sebacate or bis(2-ethylhexyl) adipate.

[0015] (6) The present invention further includes a resin component, and the resin component is a diallyl phthalate resin, a diallyl cycloalkane dicarboxylate resin, and a resin having an sp value of 9.0 to 11.0 (cal / cm 3 ) 1 / 2 The active energy ray-curable overprint varnish composition according to any one of items (1) to (5), wherein the resin is at least one selected from the group consisting of rosin-modified alkyd resins:

[0016] (7) The present invention also relates to an active energy ray-curable overprint varnish composition according to any one of items (1) to (6), in which the (A) compound having a phenylmethane skeleton and the (C) compound having a diphenyl ether skeleton are compounds represented by the following general formula (1): [ka] (In general formula (1), R 1 and R 2 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and the substituent is a hydroxyl group, an amino group, or a halogen atom, and X is a methylene group or an oxygen atom.

[0017] (8) The present invention also relates to an active energy ray-curable overprint varnish composition according to item (7), in which the compound represented by the general formula (1) is a compound represented by the following general formula (1C-1) or (1C-2): [ka] (In general formula (1C-1), L 1 and L 2 are each independently an alkylene group having 1 to 10 carbon atoms which may have a branch. [ka] (In general formula (1C-2), L 1 and L 2 are each independently an alkylene group having 1 to 10 carbon atoms which may have a branch.

[0018] (9) The present invention also relates to an active energy ray-curable overprint varnish composition according to any one of items (1) to (8), in which the compound (B) having a morpholine skeleton and a fluorene skeleton is a compound represented by the following general formula (2): [ka] (In general formula (2), R 3 and R 4 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and the substituent is a hydroxyl group, an amino group, or a halogen atom; each L is independently a divalent organic group; and n is 0 or 1.

[0019] (10) The present invention also provides an active energy ray-curable overprint varnish composition according to item (9), in which the compound represented by the general formula (2) above is a compound represented by the following general formula (2B): [ka] (In general formula (2B), R 3 and R 4 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and the substituent is a hydroxyl group, an amino group, or a halogen atom, and L is an alkylene group having 1 to 10 carbon atoms which may have a branch.

[0020] (11) The present invention also relates to an active energy ray-curable overprint varnish composition according to any one of items (1) to (10), wherein the photopolymerization initiator is at least one compound selected from the group of compounds represented by the following three chemical formulas: [ka]

[0021] (12) The present invention also relates to a method for producing a printed matter, comprising the steps of applying an actinic ray-curable overprint varnish composition according to any one of items (1) to (11) to a surface to be treated, which may or may not be printed with an ink composition, and curing the applied actinic ray-curable overprint varnish composition with actinic rays.

[0022] (13) The present invention also relates to a method for suppressing odor and migration originating from a varnish layer formed on the surface of a printed matter produced by a process for producing a printed matter, the method comprising the steps of applying an active energy ray-curable overprint varnish composition to a surface to be treated that may or may not be printed with an ink composition, and curing the applied active energy ray-curable overprint varnish composition with active energy rays, the method being characterized in that the active energy ray-curable overprint varnish composition is one described in any one of items (1) to (11). [Effects of the Invention]

[0023] According to the present invention, an active energy ray-curable overprint varnish composition is provided that can reduce the occurrence of odor and migration from the formed varnish film while maintaining the performance of the varnish composition, such as abrasion resistance and scratch resistance. DETAILED DESCRIPTION OF THE INVENTION

[0024] Below, we will explain one embodiment of the active energy ray-curable overprint varnish composition of the present invention (hereinafter also referred to as the "varnish composition of the present invention"), one embodiment of the method for producing a printed matter of the present invention, and one embodiment of the method for suppressing odor and migration originating from a varnish layer of the present invention. Note that the present invention is not limited to the following embodiment and implementation, and can be carried out with appropriate modifications within the scope of the present invention.

[0025] <Active energy ray curable overprint varnish composition> The active energy ray-curable overprint varnish composition of the present invention has the ability to cure upon irradiation with active energy rays such as ultraviolet rays or electron beams, and is preferably used as an overprint varnish for the surface of a printed material after printing. As described below, the varnish composition of the present invention contains a compound (monomer) with two or more ethylenically unsaturated bonds and a photopolymerization initiator, and radicals generated upon irradiation with active energy rays polymerize the compound with the ethylenically unsaturated bonds, thereby curing the composition to form a coating film. Therefore, when active energy rays are irradiated onto a varnish composition that is sticky on the surface of a printed material immediately after application, the varnish composition instantly dries (becomes tack-free).

[0026] The varnish composition of the present invention can be applied to, but is not limited to, printed matter obtained by offset printing or the like. A preferred example of such a printed matter is a packaging container. The cured film (i.e., varnish film) obtained by curing the varnish composition of the present invention is robust and glossy, so when applied to a packaging container, it protects the packaging container from scratches and provides the packaging container with a high glossy aesthetic. The term "overprint varnish composition" generally refers to a varnish composition applied to a printed surface. However, in the present invention, the term "overprint varnish composition" refers not only to a varnish composition applied to a printed surface, but also to a varnish composition applied to an unprinted substrate. Furthermore, in the present invention, a varnish composition applied to an unprinted substrate with an overprint varnish composition is also considered a "printed matter."

[0027] Examples of active energy rays used to cure the varnish composition of the present invention include electron beams and ultraviolet rays. Among these, ultraviolet rays are preferred as active energy rays from the viewpoints of the cost and ease of handling of the device. The wavelength of the ultraviolet rays may be appropriately determined according to the absorption wavelength of the photopolymerization initiator used, but examples thereof include 400 nm or less. Examples of ultraviolet irradiation devices that generate such ultraviolet rays include metal halide lamps, high-pressure mercury lamps, excimer lamps containing rare gases, and ultraviolet light-emitting diodes (LEDs).

[0028] The varnish composition of the present invention comprises a monomer A, which is a compound having two or more ethylenically unsaturated bonds, and a photopolymerization initiator, the monomers being monomer A having four or more ethylenically unsaturated bonds, and monomer B having an alkylene oxide-modified bisphenol A skeleton or an alkylene oxide-modified hydrogenated bisphenol A skeleton and two ethylenically unsaturated bonds, the photopolymerization initiator being at least one compound selected from the group consisting of (A) compounds having a diphenylmethane skeleton, (B) compounds having a morpholine skeleton and a fluorene skeleton, and (C) compounds having a diphenyl ether skeleton, and the proportion of monomer A relative to the total amount of the monomers is 10 to 55% by mass, and the proportion of monomer B is 10 to 46% by mass. Each component is described below.

[0029] [Photopolymerization initiator] First, we will explain the photopolymerization initiator. As already mentioned, photopolymerization initiators undergo intramolecular cleavage upon irradiation with active energy rays to generate radicals. These radicals polymerize a compound having an ethylenically unsaturated bond, as described below, to form a cured varnish film. The varnish composition of the present invention particularly contains, as a photopolymerization initiator, at least one selected from the group consisting of (A) a compound having a diphenylmethane skeleton, (B) a compound having a morpholine skeleton and a fluorene skeleton, and (C) a compound having a diphenyl ether skeleton. The inventors have found through their studies that these photopolymerization initiators can provide the remarkable effect of effectively suppressing odor and migration when applied to a varnish composition. The present invention was made based on this finding and contains a compound selected from the group consisting of (A) to (C) above as a photopolymerization initiator.

[0030] The compound (A) having a diphenylmethane skeleton (hereinafter also referred to as "compound (A)") may be any compound that has a diphenylmethane skeleton in its molecule and undergoes intramolecular cleavage to generate radicals when irradiated with active energy rays. The compound (C) having a diphenyl ether skeleton (hereinafter also referred to as "compound (C)") may be any compound that has a diphenyl ether skeleton in its molecule and undergoes intramolecular cleavage to generate radicals when irradiated with active energy rays.

[0031] More specifically, examples of the compound (A) and the compound (C) include compounds represented by the following general formula (1).

[0032] [ka]

[0033] In the above general formula (1), R 1 and R 2are each independently a hydrocarbon group having 1 to 10 carbon atoms, which may have a substituent. Preferred examples of such hydrocarbon groups include an alkyl group having 1 to 10 carbon atoms, which may have a branch, a cycloalkyl group having 1 to 10 carbon atoms, and an aryl group having 1 to 10 carbon atoms. Among these, an alkyl group having 1 to 10 carbon atoms, which may have a branch, is more preferred, and a dimethylmethyl group having a substituent is particularly preferred. Examples of the substituent include a hydroxyl group, an amino group, and a halogen atom, and among these, a hydroxyl group is preferred. In the general formula (1), X is a methylene group or an oxygen atom. That is, when X is a methylene group, the compound represented by the general formula (1) is a compound (A), and when X is an oxygen atom, the compound represented by the general formula (1) is a compound (C).

[0034] The two benzene rings contained in the compound represented by the general formula (1) are preferably substituted at the para position, and in this case, the compound represented by the general formula (1) can be represented by the following general formula (1A). 1 , R 2 and X are the same as those in the general formula (1) above.

[0035] [ka]

[0036] More specific examples of the compound (A) and the compound (C) include those represented by the following general formulae (1B-1) and (1B-2). In the following general formulae (1B-1) and (1B-2), R 1 and R 2 are the same as those in the above general formula (1).

[0037] [ka]

[0038] More specific examples of the compounds (A) and (C) include those represented by the following general formulae (1C-1) and (1C-2). 1 and L 2 are each independently an alkylene group having 1 to 10 carbon atoms which may have a branch. Of such alkylene groups, a dimethylmethylene group is particularly preferred.

[0039] [ka]

[0040] More specifically, examples of the compound (A) and the compound (C) include those represented by the following chemical formulas (1D-1) and (1D-2): It goes without saying that the compound (A) and the compound (C) in the present invention are not limited to these compounds.

[0041] [ka]

[0042] The compound (B) having a morpholine skeleton and a fluorene skeleton (hereinafter also referred to as "compound (B)") may be any compound as long as it has both a morpholine skeleton and a fluorene skeleton in its molecule and undergoes intramolecular cleavage to generate radicals when irradiated with active energy rays.

[0043] More specifically, examples of the compound (B) include compounds represented by the following general formula (2).

[0044] [ka]

[0045] In the above general formula (2), R 3 and R 4are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. Preferred examples of such hydrocarbon groups include an alkyl group having 1 to 10 carbon atoms which may have a branch, a cycloalkyl group having 1 to 10 carbon atoms, and an aryl group having 1 to 10 carbon atoms. Of these, an alkyl group having 1 to 5 carbon atoms is preferred. Examples of the substituent include a hydroxyl group, an amino group, and a halogen atom.

[0046] In the general formula (2), each L is independently a divalent organic group. Examples of such organic groups include divalent hydrocarbon groups having 1 to 10 carbon atoms, which may have a substituent. Examples of such hydrocarbon groups include alkylene groups having 1 to 10 carbon atoms, which may have a branch, cycloalkylene groups having 1 to 10 carbon atoms, and aryl groups having 1 to 10 carbon atoms. Among these, alkylene groups having 1 to 10 carbon atoms, which may have a branch, are more preferred, and dimethylmethylene groups are particularly preferred. Examples of the substituent include a hydroxyl group, an amino group, and a halogen atom. In the general formula (2), n is 0 or 1.

[0047] A specific example of the compound represented by the general formula (2) above is one represented by the following general formula (2B): 3 , R 4 and L are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and L is an alkylene group having 1 to 10 carbon atoms which may have a branch. These are the same as those in the general formula (2) above.

[0048] [ka]

[0049] More specifically, the compound (B) can be represented by the following chemical formula (2C): It goes without saying that the compound (B) in the present invention is not limited to this.

[0050] [ka]

[0051] The content of the photopolymerization initiator in the varnish composition of the present invention is preferably 2 to 30% by mass, more preferably 2 to 15% by mass, and even more preferably 2 to 13% by mass, based on the total mass of the varnish composition. Having the content of the photopolymerization initiator in the varnish composition within the above range is preferable because it allows the varnish composition to achieve both sufficient curability, good internal curability, and cost-effectiveness.

[0052] [monomer] The varnish composition of the present invention contains, as a monomer, a compound having two or more ethylenically unsaturated bonds. The varnish composition of the present invention also contains, as these monomers, a monomer A having four or more ethylenically unsaturated bonds and a monomer B having an alkylene oxide-modified bisphenol A skeleton or an alkylene oxide-modified hydrogenated bisphenol A skeleton and having two ethylenically unsaturated bonds, and is further characterized in that, based on the total amount of monomer A contained in the varnish composition, the proportion of monomer A is 10 to 55 mass % and the proportion of monomer B is 10 to 46 mass %. These details are explained below.

[0053] Compounds with ethylenically unsaturated bonds are components that polymerize to a high molecular weight through radicals generated by a photopolymerization initiator, and a variety of compounds are commercially available, ranging from low-molecular-weight compounds to those called oligomers, which have relatively high molecular weights. Furthermore, various ethylenically unsaturated bond-containing polymers with even higher molecular weights than oligomers are also commercially available. As described above, the varnish composition of the present invention contains a monomer that is a compound with two or more ethylenically unsaturated bonds. However, even compounds with molecular weights comparable to those generally referred to as oligomers and polymers can be treated as monomers in the present invention as long as they have two or more ethylenically unsaturated bonds.

[0054] Monomers are components that have two or more ethylenically unsaturated bonds and polymerize to a high molecular weight as described above, but before polymerization they are often liquid components with relatively low molecular weight. In the present invention, such relatively low molecular weight monomers can be used as solvents when dissolving resin components to form a varnish, or for the purpose of adjusting the viscosity of the varnish composition.

[0055] Examples of such monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, pentyl glycol di(meth)acrylate, neopentyl glycol di (Meth)acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate , 1,9-nonanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate, 2 -Methyl-2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethylol octane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate,2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate acrylate, 1,9-nonanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate Acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethylol octane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate Acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tricyclodecanedimethylol dicaprolactonate di(meth)acrylate, bisphenol A 1-30 alkylene oxide adduct di(meth)acrylate, bisphenol F 1-30 alkylene oxide adduct di(meth)acrylate, bisphenol S 1-30 alkylene oxide adduct di(meth)acrylate,Bifunctional monomers such as hydrogenated bisphenol A 1-30 alkylene oxide adduct di(meth)acrylate, hydrogenated bisphenol F 1-30 alkylene oxide adduct di(meth)acrylate, bisphenol A 1-30 alkylene oxide adduct dicaprolactonate di(meth)acrylate, and bisphenol F 1-30 alkylene oxide adduct dicaprolactonate di(meth)acrylate; trifunctional monomers such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tricaprolactonate tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolhexane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Examples of the monomer include tetrafunctional or higher monomers such as dipentaerythritol tetracaprolactonate tetra(meth)acrylate, diglycerin tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetracaprolactonate tetra(meth)acrylate, ditrimethylolethane tetra(meth)acrylate, ditrimethylolbutane tetra(meth)acrylate, ditrimethylolhexane tetra(meth)acrylate, ditrimethyloloctane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and tripentaerythritol polyalkylene oxide hepta(meth)acrylate. Furthermore, one type of monomer is epoxy (meth)acrylate, which is obtained by (meth)acrylic-modifying an epoxy compound. This is a compound in which (meth)acrylic acid is added to the epoxy group of an epoxy compound such as an epoxy resin by ring-opening addition. In this specification, "(meth)acrylate" means "acrylate and / or methacrylate","(Meth)acrylic acid" means "acrylic acid and / or methacrylic acid."

[0056] In the above examples, the term "bisphenol A 1-30 alkylene oxide adduct di(meth)acrylate" means "bisphenol A di(meth)acrylate modified by the addition of 1 to 30 alkylene oxide units." This also applies to the alkylene oxide adduct di(meth)acrylates of bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S.

[0057] Oligomers having two or more ethylenically unsaturated bonds that can be used as monomers in the present invention are components that polymerize to high molecular weight as described above, but because they are originally relatively high molecular weight components, they are also used to impart appropriate viscosity and elasticity to varnish compositions. Examples of such oligomers include epoxy-modified (meth)acrylates, such as esters of (meth)acrylic acid with hydroxyl groups generated after ring-opening of epoxy groups contained in epoxy compounds such as epoxy resins with an acid or base; rosin-modified epoxy acrylates; polyester-modified (meth)acrylates, such as esters of (meth)acrylic acid with terminal hydroxyl groups of condensation polymers of dibasic acids and diols; polyether-modified (meth)acrylates, such as esters of (meth)acrylic acid with terminal hydroxyl groups of polyether compounds; and urethane-modified (meth)acrylates, such as esters of (meth)acrylic acid with terminal hydroxyl groups of condensation polymers of polyisocyanate compounds and polyol compounds. Such oligomers are commercially available and can be obtained under trade names such as the Ebecryl series manufactured by Daicel-Cytec Co., Ltd., the CN and SR series manufactured by Sartomer Corporation, the Aronix M-6000 series, 7000 series, 8000 series, Aronix M-1100, Aronix M-1200, and Aronix M-1600 manufactured by Toagosei Co., Ltd., and NK Oligo manufactured by Shin-Nakamura Chemical Co., Ltd.

[0058] Polymers having two or more ethylenically unsaturated bonds that can be used as monomers in the present invention have a large molecular weight even before irradiation with active energy rays, and are therefore useful components for improving the viscoelasticity of varnish compositions. Such polymers are used, for example, in a dissolved or dispersed state in a low-viscosity liquid monomer. Examples of polymers having ethylenically unsaturated bonds include acrylic resins and acrylic-modified phenolic resins that have unreacted unsaturated groups.

[0059] The above-mentioned monomers can be used alone or in combination of two or more.

[0060] The varnish composition of the present invention contains, among these monomers, monomer A having four or more ethylenically unsaturated bonds and monomer B having an alkylene oxide-modified bisphenol A skeleton or an alkylene oxide-modified hydrogenated bisphenol A skeleton and two ethylenically unsaturated bonds. By including monomer A, the varnish composition of the present invention is able to exhibit good curability, and by including monomer B, the abrasion resistance and flexibility of the varnish film formed from the varnish composition can be improved.

[0061] Examples of monomer A include those exemplified above as "tetrafunctional or higher functional monomers." Among these, preferred examples include ditrimethylol octane tetra(meth)acrylate and dipentaerythritol penta(meth)acrylate. Even monomers not included in the above examples can be used as monomer A as long as they contain four or more ethylenically unsaturated bonds. The proportion of monomer A relative to the total monomers contained in the varnish composition is 10 to 55% by mass. By ensuring that the proportion of monomer A relative to the total monomers contained in the varnish composition is 10% by mass or more, good curability of the varnish composition is ensured. Furthermore, by ensuring that the proportion of monomer A relative to the total monomers contained in the varnish composition is 55% by mass or less, flexibility of the varnish film formed from the varnish composition is ensured. This proportion is preferably 20 to 55% by mass, more preferably 25 to 55% by mass, and even more preferably 30 to 55% by mass.

[0062] Among the various monomers exemplified above, examples of monomer B include bisphenol A1-30 alkylene oxide adduct di(meth)acrylate and hydrogenated bisphenol A1-30 alkylene oxide adduct di(meth)acrylate, but any compound having a bisphenol A skeleton or a hydrogenated bisphenol A skeleton and two ethylenically unsaturated bonds and modified by the addition of alkylene oxide may be used. Among such compounds, preferred are those having 3 to 30 alkylene oxide additions, more preferred are those having 4 to 30 alkylene oxide additions, and even more preferred are those having 4 to 20 alkylene oxide additions. Furthermore, a preferred example of the alkylene oxide added is ethylene oxide. The proportion of monomer B relative to all monomers contained in the varnish composition is 10 to 46% by mass. By ensuring that the proportion of monomer B relative to all monomers contained in the varnish composition is 10% by mass or more, the abrasion resistance of the varnish composition is improved and the flexibility of the varnish film formed from the varnish composition can be ensured. Furthermore, by ensuring that the proportion of monomer B relative to all the monomers contained in the varnish composition is 46 mass % or less, good curability of the varnish composition is ensured.

[0063] The content of the monomer in the varnish composition of the present invention is preferably 10 to 90 mass % of the total varnish composition, more preferably 20 to 90 mass %, even more preferably 40 to 90 mass %, and particularly preferably 50 to 90 mass %. By keeping the content of the monomer within the above range, the varnish composition can have good curability and a strong varnish film can be obtained.

[0064] Furthermore, in addition to the above-mentioned monomer, which is a compound having two or more ethylenically unsaturated bonds, a compound having one ethylenically unsaturated bond may be added to the varnish composition of the present invention. Examples of such compounds include alkyl acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, and dodecyl (meth)acrylate, (meth)acrylic acid, (meth)acrylates of ethylene oxide adducts, (meth)acrylates of propylene oxide adducts, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecane monomethylol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-hydroxy-3-butoxypropyl (meth)acrylate. Examples of the acrylate include 2-hydroxy-3-methoxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, β-carboxyethyl (meth)acrylate, (meth)acrylic acid dimer, ω-carboxypolycaprolactone mono(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-vinylpyrrolidone, N-vinylformamide, and (meth)acryloylmorpholine. These may be used alone or in combination of two or more.

[0065] [resin] The varnish composition of the present invention preferably further contains a resin component. The resin component contributes to imparting suitable properties such as coatability and viscoelasticity to the varnish composition. Examples of such resin components include various resins that have traditionally been used in printing varnish compositions, but those that are compatible with the above-mentioned monomers are preferred. Examples include rosin-modified alkyd resins, diallyl phthalate resins, diallyl cycloalkane dicarboxylate resins, styrene-acrylic resins, acrylic resins, alkyd resins, rosin-modified phenolic resins, rosin-modified maleic acid resins, rosin-modified petroleum resins, rosin ester resins, petroleum resin-modified phenolic resins, vegetable oil-modified alkyd resins, and petroleum resins. Among these resins, diallyl phthalate resins, diallyl cycloalkane dicarboxylate resins, and resins with an sp value of 9.0 to 11.0 (cal / cm) are preferred. 3 ) 1 / 2 At least one selected from the group consisting of rosin-modified alkyd resins represented by the formula (I) and (II), can be preferably mentioned.

[0066] Diallyl phthalate resin is a polymer of diallyl phthalate (i.e., polydiallyl phthalate). Examples of diallyl phthalate resins include polymers of diallyl phthalate and diallyl isophthalate, and various types are commercially available, so such commercially available products can be obtained and used.

[0067] Diallylcycloalkanedicarboxylate resins are a type of so-called non-phthalate allyl resin, and consist of polymers (i.e., polydiallylcycloalkanedicarboxylate) obtained by polymerization using hydrogenated diallyl phthalate or hydrogenated diallyl isophthalate as a monomer. As diallylcycloalkanedicarboxylate resins, polydiallyl-1,2-cyclohexanedicarboxylate, polydiallyl-1,3-cyclohexanedicarboxylate, and the like are commercially available, and such commercially available products can be obtained and used.

[0068] SP value is 9.0 to 11.0 (cal / cm 3 )1 / 2 The rosin-modified alkyd resin is a condensation polymer of an acid component including a resin acid, a fatty acid, and a polybasic acid, and a polyhydric alcohol, and has a solubility parameter sp value of 9.0 (cal / cm) as determined by turbidity point titration. 3 ) 1 / 2 More than 11.0(cal / cm 3 ) 1 / 2 The solubility parameter sp value determined by turbidity point titration is a value calculated according to the KWSUH and JMCORBETT formula, and J. Appl. Polym. Sci. 1968, 12, 2359 can be referenced for calculating the sp value using this method. The reason why rosin-modified alkyd resins having such an sp value range are preferred is based on the findings of the present inventors that they have good compatibility with the monomers contained in the varnish composition and can result in a varnish composition with excellent stability over time.

[0069] The resin content in the varnish composition of the present invention is preferably from 1 to 20% by mass, and more preferably from 3 to 10% by mass.

[0070] [Plasticizer] The varnish composition of the present invention preferably contains as a plasticizer a diester compound of a dicarboxylic acid having 20 or more carbon atoms per molecule. By including such a plasticizer in the varnish composition, the flexibility of the varnish film formed from the varnish composition can be improved. The reason for using a diester compound of a dicarboxylic acid having 20 or more carbon atoms per molecule as the plasticizer is based on the finding of the inventors that, in order to achieve particularly good flexibility in a varnish film containing the above-mentioned monomers A and B, as in the varnish composition of the present invention, it is necessary to use as the plasticizer a diester compound of a dicarboxylic acid having 20 or more carbon atoms per molecule.

[0071] Preferred examples of such plasticizers include bis(2-ethylhexyl) sebacate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) maleate, etc. The content of the plasticizer in the varnish composition of the present invention is preferably about 0.5 to 3 mass%, more preferably about 1 to 2.5 mass%, and even more preferably about 1.5 to 2 mass%.

[0072] [Other ingredients] In addition to the above components, other components may be added to the varnish composition of the present invention as needed, such as extender pigments, polymerization inhibitors, waxes, etc.

[0073] The extender pigment is a component that imparts properties such as viscoelasticity to the varnish composition, and various types of extender pigments that are commonly used in the preparation of ink and varnish compositions can be used. Examples of such extender pigments include clay, kaolinite (kaolin), barium sulfate, magnesium sulfate, calcium carbonate, silicon oxide (silica), bentonite, talc, mica, and titanium oxide. The amount of such extender pigment added is, for example, about 0 to 10% by mass of the total varnish composition, but is not particularly limited.

[0074] Preferred examples of polymerization inhibitors include phenolic compounds such as butylhydroxytoluene, tocopherol acetate, nitrosamines, benzotriazole, and hindered amines, with butylhydroxytoluene being a more preferred example. Adding such a polymerization inhibitor to the varnish composition can prevent the varnish composition from thickening due to the polymerization reaction occurring during storage. The content of the polymerization inhibitor in the varnish composition is, for example, approximately 0.01 to 1% by mass.

[0075] Examples of waxes include paraffin wax, carnauba wax, beeswax, microcrystalline wax, polyolefin waxes such as polyethylene wax, waxes such as Fischer-Tropsch wax, oxidized polyethylene wax, polytetrafluoroethylene wax, and amide wax, and fatty acids having a carbon number ranging from about C8 to C18, such as coconut oil fatty acid and soybean oil fatty acid. Examples of wax forms include powder (particle) and oil, and preferred powder waxes have an average particle diameter D50 ranging from 1 to 10 μm. The wax content of the entire varnish composition is about 0.1 to 15% by mass, and more preferably about 1 to 5 parts by mass.

[0076] <Manufacturing method for printed matter> The present invention also includes a method for producing a printed material, comprising the steps of applying the varnish composition of the present invention to a surface to be treated, which may or may not be printed with an ink composition, and curing the applied varnish composition with active energy rays. The term "surface to be treated, which may or may not be printed with an ink composition" refers to a printed surface to be printed with an ink composition or a surface of a substrate (usually paper) to which the ink composition is not printed. The surface to be treated, to which the varnish composition is applied, is referred to as the "treated surface." Note that the "printed surface" here naturally includes not only the image area to which the ink composition adheres as a result of printing, but also the non-image area to which the ink composition does not adhere. Furthermore, when applying the varnish composition of the present invention to a printed surface, the printed surface may be dried or cured after printing before the varnish composition is applied. Alternatively, in-line application may be performed, in which the varnish composition is applied wet-on-wet to the printed material immediately after printing. The surface to be treated, to which the varnish composition has been applied, is quickly irradiated with active energy rays to form a varnish film, which is a cured product of the applied varnish composition. The ink composition used in this case may be an oil-based ink composition or an active energy ray-curable ink composition.

[0077] The means for applying the varnish composition can be any known means without particular limitation, and examples of such means include the use of a coater employing a roll coater system or a chamber coater system, which is a simple method.

[0078] <Method for suppressing odor and migration caused by varnish layer> As already mentioned, a varnish film formed from the varnish composition of the present invention suppresses odor and migration from the varnish film. A method for suppressing odor and migration originating from a varnish layer by utilizing these properties also constitutes one aspect of the present invention.

[0079] The method of the present invention for suppressing odor and migration originating from a varnish layer comprises the steps of applying an actinic energy ray-curable overprint varnish composition to a surface to be treated, which may or may not be printed with an ink composition, and curing the applied actinic energy ray-curable overprint varnish composition with actinic energy rays, and is characterized by using the varnish composition of the present invention as the actinic energy ray-curable overprint varnish composition. The ink composition used in this case may be an oil-based ink composition or an actinic energy ray-curable ink composition. Furthermore, the term "a surface to be treated, which may or may not be printed with an ink composition" refers to a printed surface to be printed with an ink composition or a surface of a substrate (often paper) to which an ink composition is not printed, and the surface of such a printed surface or substrate to which the varnish composition is applied is referred to as the treated surface. Furthermore, the term "printed surface" as used herein naturally includes not only the image area to which the ink composition adheres as a result of printing, but also the non-image area to which the ink composition does not adhere. When applying the varnish composition of the present invention to a printed surface, the printed surface may be dried or cured after printing before applying the varnish composition, or in-line application may be performed in which the varnish composition is applied wet-on-wet to the printed material immediately after printing. [Example]

[0080] The present invention will be described in more detail below by showing examples, but the present invention is not limited to the following examples. In the following description, unless otherwise specified, "%" means "% by mass" and "parts" means parts by mass.

[0081] [Preparation of Varnish 1] A mixture of 20 parts by mass of polydiallyl phthalate (manufactured by Osaka Soda Co., Ltd., product name A-DAP), 79 parts by mass of ditrimethylolpropane tetraacrylate (DI-TMPTA), and 1% by mass of methylhydroquinone was heated at 100°C for 60 minutes to dissolve the mixture, thereby preparing varnish 1. The ditrimethylolpropane tetraacrylate used in preparing varnish 1 corresponds to monomer A in the present invention.

[0082] [Preparation of Varnish 2] A mixture of 20 parts by mass of polydiallyl isophthalate (manufactured by Osaka Soda Co., Ltd., product name ISO-DAP), 79 parts by mass of ditrimethylolpropane tetraacrylate (DI-TMPTA), and 1% by mass of methylhydroquinone was heated at 100°C for 60 minutes to dissolve, thereby preparing varnish 2. The ditrimethylolpropane tetraacrylate used in preparing varnish 2 corresponds to monomer A in the present invention.

[0083] [Preparation of Varnish 3] A mixture of 20 parts by mass of polydiallyl-1,2-cyclohexanedicarboxylate (manufactured by Osaka Soda Co., Ltd., product name RADPAR), 79 parts by mass of ditrimethylolpropane tetraacrylate (DI-TMPTA), and 1% by mass of methylhydroquinone was heated at 100°C for 60 minutes to dissolve the mixture, thereby preparing varnish 3. The ditrimethylolpropane tetraacrylate used in preparing varnish 3 corresponds to monomer A in the present invention.

[0084] [Preparation of Overprint Varnish Composition] The materials were mixed according to the formulations shown in Tables 1 to 3, and then milled in a three-roll mill to prepare overprint varnish compositions for Examples 1 to 16 and Comparative Examples 1 to 6. In Tables 1 to 3, the details of each material are shown below, and the amounts of each material are in parts by mass. In addition, for each material shown below, "Monomer 1" and "Monomer 2" correspond to Monomer A in the present invention, and "Monomer 3" to "Monomer 6" correspond to Monomer B in the present invention. In Tables 1 to 3, the values ​​shown in the "Monomer A" and "Monomer B" columns represent the proportion (% by mass) of Monomer A or Monomer B relative to the total monomers contained in each varnish composition.

[0085] Extender pigment 1: Calcium carbonate (Shiraishi Kogyo Co., Ltd., product name: Hakuenka T-CC) Extender pigment 2: Barrets Minerals, product name: Talcron MP12-50 Polymerization inhibitor: DKSH Japan, product name LUNACURE 500 Photopolymerization initiator 1: 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (compound represented by the above chemical formula (1D-1)) Photopolymerization initiator 2: 1-(9,9-dibutyl-9H-fluoren-2-yl)-2-methyl-2-morpholin-4-yl-propan-1-one (compound represented by the above chemical formula (2C)) Photopolymerization initiator 3: 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)phenyl)-2-methylpropan-1-one (compound represented by the above chemical formula (1D-2)) Photopolymerization initiator 4: BASF, product name Irgacure 184 Photopolymerization initiator 5: IGM Resins, product name Omnirad369 Photopolymerization initiator 6: BASF, product name Irgacure 907 Monomer 1: ditrimethylolpropane tetraacrylate (corresponding to Monomer A in the present invention) Monomer 2: Dipentaerythritol hexaacrylate (corresponding to Monomer A in the present invention) Monomer 3: ethylene oxide (EO)-modified (4 mol) bisphenol A diacrylate (manufactured by MIWON Corporation, product name M240; corresponds to Monomer B in the present invention) Monomer 4: ethylene oxide (EO)-modified (10 mol) bisphenol A diacrylate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name New Frontier BPE-10; corresponds to Monomer B in the present invention.) Monomer 5: ethylene oxide (EO)-modified (20 mol) bisphenol A diacrylate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name New Frontier BPE-20; corresponds to Monomer B in the present invention.) Monomer 6: ethylene oxide (EO)-modified (4 mol) hydrogenated bisphenol A diacrylate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name New Frontier HBPE-4; corresponds to Monomer B in the present invention.) Monomer 7: Difunctional bisphenol A epoxy acrylate (MIWON, product name Miramer PE210) Monomer 8: Trimethylolpropane triacrylate Monomer 9: 1,6-hexanediol diacrylate Plasticizer 1: Bis(2-ethylhexyl) sebacate Plasticizer 2: Bis(2-ethylhexyl) adipate Surface conditioner: Morimura Chemical Co., Ltd., product name MC-990 Compound Wax: Polyethylene wax (Morimura Chemical Co., Ltd., product name MC-50UV Compound)

[0086] Test pieces were prepared for each of the overprint varnish compositions of the Examples and Comparative Examples by the following procedure: First, using an RI color spreader (two-split roll, manufactured by Akira Seisakusho), 0.1 cc of an ink composition (manufactured by Sakata Inx Corporation, product name Diatone Dream Cure BM KT Red) was spread onto coated paper (manufactured by Nippon Paper Industries Co., Ltd., product name Aurora Coat), and then 0.15 cc of each overprint varnish composition to be tested was spread onto the paper, followed immediately by ultraviolet irradiation (metal halide lamp, irradiation dose: 36 mJ / cm). 2) to cure each overprint varnish composition, and this was used as a test specimen.

[0087] [Friction resistance evaluation] The surface of each test piece was rubbed 500 times with a Gakushin-type rub fastness tester (load 500 g, backing paper: wood-free paper). The condition of the printed surface after rubbing was visually observed and evaluated. The evaluation criteria were as follows, and the results are shown in the "Rubbing Resistance" column in Tables 1 to 3. ○: No scratches at all on the printed surface, or slight scratches that do not cause any practical problems are observed △: Visible scratches are observed on the printed surface ×: Peeling of the film is observed on the printed surface

[0088] [Scratch resistance evaluation] The surface of each test piece was scratched with the tip of a fingernail, and the state of peeling of the coating was visually observed and evaluated. The evaluation criteria were as follows, and the results are shown in the "Scratch Resistance" column in Tables 1 to 3. ○: No dropouts observed △: Falling off is observed, but the base material is not visible ×: Falling off is observed and the substrate is exposed

[0089] [Gloss rating] The 60° reflected gloss value of each test piece was measured using a Murakami digital gloss meter (manufactured by Murakami Color Research Laboratory Co., Ltd., light source: halogen lamp (12V, 50W)). The results are shown in the "Gloss" column of Tables 1 to 3.

[0090] [Migration Assessment] Modified polyphenylene oxide (MPPO; 60-80 mesh, product name: Tenax) was washed for 6 hours using a Soxhlet extractor with acetone as the solvent, then spread on a petri dish to evaporate the solvent, and then dried in an oven at 160°C for 6 hours. Next, for each of the Examples and Comparative Examples, the mass of the overprint varnish composition after curing was measured to determine whether it was 1-2 g / m. 2After the overprint varnish composition on the paper surface has hardened, the surface of the overprint varnish is coated with 20 or more sheets of paper (0.02 kg / cm 2 ) and covered with aluminum foil, and stored at 25°C for 10 days. After that, the surface of the painted paper was placed in a circular shape with a diameter of 112 mm (area of ​​1 dm 2 ) was cut out and used as a sample.

[0091] 4 g of MPPO was weighed out and placed in a petri dish. The sample was placed on top of the MPPO with the paint side facing up, and the petri dish was then covered. The petri dish was then inverted and placed in an incubator heated to 60°C along with a blank sample (a petri dish containing only 4 g of MPPO) and left for 10 days. The petri dish was then removed, the lid was removed, and the sample was allowed to cool to room temperature.

[0092] The MPPO in the Petri dish was transferred to an Erlenmeyer flask, and 20 mL of acetone was poured in. The mixture was shaken for 1 minute, then allowed to stand for 5 minutes. The acetone was then transferred to a 50 mL volumetric flask while filtering. This procedure was repeated, and the 50 mL volumetric flask was then filled up to the desired volume. The components (migration components) derived from the overprint varnish composition contained in the resulting solution were qualitatively and quantitatively analyzed by GC-MS and evaluated. The evaluation criteria were as follows, and the results are shown in the "Migration" column in Tables 1 to 3. ○: The amount of migration component is 5 mg / dm 2 is less than △: The amount of migration component is 5 mg / dm 2 More than 7mg / dm 2 is less than ×: The amount of migration component is 7 mg / dm 2 That's all

[0093] [Odor evaluation] The odor of the cured product of each of the overprint varnish compositions of the Examples and Comparative Examples was evaluated according to the following procedure: First, 0.0875 cc of the overprint varnish composition was sampled and spread on coated cardboard (Oji Materia Co., Ltd., product name UF Coat) using an RI spreader (two-split roll, manufactured by Akira Seisakusho), and immediately irradiated with ultraviolet light (metal halide lamp, irradiation dose: 36 mJ / cm). 2 ) to cure the applied overprint varnish composition, and prepare an evaluation piece. 0.5 g of this evaluation piece was heated at 120°C for 40 minutes using a headspace sampler, and the vaporized components were analyzed by GC-MS. The odorous components were assumed to be aldehyde substances, and were evaluated by examining their detected peak areas. The evaluation criteria were as follows, and the results are shown in the "Odor" columns of Tables 1 to 3. ◎: The peak area of ​​the aldehyde component is less than 500,000 ○: The peak area of ​​the aldehyde component is 500,000 or more and less than 1,000,000 △: The peak area of ​​the aldehyde component is 1 million or more and less than 1.5 million ×: The peak area of ​​the aldehyde component is 1.5 million or more

[0094] [Table 1]

[0095] [Table 2]

[0096] [Table 3]

[0097] As shown in Tables 1 to 3, the varnish compositions of Examples 1 to 16, which are varnish compositions of the present invention, had little odor and migration, and also had good results in both rub resistance and scratch resistance. On the other hand, the varnish compositions of Comparative Examples 1 to 3 had poor odor and migration, and the varnish compositions of Comparative Examples 4 to 6 had inferior rub resistance and / or scratch resistance to the Examples.

Claims

1. An active energy ray-curable overprint varnish composition comprising a monomer that is a compound having two or more ethylenically unsaturated bonds and a photopolymerization initiator, The monomers include a monomer A having four or more ethylenically unsaturated bonds and a monomer B having an alkylene oxide-modified bisphenol A skeleton or an alkylene oxide-modified hydrogenated bisphenol A skeleton and having two ethylenically unsaturated bonds, the photopolymerization initiator is at least one compound selected from the group consisting of (A) a compound having a diphenylmethane skeleton, (B) a compound having a morpholine skeleton and a fluorene skeleton, and (C) a compound having a diphenyl ether skeleton; An active energy ray-curable overprint varnish composition, characterized in that the proportion of the monomer A is 10 to 55 mass % and the proportion of the monomer B is 10 to 46 mass % relative to the total amount of the monomers.

2. 2. The active energy ray-curable overprint varnish composition according to claim 1, wherein the number of alkylene oxides added to said monomer B is 3 to 30.

3. 2. The active energy ray-curable overprint varnish composition according to claim 1, wherein the alkylene oxide in the monomer B is ethylene oxide.

4. 2. The active energy ray-curable overprint varnish composition according to claim 1, further comprising a diester compound of a dicarboxylic acid as a plasticizer, the compound having 20 or more carbon atoms per molecule.

5. 5. The active energy ray-curable overprint varnish composition according to claim 4, wherein the diester compound of a dicarboxylic acid is bis(2-ethylhexyl) sebacate or bis(2-ethylhexyl) adipate.

6. The resin component further contains a diallyl phthalate resin, a diallyl cycloalkane dicarboxylate resin, and a resin having an sp value of 9.0 to 11.0 (cal / cm ３ ) １／２ 2. The active energy ray-curable overprint varnish composition according to claim 1, wherein the resin is at least one selected from the group consisting of rosin-modified alkyd resins represented by the formula:

7. 2. The active energy ray-curable overprint varnish composition according to claim 1, wherein (A) the compound having a phenylmethane skeleton and (C) the compound having a diphenyl ether skeleton are compounds represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), R １ and R ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, the substituent being a hydroxyl group, an amino group or a halogen atom, and X is a methylene group or an oxygen atom.

8. The compound according to claim 7, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1C-1) or (1C-2): 【Chemistry 2】 (In general formula (1C-1), L １ and L ２ are each independently an alkylene group having 1 to 10 carbon atoms which may have a branch. 【Transformation 3】 (In general formula (1C-2), L １ and L ２ are each independently an alkylene group having 1 to 10 carbon atoms which may have a branch.

9. 2. The active energy ray-curable overprint varnish composition according to claim 1, wherein the compound (B) having a morpholine skeleton and a fluorene skeleton is a compound represented by the following general formula (2): 【Chemistry 4】 (In general formula (2), R ３ and R ４ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and the substituent is a hydroxyl group, an amino group, or a halogen atom; each L is independently a divalent organic group; and n is 0 or 1.

10. 10. The active energy ray-curable overprint varnish composition according to claim 9, wherein the compound represented by general formula (2) is a compound represented by the following general formula (2B): 【Transformation 5】 (In general formula (2B), R ３ and R ４ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and the substituent is a hydroxyl group, an amino group, or a halogen atom, and L is an alkylene group having 1 to 10 carbon atoms which may have a branch.

11. 2. The active energy ray-curable overprint varnish composition according to claim 1, wherein the photopolymerization initiator is at least one compound selected from the group of compounds represented by the following three chemical formulas: 【Transformation 6】

12. A method for producing a printed matter, comprising the steps of applying an active energy ray-curable overprint varnish composition according to any one of claims 1 to 11 to a surface to be treated, which may or may not be printed with an ink composition, and curing the applied active energy ray-curable overprint varnish composition with active energy rays.

13. A method for suppressing odors and migration originating from a varnish layer formed on the surface of a produced printed matter, comprising the steps of applying an active energy ray-curable overprint varnish composition to a surface to be treated that may or may not be printed with an ink composition, and curing the applied active energy ray-curable overprint varnish composition with active energy rays, characterized in that the active energy ray-curable overprint varnish composition is one described in any one of claims 1 to 11.

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