Varnish composition for active energy ray-curable printing ink, active energy ray-curable printing ink, and printed matter

Abstract

To provide a varnish composition for active energy ray-curable print ink, an active energy ray-curable print ink, and printed matter.SOLUTION: A varnish composition for active energy ray-curable print ink contains a rosin epoxy (meth)acrylate (A) of 0.1-30 mass%, a poly(meth)acrylate (B) and a polymer (C).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to an active energy ray-curable varnish composition for printing ink, an active energy ray-curable printing ink, and a printed matter. [Background technology]

[0002] The active energy ray curable printing ink is an ink that is cured by active energy rays such as ultraviolet rays and electron beams. The active energy ray curable printing ink may contain a reactive diluent and a resin. As the reactive diluent, polyfunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate are widely used because of their excellent curability and film hardness. In addition, as the resin, styrene acrylic resins, polyester resins, etc. are widely used because of their printability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5683757 Summary of the Invention [Problem to be solved by the invention]

[0004] However, conventional active energy ray-curable printing inks had problems with fluidity, emulsification suitability, misting resistance, and adhesion. In addition, from the perspective of carbon neutrality, there is a demand to actively use plant-derived raw materials in various industrial products.

[0005] The problem to be solved by the present invention is to provide a varnish composition for an active energy ray-curable printing ink, which is a raw material for the active energy ray-curable printing ink having good fluidity, emulsification suitability, misting resistance and adhesion, and which uses raw materials derived from plants. [Means for solving the problem]

[0006] As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by including a certain amount of rosin epoxy (meth)acrylate made from rosin, a plant-derived raw material, in an active energy ray-curable varnish composition for printing ink.

[0007] The present disclosure provides the following: (Item 1) An active energy ray-curable varnish composition for printing ink, comprising 0.1 to 30 mass % of a rosin epoxy (meth)acrylate (A), a poly(meth)acrylate (B) and a polymer (C). (Item 2) The varnish composition for active energy ray-curable printing ink according to the above item, which is for use in an active energy ray-curable lithographic printing ink. (Item 3) An active energy ray-curable printing ink comprising the active energy ray-curable printing ink varnish composition according to any one of the above items and a pigment. (Item 4) A printed matter having a cured layer of the active energy ray-curable printing ink described in the above item.

[0008] In the present disclosure, one or more of the above-described features may be provided in further combinations in addition to the combinations explicitly stated. Effect of the Invention

[0009] By using the active energy ray-curable printing ink varnish composition of the present invention, it is possible to obtain an active energy ray-curable printing ink having excellent drying properties, fluidity, emulsification suitability, misting resistance, and adhesion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Throughout this disclosure, the range of the values ​​of the physical properties, contents, etc. may be set as appropriate (for example, by selecting from the upper and lower limit values ​​described in each item below). Specifically, when A1, A2, A3, A4 (where A1>A2>A3>A4) are exemplified as the upper and lower limits of the value α, the range of the value α is exemplified as A1 or less, A2 or less, A3 or less, A2 or more, A3 or more, A4 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, A3 to A4, etc.

[0011] [Active energy ray-curable printing ink varnish composition: also referred to as composition] The present disclosure provides an active energy ray-curable varnish composition for printing ink, comprising 0.1 to 30 mass % of a rosin epoxy (meth)acrylate (A), a poly(meth)acrylate (B) and a polymer (C).

[0012] <Rosin epoxy (meth)acrylate (A): Also called component (A).> In the present disclosure, rosin epoxy (meth)acrylate means a reaction product of rosin epoxide and (meth)acrylic acid. The component (A) may be used alone or in combination of two or more kinds.

[0013] In the present disclosure, (meth)acrylate means "at least one selected from the group consisting of acrylate and methacrylate". Similarly, (meth)acrylic means "at least one selected from the group consisting of acrylic and methacrylic". In addition, (meth)acryloyl means "at least one selected from the group consisting of acryloyl and methacryloyl".

[0014] In the present disclosure, rosin epoxide means a compound having a rosin skeleton and an epoxy group. The rosin epoxide is, for example, a reaction product of rosin or a rosin derivative with epihalohydrin. The rosin, the rosin derivative, and the epihalohydrin may each be used alone or in combination of two or more kinds.

[0015] Examples of rosin include gum rosin, tall oil rosin, and wood rosin.

[0016] Generally, rosin is an amber-colored, amorphous resin obtained from pine trees, and since it is obtained from natural sources, it is a mixture. The pine species from which rosin is obtained is not particularly limited, and examples include Merkusian pine, slash pine (swamp pine), and Masson pine. The origin of the raw rosin is also not particularly limited, and examples include China, Vietnam, Indonesia, and Brazil.

[0017] Rosin can be isolated into its constituent components, called diterpene resin acids. In this disclosure, each diterpene resin acid isolated from rosin is also defined as rosin.

[0018] Examples of diterpene resin acids include abietane type diterpene resin acids, pimarane type diterpene resin acids, dehydro type diterpene resin acids, labdane type diterpene resin acids, and the like.

[0019] Examples of the abietane diterpene resin acid include abietic acid, neoabietic acid, parasthric acid, and lepopimaric acid.

[0020] Examples of pimarane-type diterpene resin acids include pimaric acid, isopimaric acid, sandaracopimaric acid, and the like.

[0021] An example of the dehydro diterpene resin acid is dehydroabietic acid.

[0022] Examples of labdane-type diterpene resin acids include communic acid and dihydroagatic acid.

[0023] In the present disclosure, a rosin derivative refers to a modified product of the above-mentioned rosin.

[0024] Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, cycloaddition rosin, and polymerized rosin.

[0025] In this disclosure, hydrogenated rosin means rosin that has been subjected to a hydrogenation reaction.

[0026] In this disclosure, disproportionated rosin refers to rosin that has been subjected to a disproportionation reaction, in which two molecules of rosin react to modify two molecules of abietic acid having conjugated double bonds, one of which becomes an aromatic and the other a molecule with a single double bond.

[0027] In the present disclosure, cycloaddition rosin refers to rosin that has been subjected to a Diels-Alder reaction. Examples of cycloaddition rosin include maleated rosin, fumarized rosin, and acrylated rosin.

[0028] In this disclosure, polymerized rosin means rosin that has been subjected to a dimerization reaction.

[0029] In one embodiment, the rosin epoxy (meth)acrylate is represented by the following formula (1): [ka] [In the formula, R aa is the rosin residue, and R ab is an alkylene group, R ac and R ad are each independently a hydrogen atom or an alkyl group; R ae is a hydrogen atom or a methyl group.

[0030] In the present disclosure, the rosin residue is represented by the formula (1), R aa and R ab It means a group obtained by removing a carboxyl group from rosin or a rosin derivative, which is used to form an ester bond between

[0031] The rosin residue is [ka] (In the formula, [ka] represents a single bond or a double bond) etc. are examples.

[0032] In one embodiment, the rosin residue is [ka] is preferred.

[0033] The alkyl group is -C n H 2n+1 (n is an integer of 1 or more). Examples of the alkyl group include a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group.

[0034] Examples of the straight-chain alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decamethyl group.

[0035] A branched alkyl group is a group in which at least one hydrogen atom of a linear alkyl group is replaced with an alkyl group. Examples of branched alkyl groups include a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, and a trimethylhexyl group (a trimethylhexamethyl group).

[0036] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, and a condensed ring cycloalkyl group.

[0037] In the present disclosure, a monocyclic ring refers to a ring structure formed by a carbon covalent bond and having no internal bridge structure. A fused ring refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., each ring shares only one side (fused) with each other). A bridged ring refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0038] Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, and a 3,5,5-trimethylcyclohexyl group.

[0039] Examples of the bridged ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, and a norbornyl group.

[0040] The condensed ring cycloalkyl group is exemplified by a bicyclodecyl group.

[0041] Examples of the alkylene group include a straight-chain alkylene group, a branched alkylene group, and a cycloalkylene group.

[0042] A straight chain alkylene group is -(CH2) n -(n is an integer of 1 or more). Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decamethylene group.

[0043] A branched alkylene group is a linear alkylene group in which at least one hydrogen atom is substituted with an alkyl group. Examples of branched alkylene groups include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group (trimethylhexamethylene group).

[0044] Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, and a condensed ring cycloalkylene group.

[0045] Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, and a 3,5,5-trimethylcyclohexylene group.

[0046] Examples of the bridged ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

[0047] The condensed ring cycloalkylene group is exemplified by a bicyclodecylene group.

[0048] The upper and lower limits of the content of the (A) component in 100% by mass of the composition are 30, 29.99, 29.9, 25, 20, 15, 10, 9, 6, 5, 3, 2, 1, 0.9, 0.7, 0.5, 0.3, 0.2, 0.1% by mass, etc. In one embodiment, the content of the (A) component in 100% by mass of the composition is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass. The content of the (A) component can also be set by combining the upper limit of less than 30% by mass with the above-mentioned lower limit.

[0049] <Poly(meth)acrylate (B): Also called component (B).> In the present disclosure, poly(meth)acrylate means a compound having two or more (meth)acryloyl groups. The component (B) may be used alone or in combination of two or more kinds.

[0050] Examples of component (B) include (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate, bisphenol A di(alkylene oxide-modified or epoxy-modified) (meth)acrylate, and the like.

[0051] <(Poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate> (Poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (A') or the like. [ka] [In the formula, n is an integer of 0 to 2, and R b1’ ~R b6 ’ each independently represents a hydrogen atom, [ka] In the formula, each q is independently an integer of 0 to 16; 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b4’ , and R b5’ may be different groups for each structural unit, Formula (A ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains two or more.

[0052] In the present disclosure, the phrase "the groups may be different for each structural unit" means, for example, when n is 2 in formula (A'), [ka] R b4A and R b4B may be a group different from R b5A and R b5B This means that the group may be different from the group.

[0053] In the present disclosure, "(poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of pentaerythritol poly(meth)acrylate, pentaerythritol polyalkylene oxide-modified (meth)acrylate, pentaerythritol polyepoxy-modified (meth)acrylate, polypentaerythritol poly(meth)acrylate, polypentaerythritol polyalkylene oxide-modified (meth)acrylate, and polypentaerythritol polyepoxy-modified (meth)acrylate."

[0054] Examples of pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0055] Examples of pentaerythritol polyalkylene oxide-modified (meth)acrylates include pentaerythritol di(ethylene oxide-modified (meth)acrylate), pentaerythritol tri(ethylene oxide-modified (meth)acrylate), pentaerythritol tetra(ethylene oxide-modified (meth)acrylate), pentaerythritol di(propylene oxide-modified (meth)acrylate), pentaerythritol tri(propylene oxide-modified (meth)acrylate), and pentaerythritol tetra(propylene oxide-modified (meth)acrylate).

[0056] Examples of the pentaerythritol polyepoxy modified (meth)acrylate include pentaerythritol diepoxy (meth)acrylate, pentaerythritol triepoxy (meth)acrylate, and pentaerythritol tetraepoxy (meth)acrylate.

[0057] Examples of polypentaerythritol poly(meth)acrylate include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

[0058] Polypentaerythritol polyalkylene oxide modified (meth)acrylates are dipentaerythritol di(ethylene oxide modified (meth)acrylate), dipentaerythritol tri(ethylene oxide modified (meth)acrylate), dipentaerythritol tetra(ethylene oxide modified (meth)acrylate), dipentaerythritol penta(ethylene oxide modified (meth)acrylate), dipentaerythritol hexa(ethylene oxide modified (meth)acrylate), dipentaerythritol di(propylene oxide) Dipentaerythritol tri(propylene oxide modified (meth)acrylate), dipentaerythritol tetra(propylene oxide modified (meth)acrylate), dipentaerythritol penta(propylene oxide modified (meth)acrylate), dipentaerythritol hexa(propylene oxide modified (meth)acrylate), tripentaerythritol di(ethylene oxide modified (meth)acrylate), tripentaerythritol tri(ethylene oxide modified (meth)acrylate) acrylate), tripentaerythritol tetra(ethylene oxide modified (meth)acrylate), tripentaerythritol penta(ethylene oxide modified (meth)acrylate), tripentaerythritol hexa(ethylene oxide modified (meth)acrylate), tripentaerythritol hepta(ethylene oxide modified (meth)acrylate), tripentaerythritol octa(ethylene oxide modified (meth)acrylate), tripentaerythritol di(propylene oxide modified (meth)acrylate), tripe Examples of the tripentaerythritol acrylate include tripentaerythritol tri(propylene oxide modified (meth)acrylate), tripentaerythritol tetra(propylene oxide modified (meth)acrylate), tripentaerythritol penta(propylene oxide modified (meth)acrylate), tripentaerythritol hexa(propylene oxide modified (meth)acrylate), tripentaerythritol hepta(propylene oxide modified (meth)acrylate), and tripentaerythritol octa(propylene oxide modified (meth)acrylate).

[0059] Examples of polypentaerythritol polyepoxy modified (meth)acrylates include dipentaerythritol diepoxy (meth)acrylate, dipentaerythritol triepoxy (meth)acrylate, dipentaerythritol tetraepoxy (meth)acrylate, dipentaerythritol pentaepoxy (meth)acrylate, dipentaerythritol hexapoxy (meth)acrylate, tripentaerythritol diepoxy (meth)acrylate, tripentaerythritol triepoxy (meth)acrylate, tripentaerythritol tetraepoxy (meth)acrylate, tripentaerythritol pentaepoxy (meth)acrylate, tripentaerythritol hexapoxy (meth)acrylate, tripentaerythritol heptaepoxy (meth)acrylate, and tripentaerythritol octaepoxy (meth)acrylate.

[0060] <(Poly)trimethylolpropane poly(alkylene oxide modified or epoxy modified) (meth)acrylate> (Poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (B') or the like. [ka] [In the formula, m is an integer of 0 to 2, and R b7’ ~R b10 ’ each independently represents a hydrogen atom, [ka] In the formula, each q is independently an integer of 0 to 16; 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b9’ may be different groups for each structural unit, Formula (B ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains two or more.

[0061] In the present disclosure, "(poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of trimethylolpropane poly(meth)acrylate, trimethylolpropane polyalkylene oxide-modified (meth)acrylate, trimethylolpropane polyepoxy-modified (meth)acrylate, polytrimethylolpropane poly(meth)acrylate, polytrimethylolpropane polyalkylene oxide-modified (meth)acrylate, and polytrimethylolpropane polyepoxy-modified (meth)acrylate."

[0062] Examples of trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate and trimethylolpropane tri(meth)acrylate.

[0063] Examples of trimethylolpropane polyalkylene oxide-modified (meth)acrylates include trimethylolpropane di(ethylene oxide-modified (meth)acrylate), trimethylolpropane tri(ethylene oxide-modified (meth)acrylate), trimethylolpropane di(propylene oxide-modified (meth)acrylate), and trimethylolpropane tri(propylene oxide-modified (meth)acrylate).

[0064] Examples of trimethylolpropane polyepoxy modified (meth)acrylates include trimethylolpropane diepoxy (meth)acrylate and trimethylolpropane triepoxy (meth)acrylate.

[0065] Examples of polytrimethylolpropane poly(meth)acrylate include ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

[0066] Examples of polytrimethylolpropane polyalkylene oxide-modified (meth)acrylates include ditrimethylolpropane di(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tetra(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane di(propylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(propylene oxide-modified (meth)acrylate), and ditrimethylolpropane tetra(propylene oxide-modified (meth)acrylate).

[0067] Examples of polytrimethylolpropane polyepoxy modified (meth)acrylates include ditrimethylolpropane diepoxy (meth)acrylate, ditrimethylolpropane triepoxy (meth)acrylate, and ditrimethylolpropane tetraepoxy (meth)acrylate.

[0068] <(Poly)glycerin poly(alkylene oxide modified or epoxy modified) (meth)acrylate> The (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (C') or the like. [ka] [In the formula, p is an integer of 0 to 7, and R b11’ ~R b14 ’ each independently represents a hydrogen atom, [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3’are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and R b13’ may be different groups for each structural unit, Formula (C ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains two or more.

[0069] In the present disclosure, "(poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of glycerin poly(meth)acrylate, glycerin polyalkylene oxide-modified (meth)acrylate, glycerin polyepoxy-modified (meth)acrylate, polyglycerin poly(meth)acrylate, polyglycerin polyalkylene oxide-modified (meth)acrylate, and polyglycerin polyepoxy-modified (meth)acrylate."

[0070] Examples of the glycerin poly(meth)acrylate include glycerin di(meth)acrylate and glycerin tri(meth)acrylate.

[0071] Examples of the glycerin polyalkylene oxide-modified (meth)acrylate include glycerin di(ethylene oxide-modified (meth)acrylate), glycerin tri(ethylene oxide-modified (meth)acrylate), glycerin di(propylene oxide-modified (meth)acrylate), and glycerin tri(propylene oxide-modified (meth)acrylate).

[0072] Examples of the glycerin polyepoxy modified (meth)acrylate include glycerin diepoxy (meth)acrylate and glycerin triepoxy (meth)acrylate.

[0073] Examples of polyglycerol poly(meth)acrylates include diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, triglycerol di(meth)acrylate, triglycerol tri(meth)acrylate, triglycerol tetra(meth)acrylate, and triglycerol penta(meth)acrylate.

[0074] Polyglycerol polyalkylene oxide modified (meth)acrylates are diglycerol di(ethylene oxide modified (meth)acrylate), diglycerol tri(ethylene oxide modified (meth)acrylate), diglycerol tetra(ethylene oxide modified (meth)acrylate), triglycerol di(ethylene oxide modified (meth)acrylate), triglycerol tri(ethylene oxide modified (meth)acrylate), triglycerol tetra(ethylene oxide modified (meth)acrylate), triglycerol penta(ethylene oxide modified (meth)acrylate), Examples of the acrylate include diglycerin di(propylene oxide-modified (meth)acrylate), diglycerin tri(propylene oxide-modified (meth)acrylate), diglycerin tetra(propylene oxide-modified (meth)acrylate), triglycerin di(propylene oxide-modified (meth)acrylate), triglycerin tri(propylene oxide-modified (meth)acrylate), triglycerin tetra(propylene oxide-modified (meth)acrylate), and triglycerin penta(propylene oxide-modified (meth)acrylate).

[0075] Examples of polyglycerol polyepoxy modified (meth)acrylates include diglycerol diepoxy (meth)acrylate, diglycerol triepoxy (meth)acrylate, diglycerol tetraepoxy (meth)acrylate, triglycerol diepoxy (meth)acrylate, triglycerol triepoxy (meth)acrylate, triglycerol tetraepoxy (meth)acrylate, and triglycerol pentaepoxy (meth)acrylate.

[0076] <Isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate> The isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (D') or the like. [ka] [In the formula, R b15’ ~R b17 ’ each independently represents a hydrogen atom, [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. and the formula (D ’ ) in [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. Contains two or more.

[0077] In the present disclosure, "isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of isocyanurate structure-containing poly(meth)acrylate, isocyanurate structure-containing polyalkylene oxide-modified (meth)acrylate, and isocyanurate structure-containing polyepoxy-modified (meth)acrylate."

[0078] Examples of the isocyanurate structure-containing poly(meth)acrylate include isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate.

[0079] Examples of the isocyanurate structure-containing polyalkylene oxide-modified (meth)acrylate include isocyanuric acid di(ethylene oxide-modified (meth)acrylate) and isocyanuric acid tri(ethylene oxide-modified (meth)acrylate).

[0080] Examples of the isocyanurate structure-containing polyepoxy-modified (meth)acrylate include isocyanuric acid diepoxy-modified (meth)acrylate and isocyanuric acid triepoxy-modified (meth)acrylate.

[0081] <(Poly)alkylene di(alkylene oxide modified or epoxy modified)(meth)acrylate> The (poly)alkylene di(alkylene oxide-modified or epoxy-modified)(meth)acrylate is a compound represented by the formula (E') or the like. [ka] [In the formula, R b18’ ~R b19 ’ are each independently [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’may be different groups for each unit. and R b20’ is an alkylene group, and r is an integer of 1 or more.

[0082] In the present disclosure, "(poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of alkylene di(meth)acrylate, alkylene dialkylene oxide-modified (meth)acrylate, alkylene diepoxy-modified (meth)acrylate, polyalkylene di(meth)acrylate, polyalkylene dialkylene oxide-modified (meth)acrylate, and polyalkylene diepoxy-modified (meth)acrylate."

[0083] Examples of alkylene di(meth)acrylates include 1,2-ethylenediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0084] The alkylene oxide modified (meth)acrylates are 1,2-ethylenediol di(ethylene oxide modified (meth)acrylate), 1,3-propanediol di(ethylene oxide modified (meth)acrylate), 1,4-butanediol di(ethylene oxide modified (meth)acrylate), 1,5-pentanediol di(ethylene oxide modified (meth)acrylate), 1,6-hexanediol di(ethylene oxide modified (meth)acrylate), 1,7-heptanediol di(ethylene oxide modified (meth)acrylate), 1,8-octanediol di(ethylene oxide modified (meth)acrylate), 1,9-nonanediol di(ethylene oxide modified (meth)acrylate), 1,10-decanediol di(ethylene oxide modified (meth)acrylate), neopentyl glycol di(ethylene oxide modified (meth)acrylate), acrylate), 1,2-ethylenediol di(propylene oxide modified (meth)acrylate), 1,3-propanediol di(propylene oxide modified (meth)acrylate), 1,4-butanediol di(propylene oxide modified (meth)acrylate), 1,5-pentanediol di(propylene oxide modified (meth)acrylate), 1,6-hexanediol di(propylene oxide modified (meth)acrylate) Examples include 1,7-heptanediol di(propylene oxide modified (meth)acrylate), 1,8-octanediol di(propylene oxide modified (meth)acrylate), 1,9-nonanediol di(propylene oxide modified (meth)acrylate), 1,10-decanediol di(propylene oxide modified (meth)acrylate), neopentyl glycol di(propylene oxide modified (meth)acrylate), and the like.

[0085] Examples of alkylene diepoxy modified (meth)acrylates include 1,2-ethylenediol diepoxy (meth)acrylate, 1,3-propanediol diepoxy (meth)acrylate, 1,4-butanediol diepoxy (meth)acrylate, 1,5-pentanediol diepoxy (meth)acrylate, 1,6-hexanediol diepoxy (meth)acrylate, 1,7-heptanediol diepoxy (meth)acrylate, 1,8-octanediol diepoxy (meth)acrylate, 1,9-nonanediol diepoxy (meth)acrylate, 1,10-decanediol diepoxy (meth)acrylate, and neopentyl glycol diepoxy (meth)acrylate.

[0086] Examples of the polyalkylene di(meth)acrylate include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate.

[0087] Examples of polyalkylene dialkylene oxide-modified (meth)acrylates include diethylene glycol di(ethylene oxide-modified (meth)acrylate), dipropylene glycol di(ethylene oxide-modified (meth)acrylate), triethylene glycol (ethylene oxide-modified (meth)acrylate), and tripropylene glycol (ethylene oxide-modified (meth)acrylate).

[0088] Examples of polyalkylene diepoxy modified (meth)acrylates include diethylene glycol diepoxy (meth)acrylate, dipropylene glycol diepoxy (meth)acrylate, triethylene glycol diepoxy (meth)acrylate, and tripropylene glycol diepoxy (meth)acrylate.

[0089] <Bisphenol A di(alkylene oxide modified or epoxy modified)(meth)acrylate> Bisphenol A di(alkylene oxide-modified or epoxy-modified)(meth)acrylate is a compound represented by formula (F') or the like. [ka] [In the formula, R b21’ ~R b22 ’ are each independently [ka] In the formula, q is an integer of 0 to 16, and R 1’ ~R 3 ’ are each independently a hydrogen atom or an alkyl group, R 1’ may be different groups for each unit. It is.]

[0090] In the present disclosure, "bisphenol A di(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of bisphenol A di(meth)acrylate, bisphenol A dialkylene oxide-modified (meth)acrylate, and bisphenol A diepoxy-modified (meth)acrylate."

[0091] Examples of bisphenol A dialkylene oxide modified (meth)acrylate include bisphenol A di(ethylene oxide modified (meth)acrylate) and bisphenol A di(propylene oxide modified (meth)acrylate).

[0092] The upper and lower limits of the content of the (B) component in 100% by mass of the composition are, for example, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40% by mass, etc. In one embodiment, the content is preferably 40 to 90% by mass.

[0093] <Polymer (C): Also referred to as component (C)> The component (C) may be used alone or in combination of two or more types.

[0094] Examples of the component (C) include diallyl phthalate resin, styrene acrylic resin, polyester resin, and rosin alkyd resin.

[0095] Examples of the diallyl phthalate resin include diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, and diallyl terephthalate prepolymer.

[0096] Styrene-acrylic resin is a polymer containing structural units derived from styrene or a derivative thereof and structural units derived from (meth)acrylic acid or a (meth)acrylic acid ester.

[0097] Examples of the styrene derivative include α-methylstyrene and styrene having at least one alkyl group having 1 to 2 carbon atoms on the aromatic ring.

[0098] Examples of upper and lower limits for the content of structural units derived from styrene or derivatives thereof relative to 100% by mass of all structural units in the styrene-acrylic resin are 85, 80, 79, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 and 1% by mass.

[0099] Examples of upper and lower limits for the content of structural units derived from styrene or derivatives thereof relative to 100 mol % of all structural units in the styrene-acrylic resin are 85, 80, 79, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2 and 1 mol %.

[0100] Examples of the (meth)acrylic acid ester include linear (meth)acrylic acid alkyl esters, branched (meth)acrylic acid alkyl esters, cycloalkyl (meth)acrylic acid esters, and substituted alkyl (meth)acrylic esters.

[0101] Examples of (meth)acrylic acid linear alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, stearyl (meth)acrylate, and lauryl (meth)acrylate.

[0102] Examples of branched alkyl (meth)acrylates include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, iso-octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0103] Examples of the cycloalkyl (meth)acrylate include cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate.

[0104] The substituted alkyl (meth)acrylate ester is exemplified by glycidyl (meth)acrylate.

[0105] Examples of upper and lower limits for the content of structural units derived from (meth)acrylic acid or (meth)acrylic acid ester relative to 100% by mass of all structural units of the styrene-acrylic resin are 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 and 15% by mass.

[0106] Examples of upper and lower limits for the content of structural units derived from (meth)acrylic acid or (meth)acrylic acid ester relative to 100 mol% of all structural units of the styrene-acrylic resin are 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 and 15 mol%, etc.

[0107] In one embodiment, the styrene acrylic resin may be produced using a branched monomer such as that exemplified by poly(meth)acrylate (B), i.e., the styrene acrylic resin may contain constitutional units derived from the branched monomer.

[0108] Examples of upper and lower limits for the content of structural units derived from branched monomers relative to 100% by mass of all structural units in the styrene-acrylic resin are 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 and 21% by mass.

[0109] The upper and lower limits of the content of the structural units derived from branched monomers relative to 100 mol % of all structural units in the styrene-acrylic resin are, for example, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 and 21 mass %.

[0110] The styrene-acrylic resin can be modified by reacting a carboxyl group or a hydroxyl group contained in the resin with an epoxide alone, or with an epoxide and a carboxylic acid anhydride.

[0111] Two or more kinds of epoxides can be used in combination. Examples of the epoxide include aromatic epoxides that do not contain a polymerizable double bond, aromatic epoxides that contain a polymerizable double bond, and the like.

[0112] The polyester resin is exemplified by a reaction product of a polycarboxylic acid or an anhydride thereof with a polyol.

[0113] Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, trimesic acid, and cyclohexanedicarboxylic acid.

[0114] Examples of polycarboxylic acid anhydrides include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like.

[0115] The polyol is exemplified by alkylene polyol.

[0116] Examples of the alkylene polyol include linear alkylene polyols and branched alkylene polyols.

[0117] Examples of linear alkylene polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.

[0118] Examples of branched alkylene polyols include neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, 1-methylethylene glycol, 1-ethylethylene glycol, trimethylolpropane, and pentaerythritol.

[0119] Examples of the cycloalkylene polyol include monocyclic cycloalkylene polyols and bridged ring cycloalkylene polyols.

[0120] Examples of monocyclic cycloalkylene polyols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2,2'-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A).

[0121] Examples of bridged ring cycloalkylene polyols include tricyclodecane dimethanol.

[0122] Examples of rosin alkyd resins include resins which are the reaction products of hydroxyl-containing resins, which are the reaction products of rosin or rosin derivatives with polyols, and polycarboxylic acids or their anhydrides, etc. Specific examples of these resins are described in JP-A-2000-143785 and the like.

[0123] Examples of the upper and lower limits of the weight average molecular weight (Mw) of the polymer (C) include 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 15,000, 12,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, and 1,000. In one embodiment, the weight average molecular weight (Mw) is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 15,000.

[0124] The upper and lower limits of the content of the component (C) in 100% by mass of the composition are, for example, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc. In one embodiment, the content is preferably 5 to 60% by mass.

[0125] <Organic solvent (D): Also referred to as component (D)> In one embodiment, the composition may contain an organic solvent. The organic solvent may be used alone or in combination of two or more kinds. The organic solvent may be the organic solvent used in producing the components (A) to (C).

[0126] Examples of organic solvents include ketone solvents such as methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, and cyclohexanone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate; ester solvents such as ethyl acetate, butyl acetate, methyl cellosolve acetate, and cellosolve acetate; petroleum solvents such as Solvesso #100 and Solvesso #150 (all trade names, manufactured by ExxonMobil Corporation); haloalkane solvents such as chloroform; and amide solvents such as dimethylformamide.

[0127] The upper and lower limits of the content of the organic solvent in 100% by mass of the composition are, for example, 2, 1.5, 1, 0.5, 0.05, 0.01, 0% by mass, etc. In one embodiment, the content is preferably 0 to 2% by mass.

[0128] <Additives> The composition may contain, as an additive, an agent that does not fall into any of the above components (A) to (D).

[0129] Examples of the additives include a surface conditioner, an antifoaming agent, a photosensitizer, an antioxidant, a light stabilizer, and a polymerization inhibitor.

[0130] In one embodiment, the content of the additive is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of the composition. Also, for example, the content of the additive is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of any of the components (A) to (E).

[0131] The composition can be produced by dispersing and mixing the components (A) to (C), and, if necessary, the component (D) and additives, by various known means. The order of addition of each component is not particularly limited. As the dispersing and mixing means, various known devices (emulsion disperser, ultrasonic disperser, etc.) can be used.

[0132] <Relative ratio of each component> The upper and lower limits of the mass ratio of the (A) component to the (B) component in the composition [total mass of the (A) component / total mass of the (B) component] are, for example, 0.75, 0.60, 0.50, 0.40, 0.33, etc. In one embodiment, the mass ratio is preferably 0.33 to 0.75.

[0133] The upper and lower limits of the mass ratio of the (A) component to the (C) component contained in the composition [total mass of the (A) component / total mass of the (C) component] are, for example, 6, 5, 4, 3, 2, 1, 0.9, 0.5, 0.1, 0.05, 0.01, 0.005, 0.002, etc. In one embodiment, the mass ratio of the (A) component to the (C) component contained in the composition [total mass of the (A) component / total mass of the (C) component] is preferably 0.002 to 6.

[0134] The upper and lower limits of the mass ratio of the (B) component to the (C) component contained in the composition [total mass of the (B) component / total mass of the (C) component] are, for example, 18, 15, 10, 9, 5, 3, 1, 0.9, 0.7, 0.67, etc. In one embodiment, the mass ratio of the (B) component to the (C) component contained in the composition [total mass of the (B) component / total mass of the (C) component] is preferably 0.67 to 18.

[0135] The above-mentioned active energy ray-curable varnish composition for printing ink can be used as an active energy ray-curable varnish composition for lithographic printing ink, or an active energy ray-curable varnish composition for offset printing ink.

[0136] [Active energy ray curable printing ink: also called ink] The present disclosure provides an active energy ray-curable printing ink comprising the above-mentioned active energy ray-curable printing ink varnish composition and a pigment.

[0137] <Pigments> The pigment used in the ink is not particularly limited, and commonly used inorganic or organic pigments can be blended. Examples of pigments include white pigments such as titanium oxide, zinc oxide, white lead, litbones, and antimony oxide, black pigments such as aniline black, iron black, and carbon black, yellow pigments such as yellow lead, yellow iron oxide, titanium yellow, Hansa Yellow (10G, 5G, 3G, and others), disazo yellow, benzidine yellow, and permanent yellow, orange pigments such as chrome vermilion, permanent orange, Balkan fast orange, and indanthrene brilliant orange, brown pigments such as iron oxide, permanent brown, and para brown, red iron oxide, cadmium red, antimony vermilion, permanent red, rhodamine lake, alizarin lake, thioindigo red, PV carmine, monolight fast red, quinacridone, and the like. Examples of the pigments include red pigments such as phosphorus-based red pigments; purple pigments such as cobalt purple, manganese purple, fast violet, methyl violet lake, indanthrene brilliant violet, and dioxazine violet; blue pigments such as ultramarine, Prussian blue, cobalt blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indanthrene blue, and indigo; green pigments such as chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobromo copper phthalocyanine; and various fluorescent pigments and metal powder pigments.

[0138] Examples of upper and lower limits for the pigment content in 100% by mass of ink are 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1% by mass, etc. In one embodiment, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass.

[0139] <Photopolymerization initiator> In one embodiment, the ink may contain a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more kinds.

[0140] The photopolymerization initiator is not particularly limited, and various known ones can be used. Examples of the photopolymerization initiator include benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, p-dimethylacetophenone, thioxanthone, alkylthioxanthone, amines, etc.

[0141] Examples of commercially available photopolymerization initiators include Omnirad 1173, Omnirad 651, Omnirad 184, Omnirad 907, Omnirad 2959, Omnirad 127, Omnirad 369, Omnirad 369E, Omnirad 379, Omnirad 379EG, Omnirad TPO, and Omnirad 819 (all manufactured by IGM Resins).

[0142] The upper and lower limits of the content of the photopolymerization initiator in 100% by mass of the ink are exemplified as 15, 13, 11, 10, 9, 7, 5, 4, 2, 1, 0.9, 0.5, 0.1, 0% by mass, etc. In one embodiment, the content is preferably 0 to 15% by mass from the viewpoint of drying property.

[0143] Examples of the upper and lower limits of the content of the rosin epoxy (meth)acrylate (A) in 100% by mass of the ink include 30, 29.99, 29.9, 25, 20, 15, 10, 9, 6, 5, 3, 2, 1, 0.9, 0.7, 0.5, 0.3, 0.2, 0.1, and 0.05% by mass. In one embodiment, the content is preferably 0.05 to 30% by mass, and more preferably 1 to 20% by mass. The content can also be set by combining the upper limit of less than 30% by mass with the lower limit.

[0144] The upper and lower limits of the content of the poly(meth)acrylate (B) in 100% by mass of the ink are exemplified as 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20% by mass, etc. In one embodiment, the content is preferably 20 to 90% by mass.

[0145] The upper and lower limits of the content of the polymer (C) in 100% by mass of the ink are, for example, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2.5% by mass, etc. In one embodiment, the content is preferably 2.5 to 60% by mass.

[0146] The upper and lower limits of the content of the organic solvent (D) in 100% by mass of the ink are, for example, 2, 1.5, 1, 0.5, 0.05, 0.01, 0% by mass, etc. In one embodiment, the content is preferably 0 to 2% by mass.

[0147] The above-mentioned active energy ray-curable printing ink can be used as an active energy ray-curable lithographic printing ink or an active energy ray-curable offset printing ink.

[0148] [Printed material] The present disclosure provides a printed matter having a cured layer of the above-mentioned active energy ray-curable printing ink.

[0149] The substrate may be any of various known substrates without any particular limitations. Examples of the substrate include paper (art paper, cast-coated paper, form paper, PPC paper, fine coated paper, craft paper, polyethylene laminated paper, glassine paper, etc.) and plastic substrates (polyolefin, polycarbonate, polymethacrylate, polyester, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.).

[0150] Examples of printing methods (coating methods) include offset printing, flexographic printing, screen printing, bar coater coating, Mayer bar coating, air knife coating, gravure coating, etc. The amount of coating is not particularly limited, but it is preferable that the mass after drying is 0.1 to 30 g / m 2 The preferred thickness is 1 to 20 g / m 2 degree is more preferable.

[0151] The curing means is exemplified by an electron beam or ultraviolet light. The light source of ultraviolet light is exemplified by a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a UV-LED, etc. The light amount, light source arrangement, and transport speed are not particularly limited, but when a high pressure mercury lamp is used, the transport speed is preferably about 5 to 50 m / min for one lamp having a light amount of about 80 to 160 W / cm. EXAMPLES

[0152] The present invention will be specifically described below through examples and comparative examples. However, the above-mentioned description of the preferred embodiment and the following examples are provided for illustrative purposes only and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described in this specification, but is limited only by the claims. In each example and comparative example, unless otherwise specified, numerical values ​​such as parts and % are based on mass.

[0153] Example 1 A varnish composition was produced by dissolving 15 parts (19% by mass in the varnish composition) of diallyl phthalate resin (product name "Daiso DAP A" manufactured by Osaka Soda Co., Ltd.) in 20 parts (26% by mass in the varnish composition) of rosin epoxy acrylate (product name "Beamset 101" manufactured by Arakawa Chemical Industries Co., Ltd.) and 42 parts (55% by mass in the varnish composition) of ditrimethylolpropane tetraacrylate. 8 parts of photopolymerization initiator (product name "Omnirad 907" manufactured by IGM Resins BV) and 15 parts of black pigment (MA-100 manufactured by Mitsubishi Chemical Co., Ltd.) were added to this varnish composition, and the mixture was milled with three rollers to prepare an ink.

[0154] Examples other than Example 1 and Comparative Examples were produced in the same manner as Example 1, except that the components of the varnish composition were changed as shown in the table below. The values ​​in the table are based on 100% by mass of the varnish composition.

[0155] [Table 1] Diallyl phthalate resin: Daiso DAP A, manufactured by Osaka Soda Co., Ltd. Weight average molecular weight: 40,000. Styrene-acrylic resin: A reaction product of styrene / 2-ethylhexyl acrylate / acrylic acid = 8 / 1 / 1 (molar ratio). Weight average molecular weight is 12,000. Polyester resin: reaction product of phthalic anhydride / 1,6-hexanediol / hydrogenated bisphenol A = 5 / 3.5 / 1.5. Weight average molecular weight 6,000. Rosin alkyd resin: reaction product of tetrahydrophthalic anhydride / 1,6-hexanediol / pentaerythritol / disproportionated rosin = 5 / 3.5 / 1.5 / 3 Weight average molecular weight 9,000

[0156] (Liquidity) 1.30 mL of ink was placed on a glass plate tilted at 60 degrees, and the ink flow was measured after leaving it for 30 minutes. The evaluation criteria are as follows: ○:60mm or more △:59~41mm ×: 40mm or less

[0157] (Emulsification suitability) 15g of the prepared ink was added to a stainless steel container, and after stirring for 5 minutes at 200 rpm with a stirrer equipped with a disper blade, water was added until no more water was absorbed into the ink. The ink was then placed on a copper plate and drained with an ointment spatula to obtain an emulsified ink. 1.30mL of the resulting emulsified ink was placed on a glass plate tilted at 60°, and the ink flow was measured after leaving it for 30 minutes, and the rate of change in fluidity before and after emulsification was measured. ○: 50% or less △: 51~99% ×: 100% or more

[0158] (Misting resistance) A 13cm x 21cm square piece of OHP film was attached to the wall behind the roller of the ink meter, and after adjusting the roller temperature to 40°C, 2.6mL of ink was placed on the roller. The roller was rotated at 1200 rpm for 2 minutes, and the mass of ink attached to the film was weighed. The evaluation criteria were as follows: ○: 39mg or less △: 40-50mg ×: 51mg or more

[0159] (Adhesion) 0.1 mL of ink was applied to a corona-treated polypropylene film using an RI tester (manufactured by Ishikawajima Industrial Machinery Co., Ltd.), and then 140 mJ / cm 2 A cross-cut pattern was made on the ink-coated film in accordance with JIS K 5400, and then a cellophane tape peeling test was carried out and the film was evaluated based on the following criteria. ◯: 90% or more of the cured film does not peel off. △: Less than 90% to approximately 50% of the cured film does not peel off. ×: 50% or more of the cured film peels off.

Claims

1. The composition comprises 1 to 20 mass% of a rosin epoxy (meth)acrylate (A), 34 to 52 mass% of a poly(meth)acrylate (B), and 15 to 24 mass% of a polymer (C); The poly(meth)acrylate (B) is at least one selected from the group consisting of ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, glycerin tri(propylene oxide modified acrylate), trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol di(propylene oxide modified acrylate), bisphenol A di(ethylene oxide modified acrylate), and bisphenol A diepoxy acrylate, The poly(meth)acrylate (B) includes at least one selected from the group consisting of ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, glycerin tri(propylene oxide modified acrylate), and trimethylolpropane triacrylate; The polymer (C) is a diallyl phthalate resin, a styrene acrylic resin, a polyester resin, or a rosin alkyd resin, The weight average molecular weight of the polymer (C) is 6,000 to 40,000; The active energy ray-curable varnish composition for a printing ink, wherein the polymer (C) has an iodine value of 0 mol / kg and / or an acid value of less than 30 mgKOH / g, and is not to be used for a film having a nitrogen element concentration of 0.5 to 10.0 atomic % on the film surface.

2. 2. The varnish composition for use in an active energy ray-curable lithographic printing ink according to claim 1, which is for use in an active energy ray-curable lithographic printing ink.

3. An active energy ray-curable printing ink comprising the active energy ray-curable printing ink varnish composition according to claim 1 or 2 and a pigment.

4. A printed matter having a cured layer of the active energy ray-curable printing ink according to claim 3.

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