Active energy ray-curable ink composition and laminate

Abstract

To provide an active energy ray-curable ink composition having improved curability and adhesiveness to a substrate, and to provide a laminate using the composition.SOLUTION: The active energy ray-curable ink composition contains a urethane (meth) acrylate (A) which is a reaction product of an isocyanate compound (a1), a (meth) acrylic compound (a2) having a hydroxyl group, and a tertiary amine compound (a3) having a hydroxyl group, and a polyfunctional (meth) acrylic compound (B). Wherein the urethane (meth) acrylate (A) has a (meth) acryloyl group concentration of 2.0 to 8.0 0mmol / g and a hydroxyl group-containing amine compound (a3) - derived nitrogen atom concentration of 0.4 to 2.0 7mmol / g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] An embodiment of the present invention relates to a novel and useful actinic ray-curable ink composition and a laminate. [Background technology]

[0002] Active energy ray-curable compositions are used in a variety of industrial fields because they instantly change from a liquid to a solid upon irradiation with active energy rays.

[0003] In recent years, in the printing industry, increasing demand for shorter delivery times and environmental friendliness has led to the widespread use of quick-drying, solvent-free active energy ray-curable inks, replacing the traditional oil-based inks. Active energy ray-curable inks contain active energy ray-curable unsaturated compounds, such as acrylic ester compounds, as components, and cure instantly upon exposure to active energy rays, forming a tough film through three-dimensional crosslinking of the unsaturated compounds. Because they cure instantly and form a tough ink film, the use of active energy ray-curable inks is also expanding in the flexible packaging industry, where post-processing is performed after printing. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 08-041151 [Patent Document 2] Japanese Patent Application Publication No. 09-031150 Summary of the Invention [Problem to be solved by the invention]

[0005] Active energy ray-curable inks often use binder resins, such as diallyl phthalate resin, to enhance printability, but most binder resins lack (meth)acryloyl groups and therefore do not contribute to the formation of three-dimensional crosslinks in the cured film of the active energy ray-curable ink, resulting in a problem of degraded ink curing properties. To address this issue, the use of binder resins with acryloyl groups, such as urethane (meth)acrylate, can form three-dimensional crosslinks in the cured film and improve curing properties. However, significant cure shrinkage occurs, which is known to reduce adhesion to the substrate, particularly on plastic substrates.

[0006] For example, Patent Document 1 discloses a urethane methacrylate made from toluene diisocyanate, polyoxyalkylene glycol, N-methyldiethanolamine, and hydroxyethyl methacrylate. However, the urethane methacrylate in Patent Document 1 has a low (meth)acryloyl group concentration, and the resulting ink does not exhibit sufficient curability. Furthermore, Patent Document 2 discloses an aqueous polyurethane resin having a high (meth)acryloyl group concentration and nitrogen atoms derived from monoethanolamine. However, the polyurethane resin in Patent Document 2 has a low concentration of nitrogen atoms derived from monoethanolamine, and the effect on improving adhesion is small. Furthermore, Patent Documents 1 and 2 do not provide examples of inks containing urethane (meth)acrylate.

[0007] An object of an embodiment of the present invention is to provide an actinic ray-curable ink composition having improved curability and adhesion to a substrate, and a laminate using the composition. [Means for solving the problem]

[0008] As a result of extensive investigations, the present inventors have found that an active energy ray-curable ink composition containing a urethane (meth)acrylate having as reaction components an isocyanate compound (a1), a (meth)acrylic compound (a2) having a hydroxyl group, and an amine compound (a3) ​​having a hydroxyl group other than (a2), is an ink composition that has excellent curability and adhesion to substrates, and have arrived at the present invention.

[0009] That is, one embodiment of the present invention is an active energy ray-curable ink composition containing a urethane (meth)acrylate (A) and a polyfunctional (meth)acrylic compound (B) other than (A), the urethane (meth)acrylate (A) is a reaction product of an isocyanate compound (a1), a (meth)acrylic compound (a2) having a hydroxyl group, and an amine compound (a3) ​​having a hydroxyl group other than (a2), the amine compound (a3) ​​having a hydroxyl group is a tertiary amine compound, the (meth)acryloyl group concentration of the urethane (meth)acrylate (A) is 2.0 to 8.0 mmol / g; The present invention relates to an active energy ray-curable ink composition, characterized in that the concentration of nitrogen atoms derived from the amine compound (a3) ​​having a hydroxyl group in the urethane (meth)acrylate (A) is 0.4 to 2.7 mmol / g.

[0010] Another embodiment of the present invention relates to the above-mentioned active energy ray-curable ink composition, wherein the amine compound (a3) ​​having a hydroxyl group is an amine compound represented by the following general formula (1): General formula (1) R 1 x -N-[(R 2 O) z -H] y (In the formula, R 1 represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, R 2represents a linear or branched alkylene group having 2 to 4 carbon atoms. x represents an integer of 0 to 2, y represents an integer of 1 to 3, and x+y=3. z represents an integer of 1 to 10. Also, if x is 2, there are two R 1 may be the same or different, and R 1 They may combine together to form a ring. Also, [(R 2 When there are two or more O)zH groups, they may be the same or different.

[0011] Another embodiment of the present invention relates to the above-mentioned active energy ray-curable ink composition, wherein the (meth)acrylic compound (a2) having a hydroxyl group includes a compound having two or more (meth)acryloyl groups in the molecule.

[0012] Another embodiment of the present invention relates to the above-mentioned active energy ray-curable ink composition, wherein the (meth)acrylic compound (a2) having a hydroxyl group is at least one selected from the group consisting of pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, and polypentaerythritol poly(meth)acrylate.

[0013] Another embodiment of the present invention relates to the above active energy ray-curable ink composition, wherein the isocyanate compound (a1) is a diisocyanate compound.

[0014] Another embodiment of the present invention relates to the above-mentioned active energy ray-curable ink composition, which is for use on plastic substrates.

[0015] Another embodiment of the present invention relates to a laminate comprising a substrate and a layer of a cured product of the above-mentioned active energy ray-curable ink composition.

[0016] Another embodiment of the present invention is a method for producing the above-mentioned active energy ray-curable ink composition, comprising the steps of: The present invention relates to a method for producing an active energy ray-curable ink composition, comprising a step of reacting an isocyanate compound (a1), a (meth)acrylic compound (a2) having a hydroxyl group, and an amine compound (a3) ​​having a hydroxyl group other than (a2) in a polyfunctional (meth)acrylic compound (B) other than (A) to obtain a urethane (meth)acrylate (A). [Effects of the Invention]

[0017] According to an embodiment of the present invention, it is possible to provide an active energy ray-curable ink composition having improved curability and adhesion to a substrate, and a laminate using the composition, which is extremely useful industrially. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below, and various modifications are possible within the scope of the gist of the present invention.

[0019] In an embodiment of the present invention, the active energy ray-curable ink composition (hereinafter also referred to as "ink") contains a "urethane (meth)acrylate (A)" and a "polyfunctional (meth)acrylic compound (B) other than the urethane (meth)acrylate (A)." The urethane (meth)acrylate (A) is a reaction product of an "isocyanate compound (a1)," a "(meth)acrylic compound (a2) having a hydroxyl group," and an "amine compound (a3) ​​having a hydroxyl group other than (a2)." This allows for both excellent curability and adhesion to plastic substrates. In this specification, the "urethane (meth)acrylate (A)," the "isocyanate compound (a1)," the "(meth)acrylic compound (a2) having a hydroxyl group," and the "amine compound (a3) ​​having a hydroxyl group" may be simply referred to as "(A)," "(a1)," "(a2)," and "(a3)," respectively. (a3) ​​is an amine compound having a hydroxyl group other than (a2).

[0020] (Urethane (meth)acrylate (A)) The urethane (meth)acrylate (A) is a reaction product of an isocyanate compound (a1), a (meth)acrylic compound (a2) having a hydroxyl group, and an amine compound (a3) ​​having a hydroxyl group other than (a2). The urethane (meth)acrylate (A) is a reaction product of the isocyanate group of the isocyanate compound (a1), the hydroxyl group of the (meth)acrylic compound (a2) having a hydroxyl group, and the hydroxyl group of the amine compound (a3) ​​having a hydroxyl group other than (a2).

[0021] The content of the urethane (meth)acrylate (A) is preferably from 5 to 60 mass %, more preferably from 10 to 40 mass %, based on the total amount of the ink, from the viewpoints of storage stability and curability.

[0022] The (meth)acryloyl group concentration of the urethane (meth)acrylate (A) is in the range of 2.0 to 8.0 mmol / g, preferably 2.5 to 7.0 mmol / g, from the viewpoint of improving curability. The (meth)acryloyl group concentration of the urethane (meth)acrylate (A) is the concentration of the number of moles of (meth)acryloyl groups (Y (mmol)) contained in the urethane (meth)acrylate (A) (X (g)) [(Y (mmol)) / (X (g))]. The (meth)acryloyl group concentration can be calculated, for example, using the mass of the raw materials used in the production of the urethane (meth)acrylate (A) and the number of moles of (meth)acryloyl groups contained in the raw materials.

[0023] The nitrogen atom concentration derived from the amine compound (a3) ​​having a hydroxyl group in the urethane (meth)acrylate (A) is in the range of 0.4 to 2.7 mmol / g, preferably 0.7 to 2.6 mmol / g, and more preferably 1.1 to 2.5 mmol / g, from the viewpoint of improving adhesion. The nitrogen atom concentration derived from the amine compound (a3) ​​having a hydroxyl group in the urethane (meth)acrylate (A) is the concentration of the number of moles of nitrogen atoms (Z (mmol)) contained in the urethane (meth)acrylate (A) (X (g)) [(Z (mmol)) / (X (g))]. The nitrogen atom concentration can be calculated, for example, using the masses of the raw materials used in the production of the urethane (meth)acrylate (A) and the number of moles of nitrogen atoms contained in the raw materials.

[0024] (Isocyanate compound (a1)) Examples of the isocyanate compound (a1) include: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, 2,2,4 -Diisocyanate compounds such as trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer diisocyanate in which the carboxyl groups of dimer acid are converted into isocyanate groups; Trifunctional or higher isocyanate compounds such as Duranate TPA-100 (Asahi Kasei Corporation, isocyanurate formed by cyclization of 3 moles of 1,6-hexamethylene diisocyanurate) and Millionate MR400 (Tosoh Corporation, polymeric MDI) Among these, diisocyanate compounds are preferred from the viewpoint of reaction control, and 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are more preferred from the viewpoint of reaction rate.

[0025] ((Meth)acrylic compound (a2) having a hydroxyl group) The (meth)acrylic compound (a2) having a hydroxyl group may be a (meth)acrylic compound having one or more hydroxyl groups, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylates, glycerin, Examples of the (meth)acrylic compound (a2) having a hydroxyl group include ethylene oxide-modified trimethylolpropane poly(meth)acrylate, diglycerin poly(meth)acrylate, trimethylolpropane poly(meth)acrylate, ethylene oxide-modified trimethylolpropane poly(meth)acrylate, propylene oxide-modified trimethylolpropane poly(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, polypentaerythritol poly(meth)acrylate, etc. These (meth)acrylic compounds (a2) having a hydroxyl group may be used alone or in combination of two or more. Among these, in order to set the (meth)acryloyl group concentration of the urethane (meth)acrylate (A) to 2.0 to 8.0 mmol / g, the (meth)acrylic compound (a2) having a hydroxyl group is preferably at least one selected from the group consisting of pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, and polypentaerythritol poly(meth)acrylate, and furthermore, in terms of curability, it is preferably at least one selected from the group consisting of pentaerythritol polyacrylate, dipentaerythritol polyacrylate, and polypentaerythritol polyacrylate.

[0026] (Amine compound (a3) ​​having a hydroxyl group other than (a2)) The amine compound (a3) ​​having a hydroxyl group other than (a2) is a compound in which the hydroxyl group in the molecule reacts with an isocyanate group to form a urethane bond.

[0027] The amine compound (a3) ​​is preferably a compound represented by the following general formula (1). General formula (1) R 1 x -N-[(R 2 O) z -H] y (In the formula, R 1 represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, R 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms. x represents an integer of 0 to 2, y represents an integer of 1 to 3, and x+y=3. z represents an integer of 1 to 10. Also, if x is 2, there are two R 1 may be the same or different, and R 1 They may combine together to form a ring. Also, [(R 2 When there are two or more O)zH groups, they may be the same or different.

[0028] In terms of availability, z in general formula (1) is preferably an integer of 1 to 5, and more preferably 1.

[0029] Specifically, the compound represented by the general formula (1) is amine compounds having one substituent having a hydroxyl group and two substituents not having a hydroxyl group, such as N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dibutylaminoethanol, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-dibutylaminopropanol, N,N-dimethylaminobutanol, N,N-diethylaminobutanol, N,N-dibutylaminobutanol, 2-(2-diethylamino)ethoxyethanol, and 1-piperidineethanol; amine compounds having two substituents having hydroxyl groups and one substituent without a hydroxyl group, such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-butyldipropanolamine, N-tert-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-butyldibutanolamine, N-tert-butyldibutanolamine, N-pentyldibutanolamine, Liponol C / 12 (N,N-bis(Lion Speciality Chemicals Co., Ltd., 2-hydroxyethyl)coconut alkylamine), Liponol C / 15 (Lion Speciality Chemicals Co., Ltd., polyoxyethylenecoconut alkylamine (5EO)), polyoxyethylenecoconut alkylamine (15EO)); amine compounds having three hydroxyl group-containing substituents, such as trimethanolamine, triethanolamine, triisopropanolamine, and tributanolamine; Examples include: The amine compounds (a3) ​​may be used either alone or in combination of two or more.

[0030] By using these amine compounds (a3) ​​which are tertiary amines, reactions between amino groups and isocyanate groups or Michael addition reactions between amino groups and acryloyl groups do not occur, and unintended crosslinking reactions can be suppressed.

[0031] For the urethane (meth)acrylate (A), polyol compounds other than (a2) and (a3) ​​that react with the isocyanate group of the isocyanate compound (a1) can be used. As the polyol compound other than (a2) and (a3), a polyol compound having two or more hydroxyl groups in the molecule can be used, and such a polyol compound preferably includes at least one selected from the group consisting of polyol compounds having 2 to 20 carbon atoms and alkylene oxide-modified polyol compounds having 2 to 20 carbon atoms.

[0032] Examples of polyol compounds having 2 to 20 carbon atoms include: Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1 linear alkylene dihydric alcohols such as 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, 1,18-octadecanediol, 1,2-octadecanediol, 1,20-eicosanediol, and 1,2-eicosanediol; branched alkylene dihydric alcohols such as neopentyl glycol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-dimethylpentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,4-diethyl-1,5-pentanediol; Cyclic alkylene dihydric alcohols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecane dimethanol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S Examples include: Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, sorbitan, sorbitol, and inositol. These polyol compounds having 2 to 20 carbon atoms may be used alone or in combination of two or more thereof. Among these, from the viewpoint of availability, it is particularly preferable to use at least one selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, glycerin, trimetrolpropane, and pentaerythritol.

[0033] Examples of alkylene oxide-modified polyol compounds having 2 to 20 carbon atoms include compounds obtained by modifying the above polyol compounds having 3 to 20 carbon atoms with alkylene oxide, such as ethylene oxide (EO-modified), propylene oxide (PO-modified), or butylene oxide (BO-modified). The alkylene oxide-modified polyol compounds having 2 to 20 carbon atoms may be used alone or in combination of two or more. Examples of alkylene oxide-modified polyol compounds having 2 to 20 carbon atoms include the PEG series (manufactured by Sanyo Chemical Industries, Ltd., polyethylene glycol), the Sannix PP series (manufactured by Sanyo Chemical Industries, Ltd., polypropylene glycol), the PTMG series (manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol), the Uniox G series (manufactured by NOF Corporation, ethylene oxide-modified glycerin), the Sannix GP series (manufactured by Sanyo Chemical Industries, Ltd., propylene oxide-modified glycerin), the Sannix TP series (manufactured by Sanyo Chemical Industries, Ltd., propylene oxide-modified trimetrol propane), and Wilbride S-753D (manufactured by NOF Corporation, EOPOBO-modified glycerin).

[0034] In a preferred embodiment, the polyol compound is at least one selected from the group consisting of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, octanediol, decanediol, glycerin, trimethylolpropane, pentaerythritol, and alkylene oxide-modified products thereof.

[0035] In the urethane (meth)acrylate (A), the content of the isocyanate compound (a1) is, for example, 5 to 60 mass%, 6 to 40 mass%, or 7 to 30 mass% based on the urethane (meth)acrylate (A) from the viewpoint of reaction control. The content of the (meth)acrylic compound (a2) having a hydroxyl group is, for example, 8 to 90 mass%, 10 to 70 mass%, or 12 to 50 mass% based on the urethane (meth)acrylate (A) from the viewpoint of curability. The content of the amine compound (a3) ​​is, for example, 0.5 to 40 mass%, 1 to 30 mass%, or 2 to 25 mass% based on the urethane (meth)acrylate (A) from the viewpoint of achieving both adhesion and curability. The content of the polyol compound is, for example, 0 to 15 mass %, 0 to 10 mass %, or 0 to 8 mass % based on the urethane (meth)acrylate (A) so as not to inhibit adhesion and curing properties.

[0036] (Method for producing urethane (meth)acrylate (A)) A method for producing a reaction product of an isocyanate compound (a1), a (meth)acrylic compound (a2) having a hydroxyl group, and an amine compound (a3) ​​having a hydroxyl group will be described. The reaction of the isocyanate compound (a1), the (meth)acrylic compound (a2) having a hydroxyl group, and the amine compound (a3) ​​having a hydroxyl group may be carried out simultaneously, or the isocyanate compound (a1) may be reacted with the (meth)acrylic compound (a2) having a hydroxyl group in advance, followed by the reaction of the amine compound (a3) ​​having a hydroxyl group. In the reaction, the isocyanate group of the isocyanate compound (a1) is reacted with the hydroxyl group of the (meth)acrylic compound (a2) having a hydroxyl group and the hydroxyl group of the amine compound (a3) ​​having a hydroxyl group. In the reaction of the isocyanate compound (a1), the (meth)acrylic compound (a2) having a hydroxyl group, and the amine compound (a3) ​​having a hydroxyl group, other optional compounds may be used as needed. However, when using optional compounds, the amount used is, for example, 10% by mass or less, 5% by mass or less, or 1% by mass or less, based on the total amount of raw material compounds, from the viewpoint of obtaining sufficient effects according to the embodiment of the present invention. From the viewpoint of effects, the optional compounds may not be used (the amount used may be 0% by mass).

[0037] The ratio (a2') / (a1') of the number of moles of hydroxyl groups (a2') contained in the (meth)acrylic compound (a2) having hydroxyl groups to the number of moles of isocyanate groups (a1') contained in the isocyanate compound (a1) is preferably 0.08 to 0.6. When [(a2') / (a1')] is in the range of 0.08 to 0.6, the (meth)acryloyl group concentration and nitrogen atom concentration of the urethane (meth)acrylate (A) become favorable, enabling both adhesion and curability to be achieved. [(a2') / (a1')] can be calculated, for example, using the number of moles of isocyanate groups contained in the isocyanate compound (a1) used as a raw material in the production of the urethane (meth)acrylate (A) and the number of moles of hydroxyl groups contained in the (meth)acrylic compound (a2) having hydroxyl groups.

[0038] The reaction proceeds without a catalyst, but can also be carried out using a catalyst. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline, and metal catalysts such as tin, zinc, aluminum, and zirconium. From the viewpoint of reactivity, it is preferable to use at least one selected from the group consisting of tin 2-ethylhexanoate, zinc acetylacetonate, and aluminum acetylacetonate. Although the reaction can be carried out in a solvent as needed, it can also be carried out in a polyfunctional (meth)acrylic compound (B) described below. The reaction in the polyfunctional (meth)acrylic compound (B) is preferred because it omits the steps of dissolving the urethane (meth)acrylate (A) in the polyfunctional (meth)acrylic compound (B) and removing the solvent. When the reaction is carried out in a polyfunctional (meth)acrylic compound (B), preferably, at least a polyfunctional (meth)acrylic compound other than the (meth)acrylic compound (a2) having a hydroxyl group is used as the polyfunctional (meth)acrylic compound (B). That is, at least a polyfunctional (meth)acrylic compound having no hydroxyl group is used as the polyfunctional (meth)acrylic compound (B). The composition obtained by the reaction contains the reaction product, urethane (meth)acrylate (A), and a polyfunctional (meth)acrylic compound having no hydroxyl group. The resulting composition may contain compounds corresponding to the polyfunctional (meth)acrylic compound (B), such as the (meth)acrylic compound (a2) having an unreacted hydroxyl group. An active energy ray-curable composition (e.g., ink) prepared using such a composition contains the reaction product urethane (meth)acrylate (A) and polyfunctional (meth)acrylic compounds (B) including the (meth)acrylic compound (a2) having an unreacted hydroxyl group and a polyfunctional (meth)acrylic compound having no hydroxyl group.

[0039] The molecular weight of the urethane (meth)acrylate (A) is preferably in the range of 2,000 to 30,000 in terms of weight average molecular weight from the viewpoint of adhesion and curability. In an embodiment of the present invention, the weight-average molecular weight is a weight-average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). The weight-average molecular weight can be measured, for example, by the following method. A gel permeation chromatograph (HLC-8320) manufactured by Tosoh Corporation is used for the measurement. A calibration curve is prepared using a standard polystyrene sample. Tetrahydrofuran is used as the eluent, and three TSKgel SuperHM-M columns (manufactured by Tosoh Corporation) are used. The measurement is performed at a flow rate of 0.6 mL / min, an injection volume of 10 μL, and a column temperature of 40°C.

[0040] Furthermore, the number of (meth)acryloyl groups contained in the urethane (meth)acrylate (A) is preferably 2 to 50 per molecule from the viewpoint of curability, and more preferably 6 to 30 per molecule. From the viewpoint of curability, the (meth)acryloyl group is preferably an acryloyl group. From the viewpoint of curability, the urethane (meth)acrylate (A) is preferably a urethane acrylate. In this specification, "(meth)acryloyl group" is a general term that refers to "acryloyl group" and "methacryloyl group," and "(meth)acrylate" is a general term that refers to "acrylate" and "methacrylate."

[0041] (Polyfunctional (meth)acrylic compound (B) other than (A)) The content of the polyfunctional (meth)acrylic compound (B) other than (A) used in the actinic ray-curable ink composition is 10 to 90 mass % relative to the total amount of the ink, more preferably 20 to 85 mass %, and even more preferably 30 to 80 mass %.

[0042] The polyfunctional (meth)acrylic compound (B) other than (A) is not particularly limited, and examples thereof include: bifunctional (meth)acrylic compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (n=2 to 20), propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (n=2 to 20), alkane (carbon number 4 to 12) glycol di(meth)acrylate, alkane (carbon number 4 to 12) glycol ethylene oxide adduct (2 to 20 moles) di(meth)acrylate, alkane (carbon number 4 to 12) glycol propylene oxide adduct (2 to 20 moles) di(meth)acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, bisphenol A ethylene oxide adduct (2 to 20 moles) di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, and hydrogenated bisphenol A ethylene oxide adduct (2 to 20 moles) di(meth)acrylate; trifunctional (meth)acrylic compounds such as glycerin tri(meth)acrylate, glycerin ethylene oxide adduct (3 to 30 mol) tri(meth)acrylate, glycerin propylene oxide adduct (3 to 30 mol) tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide adduct (3 to 30 mol) tri(meth)acrylate, and trimethylolpropane propylene oxide adduct (3 to 30 mol) tri(meth)acrylate; Pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide adduct (4 to 40 mol) tetra(meth)acrylate, pentaerythritol propylene oxide adduct (4 to 40 mol) tetra(meth)acrylate, diglycerin tetra(meth)acrylate, pentaerythritol ethylene oxide adduct (4 to 40 mol) tetra(meth)acrylate, pentaerythritol propylene oxide adduct (4 to 40 mol) tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate tetra- or higher functional (meth)acrylic compounds such as tetramethylolpropane ethylene oxide adduct (4 to 40 mol) tetra(meth)acrylate, ditrimethylolpropane propylene oxide adduct (3 to 30 mol) tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol ethylene oxide adduct (6 to 60 mol) hexa(meth)acrylate, and dipentaerythritol propylene oxide adduct (6 to 60 mol) hexa(meth)acrylate; (meth)acrylate compounds such as polyester (meth)acrylate, urethane (meth)acrylate other than (A), and epoxy (meth)acrylate; and mixtures thereof. These compounds may be used alone or in combination as a mixture of two or more. Among these, it is preferable to use a bifunctional or higher functional (meth)acrylic compound from the viewpoint of curability. Furthermore, the proportion of the bifunctional or higher functional (meth)acrylic compound in the total amount of (B) is preferably 40 to 100 mass% from the viewpoint of curability.

[0043] The active energy ray-curable ink composition may contain an active energy ray-curable compound other than (B) depending on the required physical properties of the cured film.

[0044] As the active energy ray-curable compound other than (B), a vinyl compound can be used, and examples thereof include styrene, N-vinylpyrrolidone, and divinylbenzene.

[0045] The actinic ray-curable ink composition is prepared, for example, to have a composition consisting of 0 to 30 mass% of pigment, 5 to 40 mass% of urethane (meth)acrylate (A), 20 to 80 mass% of polyfunctional (meth)acrylic compound (B), 0 to 30 mass% of resin, 0 to 20 mass% of photopolymerization initiator and / or sensitizer, and 0 to 10 mass% of other additives, based on the total mass of the ink.

[0046] The active energy ray-curable ink composition may or may not contain a pigment. Examples of pigments include inorganic pigments and organic pigments. The active energy ray-curable ink composition may be a colored ink or a clear ink. The active energy ray-curable ink composition may contain a colored pigment as a colorant, and when a colored pigment is contained, the ink becomes a colored ink. The colored ink may further contain an extender pigment. On the other hand, when the active energy ray-curable ink composition does not contain a colored pigment, the ink becomes a clear ink (also called a varnish). The clear ink may contain an extender pigment.

[0047] The actinic radiation-curable ink composition may contain a colored pigment having coloring power. The colored pigment may be either an inorganic pigment or an organic pigment, and various known pigments can be used. Examples of inorganic pigments include yellow lead, zinc yellow, iron blue, cadmium red, titanium oxide, zinc white, red iron oxide, ultramarine, carbon black, graphite, aluminum powder, and red iron oxide.

[0048] Examples of organic pigments include soluble azo pigments such as β-naphthols, β-oxynaphthoic acid pigments, β-oxynaphthoic acid anilide pigments, acetoacetate anilide pigments, and pyrazolone pigments; insoluble azo pigments such as β-naphthols, β-oxynaphthoic acid anilide pigments, acetoacetate anilide monoazo pigments, acetoacetate anilide disazo pigments, and pyrazolone pigments; phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine; polycyclic pigments and heterocyclic pigments such as quinacridones, dioxazines, threnes (pyranthrones, anthranthrones, indanthrones, anthrapyrimidines, flavanthrones, thioindigo pigments, anthraquinones, perinones, perylenes, and the like), isoindolinones, metal complex pigments, and quinophthalone pigments.

[0049] The active energy ray-curable ink composition may contain an extender pigment that does not have coloring power. When an extender pigment is used, it tends to be easier to adjust the viscosity of the ink. The extender pigment may be an inorganic pigment, and known extender pigments can be used. Examples of extender pigments include barium sulfate, magnesium silicate, alumina white, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate, silicon dioxide, and aluminum hydroxide.

[0050] The active energy ray-curable ink composition may contain a resin as needed. The resin is not particularly limited, and examples thereof include allyl resin, diallyl orthophthalate resin, diallyl isophthalate resin, diallyl terephthalate resin, polyester resin, polyvinyl chloride, poly(meth)acrylic acid ester, epoxy resin, polyurethane resin, petroleum (based) resin, cellulose derivative (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, polyamide resin, polyvinyl acetal resin, butadiene-acrylonitrile copolymer, etc. For example, as the allyl resin, a non-phthalate allyl resin that does not contain a phthalate structure may be used. These may be used alone or in combination of two or more types.

[0051] The actinic ray-curable ink composition may contain a photopolymerization initiator and a sensitizer as needed. Examples of the photopolymerization initiator include photocleavage initiators and hydrogen abstraction initiators.

[0052] Examples of photocleavage initiators include α-aminoalkylphenone compounds, α-hydroxyalkylphenone compounds, and acylphosphine oxide compounds.

[0053] More specifically, examples of the α-aminoalkylphenone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-piperidinophenyl)-butan-1-one, 1-[4-(butylsulfanyl)phenyl]-2-methyl-2-(morpholin-4-yl)propan-1-one, 3,6-bis(2-methyl-2-morpholinopropanonyl)-9-butylcarbazole, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. These compounds may be used alone or in combination of two or more.

[0054] Examples of α-hydroxyalkylphenone compounds include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxymethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one, etc. These may be used alone or in combination of two or more.

[0055] Examples of acylphosphine oxide compounds include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-bis(4-methylphenyl)phosphine oxide, ethoxyphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, etc. These may be used alone or in combination of two or more.

[0056] Examples of the hydrogen abstraction type polymerization initiator include a dialkylbenzophenone compound and a thioxanthone compound.

[0057] More specifically, examples of the dialkylaminobenzophenone compound include 4,4'-dialkylaminobenzophenones such as 4,4'-bis-(dimethylamino)benzophenone and 4,4'-bis-(diethylamino)benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide. The dialkylaminobenzophenone compound may be used alone or in combination of two or more types. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy-N,N,N-trimethyl-1-propanamine hydrochloride, and the like. These compounds may be used alone or in combination of two or more.

[0058] Sensitizers include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl)benzophenone, methyl-o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethanone, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy- Examples include 2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether, etc. These may be used alone or in combination of two or more.

[0059] A radical polymerization inhibitor may be added to the active energy ray-curable ink composition. Examples of radical polymerization inhibitors include (alkyl)phenols, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cupferron, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc. These may be used alone or in combination of two or more.

[0060] Wax may be added to the actinic ray-curable ink composition as an additive that imparts abrasion resistance, anti-blocking properties, smoothness, and scratch resistance. Examples of waxes include natural waxes such as carnauba wax, Japan wax, lanolin, montan wax, paraffin wax, and microcrystalline wax, and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compounds. These may be used alone or in combination of two or more.

[0061] In addition, additives such as ultraviolet absorbers, infrared absorbers, antibacterial agents, leveling agents, and the like can be added to the active energy ray-curable ink composition depending on the required performance.

[0062] The actinic energy ray-curable ink composition may be produced by the same method as that for conventional actinic energy ray-curable ink compositions, and is produced, for example, at a temperature between room temperature and 100° C. using ink components such as the pigment, urethane (meth)acrylate (A), polyfunctional (meth)acrylic compound (B), polymerization inhibitor, photopolymerization initiator and sensitizer, and other additives. For production, a kneader, three-roll mill, attritor, sand mill, gate mixer, or other equipment for milling, mixing, and / or preparation can be used.

[0063] Examples of printing methods for the active energy ray-curable ink composition include lithographic printing (normal lithographic printing using dampening water and waterless lithographic printing not using dampening water), letterpress printing, intaglio printing, and stencil printing, with lithographic printing and letterpress printing being preferred.

[0064] In an embodiment of the present invention, the laminate has a substrate and a layer of a cured product of the active energy ray-curable ink composition. The cured product can be formed by printing the active energy ray-curable ink composition by the above-mentioned printing method and curing it.

[0065] In one embodiment, the substrate may be, for example, a polyolefin substrate such as polyethylene or polypropylene, a polyester substrate such as polyethylene terephthalate or polylactic acid, a polycarbonate substrate, a polystyrene-based substrate such as polystyrene, AS resin or ABS resin, a nylon substrate, a polyamide substrate, a polyvinyl chloride substrate, a polyvinylidene chloride substrate, a cellophane substrate, a paper substrate, an aluminum substrate, or a substrate made of a composite material thereof. Also usable is a vapor-deposited substrate in which an inorganic compound such as silica, alumina or aluminum is vapor-deposited onto a film substrate. Furthermore, the vapor-deposited surface may be coated with polyvinyl alcohol or the like. The surface of the substrate to be printed (the surface in contact with the printing layer) is preferably treated to facilitate adhesion. Specific examples of such treatments include corona discharge treatment, ultraviolet / ozone treatment, plasma treatment, oxygen plasma treatment, and primer treatment. Furthermore, if sufficient adhesion cannot be obtained with a polyethylene terephthalate substrate, surface treatments such as acrylic coating treatment, polyester treatment, and polyvinylidene chloride treatment may be performed.

[0066] In an embodiment of the present invention, the substrate is preferably a plastic substrate. Although plastic substrates are particularly poor at exhibiting adhesion when an active energy ray-curable ink composition is used, the use of the active energy ray-curable ink composition according to an embodiment of the present invention significantly improves adhesion.

[0067] There are no particular limitations on the method for curing the actinic energy ray-curable ink composition with actinic energy rays, and any known actinic energy ray source can be used, including mercury lamps, xenon lamps, metal hydride lamps, LEDs (light-emitting diodes) such as ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs), electron beams, gas or solid-state lasers, etc. [Example]

[0068] The present invention will be described in more detail below with reference to examples, but the following examples are not intended to limit the scope of the invention. In this specification, "parts" means "parts by mass" and "%" means "% by mass".

[0069] (Production Example 1) In a four-neck flask equipped with a stirrer, condenser, thermometer, and gas inlet tube, 24.9 parts of toluene diisocyanate (toluene-2,4-diisocyanate: toluene-2,6-diisocyanate = 80:20 (mass ratio) mixture) as the isocyanate compound (a1), 16.6 parts of 2-hydroxyethyl acrylate as the (meth)acrylic compound (a2) having a hydroxyl group, 44.8 parts of MIRAMER M600 and 5 parts of LAROMER LR8863 as the polyfunctional (meth)acrylic compound (B), 0.01 parts of tin 2-ethylhexanoate as a catalyst, and 0.2 parts of tertiary butylhydroquinone as a polymerization inhibitor were added, and the mixture was stirred and reacted at 100 ° C. for 1 hour. Next, 8.5 parts of N-methyldiethanolamine as the amine compound (a3) ​​having a hydroxyl group other than (a2) was added, and the mixture was further reacted at 110 ° C. for 5 hours to obtain resin composition 1. The (meth)acryloyl group concentration of the obtained urethane (meth)acrylate (A) was 2.86 mmol / g, and the nitrogen atom concentration derived from (a3) ​​was 1.43 mmol / g. Resin composition 1 is a composition containing the urethane (meth)acrylate (A) and the polyfunctional (meth)acrylic compound (B).

[0070] (Examples 2-23, 34-40, 42) Resin compositions 2 to 23, 34 to 40, and 42 were obtained in the same manner as in Production Example 1, except that the raw materials were changed according to the formulations in Table 1.

[0071] (Manufacturing Example 24) Into a four-neck flask equipped with a stirrer, a condenser, a thermometer, and a gas inlet tube, 19.9 parts of toluene diisocyanate (a mixture of toluene-2,4-diisocyanate:toluene-2,6-diisocyanate = 80:20 (mass ratio)) as the isocyanate compound (a1), 39.8 parts of MIRAMER M500 (a mixture containing (a1) and (B) in a mass ratio of 1:1) as the (meth)acrylic compound (a2) having a hydroxyl group and the polyfunctional (meth)acrylic compound (B), 24.9 parts of MIRAMER M600 and 5 parts of LAROMER LR8863 as the polyfunctional (meth)acrylic compound (B), 0.01 parts of tin 2-ethylhexanoate as a catalyst, and 0.2 parts of tert-butylhydroquinone as a polymerization inhibitor were placed, and the mixture was reacted at 100°C for 1 hour while blowing in air with stirring. Next, 9.1 parts of N-methyldiethanolamine as an amine compound (a3) ​​having a hydroxyl group other than (a2) and 1.2 parts of ethylene glycol as a polyol compound were added, and the mixture was further reacted at 110°C for 5 hours to obtain resin composition 24. The resulting urethane (meth)acrylate (A) had a (meth)acryloyl group concentration of 3.80 mmol / g, and a nitrogen atom concentration derived from (a3) ​​of 1.52 mmol / g. Resin composition 24 is a composition containing urethane (meth)acrylate (A) and a polyfunctional (meth)acrylic compound (B).

[0072] (Examples 25-33, 41, 43, 45) Resin compositions 25 to 33, 41, 43, and 45 were obtained in the same manner as in Production Example 24, except that the raw materials were changed according to the formulations in Table 1.

[0073] (Manufacturing Example 44) A four-neck flask equipped with a stirrer, a condenser, a thermometer, and a gas inlet tube was charged with 25.8 parts of toluene diisocyanate (a mixture of toluene-2,4-diisocyanate:toluene-2,6-diisocyanate = 80:20 (mass ratio)) as the isocyanate compound (a1), 14.8 parts of MIRAMER M500 (a mixture containing (a1) and (B) in a mass ratio of 1:1) as the (meth)acrylic compound (a2) having a hydroxyl group and the polyfunctional (meth)acrylic compound (B), 37.4 parts of MIRAMER M600 and 5 parts of LAROMER LR8863 as the polyfunctional (meth)acrylic compound (B), 0.01 parts of tin 2-ethylhexanoate as a catalyst, and 0.2 parts of tert-butylhydroquinone as a polymerization inhibitor, and the mixture was reacted at 100°C for 1 hour while blowing in air with stirring. Next, 16.8 parts of N-methyldiethanolamine was added as an amine compound (a3) ​​having a hydroxyl group other than (a2), and the reaction was further carried out at 110°C. However, insoluble matter was generated during the reaction, and resin composition 44 was not obtained, so the next evaluation of the active energy ray-curable ink composition could not be carried out.

[0074] (Manufacturing Example 46) Into a four-neck flask equipped with a stirrer, a condenser, a thermometer, and a gas inlet tube, 11.1 parts of toluene diisocyanate (a mixture of toluene-2,4-diisocyanate:toluene-2,6-diisocyanate = 80:20 (mass ratio)) as the isocyanate compound (a1), 67.0 parts of MIRAMER M500 (a mixture containing (a1) and (B) in a mass ratio of 1:1) as the (meth)acrylic compound (a2) having a hydroxyl group and the polyfunctional (meth)acrylic compound (B), 11.3 parts of MIRAMER M600 and 5 parts of LAROMER LR8863 as the polyfunctional (meth)acrylic compound (B), 0.01 parts of tin 2-ethylhexanoate as a catalyst, and 0.2 parts of tert-butylhydroquinone as a polymerization inhibitor were placed, and the mixture was reacted at 100°C for 1 hour while blowing in air with stirring. Next, 5.3 parts of Sannix GP-250 was added as a polyol compound, and the reaction was continued for an additional 5 hours at 110°C to obtain resin composition 46. The resulting urethane (meth)acrylate had a (meth)acryloyl group concentration of 6.40 mmol / g, and a nitrogen atom concentration derived from (a3) ​​of 0.00 mmol / g. Resin composition 46 is a composition containing a urethane (meth)acrylate that does not contain an amine compound (a3) ​​and a polyfunctional (meth)acrylic compound (B).

[0075] (Manufacturing Example 47) Into a four-neck flask equipped with a stirrer, a condenser, a thermometer, and a gas inlet tube, 61.3 parts of MIRAMER M600 as a polyfunctional (meth)acrylic compound (B) was placed, and 1.6 parts of monoethanolamine as an amine compound having a hydroxyl group was added dropwise while cooling with water so that the temperature inside the flask did not exceed 30°C. After completion of the addition, the mixture was stirred for a further 15 minutes to complete the 1,4-addition reaction (Michael addition reaction) of the acryloyl group and the amino group. Next, to this reaction liquid were added 4.5 parts of toluene diisocyanate (a mixture of toluene-2,4-diisocyanate:toluene-2,6-diisocyanate = 80:20 (mass ratio)) as the isocyanate compound (a1), 27.4 parts of MIRAMER M500 (a mixture containing (a1) and (B) in a mass ratio of 1:1) as the (meth)acrylic compound (a2) having a hydroxyl group and the polyfunctional (meth)acrylic compound (B), 5 parts of LAROMER LR8863 as the polyfunctional (meth)acrylic compound (B), 0.01 parts of tin 2-ethylhexanoate as a catalyst, and 0.2 parts of tert-butylhydroquinone as a polymerization inhibitor, and the mixture was stirred and air was blown in to cause a reaction at 110°C for 5 hours, thereby obtaining resin composition 47. The resulting urethane (meth)acrylate had a (meth)acryloyl group concentration of 7.83 mmol / g and a nitrogen atom concentration derived from (a3) ​​of 0.52 mmol / g. Resin composition 47 is a composition containing a urethane (meth)acrylate containing a nitrogen atom derived from a primary amine compound and a polyfunctional (meth)acrylic compound (B).

[0076] [Table 1]

[0077] [Table 1]

[0078] [Table 1]

[0079] [Table 1]

[0080] Details of the materials listed in Table 1 are provided below. Isocyanate compounds (a1) Mixture of toluene diisocyanate: toluene-2,4-diisocyanate: toluene-2,6-diisocyanate = 80:20 (mass ratio) Duranate TPA-100: Asahi Kasei Corporation, an isocyanurate compound cyclized with 3 moles of 1,6-hexamethylene diisocyanurate (Meth)acrylic compounds having a hydroxyl group (a2) Aronix M306: manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate in a mass ratio of 70 / 30 MIRAMER M500: manufactured by Bigen Specialty Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a 50 / 50 (mass ratio) mixture Viscoat #802: Polypentaerythritol polyacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. Amine compounds having a hydroxyl group (a3) Liponol C / 12: N,N-bis(2-hydroxyethyl) palm alkylamine, manufactured by Lion Specialty Chemicals Co., Ltd. Liponol C / 15: Polyoxyethylene (5EO) palm alkylamine, manufactured by Lion Specialty Chemicals Co., Ltd. Liponol C / 25: Polyoxyethylene (15EO) palm alkylamine, manufactured by Lion Specialty Chemicals Co., Ltd. Polyol compounds PEG-300: Polyethylene glycol, manufactured by Sanyo Chemical Industries, Ltd. Sannix GP-250: Sanyo Chemical Industries, Ltd., propylene oxide-modified glycerin Hydrogenated bisphenol A: 2,2-bis(4-hydroxycyclohexyl)propane Sannix PP-1200: Polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd. Polyfunctional (meth)acrylic compound (B) Aronix M306: manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate in a mass ratio of 70 / 30 MIRAMER M500: manufactured by Bigen Specialty Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a 50 / 50 (mass ratio) mixture MIRAMER M600: Bigen Specialty Chemical Co., Ltd., dipentaerythritol hexaacrylate LAROMER LR8863: BASF, ethylene oxide modified trimethylolpropane triacrylate Polymerization inhibitor TBHQ: Tertiary butyl hydroquinone

[0081] (Examples 1 to 39, Comparative Examples 1 to 10) The previously prepared resin compositions 1 to 43 and 45 to 48 containing urethane (meth)acrylate were mixed with the raw materials according to the compositions in Table 2, and milled in a three-roll mill to obtain the active energy ray-curable ink compositions of Examples 1 to 39 and Comparative Examples 1 to 10.

[0082] <How to prepare test samples> The obtained active energy ray curable ink composition was applied to a corona-treated biaxially oriented polypropylene (OPP) film (Futamura Chemical Co., Ltd., product name: FOR, thickness 20 μm) using an RI tester (Tester Sangyo Co., Ltd., simple printing tester) at a rate of 5 g / m. 2 The ink composition was then cured by irradiating the ink-printed surface on the OPP film with an LED lamp (XP-9, manufactured by Air Motion Systems Co., Ltd., irradiation conditions: focal length 10 mm, output 100%) at a conveyor speed of 30 m / min to prepare a test sample. The test sample was then evaluated for adhesion and curability, and the results are shown in Table 2.

[0083] <Evaluation of Adhesion> Adhesive tape (Nichiban Cellotape®, 18mm wide) was applied to the ink-printed surface of the test sample prepared by the above method, and then peeled off perpendicularly at a 90-degree angle. The adhesion to the substrate was evaluated based on the percentage of the area of ​​the ink coating that peeled off from the OPP film. A, B, and C represent practical levels. A: The ink film does not peel off from the substrate. B: Less than 10% of the ink film has peeled off from the substrate. C: Peeling of the ink film from the substrate is 10% or more but less than 30%. D: 30% or more of the ink film has peeled off from the substrate.

[0084] <Curing evaluation (MEK rubbing evaluation)> The ink film on the ink-printed surface of the test sample prepared by the above method was rubbed back and forth with a cotton swab soaked in MEK, and the ink film was judged based on the number of times the cotton swab was rubbed back and forth until the ink film was damaged. A, B, and C were practical levels. (Evaluation criteria) A: More than 100 times B: 50 to less than 100 times C: 20 to less than 50 times D: Less than 20 times

[0085] [Table 2]

[0086] Details of the materials listed in Table 2 are provided below. Pigments Carbon black: Mitsubishi Chemical Corporation, Carbon Black MA11 Photopolymerization initiator Omnirad379EG: iGM RESINS, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one KAYACURE DETX-S: 2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.

[0087] Examples 1 to 39 were evaluated as being good in terms of "adhesion" and "curability." On the other hand, in Comparative Examples 1 and 4 to 6, although the nitrogen atom concentration was sufficient, the (meth)acryloyl group concentration was low, so the strength of the UV-cured ink coating was reduced, curability was deteriorated, and adhesion was also deteriorated. In Comparative Examples 2 and 3, the primary and secondary amino groups of the amine compound reacted with the isocyanate groups of the isocyanate compound (a1) to form urea bonds, which deteriorated the adhesion. In Comparative Example 9, the structure of the reaction product produced by the 1,4-addition reaction (Michael addition reaction) between monoethanolamine and dipentaerythritol hexaacrylate was bulky around the nitrogen atom, and therefore the adhesion was deteriorated. Furthermore, in Comparative Examples 7 and 8, the adhesion of the ink containing urethane (meth)acrylate with a nitrogen atom concentration of less than 0.4 mmol / g deteriorated. From these findings, it was found that according to the embodiment of the present invention, it is possible to obtain an active energy ray-curable ink having excellent adhesion and curability, and a laminate using the same.

Claims

1. An active energy ray-curable ink composition containing a urethane (meth)acrylate (A) and a polyfunctional (meth)acrylic compound (B) other than (A), the urethane (meth)acrylate (A) is a reaction product of an isocyanate compound (a1), a (meth)acrylic compound (a2) having a hydroxyl group, and an amine compound (a3) ​​having a hydroxyl group other than (a2), the amine compound (a3) ​​having a hydroxyl group is a tertiary amine compound, the (meth)acryloyl group concentration of the urethane (meth)acrylate (A) is 2.0 to 8.0 mmol / g; An active energy ray-curable ink composition, characterized in that the concentration of nitrogen atoms derived from the amine compound (a3) ​​having a hydroxyl group in the urethane (meth)acrylate (A) is 0.4 to 2.7 mmol / g.

2. 2. The actinic ray-curable ink composition according to claim 1, wherein the amine compound (a3) ​​having a hydroxyl group is an amine compound represented by the following general formula (1): General formula (1) R 1 x -N-[(R 2 O) z -H] y (In the formula, R 1 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, R 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms. x represents an integer of 0 to 2, y represents an integer of 1 to 3, and x+y=3. z represents an integer of 1 to 10; Also, if x is 2, there are two R 1 may be the same or different, R 1 They may combine together to form a ring. Also, [(R 2 When there are two or more O)zH groups, they may be the same or different.

3. 2. The active energy ray-curable ink composition according to claim 1, wherein the (meth)acrylic compound (a2) having a hydroxyl group includes a compound having two or more (meth)acryloyl groups in the molecule.

4. 2. The active energy ray-curable ink composition according to claim 1, wherein the (meth)acrylic compound (a2) having a hydroxyl group is at least one selected from the group consisting of pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, and polypentaerythritol poly(meth)acrylate.

5. 2. The active energy ray-curable ink composition according to claim 1, wherein the isocyanate compound (a1) is a diisocyanate compound.

6. 2. The actinic ray-curable ink composition according to claim 1, which is for use on plastic substrates.

7. A laminate comprising a substrate and a layer of a cured product of the active energy ray-curable ink composition according to any one of claims 1 to 6.

8. A method for producing the active energy ray-curable ink composition according to claim 1, comprising: A method for producing an active energy ray-curable ink composition, comprising the step of reacting an isocyanate compound (a1), a (meth)acrylic compound (a2) having a hydroxyl group, and an amine compound (a3) ​​having a hydroxyl group other than (a2) in a polyfunctional (meth)acrylic compound (B) other than (A) to obtain a urethane (meth)acrylate (A).

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