Active energy ray curing varnish composition

Abstract

To provide an active energy-ray curable varnish composition which has excellent stability, curability and transparency as an overprint varnish, uses a material having an animal or vegetable oil-derived structure, and thereby enables more blending of the animal or vegetable oil-derived material and achieves high botanical property.SOLUTION: An active energy-ray curable varnish composition contains the following component (A) and / or the following component (B), and further contains the following component (C). Component (A): an animal or vegetable oil-modified (meth)acrylate compound, component (B): a resin which has no ethylenically unsaturated bond, has a solubility parameter sp value by a sonant mark titration method of 9.0(cal / cm3)1 / 2 or more and less than 11.0(cal / cm3)1 / 2, and has a structure derived from a plant component in a polymer, and component (C): a compound other than the component (A) having an ethylenically unsaturated bond.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable varnish composition.

Background Art

[0002] As described in Patent Document 1, an electron beam-curable overprint varnish containing a resin such as polydimethylsiloxane and a rosin-modified maleic acid resin, and a compound having an ethylenically unsaturated bond, which is excellent in scratch resistance and adhesion, is known.

[0003] As described in Patent Document 2, an active energy ray-curable varnish composition containing a compound having an ethylenically unsaturated bond, a resin having a structure derived from a plant or animal component having a specific sp value, and an oil or fat derived from a plant or animal, which is excellent in stability, curability and gloss, is known.

[0004] Furthermore, as described in Patent Document 3, an active energy ray-curable ink composition having reduced temperature dependence and rate dependence of an intaglio ink containing a vegetable oil-modified (meth)acrylate monomer, a binder resin having no component derived from a vegetable oil, and a vegetable oil-modified (meth)acrylate is described. Furthermore, it is described that when the active energy ray-curable ink composition does not contain a pigment and is transparent, it becomes an overprint varnish.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention aims to achieve high botanical properties by using a material having a structure derived from vegetable oil and fat, while having excellent stability, curability, and transparency as an overprint varnish, and being able to incorporate more materials derived from vegetable oil and fat.

Means for Solving the Problems

[0007] The inventors have found that the above problems can be solved by using the following active energy ray-curable varnish composition, and thus have arrived at the following present invention. 1. An active energy ray-curable varnish composition containing the following component (A) and / or the following component (B), and further containing the following component (C). Component (A): Vegetable oil-modified (meth)acrylate compound Component (B): A resin having no ethylenically unsaturated bond and having a solubility parameter sp value of 9.0 (cal / cm 3 ) 1 / 2 or more and less than 11.0 (cal / cm 3 ) 1 / 2 and having a structure derived from a plant component in the polymer Component (C): A compound having an ethylenically unsaturated bond other than the above component (A) 2. The active energy ray-curable varnish composition according to 1, wherein the total content of component (A) and / or component (B) is 0.1 to 50.0% by mass in the non-volatile content excluding the non-reactive solvent in the active energy ray-curable varnish composition. 3. The active energy ray-curable varnish composition according to 1 or 2, wherein component (B) is a rosin-based resin. 4. The active energy ray-curable varnish composition according to any one of 1 to 3 for an aluminum-deposited paper. 5. A printed matter obtained by applying the active energy ray-curable varnish composition according to any one of 1 to 4.

Effects of the Invention

[0008] According to the present invention, it is possible to obtain an active energy ray curable varnish composition that has a high botanical content while also having excellent stability and curability, and an active energy ray curable varnish composition that exhibits excellent transparency of the film formed by the cured varnish composition. [Modes for carrying out the invention]

[0009] The present invention is based on the following matters, and this active energy ray curable varnish composition is used for the same purposes as conventional active energy ray curable varnish compositions. In this specification, the active energy ray curable varnish composition of the present invention may sometimes be simply referred to as "varnish composition". The present invention is as follows: An active energy ray curable varnish composition containing the following component (A) and / or component (B), and further containing component (C). (A) Ingredients: Modified (meth)acrylate compounds from animal and vegetable oils (B) Component: It does not have ethylenically unsaturated bonds, and its solubility parameter sp value by turbidity titration is 9.0 (cal / cm³). 3 ) 1 / 2 The above, and 11.0 (cal / cm³) 3 ) 1 / 2 resins less than 100% of which contain plant-derived structures within the polymer. (C) Component: Compounds having ethylenically unsaturated bonds other than the above component (A). In this specification, "(meth)acrylate" means "acrylate and / or methacrylate," and "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid."

[0010] [(A) component] As the (A) animal and vegetable oil-modified (meth)acrylate compound, epoxidized vegetable oil acrylate obtained by (meth)acrylic modification of epoxidized vegetable oil, which is obtained by epoxidizing vegetable oil, can be used. This is a compound obtained by ring-opening addition polymerization of (meth)acrylic acid to the epoxy group of epoxidized vegetable oil, which is obtained by epoxidizing the double bond of unsaturated vegetable oil with an oxidizing agent such as peracetic acid or perbenzoic acid. This unsaturated vegetable oil may be a triglyceride in which at least one fatty acid has at least one carbon-carbon unsaturated bond, or it may be a partial structure of unsaturated vegetable oil rather than a glyceride. Examples include hemp seed oil, linseed oil, hackberry oil, oyster oil, olive oil, cocoa oil, kapok oil, kaya oil, mustard oil, apricot kernel oil, tung oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, thorn oil, camellia oil, corn oil, rapeseed oil, niger oil, rice bran oil, palm oil, castor oil, sunflower oil, grape seed oil, henbit oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, and dehydrated castor oil. Since vegetable oil-modified (meth)acrylate compounds are derived from vegetable oils, they are useful in increasing the amount of biomass components in the varnish composition. Alternatively, (meth)acrylate compounds modified with animal oils may also be used. Furthermore, various types of epoxidized vegetable oil (meth)acrylates are commercially available and may be used. Alternatively, rosin-modified epoxy (meth)acrylate can be used. If the varnish composition contains component (A), the content of component (A) in the nonvolatile content of the varnish composition excluding the nonreactive solvent is preferably 0.1% by mass or more, more preferably 5.0% by mass or more, more preferably 50.0% by mass or less, and more preferably 35.0% by mass or less.

[0011] Furthermore, as one type of vegetable oil-modified (meth)acrylate compound, among the modified derivatives of cashew nut shell oil described later, those obtained by introducing an ethylenically unsaturated bond to the phenolic hydroxyl group of alkenyl-substituted phenols contained in cashew nut shell oil and represented by the following general formula (1) or general formula (2) are also included. These compounds are treated as compounds having an ethylenically unsaturated bond. Also, since these compounds are derived from cashew nut shell oil, they contribute to an increase in the biomass content in the varnish composition.

[0012]

Chemical formula

[0013] In the above general formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an aliphatic hydrocarbon group having 15 to 18 carbon atoms and containing 0 to 3 unsaturated bonds. In the above general formula (2), R 1 is a hydrogen atom or a methyl group, and R 2 is an aliphatic hydrocarbon group having 15 to 18 carbon atoms and containing 0 to 3 unsaturated bonds.

[0014] Also, considering the environmental aspect, it is also possible to employ a polyurethane oligomer and / or a polyurethane-polyurea oligomer using a polyester polyol obtained by using a plant-derived dicarboxylic acid component and a diol component as raw materials. As the vegetable oil-modified polyfunctional polyester acrylate oligomer, any vegetable oil-modified polyester acrylate oligomer having 2 to 6 acrylate groups in the molecule can be used without limitation. Among these, for example, when using one or more selected from the group consisting of EBECRYL 450, 452, 820, 1622, and a tall oil fatty acid-modified hexafunctional polyester acrylate (for example, AgiSyn 716, etc.), it is preferable because the biomass degree of the active energy ray-curable varnish composition can be increased. These oligomers can be used alone or in combination of two or more.

[0015] [(B) Component] (B) Component does not have ethylenically unsaturated bonds, and its solubility parameter sp value by turbidity titration is 9.0 (cal / cm³). 3 ) 1 / 2 The above, and 11.0 (cal / cm³) 3 ) 1 / 2 It is a resin with a structure derived from plant components within the polymer, and its pH is less than 9.5 (cal / cm³). 3 ) 1 / 2 The above is preferable, and 10.5 (cal / cm³) 3 ) 1 / 2 The following are preferable. Examples of such resins include rosin-modified maleic acid resins, rosin-modified phenolic resins, rosin-modified alkyd resins, polymerized rosin, disproportionated rosin, and other rosin-based resins, as well as polyamide resins, terpene phenolic resins, and cashew polymers, with rosin-based resins being preferred among them. These resins are derived from plant components such as terpenes and rosin, making them useful for ensuring biomass content. As described above, in rosin-modified phenolic resins and rosin-modified maleic acid resins, the rosin that constitutes them is a biomass-derived component, and in rosin-modified alkyd resins, in addition to rosin, long-chain fatty acids are also biomass-derived components. Therefore, the varnish composition of the present invention has an even higher biomass content by including these resins. As the above-mentioned terpene phenol resin and rosin-modified resins such as rosin-modified maleic acid resin, rosin-modified phenol resin, rosin-modified alkyd resin, polymerized rosin, disproportionated rosin, etc., commercially available products may be used, or resins synthesized by any means may be used.

[0016] The content of component (B) in the nonvolatile matter excluding the nonreactive solvent in the varnish composition is preferably 0.1% by mass or more, more preferably 3.0% by mass or more, and even more preferably 5.0% by mass or more. Furthermore, it is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 20% by mass or less.

[0017] Component (B) may be dissolved in a monomer, oligomer, and / or solvent by heating to about 70-250°C to form a varnish. It is preferable that component (B) be used in the preparation of the varnish composition in this varnish form. The method for determining the sp value in this invention is as follows. The sp value is a solubility parameter that can be measured by a simple experimental method called turbidity titration, and is calculated according to the formula by KWSUH and JMCORBETT shown below. For details on calculating the sp value using this method, refer to J.Appl.Polym.Sci.1968,12,2359. Formula sp value = (V ml 1 / 2 ·δH+V mh 1 / 2 ·δD) / (V ml 1 / 2 +V mh 1 / 2 ) In turbidity titration, 0.5 g of the sample is dissolved in 10 mL of toluene or 10 mL of trimethylolpropane triacrylate (TMPTA), which are good solvents, and n-hexane, a poor solvent with a low sp value, is added. The titration volume H (mL) at the turbidity point is read, and similarly, the titration volume D (mL) at the turbidity point is read when ethanol, a poor solvent with a high sp value, is added to the toluene solution. These values ​​are then applied to the following formula: V ml , V mh Simply calculate δH and δD and substitute them into the above formula.

[0018] The molecular volumes and sp values ​​of each solvent used in the above turbidity titration are as follows: Molecular volume of a good solvent φ0: Toluene: 106.28 mL / mol TMPTA: 279.55 mL / mol Molecular volume of low sp value poor solvent φl n-hexane: 131.61 mL / mol Molecular volume of high sp value poor solvent φh Ethanol: 58.39 mL / mol sp values ​​for each solvent: Toluene: 9.14, TMPTA: 9.88 n-Hexane: 7.28, Ethanol: 12.58

[0019] Vml=(φ0·φl) / {(1-VH)·φl+VH·φ0} Vmh=(φ0·φh) / {(1-VD)·φh+VD·φ0} VH = H / (M + H) VD = D / (M + D) δH=(δ0·M) / (M+H)+(δl·H) / (M+H) δD=(δ0·M) / (M+D)+(δl·D) / (M+D) δ0: sp value of a good solvent δl: sp value of a low-sp poor solvent δh: sp value of a high sp value poor solvent H: Titration volume (mL) of low sp value poor solvent D: Titration volume (mL) of high sp value poor solvent M: Volume of good solvent (mL) VH: Volume fraction (%) of titration volume of low sp value poor solvent VD: Volume fraction (%) of titration volume in high sp-value poor solvents

[0020] The term "vegetable oil" usually refers to triglycerides, but in this invention, the structure derived from plant components may also refer to a partial structure of a vegetable oil molecule. Furthermore, it encompasses the structures of oils and fats derived from vegetable oils, and modified vegetable oils obtained by hydrolyzing vegetable oils to remove glycerin. Examples of these vegetable oil-derived oils include those that, regardless of whether their sp value is within the above range, are chemically modified to achieve the above sp value range. Examples of such modified products include fatty acid esters of triglycerides with high sp values ​​such as coconut oil, castor oil, and tall oil; hydrogenated castor oil; polymerized castor oil; unsaturated animal and vegetable oils or epoxidized fatty acids thereof; polymers of cashew nut shell oil; and modified derivatives of cashew nut shell oil. Note that "lacking ethylenically unsaturated bonds" means that the material lacks substituents that rapidly polymerize in the presence of radicals, such as acryloyl groups, methacryloyl groups, and vinyl groups.

[0021] Unsaturated vegetable oils or epoxidized fatty acids thereof (hereinafter referred to as "epoxidized oils and fats" as appropriate) are esters of a fatty acid having at least one epoxy group and an alcohol. Examples of such epoxidized oils and fats include not only triglycerides having epoxy groups, but also esters of fatty acids having epoxy groups and alcohols (whether monoalcohols or polyalcohols). Examples of such alcohols include, but are not particularly limited to, C1-C14 alcohols such as glycerin, methanol, ethanol, propanol, isopropanol, and 2-ethylhexanol. In the case of polyhydric alcohols such as glycerin, it is sufficient that at least one fatty acid having at least one epoxy group is condensed (i.e., an ester bond is formed) to the polyhydric alcohol, and multiple fatty acids having at least one epoxy group may be condensed. In this case, each fatty acid may be selected independently of each other. Since epoxidized oils and fats exhibit a high sp value due to the presence of epoxy groups in the molecule, they may be produced by epoxidizing various animal and vegetable oils or their fatty acid esters, which originally have low sp values, as raw materials.

[0022] An epoxy group is a three-membered cyclic ether (also called an oxirane or alkylene oxide) in which an oxygen atom is bonded to each of two carbon atoms that are already bonded to each other. Examples of epoxidized oils and fats include epoxidized soybean oil (ESO), epoxidized corn oil, epoxidized sunflower oil, epoxidized linseed oil, epoxidized canola oil, epoxidized rapeseed oil, epoxidized safflower oil, epoxidized tall oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, epoxidized soybean oil, epoxidized propylene glycol dioleate, epoxidized palm oil, and epoxidized fatty acid methyl esters.

[0023] Epoxidized fats and oils can be prepared by a variety of methods. For example, epoxidized fats and oils with a triglyceride as the mother skeleton can be obtained by oxidizing vegetable or animal oils with unsaturated bonds in the fatty acid portion with an appropriate oxidizing agent or peroxide. Alternatively, epoxidized fats and oils with a non-triglyceride fatty acid ester as the mother skeleton can be obtained by reacting fatty acids derived from animal or vegetable oils with unsaturated bonds with an alcohol (whether monool or polyol) to esterify the fatty acid. Fatty acid esters can be obtained by esterification, transesterification, or ester substitution reactions, and these fatty acid esters can then be oxidized with a suitable oxidizing agent or peroxide. Note that these preparation methods are just examples; other preparation methods can be used, or commercially available epoxidized oils and fats may be purchased and used.

[0024] Cashew nut shell oil, also known as cashew nut shell liquid, is an oily liquid contained in the shells of cashew nuts, obtained as a by-product when harvesting the natural cashew nuts used for food. It contains anacardic acid, cardol, 2-methylcardol, cardanol, etc. Of these, cardanol and cardol are compounds in which a hydroxyl group and a linear hydrocarbon group are bonded to an aromatic ring, 2-methylcardanol is a compound in which a methyl group is bonded to the aromatic ring of cardanol, and cardanolic acid is a compound in which a carboxyl group is bonded to the aromatic ring of cardanol. All of these can be called alkenyl-substituted phenols. The alkenyl groups contained therein are aliphatic hydrocarbon groups with 15 to 18 carbon atoms, and their chains contain 1 to 3 unsaturated bonds. Note that the unsaturated bonds contained in these alkenyl groups are located in the middle of a linear hydrocarbon group and are different from ethylenically unsaturated bonds. Various grades of cashew nut shell oil are commercially available, so such commercially available products may be used in this invention. Such products come in several lines depending on the purity, color, and odor of cardanol. Examples of such lines include Cardolite® NX-2021, NX-2022, NX-2023D, NX-2023, UltraLITE2023, NX-2024, NX-2025, and NX-2026 from Cardolite, Inc., and CNSL, LB-7000, and LB-7250 from Tohoku Chemical Co., Ltd.

[0025] Modified derivatives of cashew nut shell oil include those obtained by introducing various groups to the phenolic hydroxyl groups of alkenyl-substituted phenols contained in cashew nut shell oil, those obtained by introducing various substituents to the unsaturated bonds of alkenyl groups, and those obtained by oxidizing and epoxidizing the unsaturated bonds of alkenyl groups. Since various types of such modified derivatives are commercially available, such commercially available products may be used in the present invention.

[0026] Among such modified derivatives, compounds represented by any of the following general formulas (3) to (6) are preferred.

[0027] [ka]

[0028] In the above general formula (3), R 1 R consists of a hydrogen atom, a glycidyl group, -(CH2)mOH (where m is an integer from 1 to 3), -(C2H4O)pH (where p is an integer from 1 to 15), and -(CH2CH(CH3)O)qH (where q is an integer from 1 to 15). 2 This is an aliphatic hydrocarbon group having 15 to 18 carbon atoms and containing 0 to 3 unsaturated bonds, or a group in which some or all of the unsaturated bonds contained in the aliphatic hydrocarbon are oxidized to form an epoxy ring, and each R 3 Each is independently OR 1 It is an alkyl group or carboxyl group having 1 to 3 carbon atoms, and n is an integer from 0 to 4.

[0029] Examples of commercially available compounds represented by the above general formula (3) include Cardolite® LITE2020, Cardolite® NC-513, NC-510, GX-5166, GX-5167, GX-5170, GX-5248, GX-5190, GX-5191, and GX-2551, all manufactured by Cardolite. Of these, LITE2020 is R 1 R is -CH2CH2OH 2 It is an alkenyl-substituted phenyl ether compound with an alkenyl group having 15 carbon atoms and n = 0, and NC-513 is R 1 R is a glycidyl group 2 R is an alkenyl-substituted phenylglycidyl ether with an alkenyl group having 15 carbon atoms and n being 0, and NC-510 is R 1 R is a hydrogen atom 2 It is an alkenyl-substituted phenol with an alkenyl group having 15 carbon atoms and n = 0, and GX-5166, 5167 and 5170 are R 1 At -(C2H4O)pH, R 2The compound is an alkenyl-substituted phenylethyl oxilate with a carbon-15 alkenyl group and n=0, where GX-5166 has p=7, GX-5167 has p=9, GX-5170 has p=12, and GX-5243, 5190 and 5191 are R 1 R is -(CH2CH(CH3)O)qH, R2 is an alkenyl group with 15 carbon atoms and n is 0, and GX-5243 has q=1, GX-5190 has q=7, and GX-5191 has q=9. GX-2551 is a mixture of compounds represented by the following chemical formulas (1), (2), and (3), and in the above general formula (3), R 1 The glycidyl group is R 2 This is an epoxidized cardanol, in which one or more unsaturated bonds in a carbon-15 alkenyl group are oxidized to form an epoxy ring, and n is 0.

[0030] [ka]

[0031] In the above general formula (4), X is a linear or branched aliphatic hydrocarbon group having 15-18 carbon atoms and containing 0-3 unsaturated bonds. A commercially available example of a compound represented by the above general formula (4) is Cardolite® NC-514 manufactured by Cardolite.

[0032] In the above general formula (5), R 2 , R 3 n and r are the same as in the general formula (1) above, and r is an integer from 1 to 5. A commercially available example of the compound represented by the general formula (5) above is Cardolite® GX-2520 manufactured by Cardolite.

[0033] In the above general formula (6), R 2 , R 3 And n are the same as those in the general formula (3) above, and R 4 R is a hydrogen atom or a hydroxyl group, 5is a hydrogen atom or -C2H4OH. Examples of commercially available compounds represented by the above general formula (6) include Cardolite® GX-9301 and GX-9302 manufactured by Cardolite.

[0034] Preferred examples of polymers of cashew nut shell oil include condensates of cashew nut shell oil and / or its modified derivatives with formaldehyde. An example of such a condensate is represented by the following general formula (7).

[0035] [ka]

[0036] In the above general formula (7), each R 1 Each is independently a hydrogen atom, -(CH2)mOH, or glycine. In the sidyl group, m is an integer from 1 to 3, and each R 2 Each of these is an aliphatic hydrocarbon group with 15 to 18 carbon atoms, each independently containing 0 to 3 unsaturated bonds, and n is an integer greater than or equal to 1.

[0037] Examples of commercially available products represented by the above general formula (7) include Cardolite® NC-547 and NX-4000 series manufactured by Cardolite. NC-547 is a formaldehyde condensate of cardanol and a cardanol-modified derivative, having the structure exemplified by the following general formula (8). The NX-4000 series is a formaldehyde condensate of cardanol, having the structure exemplified by the following general formula (9).

[0038] [ka]

[0039] In the above general formulas (8) and (9), each R 2 Each of these is an aliphatic hydrocarbon group with 15 to 18 carbon atoms, each independently containing 0 to 3 unsaturated bonds.

[0040] The animal and vegetable oils and fats are preferably non-edible oils and fats or modified versions thereof. Non-edible oils and fats here refer to all oils and fats that are not for consumption. The sp value should be 9.0 (cal / cm³). 3 ) 1 / 2 Even if the oil is less than 9.0 (cal / cm³), if chemical modification such as epoxidation is applied to that oil, the resulting modified product will have an sp value of 9.0 (cal / cm³). 3 ) 1 / 2 If the above conditions are met, the modified substance shall be treated as a specific liquid component in this invention.

[0041] Among these specific liquid components, at least one selected from the group consisting of castor oil, coconut oil, cashew nut shell oil, tall oil and their modified products, and epoxidized vegetable oils is preferred.

[0042] [Relationship between the content of component (A) and component (B)] If the varnish composition of the present invention contains only one of component (A) or component (B), it contains them in such a manner that the respective amounts of component (A) and component (B) are as described above. If the varnish composition of the present invention contains both component (A) and component (B), the total amount of component (A) and component (B) in the nonvolatile content of the varnish composition, excluding the nonreactive solvent, is preferably 0.1% by mass or more, more preferably 2.0% by mass or more, more preferably 50.0% by mass or less, and more preferably 35.0% by mass or less. Furthermore, if the varnish composition of the present invention contains both component (A) and component (B), it is preferable that the ratio of component (A) to component (B) is 1 / 4 to 4 / 1 by mass.

[0043] [(C) component] In the present invention, component (C) is a compound having an ethylenically unsaturated bond other than component (A), consisting of one or more monomers, oligomers, and polymers, and is a component that hardens upon reaction with active energy rays. The following monofunctional or more monomers can be used individually or in combination of two or more. The content of component (C) in the nonvolatile matter excluding the nonreactive solvent in the varnish composition is preferably 30.0% by mass or more, more preferably 40.0% by mass or more, even more preferably 50.0% by mass or more, and most preferably 55.0% by mass or more. Furthermore, it is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and even more preferably 85.0% by mass or less. Furthermore, among component (C), it is preferable to use a bifunctional and / or trifunctional component, and even more preferable to use a polyoxyalkylene-modified component.

[0044] (monomer) Monomers are components that possess ethylenically unsaturated bonds and polymerize as photopolymerizable components to achieve high molecular weights. However, before polymerization, they are often relatively low molecular weight liquid components. Monomers are also used as reactive solvents to dissolve separately formulated resin components or to adjust the viscosity of varnish compositions. Examples of such monomers include monofunctional monomers, which have one ethylenically unsaturated bond in their molecule, and bifunctional or multifunctional monomers, which have two or more ethylenically unsaturated bonds in their molecule. Bifunctional or multifunctional monomers can crosslink molecules during the curing of the varnish composition, thus contributing to faster curing and the formation of a strong film. Monofunctional monomers, while lacking the crosslinking ability described above, contribute to reducing curing shrinkage associated with crosslinking. These monomers can be used in various combinations as needed.

[0045] As monofunctional monomers, unsaturated carboxylic acid compounds, alkyl (meth)acrylate compounds, hydroxyl group-containing (meth)acrylate compounds, halogen-containing (meth)acrylate compounds, ether group-containing (meth)acrylate compounds, carboxyl group-containing (meth)acrylate compounds, other (meth)acrylate compounds, styrene compounds, N-vinyl compounds, arylate compounds, and other compounds having one ethylenically unsaturated bond can be used.

[0046] -Unsaturated carboxylic acid compounds- Examples of unsaturated carboxylic acid compounds include (meth)acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid, and other unsaturated carboxylic acids, as well as their salts and acid anhydrides.

[0047] -Alkyl (meth)acrylate compounds- Examples of alkyl (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and isodecyl (meth)acrylate. Examples include isomiristyl (meth)acrylate, octadecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tridecyl (meth)acrylate, nonyl (meth)acrylate, hexadecyl (meth)acrylate, myristyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3,5,5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl (meth)acrylate, tricyclodecane monomethylol (meth)acrylate, etc.

[0048] -Hydroxyl group-containing (meth)acrylate compounds- Examples of hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, and polypropylene Examples include polyalkylene glycol-modified (meth)acrylates such as ylene glycol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, glycerin mono(meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-ethylhexyl EO-modified (meth)acrylate, o-phenylphenol EO-modified (meth)acrylate, p-cumylphenol EO-modified (meth)acrylate, and nonylphenol EO-modified (meth)acrylate.

[0049] -Halogen-containing (meth)acrylate compounds- Examples of halogen-containing (meth)acrylate compounds include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H-hexafluoroisopropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,2H,2H-heptadecafluorodecyl (meth)acrylate, 2,6-dibromo-4-butylphenyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, and 2,4,6-tribromophenol 3EO (ethylene oxide)-added (meth)acrylate.

[0050] -Ether group-containing (meth)acrylate compounds- Examples of ether group-containing (meth)acrylate compounds include 1,3-butylene glycol methyl ether (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, and tetrahydrofluor Furyl (meth)acrylate, cresyl polyethylene glycol (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, p-nonylphenoxyethyl (meth)acrylate, p-nonylphenoxy polyethylene glycol (meth)acrylate, glycidyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate, hexaethylene glycol monophenyl ether mono(meth)acrylate Diethylene glycol monobutyl ether acrylate, dipropylene glycol monomethyl ether (meth)acrylate, 3-methoxybutyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate (EO repeating units 400, 700, etc.), 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxy Butyl acrylate, ethoxyethyl acrylate, ethoxyethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, alkoxylated 2-phenoxyethyl (meth)acrylate (ethoxylated 2-phenoxyethyl (meth)acrylate, propoxylated 2-phenoxyethyl (meth)acrylate, etc.), alkoxylated nonylphenyl (meth)acrylate (ethoxylated (4) nonylphenol acrylate, etc.), 2-phenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate,Examples include methylphenoxyethyl acrylate, ethoxylated succinic acid (meth)acrylate, ethoxylated tribromophenyl acrylate, ethoxylated nonylphenyl (meth)acrylate, and other alkoxy and / or phenoxy (meth)acrylates.

[0051] -Carboxyl group-containing (meth)acrylate compounds- Examples of carboxyl group-containing (meth)acrylate compounds include β-carboxyethyl (meth)acrylate, (meth)acrylate dimer, monoacryloyloxyethyl succinate, ω-carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrohydrogen phthalate, and 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate.

[0052] -Other (meth)acrylate compounds- Other (meth)acrylate compounds include, for example, benzyl acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, acryloylmorpholine, morpholinoethyl (meth)acrylate, trimethylsiloxyethyl (meth)acrylate, diphenyl-2-(meth)acryloyloxyethyl phosphate, 2-(meth)acryloyloxyethyl acid phosphate, and caprolactone-modified-2-(meth)acryloyl Xyethyl acid phosphate, 2-hydroxy-1-(meth)acryloxy-3-methacryloxypropane, acryloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, tricyclodecane monomethylol (meth)acrylate, (meth)acrylate dimer, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexa Hydrophthalic acid, 2-ethylhexyl-diglycol (meth)acrylate, aminoethyl (meth)acrylate, ethyl carbitol acrylate, ethyl diglycol acrylate, dimethylaminoethyl acrylate benzyl chloride quaternary salt, tribromophenyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, cresol (meth)acrylate, trimethylolpropane formal (meth)acrylate, neopentyl glycol (meth)acrylate Examples include fermented acid esters, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-(meth)acryloylpiperidine-2-one, 2-(meth)acrylate-1,4-dioxaspiro[4,5]decy-2-ylmethyl, N-(meth)acryloyloxyethylhexahydrophthalimide, γ-butyrolactone (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, imide acrylate, vinyl (meth)acrylate, maleimide, etc.

[0053] -Styrene-based compounds- Examples of styrene-based compounds include styrene, vinyltoluene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene, and divinylbenzene.

[0054] -N-vinyl compounds- Examples of N-vinyl compounds include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-2-caprolactam, N-vinylcarbazole, and vinylmethyloxazolidinone.

[0055] -Arylate compounds- Examples of arylate compounds include allyl glycidyl ether, diallyl phthalate, trialyl trimellitate, and isocyanuric acid trialylate.

[0056] -Other compounds containing one ethylenically unsaturated bond- As a compound having one ethylenically unsaturated bond, other "compounds having one ethylenically unsaturated bond" other than the aforementioned compound can be used. Examples of such compounds include vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl crotonate, vinyl 2-ethylhexanoate, three-membered ring compounds (e.g., vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes, 2-phenyl-3-vinyloxiranes, 2,3-divinyloxiranes, etc.), and cyclic ketene acetals (e.g., 2-methylene-1,3-dioxepane, posioxolanes, 2-methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3-dioxepane, etc.).

[0057] As polyfunctional monomers (compounds having two or more ethylenically unsaturated bonds), known polyfunctional (meth)acrylate compounds and vinyl ether group-containing (meth)acrylate compounds having two or more ethylenically unsaturated bonds, such as those listed below, can be used. Furthermore, these polyalkylene oxide modified products include, for example, 3EO (ethylene oxide) modified products, 6EO modified products, 9EO modified products (such as 3EO modified trimethylolpropane tri(meth)acrylate, 3EO modified trimethylolethane tri(meth)acrylate, and 3EO modified trimethylolhexane tri(meth)acrylate).

[0058] -Polyfunctional (meth)acrylate compounds- Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, pentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate Rate, hydroxypivalyl hydroxypivalate di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactone di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediool di(meth)acrylate, 1,2-hexadecanediool di(meth)acrylate, 2-methyl-2,4-pentanediol Di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethylol octanedi(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-Hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tricyclodecanedimethylol dicaprolactone di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, bisphenol A tetraethylene oxide adduct di(meth)acrylate (4EO-modified bisphenol A di(meth)acrylate), bisphenol F tetraethylene oxide adduct di(meth)acrylate, Difunctional monomers such as di(meth)acrylates of polyhydric alcohols such as bisphenol S tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol F tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, bisphenol A tetraethylene oxide adduct dicaprolactone di(meth)acrylate, bisphenol F tetraethylene oxide adduct dicaprolactone di(meth)acrylate, glycerin, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol;

[0059] Trifunctional monomers such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tricaprolactone tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolhexane tri(meth)acrylate, trimethyloloctan tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; and polyalkylene oxide modified products thereof, for example, 3EO (ethylene oxide) modified products, 6EO modified products, 9EO modified products (3EO modified trimethylolpropane tri(meth)acrylate, 3EO modified trimethylolethane tri(meth)acrylate, 3EO modified trimethylolhexane tri(meth)acrylate, etc.), trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetracaprolactone Examples include four- or more functional monomers such as nate tetra(meth)acrylate, diglycerin tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetracaprolactone tetra(meth)acrylate, ditrimethylolethane tetra(meth)acrylate, ditrimethylolbutane tetra(meth)acrylate, ditrimethylolhexane tetra(meth)acrylate, ditrimethyloloctane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and tripentaerythritol polyalkylene oxide hepta(meth)acrylate. Among these, trimethylolpropane triacrylate (TMPTA; trifunctional), ditrimethylolpropane tetraacrylate (DITMPTA; tetrafunctional), dipentaerythritol hexaacrylate (DPHA; hexfunctional), and hexanediol diacrylate (HDDA; bifunctional) are particularly preferred.

[0060] -Vinyl ether group-containing (meth)acrylate compounds- Examples of vinyl ether group-containing (meth)acrylate compounds include (meth)acrylate-2-vinyloxyethyl, (meth)acrylate-3-vinyloxypropyl, (meth)acrylate-1-methyl-2-vinyloxyethyl, (meth)acrylate-2-vinyloxypropyl, (meth)acrylate-4-vinyloxybutyl, (meth)acrylate-1-methyl-3-vinyloxypropyl, (meth)acrylate-1-vinyloxymethylpropyl, and (meth)acrylate-2-methyl-3-vinyloxypropyl Pill, (meth)acrylate-3-methyl-3-vinyloxypropyl, (meth)acrylate-1,1-dimethyl-2-vinyloxyethyl, (meth)acrylate-3-vinyloxybutyl, (meth)acrylate-1-methyl-2-vinyloxypropyl, (meth)acrylate-2-vinyloxybutyl, (meth)acrylate-4-vinyloxycyclohexyl, (meth)acrylate-5-vinyloxypentyl, (meth)acrylate-6-vinyloxyhexyl, (meth)acrylate-4-vinyloxymethylcyclohexyl Xylmethyl, (meth)acrylate-3-vinyloxymethylcyclohexylmethyl, (meth)acrylate-2-vinyloxymethylcyclohexylmethyl, (meth)acrylate-p-vinyloxymethylphenylmethyl, (meth)acrylate-m-vinyloxymethylphenylmethyl, (meth)acrylate-o-vinyloxymethylphenylmethyl, (meth)acrylate-2-(vinyloxyisopropoxy)ethyl, (meth)acrylate-2-(vinyloxyethoxy)propyl, (meth)acrylate-2-( Examples include vinyloxyethoxy)isopropyl, (meth)acrylate-2-(vinyloxyisopropoxy)propyl, (meth)acrylate-2-(vinyloxyisopropoxy)isopropyl, (meth)acrylate-2-(vinyloxyethoxyethoxy)ethyl, (meth)acrylate-2-(vinyloxyethoxyisopropoxy)ethyl, (meth)acrylate-2-(vinyloxyisopropoxyethoxy)ethyl, and (meth)acrylate-2-(vinyloxyisopropoxyisopropoxy)ethyl.

[0061] Among these polyfunctional monomers, 4EO-modified difunctional monomers and 3EO-modified trifunctional monomers are preferred, and it is more preferable that they contain 3EO-modified trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, and bisphenol A tetraethylene oxide adduct di(meth)acrylate (4EO-modified bisphenol A di(meth)acrylate).

[0062] (Oligomer) Oligomers are components whose ethylenically unsaturated bonds within the molecule polymerize to become high molecular weight molecules. Because they are inherently relatively high molecular weight components, they are also used to impart appropriate viscosity and elasticity to varnish compositions. Furthermore, oligomers are relatively polar, and can be expected to impart adhesion to non-absorbent media to cured varnish compositions. Examples of these oligomers include epoxy-modified (meth)acrylates, which are exemplified by esters of hydroxyl groups formed after ring-opening epoxy groups contained in epoxy compounds such as epoxy resins with acids or bases, and (meth)acrylic acid; polyester-modified (meth)acrylates, which are exemplified by esters of terminal hydroxyl groups of condensed polymers of dibasic acids and diols and (meth)acrylic acid; polyether-modified (meth)acrylates, which are exemplified by esters of terminal hydroxyl groups of polyether compounds and (meth)acrylic acid; urethane-modified (meth)acrylates, which are exemplified by esters of terminal hydroxyl groups of condensates of polyisocyanate compounds and polyol compounds and (meth)acrylic acid; and amine-modified oligomers.

[0063] Examples of oligomers possessing such ethylenically unsaturated bonds include polydiallyl phthalate, neopentyl glycol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, urethane(meth)acrylate, polyester(meth)acrylate, epoxy(meth)acrylate, unsaturated polyester, polyether(meth)acrylate, acrylic resins with unreacted unsaturated groups, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, acrylic-modified phenolic resins, and oligomers of acrylic amine compounds.

[0064] Such oligomers are commercially available, for example, Sartomer's "CN" and "SR" series, Toagosei's "Aronics M-6000" series, "7000" series, "8000" series, "Aronics M-1100", "Aronics M-1200", "Aronics M-1600", Shin Nakamura Chemical Industry's "NK Ester" and "NK Oligo", Kyoeisha Chemical Industry's "Light Acrylate", "Light Ester", "Epoxy Ester", "Urethane Acrylate" and "High-Performance Oligomer" series, Osaka Organic Chemical Industry's "Special Acrylic Monomer" series, Mitsubishi Rayon's "Acryester" and "Diabeam Oligomer" series, Nippon Kayaku's "Kayarad" and "Kayamer" series, and Nippon Shokubai's " These products are available under product names such as the "(meth)acrylic acid / methacrylic acid ester monomer" series, the "NICHIGO-UV purple light urethane acrylate oligomer" series from Nippon Synthetic Chemical Industry Co., Ltd., the "Carboxylic acid vinyl ester monomer" series from Shin-Etsu Vinyl Acetate Co., Ltd., the "Functional monomer" series from Kojin Co., Ltd., the "EBECRYL," "ACA," "KRM," "IRR," "RDX," and "OTA" series from Daicel Ornex Co., Ltd., the "Laromer" series from BASF, the "Photomer" series from Cognis Co., Ltd., the "Artresin" series from Negami Kogyo Co., Ltd., the "Bremmer" series from NOF Chemical Co., Ltd., the "New Frontier" series from Daiichi Kogyo Seiyaku Co., Ltd., the "Miramer" series from MIWON Co., Ltd., and the "AgiSyn" series from DSM Co., Ltd.

[0065] The amine-modified oligomer is not particularly limited as long as it is an amine-modified (meth)acrylate oligomer having at least one amino group and at least one (meth)acryloyl group or at least two (meth)acryloyl groups in the molecule. The amine-modified (meth)acrylate oligomer may be a synthetic product obtained by polymerizing the desired monomer, or it may be a commercially available product. For example, GENOMER5161, GENOMER5275 (RAHN), CN371, CN371NS, CN373, CN383, CN384, CN386, CN501, CN503, CN550, CN551 (Sartmar), EBECRYL80, EBECRYL81, EBECRYL83, EBECRYL7100, EBECRYL84, EBECRYLP115 (Daicel Ornex), LAROMER PO 83F, LAROMER PO 84F, Laromer LR8946, Laromer LR8956, Laromer LR8996, Laromer LR8894 (BASF), AgiSyn001, AgiSyn002, AgiSyn003, AgiSyn008 (DSM Coating Examples include Photomer4771, Photomer4775, Photomer4967, Photomer5096, Photomer5662, Photomer5930 (Cognis), DoublecureEPD, DoublecureOPD, Doublecure115, Doublecure225, Doublecure645, PolyQ222, PolyQ226, PolyQ224, and PolyQ101 (DoubleBondChemicals).

[0066] (polymer) Polymers as curable resins possessing ethylenically unsaturated bonds are components that, together with the monomers and oligomers mentioned above, become high molecular weight components. Since they already possess a large molecular weight even before irradiation with active energy rays, they are components that are useful in improving the viscoelasticity of varnish compositions. Such polymers are used, for example, in a state where they are dissolved or dispersed in monomers, which are low viscosity liquids. Examples of polymers possessing ethylenically unsaturated bonds include polydiallyl phthalate, acrylic resins with unreacted unsaturated groups, and acrylic-modified phenolic resins. Among these, polydiallyl phthalate is particularly preferred because of its excellent compatibility with the monomers and oligomers mentioned above. Furthermore, the product does not need to contain polymers having ethylenically unsaturated bonds, but if it does, the content of polymers having ethylenically unsaturated bonds relative to the total amount of photopolymerizable components is preferably 0 to 50.0% by mass, more preferably 0 to 30.0% by mass, and even more preferably 0 to 20.0% by mass.

[0067] [Oils and fats derived from animals and plants] In addition to components (A), (B), and (C) above, animal and plant-derived oils and fats that may be included in the active energy ray-curable varnish composition of the present invention are those that do not impair the effects of the present invention, do not have ethylenically unsaturated bonds, and have a solubility parameter sp value of 9.0 (cal / cm³) in the above turbidity titration method. 3 ) 1 / 2 Less than 11.0 (cal / cm³) 3 ) 1 / 2 The above-mentioned animal and plant-derived oils and fats or modified products thereof may be contained. Such animal and plant-derived oils and fats having an sp value are plant-derived oils and fats introduced into the resin in order to obtain the resin of component (B) above. Examples of such resins include hemp seed oil, linseed oil, hackberry oil, oyster oil, olive oil, cocoa oil, kapok oil, kaya oil, mustard oil, apricot kernel oil, tung oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, porcini oil, camellia oil, corn oil, rapeseed oil, niger oil, rice bran oil, palm oil, sunflower oil, grape seed oil, henbit oil, pine seed oil, cottonseed oil, peanut oil, dehydrated castor oil, refined avocado oil, kukui nut oil, grapeseed oil, sweet almond oil, corn germ oil, pistachio nut oil, hazelnut oil, macadamia nut oil, meadowhome oil, and rosehip oil. Such animal and plant-derived oils are mostly inedible and useful because they can secure biomass content without causing starvation problems. Furthermore, since animal and plant-derived oils do not polymerize, if they are liquid at 25°C as described below, they can exhibit a particularly good leveling effect and can also produce a good gloss. Not only is the effect of these animal and plant-derived oils on the curing properties of the varnish composition hardly problematic, but when coating with the varnish composition of the present invention containing animal and plant-derived oils, it is possible to obtain printed materials with an even better gloss, although the reason is unknown.

[0068] Since fats and oils derived from animals and plants have good compatibility with monomers and oligomers, there is no upper limit to the amount that can be added to the varnish composition from the viewpoint of compatibility. However, from the viewpoint of maintaining properties such as curability, in this invention, the amount of specific liquid components added to the varnish composition is preferably 50.0% by mass or less, and more preferably 30.0% by mass or less. Fats and oils derived from animals and plants are preferably liquid at 25°C.

[0069] [Photopolymerization initiator] A photopolymerization initiator is a component that generates radicals when irradiated with ultraviolet light. These radicals polymerize the compound having the ethylenically unsaturated bond, thereby curing the varnish composition. The photopolymerization initiator is not particularly limited as long as it generates radicals when irradiated with active energy rays. However, when curing the varnish composition of the present invention using an electron beam as the active energy ray, it is not necessary to add a photopolymerization initiator to the varnish composition of the present invention. Examples of photopolymerization initiators include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, triazine-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators. Among these, triazine-based photopolymerization initiators and acylphosphine oxide-based photopolymerization initiators are preferred from the viewpoint of good curability with light-emitting diode (LED) light. The above photopolymerization initiators can be used alone or in combination of two or more.

[0070] Examples of such photopolymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide, benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 Examples include hydroxycyclohexylphenyl ketone, bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, and 2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butan-1-one. Such photopolymerization initiators are commercially available, for example, from IGM RESINS BV under trade names such as Omnirad 907, Omnirad 369, Omnirad 184, Omnirad 379, Omnirad 819, and Omnirad TPO H. These photopolymerization initiators can be used individually or in combination of two or more.

[0071] The preferred content of the photopolymerization initiator in the varnish composition is 2.0 to 30.0% by mass, more preferably 3.0 to 15.0% by mass, and even more preferably 5.0 to 13.0% by mass. A photopolymerization initiator content within this range is preferable because it allows for a balance between sufficient curability, good internal curing properties, and cost-effectiveness.

[0072] (Other ingredients) The active energy ray curable varnish composition of the present invention may contain various additives as other components, such as polymerization inhibitors, sensitizers, pigments, pigment dispersants / resins for pigment dispersion, surfactants, organic solvents, ultraviolet absorbers, antioxidants, defoamers, preservatives, fungicides, rust inhibitors, thickeners, humectants, and pH adjusters. It may also contain, or may not contain, a resin that functions as a vehicle but is not curable. Furthermore, it may contain, or may not contain, a solvent. In addition, waxes such as polyethylene waxes, olefin waxes, and Fischer-Tropsch waxes can be added.

[0073] (Polymerization inhibitor) Examples of polymerization inhibitors include phenol compounds such as butylhydroxytoluene, tocopherol acetate, nitrosamines, benzotriazoles, and hindered amines, with butylhydroxytoluene being a more preferred example. Adding such polymerization inhibitors to the varnish composition suppresses the progression of polymerization reactions during storage, which can lead to thickening of the varnish composition. The content of the polymerization inhibitor in the varnish composition can be exemplified as about 0.01 to 1% by mass.

[0074] (Sensitizer) The active energy ray curable varnish composition of the present invention contains a sensitizer from the viewpoint of improving curability. The sensitizer can be used alone or in combination of two or more types.

[0075] Examples of sensitizers include anthracene-based sensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene; and thioxanthone-based sensitizers such as 2,4-diethylthioxanthone, 2,4-diethylthioxanthe-9-one, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. Of these, at least thioxanthone-based sensitizers are used. Commercially available anthracene-based sensitizers include those with trade names "DBA" and "DEA" (Kawasaki Chemical Industries Co., Ltd.), and thioxanthone-based sensitizers include those with trade names "DETX" and "ITX" (Lambson).

[0076] From the viewpoint of preventing excessive addition, the thioxanthone-based sensitizer may be included in an amount of 0.3 to 5.0 parts by mass when the total amount of photopolymerizable components is 100 parts by mass. Furthermore, it is preferable to include 1.0 part by mass or more, and preferably 4.0 parts by mass or less. In addition, as in the present invention, it is possible to use thioxanthone-based sensitizers such as 2,4-diethylthioxanthone. In the present invention, it is preferable that the total amount of photopolymerizable components is 100 parts by mass, and that the photopolymerization initiator and / or sensitizer is contained in a total of 7.0 to 30.0 parts by mass.

[0077] [Pigments] The active energy ray curable varnish composition of the present invention preferably yields a transparent film. However, pigments can be included within a range that does not impair the transparency of the film. Examples of such pigments include coloring pigments, white pigments, and metal powders. Examples of such pigments include the following organic and / or inorganic pigments that have been conventionally used in varnish compositions, without any particular limitations.

[0078] Examples of pigments include dye lake pigments, azo pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindico pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, nitro pigments, nitroso pigments, flavanthrone pigments, quinophthalone pigments, pyranthrone pigments, indanthrone pigments, and various inorganic pigments. Examples of these pigments include yellow pigments such as disazo yellow (pigment yellow 12, pigment yellow 13, pigment yellow 14, pigment yellow 17, pigment yellow 1) and Hansa yellow; magenta pigments such as brilliant carmine 6B, lake red C, watching red, and quinacridone; cyan pigments such as phthalocyanine blue, phthalocyanine green, and alkali blue; colored pigments (including achromatic pigments such as white and black) such as titanium dioxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, iron black, chromium oxide green, carbon black, and graphite; and metal powders such as aluminum paste and bronze powder.

[0079] The amount of pigment included in the varnish composition is exemplified as 10.0% by mass or less relative to the total varnish composition, depending on the desired degree of coloring, but is not particularly limited.

[0080] (Pigment dispersants / Pigment dispersion resins) When the active energy ray curable varnish composition of the present invention uses a pigment as a coloring agent, a pigment dispersant and / or a pigment dispersing resin may be incorporated. As a pigment dispersant, one or more surfactants selected from the group consisting of known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. As the surfactant, one or more can be selected from the group consisting of, for example, silicone-based surfactants (e.g., polyether-modified silicone oil, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, etc.), fluorine-based surfactants, oxyalkylene ether-based surfactants, acetylene glycol-based surfactants, phosphorus-based surfactants, sulfonic acid-based surfactants, etc. Furthermore, one or more polymer dispersants selected from the group consisting of (for example, carbodiimide-based, polyester-based, polyamine-based, polyesteramine-based, polyurethane-based, fatty acid amine-based dispersants, polyacrylate-based, polycaprolactone-based, polysiloxane-based, multi-chain polymer nonionic-based, polymer ionic-based dispersants, etc.) can be used as the pigment dispersion resin. When the active energy ray curable varnish composition of the present invention contains a pigment dispersant or a pigment dispersing resin, it is preferable that it contains 1 to 200 parts by mass when the total amount of pigment used is 100 parts by mass.

[0081] (Surfactants) The active energy ray curable varnish composition of the present invention can use any known surfactant used in active energy ray curable compositions as a leveling agent, depending on the varnish jet head used. Examples include nonionic surfactants, cationic surfactants, anionic surfactants, and betaine surfactants. Specific examples of the surfactants include silicone-based surfactants such as polyether-modified silicone oil, polyester-modified polydimethylsiloxane, and polyester-modified methylalkylpolysiloxane, as well as fluorine-based surfactants and acetylene-based surfactants. These surfactants can be used individually or in combination of two or more.

[0082] Examples of the aforementioned silicone-based surfactants include BYK-307, BYK-315N, BYK-331, BYK-333, BYK-347, BYK-348, BYK-349, BYK-345, BYK-377, BYK-378, and BYK-3455 (from BYK Chemie Co., Ltd.).

[0083] Examples of the aforementioned fluorine-based surfactants include F-410, F-444, F-553 (DIC Corporation), FS-65, FS-34, FS-35, FS-31, and FS-30 (DuPont).

[0084] Examples of the aforementioned acetylene-based surfactants include Dynol 607, Dynol 609, Olfin E1004, Olfin E1010, Olfin E1020, Olfin PD-001, Olfin PD-002W, Olfin PD-004, Olfin PD-005, Olfin EXP.4001, Olfin EXP.4200, Olfin EXP.4123, Olfin EXP.4300 (Nisshin Chemical Co.), Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol 104DPM, Surfinol 104PA, Surfinol 104PG-50, Surfinol 420, Surfinol 440, and Surfinol 465 (EVONIK).

[0085] The active energy ray curing varnish composition of the present invention does not necessarily have to contain a surfactant, but if it does contain one, the proportion of the surfactant is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, from the viewpoint of reducing the surface tension of the varnish composition and improving its applicability, and preferably 1.5% by mass or less, more preferably 1% by mass or less, from the viewpoint of suppressing foam generated in the varnish composition during compounding and improving its applicability. When a surfactant is included, the amount of surfactant is not particularly limited, but it is preferably such that the surface tension of the active energy ray curable varnish composition is 30.0 to 45.0 mN / m, and more preferably 0.10 to 1.50% by mass in the active energy ray curable varnish composition.

[0086] (Organic solvents) The active energy ray curable varnish composition of the present invention may contain an organic solvent as needed. Examples of the organic solvent include ester-based organic solvents, ether-based organic solvents, ether-ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon solvents, and nitrogen-containing organic solvents. Examples of the organic solvent include those with a boiling point of 150 to 220°C at 1 atmosphere. From the viewpoint of curability of the varnish composition and environmental issues, it is preferable to use the organic solvent as little as possible. Therefore, the proportion of the organic solvent in the varnish composition is preferably 5% by mass or less, and more preferably 2% by mass or less.

[0087] (UV absorber) UV absorbers include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, salicylate-based UV absorbers, hydroxyphenyltriazine-based UV absorbers, cyanoacrylate-based UV absorbers, nickel complex salt-based UV absorbers, and the like.

[0088] (Antioxidant) Antioxidants include phenolic antioxidants, amine antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and others.

[0089] (Antifoaming agent) Examples of defoaming agents include silicone-based defoaming agents and Pluronic®-based defoaming agents.

[0090] The viscosity of the active energy ray curing varnish composition of the present invention at 25°C is preferably 15 seconds or more, more preferably 20 seconds or more, preferably 50 seconds or less, more preferably 40 seconds or less, and even more preferably 25 seconds or less. Viscosity modifiers and the like are added to the varnish composition as needed. The viscosity described in this specification is the viscosity measured at 25°C using Zahn Cup No. 4 (manufactured by Rigosha). Furthermore, the surface tension is preferably 30.0 to 45.0 mN / m.

[0091] <Method for preparing an active energy ray curable varnish composition> Next, a method for producing the active energy ray curable varnish composition of the present invention using these materials will be described. The manufacturing method involves mixing each component in any order to produce a liquid active energy ray curable varnish composition. Therefore, the active energy ray curable varnish composition of the present invention can be obtained by dispersing and mixing each component using a disperser such as a wet circulation mill, bead mill, ball mill, sand mill, attritor, roll mill, DCP mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, high-pressure homogenizer (microfluidizer, nanomizer, ultimateizer, Genus PY, DeBEE2000, etc.), or pearl mill, and adjusting the viscosity of the active energy ray curable varnish composition as necessary. Alternatively, the active energy ray curable varnish composition may be prepared by first obtaining a base composition by mixing the pigment with the above-mentioned pigment dispersant and the above-mentioned photopolymerizable monomer, and then adding the remaining amount of the above-mentioned components to achieve the desired composition. Among the methods described above, one can adopt a method in which component (A), component (B), or a mixture of component (A) and component (B) is heated at a temperature of approximately 25°C or to any temperature between 50 and 250°C, and then component (B), which is normally solid at room temperature, is added and stirred until at least component (B) has dissolved.

[0092] <Printing method using an activated energy ray curing varnish composition> A method for manufacturing a printed material, which includes the step of applying the active energy ray curable varnish composition of the present invention, involves first printing on a substrate using an ink composition, and then applying the active energy ray curable varnish composition of the present invention to the surface of the substrate. Methods for applying the active energy ray curable varnish composition to the surface of the substrate can be known and are not limited to those mentioned above. Examples of such methods include application methods using flexographic coaters such as roll coaters and chamber coaters, gravure coaters, and application methods using offset printing.

[0093] In this way, by irradiating the varnish composition applied to the surface of the printed material with active energy rays, the undried varnish composition instantly dries. Known types of active energy rays, such as electron beams or ultraviolet rays, can be used. Furthermore, the above-mentioned substrate is not particularly limited as long as it is a substrate to which a conventionally known active energy ray curable varnish composition can be applied. Examples of such substrates include plastic, paper, metal-deposited paper capsules such as aluminum-deposited paper, gel, metal foil, glass, wood, and cloth. Furthermore, as the plastic, examples of the base material include one or more selected from the group consisting of polyester polymers (e.g., polyethylene terephthalate (PET), polyethylene naphthalate, etc.), cellulosic polymers (e.g., diacetylcellulose, triacetylcellulose (TAC), etc.), polycarbonate polymers, polyacrylic polymers (e.g., polymethyl methacrylate, etc.), vinyl chloride polymers, polyolefin polymers (e.g., polyethylene, polypropylene, polyolefin polymers having a cyclic or norbornene structure, ethylene-propylene copolymer polymers, etc.), polyamide polymers (e.g., nylon, aromatic polyamide polymers, etc.), polystyrene polymers (e.g., polystyrene, acrylonitrile-styrene copolymer polymers, etc.), polyimide polymers, polysulfone polymers, polyethersulfone polymers, polyetherketone polymers, polyphenylsulfide polymers, polyvinyl alcohol polymers, polyvinylidene chloride polymers, polyvinyl butyral polymers, polyarylate polymers, polyoxymethylene polymers, and polyepoxy polymers, as well as blends of these polymers. In particular, from the viewpoint of the excellent transparency of the present invention, it is preferable to use it in aluminum-metallized paper. [Examples]

[0094] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass percent" and "parts" or "parts by mass". The numbers for the quantities of each material in the table also represent "parts by mass". Active energy ray curable varnish compositions were prepared for each example and comparative example listed in Table 1 below, and the test results and properties of each active energy ray curable varnish composition are shown in Table 1.

[0095] (Activated energy ray curing varnish composition) The ingredients used in Table 1 below are as follows: #3628: Castor oil-modified urethane acrylate (Ito Oil Co., Ltd.) CN111: Soybean oil modified acrylate (Sartomer Co.) AGISYN 716: Tall oil-modified acrylate (DSM Corporation) Varnish 1: 50 parts by mass of rosin-modified alkyd resin (sp value = 10.0) dissolved in 50 parts by mass of dipropylene glycol diacrylate. Varnish 2: A solution prepared by dissolving 50 parts by mass of rosin ester (sp value = 10.0, Tespol 1107 manufactured by Harima Chemicals) in 50 parts by mass of dipropylene glycol diacrylate. Dipropylene glycol diacrylate is a reactive solvent. Omnirad 184: (IGM RESINS BV)

[0096] (Preparation of active energy ray curing varnish composition) Each component was blended to achieve the compositional composition (mass%) shown in Table 1, and the mixture was stirred to obtain the active energy ray curable varnish compositions of the examples and comparative examples.

[0097] <Evaluation Method> (stability) The varnish compositions of each example and comparative example were placed in brown bottles, sealed, and left at 25°C for 24 hours before being visually evaluated according to the evaluation criteria below. ○: The transparency remained the same compared to the varnish composition immediately after manufacturing. ×: Precipitates were present, or cloudiness was observed compared to the varnish composition immediately after manufacturing.

[0098] (curable) 0.3 ml of the varnish composition for the examples and comparative examples was applied to the aluminum vapor-deposited layer side of aluminum vapor-deposited paper using a two-part RI tester to create evaluation pieces. Multiple passes of UV irradiation were performed using a high-pressure mercury lamp at 120 W / cm and 130 m / min, with each pass considered as one pass, and the number of passes required for curing was evaluated. 〇: Cured in 3 passes. △: Hardened in 4-5 passes. ×: It was still uncured even after 5 passes.

[0099] (transparency) The varnish compositions of the examples and comparative examples were applied to the aluminum vapor-deposited layer side of aluminum vapor-deposited paper using a No. 4 bar coater to create evaluation pieces. The cured coatings were subjected to two passes of ultraviolet irradiation using a high-pressure mercury lamp at 120 W / cm and 130 m / min, and were visually evaluated according to the evaluation criteria below. ○: It remained transparent. △: The paint film was slightly cloudy. ×: The paint film was clearly discolored.

[0100] [Table 1]

[0101] Examples 1 to 9, which use varnish compositions in accordance with the present invention, demonstrate that the active energy ray curable varnish composition of the present invention possesses excellent stability, curability, and transparency. In contrast, Comparative Examples 1-3, which did not contain components (A) and (B), exhibited inferior transparency.

Claims

1. An active energy ray curable varnish composition containing the following component (A), or component (A) and component (B), and further containing component (C). (A) Ingredients: Modified (meth)acrylate compounds from animal and vegetable oils (B) Component: It does not contain ethylenically unsaturated bonds, and its solubility parameter sp value by turbidity titration is 9.0 (cal / cm³). ３ ) １／２ The above, and 11.0 (cal / cm³) ３ ) １／２ resins less than 100% of which contain plant-derived structures within the polymer. (C) Component: Compounds having ethylenically unsaturated bonds other than the above component (A). It is for aluminum-metallized paper, and, An active energy ray curable varnish composition in which component (A) is castor oil modified urethane acrylate or tall oil modified acrylate.

2. The active energy ray curable varnish composition according to claim 1, wherein the content of component (A), or the total content of component (A) and component (B), is 0.1 to 50.0% by mass of the nonvolatile content of the active energy ray curable varnish composition excluding the nonreactive solvent.

3. The active energy ray curable varnish composition according to claim 1 or 2, wherein component (B) is a rosin-based resin.

4. A printed article obtained by applying the active energy ray curing varnish composition according to any one of claims 1 to 3.

Images