WO2023188628A1 - Active energy ray-curable ink composition for reverse printing - Google Patents

Active energy ray-curable ink composition for reverse printing Download PDF

Info

Publication number
WO2023188628A1
WO2023188628A1 PCT/JP2022/047361 JP2022047361W WO2023188628A1 WO 2023188628 A1 WO2023188628 A1 WO 2023188628A1 JP 2022047361 W JP2022047361 W JP 2022047361W WO 2023188628 A1 WO2023188628 A1 WO 2023188628A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
active energy
ink composition
energy ray
Prior art date
Application number
PCT/JP2022/047361
Other languages
French (fr)
Japanese (ja)
Inventor
直毅 臣
Original Assignee
サカタインクス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by サカタインクス株式会社 filed Critical サカタインクス株式会社
Publication of WO2023188628A1 publication Critical patent/WO2023188628A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to an active energy ray-curable ink composition for back printing.
  • Various back-printed laminated films which are widely used as flexible packaging materials, are manufactured by methods such as dry lamination, extrusion lamination, and hot melt lamination. In all of these lamination methods, a resin film is laminated on the outermost layer via an adhesive layer formed separately from the printing layer, and urethane resin is used as the special adhesive to form the adhesive layer.
  • Various resins are used, such as epoxy resin, phenol resin, acrylic ester resin, and vinyl acetate resin.
  • reactive adhesives are usually used in laminating plastic films, which particularly require high adhesive strength and high heat resistance.
  • the mainstream of reactive adhesives is urethane-based adhesives, in which the adhesive components polyol and polyisocyanate form a urethane bond, resulting in high molecular weight and crosslinking, which then hardens to form a bond. It is.
  • two-component curing urethane adhesives are excellent in meeting the multifaceted performance requirements after adhesion, but the adhesive strength is low immediately after lamination, and in order to obtain the desired performance, it is necessary to Requires heating aging for 3 days. For this reason, the film cannot be processed immediately after lamination, resulting in poor productivity.
  • Another major issue is that a larger aging room is required, which increases costs for equipment, utilities, etc.
  • volatile solvents (VOC) are used as adhesive solvents, and although these are recovered during the process, they are never completely eliminated in the work space or the laminate, which is unfavorable in terms of the work environment.
  • various general laminated films with back printing are printed with solvent-based gravure ink or the like, and if necessary, are overcoated with white ink for reasons of concealment and design.
  • the printed material is rolled up and goes to the next process (laminate) offline.
  • the previous print is laminated and bonded with a sealant film using adhesive.
  • Adhesives develop their adhesive function by aging them in a heating room for several days, so they must be stored, which not only requires energy costs and storage space due to heating, but also temporarily slows processing and production speeds. . It has been difficult to provide the adhesive for this general laminate with a coloring function (ink).
  • Patent Documents 1 to 4 a number of active energy ray-curable adhesives have been proposed. These use prepolymers that have radically polymerizable unsaturated bonds in their molecules, and when irradiated with active energy rays, radical polymerization proceeds and instantly cures, but linear polyurethane resins that do not participate in radical polymerization are also used. Since it is contained in a large amount, it does not have the multifaceted performance of two-component urethane adhesives.
  • an adhesive has been proposed that uses a combination of a hydroxyl group-containing radically polymerizable prepolymer, a linear polymer having hydroxyl groups at both ends, an isocyanate group-containing radically polymerizable prepolymer, and polyisocyanate. .
  • This system develops a certain degree of adhesive strength by irradiating it with active energy rays, and it is possible to perform slitting immediately after lamination, but it still takes several days to adjust the temperature to the specified temperature in order to achieve the desired performance. aging is required, which cannot be said to be sufficient in terms of productivity.
  • the problem to be solved by the present invention is that the lamination process can be performed with excellent adhesion without aging after printing, and the lamination process can be performed reliably using an active energy ray-curable ink composition for back printing. It is about making things happen. Furthermore, it has easy availability, carbon-neutral superiority, and high productivity in the printing process, and is used in articles and equipment such as containers and jigs in the manufacturing process and usage process of active energy ray-curable ink compositions for back printing.
  • An active energy ray-curable ink composition for back printing that is inexpensive (excellent in economic efficiency) and can be washed away with water that does not contain volatile organic solvents, even if it adheres to
  • the object of the present invention is to obtain a method for producing a laminate using an active energy ray-curable ink composition and a laminate.
  • the present invention is as follows. 1. An active energy ray-curable ink composition for back printing containing 45.0% by mass or more of hydroxyl group-containing (meth)acrylate in all polymerizable components. 2.
  • hydroxyl group-containing (meth)acrylate Contains 5.0 to 95.0% by mass of hydroxyl group-containing (meth)acrylate
  • Curable ink composition 3.
  • the active energy ray-curable type for back printing according to 1 or 2 wherein the hydroxyl group-containing (meth)acrylate has one or more (meth)acryloyl groups in one molecule, and one or more hydroxyl groups in one molecule.
  • Ink composition 4. 4.
  • the active energy ray-curable ink composition for back printing according to any one of 1 to 4 wherein the hydroxyl group-containing (meth)acrylate has an average molecular weight of 100 to 2,000.
  • the active energy ray-curable ink composition for back printing according to any one of 1 to 6, wherein the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
  • the hydroxyl group-containing (meth)acrylate contains a hydroxyl group-containing poly(meth)acrylate, and the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol, dipentaerythritol, glycerin, diglycerin, trimethylolpropane, and ditrimethylolpropane.
  • the active energy ray-curable ink composition for back printing according to any one of 1 to 12 is printed on a printing material on which a printing layer is formed or on which a printing layer is not formed, and a sheet-like ink is applied on the printing layer.
  • a method for producing a laminate which comprises laminating materials, and then irradiating an active energy ray-curable ink composition layer for back printing with active energy rays.
  • a printing material on which a printing layer is formed or no printing layer is formed, and a printing layer formed on the printing material and comprising the active energy ray-curable ink composition for back printing according to any one of 1 to 12. , and a laminate having a sheet-like material laminated on a printing layer made of the active energy ray-curable ink composition for back printing.
  • the active energy ray-curable ink composition for back printing of the present invention has excellent printability without aging after printing, is easily available, has carbon neutrality, and has high productivity in the printing process. Even if the active energy ray-curable ink composition for back printing adheres to articles or equipment such as containers or jigs during the manufacturing process or usage process, the adhesion can be cured with water that does not contain volatile organic solvents.
  • An active energy ray-curable ink composition for back printing that can be washed and removed and is inexpensive (excellent in economic efficiency), a method for producing a laminate using the active energy ray curable ink composition for back printing, and a laminate. Obtainable.
  • the active energy ray-curable ink composition for back printing of the present invention can also be used as a printing agent for lamination. At this time, an active energy ray-curable ink composition for back printing is applied to the surface of the printing layer side of the printing material on which a printing layer is formed as necessary, and the active energy ray curable ink composition for back printing is applied.
  • a method for producing a laminate can be adopted in which the other adherend, which is a laminate layer, is laminated on the material layer, and then the active energy ray-curable ink composition layer for back printing is irradiated with active energy rays.
  • the active energy ray-curable ink composition for back printing, the method for producing a laminate, and the obtained laminate of the present invention will be explained in order below.
  • the active energy ray-curable ink composition for back printing of the present invention is sometimes simply referred to as a "composition.” Further, the object to be printed with the active energy ray-curable ink composition for back printing of the present invention is sometimes referred to as a printing substrate.
  • the active energy rays in the present invention refer to energy rays such as electron beams and ultraviolet rays that can harden acrylic monomers.
  • the active energy ray-curable ink composition for back printing of the present invention preferably has a surface tension value HLB (Davis method) of 8.0 or more, more preferably 8.6 or more, and still more preferably 9.0 or more. Further, it is preferably 20.0 or less, more preferably 16.0 or less, and even more preferably 14.0 or less.
  • HLB surface tension value
  • the hydroxyl value can be determined by the method specified in JIS K 0070:1992. When 1 g of sample is acetylated, the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group is determined and obtained.
  • the hydroxyl value of the entire hydroxyl-containing (meth)acrylate contained in the active energy ray-curable ink composition for back printing of the present invention is preferably 30 to 400 mgKOH/g, more preferably 50 mgKOH/g or more, and 100 mgKOH/g. /g or more is more preferable. Moreover, 350 mgKOH/g or less is more preferable, and 300 mgKOH/g or less is even more preferable.
  • the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
  • the hydroxyl group-containing (meth)acrylate contained in the composition of the present invention includes a hydroxyl group-containing poly(meth)acrylate, in which (meth)acrylic acid is ester bonded to a compound having two or more hydroxyl groups, and 1. (meth)acrylic acid ester of pentaerythritol, in which one or more of the hydroxyl groups of pentaerythritol remain unreacted; 2. (meth)acrylic acid ester of polypentaerythritol in which one or more of the hydroxyl groups possessed by polypentaerythritol remain unreacted; 3.
  • (meth)acrylic acid ester of glycerin in which one or more of the hydroxyl groups of glycerin remain unreacted; 4. (meth)acrylic acid ester of polyglycerin, in which one or more of the hydroxyl groups of polyglycerin remain unreacted; 5. (meth)acrylic acid ester of trimethylolpropane, in which one or more of the hydroxyl groups of trimethylolpropane remain unreacted; 6. (meth)acrylic acid ester of polytrimethylolpropane in which one or more of the hydroxyl groups possessed by polytrimethylolpropane remains unreacted;7.
  • One or more types of monohydroxyalkyl mono(meth)acrylates can be employed. Above all, 1.
  • hydroxyl group-containing (meth)acrylate It is preferable to contain a hydroxyl group-containing (meth)acrylate of 7. above. It is more preferable not to contain the hydroxyl group-containing (meth)acrylate. Furthermore, above 1. ⁇ 6.
  • hydroxyl group-containing (meth)acrylates those having two or more (meth)acryloyl groups are preferred.
  • the average molecular weight of the hydroxyl group-containing (meth)acrylate is preferably 100 to 2,000, more preferably 150 or more, and even more preferably 200 or more. Moreover, 1000 or less is more preferable, and 500 or less is still more preferable.
  • composition of the present invention contains hydroxyl group-containing (meth)acrylate in a polymerizable component of 45.0% by mass or more, preferably 70.0% by mass or more, and 90.0% by mass or more. It is more preferable that the content is 95% by mass or more. It may be 100.0% by mass. Furthermore, it is not excluded that (meth)acrylates other than hydroxyl group-containing (meth)acrylates may be contained as impurities.
  • Examples of (meth)acrylic acid esters of pentaerythritol in which one or more of the hydroxyl groups of pentaerythritol remain unreacted include (meth)acrylates of (poly)alkylene oxide-modified pentaerythritol.
  • ) may include acrylic esters, such as pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol mono(meth)acrylate, ethylene oxide modified penta Erythritol di(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, propylene oxide modified pentaerythritol mono(meth)acrylate, propylene oxide modified pentaerythritol di(meth)acrylate, propylene oxide modified pentaerythritol tri(meth)acrylate It can contain one or more of the following. These (meth)acrylic acid esters of pentaerythritol may or may not be included in the composition of the present invention.
  • (Meth)acrylic acid esters of polypentaerythritol in which one or more of the hydroxyl groups possessed by polypentaerythritol remain unreacted include (poly)alkylene oxide-modified polypentaerythritol may include (meth)acrylic acid esters of dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Tripentaerythritol mono(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, and (meth)acrylic acid esters of these polypentaerythritols
  • (meth)acrylic acid esters of polypentaerythritol may or may not be included in the composition of the present invention.
  • dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate depending on the content ratio of those compounds. , the adhesion of the printed layer may be reduced.
  • Examples of (meth)acrylic acid esters of glycerin in which one or more of the hydroxyl groups of glycerin remain unreacted include (meth)acrylic acid of glycerin modified with (poly)alkylene oxide.
  • esters such as glycerin mono(meth)acrylate, glycerin di(meth)acrylate, ethylene oxide-modified glycerin mono(meth)acrylate, ethylene oxide-modified glycerin di(meth)acrylate, propylene oxide-modified glycerin mono(meth)acrylate It can contain one or more of acrylates, propylene oxide-modified glycerin di(meth)acrylates, and the like. These (meth)acrylic acid esters of hydroxyl group-containing glycerin may or may not be included in the composition of the present invention.
  • Examples of (meth)acrylic acid esters of polyglycerin in which one or more of the hydroxyl groups of polyglycerin remain unreacted include (meth)acrylic esters of (poly)alkylene oxide-modified polyglycerin.
  • acrylic acid ester diglycerin mono(meth)acrylate, diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, triglycerin mono(meth)acrylate, triglycerin di(meth)acrylate, triglycerin It can contain one or more of glycerin tri(meth)acrylate, triglycerin tetra(meth)acrylate, alkylene oxide modified products (adducts) of (meth)acrylic acid esters of these polyglycerins, and the like. These (meth)acrylic esters of hydroxyl group-containing polyglycerin may or may not be included in the composition of the present invention.
  • (Meth)acrylic acid esters of trimethylolpropane in which one or more of the hydroxyl groups of trimethylolpropane remain unreacted include (poly)alkylene oxide-modified trimethylolpropane.
  • It can contain one or more of di(meth)acrylate, propylene oxide-modified trimethylolpropane mono(meth)acrylate, propylene oxide-modified trimethylolpropane di(meth)acrylate, and the like.
  • These hydroxyl group-containing (meth)acrylic esters of trimethylolpropane may or may not be included in the composition of the present invention.
  • (Meth)acrylic acid esters of polytrimethylolpropane in which one or more of the hydroxyl groups possessed by polytrimethylolpropane remain unreacted include (poly)alkylene oxide-modified polyesters.
  • (Meth)acrylic esters of trimethylolpropane may be included, including ditrimethylolpropane mono(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and polytrimethylols thereof. It can contain one or more types of alkylene oxide modified products (adducts) of (meth)acrylic esters of propane. These (meth)acrylic esters of hydroxyl group-containing polytrimethylolpropane may or may not be included in the composition of the present invention.
  • the monohydroxyalkyl mono(meth)acrylate contains one or more selected from alkylene glycol mono(meth)acrylate, polyalkylene glycol mono(meth)acrylate, and other hydroxyl group-containing (meth)acrylates. may be included, and may not be included.
  • Alkylene glycol mono(meth)acrylate 2-Hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl ( It can contain one or more of meth)acrylate, hydroxycyclohexyl(meth)acrylate, and the like.
  • These alkylene glycol mono(meth)acrylates may or may not be included in the composition of the present invention.
  • epoxy (meth)acrylate and 4-hydroxybutyl (meth)acrylate may not be contained.
  • polyalkylene glycol mono(meth)acrylate examples include diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol-polypropylene glycol.
  • examples include compounds with a block structure such as mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, and compounds with a random structure such as poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. .
  • These polyalkylene glycol mono(meth)acrylates may or may not be included in the composition of the present invention.
  • hydroxyl group-containing (meth)acrylates include 4-hydroxyphenyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy -3-allyloxypropyl (meth)acrylate, -2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-ethylhexyl (poly)ethylene oxide (Poly) such as modified (meth)acrylate, o-phenylphenol (poly)ethylene oxide modified (meth)acrylate, p-cumylphenol (poly)ethylene oxide modified (meth)acrylate, nonylphenol (poly)ethylene oxide modified (meth)acrylate, etc. Examples include alkylene glycol-modified (meth)acrylates. These other hydroxyl group-containing (meth)acrylates.
  • the composition of the present invention may or may not contain other compound components having double bonds.
  • Such compounds include those listed in 1. above. ⁇ 7.
  • compounds in which all of the hydroxyl groups are esterified with (meth)acrylic acid, chain alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, and ether group-containing (other than the above) It can contain meth)acrylate, vinyl ether group-containing (meth)acrylate, other (meth)acrylates, and compounds having double bonds other than (meth)acrylates. Moreover, it does not need to be contained. Furthermore, above 1. ⁇ 7. In the hydroxyl group-containing (meth)acrylate described in 1. above, all of the hydroxyl groups are further esterified with (meth)acrylic acid. ⁇ 7. When synthesizing a compound, some compounds may remain as by-products.
  • the composition of the present invention includes the above-mentioned 1. ⁇ 7.
  • all of the hydroxyl groups are further esterified with (meth)acrylic acid (a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups and no hydroxyl group). compound) may or may not be included. However, this is limited to a range that does not impair the effects of the present invention.
  • Specific compounds include pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol (100) di(meth)acrylate, (Poly)ethylene glycol di(meth)acrylate such as polyethylene glycol (400) di(meth)acrylate; (poly)propylene glycol di(meth)acrylate such as tripropylene glycol di(meth)acrylate and tetrapropylene glycol di(meth)acrylate; ) acrylate, cyclohexanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, dimethyloloctane di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, 1,3-butylene glycol di( meth)acrylate, 1,4-dimethyl-2,
  • a compound having a double bond other than the hydroxyl group-containing (meth)acrylates may or may not be included.
  • mono(meth)acrylate compounds include the following chain alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, ether group-containing (meth)acrylates other than the above, and vinyl ether group-containing (meth)acrylates. , other (meth)acrylates, and compounds having double bonds other than (meth)acrylates.
  • chain alkyl (meth)acrylate examples 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, isodecyl (meth)acrylate, isomyrist
  • Cyclic alkyl (meth)acrylate Cyclic alkyl (meth)acrylates include 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, benzyl (meth)acrylate, and the like.
  • ether group-containing (meth)acrylates other than those listed above examples include 1,3-butylene glycol methyl ether (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, Ethoxyethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene Glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxybutylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate
  • vinyl ether group-containing (meth)acrylates examples include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, and (meth)acrylate.
  • 2-vinyloxypropyl acid 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, (meth)acrylate 2-methyl-3-vinyloxypropyl acrylate, 3-methyl-3-vinyloxypropyl (meth)acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, (meth)acrylic acid -3-vinyloxybutyl, (meth)acrylic acid-1-methyl-2-vinyloxypropyl, (meth)acrylic acid-2-vinyloxybutyl, (meth)acrylic acid-4-vinyloxycyclohexyl, (meth)acrylic acid-5 -vinyloxypentyl, -6-vinyloxyhexyl (meth)acrylate, -4-vinyloxymethylcyclohexylmethyl (meth)acrylate,
  • (Other (meth)acrylates) examples include benzyl (meth)acrylate, phenyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and morpholinoethyl ( meth)acrylate, trimethylsiloxyethyl (meth)acrylate, diphenyl-2-(meth)acryloyloxyethyl phosphate, 2-(meth)acryloyloxyethyl acid phosphate, caprolactone-modified-2-(meth)acryloyloxyethyl acid phosphate, 2 -Hydroxy-1-(meth)acryloxy-3-methacryloxypropane, acryloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloyl, 2-(
  • Compounds having double bonds other than (meth)acrylates may or may not be included in the composition of the present invention.
  • Such compounds include styrene, vinyltoluene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene.
  • Other compounds include vinyl acetate, monochlorovinyl acetate, 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.
  • cyclic ketene acetals for example, 2-methylene-1, 3-dioxepane, dioxolanes, 2-methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3 -dioxepane, etc.
  • allyl glycidyl ether diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate, etc.
  • Preferred examples of such resins in the present invention include styrene acrylic oligomers, amine-modified (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and polyurethane (meth)acrylate oligomers.
  • the styrene acrylic oligomer is not particularly limited as long as it is an oligomer having at least one (meth)acryloyl group.
  • Examples of the styrene acrylic oligomer include US-1071, X-1, YS-1274, VS-1047, and RS-1191 (Seiko PMC Corporation).
  • the amine-modified (meth)acrylate oligomer is not particularly limited as long as it has at least one amino group and at least one (meth)acryloyl group.
  • the number of (meth)acryloyl groups that the amine-modified (meth)acrylate oligomer has in the molecule is not particularly limited as long as it is one or more, but it is preferably from one to six, and two or more. More preferably, the number is four or less. When the number of (meth)acryloyl groups is within the above range, the amine-modified (meth)acrylate oligomer easily reacts with the polymerizable compound.
  • the amine-modified (meth)acrylate oligomer may be a synthetic product obtained by polymerizing a desired monomer, or may be a commercially available product.
  • Examples of commercially available amine-modified (meth)acrylate oligomers include GENOMER5161, GENOMER5275 (RAHN), CN371, CN371NS, CN373, CN383, CN384, CN386, CN501, CN503, CN550, CN551 (Sartomer), and EB.
  • the epoxy (meth)acrylate oligomer is not particularly limited as long as it is an oligomer having at least one epoxy group and at least one (meth)acryloyl group.
  • the epoxy (meth)acrylate oligomer may be a synthetic product obtained by polymerizing a desired monomer, or may be a commercially available product.
  • polyester (meth)acrylate oligomer The polyester (meth)acrylate oligomer is not particularly limited as long as it has a polyester structure and at least one (meth)acryloyl group.
  • the polyurethane (meth)acrylate oligomer is not particularly limited as long as it has a polyurethane structure and at least one (meth)acryloyl group. It may be a polyurethane (meth)acrylate oligomer, a synthetic product obtained by polymerizing a desired monomer, or a commercially available product.
  • One or more selected from the group consisting of acrylic resins, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, acrylic-modified phenolic resins, acrylated amine compound oligomers, etc. can be used.
  • the composition of the present invention can contain a polymerization initiator.
  • a polymerization initiator include the following acylphosphine oxide compounds, triazine compounds, aromatic ketone compounds, aromatic onium salt compounds, organic peroxides, thioxanthone compounds, thiophenyl compounds, and anthracene compounds.
  • sulfonium salt-based compounds can be used.
  • the adhesive strength of the printed layer can be increased by not containing a polymerization initiator.
  • acylphosphine oxide type compound for example, one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. There are more than one species.
  • triazine compounds examples include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-pipenyl-4,6-bis(trichloromethyl)-s-triazine , 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy- naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine and 2,4-trich
  • the composition of the present invention may contain the following components such as resins, organic solvents, pigments and dyes, and other additives within a range that does not impair the effects of the present invention.
  • other components such as a siloxane compound, wax, and fluorine-containing compound may or may not be included.
  • the polymerizable resin having double bonds and the like preferably includes an oligomer and further has one or more hydrophilic groups selected from hydroxyl groups, carboxylic acid groups, and amino groups.
  • the polymerizable resin is preferably a resin obtained from a polymerizable resin ethylenically unsaturated group having a double bond such as a (meth)acryloyl group. Moreover, it is preferable to have a urethane group.
  • polymerizable resin and oligomer having double bonds and the like known or commercially available polymers or oligomers having ethylenically unsaturated bonds can be used.
  • polymer or oligomer having an ethylenically unsaturated bond one having one or more ethylenically unsaturated bonds selected from the group consisting of (meth)acryloyl groups, vinyl groups, etc. can be used.
  • 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, epoxy(meth)acrylate, polyester(meth)acrylate, rosin-modified epoxy(meth)acrylate, unsaturated polyester, polyether(meth)acrylate, unreacted unsaturated group One or more selected from the group consisting of acrylic resins, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, acrylic-modified phenolic resins, acrylated amine compound oligomers, etc.
  • One or more types selected from the group consisting of acrylated amine compound oligomer having a photopolymerizable functional group and two amino groups), Sartomer's "CN704" (polyfunctional urethane acrylate oligomer), etc. can be used. is not particularly limited.
  • non-polymerizable resins without double bonds examples include acrylic resins (ethylenic unsaturated monomers with carboxyl groups such as acrylic acid and methacrylic acid, and copolymerized with these ethylenically unsaturated monomers).
  • Organic solvent examples include monoalcohols, polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, ketones, ethers, esters, and nitrogen-containing compounds. These may be used alone or in combination of two or more.
  • the monoalcohols include n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, or isomers thereof;
  • Examples include cyclopentanol and cyclohexanol, and preferably alcohols having an alkyl group of 1 to 6 carbon atoms can be used.
  • polyhydric alcohols examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,2- Hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol, diethylene glycol, dipropylene Glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, etc.
  • the lower alkyl ethers of the polyhydric alcohols mentioned above include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol Isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n-propyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -n-butyl ether etc.
  • ketones include methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
  • ethers include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane.
  • esters include propylene carbonate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethyl butyrate, dibutyl phthalate, dioctyl phthalate, and cyclic esters such as ⁇ -caprolactone and ⁇ -caprolactam. etc.
  • the content of the organic solvent is preferably as low as possible, and more preferably not included. Preferably, it does not contain water.
  • the moisture content of the composition of the invention may be 0.01 to 5.00% by weight.
  • the composition of the present invention may contain pigments and dyes as colorants for active coloring.
  • pigments or dyes for purposes other than active coloring or coloring
  • one or more of the following pigments can be contained in any desired amount.
  • active coloring is not required, the content of pigments and dyes may be reduced or may not be included.
  • the composition of the present invention also functions as a so-called clear ink composition.
  • known organic pigments and inorganic pigments can be used without particular limitation.
  • organic 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, Examples include isoindolinone-based, nitro-based, nitroso-based, anthraquinone-based, flavanthrone-based, quinophthalone-based, pyranthrone-based, and indanthrone-based pigments.
  • inorganic pigments include carbon black, titanium oxide, red iron oxide, graphite, iron black, chromium oxide green, aluminum oxide, aluminum hydroxide, and the like.
  • a known pigment dispersant may be contained together with the above pigment.
  • the laminate in the present invention includes laminates having the following four structures.
  • the arbitrary printing layer is a printing layer formed by forming a known printing ink composition by an arbitrary printing method.
  • printing an active energy ray-curable ink composition for back printing with dry-on wet means that after the previously printed active energy ray curable ink composition for back printing is cured, the layer above it is printed with the active energy ray curable ink composition for back printing. This refers to printing with an active energy ray-curable ink composition.
  • Wet-on-wet printing of an active energy ray-curable ink composition for back printing means that the previously printed active energy ray curable ink composition for back printing is not cured or remains only semi-cured. This refers to printing on the upper layer with an active energy ray-curable ink composition for back printing.
  • a printing layer having an arbitrary printing layer on one side of a raw material that is a printing material, and a printing layer formed on the printing layer consisting of an active energy ray-curable ink composition for back printing, and the active energy for back printing.
  • a laminate having a structure in which a laminate layer is formed on a printing layer made of a line-curable ink composition. 2. Having an optional printing layer and/or a printing layer made of an active energy ray-curable ink composition for back printing on one side of the original fabric that is the printing target, and the side of the original fabric that does not have the printing layer.
  • Case 1 is a typical laminate produced by back printing
  • cases 2 and 3 can also be said to be laminates produced by back printing, which is a combination of front printing and back printing.
  • printing layers may be formed in advance on both sides of the printing material.
  • each arbitrary printing layer consists of one layer or two or more layers, and in the case of two or more layers, the composition including pigments and dyes may be the same or different from each other, and in-line or formed offline (dry-on-wet or wet-on-wet).
  • the printing layer made of the active energy ray-curable ink composition for back printing also consists of one layer or two or more layers, and may have the same composition or different compositions including pigments and dyes, and can be used in-line or off-line. (dry-on-wet or wet-on-wet).
  • layers other than the printing layer and the active energy ray-curable ink composition for back printing which may be provided inside the original fabric that is the printing material, the laminate layer, or the laminate, are made of different materials. It may be made of the same material. It is sufficient that at least one layer can transmit the active energy rays necessary for curing.
  • the active energy ray-curable ink composition layer for back printing of the present invention is formed by laminating two sheet-like materials sandwiching the layer.
  • Materials for the original fabric, the laminate layer, or the layers that may be provided inside the laminate include synthetic paper, resin, art paper, coated paper, cast paper, recycled paper, resin-laminated paper, metal-deposited paper, and metal oxide. You can choose from paper such as metal-deposited paper, metal, etc.
  • These printing materials and sheet-like materials may or may not be subjected to known surface treatments, chemical treatments, printing, painting, vapor deposition, etc. in advance.
  • printing or painting when printing or painting consists of an active energy ray-curable ink composition or coating composition, printing or painting is performed on at least one side of one side of the adherend without irradiation with active energy rays. , or after irradiation with active energy rays is limited to an extent that curing is incomplete, print the active energy ray-curable ink composition for reverse printing of the present invention on one side and overlap the other sheet-like material. Then, curing may be completed by irradiating active energy rays. Further, after the layer obtained by printing or painting is completely cured by irradiation with electron beams or UV, the active energy ray-curable ink composition for back printing of the present invention is printed on one side.
  • the sheet-like materials may be further stacked, and then active energy rays may be irradiated to complete curing.
  • the irradiation amount of the electron beam capable of curing is preferably 10 kGy or more, more preferably 100 kGy or more. Moreover, 500 kGy or less is preferable, and 300 kGy or less is more preferable. Further, when the composition contains a polymerization initiator, the amount of ultraviolet ray irradiation is preferably 400 mJ/cm 2 or more.
  • the shape of the laminate may be sheet-like, block-like, or the like, as long as at least either the printing material or the sheet-like material can transmit the active energy rays necessary for curing.
  • those made of resin may be modified or unmodified resins known for use in materials to be adhered.
  • Stretched or unstretched resins can be used as such resins, and these resins include polyolefin resins (polyethylene, polypropylene, ethylene-propylene copolymers, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide resins, etc.
  • Resin nylon 6, nylon 66, nylon 11, nylon 12, etc.
  • polyvinyl chloride polyvinyl acetate, polyvinyl alcohol, polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), polycarbonate, polyamideimide, polyimide, epoxy
  • resins such as resins, phenol resins, melamine resins, and urethane resins, laminates of these resins and the above-mentioned papers, and laminates of these resin films and metals or metal oxides.
  • the method for producing a laminate in the present invention includes printing the active energy ray-curable ink composition for back printing of the present invention on the surface of a printing material by a known printing means (gravure printing, flexographic printing, inkjet printing, etc.). Form a printing layer.
  • the coating amount of the active energy ray-curable ink composition for back printing of the present invention on the printing substrate is 1.50 g/solid content in the printing section. m 2 or more is preferable, 1.80 g/m 2 or more is more preferable, and even more preferably 2.00 g/m 2 or more.
  • the above-mentioned paper or metal may be selected as the printing material, and in that case, it is preferable to bond it with the above-mentioned sheet-like material in order to cure it with active energy rays.
  • paper it may be either coated paper or coated paper, and is not particularly limited, such as paper on which a printing layer or metal layer has already been formed, or paper on which a resin film is laminated.
  • metal film-form aluminum, zinc, copper, iron, tin, etc. are not particularly limited.
  • the laminate of the present invention can be used in the same manner as the known use as a sheet having a resin layer, such as a back-printed printed matter having a printing layer between two resin sheets, etc. Examples include surface-printed printed matter having a printed layer on the outer surface of a laminate of layers.
  • two or more layers of the active energy ray-curable ink composition for back-printing of the present invention are wetted onto one side of a film such as polyethylene terephthalate as a raw material to be printed using a known printing means.
  • a film such as polyethylene terephthalate as a raw material to be printed using a known printing means.
  • LLDPE low density polyethylene
  • the first layer can be printed with a white ink composition
  • the second and higher layers can be printed with an ink composition of a color other than white.
  • the active energy ray-curable ink compositions for back printing of the present invention may have the same composition or different compositions except for pigments and dyes.
  • two or more layers were printed by wet-on-wet, but layers other than the top layer may be cured by active energy rays immediately after printing and printed by dry-on-wet.
  • a known ink composition gravure ink composition, water-based flexo ink composition, EB offset ink composition, etc. composition, EB flexo ink composition, waterless EB offset ink composition, inkjet ink composition, etc.
  • the active energy ray curable ink composition for back printing of the present invention is printed on the printing layer of this active energy ray curable ink composition for back printing using a known printing means.
  • a resin film such as a sealant film or the like is laminated on the printing layer made of the active energy ray-curable ink composition for back printing of the present invention, and active energy rays are irradiated from either side.
  • one of the layers made of the active energy ray-curable ink composition for back printing of the present invention is a white ink composition, but a known ink composition may be used as the white ink composition.
  • the active energy ray-curable ink composition for back printing of the present invention is applied to one side of a film such as polyethylene terephthalate as a printing material by a known printing method.
  • a film such as polyethylene terephthalate
  • one or more printed layers are printed by dry-on-wet or wet-on-wet, and a film such as low-density polyethylene (LLDPE) is laminated on the surface including the obtained printed layer.
  • LLDPE low-density polyethylene
  • the composition can be printed in one or more layers by known printing means and dried and/or cured. This method can be said to be a combination of back printing and front printing.
  • Another method for obtaining a laminate having the structure described in 2 above is to apply a known ink composition and/or an active energy ray-curable ink for back printing on one side of a film such as polyethylene terephthalate as a raw material to be printed. After printing the composition by any means and drying or curing the obtained printed layer, the back printing of the present invention is applied to the other side of the film such as polyethylene terephthalate having the formed printed layer on which the printed layer is not formed.
  • One or more layers of an active energy ray-curable ink composition for printing are printed using a known printing means, a film such as low density polyethylene (LLDPE) is laminated on the layer of the active energy ray-curable ink composition for back printing, and then a film such as low density polyethylene (LLDPE) is It can be obtained by irradiating energy rays.
  • LLDPE low density polyethylene
  • one or more layers of a known ink composition are printed on one side of a film such as polyethylene terephthalate as a raw material to be printed using a known printing means. dry and/or harden.
  • a film such as polyethylene terephthalate as a raw material to be printed using a known printing means. dry and/or harden.
  • the active energy ray-curable ink composition for back printing of the present invention is printed using a known printing method, such as dry-on wet or wet-on-wet, so as to form one or more printed layers.
  • a film such as low density polyethylene (LLDPE) is laminated on the surface including the obtained printed layer.
  • LLDPE low density polyethylene
  • active energy rays are irradiated from either side to obtain a laminate, and a known ink composition and/or active energy ray curing for back printing is applied to the surface of the above-mentioned polyethylene terephthalate film of the laminate.
  • a laminate can be obtained by printing the mold ink composition by any means and drying and/or curing the printed layer.
  • Another method for obtaining a laminate having the structure described in 3 above is to apply a known ink composition and/or an active energy ray-curable ink for back printing on one side of a film such as polyethylene terephthalate as a raw material to be printed.
  • the steps of drying and/or curing the printed layer may be performed in any order.
  • one or more layers of the active energy ray-curable ink composition for back printing of the present invention are printed by a known printing means, and then on the active energy ray curable ink composition layer for back printing. It can be obtained by laminating a film such as low-density polyethylene (LLDPE) on the substrate and then irradiating it with active energy rays.
  • LLDPE low-density polyethylene
  • the active energy ray-curable ink composition for back printing of the present invention is applied to one side of a film such as polyethylene terephthalate as a printing material by known printing means.
  • a film such as polyethylene terephthalate as a printing material by known printing means.
  • one or more printed layers are printed by dry-on-wet or wet-on-wet, and a film such as low-density polyethylene (LLDPE) is laminated on the surface including the obtained printed layer.
  • LLDPE low-density polyethylene
  • it can be obtained by irradiating active energy rays from either side.
  • one of the layers made of the active energy ray-curable ink composition for back printing of the present invention is a white ink composition.
  • the laminate of the present invention can be used for packaging purposes.
  • any edges of the two outermost thermoplastic resin layers of the laminate may be heat-welded in close contact with each other, or any edges of the two outermost thermoplastic resin layers of the laminate may be bonded together. It can be made into a packaging bag or the like by bonding it with an adhesive or the like. Furthermore, a single laminate can be folded in half and the edges of opposing surfaces can be heat-welded or adhered as described above to make a packaging bag or the like.
  • the equipment used to prepare the active energy ray-curable ink compositions for back printing in Examples 1 and 2 was able to be dissolved and cleaned efficiently and in a favorable environment without using volatile organic solvents.
  • the instruments used in the comparative example they could not be cleaned with the alkaline water described below, but were cleaned using a volatile organic solvent.
  • PETA Pentaerythritol triacrylate (HLB10.9, molecular weight 298.29, hydroxyl value 188mgKOH/g)
  • TMPG Trimethylolpropane diacrylate (HLB8.9, molecular weight 242, hydroxyl value 232mgKOH/g)
  • GGA Glycerin diacrylate (HLB10.4, molecular weight 200, hydroxyl value 281mgKOH/g) 15EO-TMPG: Ethylene oxide (15) modified trimethylolpropane diacrylate (HLB13.9, molecular weight 902, hydroxyl value 62mgKOH/g)
  • DPTA dipentaerythritol triacrylate (HLB13.6, molecular weight 416, hydroxyl value 135mgKOH/g)
  • X-1 Styrene acrylic resin, weight average molecular weight 18,000, acid value 110 (Seiko PMC Co., Ltd.)
  • YS-1274 St
  • Example and comparative example An active energy ray-curable ink composition for back printing shown in Example 1 in the table below was prepared. This composition was applied onto a plain S46C original fabric in the coating amounts shown in Table 1. Without aging, an LLDPE film (TUX-HC (Mitsui Chemicals Tohcello Co., Ltd.) thickness 50 ⁇ m) (hereinafter referred to as "LLDPE film”) or CPP (unoriented polypropylene) film was layered on the coated surface as a sealant. These films were laminated by irradiating them with active energy rays at the doses shown in Table 1 without aging. The equipment used for production was washed with household detergent (weak alkaline).
  • the adhered active energy ray-curable ink composition for back printing could also be quickly removed.
  • the composition was applied on plain PTM, P2161, FOR, ONM, and N1102, and an LLDPE film or CPP film was layered on each as a sealant, and active energy rays were irradiated at the dose shown in Table 1. These films were then laminated.
  • plain S46C, PTM, P2161, FOR, ONM, and N1102 the composition was applied to the hardened printed matter printed with an EB offset ink composition, including those printed areas, and also to areas other than the printed areas. did.
  • an LLDPE film or a CPP film was layered as a sealant on the coated surface, and active energy rays were irradiated at the dose shown in Table 1 to stack these films.
  • an electron beam irradiation device manufactured by I-Electron Beam Co., Ltd. was used, the acceleration voltage was set to 90 kV in an atmosphere with an oxygen concentration of 200 ppm, and the irradiation amount of one electron beam irradiation was basically 30 kGy. The irradiation was performed multiple times to achieve the irradiation doses shown in Table 1.
  • Examples 25 and 26 and Comparative Examples 12 and 13 which contained a polymerization initiator, ultraviolet rays were irradiated at 400 mJ/cm 2 .
  • printed matter printed with solvent-based gravure ink and dried and solidified can be used for back printing, including those printed areas, as well as areas other than the printed areas.
  • An active energy ray curable ink composition was applied.
  • an LLDPE film or a CPP film was layered as a sealant on the coated surface, and active energy rays were irradiated at the dose shown in Table 1 to stack these films. This was similarly carried out for Examples 2 to 26 and Comparative Examples 1 to 13.
  • ⁇ Tensile strength> The laminate aged at 40°C for 1 day was cut into 15 mm width pieces, and the film and sealant film were separated using an Orientec Tensilon universal testing machine at an ambient temperature of 25°C and a peeling speed of 300 mm/min.
  • the tensile strength when peeled using the 180 degree peeling method was defined as the laminate strength (N/15 mm).
  • F means film breakage
  • B means peeling from the original fabric side
  • S means peeling from the sealant film side.
  • the above-mentioned peel strength and tensile strength are listed side by side.
  • 7.0F means that the peel strength is 7.0 g/15 mm and the film was broken when the tensile strength was measured.
  • Laminated body B consisting of PTM/active energy ray curable ink composition layer for back printing/aluminum foil (thickness 9 ⁇ m)/active energy ray curable ink composition layer for back printing/LLDPE film by laminating the side surfaces together. I got it. The pasting procedure may be reversed. Using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.), an electron beam with an irradiation dose of 150 kGy and 90 kV was irradiated from the second transparent film side of the laminate B to bond it. The PTM and LLDPE films adhered to each other with sufficient strength. In addition, the instruments used in the production were washed with water using a household detergent (weak alkali), and the active energy ray-curable ink composition for back printing that had adhered to them could be quickly removed.
  • EB device electron beam irradiation device
  • the aluminum foil side of the laminate A that had been irradiated with electron beams was laminated with the LLDPE film to create a laminate B, which was then irradiated using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.).
  • EB device electron beam irradiation device
  • the LLDPE film was bonded by irradiating the LLDPE film with an electron beam at a dose of 150 kGy and 90 kV.
  • the PTM and LLDPE films adhered to each other with sufficient strength.
  • the instruments used in the production were washed with water using a household detergent (weak alkali), and the active energy ray-curable ink composition for back printing that had adhered to them could be quickly removed.
  • the aluminum foil side of the laminate A that has been irradiated with the electron beam is laminated with a second transparent film to create the laminate B.
  • the PTM and LLDPE films adhered to each other with sufficient strength.
  • the instruments used in the production were washed with water using a household detergent (weak alkali), and the active energy ray-curable ink composition for back printing that had adhered to them could be quickly removed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention addresses the problem of obtaining: an active energy ray-curable ink composition which is for reverse printing, and which has excellent printability even without post-printing aging, and also ensures easy availability, carbon-neutrality advantages, high productivity in the printing process, and cost-effectiveness (excellent economic efficiency); a method for manufacturing printed matter using said active energy ray-curable ink composition for reverse printing; and printed matter obtained thereby. To solve the problem, provided is an active energy ray-curable ink composition for reverse printing, the composition containing 45.0 mass% of a hydroxyl group-containing (meth)acrylate in all polymerizable components.

Description

裏刷り用活性エネルギー線硬化型インキ組成物Active energy ray-curable ink composition for back printing
　本発明は、裏刷り用活性エネルギー線硬化型インキ組成物に関する。 The present invention relates to an active energy ray-curable ink composition for back printing.
　軟包装材として広く用いられている裏刷り印刷された各種積層フィルムは、ドライラミネーション、押し出しラミネーション、ホットメルトラミネーション等の方法により製造されている。これらのラミネーション方法は、いずれも印刷層とは別に形成された接着剤層を介して、最外層に樹脂フィルムを積層するものであり、接着剤層を形成する専用の接着剤としては、ウレタン樹脂、エポキシ樹脂、フェノール樹脂、アクリル酸エステル系樹脂、酢酸ビニル系樹脂等の様々な樹脂が使用されている。これらの接着剤の中で、特に高い接着強度及び高い耐熱性を要求されるプラスチックフィルムのラミネートにおいては、通常反応型接着剤が使用されている。反応型接着剤としては、ウレタン系のものが主流であり、この接着剤は接着剤成分のポリオールとポリイソシアネートがウレタン結合を形成し、高分子量化や架橋が起こり、硬化することにより接着するものである。
　中でも２液硬化型ウレタン系接着剤は接着後の多面的な要求性能を充たす優れたものであるが、ラミネート直後は接着強度が低く、所望の性能を得るためには４０～６０℃で２～３日間の加温エージングを必要とする。このため、ラミネート直後にフィルムを加工することは出来ず生産性が悪い。更に大きなエージングルームが必要となり設備、光熱費などのコストがかかることも大きな課題である。また、接着剤溶媒として揮発性溶剤（VOC）を使用し、これらは工程内で回収するものの、作業空間やラミネート物において全くのゼロになることはなく、作業環境面で好ましくない。 Various back-printed laminated films, which are widely used as flexible packaging materials, are manufactured by methods such as dry lamination, extrusion lamination, and hot melt lamination. In all of these lamination methods, a resin film is laminated on the outermost layer via an adhesive layer formed separately from the printing layer, and urethane resin is used as the special adhesive to form the adhesive layer. Various resins are used, such as epoxy resin, phenol resin, acrylic ester resin, and vinyl acetate resin. Among these adhesives, reactive adhesives are usually used in laminating plastic films, which particularly require high adhesive strength and high heat resistance. The mainstream of reactive adhesives is urethane-based adhesives, in which the adhesive components polyol and polyisocyanate form a urethane bond, resulting in high molecular weight and crosslinking, which then hardens to form a bond. It is.
Among these, two-component curing urethane adhesives are excellent in meeting the multifaceted performance requirements after adhesion, but the adhesive strength is low immediately after lamination, and in order to obtain the desired performance, it is necessary to Requires heating aging for 3 days. For this reason, the film cannot be processed immediately after lamination, resulting in poor productivity. Another major issue is that a larger aging room is required, which increases costs for equipment, utilities, etc. In addition, volatile solvents (VOC) are used as adhesive solvents, and although these are recovered during the process, they are never completely eliminated in the work space or the laminate, which is unfavorable in terms of the work environment.
　また、一般的な裏刷り印刷された各種積層フィルムは、フィルムに溶剤性グラビアインキ等で印刷し、必要に応じて隠蔽性付与やデザイン性を理由に、白インキでオーバーコートされる。印刷物は巻き取られ、オフラインで次工程（ラミネート）に入る。ラミネーターを用いて、先の印刷物は接着剤を用いてシーラントフィルムとラミネートされ接合される。接着剤は加温室で数日エージング処理することで接着機能を発現するため、保管する必要があり、その間加温によるエネルギーコストや保管スペースを要するだけでなく、加工生産速度が一時的に停滞する。
　この一般的なラミネート積層体の接着剤には着色機能（インキ）を備えることが困難であった。
　同様に、下記特許文献１～４に示すように、数々の活性エネルギー線硬化型接着剤が提唱されている。これらは分子内にラジカル重合性不飽和結合を有するプレポリマーを用い、活性エネルギー線を照射することによりラジカル重合が進行し瞬時に硬化するものであるが、ラジカル重合に関与しない線状ポリウレタン樹脂も多く含まれているため、２液硬化型ウレタン系接着剤の様な多面的な性能を充たすものではない。また、これを改良したものとして、水酸基含有ラジカル重合性プレポリマー、両末端に水酸基を有する線状ポリマーとイソシアネート基含有ラジカル重合性プレポリマー、ポリイソシアネートを配合して用いる接着剤が提案されている。この系は活性エネルギー線を照射することである程度の接着強度が発現し、ラミネート直後にスリッティング加工が可能とあるが、所望の性能を発現するには、やはり所定の温度に調整して数日のエージングが必要であり、生産性の面では充分とは言えない。
　これらの点からみて、下記特許文献１～４に記載の接着剤において、着色機能を備えてインキ組成物にすることが困難であった。
　また、活性エネルギー線硬化型インキ組成物が水溶性ではない場合には、そのインキ組成物の使用後における清掃時に有機溶媒を使用する必要がある等、簡単な手段による処理を行なうことができなかったりした。 In addition, various general laminated films with back printing are printed with solvent-based gravure ink or the like, and if necessary, are overcoated with white ink for reasons of concealment and design. The printed material is rolled up and goes to the next process (laminate) offline. Using a laminator, the previous print is laminated and bonded with a sealant film using adhesive. Adhesives develop their adhesive function by aging them in a heating room for several days, so they must be stored, which not only requires energy costs and storage space due to heating, but also temporarily slows processing and production speeds. .
It has been difficult to provide the adhesive for this general laminate with a coloring function (ink).
Similarly, as shown in Patent Documents 1 to 4 below, a number of active energy ray-curable adhesives have been proposed. These use prepolymers that have radically polymerizable unsaturated bonds in their molecules, and when irradiated with active energy rays, radical polymerization proceeds and instantly cures, but linear polyurethane resins that do not participate in radical polymerization are also used. Since it is contained in a large amount, it does not have the multifaceted performance of two-component urethane adhesives. Furthermore, as an improvement on this, an adhesive has been proposed that uses a combination of a hydroxyl group-containing radically polymerizable prepolymer, a linear polymer having hydroxyl groups at both ends, an isocyanate group-containing radically polymerizable prepolymer, and polyisocyanate. . This system develops a certain degree of adhesive strength by irradiating it with active energy rays, and it is possible to perform slitting immediately after lamination, but it still takes several days to adjust the temperature to the specified temperature in order to achieve the desired performance. aging is required, which cannot be said to be sufficient in terms of productivity.
In view of these points, it has been difficult to use the adhesives described in Patent Documents 1 to 4 below to provide an ink composition with a coloring function.
Furthermore, if the active energy ray-curable ink composition is not water-soluble, it is not possible to treat it by simple means, such as the need to use an organic solvent when cleaning the ink composition after use. It was.
特開平６－１８４４９８号公報Japanese Patent Application Publication No. 6-184498 特開２０００－１７２３５号公報Japanese Patent Application Publication No. 2000-17235 特開２０１５－１３９３５号公報Japanese Patent Application Publication No. 2015-13935 特開２０２１－１６５３２９号公報JP 2021-165329 Publication
　本発明が解決する課題は、印刷後にエージングしなくとも、その後に優れた接着性でラミネート工程を行なうことができ、さらに裏刷り用活性エネルギー線硬化型インキ組成物によって、確実にラミネート工程を行えることを実現することである。更に入手容易性、カーボンニュートラル優位性、印刷工程での高い生産性を有し、裏刷り用活性エネルギー線硬化型インキ組成物の製造工程や使用工程等において、容器や治具等の物品や装置に付着した場合であっても、揮発性有機溶剤を含有しない水によって、付着硬化物を洗浄除去でき、安価な（経済性に優れる）裏刷り用活性エネルギー線硬化型インキ組成物、その裏刷り用活性エネルギー線硬化型インキ組成物を使用した積層体の製造方法及び積層体を得ることである。 The problem to be solved by the present invention is that the lamination process can be performed with excellent adhesion without aging after printing, and the lamination process can be performed reliably using an active energy ray-curable ink composition for back printing. It is about making things happen. Furthermore, it has easy availability, carbon-neutral superiority, and high productivity in the printing process, and is used in articles and equipment such as containers and jigs in the manufacturing process and usage process of active energy ray-curable ink compositions for back printing. An active energy ray-curable ink composition for back printing that is inexpensive (excellent in economic efficiency) and can be washed away with water that does not contain volatile organic solvents, even if it adheres to The object of the present invention is to obtain a method for producing a laminate using an active energy ray-curable ink composition and a laminate.
　本発明者は、上記の課題を解決するため鋭意研究した結果、特定の組成とすることにより、上記課題を解決し得ることを見出し、本発明を完成するに至った。
　すなわち、本発明は以下の通りである。
１．全重合性成分中に、水酸基含有（メタ）アクリレートを４５．０質量％以上含有する裏刷り用活性エネルギー線硬化型インキ組成物。
２．水酸基含有（メタ）アクリレートを５．０～９５．０質量％含有し、
更にカルボン酸基、ヒドロキシル基及びウレタン基のうち１種以上、及び、エチレン性不飽和基を有し、重量平均分子量が５００～１０００００の樹脂を含有する、１に記載の裏刷り用活性エネルギー線硬化型インキ組成物。
３．水酸基含有（メタ）アクリレートが、１分子中に（メタ）アクリロイル基を１つ以上有し、かつ１分子中に水酸基を１つ以上有する、１又は２に記載の裏刷り用活性エネルギー線硬化型インキ組成物。
４．水酸基含有（メタ）アクリレートの表面張力値（デイビス法）が８．０～２０．０である１～３のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
５．水酸基含有（メタ）アクリレートの平均分子量が１００～２０００である１～４のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
６．水酸基含有（メタ）アクリレートの水酸基価が５０～４００ｍｇＫＯＨ／ｇである１～５のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
７．活性エネルギー線による重合性成分全体の水酸基価が３０ｍｇＫＯＨ／ｇ以上である１～６のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
８．水酸基含有（メタ）アクリレートが、水酸基含有ポリ（メタ）アクリレートを含有し、その水酸基含有ポリ（メタ）アクリレートが、ペンタエリスリトール、ジペンタエリスリトール、グリセリン、ジグリセリン、トリメチロールプロパン、及びジトリメチロールプロパンの１種以上の化合物と、（メタ）アクリル酸が、エステル結合してなる化合物である１～７のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
９．裏刷り用活性エネルギー線硬化型インキ組成物の含水率が０．０１～５．００質量％である１～８のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
１０．水酸基含有ポリ（メタ）アクリレートが、１分子あたり２～４の（メタ）アクリロイル基を有する化合物である１～９のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
１１．水酸基含有ポリ（メタ）アクリレートが、ペンタエリスリトールジ（メタ）アクリレート、及び／又はペンタエリスリトールトリ（メタ）アクリレートを含有する８～１０のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
１２．１０～５００ｋＧｙの電子線で硬化可能な１～１１のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。
１３．印刷層が形成された又は印刷層が形成されていない被印刷物に、１～１２のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物により印刷し、その印刷層の上にシート状物を積層し、次いで、裏刷り用活性エネルギー線硬化型インキ組成物層に活性エネルギー線を照射する積層体の製造方法。
１４．印刷層が形成された又は印刷層が形成されていない被印刷物、その被印刷物の上に形成された１～１２のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層、及び該裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層上に積層されたシート状物を有する積層体。 As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention discovered that the above-mentioned problems could be solved by using a specific composition, and completed the present invention.
That is, the present invention is as follows.
1. An active energy ray-curable ink composition for back printing containing 45.0% by mass or more of hydroxyl group-containing (meth)acrylate in all polymerizable components.
2. Contains 5.0 to 95.0% by mass of hydroxyl group-containing (meth)acrylate,
The active energy ray for back printing according to 1, further comprising a resin having one or more of carboxylic acid groups, hydroxyl groups, and urethane groups and an ethylenically unsaturated group and having a weight average molecular weight of 500 to 100,000. Curable ink composition.
3. The active energy ray-curable type for back printing according to 1 or 2, wherein the hydroxyl group-containing (meth)acrylate has one or more (meth)acryloyl groups in one molecule, and one or more hydroxyl groups in one molecule. Ink composition.
4. 4. The active energy ray-curable ink composition for back printing according to any one of 1 to 3, wherein the hydroxyl group-containing (meth)acrylate has a surface tension value (Davis method) of 8.0 to 20.0.
5. 5. The active energy ray-curable ink composition for back printing according to any one of 1 to 4, wherein the hydroxyl group-containing (meth)acrylate has an average molecular weight of 100 to 2,000.
6. The active energy ray-curable ink composition for back printing according to any one of 1 to 5, wherein the hydroxyl group-containing (meth)acrylate has a hydroxyl value of 50 to 400 mgKOH/g.
7. 7. The active energy ray-curable ink composition for back printing according to any one of 1 to 6, wherein the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
8. The hydroxyl group-containing (meth)acrylate contains a hydroxyl group-containing poly(meth)acrylate, and the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol, dipentaerythritol, glycerin, diglycerin, trimethylolpropane, and ditrimethylolpropane. 8. The active energy ray-curable ink composition for back printing according to any one of 1 to 7, which is a compound formed by an ester bond between one or more compounds and (meth)acrylic acid.
9. The active energy ray-curable ink composition for back printing according to any one of 1 to 8, wherein the active energy ray curable ink composition for back printing has a water content of 0.01 to 5.00% by mass.
10. 10. The active energy ray-curable ink composition for back printing according to any one of 1 to 9, wherein the hydroxyl group-containing poly(meth)acrylate is a compound having 2 to 4 (meth)acryloyl groups per molecule.
11. The active energy ray-curable ink composition for back printing according to any one of 8 to 10, wherein the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol di(meth)acrylate and/or pentaerythritol tri(meth)acrylate. .
12. The active energy ray-curable ink composition for back printing according to any one of 1 to 11, which is curable with an electron beam of 10 to 500 kGy.
13. The active energy ray-curable ink composition for back printing according to any one of 1 to 12 is printed on a printing material on which a printing layer is formed or on which a printing layer is not formed, and a sheet-like ink is applied on the printing layer. A method for producing a laminate, which comprises laminating materials, and then irradiating an active energy ray-curable ink composition layer for back printing with active energy rays.
14. A printing material on which a printing layer is formed or no printing layer is formed, and a printing layer formed on the printing material and comprising the active energy ray-curable ink composition for back printing according to any one of 1 to 12. , and a laminate having a sheet-like material laminated on a printing layer made of the active energy ray-curable ink composition for back printing.
　本発明の裏刷り用活性エネルギー線硬化型インキ組成物によれば、印刷後にエージングしなくとも印刷性に優れ、更に入手容易性、カーボンニュートラル優位性、印刷工程での高い生産性を有し、裏刷り用活性エネルギー線硬化型インキ組成物の製造工程や使用工程等において、容器や治具等の物品や装置に付着した場合であっても、揮発性有機溶剤を含有しない水によって、付着硬化物を洗浄除去でき、安価な（経済性に優れる）裏刷り用活性エネルギー線硬化型インキ組成物、その裏刷り用活性エネルギー線硬化型インキ組成物を使用した積層体の製造方法及び積層体を得ることができる。 According to the active energy ray-curable ink composition for back printing of the present invention, it has excellent printability without aging after printing, is easily available, has carbon neutrality, and has high productivity in the printing process. Even if the active energy ray-curable ink composition for back printing adheres to articles or equipment such as containers or jigs during the manufacturing process or usage process, the adhesion can be cured with water that does not contain volatile organic solvents. An active energy ray-curable ink composition for back printing that can be washed and removed and is inexpensive (excellent in economic efficiency), a method for producing a laminate using the active energy ray curable ink composition for back printing, and a laminate. Obtainable.
　本発明の裏刷り用活性エネルギー線硬化型インキ組成物は、ラミネート用印刷剤としても使用できる。このときには、必要に応じて印刷層を形成してなる被印刷物の印刷層側の表面に、裏刷り用活性エネルギー線硬化型インキ組成物を塗布し、その裏刷り用活性エネルギー線硬化型インキ組成物層の上にラミネート層である他方の被接着物を積層し、次いで、裏刷り用活性エネルギー線硬化型インキ組成物層に活性エネルギー線を照射する積層体の製造方法を採用できる。本発明の裏刷り用活性エネルギー線硬化型インキ組成物、積層体の製造方法、及び得られた積層体について、以下に順に説明する。なお、本発明の裏刷り用活性エネルギー線硬化型インキ組成物を、単に「組成物」というときがある。また、本発明の裏刷り用活性エネルギー線硬化型インキ組成物を印刷する対象を被印刷物というときがある。そして、本発明における活性エネルギー線とは、電子線や紫外線等のアクリル系モノマー等を硬化させることができるエネルギー線を示す。 The active energy ray-curable ink composition for back printing of the present invention can also be used as a printing agent for lamination. At this time, an active energy ray-curable ink composition for back printing is applied to the surface of the printing layer side of the printing material on which a printing layer is formed as necessary, and the active energy ray curable ink composition for back printing is applied. A method for producing a laminate can be adopted in which the other adherend, which is a laminate layer, is laminated on the material layer, and then the active energy ray-curable ink composition layer for back printing is irradiated with active energy rays. The active energy ray-curable ink composition for back printing, the method for producing a laminate, and the obtained laminate of the present invention will be explained in order below. Note that the active energy ray-curable ink composition for back printing of the present invention is sometimes simply referred to as a "composition." Further, the object to be printed with the active energy ray-curable ink composition for back printing of the present invention is sometimes referred to as a printing substrate. The active energy rays in the present invention refer to energy rays such as electron beams and ultraviolet rays that can harden acrylic monomers.
＜表面張力値（デイビス法）＞
　本発明の裏刷り用活性エネルギー線硬化型インキ組成物は、表面張力値ＨＬＢ（デイビス法）は８．０以上が好ましく、８．６以上がより好ましく、９．０以上が更に好ましい。また２０．０以下が好ましく、１６．０以下がより好ましく、１４．０以下が更に好ましい。
　デイビス法により表面張力値を求めるにあたり、予め定められている官能基毎の基数に基づき、ＨＬＢ値＝７＋Σ（親水基の基数）＋Σ（親油基の基数）により求めた。 <Surface tension value (Davis method)>
The active energy ray-curable ink composition for back printing of the present invention preferably has a surface tension value HLB (Davis method) of 8.0 or more, more preferably 8.6 or more, and still more preferably 9.0 or more. Further, it is preferably 20.0 or less, more preferably 16.0 or less, and even more preferably 14.0 or less.
In determining the surface tension value by the Davis method, the HLB value was determined based on the predetermined number of bases for each functional group, as follows: HLB value = 7 + Σ (number of bases of hydrophilic groups) + Σ (number of bases of lipophilic groups).
＜水酸基価＞
　水酸基価は、ＪＩＳ　Ｋ　００７０：１９９２に規定する方法により求めることができる。試料１ｇをアセチル化させたとき、水酸基と結合した酢酸を中和するのに必要とする水酸化カリウムのｍｇ数を求めて得る。本発明の裏刷り用活性エネルギー線硬化型インキ組成物が含有する水酸基含有（メタ）アクリレート全体のこのような水酸基価としては３０～４００ｍｇＫＯＨ／ｇが好ましく、中でも５０ｍｇＫＯＨ／ｇ以上がより好ましく、１００ｍｇＫＯＨ／ｇ以上がさらに好ましい。また、３５０ｍｇＫＯＨ／ｇ以下がより好ましく、３００ｍｇＫＯＨ／ｇ以下がさらに好ましい。
　また、水酸基含有（メタ）アクリレート以外の活性エネルギー線による重合性成分を含有する場合、活性エネルギー線による重合性成分全体の水酸基価が３０ｍｇＫＯＨ／ｇ以上であることが好ましい。 <Hydroxyl value>
The hydroxyl value can be determined by the method specified in JIS K 0070:1992. When 1 g of sample is acetylated, the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group is determined and obtained. The hydroxyl value of the entire hydroxyl-containing (meth)acrylate contained in the active energy ray-curable ink composition for back printing of the present invention is preferably 30 to 400 mgKOH/g, more preferably 50 mgKOH/g or more, and 100 mgKOH/g. /g or more is more preferable. Moreover, 350 mgKOH/g or less is more preferable, and 300 mgKOH/g or less is even more preferable.
Further, when containing a component other than hydroxyl group-containing (meth)acrylate that is polymerizable by active energy rays, it is preferable that the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
＜水酸基含有（メタ）アクリレート＞
　本発明の組成物に含有される水酸基含有（メタ）アクリレートは水酸基含有ポリ（メタ）アクリレートを含み、2つ以上の水酸基を有する化合物を（メタ）アクリル酸がエステル結合してなり、１．ペンタエリスリトールの（メタ）アクリル酸エステルであって、ペンタエリスリトールが有している水酸基のうちの１つ以上が未反応で残っているもの、２．ポリペンタエリスリトールの（メタ）アクリル酸エステルであって、ポリペンタエリスリトールが有している水酸基のうちの１つ以上が未反応で残っているもの、３．グリセリンの（メタ）アクリル酸エステルであって、グリセリンが有している水酸基のうちの１つ以上が未反応で残っているもの、４．ポリグリセリンの（メタ）アクリル酸エステルであって、ポリグリセリンが有している水酸基のうちの１つ以上が未反応で残っているもの、５．トリメチロールプロパンの（メタ）アクリル酸エステルであって、トリメチロールプロパンが有している水酸基のうちの１つ以上が未反応で残っているもの、６．ポリトリメチロールプロパンの（メタ）アクリル酸エステルであって、ポリトリメチロールプロパンが有している水酸基のうちの１つ以上が未反応で残っているもの、７．モノヒドロキシアルキルモノ（メタ）アクリレート等、から１種以上を採用できる。中でも上記１．～６．の水酸基含有（メタ）アクリレートを含有させることが好ましく、上記７．の水酸基含有（メタ）アクリレートを含有させないことがより好ましい。さらに、上記１．～６．の水酸基含有（メタ）アクリレートの中でも（メタ）アクリロイル基を２以上有するものが好ましい。
　水酸基含有（メタ）アクリレートの平均分子量は１００～２０００が好ましく、中でも１５０以上がより好ましく、２００以上が更に好ましい。また１０００以下がより好ましく、５００以下が更に好ましい。
　本発明の組成物が含有する重合性成分中に、水酸基含有（メタ）アクリレートを４５．０質量％以上含有し、７０．０質量％以上含有することが好ましく、９０．０質量％以上含有することがより好ましく、９５質量％以上含有することがさらに好ましい。１００．０質量％であっても良い。また不純物として水酸基含有（メタ）アクリレート以外の（メタ）アクリレートを含有することを排除しない。 <Hydroxy group-containing (meth)acrylate>
The hydroxyl group-containing (meth)acrylate contained in the composition of the present invention includes a hydroxyl group-containing poly(meth)acrylate, in which (meth)acrylic acid is ester bonded to a compound having two or more hydroxyl groups, and 1. (meth)acrylic acid ester of pentaerythritol, in which one or more of the hydroxyl groups of pentaerythritol remain unreacted; 2. (meth)acrylic acid ester of polypentaerythritol in which one or more of the hydroxyl groups possessed by polypentaerythritol remain unreacted; 3. (meth)acrylic acid ester of glycerin in which one or more of the hydroxyl groups of glycerin remain unreacted; 4. (meth)acrylic acid ester of polyglycerin, in which one or more of the hydroxyl groups of polyglycerin remain unreacted; 5. (meth)acrylic acid ester of trimethylolpropane, in which one or more of the hydroxyl groups of trimethylolpropane remain unreacted; 6. (meth)acrylic acid ester of polytrimethylolpropane in which one or more of the hydroxyl groups possessed by polytrimethylolpropane remains unreacted;7. One or more types of monohydroxyalkyl mono(meth)acrylates can be employed. Above all, 1. ~6. It is preferable to contain a hydroxyl group-containing (meth)acrylate of 7. above. It is more preferable not to contain the hydroxyl group-containing (meth)acrylate. Furthermore, above 1. ~6. Among the hydroxyl group-containing (meth)acrylates, those having two or more (meth)acryloyl groups are preferred.
The average molecular weight of the hydroxyl group-containing (meth)acrylate is preferably 100 to 2,000, more preferably 150 or more, and even more preferably 200 or more. Moreover, 1000 or less is more preferable, and 500 or less is still more preferable.
The composition of the present invention contains hydroxyl group-containing (meth)acrylate in a polymerizable component of 45.0% by mass or more, preferably 70.0% by mass or more, and 90.0% by mass or more. It is more preferable that the content is 95% by mass or more. It may be 100.0% by mass. Furthermore, it is not excluded that (meth)acrylates other than hydroxyl group-containing (meth)acrylates may be contained as impurities.
（上記１．について）
　１．ペンタエリスリトールの（メタ）アクリル酸エステルであって、ペンタエリスリトールが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のペンタエリスリトールの（メタ）アクリル酸エステルを包含しても良く、ペンタエリスリトールモノ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールモノ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールジ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキサイド変性ペンタエリスリトールモノ（メタ）アクリレート、プロピレンオキサイド変性ペンタエリスリトールジ（メタ）アクリレート、プロピレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート等から１種以上を含有できる。これらのペンタエリスリトールの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 1. above)
1. Examples of (meth)acrylic acid esters of pentaerythritol in which one or more of the hydroxyl groups of pentaerythritol remain unreacted include (meth)acrylates of (poly)alkylene oxide-modified pentaerythritol. ) may include acrylic esters, such as pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol mono(meth)acrylate, ethylene oxide modified penta Erythritol di(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, propylene oxide modified pentaerythritol mono(meth)acrylate, propylene oxide modified pentaerythritol di(meth)acrylate, propylene oxide modified pentaerythritol tri(meth)acrylate It can contain one or more of the following. These (meth)acrylic acid esters of pentaerythritol may or may not be included in the composition of the present invention.
（上記２．について）
　２．ポリペンタエリスリトールの（メタ）アクリル酸エステルであって、ポリペンタエリスリトールが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のポリペンタエリスリトールの（メタ）アクリル酸エステルを包含しても良く、ジペンタエリスリトールモノ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、トリペンタエリスリトールモノ（メタ）アクリレート、トリペンタエリスリトールジ（メタ）アクリレート、トリペンタエリスリトールトリ（メタ）アクリレート、トリペンタエリスリトールテトラ（メタ）アクリレート、及びこれらのポリペンタエリスリトールの（メタ）アクリル酸エステルのアルキレンオキサイド変性物（付加物）等から１種以上を含有できる。これらのポリペンタエリスリトールの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。
　なお、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、及びトリペンタエリスリトールヘプタ（メタ）アクリレートを使用すると、それらの化合物の含有比率によっては、印刷層の接着力が低下する可能性がある。 (Regarding 2. above)
2. (Meth)acrylic acid esters of polypentaerythritol in which one or more of the hydroxyl groups possessed by polypentaerythritol remain unreacted include (poly)alkylene oxide-modified polypentaerythritol may include (meth)acrylic acid esters of dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Tripentaerythritol mono(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, and (meth)acrylic acid esters of these polypentaerythritols It can contain one or more types of alkylene oxide modified products (adducts) and the like. These (meth)acrylic acid esters of polypentaerythritol may or may not be included in the composition of the present invention.
In addition, when using dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate, depending on the content ratio of those compounds. , the adhesion of the printed layer may be reduced.
（上記３．について）
　グリセリンの（メタ）アクリル酸エステルであって、グリセリンが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のグリセリンの（メタ）アクリル酸エステルを包含しても良く、グリセリンモノ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、エチレンオキサイド変性グリセリンモノ（メタ）アクリレート、エチレンオキサイド変性グリセリンジ（メタ）アクリレート、プロピレンオキサイド変性グリセリンモノ（メタ）アクリレート、プロピレンオキサイド変性グリセリンジ（メタ）アクリレート等から１種以上を含有できる。これらの水酸基含有グリセリンの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 3. above)
Examples of (meth)acrylic acid esters of glycerin in which one or more of the hydroxyl groups of glycerin remain unreacted include (meth)acrylic acid of glycerin modified with (poly)alkylene oxide. May include esters, such as glycerin mono(meth)acrylate, glycerin di(meth)acrylate, ethylene oxide-modified glycerin mono(meth)acrylate, ethylene oxide-modified glycerin di(meth)acrylate, propylene oxide-modified glycerin mono(meth)acrylate It can contain one or more of acrylates, propylene oxide-modified glycerin di(meth)acrylates, and the like. These (meth)acrylic acid esters of hydroxyl group-containing glycerin may or may not be included in the composition of the present invention.
（上記４．について）
　ポリグリセリンの（メタ）アクリル酸エステルであって、ポリグリセリンが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のポリグリセリンの（メタ）アクリル酸エステルを包含しても良く、ジグリセリンモノ（メタ）アクリレート、ジグリセリンジ（メタ）アクリレート、ジグリセリントリ（メタ）アクリレート、トリグリセリンモノ（メタ）アクリレート、トリグリセリンジ（メタ）アクリレート、トリグリセリントリ（メタ）アクリレート、トリグリセリンテトラ（メタ）アクリレート及びこれらのポリグリセリンの（メタ）アクリル酸エステルのアルキレンオキサイド変性物（付加物）等から１種以上を含有できる。
　これらの水酸基含有ポリグリセリンの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 4. above)
Examples of (meth)acrylic acid esters of polyglycerin in which one or more of the hydroxyl groups of polyglycerin remain unreacted include (meth)acrylic esters of (poly)alkylene oxide-modified polyglycerin. ) acrylic acid ester, diglycerin mono(meth)acrylate, diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, triglycerin mono(meth)acrylate, triglycerin di(meth)acrylate, triglycerin It can contain one or more of glycerin tri(meth)acrylate, triglycerin tetra(meth)acrylate, alkylene oxide modified products (adducts) of (meth)acrylic acid esters of these polyglycerins, and the like.
These (meth)acrylic esters of hydroxyl group-containing polyglycerin may or may not be included in the composition of the present invention.
（上記５．について）
　トリメチロールプロパンの（メタ）アクリル酸エステルであって、トリメチロールプロパンが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のトリメチロールプロパンの（メタ）アクリル酸エステルを包含しても良く、トリメチロールプロパンモノ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパンモノ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパンジ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパンモノ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパンジ（メタ）アクリレート等から１種以上を含有できる。これらの水酸基含有トリメチロールプロパンの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 5. above)
(Meth)acrylic acid esters of trimethylolpropane in which one or more of the hydroxyl groups of trimethylolpropane remain unreacted include (poly)alkylene oxide-modified trimethylolpropane. may include (meth)acrylic acid esters of trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, ethylene oxide-modified trimethylolpropane mono(meth)acrylate, ethylene oxide-modified trimethylolpropane. It can contain one or more of di(meth)acrylate, propylene oxide-modified trimethylolpropane mono(meth)acrylate, propylene oxide-modified trimethylolpropane di(meth)acrylate, and the like. These hydroxyl group-containing (meth)acrylic esters of trimethylolpropane may or may not be included in the composition of the present invention.
（上記６．について）
　ポリトリメチロールプロパンの（メタ）アクリル酸エステルであって、ポリトリメチロールプロパンが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のポリトリメチロールプロパンの（メタ）アクリル酸エステルを包含しても良く、ジトリメチロールプロパンモノ（メタ）アクリレート、ジトリメチロールプロパンジ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、及びこれらのポリトリメチロールプロパンの（メタ）アクリル酸エステルのアルキレンオキサイド変性物（付加物）等から１種以上を含有できる。これらの水酸基含有ポリトリメチロールプロパンの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 6. above)
(Meth)acrylic acid esters of polytrimethylolpropane in which one or more of the hydroxyl groups possessed by polytrimethylolpropane remain unreacted include (poly)alkylene oxide-modified polyesters. (Meth)acrylic esters of trimethylolpropane may be included, including ditrimethylolpropane mono(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and polytrimethylols thereof. It can contain one or more types of alkylene oxide modified products (adducts) of (meth)acrylic esters of propane. These (meth)acrylic esters of hydroxyl group-containing polytrimethylolpropane may or may not be included in the composition of the present invention.
（上記７．について）
　モノヒドロキシアルキルモノ（メタ）アクリレートとしては、アルキレングリコ－ルモノ（メタ）アクリレート、ポリアルキレングリコ－ルモノ（メタ）アクリレート及びその他の水酸基含有（メタ）アクリレート類から選ばれた１種以上を含有しても良く、含有しなくても良い。 (Regarding 7. above)
The monohydroxyalkyl mono(meth)acrylate contains one or more selected from alkylene glycol mono(meth)acrylate, polyalkylene glycol mono(meth)acrylate, and other hydroxyl group-containing (meth)acrylates. may be included, and may not be included.
（アルキレングリコ－ルモノ（メタ）アクリレート）
　２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、ヒドロキシシクロヘキシル（メタ）アクリレート等から１種以上を含有できる。これらのアルキレングリコ－ルモノ（メタ）アクリレートは、本発明の組成物に含有させてもよく、含有させなくてもよい。特にエポキシ（メタ）アクリレート及び４－ヒドロキシブチル（メタ）アクリレートは含有させなくてもよい。 (Alkylene glycol mono(meth)acrylate)
2-Hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl ( It can contain one or more of meth)acrylate, hydroxycyclohexyl(meth)acrylate, and the like. These alkylene glycol mono(meth)acrylates may or may not be included in the composition of the present invention. In particular, epoxy (meth)acrylate and 4-hydroxybutyl (meth)acrylate may not be contained.
（ポリアルキレングリコ－ルモノ（メタ）アクリレート）
　ポリアルキレングリコ－ルモノ（メタ）アクリレートとしては、ジエチレングリコールモノ（メタ）アクリレート、ジプロピレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレートや、ポリエチレングリコール－ポリプロピレングリコールモノ（メタ）アクリレート、ポリオキシブチレン－ポリオキシプロピレンモノ（メタ）アクリレート等のブロック構造を有する化合物、ポリ（プロピレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート等のランダム構造を有する化合物が挙げられる。これらのポリアルキレングリコ－ルモノ（メタ）アクリレートは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Polyalkylene glycol mono(meth)acrylate)
Examples of polyalkylene glycol mono(meth)acrylate include diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol-polypropylene glycol. Examples include compounds with a block structure such as mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, and compounds with a random structure such as poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. . These polyalkylene glycol mono(meth)acrylates may or may not be included in the composition of the present invention.
（その他の水酸基含有（メタ）アクリレート類）
　その他の水酸基含有（メタ）アクリレート類としては、４－ヒドロキシフェニル（メタ）アクリレート、２－ヒドロキシ－３－クロロプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－アリルオキシプロピル（メタ）アクリレート、（メタ）アクリル酸－２－ヒドロキシ－３－アリルオキシプロピル、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシプロピルフタレート、２－エチルヘキシル（ポリ）エチレンオキサイド変性（メタ）アクリレート、ｏ－フェニルフェノール（ポリ）エチレンオキサイド変性アクリレート、ｐ－クミルフェノール（ポリ）エチレンオキサイド変性（メタ）アクリレート、ノニルフェノール（ポリ）エチレンオキサイド変性（メタ）アクリレート等の（ポリ）アルキレングリコール変性（メタ）アクリレート類等が挙げられる。これらのその他の水酸基含有（メタ）アクリレート類は、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Other hydroxyl group-containing (meth)acrylates)
Other hydroxyl group-containing (meth)acrylates include 4-hydroxyphenyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy -3-allyloxypropyl (meth)acrylate, -2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-ethylhexyl (poly)ethylene oxide (Poly) such as modified (meth)acrylate, o-phenylphenol (poly)ethylene oxide modified (meth)acrylate, p-cumylphenol (poly)ethylene oxide modified (meth)acrylate, nonylphenol (poly)ethylene oxide modified (meth)acrylate, etc. Examples include alkylene glycol-modified (meth)acrylates. These other hydroxyl group-containing (meth)acrylates may or may not be included in the composition of the present invention.
＜その他の二重結合を有する化合物成分＞
　本発明の組成物には、その他の二重結合を有する化合物成分を含有させても良く、含有させなくても良い。そのような化合物としては、上記１．～７．に記載の水酸基含有（メタ）アクリレートにおいて、更に水酸基の全てが（メタ）アクリル酸によりエステル化された化合物、鎖状アルキル（メタ）アクリレート、環状アルキル（メタ）アクリレート、上記以外のエーテル基含有（メタ）アクリレート、ビニルエーテル基含有（メタ）アクリレート、その他の（メタ）アクリレート、（メタ）アクリレート類以外の二重結合を有する化合物、を含有することができる。また含有しなくても良い。更に、上記１．～７．に記載の水酸基含有（メタ）アクリレートにおいて、更に水酸基の全てが（メタ）アクリル酸によりエステル化された化合物としては、上記１．～７．の化合物を合成する際に、副生成物として得られる化合物が残っている場合のものがある。 <Other compound components having double bonds>
The composition of the present invention may or may not contain other compound components having double bonds. Such compounds include those listed in 1. above. ~7. In the hydroxyl group-containing (meth)acrylates described in , compounds in which all of the hydroxyl groups are esterified with (meth)acrylic acid, chain alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, and ether group-containing (other than the above) It can contain meth)acrylate, vinyl ether group-containing (meth)acrylate, other (meth)acrylates, and compounds having double bonds other than (meth)acrylates. Moreover, it does not need to be contained. Furthermore, above 1. ~7. In the hydroxyl group-containing (meth)acrylate described in 1. above, all of the hydroxyl groups are further esterified with (meth)acrylic acid. ~7. When synthesizing a compound, some compounds may remain as by-products.
（上記１．～７．に記載の水酸基含有（メタ）アクリレートにおいて、更に水酸基の全てが（メタ）アクリル酸によりエステル化された化合物）
　本発明の組成物には、上記１．～７．に記載の水酸基含有（メタ）アクリレートにおいて、更に水酸基の全てが（メタ）アクリル酸によりエステル化された化合物（２以上の（メタ）アクリロイル基を有し、水酸基を有しない多官能（メタ）アクリレート化合物）を含有させても良く、含有させなくても良い。但し、本発明による効果を毀損しない範囲に限られる。具体的な化合物として、ペンタエリスリトールテトラ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコール（１００）ジ（メタ）アクリレート、ポリエチレングリコール（４００）ジ（メタ）アクリレート等の（ポリ）エチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラプロピレングリコールジ（メタ）アクリレート等の（ポリ）プロピレングリコールジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、ジメチロールオクタンジ（メタ）アクリレート、ジメチロール－トリシクロデカンジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ジメチル－２，４－ペンタンジオールジ（メタ）アクリレート、１，５－ジメチル－２，５－ヘキサンジオールジ（メタ）アクリレート、１，５－ペンタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，７－ヘプタンジオールジ（メタ）アクリレート、１，８－オクタンジオールジ（メタ）アクリレート等のアルキレンジオールジ（メタ）アクリレート等が挙げられる。 (A compound in which all of the hydroxyl groups in the hydroxyl group-containing (meth)acrylates described in 1. to 7. above are further esterified with (meth)acrylic acid)
The composition of the present invention includes the above-mentioned 1. ~7. In the hydroxyl group-containing (meth)acrylate described in , all of the hydroxyl groups are further esterified with (meth)acrylic acid (a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups and no hydroxyl group). compound) may or may not be included. However, this is limited to a range that does not impair the effects of the present invention. Specific compounds include pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol (100) di(meth)acrylate, (Poly)ethylene glycol di(meth)acrylate such as polyethylene glycol (400) di(meth)acrylate; (poly)propylene glycol di(meth)acrylate such as tripropylene glycol di(meth)acrylate and tetrapropylene glycol di(meth)acrylate; ) acrylate, cyclohexanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, dimethyloloctane di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, 1,3-butylene glycol di( meth)acrylate, 1,4-dimethyl-2,4-pentanediol di(meth)acrylate, 1,5-dimethyl-2,5-hexanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate Examples include alkylene diol di(meth)acrylates such as acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, and 1,8-octanediol di(meth)acrylate. .
　更に、別の水酸基含有（メタ）アクリレート類以外の二重結合を有する化合物を含有させても良く、含有させなくても良い。そのような化合物として、モノ（メタ）アクリレート化合物として、以下の、鎖状アルキル（メタ）アクリレート、環状アルキル（メタ）アクリレート、上記以外のエーテル基含有（メタ）アクリレート、ビニルエーテル基含有（メタ）アクリレート、その他の（メタ）アクリレート、（メタ）アクリレート類以外の二重結合を有する化合物等が挙げられる。 Further, a compound having a double bond other than the hydroxyl group-containing (meth)acrylates may or may not be included. As such compounds, mono(meth)acrylate compounds include the following chain alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, ether group-containing (meth)acrylates other than the above, and vinyl ether group-containing (meth)acrylates. , other (meth)acrylates, and compounds having double bonds other than (meth)acrylates.
（鎖状アルキル（メタ）アクリレート）
　鎖状アルキル（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔ－ブチルアクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、トリデシル（メタ）アクリレート、ノニル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、イソボルニル（メタ）アクリレートが挙げられる。 (chain alkyl (meth)acrylate)
Examples of chain alkyl (meth)acrylates 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, isodecyl (meth)acrylate, isomyristyl (meth)acrylate, octadecyl (meth)acrylate, dicyclopentanyl (meth)acrylate Examples include acrylate, tridecyl (meth)acrylate, nonyl (meth)acrylate, hexadecyl (meth)acrylate, myristyl (meth)acrylate, and isobornyl (meth)acrylate.
（環状アルキル（メタ）アクリレート）
　環状アルキル（メタ）アクリレートとしては、シクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、１－アダマンチル（メタ）アクリレート、３，５，５－トリメチルシクロヘキシルアクリレート、４－ｔ－ブチルシクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。 (Cyclic alkyl (meth)acrylate)
Cyclic alkyl (meth)acrylates include 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, benzyl (meth)acrylate, and the like.
（上記以外のエーテル基含有（メタ）アクリレート）
　上記以外のエーテル基含有（メタ）アクリレートとしては、１，３－ブチレングリコールメチルエーテル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、エトキシエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、ブトキシエチレングリコール（メタ）アクリレート、ブトキシジエチレングリコール（メタ）アクリレート、メトキシプロピレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、メトキシトリプロピレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、メトキシブチレングリコール（メタ）アクリレート、２－（２－エトキシエトキシ）エチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート（ＥＯ繰返し単位数４００、７００等）、エチルカルビトール（メタ）アクリレート、２－エチルヘキシルカルビトール（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、クレジルポリエチレングリコール（メタ）アクリレート、（メタ）アクリル酸－２－（ビニロキシエトキシ）エチル、フェノキシエチル（メタ）アクリレート、ｐ－ノニルフェノキシエチル（メタ）アクリレート、ｐ－ノニルフェノキシポリエチレングリコール（メタ）アクリレート、グリシジル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシ－ポリエチレングリコール（メタ）アクリレート、ヘキサエチレングリコールモノフェニルエーテルモノ（メタ）アクリレート、アルコキシ化２－フェノキシエチル（メタ）アクリレート（エトキシ化２－フェノキシエチル（メタ）アクリレート、プロポキシ化２－フェノキシエチル（メタ）アクリレート等）、アルコキシ化ノニルフェニル（メタ）アクリレート（エトキシ化（４）ノニルフェノールアクリレート等）、２－フェノキシエチル（メタ）アクリレート、パラクミルフェノキシエチレングリコール（メタ）アクリレート、メチルフェノキシエチルアクリレート、エトキシ化コハク酸（メタ）アクリレート、エトキシ化トリブロモフェニルアクリレート、エトキシ化ノニルフェニル（メタ）アクリレート、等のアルコキシ及び又はフェノキシ系（メタ）アクリレート類等が挙げられる。 (Ether group-containing (meth)acrylates other than those listed above)
Examples of ether group-containing (meth)acrylates other than those listed above include 1,3-butylene glycol methyl ether (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, Ethoxyethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene Glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxybutylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate (EO repeating unit number 400, 700 etc.), ethyl carbitol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cresyl polyethylene glycol (meth)acrylate, (meth)acrylic acid-2-(vinyloxy) ethoxy)ethyl, phenoxyethyl (meth)acrylate, p-nonylphenoxyethyl (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, glycidyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy-polyethylene glycol ( meth)acrylate, hexaethylene glycol monophenyl ether mono(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, methylphenoxyethyl acrylate, ethoxylated succinic acid (meth)acrylate, ) acrylate, ethoxylated tribromophenyl acrylate, ethoxylated nonylphenyl (meth)acrylate, and alkoxy- and/or phenoxy-based (meth)acrylates.
（ビニルエーテル基含有（メタ）アクリレート）
　ビニルエーテル基含有（メタ）アクリレートとしては、（メタ）アクリル酸－２－ビニロキシエチル、（メタ）アクリル酸－３－ビニロキシプロピル、（メタ）アクリル酸－１－メチル－２－ビニロキシエチル、（メタ）アクリル酸－２－ビニロキシプロピル、（メタ）アクリル酸－４－ビニロキシブチル、（メタ）アクリル酸－１－メチル－３－ビニロキシプロピル、（メタ）アクリル酸－１－ビニロキシメチルプロピル、（メタ）アクリル酸－２－メチル－３－ビニロキシプロピル、（メタ）アクリル酸－３－メチル－３－ビニロキシプロピル、（メタ）アクリル酸－１，１－ジメチル－２－ビニロキシエチル、（メタ）アクリル酸－３－ビニロキシブチル、（メタ）アクリル酸－１－メチル－２－ビニロキシプロピル、（メタ）アクリル酸－２－ビニロキシブチル、（メタ）アクリル酸－４－ビニロキシシクロヘキシル、（メタ）アクリル酸－５－ビニロキシペンチル、（メタ）アクリル酸－６－ビニロキシヘキシル、（メタ）アクリル酸－４－ビニロキシメチルシクロヘキシルメチル、（メタ）アクリル酸－３－ビニロキシメチルシクロヘキシルメチル、（メタ）アクリル酸－２－ビニロキシメチルシクロヘキシルメチル、（メタ）アクリル酸－ｐ－ビニロキシメチルフェニルメチル、（メタ）アクリル酸－ｍ－ビニロキシメチルフェニルメチル、（メタ）アクリル酸－ｏ－ビニロキシメチルフェニルメチル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシ）エチル、（メタ）アクリル酸－２－（ビニロキシエトキシ）プロピル、（メタ）アクリル酸－２－（ビニロキシエトキシ）イソプロピル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシ）プロピル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシ）イソプロピル、（メタ）アクリル酸－２－（ビニロキシエトキシエトキシ）エチル、（メタ）アクリル酸－２－（ビニロキシエトキシイソプロポキシ）エチル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシエトキシ）エチル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシイソプロポキシ）エチル等が挙げられる。 ((Meth)acrylate containing vinyl ether group)
Examples of vinyl ether group-containing (meth)acrylates include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, and (meth)acrylate. 2-vinyloxypropyl acid, 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, (meth)acrylate 2-methyl-3-vinyloxypropyl acrylate, 3-methyl-3-vinyloxypropyl (meth)acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, (meth)acrylic acid -3-vinyloxybutyl, (meth)acrylic acid-1-methyl-2-vinyloxypropyl, (meth)acrylic acid-2-vinyloxybutyl, (meth)acrylic acid-4-vinyloxycyclohexyl, (meth)acrylic acid-5 -vinyloxypentyl, -6-vinyloxyhexyl (meth)acrylate, -4-vinyloxymethylcyclohexylmethyl (meth)acrylate, -3-vinyloxymethylcyclohexylmethyl (meth)acrylate, (meth)acrylic acid -2-vinyloxymethylcyclohexylmethyl, p-vinyloxymethylphenylmethyl (meth)acrylate, m-vinyloxymethylphenylmethyl (meth)acrylate, o-vinyloxymethylphenylmethyl (meth)acrylate , 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxy)isopropyl (meth)acrylate, (meth) 2-(vinyloxyisopropoxy)propyl acrylate, 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)ethyl (meth)acrylate, (meth)acrylic acid -2-(vinyloxyethoxyisopropoxy)ethyl, (meth)acrylic acid-2-(vinyloxyisopropoxyethoxy)ethyl, (meth)acrylic acid-2-(vinyloxyisopropoxyisopropoxy)ethyl, etc. .
（その他の（メタ）アクリレート）
　その他の（メタ）アクリレートとしては、例えば、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、モルホリノエチル（メタ）アクリレート、トリメチルシロキシエチル（メタ）アクリレート、ジフェニル－２－（メタ）アクリロイルオキシエチルホスフェート、２－（メタ）アクリロイルオキシエチルアシッドホスフェート、カプロラクトン変性－２－（メタ）アクリロイルオキシエチルアシッドホスフェート、２－ヒドロキシ－１－（メタ）アクリロキシ－３－メタクリロキシプロパン、アクリロキシエチルフタレート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシエチルフタレート、２－（メタ）アクリロイロキシプロピルフタレート、トリシクロデカンモノメチロール（メタ）アクリレート、（メタ）アクリル酸ダイマー、ジエチルアミノエチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－エチルヘキシル－ジグリコール（メタ）アクリレート、アミノエチル（メタ）アクリレート、エチルカルビトールアクリレート、エチルジグリコールアクリレート、ジメチルアミノエチルアクリレートベンジルクロライド４級塩、トリブロモフェニル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、クレゾール（メタ）アクリレート、トリメチロールプロパンフォルマル（メタ）アクリレート、ネオペンチルグリコール（メタ）アクリル酸安息香酸エステル、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート、１－（メタ）アクリロイルピペリジン－２－オン、２－（メタ）アクリル酸－１，４－ジオキサスピロ［４，５］デシ－２－イルメチル、Ｎ－（メタ）アクリロイルオキシエチルヘキサヒドロフタルイミド、γ－ブチロラクトン（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリルアクリレート、イミドアクリレート、（メタ）アクリル酸ビニル、マレイミド等が挙げられる。 (Other (meth)acrylates)
Examples of other (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and morpholinoethyl ( meth)acrylate, trimethylsiloxyethyl (meth)acrylate, diphenyl-2-(meth)acryloyloxyethyl phosphate, 2-(meth)acryloyloxyethyl acid phosphate, caprolactone-modified-2-(meth)acryloyloxyethyl acid phosphate, 2 -Hydroxy-1-(meth)acryloxy-3-methacryloxypropane, acryloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, tricyclo Decane monomethylol (meth)acrylate, (meth)acrylic acid dimer, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic 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-cyclohexane di Methanol mono(meth)acrylate, cresol (meth)acrylate, trimethylolpropane formal(meth)acrylate, neopentyl glycol(meth)acrylic acid benzoate, (2-methyl-2-ethyl-1,3-dioxolane) 4-yl)methyl(meth)acrylate, 1-(meth)acryloylpiperidin-2-one, 2-(meth)acrylic acid-1,4-dioxaspiro[4,5]dec-2-ylmethyl, N-(meth)acrylate ) Acryloyloxyethylhexahydrophthalimide, γ-butyrolactone (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, imide acrylate, vinyl (meth)acrylate, maleimide, and the like.
（（メタ）アクリレート類以外の二重結合を有する低分子化合物）
　（メタ）アクリレート類以外の二重結合を有する化合物は、本発明の組成物に含有させてもよく、含有させなくてもよい。
　このような化合物として、スチレン、ビニルトルエン、ｐ－ヒドロキシスチレン、ｐ－クロロスチレン、ｐ－ブロモスチレン、ｐ－メチルスチレン、ｐ－メトキシスチレン、ｐ－ｔ－ブトキシスチレン、ｐ－ｔ－ブトキシカルボニルスチレン、ｐ－ｔ－ブトキシカルボニルオキシスチレン、２，４－ジフェニル－４－メチル－１－ペンテン、ジビニルベンゼン、窒素含有化合物として、（メタ）アクリルアミド、アクリロイルモルホリン、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタムＮ－ビニルカルバゾール等が挙げられる。
　その他の化合物としては、酢酸ビニル、モノクロロ酢酸ビニル、安息香酸ビニル、ピバル酸ビニル、酪酸ビニル、ラウリン酸ビニル、アジピン酸ジビニル、クロトン酸ビニル、２－エチルヘキサン酸ビニル、三員環化合物類（例えば、ビニルシクロプロパン類、１－フェニル－２－ビニルシクロプロパン類、２－フェニル－３－ビニルオキシラン類、２，３－ジビニルオキシラン類等）、環状ケテンアセタール類（例えば、２－メチレン－１，３－ジオキセパン、ジオキソラン類、２－メチレン－４－フェニル－１，３－ジオキセパン、４，７－ジメチル－２－メチレン－１，３－ジオキセパン、５，６－ベンゾ－２－メチレン－１，３－ジオキセパン等）、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート、イソシアヌル酸トリアリレート等が挙げられる。 (Low molecular compounds with double bonds other than (meth)acrylates)
Compounds having double bonds other than (meth)acrylates may or may not be included in the composition of the present invention.
Such 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, divinylbenzene, nitrogen-containing compounds such as (meth)acrylamide, acryloylmorpholine, N-vinylformamide, N-vinylacetamide, Examples include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, and the like.
Other compounds include vinyl acetate, monochlorovinyl acetate, 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.), cyclic ketene acetals (for example, 2-methylene-1, 3-dioxepane, dioxolanes, 2-methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3 -dioxepane, etc.), allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate, etc.
＜カルボン酸基、ヒドロキシル基及びウレタン基のうち１種以上を有し、かつ、エチレン性不飽和基を有して、重量平均分子量が５００～１０００００の樹脂＞
　本発明におけるこのような樹脂として、スチレンアクリルオリゴマー、アミン変性（メタ）アクリレートオリゴマー、エポキシ（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー、ポリウレタン（メタ）アクリレートオリゴマー等が好ましい。 <Resin having at least one type of carboxylic acid group, hydroxyl group, and urethane group, and having an ethylenically unsaturated group and having a weight average molecular weight of 500 to 100,000>
Preferred examples of such resins in the present invention include styrene acrylic oligomers, amine-modified (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and polyurethane (meth)acrylate oligomers.
（スチレンアクリルオリゴマー）
　スチレンアクリルオリゴマーとしては、少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。
　スチレンアクリルオリゴマーは、例えば、ＵＳ－１０７１、Ｘ－１、ＹＳ－１２７４、ＶＳ－１０４７、ＲＳ－１１９１（星光ＰＭＣ社）が挙げられる。 (Styrene acrylic oligomer)
The styrene acrylic oligomer is not particularly limited as long as it is an oligomer having at least one (meth)acryloyl group.
Examples of the styrene acrylic oligomer include US-1071, X-1, YS-1274, VS-1047, and RS-1191 (Seiko PMC Corporation).
（アミン変性（メタ）アクリレートオリゴマー）
　アミン変性（メタ）アクリレートオリゴマーとしては、少なくとも１つのアミノ基と、少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。一方、前記アミン変性（メタ）アクリレートオリゴマーが分子中に有する（メタ）アクリロイル基の数は、１つ以上であれば特に制限されないが、１つ以上６つ以下であることが好ましく、２つ以上４つ以下であることがより好ましい。（メタ）アクリロイル基の数が上記範囲であると、アミン変性（メタ）アクリレートオリゴマーが重合性化合物と反応しやすくなる。
　前記アミン変性（メタ）アクリレートオリゴマーは、所望のモノマーを重合した合成品であってもよく、市販品であってもよい。前記アミン変性（メタ）アクリレートオリゴマーの市販品としては、例えば、ＧＥＮＯＭＥＲ５１６１、ＧＥＮＯＭＥＲ５２７５（ＲＡＨＮ社）、ＣＮ３７１、ＣＮ３７１ＮＳ、ＣＮ３７３、ＣＮ３８３、ＣＮ３８４、ＣＮ３８６、ＣＮ５０１、ＣＮ５０３、ＣＮ５５０、ＣＮ５５１（サートマー社）、ＥＢＥＣＲＹＬ８０、ＥＢＥＣＲＹＬ８１、ＥＢＥＣＲＹＬ８３、ＥＢＥＣＲＹＬ７１００、ＥＢＥＣＲＹＬ８４、ＥＢＥＣＲＹＬＰ１１５（ダイセル・オルネクス社）、Ｌａｒｏｍｅｒ　ＰＯ　８３Ｆ、Ｌａｒｏｍｅｒ　ＰＯ　８４Ｆ、Ｌａｒｏｍｅｒ　ＬＲ８９４６、Ｌａｒｏｍｅｒ　ＬＲ８９５６、Ｌａｒｏｍｅｒ ＬＲ８９９６、Ｌａｒｏｍｅｒ　ＬＲ８８９４（ＢＡＳＦ社）、ＡｇｉＳｙｎ００１、ＡｇｉＳｙｎ００２、Ａｇｉｓｙｎ００３、Ａｇｉｓｙｎ００８（ＤＳＭ Ｃｏａｔｉｎｇ　Ｒｅｓｉｎ社）、Ｐｈｏｔｏｍｅｒ４７７１、Ｐｈｏｔｏｍｅｒ４７７５、Ｐｈｏｔｏｍｅｒ４９６７、Ｐｈｏｔｏｍｅｒ５０９６、Ｐｈｏｔｏｍｅｒ５６６２、Ｐｈｏｔｏｍｅｒ５９３０（コグニス社）、ＤｏｕｂｌｅｃｕｒｅＥＰＤ、ＤｏｕｂｌｅｃｕｒｅＯＰＤ、Ｄｏｕｂｌｅｃｕｒｅ１１５、Ｄｏｕｂｌｅｃｕｒｅ２２５、Ｄｏｕｂｌｅｃｕｒｅ６４５、ＰｏｌｙＱ２２２、ＰｏｌｙＱ２２６、ＰｏｌｙＱ２２４、ＰｏｌｙＱ１０１（ＤｏｕｂｌｅＢｏｎｄＣｈｅｍｉｃａｌｓ社）が挙げられる。なかでも、分子内に２個の光重合性官能基を有するオリゴマーが好ましく、光重合性官能基が（メタ）アクリロイル基であることがより好ましい。 (Amine-modified (meth)acrylate oligomer)
The amine-modified (meth)acrylate oligomer is not particularly limited as long as it has at least one amino group and at least one (meth)acryloyl group. On the other hand, the number of (meth)acryloyl groups that the amine-modified (meth)acrylate oligomer has in the molecule is not particularly limited as long as it is one or more, but it is preferably from one to six, and two or more. More preferably, the number is four or less. When the number of (meth)acryloyl groups is within the above range, the amine-modified (meth)acrylate oligomer easily reacts with the polymerizable compound.
The amine-modified (meth)acrylate oligomer may be a synthetic product obtained by polymerizing a desired monomer, or may be a commercially available product. Examples of commercially available amine-modified (meth)acrylate oligomers include GENOMER5161, GENOMER5275 (RAHN), CN371, CN371NS, CN373, CN383, CN384, CN386, CN501, CN503, CN550, CN551 (Sartomer), and EB. ECRYL80, EBECRYL81, EBECRYL83, EBECRYL7100, EBECRYL84, EBECRYLP115 (Daicel Allnex), Laromer PO 83F, Laromer PO 84F, Laromer LR8946, Laromer LR895 6, Laromer LR8996, Laromer LR8894 (BASF), AgiSyn001, AgiSyn002, Agisyn003, Agisyn008 (DSM Coating Resin), Photomer4771, Photomer4775, Photomer4967, Photomer5096, Photomer5662, Photomer5930 (Cognis), DoublecureEPD, DoublecureOPD, D Examples include doublecure 115, doublecure 225, doublecure 645, PolyQ222, PolyQ226, PolyQ224, and PolyQ101 (DoubleBond Chemicals). Among these, oligomers having two photopolymerizable functional groups in the molecule are preferable, and it is more preferable that the photopolymerizable functional groups are (meth)acryloyl groups.
（エポキシ（メタ）アクリレートオリゴマー）
　エポキシ（メタ）アクリレートオリゴマーとしては、少なくとも１つのエポキシ基と、少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。エポキシ（メタ）アクリレートオリゴマーは、所望のモノマーを重合した合成品であってもよく、市販品であってもよい。例えば、ＥＢＥＣＲＹＬ６００、ＥＢＥＣＲＹＬ６０５、ＥＢＥＣＲＹＬ３６０６、ＥＢＥＣＲＹＬ３５００、ＥＢＥＣＲＹＬ８６０（ダイセル・オルネクス社）、ＣＮ１１６、ＣＮ１２０Ｂ６０、ＣＮ１２０Ｍ５０、ＣＮ１３１Ｂ、ＣＮ１３２、ＣＮ１３７、ＣＮ１５２、ＣＮ１５３、ＣＮ２１０２Ｅ、ＣＮ２００３（サートマー社）、Ｍｉｒａｍｅｒ　ＰＵ２１００、Ｍｉｒａｍｅｒ　ＰＥ２１０（ＭＩＷＯＮ社）等が挙げられる。 (Epoxy (meth)acrylate oligomer)
The epoxy (meth)acrylate oligomer is not particularly limited as long as it is an oligomer having at least one epoxy group and at least one (meth)acryloyl group. The epoxy (meth)acrylate oligomer may be a synthetic product obtained by polymerizing a desired monomer, or may be a commercially available product. For example, EBECRYL600, EBECRYL605, EBECRYL3606, EBECRYL3500, EBECRYL860 (Daicel Allnex), CN116, CN120B60, CN120M50, CN131B, CN132, CN137, CN152, CN153 , CN2102E, CN2003 (Sartmer), Miramer PU2100, Miramer PE210 (MIWON) ) etc.
（ポリエステル（メタ）アクリレートオリゴマー）
　ポリエステル（メタ）アクリレートオリゴマーとしては、ポリエステル構造と、少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。ＥＢＥＣＲＹＬ８１１、ＥＢＥＣＲＹＬ８８４、ＥＢＥＣＲＹＬ８８５、ＥＢＥＣＲＹＬ８１２、ＥＢＥＣＲＹＬ８００、ＥＢＥＣＲＹＬ８１０、ＥＢＥＣＲＹＬ４５０、ＥＢＥＣＲＹＬ８７０、ＥＢＥＣＲＹＬ１８３０、ＯＴＡ４８０、ＰＥＴＲＡ（ダイセル・オルネクス社）や、トール油脂肪酸変性６官能ポリエステルアクリレート（例えば、ＡｇｉＳｙｎ７１６等）、Ｍｉｒａｍｅｒ　ＰＳ４２０（ＭＩＷＯＮ社）等が挙げられる。 (Polyester (meth)acrylate oligomer)
The polyester (meth)acrylate oligomer is not particularly limited as long as it has a polyester structure and at least one (meth)acryloyl group. EBECRYL811, EBECRYL884, EBECRYL885, EBECRYL812, EBECRYL800, EBECRYL810, EBECRYL450, EBECRYL870, EBECRYL1830, OTA480, PETRA (Daicel Allnex) , tall oil fatty acid modified hexafunctional polyester acrylate (for example, AgiSyn716, etc.), Miramer PS420 (MIWON) etc.
（ポリウレタン（メタ）アクリレートオリゴマー）
　ポリウレタン（メタ）アクリレートオリゴマーとしてはポリウレタン構造と少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。ポリウレタン（メタ）アクリレートオリゴマー、所望のモノマーを重合した合成品であってもよく、市販品であってもよい。例えば、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ４５１３、ＥＢＥＣＲＹＬ４７３８、ＥＢＥＣＲＹＬ４７４０、ＥＢＥＣＲＹＬ８４６５、ＥＢＥＣＲＹＬ９２６０、ＥＢＥＣＲＹＬ４６６６、ＥＢＥＣＲＹＬ８２１０、ＥＢＥＣＲＹＬ８６０６、ＥＢＥＣＲＹＬ１２９０、ＥＢＥＣＲＹＬ５１２９、ＥＢＥＣＲＹＬ８３０１Ｒ、ＫＲＭ８２００、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ２２０等（ダイセル・オルネクス社）、Ｍｉｒａｍｅｒ　ＰＵ２１００、Ｍｉｒａｍｅｒ　ＷＳ２６００、Ｍｉｒａｍｅｒ　ＷＳ４０００（ＭＩＷＯＮ社）等が挙げられる。 (Polyurethane (meth)acrylate oligomer)
The polyurethane (meth)acrylate oligomer is not particularly limited as long as it has a polyurethane structure and at least one (meth)acryloyl group. It may be a polyurethane (meth)acrylate oligomer, a synthetic product obtained by polymerizing a desired monomer, or a commercially available product. For example, EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL4513, EBECRYL4738, EBECRYL4740, EBECRYL8465, EBECRYL9260, EB ECRYL4666, EBECRYL8210, EBECRYL8606, EBECRYL1290, EBECRYL5129, EBECRYL8301R, KRM8200, EBECRYL210, EBECRYL220, etc. (Daicel Allnex), Miramer PU21 00, Examples include Miramer WS2600 and Miramer WS4000 (MIWON).
　ネオペンチルグリコールオリゴ（メタ）アクリレート、１，４－ブタンジオールオリゴ（メタ）アクリレート、１，６－ヘキサンジオールオリゴ（メタ）アクリレート、トリメチロールプロパンオリゴ（メタ）アクリレート、ペンタエリスリトールオリゴ（メタ）アクリレート、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、ロジン変性エポキシ（メタ）アクリレート、不飽和ポリエステル、ポリエーテル（メタ）アクリレート、未反応の不飽和基を備えたアクリル樹脂、不飽和ポリエーテル、不飽和ポリアミド、不飽和ポリウレタン、アクリル変性フェノール系樹脂、アクリル化アミン化合物オリゴマー等からなる群より選ばれる１種以上を用いることができる。 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, epoxy (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, rosin-modified epoxy (meth)acrylate, unsaturated polyester, polyether (meth)acrylate, unreacted unsaturated group One or more selected from the group consisting of acrylic resins, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, acrylic-modified phenolic resins, acrylated amine compound oligomers, etc. can be used.
（重合開始剤）
　本発明の組成物には重合開始剤を含有できる。その重合開始剤としては、例えば、以下の、アシルフォスフィンオキサイド系化合物、トリアジン系化合物、芳香族ケトン系化合物、芳香族オニウム塩系化合物、有機過酸化物、チオキサントン系化合物、チオフェニル系化合物、アントラセン系化合物、ヘキサアリールビスイミダゾール系化合物、ケトオキシムエステル系化合物、ボレート系化合物、アジニウム系化合物、メタロセン系化合物、活性エステル系化合物、ハロゲン化炭化水素系化合物及びアルキルアミン系化合物、ヨードニウム塩系化合物及びスルフォニウム塩系化合物等からなる群より選ばれる１種以上を用いることができる。
　但し、特に電子線照射により架橋・硬化を行うための本発明の組成物には、このような重合開始剤を含有させなくても良い。重合開始剤を含有しないほうが、印刷層の接着力を高くすることができる。また特に紫外線照射により架橋・硬化を行うには、このような重合開始剤を含有させることが必要であり、それによって、接着力を高くすることができる。 (Polymerization initiator)
The composition of the present invention can contain a polymerization initiator. Examples of the polymerization initiator include the following acylphosphine oxide compounds, triazine compounds, aromatic ketone compounds, aromatic onium salt compounds, organic peroxides, thioxanthone compounds, thiophenyl compounds, and anthracene compounds. -based compounds, hexaarylbisimidazole-based compounds, ketoxime ester-based compounds, borate-based compounds, azinium-based compounds, metallocene-based compounds, active ester-based compounds, halogenated hydrocarbon-based compounds and alkylamine-based compounds, iodonium salt-based compounds, and One or more types selected from the group consisting of sulfonium salt compounds and the like can be used.
However, it is not necessary to contain such a polymerization initiator, especially in the composition of the present invention for crosslinking and curing by electron beam irradiation. The adhesive strength of the printed layer can be increased by not containing a polymerization initiator. Furthermore, in order to perform crosslinking and curing particularly by irradiation with ultraviolet rays, it is necessary to include such a polymerization initiator, thereby increasing the adhesive strength.
　アシルフォスフィンオキサイド系化合物としては、例えば、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイドやビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等からなる群より選ばれる１種以上が挙げられる。 As the acylphosphine oxide type compound, for example, one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. There are more than one species.
　トリアジン系化合物としては、例えば、２，４，６－トリクロロ－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－トリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ピペニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－スチリル－ｓ－トリアジン、２－（ナフト－１－イル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシ－ナフト－１－イル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－トリクロロメチル－（ピペロニル）－６－トリアジン及び２，４－トリクロロメチル（４’－メトキシスチリル）－６－トリアジン等からなる群より選ばれる１種以上が挙げられる。 Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-pipenyl-4,6-bis(trichloromethyl)-s-triazine , 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy- naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine and 2,4-trichloromethyl(4'-methoxystyryl)- One or more types selected from the group consisting of 6-triazine and the like can be mentioned.
　更に、例えば、ベンゾフェノン、ジエチルチオキサントン、２－メチル－１－（４－メチルチオ）フェニル－２－モルフォリノプロパン－１－オン、４－ベンゾイル－４’－メチルジフェニルサルファイド、１－クロロ－４－プロポキシチオキサントン、イソプロピルチオキサントン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２，２－ジメチル－２－ヒドロキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２－ベンジル－２－ジメチルアミノ－１－（モルホリノフェニル）－ブタン－１－オン等からなる群より選ばれる１種以上が挙げられる。 Furthermore, for example, benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, 1-chloro-4-propoxy Thioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- Methyl-1-propan-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butane- One or more types selected from the group consisting of 1-one and the like can be mentioned.
＜その他の成分＞
　本発明の組成物は、以下の樹脂、有機溶剤、顔料及び染料、その他の添加剤等の成分を本発明による効果を毀損しない範囲において含有できる。その他に、表面調整剤、光安定化剤、表面処理剤、酸化防止剤、老化防止剤、架橋促進剤、可塑剤、紫外線吸収剤、防黴剤、防腐剤、消泡剤、保湿剤等を含有でき、又は含有させなくても良い。
　なお、シロキサン系化合物、ワックス、ふっ素含有化合物これらのその他の成分を含有させても良く、含有させないこともできる。 <Other ingredients>
The composition of the present invention may contain the following components such as resins, organic solvents, pigments and dyes, and other additives within a range that does not impair the effects of the present invention. In addition, surface conditioners, light stabilizers, surface treatment agents, antioxidants, anti-aging agents, crosslinking accelerators, plasticizers, ultraviolet absorbers, fungicides, preservatives, antifoaming agents, humectants, etc. It may be included or may not be included.
Note that other components such as a siloxane compound, wax, and fluorine-containing compound may or may not be included.
（樹脂）
　上記の樹脂としては、その他の二重結合等を有する重合性樹脂、及び、二重結合等を有しない非重合性樹脂から１種以上を採用できる。また含有しなくても良い。
　二重結合等を有する重合性樹脂はオリゴマーを含み、更に水酸基、カルボン酸基及びアミノ基から選ばれた１種以上の親水性基を有する樹脂が好ましい。更に重合性樹脂は（メタ）アクリロイル基等の二重結合等を有する重合性樹脂エチレン性不飽和基により得られた樹脂であることが好ましい。またウレタン基を有することが好ましい。 (resin)
As the above-mentioned resin, one or more types can be employed from polymerizable resins having other double bonds and non-polymerizable resins having no double bonds. Moreover, it does not need to be contained.
The polymerizable resin having double bonds and the like preferably includes an oligomer and further has one or more hydrophilic groups selected from hydroxyl groups, carboxylic acid groups, and amino groups. Further, the polymerizable resin is preferably a resin obtained from a polymerizable resin ethylenically unsaturated group having a double bond such as a (meth)acryloyl group. Moreover, it is preferable to have a urethane group.
　二重結合等を有する重合性樹脂及びオリゴマーとしては、公知又は市販のエチレン性不飽和結合を備えたポリマー又はオリゴマーを用いることができる。エチレン性不飽和結合を備えたポリマー又はオリゴマーとしては、（メタ）アクリロイル基やビニル基等からなる群より選ばれる１種以上のエチレン性不飽和結合を１つ以上有するものを用いることができる。例えば、ポリジアリルフタレート、ネオペンチルグリコールオリゴ（メタ）アクリレート、１，４一ブタンジオールオリゴ（メタ）アクリレート、１，６－ヘキサンジオールオリゴ（メタ）アクリレート、トリメチロールプロパンオリゴ（メタ）アクリレート、ペンタエリスリトールオリゴ（メタ）アクリレート、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ロジン変性エポキシ（メタ）アクリレート、不飽和ポリエステル、ポリエーテル（メタ）アクリレート、未反応の不飽和基を備えたアクリル樹脂、不飽和ポリエーテル、不飽和ポリアミド、不飽和ポリウレタン、アクリル変性フェノール系樹脂、アクリル化アミン化合物オリゴマー等からなる群より選ばれる１種以上を用いることができる。
　具体的には、例えば、共栄社化学社製の「ライトアクリレート」、「ライトエステル」、「エポキシエステル」、「ウレタンアクリレート」及び「高機能性オリゴマー」シリーズ、新中村化学社製の「ＮＫエステル」及び「ＮＫオリゴ」シリーズ、日立化成社製の「ファンクリル」シリーズ、東亞合成社製の「アロニックス」シリーズ、大八化学工業社製の「機能性モノマー」シリーズ、大阪有機化学工業社製の「特殊アクリルモノマー」シリーズ、三菱ケミカル社製の「アクリエステル」及び「ダイヤビームオリゴマー」シリーズ、日本化薬社製の「カヤラッド」及び「カヤマー」シリーズ、日本触媒社製の「（メタ）アクリル酸／メタクリル酸エステルモノマー」シリーズ、日本合成化学工業社製の「ＮＩＣＨＩＧＯ－ＵＶ紫光ウレタンアクリレートリゴマー」シリーズ、日本酢ビ・ポバール社製の「カルボン酸ビニルエステルモノマー」シリーズ、興人社製の「機能性モノマー」シリーズ、ダイセル・オルネクス社製の「ＥＢＥＣＲＹＬ」、「ＡＣＡ」、「ＫＲＭ」、「ＩＲＲ」、「ＲＤＸ」及び「ＯＴＡ」シリーズ、アルケマ社製の「ＣＮ」及び「ＳＲ」シリーズ、ＢＡＳＦ社製「Ｌａｒｏｍｅｒ」シリーズ、コグニス社製「フォトマー」シリーズ、根上工業社製「アートレジン」シリーズ、日油社製の「ブレンマー」シリーズ、第一工業製薬社製の「ニューフロンティア」シリーズ、ＭＩＷＯＮ社製の「Ｍｉｒａｍｅｒ」シリーズ、ＤＳＭ社製の「ＡｇｉＳｙｎ」シリーズ、荒川化学社製「ビームセット」シリーズの変性アクリルオリゴマーである２５５、２６１、２６５、２７１、サートマー社製「ＣＮ３７１」（分子内に２個の光重合性官能基及び２個のアミノ基を有するアクリル化アミン化合物のオリゴマー）、サートマー社製「ＣＮ７０４」（多官能ウレタンアクリレートオリゴマー）等からなる群より選ばれる１種以上を用いることができるが特に限定されない。 As the polymerizable resin and oligomer having double bonds and the like, known or commercially available polymers or oligomers having ethylenically unsaturated bonds can be used. As the polymer or oligomer having an ethylenically unsaturated bond, one having one or more ethylenically unsaturated bonds selected from the group consisting of (meth)acryloyl groups, vinyl groups, etc. can be used. For example, 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, epoxy(meth)acrylate, polyester(meth)acrylate, rosin-modified epoxy(meth)acrylate, unsaturated polyester, polyether(meth)acrylate, unreacted unsaturated group One or more selected from the group consisting of acrylic resins, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, acrylic-modified phenolic resins, acrylated amine compound oligomers, etc. can be used.
Specifically, for example, "Light Acrylate", "Light Ester", "Epoxy Ester", "Urethane Acrylate", and "Highly Functional Oligomer" series manufactured by Kyoeisha Chemical Co., Ltd., and "NK Ester" manufactured by Shin Nakamura Chemical Co., Ltd. and "NK Oligo" series, "Funkryl" series manufactured by Hitachi Chemical Co., Ltd., "Aronix" series manufactured by Toagosei Co., Ltd., "Functional Monomer" series manufactured by Daihachi Kagaku Kogyo Co., Ltd., "Osaka Organic Chemical Industry Co., Ltd.""Special Acrylic Monomer" series, Mitsubishi Chemical's "Acryester" and "Diabeam Oligomer" series, Nippon Kayaku's "Kayarad" and "Kayamar" series, Nippon Shokubai's "(meth)acrylic acid/ "Methacrylic Acid Ester Monomer" series, "NICHIGO-UV Purple Light Urethane Acrylate Trigomer" series manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., "Carboxylic Acid Vinyl Ester Monomer" series manufactured by Nippon Acetate & Poval Co., Ltd., and "Functional Monomer" series manufactured by Kojinsha Co., Ltd. "Monomer" series, "EBECRYL", "ACA", "KRM", "IRR", "RDX" and "OTA" series manufactured by Daicel Allnex, "CN" and "SR" series manufactured by Arkema, BASF “Laromer” series manufactured by Cognis, “Art Resin” series manufactured by Negami Kogyo, “Blenmar” series manufactured by NOF Corporation, “New Frontier” series manufactured by Daiichi Kogyo Seiyaku, manufactured by MIWON 'Miramer' series, DSM's 'AgiSyn' series, Arakawa Chemical's 'Beamset' series of modified acrylic oligomers 255, 261, 265, 271, Sartomer's 'CN371' (2 oligomers in the molecule). One or more types selected from the group consisting of acrylated amine compound oligomer having a photopolymerizable functional group and two amino groups), Sartomer's "CN704" (polyfunctional urethane acrylate oligomer), etc. can be used. is not particularly limited.
　二重結合等を有しない非重合性樹脂としては、アクリル系樹脂（アクリル酸、メタクリル酸等のカルボキシル基を有するエチレン性不飽和単量体と、これらのエチレン性不飽和単量体と共重合可能なスチレン、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、アリルアクリレート、アリルメタクリレート、ベンジルアクリレート、ベンジルメタクリレート、シクロヘキシルアクリレート、シクロヘキシルメタクリレート、グリセロールモノアクリレート、グリセロールメタクリレート、Ｎ－フェニルマレイミド、ポリスチレンマクロモノマー及びポリメチルメタクリレートマクロモノマーからなる群より選択される少なくとも１種のエチレン性不飽和単量体との共重合体）、ポリウレタン系樹脂（ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネートなどの脂肪族ジイソシアネート化合物；イソホロンジイソシアネート、水添キシリレンジイソシアネートなどの脂環族ジイソシアネート化合物；キシリレンジイソシアネート、α，α，α’，α’－テトラメチルキシリレンジイソシアネートなどの芳香脂肪族ジイソシアネート化合物；トルイレンジイソシアネート、ジフェニルメタンジイソシアネートなどの芳香族ジイソシアネート化合物等のジイソシアネート化合物と、ポリエステルジオール化合物、ポリエーテルジオール化合物、ポリカーボネート化合物、ポリブタジエングリコール化合物などの高分子ジオール等のジオール化合物を反応させて得られたウレタンプレポリマーに、さらに、鎖伸長剤および反応停止剤を反応させて得られる樹脂）、その他にポリエステル系樹脂、セルロース誘導体等の公知の樹脂を配合できる。
　但し、ロジン変性ポリエステル、アクリル樹脂、ジアリルフタレート樹脂を含有してもしなくても良い。 Examples of non-polymerizable resins without double bonds include acrylic resins (ethylenic unsaturated monomers with carboxyl groups such as acrylic acid and methacrylic acid, and copolymerized with these ethylenically unsaturated monomers). Possible styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer and Copolymers with at least one ethylenically unsaturated monomer selected from the group consisting of polymethyl methacrylate macromonomers), polyurethane resins (such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc.) Aliphatic diisocyanate compounds; alicyclic diisocyanate compounds such as isophorone diisocyanate and hydrogenated xylylene diisocyanate; aromatic aliphatic diisocyanate compounds such as xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate; toluylene diisocyanate; Urethane prepolymer obtained by reacting diisocyanate compounds such as aromatic diisocyanate compounds such as isocyanate and diphenylmethane diisocyanate with diol compounds such as polymeric diols such as polyester diol compounds, polyether diol compounds, polycarbonate compounds, and polybutadiene glycol compounds. In addition, known resins such as polyester resins and cellulose derivatives can be blended.
However, it may or may not contain rosin-modified polyester, acrylic resin, or diallyl phthalate resin.
（有機溶剤）
　含有させても良い有機溶剤としては、例えば、モノアルコール類、多価アルコール類、多価アルコールの低級アルキルエーテル類、ケトン類、エーテル類、エステル類、窒素含有化合物類等を挙げることができる。これらは単独で用いてもよく、２種以上を併用してもよい。
　上記モノアルコール類としては、ｎ－プロパノール、ｎ－ブタノール、イソブタノール、ｎ－ペンタノール、ｎ－ヘキサノール、ｎ－ヘプタノール、ｎ－オクタノール、ｎ－ノニルアルコール、ｎ－デカノール、又はこれらの異性体、シクロペンタノール、シクロヘキサノール等が挙げられ、好ましくはアルキル基の炭素数が１～６のアルコールを使用できる。
　上記多価アルコール類としては、エチレングリコール、プロピレングリコール、１，３－ブチレングリコール、１，４－ブチレングリコール、１，２－ペンタンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、１，２－ヘキサンジオール、１，６－ヘキサンジオール、１，２－シクロヘキサンジオール、ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、グリセリン、ペンタエリスリトール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、チオジグリコール等を使用できる。
　上記多価アルコールの低級アルキルエーテル類としては、エチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコール－ｎ－プロピルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノ－ｎ－プロピルエーテル、ジプロピレングリコールモノ－ｎ－ブチルエーテル等を使用できる。
　上記ケトン類の具体例としては、メチルブチルケトン、メチルイソブチルケトン、ジイソプロピルケトン、シクロペンタノン、シクロヘキサノン等が挙げられる。
　上記エーテル類の具体例としては、イソプロピルエーテル、ｎ－ブチルエーテル、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン等である。
　上記エステル類としては、プロピレンカルボネート、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸アミル、乳酸エチル、酪酸エチル、ジブチルフタレート、ジオクチルフタレート、及び、ε－カプロラクトン、ε－カプロラクタム等の環状エステル等がある。
　上記有機溶剤の含有量としては、極力少なくすることが好ましく、配合しないことがより好ましい。水を含まないことが望ましい。本発明の組成物の含水率は０．０１～５．００質量％であってもよい。 (Organic solvent)
Examples of organic solvents that may be included include monoalcohols, polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, ketones, ethers, esters, and nitrogen-containing compounds. These may be used alone or in combination of two or more.
The monoalcohols include n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, or isomers thereof; Examples include cyclopentanol and cyclohexanol, and preferably alcohols having an alkyl group of 1 to 6 carbon atoms can be used.
Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,2- Hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol, diethylene glycol, dipropylene Glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, etc. can be used.
The lower alkyl ethers of the polyhydric alcohols mentioned above include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol Isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n-propyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -n-butyl ether etc. can be used.
Specific examples of the ketones include methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
Specific examples of the above ethers include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane.
The above esters include propylene carbonate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethyl butyrate, dibutyl phthalate, dioctyl phthalate, and cyclic esters such as ε-caprolactone and ε-caprolactam. etc.
The content of the organic solvent is preferably as low as possible, and more preferably not included. Preferably, it does not contain water. The moisture content of the composition of the invention may be 0.01 to 5.00% by weight.
（顔料及び染料）
　本発明の組成物には、その用途からみて、積極的な着色のために着色材として顔料や染料を配合することができる。但し積極的な着色又は着色以外の目的で顔料や染料を含有させる際には、以下の顔料から１種以上を任意の含有量で含有させることができる。また積極的な着色を必要としない場合には顔料及び染料の含有量を減少させたり、含有させなくてもよい。これらの場合には本発明の組成物はいわゆるクリアインキ組成物としても機能する。
　このような顔料及び染料としては、公知の有機顔料や無機顔料を特に制限なく使用できる。　
　そして有機顔料としては、例えば、染料レーキ顔料、アゾ系、ベンズイミダゾロン系、フタロシアニン系、キナクリドン系、アントラキノン系、ジオキサジン系、インジゴ系、チオインジコ系、ペリレン系、ペリノン系、ジケトピロロピロール系、イソインドリノン系、ニトロ系、ニトロソ系、アンスラキノン系、フラバンスロン系、キノフタロン系、ピランスロン系、インダンスロン系の顔料等が挙げられる。無機顔料としては、カーボンブラック、酸化チタン、ベンガラ、黒鉛、鉄黒、酸化クロムグリーン、酸化アルミニウム、水酸化アルミニウム等が挙げられる。
　なお、上記顔料と共に公知の顔料分散剤を含有していてもよい。 (pigments and dyes)
In view of its intended use, the composition of the present invention may contain pigments and dyes as colorants for active coloring. However, when containing pigments or dyes for purposes other than active coloring or coloring, one or more of the following pigments can be contained in any desired amount. Furthermore, if active coloring is not required, the content of pigments and dyes may be reduced or may not be included. In these cases, the composition of the present invention also functions as a so-called clear ink composition.
As such pigments and dyes, known organic pigments and inorganic pigments can be used without particular limitation.
Examples of organic 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, Examples include isoindolinone-based, nitro-based, nitroso-based, anthraquinone-based, flavanthrone-based, quinophthalone-based, pyranthrone-based, and indanthrone-based pigments. Examples of inorganic pigments include carbon black, titanium oxide, red iron oxide, graphite, iron black, chromium oxide green, aluminum oxide, aluminum hydroxide, and the like.
In addition, a known pigment dispersant may be contained together with the above pigment.
＜積層体及び積層体の製造方法＞
　本発明における積層体は、以下の４通りの構造の積層体を包含する。それぞれの構造において、任意の印刷層とは、公知の印刷用インキ組成物を任意の印刷方法により形成してなる印刷層である。なお、裏刷り用活性エネルギー線硬化型インキ組成物をドライオンウェットで印刷するとは、先に印刷した裏刷り用活性エネルギー線硬化型インキ組成物を硬化した後に、その上の層に裏刷り用活性エネルギー線硬化型インキ組成物で印刷することをいう。
　裏刷り用活性エネルギー線硬化型インキ組成物をウェットオンウェットで印刷するとは、先に印刷した裏刷り用活性エネルギー線硬化型インキ組成物を硬化せず、又は半硬化にとどめた状態で、その上の層に裏刷り用活性エネルギー線硬化型インキ組成物で印刷することをいう。 <Laminated body and method for manufacturing the laminate>
The laminate in the present invention includes laminates having the following four structures. In each structure, the arbitrary printing layer is a printing layer formed by forming a known printing ink composition by an arbitrary printing method. Note that printing an active energy ray-curable ink composition for back printing with dry-on wet means that after the previously printed active energy ray curable ink composition for back printing is cured, the layer above it is printed with the active energy ray curable ink composition for back printing. This refers to printing with an active energy ray-curable ink composition.
Wet-on-wet printing of an active energy ray-curable ink composition for back printing means that the previously printed active energy ray curable ink composition for back printing is not cured or remains only semi-cured. This refers to printing on the upper layer with an active energy ray-curable ink composition for back printing.
　１．被印刷物である原反の片面に任意の印刷層を有し、その印刷層の上に形成された裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層、及びその該裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層上にラミネート層を形成してなる構造の積層体。
　２．被印刷物である原反の片面に任意の印刷層及び／又は裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層を有し、その印刷層を有する面ではない側の原反の面の上に形成された本発明の裏刷り用活性エネルギー線硬化型インキ組成物からなる１層以上の印刷層、及びその該裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層上にラミネート層を形成してなる構造の積層体。
　３．被印刷物である原反の片面に任意の印刷層及び／又は裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層を有し、原反の他面に任意の印刷層を有し、その原反の他面に有する任意の印刷層の上に裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層を有し、及びその該裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層上にラミネート層を形成してなる構造の積層体。
　４．被印刷物である原反の片面に任意の印刷層を有さず、原反の上に形成された裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層、及びその該裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層上にラミネート層を形成してなる構造の積層体。 1. A printing layer having an arbitrary printing layer on one side of a raw material that is a printing material, and a printing layer formed on the printing layer consisting of an active energy ray-curable ink composition for back printing, and the active energy for back printing. A laminate having a structure in which a laminate layer is formed on a printing layer made of a line-curable ink composition.
2. Having an optional printing layer and/or a printing layer made of an active energy ray-curable ink composition for back printing on one side of the original fabric that is the printing target, and the side of the original fabric that does not have the printing layer. one or more printed layers made of the active energy ray-curable ink composition for back printing of the present invention formed thereon, and a laminate layer on the printed layer made of the active energy ray-curable ink composition for back printing of the present invention. A laminate with a structure formed by forming.
3. It has an arbitrary printing layer and/or a printing layer made of an active energy ray-curable ink composition for back printing on one side of the original fabric that is the printing target, and an arbitrary printing layer on the other side of the original fabric, and A printing layer comprising an active energy ray-curable ink composition for back printing on any printing layer on the other side of the original fabric, and printing comprising the active energy ray curable ink composition for back printing. A laminate with a structure in which a laminate layer is formed on top of the other.
4. A printing layer consisting of an active energy ray-curable ink composition for back printing formed on one side of the original fabric, which is the printing target, without any printing layer, and the active energy for the back printing. A laminate having a structure in which a laminate layer is formed on a printing layer made of a line-curable ink composition.
　１の場合は、典型的な裏刷り印刷による積層体であり、２及び３の場合は、表刷り印刷と裏刷り印刷が複合した裏刷り印刷による積層体ともいえる。また４の場合には、なお、被印刷物の両面に予め印刷層が形成されていても良い。
　そしていずれの場合においても、各任意の印刷層は１層又は２層以上からなり、２層以上の場合には、顔料及び染料を含めて互いに同じ組成でも良く、あるいは異なっていてもよく、インライン又はオフライン（ドライオンウェット又はウェットオンウェット）で形成される。裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層も１層又は２層以上からなる層からなり、顔料及び染料を含めて互いに同じ組成でも良く、あるいは異なっていてもよく、インライン又はオフライン（ドライオンウェット又はウェットオンウェット）で形成される。
　さらに、印刷層や裏刷り用活性エネルギー線硬化型インキ組成物以外の層である、被印刷物である原反や、ラミネート層、あるいは積層体の内部に設けられてもよい層は、互いに異なる材料からなっても良く、同じ材料からなっても良い。少なくも一方の層が硬化に必要な活性エネルギー線を透過できれば良い。本発明の裏刷り用活性エネルギー線硬化型インキ組成物層により、それの層を挟む２つのシート状物を積層したものである。原反や、ラミネート層、あるいは積層体の内部に設けられてもよい層の材料としては合成紙、樹脂、アート紙、コート紙、キャスト紙、更紙、樹脂ラミネート紙、金属蒸着紙、金属酸化物蒸着紙等の紙及び金属等から選択できる。そしてこれらの被印刷物及びシート状物は、予め公知の表面処理や化学的処理、印刷、塗装、蒸着等がなされていても良く、なされていなくても良い。この中で、印刷や塗装が活性エネルギー線硬化型のインキ組成物や塗料組成物からなるときには、一方の被接着物の片面の少なくとも１部に印刷又は塗装をし、活性エネルギー線を照射せず、又は硬化が不完全な状態となる程度の活性エネルギー線照射に留めた後に、片面上に本発明の裏刷り用活性エネルギー線硬化型インキ組成物を印刷して他方のシート状物を重ねて、その後に活性エネルギー線を照射して硬化を完了しても良い。また該印刷又は塗装を行って得た層に対して、電子線やＵＶを照射する等して完全に硬化した後に、片面上に本発明の裏刷り用活性エネルギー線硬化型インキ組成物を印刷してさらにシート状物を重ねて、その後に活性エネルギー線を照射して硬化を完了しても良い。
　硬化可能な電子線の照射量としては１０ｋＧｙ以上が好ましく、１００ｋＧｙ以上がより好ましい。また５００ｋＧｙ以下が好ましく、３００ｋＧｙ以下がより好ましい。また、組成物が重合開始剤を含有するとき、紫外線の照射量としては、４００ｍＪ／ｃｍ２以上が好ましい。 Case 1 is a typical laminate produced by back printing, and cases 2 and 3 can also be said to be laminates produced by back printing, which is a combination of front printing and back printing. In the case of 4, printing layers may be formed in advance on both sides of the printing material.
In any case, each arbitrary printing layer consists of one layer or two or more layers, and in the case of two or more layers, the composition including pigments and dyes may be the same or different from each other, and in-line or formed offline (dry-on-wet or wet-on-wet). The printing layer made of the active energy ray-curable ink composition for back printing also consists of one layer or two or more layers, and may have the same composition or different compositions including pigments and dyes, and can be used in-line or off-line. (dry-on-wet or wet-on-wet).
Furthermore, layers other than the printing layer and the active energy ray-curable ink composition for back printing, which may be provided inside the original fabric that is the printing material, the laminate layer, or the laminate, are made of different materials. It may be made of the same material. It is sufficient that at least one layer can transmit the active energy rays necessary for curing. The active energy ray-curable ink composition layer for back printing of the present invention is formed by laminating two sheet-like materials sandwiching the layer. Materials for the original fabric, the laminate layer, or the layers that may be provided inside the laminate include synthetic paper, resin, art paper, coated paper, cast paper, recycled paper, resin-laminated paper, metal-deposited paper, and metal oxide. You can choose from paper such as metal-deposited paper, metal, etc. These printing materials and sheet-like materials may or may not be subjected to known surface treatments, chemical treatments, printing, painting, vapor deposition, etc. in advance. In this case, when printing or painting consists of an active energy ray-curable ink composition or coating composition, printing or painting is performed on at least one side of one side of the adherend without irradiation with active energy rays. , or after irradiation with active energy rays is limited to an extent that curing is incomplete, print the active energy ray-curable ink composition for reverse printing of the present invention on one side and overlap the other sheet-like material. Then, curing may be completed by irradiating active energy rays. Further, after the layer obtained by printing or painting is completely cured by irradiation with electron beams or UV, the active energy ray-curable ink composition for back printing of the present invention is printed on one side. Then, the sheet-like materials may be further stacked, and then active energy rays may be irradiated to complete curing.
The irradiation amount of the electron beam capable of curing is preferably 10 kGy or more, more preferably 100 kGy or more. Moreover, 500 kGy or less is preferable, and 300 kGy or less is more preferable. Further, when the composition contains a polymerization initiator, the amount of ultraviolet ray irradiation is preferably 400 mJ/cm 2 or more.
　また積層体の形状は、シート状や塊状等であり、少なくとも被印刷物及びシート状物のいずれかが硬化に必要な活性エネルギー線を透過できる程度の形状であれば良い。
　このような積層体を構成する被印刷物及びシート状物の材料のうち、樹脂からなるものとしては、被接着物用として公知の変性又は未変性の樹脂でよい。このような樹脂として延伸又は無延伸のものを使用でき、それらの樹脂としては、ポリオレフィン樹脂（ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体等）、ポリエステル樹脂（ポリエチレンテレフタレート、ポリブチレンテレフタレート等）、ポリアミド樹脂（ナイロン６、ナイロン６６、ナイロン１１、ナイロン１２等）、ポリ塩化ビニル、ポリ酢酸ビニル、ポリビニルアルコール、ポリスチレン、ＡＢＳ樹脂（アクリロニトリル－ブタジエン－スチレン共重合体）、ポリカーボネート、ポリアミドイミド、ポリイミド、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ウレタン樹脂等の公知の樹脂や、これらの樹脂と上記の紙との積層体、これらの樹脂フィルムと金属や金属酸化物の積層体が挙げられる。
　本発明における積層体の製造方法としては、被印刷物の表面に本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段（グラビア印刷、フレキソ印刷、インクジェット印刷等）により印刷して印刷層を形成する。
　このとき、被印刷物への本発明の裏刷り用活性エネルギー線硬化型インキ組成物の塗布量としては、優れた接着強度を得るために、印刷部において、固形分の塗布量として１．５０ｇ／ｍ２以上が好ましく、１．８０ｇ／ｍ２以上がより好ましく、２．００ｇ／ｍ２以上が更に好ましい。
　次いで、この印刷層の上に、別のシート状物を重ねて、被印刷物及びシート状物のいずれか一方の側から必要な活性エネルギー線を照射して、本発明の積層体を得ることができる。そして、電子線を照射した後にいわゆるエージングとして、一定時間、一定の温度に加温する工程を必要としない。また、活性エネルギー線として紫外線を照射する際には、エージングとして、一定時間、一定の温度に加温等する工程を設けても良い。 The shape of the laminate may be sheet-like, block-like, or the like, as long as at least either the printing material or the sheet-like material can transmit the active energy rays necessary for curing.
Among the materials for the printing material and the sheet-like material constituting such a laminate, those made of resin may be modified or unmodified resins known for use in materials to be adhered. Stretched or unstretched resins can be used as such resins, and these resins include polyolefin resins (polyethylene, polypropylene, ethylene-propylene copolymers, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide resins, etc. Resin (nylon 6, nylon 66, nylon 11, nylon 12, etc.), polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), polycarbonate, polyamideimide, polyimide, epoxy Examples include well-known resins such as resins, phenol resins, melamine resins, and urethane resins, laminates of these resins and the above-mentioned papers, and laminates of these resin films and metals or metal oxides.
The method for producing a laminate in the present invention includes printing the active energy ray-curable ink composition for back printing of the present invention on the surface of a printing material by a known printing means (gravure printing, flexographic printing, inkjet printing, etc.). Form a printing layer.
At this time, in order to obtain excellent adhesive strength, the coating amount of the active energy ray-curable ink composition for back printing of the present invention on the printing substrate is 1.50 g/solid content in the printing section. m 2 or more is preferable, 1.80 g/m 2 or more is more preferable, and even more preferably 2.00 g/m 2 or more.
Next, another sheet-like material is stacked on top of this printing layer, and necessary active energy rays are irradiated from either side of the printing material or the sheet-like material to obtain the laminate of the present invention. can. Furthermore, there is no need for a step of heating to a constant temperature for a certain period of time as so-called aging after electron beam irradiation. Further, when irradiating ultraviolet rays as active energy rays, a step of heating to a constant temperature for a certain period of time may be provided as aging.
　樹脂以外のものとして、上記の紙や金属を被印刷物として選択してもよく、その場合には、上記のシート状物との間で接着させることが、活性エネルギー線による硬化を行なう上で好ましい。紙の場合には塗工紙及び被塗工紙のいずれでも良く、既に印刷層や金属層を形成した紙、あるいは樹脂フィルムを積層させてなる紙等、特に限定されない。金属の場合には、フィルム状のアルミニウム、亜鉛、銅、鉄、スズ等特に限定されない。
　本発明の積層体の用途としては、樹脂層を有するシート状としての公知の用途と共通し、２つの樹脂シート等の層の間に印刷層を有する裏刷り印刷物や、２つの樹脂シート等の層の積層物の外面に印刷層を有する表刷り印刷物等が挙げられる。 In addition to resin, the above-mentioned paper or metal may be selected as the printing material, and in that case, it is preferable to bond it with the above-mentioned sheet-like material in order to cure it with active energy rays. . In the case of paper, it may be either coated paper or coated paper, and is not particularly limited, such as paper on which a printing layer or metal layer has already been formed, or paper on which a resin film is laminated. In the case of metal, film-form aluminum, zinc, copper, iron, tin, etc. are not particularly limited.
The laminate of the present invention can be used in the same manner as the known use as a sheet having a resin layer, such as a back-printed printed matter having a printing layer between two resin sheets, etc. Examples include surface-printed printed matter having a printed layer on the outer surface of a laminate of layers.
　裏刷り印刷物としては、被印刷物である原反として、例えばポリエチレンテレフタレート等のフィルムの片面に、本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段で、２層以上をウェットオンウェットで印刷し、得られた印刷層を含む表面に、形成した印刷層上に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層し、次いでいずれかの面から活性エネルギー線を照射して得ることができる。このとき、１層目の印刷を白色インキ組成物で行い、２層目以上を白色以外の色インキ組成物にて行なうことができる。なお、それぞれの本発明の裏刷り用活性エネルギー線硬化型インキ組成物は、顔料や染料以外について、互いに同じ組成でも良く、異なる組成でも良い。ここで、２層以上をウェットオンウェットで印刷したが、最上層以外の層は印刷後すぐに活性エネルギー線により硬化して、ドライオンウェットで印刷してもよい。
　上記１の構造の積層体を得る方法として、被印刷物である原反として、例えばポリエチレンテレフタレート等のフィルムの片面に、公知のインキ組成物（グラビアインキ組成物、水性フレキソインキ組成物、ＥＢオフセットインキ組成物、ＥＢフレキソインキ組成物、水なしＥＢオフセットインキ組成物、インクジェットインキ組成物等）を印刷し乾燥や硬化を行なう。その後、この裏刷り用活性エネルギー線硬化型インキ組成物の印刷層の上に本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段で印刷をする。その後、シーラントフィルム等の樹脂フィルム等を本発明の裏刷り用活性エネルギー線硬化型インキ組成物による印刷層上にラミネートし、いずれかの面から活性エネルギー線を照射して得ることができる。このとき、本発明の裏刷り用活性エネルギー線硬化型インキ組成物からなる層のいずれかを白色インキ組成物とすることが好ましいが、公知のインキ組成物を白色インキ組成物にしても良い。 For back-printing printed matter, two or more layers of the active energy ray-curable ink composition for back-printing of the present invention are wetted onto one side of a film such as polyethylene terephthalate as a raw material to be printed using a known printing means. On-wet printing, laminating a film such as low density polyethylene (LLDPE) on the formed printed layer on the surface containing the obtained printed layer, and then irradiating active energy rays from either side. I can do it. At this time, the first layer can be printed with a white ink composition, and the second and higher layers can be printed with an ink composition of a color other than white. The active energy ray-curable ink compositions for back printing of the present invention may have the same composition or different compositions except for pigments and dyes. Here, two or more layers were printed by wet-on-wet, but layers other than the top layer may be cured by active energy rays immediately after printing and printed by dry-on-wet.
As a method for obtaining a laminate having the structure described in 1 above, a known ink composition (gravure ink composition, water-based flexo ink composition, EB offset ink composition, etc. composition, EB flexo ink composition, waterless EB offset ink composition, inkjet ink composition, etc.) is printed and dried and cured. Thereafter, the active energy ray curable ink composition for back printing of the present invention is printed on the printing layer of this active energy ray curable ink composition for back printing using a known printing means. Thereafter, a resin film such as a sealant film or the like is laminated on the printing layer made of the active energy ray-curable ink composition for back printing of the present invention, and active energy rays are irradiated from either side. At this time, it is preferable that one of the layers made of the active energy ray-curable ink composition for back printing of the present invention is a white ink composition, but a known ink composition may be used as the white ink composition.
　上記２の構造の積層体を得る方法として、被印刷物である原反として、例えばポリエチレンテレフタレート等のフィルムの片面に、本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段で、１層以上の印刷層となるようにドライオンウェット又はウェットオンウェット等で印刷し、得られた印刷層を含む表面に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層する。次いでいずれかの面から活性エネルギー線を照射して積層体を得ておき、その積層体のいずれかの表面に、公知のインキ組成物及び／又は本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段で一層以上印刷し、乾燥及び／又は硬化することができる。この方法は裏刷り印刷と表刷り印刷を組み合わせた方法ともいえる。
　上記２の構造の積層体を得る別の方法として、被印刷物である原反として、例えば、ポリエチレンテレフタレート等のフィルムの片面に、公知のインキ組成物及び／又は裏刷り用活性エネルギー線硬化型インキ組成物を任意の手段で印刷し、得られた印刷層を乾燥又は硬化した後、形成した印刷層を有するポリエチレンテレフタレート等のフィルムの印刷層が形成されていない他面に、本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段で一層以上印刷し、その裏刷り用活性エネルギー線硬化型インキ組成物層上に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層し、次いで活性エネルギー線を照射して得ることができる。 As a method for obtaining a laminate having the structure described in 2 above, the active energy ray-curable ink composition for back printing of the present invention is applied to one side of a film such as polyethylene terephthalate as a printing material by a known printing method. , one or more printed layers are printed by dry-on-wet or wet-on-wet, and a film such as low-density polyethylene (LLDPE) is laminated on the surface including the obtained printed layer. Next, active energy rays are irradiated from either side to obtain a laminate, and either surface of the laminate is coated with a known ink composition and/or the active energy ray-curable ink for back printing of the present invention. The composition can be printed in one or more layers by known printing means and dried and/or cured. This method can be said to be a combination of back printing and front printing.
Another method for obtaining a laminate having the structure described in 2 above is to apply a known ink composition and/or an active energy ray-curable ink for back printing on one side of a film such as polyethylene terephthalate as a raw material to be printed. After printing the composition by any means and drying or curing the obtained printed layer, the back printing of the present invention is applied to the other side of the film such as polyethylene terephthalate having the formed printed layer on which the printed layer is not formed. One or more layers of an active energy ray-curable ink composition for printing are printed using a known printing means, a film such as low density polyethylene (LLDPE) is laminated on the layer of the active energy ray-curable ink composition for back printing, and then a film such as low density polyethylene (LLDPE) is It can be obtained by irradiating energy rays.
　上記３の構造の積層体を得る方法として、被印刷物である原反として、例えばポリエチレンテレフタレート等のフィルムの片面に、公知のインキ組成物を公知の印刷手段で１層以上印刷してこの印刷層を乾燥及び／又は硬化する。得られた印刷層上に、本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段で、１層以上の印刷層となるようにドライオンウェット又はウェットオンウェット等で印刷し、得られた印刷層を含む表面に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層する。次いでいずれかの面から活性エネルギー線を照射して積層体を得ておき、その積層体の上記のポリエチレンテレフタレート等のフィルムの表面に、公知のインキ組成物及び／又は裏刷り用活性エネルギー線硬化型インキ組成物を任意の手段で印刷し、この印刷層を乾燥及び／又は硬化して、積層体を得ることができる。
　上記３の構造の積層体を得る別の方法として、被印刷物である原反として、例えば、ポリエチレンテレフタレート等のフィルムの片面に、公知のインキ組成物及び／又は裏刷り用活性エネルギー線硬化型インキ組成物を任意の手段で印刷し、この印刷層を乾燥及び／又は硬化する工程と、ポリエチレンテレフタレート等のフィルムの他面に、公知のインキ組成物を任意の手段で１層以上印刷してこの印刷層を乾燥及び／又は硬化する工程を、任意の順に行なう。その後他面側の印刷層の上に、本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段で一層以上印刷し、その裏刷り用活性エネルギー線硬化型インキ組成物層上に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層し、次いで活性エネルギー線を照射して得ることができる。 As a method for obtaining a laminate having the structure described in 3 above, one or more layers of a known ink composition are printed on one side of a film such as polyethylene terephthalate as a raw material to be printed using a known printing means. dry and/or harden. On the obtained printing layer, the active energy ray-curable ink composition for back printing of the present invention is printed using a known printing method, such as dry-on wet or wet-on-wet, so as to form one or more printed layers. , A film such as low density polyethylene (LLDPE) is laminated on the surface including the obtained printed layer. Next, active energy rays are irradiated from either side to obtain a laminate, and a known ink composition and/or active energy ray curing for back printing is applied to the surface of the above-mentioned polyethylene terephthalate film of the laminate. A laminate can be obtained by printing the mold ink composition by any means and drying and/or curing the printed layer.
Another method for obtaining a laminate having the structure described in 3 above is to apply a known ink composition and/or an active energy ray-curable ink for back printing on one side of a film such as polyethylene terephthalate as a raw material to be printed. A step of printing the composition by any means and drying and/or curing this printed layer, and printing one or more layers of a known ink composition on the other side of the film such as polyethylene terephthalate by any means. The steps of drying and/or curing the printed layer may be performed in any order. Thereafter, on the printing layer on the other side, one or more layers of the active energy ray-curable ink composition for back printing of the present invention are printed by a known printing means, and then on the active energy ray curable ink composition layer for back printing. It can be obtained by laminating a film such as low-density polyethylene (LLDPE) on the substrate and then irradiating it with active energy rays.
　上記４の構造の積層体を得る方法として、被印刷物である原反として、例えばポリエチレンテレフタレート等のフィルムの片面に、本発明の裏刷り用活性エネルギー線硬化型インキ組成物を公知の印刷手段で、１層以上の印刷層となるようにドライオンウェット又はウェットオンウェット等で印刷し、得られた印刷層を含む表面に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層する。次いで、いずれかの面から活性エネルギー線を照射して得ることができる。このとき、本発明の裏刷り用活性エネルギー線硬化型インキ組成物からなる層のいずれかを白色インキ組成物とすることが好ましい。 As a method for obtaining a laminate having the structure described in 4 above, the active energy ray-curable ink composition for back printing of the present invention is applied to one side of a film such as polyethylene terephthalate as a printing material by known printing means. , one or more printed layers are printed by dry-on-wet or wet-on-wet, and a film such as low-density polyethylene (LLDPE) is laminated on the surface including the obtained printed layer. Next, it can be obtained by irradiating active energy rays from either side. At this time, it is preferable that one of the layers made of the active energy ray-curable ink composition for back printing of the present invention is a white ink composition.
　なお、それぞれの方法において、紙や金属を積層させる際には、例えば、上記裏刷り印刷や表刷り印刷において、ポリエチレンテレフタレート等フィルムと低密度ポリエチレン等のフィルムの間にある裏刷り用活性エネルギー線硬化型インキ組成物の印刷層に代えて、裏刷り用活性エネルギー線硬化型インキ組成物の印刷層が両面に形成された紙や金属層を採用できる。この場合には、積層体の両面のそれぞれから活性エネルギー線を照射することになる。
　これらの裏刷り印刷により、本発明の裏刷り用活性エネルギー線硬化型インキ組成物によるラミネートと印刷を同時に行なうことができる。 In addition, in each method, when laminating paper or metal, for example, in the above-mentioned back printing or front printing, active energy rays for back printing between a film such as polyethylene terephthalate and a film such as low density polyethylene are used. Instead of the printed layer of the curable ink composition, a paper or metal layer having printed layers of the active energy ray-curable ink composition for back printing formed on both sides can be used. In this case, active energy rays are irradiated from both surfaces of the laminate.
By these back printing operations, lamination and printing using the active energy ray-curable ink composition for back printing of the present invention can be performed simultaneously.
＜積層体の用途＞
　本発明の積層体は包装用途に使用できる。この場合には、積層体の最外面の２つの熱可塑性樹脂層の任意の縁同士を密着させた状態で加熱溶着したり、積層体の最外面の２つの熱可塑性樹脂層の任意の縁同士を接着剤等により接着させたりして包装用袋等にすることができる。また１枚の積層体を二つ折りにして、対向する面の縁同士を上記のようにして加熱溶着したり、接着したりして包装用袋等にすることができる。 <Applications of laminate>
The laminate of the present invention can be used for packaging purposes. In this case, any edges of the two outermost thermoplastic resin layers of the laminate may be heat-welded in close contact with each other, or any edges of the two outermost thermoplastic resin layers of the laminate may be bonded together. It can be made into a packaging bag or the like by bonding it with an adhesive or the like. Furthermore, a single laminate can be folded in half and the edges of opposing surfaces can be heat-welded or adhered as described above to make a packaging bag or the like.
　以下に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味するものである。また、表中の各材料の分量の数字についても「質量部」である。
　下記表１に記載の組成になるように、各実施例及び各比較例の裏刷り用活性エネルギー線硬化型インキ組成物を調製し、その硬化について示した。なお、裏刷り用活性エネルギー線硬化型インキ組成物の調製に使用した容器等の器具等を下記のアルカリ水で洗浄した。実施例１及び２の裏刷り用活性エネルギー線硬化型インキ組成物の調製に使用した器具を、溶解させて効率よく、かつ揮発性有機溶媒を使用せずに、好ましい環境にて洗浄できた。比較例に使用した器具に関しては、下記のアルカリ水により洗浄できず、揮発性有機溶媒を使用して洗浄した。 EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass." In addition, the numbers for the quantities of each material in the table are also "parts by mass."
Active energy ray-curable ink compositions for back printing of each Example and each Comparative Example were prepared so as to have the compositions shown in Table 1 below, and their curing was shown. Note that the containers and other equipment used for preparing the active energy ray-curable ink composition for back printing were washed with the following alkaline water. The equipment used to prepare the active energy ray-curable ink compositions for back printing in Examples 1 and 2 was able to be dissolved and cleaned efficiently and in a favorable environment without using volatile organic solvents. Regarding the instruments used in the comparative example, they could not be cleaned with the alkaline water described below, but were cleaned using a volatile organic solvent.
　ＰＥＴＡ　：　ペンタエリスリトールトリアクリレート(ＨＬＢ１０．９、分子量２９８．２９、水酸基価１８８ｍｇＫＯＨ／ｇ)
　ＴＭＰＧ　：　トリメチロールプロパンジアクリレート（ＨＬＢ８．９、分子量２４２、水酸基価２３２ｍｇＫＯＨ／ｇ）
　ＧＧＡ　：　グリセリンジアクリレート（ＨＬＢ１０．４、分子量２００、水酸基価２８１ｍｇＫＯＨ／ｇ）
　１５ＥＯ－ＴＭＰＧ　：　エチレンオキサイド（１５）変性トリメチロールプロパンジアクリレート（ＨＬＢ１３．９、分子量９０２、水酸基価６２ｍｇＫＯＨ／ｇ）
　ＤＰＴＡ　：　ジペンタエリスリトールトリアクリレート（ＨＬＢ１３．６、分子量４１６、水酸基価１３５ｍｇＫＯＨ／ｇ）
　Ｘ－１　：　スチレンアクリル樹脂、重量平均分子量１８，０００、酸価１１０（星光ＰＭＣ社）
　ＹＳ－１２７４　：　スチレンアクリル樹脂、重量平均分子量１９，０００、酸価２００（星光ＰＭＣ社）
　Ｍｉｒａｍｅｒ　ＰＵ２１００　：　２官能ウレタンアクリレート、分子量１，４００（ＭＩＷＯＮ社）
　Ｍｉｒａｍｅｒ　ＰＥ２１０　：　２官能ビスフェノールＡエポキシジアクリレート、分子量５２０（ＭＩＷＯＮ社）
　Ｍｉｒａｍｅｒ　ＰＳ４２０　：　４官能ポリエステルアクリレート、重量平均分子量３，０００（ＭＩＷＯＮ社）
　ＴＭＰＴＡ　：　トリメチロールプロパントリアクリレート(分子量２９６．３２) 
　６ＥＯ－ＴＭＰＴＡ：６モルエチレンオキサイド変性トリメチロールプロパントリアクリレート（ＨＬＢ１０．４８、分子量５６０）
　１５ＥＯ－ＴＭＰＴＡ：１５モルエチレンオキサイド変性トリメチロールプロパントリアクリレート（ＨＬＢ１３．４５、分子量９５６）
　ＧＰＴＡ　：　３モルＰＯ変性グリセリントリアクリレート（ＨＬＢ９．４８、分子量４２８）
　ＤＩ－ＴＭＰＴＡ　：　ジトリメチロールプロパンテトラアクリレート（ＨＬＢ８．４、分子量４６６）
（重合禁止剤）
　ＢＨＴ　：　２，６―ジ－ｔｅｒｔ―ブチル―ｐ－クレゾール
（光重合開始剤）
　Ｉｒｕｇａｃｕｒｅ１８４　：１－ヒドロキシシクロヘキシル－フェニルケトン
（顔料）
　酸化チタン：ＣＲ－９０（石原産業社）
　カーボンブラック：ＭＡ－７０（ＣＡＢＯＴ社）
　炭酸カルシウム：Ｔ－ＤＤ（白石カルシウム社）
　硫酸バリウム：Ｗ－１（竹原化学社）
　シリカ：レオロシールＣＰ１０２（トクヤマ社）
　藍顔料：ＵＮＩＯＮ　ＢＬＵＥ　ＦＧ－７３３０（東洋カラー社） PETA: Pentaerythritol triacrylate (HLB10.9, molecular weight 298.29, hydroxyl value 188mgKOH/g)
TMPG: Trimethylolpropane diacrylate (HLB8.9, molecular weight 242, hydroxyl value 232mgKOH/g)
GGA: Glycerin diacrylate (HLB10.4, molecular weight 200, hydroxyl value 281mgKOH/g)
15EO-TMPG: Ethylene oxide (15) modified trimethylolpropane diacrylate (HLB13.9, molecular weight 902, hydroxyl value 62mgKOH/g)
DPTA: dipentaerythritol triacrylate (HLB13.6, molecular weight 416, hydroxyl value 135mgKOH/g)
X-1: Styrene acrylic resin, weight average molecular weight 18,000, acid value 110 (Seiko PMC Co., Ltd.)
YS-1274: Styrene acrylic resin, weight average molecular weight 19,000, acid value 200 (Seiko PMC Co., Ltd.)
Miramer PU2100: Bifunctional urethane acrylate, molecular weight 1,400 (MIWON)
Miramer PE210: Bifunctional bisphenol A epoxy diacrylate, molecular weight 520 (MIWON)
Miramer PS420: Tetrafunctional polyester acrylate, weight average molecular weight 3,000 (MIWON)
TMPTA: Trimethylolpropane triacrylate (molecular weight 296.32)
6EO-TMPTA: 6 mole ethylene oxide modified trimethylolpropane triacrylate (HLB10.48, molecular weight 560)
15EO-TMPTA: 15 mole ethylene oxide modified trimethylolpropane triacrylate (HLB13.45, molecular weight 956)
GPTA: 3M PO modified glycerin triacrylate (HLB9.48, molecular weight 428)
DI-TMPTA: ditrimethylolpropane tetraacrylate (HLB8.4, molecular weight 466)
(Polymerization inhibitor)
BHT: 2,6-di-tert-butyl-p-cresol (photopolymerization initiator)
Irugacure184: 1-hydroxycyclohexyl-phenyl ketone (pigment)
Titanium oxide: CR-90 (Ishihara Sangyo Co., Ltd.)
Carbon black: MA-70 (CABOT)
Calcium carbonate: T-DD (Shiraishi Calcium Co., Ltd.)
Barium sulfate: W-1 (Takehara Chemical Co., Ltd.)
Silica: Rheolo Seal CP102 (Tokuyama)
Indigo pigment: UNION BLUE FG-7330 (Toyo Color Co., Ltd.)
＜積層体の作成＞
　（原反）（化学処理された面を有するときには、その面を組成物の塗布面とした。化学処理された面がなく、コロナ等による放電処理された面があるときには、その面を組成物の塗布面とした。）
　Ｓ４６Ｃ：易接着ポリエチレンテレフタレート、厚さ１２μｍ、ＰＯＬＹＰＬＥＸ社
　ＰＴＭ：易接着２軸延伸ポリエチレンテレフタレート、厚さ１２μｍ、ユニチカ社
　Ｐ２１６１：２軸延伸ポリプロピレン、厚さ２０μｍ、東洋紡社
　ＦＯＲ：コロナ表面処理２軸延伸ポリプロピレン、厚さ２０μｍ、フタムラ化学社
　ＯＮＭ：コロナ表面処理易接着２軸延伸ナイロン、厚さ１５μｍ、ユニチカ社
　Ｎ１１０２：コロナ表面処理ナイロン、厚さ１５μｍ、東洋紡社
　（シーラント（接着されるフィルム））
　ＬＬＤＰＥ：ＴＵＸ－ＨＣ（低密度ポリエチレン）厚さ５０μｍ、三井化学東セロ社
　ＣＰＰ：無延伸ポリプロピレン、Ｐ－１１２８、厚さ２５μｍ、東洋紡社 <Creation of laminate>
(Original fabric) (When it has a chemically treated side, that side was used as the side to which the composition was applied. When there is no chemically treated side and there is a side that has been subjected to discharge treatment by corona etc., that side is used as the side to which the composition is applied. )
S46C: Easy-adhesion polyethylene terephthalate, thickness 12 μm, POLYPLEX Co., Ltd. PTM: Easy-adhesion biaxially stretched polyethylene terephthalate, thickness 12 μm, Unitika P2161: Biaxially stretched polypropylene, thickness 20 μm, Toyobo Co., Ltd. FOR: Corona surface treatment biaxial stretching Polypropylene, 20 μm thick, Futamura Chemical Co., Ltd. ONM: Corona surface treated biaxially stretched nylon for easy adhesion, 15 μm thick, Unitika N1102: Corona surface treated nylon, 15 μm thick, Toyobo Co., Ltd. (Sealant (film to be bonded))
LLDPE: TUX-HC (low-density polyethylene), thickness 50 μm, Mitsui Chemicals Tohcello Co., Ltd. CPP: Unoriented polypropylene, P-1128, thickness 25 μm, Toyobo Co., Ltd.
（実施例及び比較例）
　下記表中の実施例１に示す裏刷り用活性エネルギー線硬化型インキ組成物を調製した。この組成物を原反である無地のＳ４６Ｃ上に、表１中の塗布量になるように塗布した。エージングを行なうこと無く、次いで、その塗布面上にシーラントとしてＬＬＤＰＥフィルム（ＴＵＸ－ＨＣ（三井化学東セロ社）厚さ５０μｍ）（以下「ＬＬＤＰＥフィルム」という）又はＣＰＰ（無延伸ポリプロピレン）フィルムを重ねて、エージングを行なうこと無く、表１中の照射量で活性エネルギー線を照射して、これらのフィルムを積層させた。製造に使用した器具類は、家庭用洗剤（弱アルカリ）を用いて水洗浄をした。付着した裏刷り用活性エネルギー線硬化型インキ組成物も速やかに除去できた。
　同様にして、無地のＰＴＭ、Ｐ２１６１、ＦＯＲ、ＯＮＭ、Ｎ１１０２上に組成物を塗布し、それぞれに対してシーラントとしてＬＬＤＰＥフィルム又はＣＰＰフィルムを重ねて、表１中の照射量で活性エネルギー線を照射して、これらのフィルムを積層させた。
　そして無地のＳ４６Ｃ、ＰＴＭ、Ｐ２１６１、ＦＯＲ、ＯＮＭ、Ｎ１１０２に代えて、ＥＢオフセットインキ組成物で印刷し硬化した印刷物上に、それらの印刷箇所を含み、印刷箇所以外の部位にも組成物を塗布した。次いで、エージングを行なうこと無く、その塗布面上にシーラントとしてＬＬＤＰＥフィルム又はＣＰＰフィルムを重ねて、表１中の照射量で活性エネルギー線を照射して、これらのフィルムを積層させた。
　実施例及び比較例においては、アイ・エレクトロンビーム社の電子線照射装置を用い、酸素濃度が２００ｐｐｍの雰囲気下で、加速電圧を９０ｋＶとし、１回の電子線の照射の照射量は３０ｋＧｙを基本として、表１中の照射量になるように複数回照射した。なお、紫外線を照射する場合であり、重合開始剤を含有した実施例２５及び２６と比較例１２及び１３については、いずれも紫外線を４００ｍＪ／ｃｍ２になるように照射した。
　また、無地のＳ４６Ｃ、ＰＴＭ、Ｐ２１６１、ＦＯＲ、ＯＮＭ、Ｎ１１０２に代えて、溶剤性グラビアインキにより印刷し乾燥固化した印刷物上に、それらの印刷箇所を含み、印刷箇所以外の部位にも裏刷り用活性エネルギー線硬化型インキ組成物を塗布した。次いで、エージングを行なうこと無く、その塗布面上にシーラントとしてＬＬＤＰＥフィルム又はＣＰＰフィルムを重ねて、表１中の照射量で活性エネルギー線を照射して、これらのフィルムを積層させた。
　これを、同様にして実施例２～２６及び比較例１～１３についても行った。 (Example and comparative example)
An active energy ray-curable ink composition for back printing shown in Example 1 in the table below was prepared. This composition was applied onto a plain S46C original fabric in the coating amounts shown in Table 1. Without aging, an LLDPE film (TUX-HC (Mitsui Chemicals Tohcello Co., Ltd.) thickness 50 μm) (hereinafter referred to as "LLDPE film") or CPP (unoriented polypropylene) film was layered on the coated surface as a sealant. These films were laminated by irradiating them with active energy rays at the doses shown in Table 1 without aging. The equipment used for production was washed with household detergent (weak alkaline). The adhered active energy ray-curable ink composition for back printing could also be quickly removed.
In the same way, the composition was applied on plain PTM, P2161, FOR, ONM, and N1102, and an LLDPE film or CPP film was layered on each as a sealant, and active energy rays were irradiated at the dose shown in Table 1. These films were then laminated.
Then, instead of plain S46C, PTM, P2161, FOR, ONM, and N1102, the composition was applied to the hardened printed matter printed with an EB offset ink composition, including those printed areas, and also to areas other than the printed areas. did. Next, without aging, an LLDPE film or a CPP film was layered as a sealant on the coated surface, and active energy rays were irradiated at the dose shown in Table 1 to stack these films.
In the Examples and Comparative Examples, an electron beam irradiation device manufactured by I-Electron Beam Co., Ltd. was used, the acceleration voltage was set to 90 kV in an atmosphere with an oxygen concentration of 200 ppm, and the irradiation amount of one electron beam irradiation was basically 30 kGy. The irradiation was performed multiple times to achieve the irradiation doses shown in Table 1. In addition, in Examples 25 and 26 and Comparative Examples 12 and 13, which contained a polymerization initiator, ultraviolet rays were irradiated at 400 mJ/cm 2 .
In addition, in place of plain S46C, PTM, P2161, FOR, ONM, N1102, printed matter printed with solvent-based gravure ink and dried and solidified can be used for back printing, including those printed areas, as well as areas other than the printed areas. An active energy ray curable ink composition was applied. Next, without aging, an LLDPE film or a CPP film was layered as a sealant on the coated surface, and active energy rays were irradiated at the dose shown in Table 1 to stack these films.
This was similarly carried out for Examples 2 to 26 and Comparative Examples 1 to 13.
＜アルカリ水への浸漬結果＞
　実施例及び比較例の裏刷り用活性エネルギー線硬化型インキ組成物を、マジックリン（花王社）を１．０質量％の濃度になるように水に溶解して得た２５℃のアルカリ水に浸漬した結果は以下のとおりであった。
　全ての実施例にて接着剤層が溶解した。
　全ての比較例にて接着剤層が溶解しなかった。 <Results of immersion in alkaline water>
The active energy ray-curable ink compositions for back printing of Examples and Comparative Examples were added to 25°C alkaline water obtained by dissolving Magiclin (Kao Corporation) in water to a concentration of 1.0% by mass. The immersion results were as follows.
The adhesive layer dissolved in all examples.
In all comparative examples, the adhesive layer did not dissolve.
＜剥離強度の測定＞
　実施例及び比較例の積層体について、電子線照射後又は紫外線照射後、直ちに、引張試験機（安田精機製作所社）を用いて、測定温度２５℃、引張速度２００ｍｍ／ｍｉｎで得られた樹脂フィルムを引張り、破断した時の強度を求めた。
　４０℃で１日経時した積層体を１５ｍｍ幅に切断し、剥離試験機（安田精機製作所社）を用いて、ラミネート強度としてＴ型剥離強度（ｇ／１５ｍｍ）を測定した。
＜引張強度＞
　４０℃で１日経時した積層体を１５ｍｍ幅に切断し、原反とシーラントのフィルムとの間を、オリエンテック社テンシロン万能試験機を用いて、雰囲気温度２５℃、剥離速度を３００ｍｍ／分に設定し、１８０度剥離方法で剥離した際の引張強度をラミネート強度（Ｎ／１５ｍｍ）とした。表中のラミネート強度を示す数値の後に記載した記号について、Ｆはフィルム破断、Ｂは原反側からの剥離、Ｓはシーラントフィルム側からの剥離を意味する。
　なお、下記表中には、上記剥離強度と引張強度を並べて記載した。例えば７．０Ｆは、剥離強度が７．０ｇ／１５ｍｍであり、かつ、引張強度の測定によりフィルム破断したことを意味する。 <Measurement of peel strength>
Resin films obtained for the laminates of Examples and Comparative Examples immediately after electron beam irradiation or ultraviolet ray irradiation using a tensile tester (Yasuda Seiki Seisakusho Co., Ltd.) at a measurement temperature of 25° C. and a tensile speed of 200 mm/min. was pulled and the strength at break was determined.
The laminate aged at 40° C. for 1 day was cut into 15 mm width pieces, and the T-peel strength (g/15 mm) was measured as the laminate strength using a peel tester (Yasuda Seiki Seisakusho Co., Ltd.).
<Tensile strength>
The laminate aged at 40°C for 1 day was cut into 15 mm width pieces, and the film and sealant film were separated using an Orientec Tensilon universal testing machine at an ambient temperature of 25°C and a peeling speed of 300 mm/min. The tensile strength when peeled using the 180 degree peeling method was defined as the laminate strength (N/15 mm). Regarding the symbols written after the numerical values indicating laminate strength in the table, F means film breakage, B means peeling from the original fabric side, and S means peeling from the sealant film side.
In addition, in the table below, the above-mentioned peel strength and tensile strength are listed side by side. For example, 7.0F means that the peel strength is 7.0 g/15 mm and the film was broken when the tensile strength was measured.
（応用実施例１）
　原反である無地のＰＴＭ及びシーラントとしてＬＬＤＰＥフィルム（厚さ５０μｍ）のそれぞれの片面に、塗布量が２．０ｇ／ｍ２となるように上記の裏刷り用活性エネルギー線硬化型インキ組成物を塗工してインキ組成物層を形成した。エージングをすること無く、ＰＴＭと中間に挟むアルミニウム箔を重ね張り合わせ積層体Ａを作成し、さらにエージングをすること無く、積層体Ａのアルミニウム箔側とＬＬＤＰＥフィルムの活性エネルギー線硬化型接着剤層形成側の面を重ね張り合わせ、ＰＴＭ／裏刷り用活性エネルギー線硬化型インキ組成物層／アルミニウム箔（厚さ９μｍ）／裏刷り用活性エネルギー線硬化型インキ組成物層／ＬＬＤＰＥフィルムからなる積層体Ｂを得た。張り合わせ手順は逆でもよい。電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線を積層体Ｂの第２の透明フィルム側から照射して接着させた。
　ＰＴＭ及びＬＬＤＰＥフィルムは互いに十分な強度で接着をしていた。また、製造に使用した器具類は、家庭用洗剤（弱アルカリ）を用いて水洗浄をし、付着していた裏刷り用活性エネルギー線硬化型インキ組成物も速やかに除去できた。 (Application example 1)
The above active energy ray-curable ink composition for back printing was applied to one side of each of plain PTM as the original fabric and LLDPE film (thickness 50 μm) as a sealant at a coating amount of 2.0 g/m 2 . An ink composition layer was formed by coating. Laminate A is created by laminating PTM and aluminum foil sandwiched between them without aging, and an active energy ray-curable adhesive layer is formed between the aluminum foil side of laminate A and the LLDPE film without aging. Laminated body B consisting of PTM/active energy ray curable ink composition layer for back printing/aluminum foil (thickness 9 μm)/active energy ray curable ink composition layer for back printing/LLDPE film by laminating the side surfaces together. I got it. The pasting procedure may be reversed. Using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.), an electron beam with an irradiation dose of 150 kGy and 90 kV was irradiated from the second transparent film side of the laminate B to bond it.
The PTM and LLDPE films adhered to each other with sufficient strength. In addition, the instruments used in the production were washed with water using a household detergent (weak alkali), and the active energy ray-curable ink composition for back printing that had adhered to them could be quickly removed.
（応用実施例２）
　原反である無地のＰＴＭ及びシーラントとしてＬＬＤＰＥフィルム（厚さ５０μｍ）のそれぞれの片面に、塗布量が２．０ｇ／ｍ２となるように上記の裏刷り用活性エネルギー線硬化型インキ組成物を塗工してインキ層を形成した。そして、エージングをすること無く、ＰＴＭと中間に挟むアルミニウム箔（厚さ９μｍ）を重ね張り合わせ積層体Ａを作成し、電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線をＰＴＭ側から照射して接着させた（アルミニウム箔側からでもよい）。
　次に、エージングをすること無く、電子線照射した積層体Ａのアルミニウム箔側と、ＬＬＤＰＥフィルムを張り合わせ、積層体Ｂを作成し、電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線をLＬＤＰＥフィルム側から照射して接着させた。
　ＰＴＭ及びＬＬＤＰＥフィルムは互いに十分な強度で接着をしていた。また、製造に使用した器具類は、家庭用洗剤（弱アルカリ）を用いて水洗浄をし、付着していた裏刷り用活性エネルギー線硬化型インキ組成物も速やかに除去できた。 (Application example 2)
The above active energy ray-curable ink composition for back printing was applied to one side of each of plain PTM as the original fabric and LLDPE film (thickness 50 μm) as a sealant at a coating amount of 2.0 g/m 2 . An ink layer was formed by coating. Then, without aging, PTM and aluminum foil (thickness 9 μm) sandwiched between them were laminated together to create a laminate A, and an irradiation dose of 150 kGy was applied using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.). A 90 kV electron beam was irradiated from the PTM side for adhesion (or from the aluminum foil side).
Next, without aging, the aluminum foil side of the laminate A that had been irradiated with electron beams was laminated with the LLDPE film to create a laminate B, which was then irradiated using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.). The LLDPE film was bonded by irradiating the LLDPE film with an electron beam at a dose of 150 kGy and 90 kV.
The PTM and LLDPE films adhered to each other with sufficient strength. In addition, the instruments used in the production were washed with water using a household detergent (weak alkali), and the active energy ray-curable ink composition for back printing that had adhered to them could be quickly removed.
（応用実施例３）
　原反である印刷済のＰＴＭの印刷側面及びシーラントとしてＬＬＤＰＥフィルム（厚さ５０μｍ）の片面に、塗布量が２．０ｇ／ｍ２となるように上記の裏刷り用活性エネルギー線硬化型インキ組成物を塗工してインキ層を形成した。エージングをすること無く、ＰＴＭとアルミニウム箔（厚さ９μｍ）を重ね張り合わせ積層体Ａを作成し、電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線をＰＴＭ側から照射して接着させた。（アルミニウム箔側からでもよい。）次に、電子線照射した積層体Ａのアルミニウム箔側と、第２の透明フィルムを張り合わせ、積層体Ｂを作成し、電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線を第２の透明フィルム側から照射して接着させた。
　ＰＴＭ及びＬＬＤＰＥフィルムは互いに十分な強度で接着をしていた。また、製造に使用した器具類は、家庭用洗剤（弱アルカリ）を用いて水洗浄をし、付着していた裏刷り用活性エネルギー線硬化型インキ組成物も速やかに除去できた。 (Application example 3)
The above active energy ray-curable ink composition for back printing was applied to the printing side of the printed PTM as the original film and to one side of the LLDPE film (thickness 50 μm) as a sealant so that the coating amount was 2.0 g/m 2 . The material was coated to form an ink layer. A laminate A was created by laminating PTM and aluminum foil (9 μm thick) without aging, and irradiated with an electron beam of 150 kGy and 90 kV using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.). It was irradiated from the PTM side and bonded. (You can also start from the aluminum foil side.) Next, the aluminum foil side of the laminate A that has been irradiated with the electron beam is laminated with a second transparent film to create the laminate B. An electron beam of 150 kGy and 90 kV was irradiated from the second transparent film side to bond the film.
The PTM and LLDPE films adhered to each other with sufficient strength. In addition, the instruments used in the production were washed with water using a household detergent (weak alkali), and the active energy ray-curable ink composition for back printing that had adhered to them could be quickly removed.
　本発明に沿った例である各実施例によれば、十分に高い接着性を発揮できた。そのため、引張強度を測定する際には、フィルムの破断を起こすほどであった。　
　しかしながら、水酸基含有（メタ）アクリレートを４５．０質量％以上含有しない活性エネルギー線硬化型接着剤組成物を使用した各比較例によれば、弱い接着力を呈するに留まった。
　さらに、水酸基含有（メタ）アクリレートを含有しない活性エネルギー線硬化型接着剤組成物を使用した場合には、原反側から剥離するほどに十分な引張強度を示さなかった。
　また、本発明の活性エネルギー線硬化型接着剤組成物はアルカリ水に溶解除去された。 According to each example that is an example in accordance with the present invention, sufficiently high adhesiveness could be exhibited. Therefore, when measuring the tensile strength, the film was even broken.
However, in each comparative example using an active energy ray-curable adhesive composition that does not contain 45.0% by mass or more of hydroxyl group-containing (meth)acrylate, only weak adhesive strength was exhibited.
Furthermore, when an active energy ray-curable adhesive composition containing no hydroxyl group-containing (meth)acrylate was used, it did not exhibit sufficient tensile strength to the extent that it could be peeled off from the original fabric side.
Further, the active energy ray-curable adhesive composition of the present invention was dissolved and removed in alkaline water.

Claims (14)

  1. 　全重合性成分中に、水酸基含有（メタ）アクリレートを４５．０質量％以上含有する裏刷り用活性エネルギー線硬化型インキ組成物。 An active energy ray-curable ink composition for back printing containing 45.0% by mass or more of hydroxyl group-containing (meth)acrylate in all polymerizable components.
  2. 　水酸基含有（メタ）アクリレートを５．０～９５．０質量％含有し、
    　更にカルボン酸基、ヒドロキシル基及びウレタン基のうち１種以上、及び、エチレン性不飽和基を有し、重量平均分子量が５００～１０００００の樹脂を含有する、請求項１に記載の裏刷り用活性エネルギー線硬化型インキ組成物。     Contains 5.0 to 95.0% by mass of hydroxyl group-containing (meth)acrylate,
    The active for back printing according to claim 1, further comprising a resin having one or more of carboxylic acid groups, hydroxyl groups, and urethane groups and an ethylenically unsaturated group and having a weight average molecular weight of 500 to 100,000. Energy ray curable ink composition.
  3. 　水酸基含有（メタ）アクリレートが、１分子中に（メタ）アクリロイル基を１つ以上有し、かつ１分子中に水酸基を１つ以上有する、請求項１又は２に記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray for back printing according to claim 1 or 2, wherein the hydroxyl group-containing (meth)acrylate has one or more (meth)acryloyl groups in one molecule and one or more hydroxyl groups in one molecule. Curable ink composition.
  4. 　水酸基含有（メタ）アクリレートの表面張力値（デイビス法）が８．０～２０．０である請求項１～３のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition for back printing according to any one of claims 1 to 3, wherein the hydroxyl group-containing (meth)acrylate has a surface tension value (Davis method) of 8.0 to 20.0.
  5. 　水酸基含有（メタ）アクリレートの平均分子量が１００～２０００である請求項１～４のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition for back printing according to any one of claims 1 to 4, wherein the hydroxyl group-containing (meth)acrylate has an average molecular weight of 100 to 2,000.
  6. 　水酸基含有（メタ）アクリレートの水酸基価が５０～４００ｍｇＫＯＨ／ｇである請求項１～５のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition for back printing according to any one of claims 1 to 5, wherein the hydroxyl group-containing (meth)acrylate has a hydroxyl value of 50 to 400 mgKOH/g.
  7. 　活性エネルギー線による重合性成分全体の水酸基価が３０ｍｇＫＯＨ／ｇ以上である請求項１～６のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition for back printing according to any one of claims 1 to 6, wherein the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
  8. 　水酸基含有（メタ）アクリレートが、水酸基含有ポリ（メタ）アクリレートを含有し、その水酸基含有ポリ（メタ）アクリレートが、ペンタエリスリトール、ジペンタエリスリトール、グリセリン、ジグリセリン、トリメチロールプロパン、及びジトリメチロールプロパンの１種以上の化合物と、（メタ）アクリル酸が、エステル結合してなる化合物である請求項１～７のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The hydroxyl group-containing (meth)acrylate contains a hydroxyl group-containing poly(meth)acrylate, and the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol, dipentaerythritol, glycerin, diglycerin, trimethylolpropane, and ditrimethylolpropane. The active energy ray-curable ink composition for back printing according to any one of claims 1 to 7, which is a compound formed by an ester bond between one or more compounds and (meth)acrylic acid.
  9. 　裏刷り用活性エネルギー線硬化型インキ組成物の含水率が０．０１～５．００質量％である請求項１～８のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition for back printing according to any one of claims 1 to 8, wherein the water content of the active energy ray curable ink composition for back printing is 0.01 to 5.00% by mass.
  10. 　水酸基含有ポリ（メタ）アクリレートが、１分子あたり２～４の（メタ）アクリロイル基を有する化合物である請求項１～９のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition for back printing according to any one of claims 1 to 9, wherein the hydroxyl group-containing poly(meth)acrylate is a compound having 2 to 4 (meth)acryloyl groups per molecule.
  11. 　水酸基含有ポリ（メタ）アクリレートが、ペンタエリスリトールジ（メタ）アクリレート、及び／又はペンタエリスリトールトリ（メタ）アクリレートを含有する請求項８～１０のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink for back printing according to any one of claims 8 to 10, wherein the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol di(meth)acrylate and/or pentaerythritol tri(meth)acrylate. Composition.
  12. 　１０～５００ｋＧｙの電子線で硬化可能な請求項１～１１のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition for back printing according to any one of claims 1 to 11, which is curable with an electron beam of 10 to 500 kGy.
  13. 　印刷層が形成された又は印刷層が形成されていない被印刷物に、請求項１～１２のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物により印刷し、その印刷層の上にシート状物を積層し、次いで、裏刷り用活性エネルギー線硬化型インキ組成物層に活性エネルギー線を照射する積層体の製造方法。 Printing is performed on a printing material on which a printing layer is formed or on which a printing layer is not formed, using the active energy ray-curable ink composition for back printing according to any one of claims 1 to 12, and on the printing layer. A method for producing a laminate, comprising laminating sheet-like materials, and then irradiating an active energy ray-curable ink composition layer for back printing with active energy rays.
  14. 　印刷層が形成された又は印刷層が形成されていない被印刷物、その被印刷物の上に形成された請求項１～１２のいずれかに記載の裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層、及び該裏刷り用活性エネルギー線硬化型インキ組成物からなる印刷層上に積層されたシート状物を有する積層体。  A printing material on which a printing layer is formed or no printing layer is formed, and an active energy ray-curable ink composition for back printing according to any one of claims 1 to 12 formed on the printing material. A laminate comprising a printing layer and a sheet material laminated on the printing layer made of the active energy ray-curable ink composition for back printing.​
PCT/JP2022/047361 2022-03-31 2022-12-22 Active energy ray-curable ink composition for reverse printing WO2023188628A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-060200 2022-03-31
JP2022060200A JP7110508B1 (en) 2022-03-31 2022-03-31 Active energy ray-curable ink composition for reverse printing

Publications (1)

Publication Number Publication Date
WO2023188628A1 true WO2023188628A1 (en) 2023-10-05

Family

ID=82656895

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/047361 WO2023188628A1 (en) 2022-03-31 2022-12-22 Active energy ray-curable ink composition for reverse printing

Country Status (2)

Country Link
JP (1) JP7110508B1 (en)
WO (1) WO2023188628A1 (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004123802A (en) * 2002-09-30 2004-04-22 Toyo Ink Mfg Co Ltd Printing ink, printed matter, and production method for printed matter
JP2014177572A (en) * 2013-03-15 2014-09-25 Dic Corp Active energy ray-curable inkjet recording ink and ink set
WO2018008639A1 (en) * 2016-07-04 2018-01-11 東洋インキＳｃホールディングス株式会社 Non-aqueous printing ink composition
WO2018163942A1 (en) * 2017-03-07 2018-09-13 東レ株式会社 Actinic-ray-curable ink for lithographic printing and method for producing printed matter using same
JP2021098773A (en) * 2019-12-20 2021-07-01 東レ株式会社 Ink for active energy ray-curable lithographic printing, and method for producing printed matter using the same
WO2021201104A1 (en) * 2020-03-31 2021-10-07 東レ株式会社 Coating agent for printing films, laminate, and method for manufacturing printed article
JP2021165329A (en) * 2020-04-06 2021-10-14 東亞合成株式会社 Active energy ray-curable adhesive composition
JP2021195467A (en) * 2020-06-16 2021-12-27 東洋インキＳｃホールディングス株式会社 Primer ink for inkjet printing and inkjet ink set
JP7078189B1 (en) * 2021-12-17 2022-05-31 東洋インキＳｃホールディングス株式会社 Easy deinking laminate and its manufacturing method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004123802A (en) * 2002-09-30 2004-04-22 Toyo Ink Mfg Co Ltd Printing ink, printed matter, and production method for printed matter
JP2014177572A (en) * 2013-03-15 2014-09-25 Dic Corp Active energy ray-curable inkjet recording ink and ink set
WO2018008639A1 (en) * 2016-07-04 2018-01-11 東洋インキＳｃホールディングス株式会社 Non-aqueous printing ink composition
WO2018163942A1 (en) * 2017-03-07 2018-09-13 東レ株式会社 Actinic-ray-curable ink for lithographic printing and method for producing printed matter using same
JP2021098773A (en) * 2019-12-20 2021-07-01 東レ株式会社 Ink for active energy ray-curable lithographic printing, and method for producing printed matter using the same
WO2021201104A1 (en) * 2020-03-31 2021-10-07 東レ株式会社 Coating agent for printing films, laminate, and method for manufacturing printed article
JP2021165329A (en) * 2020-04-06 2021-10-14 東亞合成株式会社 Active energy ray-curable adhesive composition
JP2021195467A (en) * 2020-06-16 2021-12-27 東洋インキＳｃホールディングス株式会社 Primer ink for inkjet printing and inkjet ink set
JP7078189B1 (en) * 2021-12-17 2022-05-31 東洋インキＳｃホールディングス株式会社 Easy deinking laminate and its manufacturing method

Also Published As

Publication number Publication date
JP7110508B1 (en) 2022-08-01
JP2023150872A (en) 2023-10-16

Similar Documents

Publication Publication Date Title
JP2019104180A (en) Printed matter
KR100696967B1 (en) Active energy beam-curable adhesive composition and method for producing a laminate
WO2011040533A1 (en) Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board
WO2023188627A1 (en) Active energy ray-curable adhesive composition
KR20060081710A (en) Film for hydraulic transfer and hydraulically transferred body
WO2011064977A1 (en) Actinic-radiation curable jet-printing ink composition and thermoplastic resin sheet with pattern
KR20210141934A (en) Electron Beam Curable Printing Ink Composition and Electron Beam Curable Overprint Varnish Composition
WO2023188628A1 (en) Active energy ray-curable ink composition for reverse printing
JP6926395B2 (en) Polymerizable composition
JP7137726B1 (en) Active energy ray-curable adhesive composition
JP2010248281A (en) Active energy ray-curable adhesive composition for plastic film or sheet
JP4161251B2 (en) White coated polyester film
JP4277650B2 (en) Water pressure transfer film and water pressure transfer body
JP5679750B2 (en) Laminate for transfer printing
JP7326673B1 (en) Laminate containing primer layer
JP2005126540A (en) Ultraviolet-curable ink-jet ink composition
JP2006021377A (en) Decorative metallic tone film and its manufacturing method
JP2014159128A (en) Method for manufacturing thermal transfer film, and method for manufacturing decorative product using the same
JP2007090657A (en) Decorative sheet and method for manufacturing the same
JP2021066802A (en) Pigment dispersion composition, curable composition, stored container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, cured product, and decorated product
JP2021123609A (en) Active energy ray-curable primer coating composition for olefinic resin base material, and laminate
JP4020113B2 (en) Water pressure transfer film and water pressure transfer body
US20130029046A1 (en) Printing ink containing a divinyl ester
US20210261803A1 (en) Pigment dispersion composition, curable composition, accommodating container, device for forming two or three dimensional images, method of forming two-dimensional or three-dimensional images, cured matter, and decoration
JP7430124B2 (en) Recycled thermal transfer system, recycled polyvinyl alcohol resin film, decorative film for thermal transfer, and transfer molded products

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22935754

Country of ref document: EP

Kind code of ref document: A1