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WO2023188628A1 - Composition d'encre durcissable par un rayonnement d'énergie active pour impression recto-verso - Google Patents

Composition d'encre durcissable par un rayonnement d'énergie active pour impression recto-verso Download PDF

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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
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Prior art keywords
meth
acrylate
active energy
ink composition
energy ray
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PCT/JP2022/047361
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English (en)
Japanese (ja)
Inventor
直毅 臣
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Sakata Inx Corp
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Sakata Inx Corp
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    • 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.

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Abstract

La présente invention aborde le problème consistant à obtenir : une composition d'encre durcissable par un rayonnement d'énergie active qui est destinée à l'impression recto-verso, qui présente une excellente capacité d'impression, même sans vieillissement après impression, et qui offre également une bonne disponibilité, des avantages de neutralité carbone, une productivité élevée dans le processus d'impression, et une bonne rentabilité (excellente efficacité économique) ; un procédé de fabrication d'imprimés utilisant ladite composition d'encre durcissable par un rayonnement d'énergie active pour impression recto-verso ; et des imprimés ainsi obtenus. La solution de l'invention porte sur une composition d'encre durcissable par un rayonnement d'énergie active pour impression recto-verso, la composition contenant 45,0 % en masse d'un (méth)acrylate contenant un groupe hydroxy dans tous les composants polymérisables.
PCT/JP2022/047361 2022-03-31 2022-12-22 Composition d'encre durcissable par un rayonnement d'énergie active pour impression recto-verso Ceased WO2023188628A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004123802A (ja) * 2002-09-30 2004-04-22 Toyo Ink Mfg Co Ltd 印刷インキ、印刷物および印刷物の製造方法
JP2014177572A (ja) * 2013-03-15 2014-09-25 Dic Corp 活性エネルギー線硬化型インクジェット記録用インク及びインクセット
WO2018008639A1 (fr) * 2016-07-04 2018-01-11 東洋インキＳｃホールディングス株式会社 Composition d'encre d'impression non aqueuse
WO2018163942A1 (fr) * 2017-03-07 2018-09-13 東レ株式会社 Encre durcissable par rayonnement actinique pour impression lithographique et procédé de production de matière imprimée l'utilisant
JP2021098773A (ja) * 2019-12-20 2021-07-01 東レ株式会社 活性エネルギー線硬化型平版印刷用インキ、およびそれを用いた印刷物の製造方法
WO2021201104A1 (fr) * 2020-03-31 2021-10-07 東レ株式会社 Agent de revêtement pour films d'impression, stratifié, et procédé permettant de fabriquer un article imprimé
JP2021165329A (ja) * 2020-04-06 2021-10-14 東亞合成株式会社 活性エネルギー線硬化型接着剤組成物
JP2021195467A (ja) * 2020-06-16 2021-12-27 東洋インキＳｃホールディングス株式会社 インクジェット印刷用プライマーインキ及びインクジェットインキセット
JP7078189B1 (ja) * 2021-12-17 2022-05-31 東洋インキＳｃホールディングス株式会社 易脱墨性積層体、及び、その製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004123802A (ja) * 2002-09-30 2004-04-22 Toyo Ink Mfg Co Ltd 印刷インキ、印刷物および印刷物の製造方法
JP2014177572A (ja) * 2013-03-15 2014-09-25 Dic Corp 活性エネルギー線硬化型インクジェット記録用インク及びインクセット
WO2018008639A1 (fr) * 2016-07-04 2018-01-11 東洋インキＳｃホールディングス株式会社 Composition d'encre d'impression non aqueuse
WO2018163942A1 (fr) * 2017-03-07 2018-09-13 東レ株式会社 Encre durcissable par rayonnement actinique pour impression lithographique et procédé de production de matière imprimée l'utilisant
JP2021098773A (ja) * 2019-12-20 2021-07-01 東レ株式会社 活性エネルギー線硬化型平版印刷用インキ、およびそれを用いた印刷物の製造方法
WO2021201104A1 (fr) * 2020-03-31 2021-10-07 東レ株式会社 Agent de revêtement pour films d'impression, stratifié, et procédé permettant de fabriquer un article imprimé
JP2021165329A (ja) * 2020-04-06 2021-10-14 東亞合成株式会社 活性エネルギー線硬化型接着剤組成物
JP2021195467A (ja) * 2020-06-16 2021-12-27 東洋インキＳｃホールディングス株式会社 インクジェット印刷用プライマーインキ及びインクジェットインキセット
JP7078189B1 (ja) * 2021-12-17 2022-05-31 東洋インキＳｃホールディングス株式会社 易脱墨性積層体、及び、その製造方法

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