WO2024070376A1 - Active energy ray-curable ink composition, and printed object - Google Patents
Active energy ray-curable ink composition, and printed object Download PDFInfo
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- WO2024070376A1 WO2024070376A1 PCT/JP2023/030720 JP2023030720W WO2024070376A1 WO 2024070376 A1 WO2024070376 A1 WO 2024070376A1 JP 2023030720 W JP2023030720 W JP 2023030720W WO 2024070376 A1 WO2024070376 A1 WO 2024070376A1
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- WIPO (PCT)
- Prior art keywords
- acrylate
- ink composition
- mass
- content
- meth
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000006187 phenyl benzyl group Chemical group 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229940042585 tocopherol acetate Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/28—Printing on other surfaces than ordinary paper on metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
Definitions
- the present invention relates to an active energy ray-curable ink composition and a printed matter. More specifically, the present invention relates to an active energy ray-curable ink composition and a printed matter obtained by the same, which have excellent processability that allows them to be used in applications for drip cans, and which have blocking resistance that allows them to be stacked flat without the need for a varnish coating.
- Patent Document 1 proposes an active energy ray-curable printing ink composition that is less likely to whiten during retort treatment after printing.
- Dry cans are prone to cracking during punching.
- the cracks that occur become even larger during the subsequent retort treatment.
- conventional dry cans are prone to a loss of gloss.
- gloss decreases the luster of the can surface is lost and the commercial value is likely to decrease.
- ink compositions are required to have excellent processability so as not to cause cracks during punching.
- metal substrates on which indications and the like are printed may be stored flat without being coated with varnish before punching. In this case, the printed indications are transferred to the backside of other metal substrates.
- the backside of the metal substrate is the surface that comes into direct contact with food and the like. Therefore, from a hygienic standpoint, excellent blocking resistance is required to prevent offset.
- the active energy ray-curable printing ink composition described in Patent Document 1 does not achieve both processability and blocking resistance.
- the present invention has been made in consideration of these circumstances, and aims to provide an active energy ray-curable ink composition and printed matter that have excellent processability that allows the resulting printed matter to be used in drip can applications and have blocking resistance that allows the printed matter to be stacked flat without the need for a varnish coating.
- the active energy beam-curable ink composition of one embodiment of the present invention that solves the above problems includes a pigment, a polyester resin, an acrylate monomer, and a photopolymerization initiator
- the acrylate monomer includes an acrylate monomer having an isocyanurate ring, a bifunctional acrylate, and a monofunctional acrylate
- the content of the acrylate monomer having an isocyanurate ring is 25 to 50 mass% of the total amount of the acrylate monomer
- the content of the monofunctional acrylate is 8 to 30 mass% of the total amount of the acrylate monomer
- the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate is 30 to 75 mass% of the total amount of the acrylate monomer.
- one aspect of the present invention that solves the above problem is a printed matter in which the above-mentioned active energy ray-curable ink composition is printed on a substrate.
- An active energy ray curable ink composition (hereinafter also referred to as ink composition) according to one embodiment of the present invention contains a pigment, a polyester resin, an acrylate monomer, and a photopolymerization initiator.
- the acrylate monomer contains an acrylate monomer having an isocyanurate ring, a bifunctional acrylate, and a monofunctional acrylate.
- the content of the acrylate monomer having an isocyanurate ring is 25 to 50% by mass in the total amount of the acrylate monomer.
- the content of the monofunctional acrylate is 8 to 30% by mass in the total amount of the acrylate monomer.
- the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate is 30 to 75% by mass in the total amount of the acrylate monomer.
- the pigment is not particularly limited, and may be, for example, any of a variety of inorganic or organic pigments.
- the inorganic and organic pigments are preferably heat-resistant, light-resistant, and retort-resistant.
- Inorganic pigments include titanium oxide, silica, and carbon black.
- Organic pigments include phthalocyanine pigments, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, and quinophthalone pigments.
- the pigment content is adjusted appropriately depending on the type and purpose.
- the pigment content in the ink composition is preferably 10% by mass or more.
- the pigment content in the ink composition is preferably 60% by mass or less.
- the polyester resin is a polyester composed of an acid component containing a polybasic acid and a polyhydric alcohol component.
- the acid component containing a polybasic acid is preferably a divalent acid
- the polyhydric alcohol component is preferably a divalent alcohol.
- the polybasic acid contained in the acid component is not particularly limited.
- the polybasic acid is a compound having multiple carboxy groups, and is a component for polycondensation with the polyhydric alcohol component to increase the molecular weight.
- Compounds such as aromatic polybasic acids, aliphatic polybasic acids, alicyclic polybasic acids, and ⁇ , ⁇ -unsaturated dicarboxylic acids can be used as the polybasic acid.
- the acid component containing the polybasic acid preferably contains at least one selected from the group consisting of alicyclic polybasic acids, anhydrides of alicyclic polybasic acids, aromatic polybasic acids, and anhydrides of aromatic polybasic acids.
- the compound having multiple carboxy groups has two or more carboxy groups, and may be an acid anhydride of these.
- an acid anhydride group is generated by dehydration from two carboxy groups, in this embodiment, one acid anhydride group corresponds to two carboxy groups.
- aromatic polybasic acids examples include orthophthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, and biphenyldicarboxylic acid.
- aliphatic polybasic acids examples include succinic acid, azelaic acid, dodecanedioic acid, and dimer acid.
- alicyclic polybasic acids include 1,2,3,6-tetrahydrophthalic acid, hexahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
- ⁇ , ⁇ -unsaturated dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, and citraconic acid.
- Alkyl esters and acid anhydrides of these compounds can also be used.
- the acid component preferably contains at least one selected from the group consisting of alicyclic polybasic acids or their anhydrides, and aromatic polybasic acids or their anhydrides, more preferably contains at least one selected from the group consisting of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, and isophthalic acid, and more preferably contains at least one selected from the group consisting of tetrahydrophthalic anhydride and hexahydrophthalic anhydride. This gives the ink composition better hot water retort resistance.
- the polyhydric alcohol component is ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, poly(ethyleneoxy)glycol, poly(tetramethyleneoxy)glycol, alkylene oxide adducts of bisphenol A, alkylene oxide adducts of hydrogenated bisphenol A, etc.
- the polyhydric alcohol component contains at least one selected from the group consisting of hydrogenated bisphenol A, 1,6-hexanediol, cyclohexanedimethanol, and diethylene glycol. This provides the ink composition with better hot water retort resistance.
- the weight average molecular weight of the polyester resin of this embodiment is preferably 1000 or more, and more preferably 1300 or more.
- the weight average molecular weight of the polyester resin is preferably 5000 or less, and more preferably 3000 or less.
- the weight average molecular weight of the polyester resin of this embodiment can be determined as a polystyrene-equivalent weight average molecular weight, for example, by gel permeation chromatography (GPC).
- the hydroxyl excess ratio of the polyester resin of this embodiment is preferably 1.0 or more, and more preferably 1.15 or more.
- the hydroxyl excess ratio is preferably 2.0 or less, and more preferably 1.90 or less. If the hydroxyl excess ratio is less than 1.0, the ink composition will produce a film with poor hot water retort resistance.
- the hydroxyl excess ratio (OH amount/COOH amount), which is the molar ratio of hydroxyl groups to carboxy groups, can be obtained by calculating the OH amount and the COOH amount according to the following formula based on the blending of the monomers used, and then calculating the OH amount/COOH amount.
- OH amount number of moles of each monomer used in the compounding
- COOH amount number of moles of each monomer used in the compounding ⁇ valence
- the acid value of the polyester resin is not particularly limited.
- the acid value of the polyester resin is preferably 0.1 mgKOH/g or more.
- the acid value of the polyester resin is preferably 35 mgKOH/g or less.
- the acid value can be calculated, for example, by neutralization titration.
- the content of the polyester resin in the ink composition is preferably 10% by mass or more.
- the content of the polyester resin in the ink composition is preferably 40% by mass or less.
- ink resins In addition to the polyester resins, conventional ink resins may be used in combination.
- ink resins include petroleum resins, epoxy resins, allyl resins, and ketone resins.
- the acrylate monomer includes an acrylate monomer having an isocyanurate ring, a difunctional acrylate, and a monofunctional acrylate.
- the acrylate monomer having an isocyanurate ring is not particularly limited.
- the acrylate monomer having an isocyanurate ring is an isocyanuric acid EO-modified triacrylate, an isocyanuric acid EO-modified diacrylate, an isocyanuric acid ⁇ -caprolactone-modified triacrylate, etc.
- the acrylate monomer having an isocyanurate ring is preferably an isocyanuric acid EO-modified triacrylate or an isocyanuric acid EO-modified diacrylate, in view of excellent blocking resistance of a printed matter obtained using the ink composition.
- the content of the acrylate monomer having an isocyanurate ring may be 25% by mass or more, and preferably 30% by mass or more, based on the total amount of acrylate monomers.
- the content of the acrylate monomer having an isocyanurate ring may be 50% by mass or less, and preferably 45% by mass or less, based on the total amount of acrylate monomers. If the content of the acrylate monomer having an isocyanurate ring is less than 25% by mass, the printed matter obtained using the ink composition will have poor processability when used for dry cartridge cans.
- the acrylate monomer having an isocyanurate ring if the content of the acrylate monomer having an isocyanurate ring is more than 50% by mass, the acrylate monomer having an isocyanurate ring will precipitate in the ink composition, making it unsuitable as an ink composition.
- Bifunctional acrylates are not particularly limited.
- Examples of bifunctional acrylates include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene ...
- glycol di(meth)acrylate dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester di(meth)acrylate, neopentyl glycol EO-modified di(meth)acrylate, neopentyl glycol PO-modified di(meth)acrylate, bisphenol A (EO-modified) di(meth)acrylate, bisphenol A (PO-modified) di(meth)acrylate, trimethylolpropane EO-modified di(meth)acrylate, trimethylolpropane PO-modified di(meth)acrylate, and the like.
- the content of the bifunctional acrylate is preferably 5% by mass or more, and more preferably 10% by mass or more, of the total amount of acrylate monomers.
- the content of the bifunctional acrylate is preferably 65% by mass or less, and more preferably 50% by mass or less, of the total amount of acrylate monomers.
- Monofunctional acrylates are not particularly limited. Examples of monofunctional acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenol EO modified (meth)acrylate, nonylphenol EO modified (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl ...
- acryloyloxyethyl (meth)acrylate isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, and N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide.
- the content of the monofunctional acrylate may be 8% by mass or more, and preferably 10% by mass or more, based on the total amount of acrylate monomers.
- the content of the monofunctional acrylate may be 30% by mass or less, and preferably 25% by mass or less, based on the total amount of acrylate monomers. If the content of the monofunctional acrylate is less than 8% by mass, the printed matter obtained using the ink composition will have poor processability when used for dry cartridge cans. On the other hand, if the content of the monofunctional acrylate is more than 30% by mass, the printed matter obtained using the ink composition will have poor blocking resistance.
- the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate may be 30% by mass or more, preferably 40% by mass or more, of the total amount of the acrylate monomer.
- the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate may be 75% by mass or less, preferably 65% by mass or less, of the total amount of the acrylate monomer. If the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate is less than 30% by mass, the printed matter obtained using the ink composition has poor processability in DR can applications. On the other hand, if the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate exceeds 75% by mass, the printed matter obtained using the ink composition has poor blocking resistance.
- the acrylate monomer may include other acrylate monomers in addition to the above-mentioned acrylate monomer having an isocyanurate ring, bifunctional acrylate, and monofunctional acrylate.
- the other acrylate monomer is not particularly limited.
- the other acrylate monomer may be a trifunctional acrylate, a tetrafunctional acrylate, a pentafunctional acrylate, a hexafunctional acrylate, etc., a di(meth)acrylate monomer in which two hydroxyl groups of a diol compound are substituted with (meth)acryloyloxy groups, a di- or tri(meth)acrylate monomer in which two or three hydroxyl groups of a triol compound are substituted with (meth)acryloyloxy groups, etc.
- the trifunctional acrylate is not particularly limited.
- Examples of trifunctional acrylates include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and EO- and PO-modified versions of these.
- the tetrafunctional acrylate is not particularly limited.
- Examples of the tetrafunctional acrylate include ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate.
- the pentafunctional acrylate is not particularly limited.
- One example of the pentafunctional acrylate is dipentaerythritol penta(meth)acrylate.
- the hexafunctional acrylate is not particularly limited.
- One example of the hexafunctional acrylate is dipentaerythritol hexa(meth)acrylate.
- the polyfunctional acrylate may be a poly(meth)acrylate in which multiple hydroxyl groups of dipentaerythritol are substituted with (meth)acryloyloxy groups, such as dipentaerythritol hexa(meth)acrylate.
- the content of the acrylate monomer in the ink composition is preferably 15% by mass or more, and more preferably 20% by mass or more.
- the content of the acrylate monomer in the ink composition is preferably 55% by mass or less, and more preferably 50% by mass or less.
- the photopolymerization initiator is a component that generates radicals when irradiated with active energy rays, and is blended in order to cure the ink composition.
- the photopolymerization initiator is not particularly limited.
- photopolymerization initiators include benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, and 2-benzy
- the content of the photopolymerization initiator is not particularly limited.
- the content of the photopolymerization initiator in the ink composition is preferably 1% by mass or more, and more preferably 2% by mass or more.
- the content of the photopolymerization initiator in the ink composition is preferably 20% by mass or less, and more preferably 15% by mass or less.
- the ink composition is sufficiently easy to cure.
- the ink composition of the present embodiment may contain optional components such as an extender pigment, a wax, a polymerization inhibitor, a dispersant, etc., in addition to the above-mentioned pigment, polyester resin, acrylate monomer, and photopolymerization initiator.
- the extender pigment is preferably included to impart viscoelasticity to the ink composition, adjust the flowability, prevent misting, etc.
- the extender pigment is not particularly limited.
- extender pigments include clay, talc, mica, kaolinite (kaolin), barium sulfate, magnesium sulfate, calcium carbonate, silicon oxide, aluminum oxide, bentonite, ground calcium carbonate, barium carbonate, zirconia, alumina, etc.
- the content of the extender pigment is not particularly limited.
- the content of the extender pigment in the ink composition is preferably greater than 0 mass%, and more preferably 1 mass% or more.
- the content of the extender pigment in the ink composition is preferably 30 mass% or less, and more preferably 15 mass% or less.
- the wax is not particularly limited.
- the wax may be a polyethylene wax, an olefin wax, a Fischer-Tropsch wax, or the like.
- the wax content is not particularly limited.
- the wax content in the ink composition is preferably greater than 0 mass%, and more preferably 1 mass% or more.
- the wax content in the ink composition is preferably 30 mass% or less, and more preferably 15 mass% or less.
- the polymerization inhibitor is not particularly limited.
- examples of the polymerization inhibitor include phenolic compounds such as butylhydroxytoluene, tocopherol acetate, nitrosamines, benzotriazoles, hindered amines, etc.
- the content of the polymerization inhibitor is not particularly limited.
- the content of the polymerization inhibitor in the ink composition is preferably greater than 0 mass%, and more preferably 0.1 mass% or more.
- the content of the polymerization inhibitor in the ink composition is preferably 10 mass% or less, and more preferably 5 mass% or less.
- the dispersant is not particularly limited.
- examples of the dispersant include carbodiimide-based dispersants, polyester amine-based dispersants, fatty acid amine-based dispersants, modified polyacrylate-based dispersants, modified polyurethane-based dispersants, multi-chain polymeric nonionic dispersants, polymeric ionic surfactants, etc.
- the content of the dispersant is not particularly limited.
- the content of the dispersant is preferably 1 to 200% by mass, assuming that the colorant is 100% by mass.
- the method for preparing the ink composition of this embodiment is not particularly limited.
- the ink composition can be prepared by a conventional method using a roll mill, a ball mill, a bead mill, or the like.
- a printed matter according to one embodiment of the present invention is a printed matter in which the active energy ray-curable ink composition according to the above embodiment is printed on a substrate.
- a printed matter consisting of a coating formed by printing the ink composition on a metal plate or a metal substrate provided with a base coat layer will be described.
- the ink composition of the above embodiment is printed on a substrate such as a metal substrate to form a film.
- the metal substrate is not particularly limited.
- the metal plate may be a metal substrate such as stainless steel, aluminum, tin-plated steel, or tin-free steel, or a metal base plate having a base coat (primer) layer provided on the metal substrate.
- a base coat composition such as a size paint or white coating that is commonly used in metal printing may be used to form the base coat layer.
- the metal substrate may also be laminated with a PET film.
- the method for printing the ink composition of this embodiment on a metal substrate is not particularly limited.
- the printing method is a normal printing method such as an offset method using dampening water or a dry offset method.
- the ink film may have a thickness of 0.1 to 6 ⁇ m.
- the conditions for curing the ink composition are not particularly limited.
- the active energy rays used in the active energy ray curing reaction are ultraviolet rays, electron beams, etc.
- ultraviolet light sources include xenon lamps, high-pressure mercury lamps, metal halide lamps, gallium lamps, ultraviolet light-emitting diodes (UV-LEDs), ultraviolet laser diodes (UV-LDs), etc., and ultraviolet irradiation devices having these light sources can be used.
- the light quantity, light source arrangement, transport speed, etc. can be adjusted as necessary.
- a high-pressure mercury lamp it is preferable to cure at a transport speed of about 2 to 100 m/min for one lamp with a light quantity of about 80 to 160 W/cm.
- electron beams it is preferable to cure at a transport speed of about 5 to 50 m/min using an electron beam accelerator with an acceleration voltage of about 10 to 300 kV.
- thermosetting topcoat varnish may be formed on the ink layer.
- the layer of thermosetting topcoat varnish may be any water-based or solvent-based thermosetting topcoat varnish.
- Commercially available solvent-based thermosetting topcoat varnishes include polyester/amino-based topcoat varnishes manufactured by Toyochem Co., Ltd.
- the printed matter of this embodiment is formed with a film made of the ink composition described above. Therefore, even if the printed matter is stacked flat without such a varnish layer, the film is unlikely to transfer onto the back of another printed matter, and blocking resistance is excellent.
- the method for forming the varnish layer is not particularly limited.
- the varnish layer is applied with a roll coater, and then heated and dried at 150°C to 250°C for 5 seconds to 15 minutes, forming a coating film that is excellent in appearance, hardness, processability, and retort resistance.
- the thickness of the varnish layer is not particularly limited.
- the thickness of the varnish layer is preferably 3 ⁇ m or more.
- the thickness of the varnish layer is preferably 10 ⁇ m or less.
- the ink composition of the above embodiment has excellent processability when producing drop-resistant cans, and is less likely to crack or turn white after hot water retort treatment. Therefore, it is suitable for printing on metal, and is particularly suitable for printing on metal on drop-resistant cans.
- the ink composition of this embodiment provides printed matter that has excellent processability that makes it suitable for use in drip cans, and has blocking resistance that allows it to be stacked flat without the need for a varnish coating.
- the above describes one embodiment of the present invention.
- the present invention is not particularly limited to the above embodiment.
- An active energy ray curable ink composition comprising a pigment, a polyester resin, an acrylate monomer, and a photopolymerization initiator, the acrylate monomer comprising an acrylate monomer having an isocyanurate ring, a bifunctional acrylate, and a monofunctional acrylate, the content of the acrylate monomer having an isocyanurate ring being 25-50% by mass in the total amount of the acrylate monomer, the content of the monofunctional acrylate being 8-30% by mass in the total amount of the acrylate monomer, and the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate being 30-75% by mass in the total amount of the acrylate monomer.
- the printed matter obtained using the active energy ray-curable ink composition has excellent processability that allows it to be used in drip can applications, and has blocking resistance that allows it to be stacked flat without the need for a varnish coating.
- the printed matter obtained using the active energy ray-curable ink composition has better hot water retort resistance.
- the resulting DR can is less susceptible to whitening and less prone to loss of gloss.
- printed matter obtained using the active energy ray-curable ink composition is particularly suitable for use in drip cans.
- the printed matter has excellent workability that allows it to be used for drip cans, and it has blocking resistance that allows it to be stacked flat even without being coated with varnish.
- the raw materials used are as follows: ⁇ Pigments> LIONOL BLUE FG-7351: Pigment Blue 15:3, manufactured by Toyo Color Co., Ltd. ⁇ Acid and alcohol for polyester resin synthesis> Tetrahydrophthalic anhydride: Rikacid TH, 152 g/mol, valence 2, manufactured by New Japan Chemical Co., Ltd. Hydrogenated bisphenol A: Rikabinol HB, 240 g/mol, valence 2, manufactured by New Japan Chemical Co., Ltd. 1,6 hexanediol: 1,6 hexanediol, 118 g/mol, valence 2, manufactured by UBE Co., Ltd.
- ARONIX M-408 ditrimethylolpropane tetraacrylate, tetrafunctional acrylate, manufactured by Toagosei Co., Ltd.
- OTA480 glycerin PO modified triacrylate, trifunctional acrylate, manufactured by Daicel Allnex Co., Ltd.
- Laromer LR 8863 trimethylolpropane EO modified triacrylate, trifunctional acrylate, manufactured by BASF Corporation
- MIRAMER M370 isocyanuric acid EO modified triacrylate (>99.9%), acrylate monomer having an isocyanurate ring, manufactured by MIWON SPECIALTY CHEMICAL Co., Ltd.
- ARONIX M-315 isocyanuric acid EO modified triacrylate and diacrylate (diacrylate ratio: 3 to 13%), acrylate monomer having an isocyanurate ring, MIRAMER manufactured by Toagosei Co., Ltd.
- M216 Neopentyl glycol PO modified diacrylate, bifunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL KAYARAD HX220: Caprolactone modified hydroxypivalic acid neopentyl glycol ester diacrylate, bifunctional acrylate, manufactured by Nippon Kayaku Co., Ltd.
- Iupimer UV SA-1002N Tricyclodecane dimethanol diacrylate, bifunctional acrylate, manufactured by Mitsubishi Chemical Co., Ltd.
- ARONIX M-101A Phenol EO modified acrylate, monofunctional acrylate, manufactured by Toagosei Co., Ltd.
- MIRAMER M1140 Isobornyl acrylate, monofunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL
- MIRAMER M150 Tetrahydrofurfuryl acrylate, monofunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL Co., Ltd.
- Omnirad 379 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, manufactured by IGM Resins Omnirad EMK: 4,4-bis(diethylamino)benzophenone, manufactured by IGM Resins Omnirad DETX: 2,4-diethylthioxanthone, manufactured by IGM Resins ⁇ Additives> SST-3T1-RC: Polytetrafluoroethylene, manufactured by Shamrock
- Example 1 The ink composition of Example 1 was prepared by mixing the components according to the recipe shown in Table 1 and milling and stirring them in a three-roll mill heated to 40° C. The ink composition obtained was evaluated for processability, blocking resistance, the presence or absence of precipitation, and the presence or absence of whitening by the following evaluation methods. The results are shown in Table 1.
- Examples 2 to 16 Comparative Examples 1 to 16> Ink compositions were prepared and evaluated in the same manner as in Example 1, except that the formulations were changed as shown in Tables 1 and 2. The results are shown in Tables 1 and 2.
- the metal plate used for the evaluation was prepared by coating an electric tinplate (ET2.8/2.8 T2.5B manufactured by Nippon Steel & Sumitomo Metal Corporation) with a polyester/amino-based base coating (manufactured by Toyochem Co., Ltd.) in a coating amount of 140 mg/ 100 cm2 and baking at 180°C for 10 minutes to prepare a base coat layer.
- an electric tinplate E2.8/2.8 T2.5B manufactured by Nippon Steel & Sumitomo Metal Corporation
- a polyester/amino-based base coating manufactured by Toyochem Co., Ltd.
- the obtained ink was applied to the base coat layer of the metal plate using an RI tester (manufactured by Tester Sangyo Co., Ltd.) to a film thickness of 1.5 ⁇ m, and the ink was cured by irradiating the printed matter with ultraviolet light using a concentrating metal halide lamp (manufactured by Eye Graphics Co., Ltd., 120 W/cm) irradiation device at a distance of 11 cm from the printed matter and at a conveyor speed of 30 m/min, to prepare a test sample A.
- RI tester manufactured by Tester Sangyo Co., Ltd.
- a concentrating metal halide lamp manufactured by Eye Graphics Co., Ltd., 120 W/cm
- test sample B After printing twice under the same printing conditions, a polyester/amino-based top coating (manufactured by Toyochem Co., Ltd.) was applied in an amount of 70 mg/ 100 cm2 and baked at 180°C for 10 minutes to prepare test sample B. Using the obtained test samples A and B, evaluations were carried out by the following methods. Note that the RI tester is a test machine that spreads ink on a recording medium, and it is possible to adjust the amount of ink transferred and the printing pressure.
- Test sample B prepared by the above method was punched out into a cylindrical shape with a diameter of 80 mm and a height of 50 mm by pressing to obtain a processed product.
- the processed product was sterilized for 90 minutes while immersed in hot water at 125°C, and then the gloss loss on the side surface of the processed product was visually evaluated according to the following criteria. A or better was judged to be at a practical level. (Evaluation criteria) A: The decrease in gloss was very small. ⁇ : A decrease in gloss was observed, but some gloss remained. ⁇ : The gloss was significantly reduced. ⁇ : The gloss loss was very large. -: Precipitation occurred and evaluation was not possible.
- ⁇ Blocking resistance> The test sample A prepared by the above method was cut to 3 cm x 5 cm, and an electric tinplate cut to the same size was placed on the opposite side of the ink film, and the sample was left to stand in an electric oven at 40°C for 1 hour while applying a load of 3 kg/ cm2 using a blocking tester (manufactured by Tester Sangyo Co., Ltd.), and then removed.
- the ink was visually checked to see whether it had transferred to the opposite electric tinplate, and evaluated according to the following criteria. Good or bad was judged to be at a practical level. (Evaluation criteria) ⁇ : No bleeding occurred. ⁇ : Slight offset was observed. ⁇ : Clear offset was observed. ⁇ : Clear offset was observed, and peeling of the ink film was observed. -: Precipitation occurred and evaluation was not possible.
- Test sample B prepared by the above method was immersed in hot water at 125° C. for 90 minutes for sterilization, and then the degree of whitening of the coating surface was visually evaluated according to the following criteria. A or better was judged to be at a practical level. (Evaluation criteria) ⁇ : No whitening occurred. ⁇ : slight whitening was observed. ⁇ : Obvious whitening was observed. ⁇ : The entire coating film was completely whitened. -: Precipitation occurred and evaluation was not possible.
- the ink compositions of Examples 1 to 16 of the present invention did not cause precipitation.
- printed matter using the ink compositions had processability suitable for use in drop-dryer cans, and was less susceptible to whitening even when subjected to hot water retort treatment.
- the printed matter did not show through even when stacked flat, and had excellent blocking resistance.
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Abstract
Provided are: an active energy ray-curable ink composition, with which an obtained printed object exhibits excellent processability able to be used in DR can applications and exhibits anti-blocking properties that allow printed objects to be piled up even if a varnish is not applied; and a printed object. This active energy ray-curable ink composition contains a pigment, a polyester resin, an acrylate monomer and a photopolymerization initiator. The acrylate monomer includes an acrylate monomer having an isocyanurate ring, a difunctional acrylate and a monofunctional acrylate. The content of the acrylate monomer having an isocyanurate ring is 25-50 mass% of the total amount of acrylate monomers. The content of the monofunctional acrylate is 8-30 mass% of the total amount of acrylate monomers. The total content of the monofunctional acrylate and the difunctional acrylate is 30-75 mass% of the total amount of acrylate monomers.
Description
本発明は、活性エネルギー線硬化型インキ組成物および印刷物に関する。より詳細には、本発明は、得られる印刷物が、ＤＲ缶用途に使用可能な優れた加工性を有し、ニスを塗工しなくても、平積みすることのできる耐ブロッキング性を有する、活性エネルギー線硬化型インキ組成物および印刷物に関する。
The present invention relates to an active energy ray-curable ink composition and a printed matter. More specifically, the present invention relates to an active energy ray-curable ink composition and a printed matter obtained by the same, which have excellent processability that allows them to be used in applications for drip cans, and which have blocking resistance that allows them to be stacked flat without the need for a varnish coating.
食料缶などの金属容器の表面には、内容物の表示や装飾等が施されている。ＤＲ缶は、金属基材に表示等を印刷し、打ち抜き加工を行うことにより作製される。ＤＲ缶は、食品を入れて封がされた後、レトルト処理が行われる。特許文献１には、印刷後のレトルト処理において白化を生じにくい、活性エネルギー線硬化型印刷インキ組成物が提案されている。
The surfaces of metal containers such as food cans are decorated and labeled with information about the contents. Dried cans are produced by printing information on a metal substrate and then punching out the information. Dried cans are filled with food and sealed, after which they are retorted. Patent Document 1 proposes an active energy ray-curable printing ink composition that is less likely to whiten during retort treatment after printing.
ＤＲ缶は、打ち抜き加工時にクラックが発生しやすい。発生したクラックは、その後のレトルト処理によってさらに大きくなる。その結果、従来のＤＲ缶は、グロスが低下しやすい。グロスが低下すると、缶表面の艶が失われ、商品価値が低下しやすい。そのため、インキ組成物は、打ち抜き加工時にクラックを発生しないように、優れた加工性が要求される。また、表示等が印刷された金属基材は、打ち抜き加工前に、ニスが塗工されることなく平積みで保管されることがある。この場合、印刷された表示が、他の金属基材の裏面に写る。ＤＲ缶において、金属基材の裏面は、食品等が直接接触する面である。そのため、衛生面からも、裏移りを防止する優れた耐ブロッキング性が要求される。特許文献１に記載の活性エネルギー線硬化型印刷インキ組成物は、これら加工性および耐ブロッキング性が両立できていない。
Dry cans are prone to cracking during punching. The cracks that occur become even larger during the subsequent retort treatment. As a result, conventional dry cans are prone to a loss of gloss. When gloss decreases, the luster of the can surface is lost and the commercial value is likely to decrease. For this reason, ink compositions are required to have excellent processability so as not to cause cracks during punching. In addition, metal substrates on which indications and the like are printed may be stored flat without being coated with varnish before punching. In this case, the printed indications are transferred to the backside of other metal substrates. In dry cans, the backside of the metal substrate is the surface that comes into direct contact with food and the like. Therefore, from a hygienic standpoint, excellent blocking resistance is required to prevent offset. The active energy ray-curable printing ink composition described in Patent Document 1 does not achieve both processability and blocking resistance.
本発明は、このような事情に鑑みなされたものであり、得られる印刷物が、ＤＲ缶用途に使用可能な優れた加工性を有し、ニスを塗工しなくても、平積みすることのできる耐ブロッキング性を有する、活性エネルギー線硬化型インキ組成物および印刷物を提供することを目的とする。
The present invention has been made in consideration of these circumstances, and aims to provide an active energy ray-curable ink composition and printed matter that have excellent processability that allows the resulting printed matter to be used in drip can applications and have blocking resistance that allows the printed matter to be stacked flat without the need for a varnish coating.
上記課題を解決する本発明の一態様の活性エネルギー線硬化型インキ組成物は、顔料と、ポリエステル樹脂と、アクリレートモノマーと、光重合開始剤とを含み、前記アクリレートモノマーは、イソシアヌレート環を有するアクリレートモノマーと、２官能のアクリレートと、単官能のアクリレートとを含み、前記イソシアヌレート環を有するアクリレートモノマーの含有量は、アクリレートモノマー全量中、２５～５０質量％であり、前記単官能のアクリレートの含有量は、アクリレートモノマー全量中、８～３０質量％であり、前記単官能のアクリレートの含有量と、前記２官能のアクリレートの含有量との合計は、アクリレートモノマー全量中、３０～７５質量％である、活性エネルギー線硬化型インキ組成物である。
The active energy beam-curable ink composition of one embodiment of the present invention that solves the above problems includes a pigment, a polyester resin, an acrylate monomer, and a photopolymerization initiator, the acrylate monomer includes an acrylate monomer having an isocyanurate ring, a bifunctional acrylate, and a monofunctional acrylate, the content of the acrylate monomer having an isocyanurate ring is 25 to 50 mass% of the total amount of the acrylate monomer, the content of the monofunctional acrylate is 8 to 30 mass% of the total amount of the acrylate monomer, and the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate is 30 to 75 mass% of the total amount of the acrylate monomer.
また、上記課題を解決する本発明の一態様の印刷物は、上記活性エネルギー線硬化型インキ組成物が、基材に印刷された、印刷物である。
In addition, one aspect of the present invention that solves the above problem is a printed matter in which the above-mentioned active energy ray-curable ink composition is printed on a substrate.
＜活性エネルギー線硬化型インキ組成物＞
本発明の一実施形態の活性エネルギー線硬化型インキ組成物（以下、インキ組成物ともいう）は、顔料と、ポリエステル樹脂と、アクリレートモノマーと、光重合開始剤とを含む。アクリレートモノマーは、イソシアヌレート環を有するアクリレートモノマーと、２官能のアクリレートと、単官能のアクリレートとを含む。イソシアヌレート環を有するアクリレートモノマーの含有量は、アクリレートモノマー全量中、２５～５０質量％である。単官能のアクリレートの含有量は、アクリレートモノマー全量中、８～３０質量％である。単官能のアクリレートの含有量と、２官能のアクリレートの含有量との合計は、アクリレートモノマー全量中、３０～７５質量％である。以下、それぞれについて説明する。 <Active energy ray curable ink composition>
An active energy ray curable ink composition (hereinafter also referred to as ink composition) according to one embodiment of the present invention contains a pigment, a polyester resin, an acrylate monomer, and a photopolymerization initiator. The acrylate monomer contains an acrylate monomer having an isocyanurate ring, a bifunctional acrylate, and a monofunctional acrylate. The content of the acrylate monomer having an isocyanurate ring is 25 to 50% by mass in the total amount of the acrylate monomer. The content of the monofunctional acrylate is 8 to 30% by mass in the total amount of the acrylate monomer. The sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate is 30 to 75% by mass in the total amount of the acrylate monomer. Each of these will be described below.
本発明の一実施形態の活性エネルギー線硬化型インキ組成物（以下、インキ組成物ともいう）は、顔料と、ポリエステル樹脂と、アクリレートモノマーと、光重合開始剤とを含む。アクリレートモノマーは、イソシアヌレート環を有するアクリレートモノマーと、２官能のアクリレートと、単官能のアクリレートとを含む。イソシアヌレート環を有するアクリレートモノマーの含有量は、アクリレートモノマー全量中、２５～５０質量％である。単官能のアクリレートの含有量は、アクリレートモノマー全量中、８～３０質量％である。単官能のアクリレートの含有量と、２官能のアクリレートの含有量との合計は、アクリレートモノマー全量中、３０～７５質量％である。以下、それぞれについて説明する。 <Active energy ray curable ink composition>
An active energy ray curable ink composition (hereinafter also referred to as ink composition) according to one embodiment of the present invention contains a pigment, a polyester resin, an acrylate monomer, and a photopolymerization initiator. The acrylate monomer contains an acrylate monomer having an isocyanurate ring, a bifunctional acrylate, and a monofunctional acrylate. The content of the acrylate monomer having an isocyanurate ring is 25 to 50% by mass in the total amount of the acrylate monomer. The content of the monofunctional acrylate is 8 to 30% by mass in the total amount of the acrylate monomer. The sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate is 30 to 75% by mass in the total amount of the acrylate monomer. Each of these will be described below.
（顔料）
顔料は特に限定されない。一例を挙げると、顔料は、各種無機顔料または有機顔料である。 (Pigment)
The pigment is not particularly limited, and may be, for example, any of a variety of inorganic or organic pigments.
顔料は特に限定されない。一例を挙げると、顔料は、各種無機顔料または有機顔料である。 (Pigment)
The pigment is not particularly limited, and may be, for example, any of a variety of inorganic or organic pigments.
無機顔料、有機顔料は、耐熱性、耐光性、レトルト耐性を有するものであることが好ましい。無機顔料は、酸化チタン、シリカ、カーボンブラック等である。有機顔料は、フタロシアニン系顔料、アゾ系顔料、キナクリドン系顔料、ジケトピロロピロール系顔料、キノフタロン系顔料等である。
The inorganic and organic pigments are preferably heat-resistant, light-resistant, and retort-resistant. Inorganic pigments include titanium oxide, silica, and carbon black. Organic pigments include phthalocyanine pigments, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, and quinophthalone pigments.
顔料の含有量は、種類や目的によって適宜調整される。一例を挙げると、顔料の含有量は、インキ組成物中、１０質量％以上であることが好ましい。また、顔料の含有量は、インキ組成物中、６０質量％以下であることが好ましい。顔料の含有量が上記範囲内であることにより、インキ組成物は、分散安定性が優れ、皮膜物性においては、顔料濃度が高いことによる弊害を回避できる。
The pigment content is adjusted appropriately depending on the type and purpose. As an example, the pigment content in the ink composition is preferably 10% by mass or more. Also, the pigment content in the ink composition is preferably 60% by mass or less. By keeping the pigment content within the above range, the ink composition has excellent dispersion stability, and in terms of film properties, adverse effects caused by a high pigment concentration can be avoided.
（ポリエステル樹脂）
ポリエステル樹脂は、多塩基酸を含む酸成分と多価アルコール成分とを構成成分とするポリエステルである。ポリエステル樹脂は、多塩基酸を含む酸成分が２価の酸であり、多価アルコール成分が２価のアルコールであることが好ましい。これにより、得られる皮膜は、熱水レトルト耐性が優れる。また、得られる皮膜は、金属基材に対する密着性および耐ブロッキング性がより優れる。 (Polyester resin)
The polyester resin is a polyester composed of an acid component containing a polybasic acid and a polyhydric alcohol component. In the polyester resin, the acid component containing a polybasic acid is preferably a divalent acid, and the polyhydric alcohol component is preferably a divalent alcohol. This provides the resulting coating with excellent hot water retort resistance. The resulting coating also provides excellent adhesion to metal substrates and blocking resistance.
ポリエステル樹脂は、多塩基酸を含む酸成分と多価アルコール成分とを構成成分とするポリエステルである。ポリエステル樹脂は、多塩基酸を含む酸成分が２価の酸であり、多価アルコール成分が２価のアルコールであることが好ましい。これにより、得られる皮膜は、熱水レトルト耐性が優れる。また、得られる皮膜は、金属基材に対する密着性および耐ブロッキング性がより優れる。 (Polyester resin)
The polyester resin is a polyester composed of an acid component containing a polybasic acid and a polyhydric alcohol component. In the polyester resin, the acid component containing a polybasic acid is preferably a divalent acid, and the polyhydric alcohol component is preferably a divalent alcohol. This provides the resulting coating with excellent hot water retort resistance. The resulting coating also provides excellent adhesion to metal substrates and blocking resistance.
酸成分に含まれる多塩基酸は特に限定されない。多塩基酸は、複数のカルボキシ基を有する化合物であり、多価アルコール成分と縮重合して高分子量化させるための成分である。多塩基酸としては芳香族多塩基酸、脂肪族多塩基酸、脂環式多塩基酸、α、β－不飽和ジカルボン酸等の化合物を使用できる。これらの中でも、多塩基酸を含む酸成分は、脂環式多塩基酸、脂環式多塩基酸の無水物、芳香族系多塩基酸および芳香族系多塩基酸の無水物からなる群から選択される少なくとも１種を含むことが好ましい。複数のカルボキシ基を有する化合物は、２または３以上のカルボキシ基を備えており、これらの酸無水物であってもよい。また、酸無水物基は、２つのカルボキシ基から脱水によって生成するものであるため、本実施形態においては、酸無水物基１個はカルボキシ基２個に相当するものとする。
The polybasic acid contained in the acid component is not particularly limited. The polybasic acid is a compound having multiple carboxy groups, and is a component for polycondensation with the polyhydric alcohol component to increase the molecular weight. Compounds such as aromatic polybasic acids, aliphatic polybasic acids, alicyclic polybasic acids, and α,β-unsaturated dicarboxylic acids can be used as the polybasic acid. Among these, the acid component containing the polybasic acid preferably contains at least one selected from the group consisting of alicyclic polybasic acids, anhydrides of alicyclic polybasic acids, aromatic polybasic acids, and anhydrides of aromatic polybasic acids. The compound having multiple carboxy groups has two or more carboxy groups, and may be an acid anhydride of these. In addition, since an acid anhydride group is generated by dehydration from two carboxy groups, in this embodiment, one acid anhydride group corresponds to two carboxy groups.
芳香族多塩基酸としては、たとえば、オルソフタル酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、トリメリット酸、ピロメリット酸およびビフェニルジカルボン酸等が挙げられる。脂肪族多塩基酸としては、たとえばコハク酸、アゼライン酸、ドデカンジオン酸、およびダイマー酸等が挙げられる。脂環式多塩基酸としては、たとえば１，２，３，６－テトラヒドロフタル酸、ヘキサヒドロフタル酸、１，３－シクロヘキサンジカルボン酸、および１，４－シクロヘキサンジカルボン酸等が挙げられる。α、β－不飽和ジカルボン酸としては、たとえば、フマル酸、マレイン酸、イタコン酸、シトラコン酸等が挙げられる。なお、これらの化合物のアルキルエステル、および酸無水物も使用することができる。これらの中でも、酸成分は、脂環式多塩基酸またはその無水物、芳香族系多塩基酸またはその無水物からなる群から選択される少なくとも１種を含むことが好ましく、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水フタル酸、イソフタル酸からなる群から選択される少なくとも１種を含むことがより好ましく、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、からなる群から選択される少なくとも１種を含むことがより好ましい。これにより、インキ組成物は、より優れた熱水レトルト耐性を有する。
Examples of aromatic polybasic acids include orthophthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, and biphenyldicarboxylic acid. Examples of aliphatic polybasic acids include succinic acid, azelaic acid, dodecanedioic acid, and dimer acid. Examples of alicyclic polybasic acids include 1,2,3,6-tetrahydrophthalic acid, hexahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of α,β-unsaturated dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, and citraconic acid. Alkyl esters and acid anhydrides of these compounds can also be used. Among these, the acid component preferably contains at least one selected from the group consisting of alicyclic polybasic acids or their anhydrides, and aromatic polybasic acids or their anhydrides, more preferably contains at least one selected from the group consisting of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, and isophthalic acid, and more preferably contains at least one selected from the group consisting of tetrahydrophthalic anhydride and hexahydrophthalic anhydride. This gives the ink composition better hot water retort resistance.
多価アルコール成分は、エチレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、１，６－ヘキサンジオール、１，４－シクロヘキサンジメタノール、キシリレングリコール、ジメチロールプロピオン酸、グリセリン、トリメチロールプロパン、ポリ（エチレンオキシ）グリコール、ポリ（テトラメチレンオキシ）グリコール、ビスフェノールＡのアルキレンオキサイド付加物、水添ビスフェノールＡのアルキレンオキサイド付加物等である。これらの中でも、多価アルコール成分は、水添ビスフェノールＡ、１，６－ヘキサンジオール、シクロヘキサンジメタノール、ジエチレングリコールからなる群から選択される少なくとも１種を含むことが好ましい。これにより、インキ組成物は、より優れた熱水レトルト耐性を有する。
The polyhydric alcohol component is ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, poly(ethyleneoxy)glycol, poly(tetramethyleneoxy)glycol, alkylene oxide adducts of bisphenol A, alkylene oxide adducts of hydrogenated bisphenol A, etc. Among these, it is preferable that the polyhydric alcohol component contains at least one selected from the group consisting of hydrogenated bisphenol A, 1,6-hexanediol, cyclohexanedimethanol, and diethylene glycol. This provides the ink composition with better hot water retort resistance.
本実施形態のポリエステル樹脂の重量平均分子量は、１０００以上であることが好ましく、１３００以上であることがより好ましい。また、ポリエステル樹脂の重量平均分子量は、５０００以下であることが好ましく、３０００以下であることがより好ましい。ポリエステル樹脂の重合平均分子量が上記範囲内であることにより、本実施形態のインキ組成物を用いて得られる皮膜は、より優れた金属基材に対する密着性および耐ブロッキング性を有する。なお、本実施形態のポリエステル樹脂の重量平均分子量は、たとえば、ゲル浸透クロマトグラフィー（ＧＰＣ）法によって、ポリスチレン換算の重量平均分子量として求めることができる。
The weight average molecular weight of the polyester resin of this embodiment is preferably 1000 or more, and more preferably 1300 or more. The weight average molecular weight of the polyester resin is preferably 5000 or less, and more preferably 3000 or less. When the weight average molecular weight of the polyester resin is within the above range, the film obtained using the ink composition of this embodiment has better adhesion to metal substrates and blocking resistance. The weight average molecular weight of the polyester resin of this embodiment can be determined as a polystyrene-equivalent weight average molecular weight, for example, by gel permeation chromatography (GPC).
本実施形態のポリエステル樹脂の水酸基過剰率は、１．０以上であることが好ましく、１．１５以上であることがより好ましい。また、水酸基過剰率は、２．０以下であることが好ましく、１．９０以下であることがより好ましい。水酸基過剰率が１．０未満である場合、インキ組成物は、得られる皮膜の熱水レトルト耐性が劣る。
The hydroxyl excess ratio of the polyester resin of this embodiment is preferably 1.0 or more, and more preferably 1.15 or more. The hydroxyl excess ratio is preferably 2.0 or less, and more preferably 1.90 or less. If the hydroxyl excess ratio is less than 1.0, the ink composition will produce a film with poor hot water retort resistance.
なお、本実施形態において、カルボキシ基に対する水酸基のモル比率である水酸基過剰率（ＯＨ量／ＣＯＯＨ量）は、用いたモノマーの配合に基づき、以下の式によりＯＨ量およびＣＯＯＨ量を算出し、ＯＨ量／ＣＯＯＨ量を算出することにより求め得る。
ＯＨ量＝配合に使用した各モノマーのモル数×価数
ＣＯＯＨ量＝配合に使用した各モノマーのモル数×価数 In this embodiment, the hydroxyl excess ratio (OH amount/COOH amount), which is the molar ratio of hydroxyl groups to carboxy groups, can be obtained by calculating the OH amount and the COOH amount according to the following formula based on the blending of the monomers used, and then calculating the OH amount/COOH amount.
OH amount = number of moles of each monomer used in the compounding × valence COOH amount = number of moles of each monomer used in the compounding × valence
ＯＨ量＝配合に使用した各モノマーのモル数×価数
ＣＯＯＨ量＝配合に使用した各モノマーのモル数×価数 In this embodiment, the hydroxyl excess ratio (OH amount/COOH amount), which is the molar ratio of hydroxyl groups to carboxy groups, can be obtained by calculating the OH amount and the COOH amount according to the following formula based on the blending of the monomers used, and then calculating the OH amount/COOH amount.
OH amount = number of moles of each monomer used in the compounding × valence COOH amount = number of moles of each monomer used in the compounding × valence
ポリエステル樹脂の酸価は特に限定されない。一例を挙げると、ポリエステル樹脂の酸価は、０．１ｍｇＫＯＨ／ｇ以上であることが好ましい。また、ポリエステル樹脂の酸価は、３５ｍｇＫＯＨ／ｇ以下であることが好ましい。ポリエステル樹脂の酸価が上記範囲内であることにより、インキ組成物は、より優れた熱水レトルト耐性を有する。なお、本実施形態において、酸価は、たとえば、中和滴定法により算出することができる。
The acid value of the polyester resin is not particularly limited. As an example, the acid value of the polyester resin is preferably 0.1 mgKOH/g or more. Also, the acid value of the polyester resin is preferably 35 mgKOH/g or less. When the acid value of the polyester resin is within the above range, the ink composition has better hot water retort resistance. In this embodiment, the acid value can be calculated, for example, by neutralization titration.
ポリエステル樹脂の含有量は、インキ組成物中、１０質量％以上であることが好ましい。また、ポリエステル樹脂の含有量は、インキ組成物中、４０質量％以下であることが好ましい。ポリエステル樹脂の含有量が上記範囲内であることにより、本実施形態のインキ組成物を用いて得られる皮膜は、より優れた金属基材に対する密着性および耐ブロッキング性を有する。
The content of the polyester resin in the ink composition is preferably 10% by mass or more. The content of the polyester resin in the ink composition is preferably 40% by mass or less. By having the content of the polyester resin within the above range, the film obtained using the ink composition of this embodiment has better adhesion to metal substrates and blocking resistance.
また、上記ポリエステル樹脂に加え、従来用いられるインキ用樹脂が併用されてもよい。インキ用樹脂は、石油樹脂、エポキシ樹脂、アリル樹脂、ケトン樹脂などである。
In addition to the polyester resins, conventional ink resins may be used in combination. Examples of ink resins include petroleum resins, epoxy resins, allyl resins, and ketone resins.
（アクリレートモノマー）
アクリレートモノマーは、イソシアヌレート環を有するアクリレートモノマーと、２官能のアクリレートと、単官能のアクリレートとを含む。 (Acrylate Monomer)
The acrylate monomer includes an acrylate monomer having an isocyanurate ring, a difunctional acrylate, and a monofunctional acrylate.
アクリレートモノマーは、イソシアヌレート環を有するアクリレートモノマーと、２官能のアクリレートと、単官能のアクリレートとを含む。 (Acrylate Monomer)
The acrylate monomer includes an acrylate monomer having an isocyanurate ring, a difunctional acrylate, and a monofunctional acrylate.
・イソシアヌレート環を有するアクリレートモノマー
イソシアヌレート環を有するアクリレートモノマーは特に限定されない。一例を挙げると、イソシアヌレート環を有するアクリレートモノマーは、イソシアヌル酸ＥＯ変性トリアクリレート、イソシアヌル酸ＥＯ変性ジアクリレート、イソシアヌル酸ε－カプロラクトン変性トリアクリレート等である。これらの中でも、イソシアヌレート環を有するアクリレートモノマーは、インキ組成物を用いて得られる印刷物の耐ブロッキング性が優れる点から、イソシアヌル酸ＥＯ変性トリアクリレート、イソシアヌル酸ＥＯ変性ジアクリレートであることが好ましい。 Acrylate Monomer Having an Isocyanurate Ring The acrylate monomer having an isocyanurate ring is not particularly limited. For example, the acrylate monomer having an isocyanurate ring is an isocyanuric acid EO-modified triacrylate, an isocyanuric acid EO-modified diacrylate, an isocyanuric acid ε-caprolactone-modified triacrylate, etc. Among these, the acrylate monomer having an isocyanurate ring is preferably an isocyanuric acid EO-modified triacrylate or an isocyanuric acid EO-modified diacrylate, in view of excellent blocking resistance of a printed matter obtained using the ink composition.
イソシアヌレート環を有するアクリレートモノマーは特に限定されない。一例を挙げると、イソシアヌレート環を有するアクリレートモノマーは、イソシアヌル酸ＥＯ変性トリアクリレート、イソシアヌル酸ＥＯ変性ジアクリレート、イソシアヌル酸ε－カプロラクトン変性トリアクリレート等である。これらの中でも、イソシアヌレート環を有するアクリレートモノマーは、インキ組成物を用いて得られる印刷物の耐ブロッキング性が優れる点から、イソシアヌル酸ＥＯ変性トリアクリレート、イソシアヌル酸ＥＯ変性ジアクリレートであることが好ましい。 Acrylate Monomer Having an Isocyanurate Ring The acrylate monomer having an isocyanurate ring is not particularly limited. For example, the acrylate monomer having an isocyanurate ring is an isocyanuric acid EO-modified triacrylate, an isocyanuric acid EO-modified diacrylate, an isocyanuric acid ε-caprolactone-modified triacrylate, etc. Among these, the acrylate monomer having an isocyanurate ring is preferably an isocyanuric acid EO-modified triacrylate or an isocyanuric acid EO-modified diacrylate, in view of excellent blocking resistance of a printed matter obtained using the ink composition.
イソシアヌレート環を有するアクリレートモノマーの含有量は、アクリレートモノマー全量中、２５質量％以上であればよく、３０質量％以上であることが好ましい。また、イソシアヌレート環を有するアクリレートモノマーの含有量は、アクリレートモノマー全量中、５０質量％以下であればよく、４５質量％以下であることが好ましい。イソシアヌレート環を有するアクリレートモノマーの含有量が２５質量％未満である場合、インキ組成物を用いて得られる印刷物は、ＤＲ缶用途における加工性が劣る。一方、イソシアヌレート環を有するアクリレートモノマーの含有量が５０質量％を超える場合、インキ組成物は、イソシアヌレート環を有するアクリレートモノマーが析出し、インキ組成物として不適である。
The content of the acrylate monomer having an isocyanurate ring may be 25% by mass or more, and preferably 30% by mass or more, based on the total amount of acrylate monomers. The content of the acrylate monomer having an isocyanurate ring may be 50% by mass or less, and preferably 45% by mass or less, based on the total amount of acrylate monomers. If the content of the acrylate monomer having an isocyanurate ring is less than 25% by mass, the printed matter obtained using the ink composition will have poor processability when used for dry cartridge cans. On the other hand, if the content of the acrylate monomer having an isocyanurate ring is more than 50% by mass, the acrylate monomer having an isocyanurate ring will precipitate in the ink composition, making it unsuitable as an ink composition.
・２官能のアクリレート
２官能のアクリレートは特に限定されない。一例を挙げると、２官能のアクリレートは、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（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、３－メチル－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、ネオペンチルグリコールジ（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、１，９－ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、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ジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（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、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコ－ルヒドロキシピバリン酸エステルジ（メタ）アクリレ－ト、ネオペンチルグリコールＥＯ変性ジ（メタ）アクリレート、ネオペンチルグリコールＰＯ変性ジ（メタ）アクリレート、ビスフェノールＡ（ＥＯ変性）ジ（メタ）アクリレート、ビスフェノールＡ（ＰＯ変性）ジ（メタ）アクリレート、トリメチロールプロパンＥＯ変性ジ（メタ）アクリレート、トリメチロールプロパンＰＯ変性ジ（メタ）アクリレート等である。 Bifunctional acrylates are not particularly limited. Examples of bifunctional acrylates include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene ... glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester di(meth)acrylate, neopentyl glycol EO-modified di(meth)acrylate, neopentyl glycol PO-modified di(meth)acrylate, bisphenol A (EO-modified) di(meth)acrylate, bisphenol A (PO-modified) di(meth)acrylate, trimethylolpropane EO-modified di(meth)acrylate, trimethylolpropane PO-modified di(meth)acrylate, and the like.
２官能のアクリレートは特に限定されない。一例を挙げると、２官能のアクリレートは、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（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、３－メチル－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、ネオペンチルグリコールジ（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、１，９－ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、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ジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（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、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコ－ルヒドロキシピバリン酸エステルジ（メタ）アクリレ－ト、ネオペンチルグリコールＥＯ変性ジ（メタ）アクリレート、ネオペンチルグリコールＰＯ変性ジ（メタ）アクリレート、ビスフェノールＡ（ＥＯ変性）ジ（メタ）アクリレート、ビスフェノールＡ（ＰＯ変性）ジ（メタ）アクリレート、トリメチロールプロパンＥＯ変性ジ（メタ）アクリレート、トリメチロールプロパンＰＯ変性ジ（メタ）アクリレート等である。 Bifunctional acrylates are not particularly limited. Examples of bifunctional acrylates include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene ... glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester di(meth)acrylate, neopentyl glycol EO-modified di(meth)acrylate, neopentyl glycol PO-modified di(meth)acrylate, bisphenol A (EO-modified) di(meth)acrylate, bisphenol A (PO-modified) di(meth)acrylate, trimethylolpropane EO-modified di(meth)acrylate, trimethylolpropane PO-modified di(meth)acrylate, and the like.
２官能のアクリレートの含有量は、アクリレートモノマー全量中、５質量％以上であることが好ましく、１０質量％以上であることがより好ましい。また、２官能のアクリレートの含有量は、アクリレートモノマー全量中、６５質量％以下であることが好ましく、５０質量％以下であることがより好ましい。２官能のアクリレートの含有量が上記範囲内であることにより、インキ組成物を用いて得られる印刷物は、加工性が優れる。
The content of the bifunctional acrylate is preferably 5% by mass or more, and more preferably 10% by mass or more, of the total amount of acrylate monomers. The content of the bifunctional acrylate is preferably 65% by mass or less, and more preferably 50% by mass or less, of the total amount of acrylate monomers. When the content of the bifunctional acrylate is within the above range, the printed matter obtained using the ink composition has excellent processability.
・単官能のアクリレート
単官能のアクリレートは特に限定されない。一例を挙げると、単官能のアクリレートは、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、ブチル（メタ）アクリレート、アミル（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、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、フェノールＥＯ変性（メタ）アクリレート、ノニルフェノールＥＯ変性（メタ）アクリレート、グリシジル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、イソボルニル（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、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（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、テトラヒドロフルフリル（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、ベンジル（メタ）アクリレート、フェニルベンジル（メタ）アクリレート、コハク酸モノ（２－アクリロイルオキシエチル）、Ｎ－［２－（アクリロイルオキシ）エチル］フタルイミド、Ｎ－［２－（アクリロイルオキシ）エチル］テトラヒドロフタルイミド等である。 Monofunctional acrylates are not particularly limited. Examples of monofunctional acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenol EO modified (meth)acrylate, nonylphenol EO modified (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl ... acryloyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, and N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide.
単官能のアクリレートは特に限定されない。一例を挙げると、単官能のアクリレートは、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、ブチル（メタ）アクリレート、アミル（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、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、フェノールＥＯ変性（メタ）アクリレート、ノニルフェノールＥＯ変性（メタ）アクリレート、グリシジル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、イソボルニル（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、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（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、テトラヒドロフルフリル（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、ベンジル（メタ）アクリレート、フェニルベンジル（メタ）アクリレート、コハク酸モノ（２－アクリロイルオキシエチル）、Ｎ－［２－（アクリロイルオキシ）エチル］フタルイミド、Ｎ－［２－（アクリロイルオキシ）エチル］テトラヒドロフタルイミド等である。 Monofunctional acrylates are not particularly limited. Examples of monofunctional acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenol EO modified (meth)acrylate, nonylphenol EO modified (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl ... acryloyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, and N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide.
単官能のアクリレートの含有量は、アクリレートモノマー全量中、８質量％以上であればよく、１０質量％以上であることが好ましい。また、単官能のアクリレートの含有量は、アクリレートモノマー全量中、３０質量％以下であればよく、２５質量％以下であることが好ましい。単官能のアクリレートの含有量が８質量％未満である場合、インキ組成物を用いて得られる印刷物は、ＤＲ缶用途における加工性が劣る。一方、単官能のアクリレートの含有量が３０質量％を超える場合、インキ組成物を用いて得られる印刷物は、耐ブロッキング性が劣る。
The content of the monofunctional acrylate may be 8% by mass or more, and preferably 10% by mass or more, based on the total amount of acrylate monomers. The content of the monofunctional acrylate may be 30% by mass or less, and preferably 25% by mass or less, based on the total amount of acrylate monomers. If the content of the monofunctional acrylate is less than 8% by mass, the printed matter obtained using the ink composition will have poor processability when used for dry cartridge cans. On the other hand, if the content of the monofunctional acrylate is more than 30% by mass, the printed matter obtained using the ink composition will have poor blocking resistance.
アクリレートモノマー全体の説明に戻り、単官能のアクリレートの含有量と２官能のアクリレートの含有量との合計は、アクリレートモノマー全量中、３０質量％以上であればよく、４０質量％以上であることが好ましい。また、単官能のアクリレートの含有量と２官能のアクリレートの含有量との合計は、アクリレートモノマー全量中、７５質量％以下であればよく、６５質量％以下であることが好ましい。単官能のアクリレートの含有量と２官能のアクリレートの含有量との合計が３０質量％未満である場合、インキ組成物を用いて得られる印刷物は、ＤＲ缶用途における加工性が劣る。一方、単官能のアクリレートの含有量と２官能のアクリレートの含有量との合計が７５質量％を超える場合、インキ組成物を用いて得られる印刷物は、耐ブロッキング性が劣る。
Returning to the explanation of the acrylate monomer as a whole, the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate may be 30% by mass or more, preferably 40% by mass or more, of the total amount of the acrylate monomer. The sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate may be 75% by mass or less, preferably 65% by mass or less, of the total amount of the acrylate monomer. If the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate is less than 30% by mass, the printed matter obtained using the ink composition has poor processability in DR can applications. On the other hand, if the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate exceeds 75% by mass, the printed matter obtained using the ink composition has poor blocking resistance.
なお、アクリレートモノマーは、上記したイソシアヌレート環を有するアクリレートモノマー、２官能のアクリレートおよび単官能のアクリレートのほか、その他のアクリレートモノマーを含んでもよい。その他のアクリレートモノマーは特に限定されない。一例を挙げると、その他のアクリレートモノマーは、３官能アクリレート、４官能アクリレート、５官能アクリレート、６官能アクリレート等であってよく、ジオール化合物の２つの水酸基が（メタ）アクリロイルオキシ基によって置換されたジ（メタ）アクリレートモノマー、トリオール化合物の２つまたは３つの水酸基が（メタ）アクリロイルオキシ基によって置換されたジまたはトリ（メタ）アクリレートモノマー等であってもよい。
The acrylate monomer may include other acrylate monomers in addition to the above-mentioned acrylate monomer having an isocyanurate ring, bifunctional acrylate, and monofunctional acrylate. The other acrylate monomer is not particularly limited. For example, the other acrylate monomer may be a trifunctional acrylate, a tetrafunctional acrylate, a pentafunctional acrylate, a hexafunctional acrylate, etc., a di(meth)acrylate monomer in which two hydroxyl groups of a diol compound are substituted with (meth)acryloyloxy groups, a di- or tri(meth)acrylate monomer in which two or three hydroxyl groups of a triol compound are substituted with (meth)acryloyloxy groups, etc.
３官能アクリレートは特に限定されない。一例を挙げると、３官能アクリレートは、トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（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、また、それらのＥＯ変性物およびＰＯ変性物等である。
The trifunctional acrylate is not particularly limited. Examples of trifunctional acrylates include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and EO- and PO-modified versions of these.
４官能アクリレートは特に限定されない。一例を挙げると、４官能アクリレートは、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等である。
The tetrafunctional acrylate is not particularly limited. Examples of the tetrafunctional acrylate include ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate.
５官能アクリレートは特に限定されない。一例を挙げると、５官能アクリレートは、ジペンタエリスリトールペンタ（メタ）アクリレート等である。
The pentafunctional acrylate is not particularly limited. One example of the pentafunctional acrylate is dipentaerythritol penta(meth)acrylate.
６官能アクリレートは特に限定されない。一例を挙げると、６官能アクリレートは、ジペンタエリスリトールヘキサ（メタ）アクリレート等である。
The hexafunctional acrylate is not particularly limited. One example of the hexafunctional acrylate is dipentaerythritol hexa(meth)acrylate.
ほかにも、多官能アクリレートは、ジペンタエリスリトールヘキサ（メタ）アクリレート等のジペンタエリスリトールの複数の水酸基が（メタ）アクリロイルオキシ基によって置換されたポリ（メタ）アクリレートであってもよい。
In addition, the polyfunctional acrylate may be a poly(meth)acrylate in which multiple hydroxyl groups of dipentaerythritol are substituted with (meth)acryloyloxy groups, such as dipentaerythritol hexa(meth)acrylate.
アクリレートモノマーの含有量は、インキ組成物中、１５質量％以上であることが好ましく、２０質量％以上であることがより好ましい。また、アクリレートモノマーの含有量は、インキ組成物中、５５質量％以下であることが好ましく、５０質量％以下であることがより好ましい。アクリレートモノマーの含有量が上記範囲内であることにより、インキ組成物は、より優れた金属基材に対する密着性および耐ブロッキング性を有する。
The content of the acrylate monomer in the ink composition is preferably 15% by mass or more, and more preferably 20% by mass or more. The content of the acrylate monomer in the ink composition is preferably 55% by mass or less, and more preferably 50% by mass or less. By having the content of the acrylate monomer within the above range, the ink composition has better adhesion to metal substrates and blocking resistance.
（光重合開始剤）
光重合開始剤は、活性エネルギー線の照射を受けてラジカルを発生させる成分であり、インキ組成物を硬化させるために配合される。 (Photopolymerization initiator)
The photopolymerization initiator is a component that generates radicals when irradiated with active energy rays, and is blended in order to cure the ink composition.
光重合開始剤は、活性エネルギー線の照射を受けてラジカルを発生させる成分であり、インキ組成物を硬化させるために配合される。 (Photopolymerization initiator)
The photopolymerization initiator is a component that generates radicals when irradiated with active energy rays, and is blended in order to cure the ink composition.
光重合開始剤は特に限定されない。一例を挙げると、光重合開始剤は、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、ビス－２，６－ジメトキシベンゾイル－２，４，４－トリメチルペンチルフォスフィンオキサイド、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、２，４，６－トリメチルベンジル－ジフェニルフォスフィンオキサイド、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－オン等である。
The photopolymerization initiator is not particularly limited. Examples of photopolymerization initiators include benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, and 2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butan-1-one.
光重合開始剤の含有量は特に限定されない。一例を挙げると、光重合開始剤の含有量は、インキ組成物中、１質量％以上であることが好ましく、２質量％以上であることがより好ましい。また、光重合開始剤の含有量は、インキ組成物中、２０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。光重合開始剤の含有量が上記範囲内であることにより、インキ組成物は、充分に硬化しやすい。
The content of the photopolymerization initiator is not particularly limited. As an example, the content of the photopolymerization initiator in the ink composition is preferably 1% by mass or more, and more preferably 2% by mass or more. Furthermore, the content of the photopolymerization initiator in the ink composition is preferably 20% by mass or less, and more preferably 15% by mass or less. When the content of the photopolymerization initiator is within the above range, the ink composition is sufficiently easy to cure.
（任意成分）
本実施形態のインキ組成物は、上記した顔料、ポリエステル樹脂、アクリレートモノマーおよび光重合開始剤のほか、体質顔料、ワックス、重合禁止剤、分散剤等の任意成分を含んでもよい。 (Optional ingredients)
The ink composition of the present embodiment may contain optional components such as an extender pigment, a wax, a polymerization inhibitor, a dispersant, etc., in addition to the above-mentioned pigment, polyester resin, acrylate monomer, and photopolymerization initiator.
本実施形態のインキ組成物は、上記した顔料、ポリエステル樹脂、アクリレートモノマーおよび光重合開始剤のほか、体質顔料、ワックス、重合禁止剤、分散剤等の任意成分を含んでもよい。 (Optional ingredients)
The ink composition of the present embodiment may contain optional components such as an extender pigment, a wax, a polymerization inhibitor, a dispersant, etc., in addition to the above-mentioned pigment, polyester resin, acrylate monomer, and photopolymerization initiator.
体質顔料は、インキ組成物に粘弾性を付与したり、流動性を調整したり、ミスチングを防止する等のために、好適に含まれる。
The extender pigment is preferably included to impart viscoelasticity to the ink composition, adjust the flowability, prevent misting, etc.
体質顔料は特に限定されない。一例を挙げると、体質顔料は、クレー、タルク、マイカ、カオリナイト（カオリン）、硫酸バリウム、硫酸マグネシウム、炭酸カルシウム、酸化ケイ素、酸化アルミニウム、ベントナイト、重質炭酸カルシウム、炭酸バリウム、ジルコニア、アルミナ等である。
The extender pigment is not particularly limited. Examples of extender pigments include clay, talc, mica, kaolinite (kaolin), barium sulfate, magnesium sulfate, calcium carbonate, silicon oxide, aluminum oxide, bentonite, ground calcium carbonate, barium carbonate, zirconia, alumina, etc.
体質顔料が含まれる場合において、体質顔料の含有量は特に限定されない。一例を挙げると、体質顔料の含有量は、インキ組成物中、０質量％を超えることが好ましく、１質量％以上であることがより好ましい。また、体質顔料の含有量は、インキ組成物中、３０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。体質顔料の含有量が上記範囲内であることにより、インキ組成物は、粘弾性、流動性が調整されやすく、ミスチングが防がれやすい。
When an extender pigment is included, the content of the extender pigment is not particularly limited. As an example, the content of the extender pigment in the ink composition is preferably greater than 0 mass%, and more preferably 1 mass% or more. The content of the extender pigment in the ink composition is preferably 30 mass% or less, and more preferably 15 mass% or less. By having the content of the extender pigment within the above range, the viscoelasticity and fluidity of the ink composition can be easily adjusted, and misting can be easily prevented.
ワックスは特に限定されない。一例を挙げると、ワックスは、ポリエチレン系ワックス、オレフィン系ワックス、フィッシャートロプシュワックス等のワックス類である。
The wax is not particularly limited. For example, the wax may be a polyethylene wax, an olefin wax, a Fischer-Tropsch wax, or the like.
ワックスが含まれる場合において、ワックスの含有量は特に限定されない。一例を挙げると、ワックスの含有量は、インキ組成物中、０質量％を超えることが好ましく、１質量％以上であることがより好ましい。また、ワックスの含有量は、インキ組成物中、３０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。
When wax is included, the wax content is not particularly limited. As an example, the wax content in the ink composition is preferably greater than 0 mass%, and more preferably 1 mass% or more. The wax content in the ink composition is preferably 30 mass% or less, and more preferably 15 mass% or less.
重合禁止剤は特に限定されない。一例を挙げると、重合禁止剤は、ブチルヒドロキシトルエン等のフェノール化合物、酢酸トコフェロール、ニトロソアミン、ベンゾトリアゾール、ヒンダードアミン等である。
The polymerization inhibitor is not particularly limited. Examples of the polymerization inhibitor include phenolic compounds such as butylhydroxytoluene, tocopherol acetate, nitrosamines, benzotriazoles, hindered amines, etc.
重合禁止剤が含まれる場合において、重合禁止剤の含有量は特に限定されない。一例を挙げると、重合禁止剤の含有量は、インキ組成物中、０質量％を超えることが好ましく、０．１質量％以上であることがより好ましい。また、重合禁止剤の含有量は、インキ組成物中、１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。
When a polymerization inhibitor is included, the content of the polymerization inhibitor is not particularly limited. As an example, the content of the polymerization inhibitor in the ink composition is preferably greater than 0 mass%, and more preferably 0.1 mass% or more. In addition, the content of the polymerization inhibitor in the ink composition is preferably 10 mass% or less, and more preferably 5 mass% or less.
分散剤は特に限定されない。一例を挙げると、分散剤は、カルボジイミド系分散剤、ポリエステルアミン系分散剤、脂肪酸アミン系分散剤、変性ポリアクリレート系分散剤、変性ポリウレタン系分散剤、多鎖型高分子非イオン系分散剤、高分子イオン活性剤等である。
The dispersant is not particularly limited. Examples of the dispersant include carbodiimide-based dispersants, polyester amine-based dispersants, fatty acid amine-based dispersants, modified polyacrylate-based dispersants, modified polyurethane-based dispersants, multi-chain polymeric nonionic dispersants, polymeric ionic surfactants, etc.
分散剤が含まれる場合において、分散剤の含有量は特に限定されない。一例を挙げると、分散剤の含有量は、着色剤を１００質量％とした場合において、１～２００質量％であることが好ましい。
When a dispersant is included, the content of the dispersant is not particularly limited. As an example, the content of the dispersant is preferably 1 to 200% by mass, assuming that the colorant is 100% by mass.
本実施形態のインキ組成物の調製方法は特に限定されない。一例を挙げると、インキ組成物は、ロールミル、ボールミル、ビーズミルなどを用いて、常法によって調製することができる。
The method for preparing the ink composition of this embodiment is not particularly limited. As an example, the ink composition can be prepared by a conventional method using a roll mill, a ball mill, a bead mill, or the like.
＜印刷物＞
本発明の一実施形態の印刷物は、上記実施形態の活性エネルギー線硬化型インキ組成物が、基材に印刷された、印刷物である。以下、一例として、金属板またはベースコート層を設けた金属基材に、上記したインキ組成物が印刷されて形成された皮膜とからなる印刷物について説明する。 <Printed materials>
A printed matter according to one embodiment of the present invention is a printed matter in which the active energy ray-curable ink composition according to the above embodiment is printed on a substrate. Hereinafter, as an example, a printed matter consisting of a coating formed by printing the ink composition on a metal plate or a metal substrate provided with a base coat layer will be described.
本発明の一実施形態の印刷物は、上記実施形態の活性エネルギー線硬化型インキ組成物が、基材に印刷された、印刷物である。以下、一例として、金属板またはベースコート層を設けた金属基材に、上記したインキ組成物が印刷されて形成された皮膜とからなる印刷物について説明する。 <Printed materials>
A printed matter according to one embodiment of the present invention is a printed matter in which the active energy ray-curable ink composition according to the above embodiment is printed on a substrate. Hereinafter, as an example, a printed matter consisting of a coating formed by printing the ink composition on a metal plate or a metal substrate provided with a base coat layer will be described.
上記実施形態のインキ組成物は、金属基材等の基材に印刷されて、皮膜を形成する。金属基材は特に限定されない。一例を挙げると、金属板は、ステンレススチール、アルミニウム、錫メッキ鋼板、ティンフリースチール等の金属基材、または、これらの金属基材上にベースコート（プライマー）層を設けた金属下地板等である。ベースコート層の形成には、たとえば金属印刷において一般的に用いられるサイズ塗料やホワイトコーティングなどのベースコート用組成物が用いられてもよい。また、金属基材は、ＰＥＴフィルムがラミネート処理されていてもよい。
The ink composition of the above embodiment is printed on a substrate such as a metal substrate to form a film. The metal substrate is not particularly limited. As an example, the metal plate may be a metal substrate such as stainless steel, aluminum, tin-plated steel, or tin-free steel, or a metal base plate having a base coat (primer) layer provided on the metal substrate. A base coat composition such as a size paint or white coating that is commonly used in metal printing may be used to form the base coat layer. The metal substrate may also be laminated with a PET film.
金属基材に本実施形態のインキ組成物を印刷する方法は特に限定されない。一例を挙げると、印刷方法は、湿し水を利用したオフセット方式、ドライオフセット方式等の通常の印刷方式である。
The method for printing the ink composition of this embodiment on a metal substrate is not particularly limited. For example, the printing method is a normal printing method such as an offset method using dampening water or a dry offset method.
得られるインキ皮膜の膜厚は特に限定されない。一例を挙げると、インキ皮膜の膜厚は、０．１～６μｍである。
There are no particular limitations on the thickness of the resulting ink film. For example, the ink film may have a thickness of 0.1 to 6 μm.
インキ組成物を硬化する条件は特に限定されない。活性エネルギー線硬化反応に用いる活性エネルギー線は、紫外線や電子線等である。紫外線の光源は、キセノンランプ、高圧水銀灯、メタルハライドランプ、ガリウムランプ、紫外線発光ダイオード（ＵＶ－ＬＥＤ）、紫外線レーザーダイオード（ＵＶ－ＬＤ）などが挙げられ、これらの光源を有する紫外線照射装置などが利用できる。なお、光量や光源配置、搬送速度等は必要に応じて調整され得る。高圧水銀灯を使用する場合には、８０～１６０Ｗ／ｃｍ程度の光量を有するランプ１灯に対して搬送速度２～１００ｍ／分程度で硬化させるのが好ましい。一方、電子線の場合には、１０～３００ｋＶ程度の加速電圧を有する電子線加速装置により、搬送速度５～５０ｍ／分程度の条件で硬化させるのが好ましい。
The conditions for curing the ink composition are not particularly limited. The active energy rays used in the active energy ray curing reaction are ultraviolet rays, electron beams, etc. Examples of ultraviolet light sources include xenon lamps, high-pressure mercury lamps, metal halide lamps, gallium lamps, ultraviolet light-emitting diodes (UV-LEDs), ultraviolet laser diodes (UV-LDs), etc., and ultraviolet irradiation devices having these light sources can be used. The light quantity, light source arrangement, transport speed, etc. can be adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a transport speed of about 2 to 100 m/min for one lamp with a light quantity of about 80 to 160 W/cm. On the other hand, in the case of electron beams, it is preferable to cure at a transport speed of about 5 to 50 m/min using an electron beam accelerator with an acceleration voltage of about 10 to 300 kV.
インキ層上には、熱硬化性トップコート用ニス層が形成されてもよい。熱硬化性トップコート用ニス層は、任意の水性型、溶剤型の熱硬化性トップコート用ニスが例示できる。市販で入手可能な溶剤型熱硬化性トップコート用ニスとしては、トーヨーケム（株）製のポリエステル／アミノ系トップコート用ニスなどがある。
A layer of thermosetting topcoat varnish may be formed on the ink layer. The layer of thermosetting topcoat varnish may be any water-based or solvent-based thermosetting topcoat varnish. Commercially available solvent-based thermosetting topcoat varnishes include polyester/amino-based topcoat varnishes manufactured by Toyochem Co., Ltd.
本実施形態の印刷物は、上記したインキ組成物からなる皮膜が形成されている。そのため、このようなニス層が設けられることなく、平積みされる場合であっても、皮膜が、別の印刷物の裏面に写りにくく、耐ブロッキング性が優れる。
The printed matter of this embodiment is formed with a film made of the ink composition described above. Therefore, even if the printed matter is stacked flat without such a varnish layer, the film is unlikely to transfer onto the back of another printed matter, and blocking resistance is excellent.
ニス層を形成する方法は特に限定されない。一例を挙げると、ニス層は、ロールコーター塗装された後、１５０℃～２５０℃で５秒～１５分間加熱乾燥されることによって、外観、硬度、加工性、レトルト耐性に優れる塗膜を形成することができる。
The method for forming the varnish layer is not particularly limited. As an example, the varnish layer is applied with a roll coater, and then heated and dried at 150°C to 250°C for 5 seconds to 15 minutes, forming a coating film that is excellent in appearance, hardness, processability, and retort resistance.
ニス層が形成される場合、ニス層の厚みは特に限定されない。一例を挙げると、ニス層の厚みは、３μｍ以上であることが好ましい。また、ニス層の厚みは、１０μｍ以下であることが好ましい。ニス層の厚みが上記範囲内であることにより、印刷物は、ＤＲ缶を作製する際の打ち抜き加工等において、クラックを生じにくく、レトルト処理後の白化が抑制される。
When a varnish layer is formed, the thickness of the varnish layer is not particularly limited. As an example, the thickness of the varnish layer is preferably 3 μm or more. Also, the thickness of the varnish layer is preferably 10 μm or less. By having the thickness of the varnish layer within the above range, the printed matter is less likely to crack during punching processes, etc., when producing DR cans, and whitening after retort processing is suppressed.
このように、上記実施形態のインキ組成物は、ＤＲ缶を作製する際の加工性が優れ、クラックや、熱水レトルト処理後の白化を生じにくい。そのため、金属印刷用として好適であり、特にＤＲ缶への金属印刷用として好適である。
As described above, the ink composition of the above embodiment has excellent processability when producing drop-resistant cans, and is less likely to crack or turn white after hot water retort treatment. Therefore, it is suitable for printing on metal, and is particularly suitable for printing on metal on drop-resistant cans.
以上、本実施形態のインキ組成物によれば、得られる印刷物は、ＤＲ缶用途に使用可能な優れた加工性を有し、ニスを塗工しなくても、平積みすることのできる耐ブロッキング性を有する。
As described above, the ink composition of this embodiment provides printed matter that has excellent processability that makes it suitable for use in drip cans, and has blocking resistance that allows it to be stacked flat without the need for a varnish coating.
以上、本発明の一実施形態について説明した。本発明は、上記実施形態に格別限定されない。なお、上記した実施形態は、以下の構成を有する発明を主に説明するものである。
The above describes one embodiment of the present invention. The present invention is not particularly limited to the above embodiment. Note that the above embodiment mainly describes an invention having the following configuration.
（１）顔料と、ポリエステル樹脂と、アクリレートモノマーと、光重合開始剤とを含み、前記アクリレートモノマーは、イソシアヌレート環を有するアクリレートモノマーと、２官能のアクリレートと、単官能のアクリレートとを含み、前記イソシアヌレート環を有するアクリレートモノマーの含有量は、アクリレートモノマー全量中、２５～５０質量％であり、前記単官能のアクリレートの含有量は、アクリレートモノマー全量中、８～３０質量％であり、前記単官能のアクリレートの含有量と、前記２官能のアクリレートの含有量との合計は、アクリレートモノマー全量中、３０～７５質量％である、活性エネルギー線硬化型インキ組成物。
(1) An active energy ray curable ink composition comprising a pigment, a polyester resin, an acrylate monomer, and a photopolymerization initiator, the acrylate monomer comprising an acrylate monomer having an isocyanurate ring, a bifunctional acrylate, and a monofunctional acrylate, the content of the acrylate monomer having an isocyanurate ring being 25-50% by mass in the total amount of the acrylate monomer, the content of the monofunctional acrylate being 8-30% by mass in the total amount of the acrylate monomer, and the sum of the content of the monofunctional acrylate and the content of the bifunctional acrylate being 30-75% by mass in the total amount of the acrylate monomer.
このような構成によれば、活性エネルギー線硬化型インキ組成物を用いて得られる印刷物は、ＤＲ缶用途に使用可能な優れた加工性を有し、ニスを塗工しなくても、平積みすることのできる耐ブロッキング性を有する。
With this configuration, the printed matter obtained using the active energy ray-curable ink composition has excellent processability that allows it to be used in drip can applications, and has blocking resistance that allows it to be stacked flat without the need for a varnish coating.
（２）前記ポリエステル樹脂の水酸基過剰率は、１．０以上である、（１）記載の活性エネルギー線硬化型インキ組成物。
(2) The active energy ray-curable ink composition according to (1), wherein the hydroxyl excess rate of the polyester resin is 1.0 or more.
このような構成によれば、活性エネルギー線硬化型インキ組成物を用いて得られる印刷物は、熱水レトルト耐性がより優れる。その結果、得られるＤＲ缶は、より白化を生じにくく、グロスの低下が起こりにくい。
With this configuration, the printed matter obtained using the active energy ray-curable ink composition has better hot water retort resistance. As a result, the resulting DR can is less susceptible to whitening and less prone to loss of gloss.
（３）金属印刷用である、（１）または（２）記載の活性エネルギー線硬化型インキ組成物。
(3) An active energy ray-curable ink composition according to (1) or (2) for use in metal printing.
このような構成によれば、活性エネルギー線硬化型インキ組成物を用いて得られる印刷物は、ＤＲ缶用途において特に好適である。
With this configuration, printed matter obtained using the active energy ray-curable ink composition is particularly suitable for use in drip cans.
（４）（１）～（３）のいずれかに記載の活性エネルギー線硬化型インキ組成物が、基材に印刷された、印刷物。
(4) A printed matter in which the active energy ray-curable ink composition described in any one of (1) to (3) is printed on a substrate.
このような構成によれば、印刷物は、ＤＲ缶用途に使用可能な優れた加工性を有し、ニスを塗工しなくても、平積みすることのできる耐ブロッキング性を有する。
With this configuration, the printed matter has excellent workability that allows it to be used for drip cans, and it has blocking resistance that allows it to be stacked flat even without being coated with varnish.
以下、実施例と比較例とにより本発明をより詳細に説明する。本発明は、これら実施例に限定されない。なお、表中の各数値は質量％基準によるものである。
The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to these examples. Note that the values in the table are based on mass %.
使用した原料は、以下の通りである。
＜顔料＞
ＬＩＯＮＯＬ ＢＬＵＥ ＦＧ－７３５１：Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：３、トーヨーカラー（株）製
＜ポリエステル樹脂合成用の酸およびアルコール＞
テトラヒドロ無水フタル酸：リカシッドＴＨ、１５２ｇ／ｍｏｌ、価数２、新日本理化（株）製
水添ビスフェノールＡ：リカビノールＨＢ、２４０ｇ／ｍｏｌ、価数２、新日本理化（株）製
１，６ヘキサンジオール：１，６ヘキサンジオール、１１８ｇ／ｍｏｌ、価数２、ＵＢＥ（株）製
＜アクリレートモノマー＞
アロニックス Ｍ－４０８：ジトリメチロールプロパンテトラアクリレート、４官能アクリレート、東亞合成（株）製
ＯＴＡ４８０：グリセリンＰＯ変性トリアクリレート、３官能アクリレート、ダイセル・オルネクス（株）製
Ｌａｒｏｍｅｒ ＬＲ ８８６３：トリメチロールプロパンＥＯ変性トリアクリレート、３官能アクリレート、ＢＡＳＦ社製
ＭＩＲＡＭＥＲ Ｍ３７０：イソシアヌル酸ＥＯ変性トリアクリレート（＞９９．９％）、イソシアヌレート環を有するアクリレートモノマー、ＭＩＷＯＮ ＳＰＥＣＩＡＬＴＹ ＣＨＥＭＩＣＡＬ社製
アロニックス Ｍ－３１５：イソシアヌル酸ＥＯ変性トリアクリレートおよびジアクリレート（ジアクリレート比率：３～１３％）、イソシアヌレート環を有するアクリレートモノマー、東亞合成（株）製
ＭＩＲＡＭＥＲ Ｍ２１６：ネオペンチルグリコールＰＯ変性ジアクリレート、２官能アクリレート、ＭＩＷＯＮ ＳＰＥＣＩＡＬＴＹ ＣＨＥＭＩＣＡＬ社製
ＫＡＹＡＲＡＤ ＨＸ２２０：カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールエステルジアクリレート、２官能アクリレート、日本化薬（株）製
ユピマーＵＶ ＳＡ－１００２Ｎ：トリシクロデカンジメタノールジアクリレート、２官能アクリレート、三菱化学（株）製
アロニックスＭ－１０１Ａ：フェノールＥＯ変性アクリレート、単官能アクリレート、東亞合成（株）製
ＭＩＲＡＭＥＲ Ｍ１１４０：イソボルニルアクリレート、単官能アクリレート、ＭＩＷＯＮ ＳＰＥＣＩＡＬＴＹ ＣＨＥＭＩＣＡＬ社製
ＭＩＲＡＭＥＲ Ｍ１５０：テトラヒドロフルフリルアクリレート、単官能アクリレート、ＭＩＷＯＮ ＳＰＥＣＩＡＬＴＹ ＣＨＥＭＩＣＡＬ社製
＜光重合開始剤＞
Ｏｍｎｉｒａｄ ３７９：２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、ＩＧＭ Ｒｅｓｉｎｓ社製
Ｏｍｎｉｒａｄ ＥＭＫ：４，４－ビス（ジエチルアミノ）ベンゾフェノン、ＩＧＭ Ｒｅｓｉｎｓ社製
Ｏｍｎｉｒａｄ ＤＥＴＸ：２，４－ジエチルチオキサントン、ＩＧＭ Ｒｅｓｉｎｓ社製
＜添加剤＞
ＳＳＴ－３Ｔ１－ＲＣ：ポリテトラフルオロエチレン、Ｓｈａｍｒｏｃｋ社製 The raw materials used are as follows:
<Pigments>
LIONOL BLUE FG-7351: Pigment Blue 15:3, manufactured by Toyo Color Co., Ltd. <Acid and alcohol for polyester resin synthesis>
Tetrahydrophthalic anhydride: Rikacid TH, 152 g/mol, valence 2, manufactured by New Japan Chemical Co., Ltd. Hydrogenated bisphenol A: Rikabinol HB, 240 g/mol, valence 2, manufactured by New Japan Chemical Co., Ltd. 1,6 hexanediol: 1,6 hexanediol, 118 g/mol, valence 2, manufactured by UBE Co., Ltd. <Acrylate monomer>
ARONIX M-408: ditrimethylolpropane tetraacrylate, tetrafunctional acrylate, manufactured by Toagosei Co., Ltd. OTA480: glycerin PO modified triacrylate, trifunctional acrylate, manufactured by Daicel Allnex Co., Ltd. Laromer LR 8863: trimethylolpropane EO modified triacrylate, trifunctional acrylate, manufactured by BASF Corporation MIRAMER M370: isocyanuric acid EO modified triacrylate (>99.9%), acrylate monomer having an isocyanurate ring, manufactured by MIWON SPECIALTY CHEMICAL Co., Ltd. ARONIX M-315: isocyanuric acid EO modified triacrylate and diacrylate (diacrylate ratio: 3 to 13%), acrylate monomer having an isocyanurate ring, MIRAMER manufactured by Toagosei Co., Ltd. M216: Neopentyl glycol PO modified diacrylate, bifunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL KAYARAD HX220: Caprolactone modified hydroxypivalic acid neopentyl glycol ester diacrylate, bifunctional acrylate, manufactured by Nippon Kayaku Co., Ltd. Iupimer UV SA-1002N: Tricyclodecane dimethanol diacrylate, bifunctional acrylate, manufactured by Mitsubishi Chemical Co., Ltd. ARONIX M-101A: Phenol EO modified acrylate, monofunctional acrylate, manufactured by Toagosei Co., Ltd. MIRAMER M1140: Isobornyl acrylate, monofunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL MIRAMER M150: Tetrahydrofurfuryl acrylate, monofunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL Co., Ltd. <Photopolymerization initiator>
Omnirad 379: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, manufactured by IGM Resins Omnirad EMK: 4,4-bis(diethylamino)benzophenone, manufactured by IGM Resins Omnirad DETX: 2,4-diethylthioxanthone, manufactured by IGM Resins <Additives>
SST-3T1-RC: Polytetrafluoroethylene, manufactured by Shamrock
＜顔料＞
ＬＩＯＮＯＬ ＢＬＵＥ ＦＧ－７３５１：Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：３、トーヨーカラー（株）製
＜ポリエステル樹脂合成用の酸およびアルコール＞
テトラヒドロ無水フタル酸：リカシッドＴＨ、１５２ｇ／ｍｏｌ、価数２、新日本理化（株）製
水添ビスフェノールＡ：リカビノールＨＢ、２４０ｇ／ｍｏｌ、価数２、新日本理化（株）製
１，６ヘキサンジオール：１，６ヘキサンジオール、１１８ｇ／ｍｏｌ、価数２、ＵＢＥ（株）製
＜アクリレートモノマー＞
アロニックス Ｍ－４０８：ジトリメチロールプロパンテトラアクリレート、４官能アクリレート、東亞合成（株）製
ＯＴＡ４８０：グリセリンＰＯ変性トリアクリレート、３官能アクリレート、ダイセル・オルネクス（株）製
Ｌａｒｏｍｅｒ ＬＲ ８８６３：トリメチロールプロパンＥＯ変性トリアクリレート、３官能アクリレート、ＢＡＳＦ社製
ＭＩＲＡＭＥＲ Ｍ３７０：イソシアヌル酸ＥＯ変性トリアクリレート（＞９９．９％）、イソシアヌレート環を有するアクリレートモノマー、ＭＩＷＯＮ ＳＰＥＣＩＡＬＴＹ ＣＨＥＭＩＣＡＬ社製
アロニックス Ｍ－３１５：イソシアヌル酸ＥＯ変性トリアクリレートおよびジアクリレート（ジアクリレート比率：３～１３％）、イソシアヌレート環を有するアクリレートモノマー、東亞合成（株）製
ＭＩＲＡＭＥＲ Ｍ２１６：ネオペンチルグリコールＰＯ変性ジアクリレート、２官能アクリレート、ＭＩＷＯＮ ＳＰＥＣＩＡＬＴＹ ＣＨＥＭＩＣＡＬ社製
ＫＡＹＡＲＡＤ ＨＸ２２０：カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールエステルジアクリレート、２官能アクリレート、日本化薬（株）製
ユピマーＵＶ ＳＡ－１００２Ｎ：トリシクロデカンジメタノールジアクリレート、２官能アクリレート、三菱化学（株）製
アロニックスＭ－１０１Ａ：フェノールＥＯ変性アクリレート、単官能アクリレート、東亞合成（株）製
ＭＩＲＡＭＥＲ Ｍ１１４０：イソボルニルアクリレート、単官能アクリレート、ＭＩＷＯＮ ＳＰＥＣＩＡＬＴＹ ＣＨＥＭＩＣＡＬ社製
ＭＩＲＡＭＥＲ Ｍ１５０：テトラヒドロフルフリルアクリレート、単官能アクリレート、ＭＩＷＯＮ ＳＰＥＣＩＡＬＴＹ ＣＨＥＭＩＣＡＬ社製
＜光重合開始剤＞
Ｏｍｎｉｒａｄ ３７９：２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、ＩＧＭ Ｒｅｓｉｎｓ社製
Ｏｍｎｉｒａｄ ＥＭＫ：４，４－ビス（ジエチルアミノ）ベンゾフェノン、ＩＧＭ Ｒｅｓｉｎｓ社製
Ｏｍｎｉｒａｄ ＤＥＴＸ：２，４－ジエチルチオキサントン、ＩＧＭ Ｒｅｓｉｎｓ社製
＜添加剤＞
ＳＳＴ－３Ｔ１－ＲＣ：ポリテトラフルオロエチレン、Ｓｈａｍｒｏｃｋ社製 The raw materials used are as follows:
<Pigments>
LIONOL BLUE FG-7351: Pigment Blue 15:3, manufactured by Toyo Color Co., Ltd. <Acid and alcohol for polyester resin synthesis>
Tetrahydrophthalic anhydride: Rikacid TH, 152 g/mol, valence 2, manufactured by New Japan Chemical Co., Ltd. Hydrogenated bisphenol A: Rikabinol HB, 240 g/mol, valence 2, manufactured by New Japan Chemical Co., Ltd. 1,6 hexanediol: 1,6 hexanediol, 118 g/mol, valence 2, manufactured by UBE Co., Ltd. <Acrylate monomer>
ARONIX M-408: ditrimethylolpropane tetraacrylate, tetrafunctional acrylate, manufactured by Toagosei Co., Ltd. OTA480: glycerin PO modified triacrylate, trifunctional acrylate, manufactured by Daicel Allnex Co., Ltd. Laromer LR 8863: trimethylolpropane EO modified triacrylate, trifunctional acrylate, manufactured by BASF Corporation MIRAMER M370: isocyanuric acid EO modified triacrylate (>99.9%), acrylate monomer having an isocyanurate ring, manufactured by MIWON SPECIALTY CHEMICAL Co., Ltd. ARONIX M-315: isocyanuric acid EO modified triacrylate and diacrylate (diacrylate ratio: 3 to 13%), acrylate monomer having an isocyanurate ring, MIRAMER manufactured by Toagosei Co., Ltd. M216: Neopentyl glycol PO modified diacrylate, bifunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL KAYARAD HX220: Caprolactone modified hydroxypivalic acid neopentyl glycol ester diacrylate, bifunctional acrylate, manufactured by Nippon Kayaku Co., Ltd. Iupimer UV SA-1002N: Tricyclodecane dimethanol diacrylate, bifunctional acrylate, manufactured by Mitsubishi Chemical Co., Ltd. ARONIX M-101A: Phenol EO modified acrylate, monofunctional acrylate, manufactured by Toagosei Co., Ltd. MIRAMER M1140: Isobornyl acrylate, monofunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL MIRAMER M150: Tetrahydrofurfuryl acrylate, monofunctional acrylate, manufactured by MIWON SPECIALTY CHEMICAL Co., Ltd. <Photopolymerization initiator>
Omnirad 379: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, manufactured by IGM Resins Omnirad EMK: 4,4-bis(diethylamino)benzophenone, manufactured by IGM Resins Omnirad DETX: 2,4-diethylthioxanthone, manufactured by IGM Resins <Additives>
SST-3T1-RC: Polytetrafluoroethylene, manufactured by Shamrock
＜樹脂１の調製＞
攪拌機、水分離器付き還流冷却器、および温度計を備えた４つ口フラスコに、テトラヒドロ無水フタル酸：３４．５質量％、水添ビスフェノールＡ：６０．３質量％、１、６ヘキサンジオール：５．２質量％を仕込み、窒素ガスを吹き込みながら、２２０℃で常法にてエステル化し、酸価１５．１、重量平均分子量１８３４のポリエステル樹脂（樹脂１）を得た。得られた樹脂１の水酸基過剰率は１．３であった。
＜樹脂２の調製＞
攪拌機、水分離器付き還流冷却器、および温度計を備えた４つ口フラスコに、テトラヒドロ無水フタル酸：２８．７質量％、水添ビスフェノールＡ：６５．６質量％、１、６ヘキサンジオール：５．７質量％を仕込み、窒素ガスを吹き込みながら、２２０℃で常法にてエステル化し、酸価１２．５、重量平均分子量１０６９のポリエステル樹脂（樹脂２）を得た。得られた樹脂２の水酸基過剰率は１．７であった。
＜樹脂３の調製＞
攪拌機、水分離器付き還流冷却器、および温度計を備えた４つ口フラスコに、テトラヒドロ無水フタル酸：４３．３質量％、水添ビスフェノールＡ：５２．２質量％、１、６ヘキサンジオール：４．５質量％を仕込み、窒素ガスを吹き込みながら、２２０℃で常法にてエステル化し、酸価６５．０、重量平均分子量２７６７のポリエステル樹脂（樹脂１）を得た。得られた樹脂３の水酸基過剰率は０．９であった。 <Preparation of Resin 1>
A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 34.5% by mass of tetrahydrophthalic anhydride, 60.3% by mass of hydrogenated bisphenol A, and 5.2% by mass of 1,6-hexanediol, and esterification was carried out in a conventional manner at 220° C. while blowing in nitrogen gas, to obtain a polyester resin (resin 1) having an acid value of 15.1 and a weight average molecular weight of 1834. The hydroxyl excess ratio of the obtained resin 1 was 1.3.
<Preparation of Resin 2>
A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 28.7% by mass of tetrahydrophthalic anhydride, 65.6% by mass of hydrogenated bisphenol A, and 5.7% by mass of 1,6-hexanediol, and esterification was carried out in a conventional manner at 220° C. while blowing in nitrogen gas, to obtain a polyester resin (resin 2) having an acid value of 12.5 and a weight average molecular weight of 1069. The hydroxyl excess ratio of the obtained resin 2 was 1.7.
<Preparation of Resin 3>
A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 43.3% by mass of tetrahydrophthalic anhydride, 52.2% by mass of hydrogenated bisphenol A, and 4.5% by mass of 1,6-hexanediol, and esterification was carried out in a conventional manner at 220° C. while blowing in nitrogen gas, to obtain a polyester resin (resin 1) having an acid value of 65.0 and a weight average molecular weight of 2767. The hydroxyl excess ratio of the obtained resin 3 was 0.9.
攪拌機、水分離器付き還流冷却器、および温度計を備えた４つ口フラスコに、テトラヒドロ無水フタル酸：３４．５質量％、水添ビスフェノールＡ：６０．３質量％、１、６ヘキサンジオール：５．２質量％を仕込み、窒素ガスを吹き込みながら、２２０℃で常法にてエステル化し、酸価１５．１、重量平均分子量１８３４のポリエステル樹脂（樹脂１）を得た。得られた樹脂１の水酸基過剰率は１．３であった。
＜樹脂２の調製＞
攪拌機、水分離器付き還流冷却器、および温度計を備えた４つ口フラスコに、テトラヒドロ無水フタル酸：２８．７質量％、水添ビスフェノールＡ：６５．６質量％、１、６ヘキサンジオール：５．７質量％を仕込み、窒素ガスを吹き込みながら、２２０℃で常法にてエステル化し、酸価１２．５、重量平均分子量１０６９のポリエステル樹脂（樹脂２）を得た。得られた樹脂２の水酸基過剰率は１．７であった。
＜樹脂３の調製＞
攪拌機、水分離器付き還流冷却器、および温度計を備えた４つ口フラスコに、テトラヒドロ無水フタル酸：４３．３質量％、水添ビスフェノールＡ：５２．２質量％、１、６ヘキサンジオール：４．５質量％を仕込み、窒素ガスを吹き込みながら、２２０℃で常法にてエステル化し、酸価６５．０、重量平均分子量２７６７のポリエステル樹脂（樹脂１）を得た。得られた樹脂３の水酸基過剰率は０．９であった。 <Preparation of Resin 1>
A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 34.5% by mass of tetrahydrophthalic anhydride, 60.3% by mass of hydrogenated bisphenol A, and 5.2% by mass of 1,6-hexanediol, and esterification was carried out in a conventional manner at 220° C. while blowing in nitrogen gas, to obtain a polyester resin (resin 1) having an acid value of 15.1 and a weight average molecular weight of 1834. The hydroxyl excess ratio of the obtained resin 1 was 1.3.
<Preparation of Resin 2>
A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 28.7% by mass of tetrahydrophthalic anhydride, 65.6% by mass of hydrogenated bisphenol A, and 5.7% by mass of 1,6-hexanediol, and esterification was carried out in a conventional manner at 220° C. while blowing in nitrogen gas, to obtain a polyester resin (resin 2) having an acid value of 12.5 and a weight average molecular weight of 1069. The hydroxyl excess ratio of the obtained resin 2 was 1.7.
<Preparation of Resin 3>
A four-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 43.3% by mass of tetrahydrophthalic anhydride, 52.2% by mass of hydrogenated bisphenol A, and 4.5% by mass of 1,6-hexanediol, and esterification was carried out in a conventional manner at 220° C. while blowing in nitrogen gas, to obtain a polyester resin (resin 1) having an acid value of 65.0 and a weight average molecular weight of 2767. The hydroxyl excess ratio of the obtained resin 3 was 0.9.
＜実施例１＞
表１に記載の処方に従い、各成分を混合した後、４０℃に加熱した３本ロールミルにて練肉攪拌することにより、実施例１のインキ組成物を調製した。得られたインキ組成物について、以下の評価方法により、加工性、耐ブロッキング性、析出の有無、白化の有無を評価した。結果を表１に示す。 Example 1
The ink composition of Example 1 was prepared by mixing the components according to the recipe shown in Table 1 and milling and stirring them in a three-roll mill heated to 40° C. The ink composition obtained was evaluated for processability, blocking resistance, the presence or absence of precipitation, and the presence or absence of whitening by the following evaluation methods. The results are shown in Table 1.
表１に記載の処方に従い、各成分を混合した後、４０℃に加熱した３本ロールミルにて練肉攪拌することにより、実施例１のインキ組成物を調製した。得られたインキ組成物について、以下の評価方法により、加工性、耐ブロッキング性、析出の有無、白化の有無を評価した。結果を表１に示す。 Example 1
The ink composition of Example 1 was prepared by mixing the components according to the recipe shown in Table 1 and milling and stirring them in a three-roll mill heated to 40° C. The ink composition obtained was evaluated for processability, blocking resistance, the presence or absence of precipitation, and the presence or absence of whitening by the following evaluation methods. The results are shown in Table 1.
＜実施例２～１６、比較例１～１６＞
表１～表２に記載の処方に変更した以外は、実施例１と同様の方法により、インキ組成物を調製し、評価した。結果を表１～表２に示す。 <Examples 2 to 16, Comparative Examples 1 to 16>
Ink compositions were prepared and evaluated in the same manner as in Example 1, except that the formulations were changed as shown in Tables 1 and 2. The results are shown in Tables 1 and 2.
表１～表２に記載の処方に変更した以外は、実施例１と同様の方法により、インキ組成物を調製し、評価した。結果を表１～表２に示す。 <Examples 2 to 16, Comparative Examples 1 to 16>
Ink compositions were prepared and evaluated in the same manner as in Example 1, except that the formulations were changed as shown in Tables 1 and 2. The results are shown in Tables 1 and 2.
評価に使用する金属板として、電気ブリキ板（新日鉄住金（株）製のＥＴ２．８／２．８ Ｔ２．５Ｂ）に、ポリエステル／アミノ系ベースコーティング（トーヨーケム（株）製）を塗膜量１４０ｍｇ／１００ｃｍ2で塗装し、１８０℃、１０分間焼付けしたベースコート層を設けた金属板を作成した。得られたインキを、ＲＩテスター（テスター産業（株）製）を用いて、上記金属板のベースコート層上に、膜厚１．５μｍになるように展色し、集光型メタルハライドランプ（アイグラフィックス（株）製、１２０Ｗ／ｃｍ）照射装置を用いて、印刷物との距離１１ｃｍ、コンベア速度３０ｍ／分で紫外線を印刷物に照射しインキを硬化させ、試験サンプルＡとした。また、同様の印刷条件で２度刷りした後に、ポリエステル／アミノ系トップコーティング（トーヨーケム（株）製）を塗布量７０ｍｇ／１００ｃｍ2で塗装し、１８０℃、１０分間焼付け、試験サンプルＢを作成した。得られた試験サンプルＡ、およびＢを用いて、以下の方法により評価を行なった。なお、ＲＩテスターとは、被記録媒体にインキを展色させる試験機であり、インキの転移量や印圧を調整することができる。
The metal plate used for the evaluation was prepared by coating an electric tinplate (ET2.8/2.8 T2.5B manufactured by Nippon Steel & Sumitomo Metal Corporation) with a polyester/amino-based base coating (manufactured by Toyochem Co., Ltd.) in a coating amount of 140 mg/ 100 cm2 and baking at 180°C for 10 minutes to prepare a base coat layer. The obtained ink was applied to the base coat layer of the metal plate using an RI tester (manufactured by Tester Sangyo Co., Ltd.) to a film thickness of 1.5 μm, and the ink was cured by irradiating the printed matter with ultraviolet light using a concentrating metal halide lamp (manufactured by Eye Graphics Co., Ltd., 120 W/cm) irradiation device at a distance of 11 cm from the printed matter and at a conveyor speed of 30 m/min, to prepare a test sample A. In addition, after printing twice under the same printing conditions, a polyester/amino-based top coating (manufactured by Toyochem Co., Ltd.) was applied in an amount of 70 mg/ 100 cm2 and baked at 180°C for 10 minutes to prepare test sample B. Using the obtained test samples A and B, evaluations were carried out by the following methods. Note that the RI tester is a test machine that spreads ink on a recording medium, and it is possible to adjust the amount of ink transferred and the printing pressure.
＜加工性＞
上記方法で作成した試験サンプルＢを、プレス加工により直径８０ｍｍ、高さ５０ｍｍの円筒状に打ち抜き、加工品を得た。得られた加工品を１２５℃の熱水に浸漬したまま９０分間滅菌処理を行い、その後、加工品側面の光沢低下を目視により以下の基準で評価した。○△以上を実用レベルと判断した。
（評価基準）
○：光沢低下が非常に小さかった。
○△：光沢低下は見られたが、ある程度光沢が残っていた。
△：光沢低下が大きかった。
×：光沢低下が非常に大きかった。
－：析出を生じたため、評価できなかった。 <Processability>
Test sample B prepared by the above method was punched out into a cylindrical shape with a diameter of 80 mm and a height of 50 mm by pressing to obtain a processed product. The processed product was sterilized for 90 minutes while immersed in hot water at 125°C, and then the gloss loss on the side surface of the processed product was visually evaluated according to the following criteria. A or better was judged to be at a practical level.
(Evaluation criteria)
A: The decrease in gloss was very small.
◯△: A decrease in gloss was observed, but some gloss remained.
Δ: The gloss was significantly reduced.
×: The gloss loss was very large.
-: Precipitation occurred and evaluation was not possible.
上記方法で作成した試験サンプルＢを、プレス加工により直径８０ｍｍ、高さ５０ｍｍの円筒状に打ち抜き、加工品を得た。得られた加工品を１２５℃の熱水に浸漬したまま９０分間滅菌処理を行い、その後、加工品側面の光沢低下を目視により以下の基準で評価した。○△以上を実用レベルと判断した。
（評価基準）
○：光沢低下が非常に小さかった。
○△：光沢低下は見られたが、ある程度光沢が残っていた。
△：光沢低下が大きかった。
×：光沢低下が非常に大きかった。
－：析出を生じたため、評価できなかった。 <Processability>
Test sample B prepared by the above method was punched out into a cylindrical shape with a diameter of 80 mm and a height of 50 mm by pressing to obtain a processed product. The processed product was sterilized for 90 minutes while immersed in hot water at 125°C, and then the gloss loss on the side surface of the processed product was visually evaluated according to the following criteria. A or better was judged to be at a practical level.
(Evaluation criteria)
A: The decrease in gloss was very small.
◯△: A decrease in gloss was observed, but some gloss remained.
Δ: The gloss was significantly reduced.
×: The gloss loss was very large.
-: Precipitation occurred and evaluation was not possible.
＜耐ブロッキング性＞
上記方法で作成した試験サンプルＡを３ｃｍ×５ｃｍにカットし、インキ皮膜の対面に同じ大きさにカットした電気ブリキ板を重ね、ブロッキングテスター（テスター産業（株）製）にて３ｋｇ／ｃｍ2の荷重をかけたまま４０℃の電気オーブンに１時間静置後取出し、対面の電気ブリキ板にインキが裏移りしているかどうかを目視により以下の基準で評価した。○△以上を実用レベルと判断した。
（評価基準）
○：裏移りしなかった。
○△：僅かに裏移りが確認できた。
△：明らかな裏移りが確認できた。
×：明らかな裏移りが確認でき、インキ皮膜の剥離が確認できた。
－：析出を生じたため、評価できなかった。 <Blocking resistance>
The test sample A prepared by the above method was cut to 3 cm x 5 cm, and an electric tinplate cut to the same size was placed on the opposite side of the ink film, and the sample was left to stand in an electric oven at 40°C for 1 hour while applying a load of 3 kg/ cm2 using a blocking tester (manufactured by Tester Sangyo Co., Ltd.), and then removed. The ink was visually checked to see whether it had transferred to the opposite electric tinplate, and evaluated according to the following criteria. Good or bad was judged to be at a practical level.
(Evaluation criteria)
○: No bleeding occurred.
◯△: Slight offset was observed.
△: Clear offset was observed.
×: Clear offset was observed, and peeling of the ink film was observed.
-: Precipitation occurred and evaluation was not possible.
上記方法で作成した試験サンプルＡを３ｃｍ×５ｃｍにカットし、インキ皮膜の対面に同じ大きさにカットした電気ブリキ板を重ね、ブロッキングテスター（テスター産業（株）製）にて３ｋｇ／ｃｍ2の荷重をかけたまま４０℃の電気オーブンに１時間静置後取出し、対面の電気ブリキ板にインキが裏移りしているかどうかを目視により以下の基準で評価した。○△以上を実用レベルと判断した。
（評価基準）
○：裏移りしなかった。
○△：僅かに裏移りが確認できた。
△：明らかな裏移りが確認できた。
×：明らかな裏移りが確認でき、インキ皮膜の剥離が確認できた。
－：析出を生じたため、評価できなかった。 <Blocking resistance>
The test sample A prepared by the above method was cut to 3 cm x 5 cm, and an electric tinplate cut to the same size was placed on the opposite side of the ink film, and the sample was left to stand in an electric oven at 40°C for 1 hour while applying a load of 3 kg/ cm2 using a blocking tester (manufactured by Tester Sangyo Co., Ltd.), and then removed. The ink was visually checked to see whether it had transferred to the opposite electric tinplate, and evaluated according to the following criteria. Good or bad was judged to be at a practical level.
(Evaluation criteria)
○: No bleeding occurred.
◯△: Slight offset was observed.
△: Clear offset was observed.
×: Clear offset was observed, and peeling of the ink film was observed.
-: Precipitation occurred and evaluation was not possible.
＜析出の有無＞
作製したインキについて、１０℃条件下にて２４０時間放置した後に、インキ中の析出物の有無を目視により以下の基準で評価した。
（評価基準）
○：析出物がなかった。
×：析出物があった。 <Presence or absence of precipitation>
The prepared ink was allowed to stand at 10° C. for 240 hours, and then the presence or absence of precipitates in the ink was visually observed and evaluated according to the following criteria.
(Evaluation criteria)
A: No precipitate was observed.
×: Precipitation was observed.
作製したインキについて、１０℃条件下にて２４０時間放置した後に、インキ中の析出物の有無を目視により以下の基準で評価した。
（評価基準）
○：析出物がなかった。
×：析出物があった。 <Presence or absence of precipitation>
The prepared ink was allowed to stand at 10° C. for 240 hours, and then the presence or absence of precipitates in the ink was visually observed and evaluated according to the following criteria.
(Evaluation criteria)
A: No precipitate was observed.
×: Precipitation was observed.
＜白化の有無＞
上記方法で作成した試験サンプルＢを１２５℃の熱水に浸漬したまま９０分間滅菌処理を行い、その後、塗膜表面の白化度合いを目視により以下の基準で評価した。○△以上を実用レベルと判断した。
（評価基準）
○：白化がなかった。
○△：僅かに白化があった。
△：明らかな白化が確認できた。
×：塗膜全体が完全に白化した。
－：析出を生じたため、評価できなかった。 <Whether or not bleaching occurs>
Test sample B prepared by the above method was immersed in hot water at 125° C. for 90 minutes for sterilization, and then the degree of whitening of the coating surface was visually evaluated according to the following criteria. A or better was judged to be at a practical level.
(Evaluation criteria)
○: No whitening occurred.
◯△: slight whitening was observed.
△: Obvious whitening was observed.
×: The entire coating film was completely whitened.
-: Precipitation occurred and evaluation was not possible.
上記方法で作成した試験サンプルＢを１２５℃の熱水に浸漬したまま９０分間滅菌処理を行い、その後、塗膜表面の白化度合いを目視により以下の基準で評価した。○△以上を実用レベルと判断した。
（評価基準）
○：白化がなかった。
○△：僅かに白化があった。
△：明らかな白化が確認できた。
×：塗膜全体が完全に白化した。
－：析出を生じたため、評価できなかった。 <Whether or not bleaching occurs>
Test sample B prepared by the above method was immersed in hot water at 125° C. for 90 minutes for sterilization, and then the degree of whitening of the coating surface was visually evaluated according to the following criteria. A or better was judged to be at a practical level.
(Evaluation criteria)
○: No whitening occurred.
◯△: slight whitening was observed.
△: Obvious whitening was observed.
×: The entire coating film was completely whitened.
-: Precipitation occurred and evaluation was not possible.
表１～表２に記載のとおり、本発明の実施例１～１６のインキ組成物は、析出を生じなかった。また、インキ組成物を用いた印刷物は、ＤＲ缶の用途に適した加工性を有し、熱水レトルト処理を行った場合であっても白化を生じにくかった。さらに、印刷物は、平積みした場合であっても裏写りがなく、耐ブロッキング性が優れた。
As shown in Tables 1 and 2, the ink compositions of Examples 1 to 16 of the present invention did not cause precipitation. In addition, printed matter using the ink compositions had processability suitable for use in drop-dryer cans, and was less susceptible to whitening even when subjected to hot water retort treatment. Furthermore, the printed matter did not show through even when stacked flat, and had excellent blocking resistance.
Claims (4)
- 顔料と、ポリエステル樹脂と、アクリレートモノマーと、光重合開始剤とを含み、
前記アクリレートモノマーは、イソシアヌレート環を有するアクリレートモノマーと、２官能のアクリレートと、単官能のアクリレートとを含み、
前記イソシアヌレート環を有するアクリレートモノマーの含有量は、アクリレートモノマー全量中、２５～５０質量％であり、
前記単官能のアクリレートの含有量は、アクリレートモノマー全量中、８～３０質量％であり、
前記単官能のアクリレートの含有量と、前記２官能のアクリレートの含有量との合計は、アクリレートモノマー全量中、３０～７５質量％である、活性エネルギー線硬化型インキ組成物。 A composition comprising a pigment, a polyester resin, an acrylate monomer, and a photopolymerization initiator,
The acrylate monomer includes an acrylate monomer having an isocyanurate ring, a difunctional acrylate, and a monofunctional acrylate,
The content of the acrylate monomer having an isocyanurate ring is 25 to 50 mass% based on the total amount of the acrylate monomers,
The content of the monofunctional acrylate is 8 to 30 mass% based on the total amount of the acrylate monomers,
an active energy ray-curable ink composition, wherein the total content of the monofunctional acrylate and the bifunctional acrylate is 30 to 75 mass % based on the total amount of the acrylate monomers. - 前記ポリエステル樹脂の水酸基過剰率は、１．０以上である、請求項１記載の活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition according to claim 1, wherein the hydroxyl excess rate of the polyester resin is 1.0 or more.
- 金属印刷用である、請求項１または２記載の活性エネルギー線硬化型インキ組成物。 The active energy ray-curable ink composition according to claim 1 or 2, which is for metal printing.
- 請求項１または２記載の活性エネルギー線硬化型インキ組成物が、基材に印刷された、印刷物。 A printed matter in which the active energy ray-curable ink composition according to claim 1 or 2 is printed on a substrate.
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| JP2022-155491 | 2022-09-28 | ||
| JP2022155491A JP7319506B1 (en) | 2022-09-28 | 2022-09-28 | Active energy ray-curable ink composition and printed matter |
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| Publication Number | Publication Date |
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| WO2024070376A1 true WO2024070376A1 (en) | 2024-04-04 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004514014A (en) * | 2000-11-09 | 2004-05-13 | スリーエム イノベイティブ プロパティズ カンパニー | Weather-resistant, ink-jettable, radiation-curable fluid compositions particularly suitable for outdoor applications |
| JP2010013528A (en) * | 2008-07-02 | 2010-01-21 | Toyobo Co Ltd | Polyester resin, photo curable-thermosetting resin composition, photo curable-thermosetting resin layer, ink, adhesive, and printed circuit board |
| JP2011127112A (en) * | 2009-12-18 | 2011-06-30 | Xerox Corp | Curable solid ink composition |
| WO2015115600A1 (en) * | 2014-01-31 | 2015-08-06 | 富士フイルム株式会社 | Inkjet ink composition for printing building materials, inkjet ink set for printing building materials, inkjet recording method, and decorative building materials |
| JP2020183463A (en) * | 2019-04-26 | 2020-11-12 | Ｋｊケミカルズ株式会社 | Active energy ray-curable resin composition |
-
2022
- 2022-09-28 JP JP2022155491A patent/JP7319506B1/en active Active
-
2023
- 2023-08-25 WO PCT/JP2023/030720 patent/WO2024070376A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004514014A (en) * | 2000-11-09 | 2004-05-13 | スリーエム イノベイティブ プロパティズ カンパニー | Weather-resistant, ink-jettable, radiation-curable fluid compositions particularly suitable for outdoor applications |
| JP2010013528A (en) * | 2008-07-02 | 2010-01-21 | Toyobo Co Ltd | Polyester resin, photo curable-thermosetting resin composition, photo curable-thermosetting resin layer, ink, adhesive, and printed circuit board |
| JP2011127112A (en) * | 2009-12-18 | 2011-06-30 | Xerox Corp | Curable solid ink composition |
| WO2015115600A1 (en) * | 2014-01-31 | 2015-08-06 | 富士フイルム株式会社 | Inkjet ink composition for printing building materials, inkjet ink set for printing building materials, inkjet recording method, and decorative building materials |
| JP2020183463A (en) * | 2019-04-26 | 2020-11-12 | Ｋｊケミカルズ株式会社 | Active energy ray-curable resin composition |
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| JP7319506B1 (en) | 2023-08-02 |
| JP2024049184A (en) | 2024-04-09 |
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