WO2022255110A1 - 活性エネルギー線硬化性インク組成物及び印刷物の製造方法 - Google Patents

活性エネルギー線硬化性インク組成物及び印刷物の製造方法 Download PDF

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Publication number
WO2022255110A1
WO2022255110A1 PCT/JP2022/020759 JP2022020759W WO2022255110A1 WO 2022255110 A1 WO2022255110 A1 WO 2022255110A1 JP 2022020759 W JP2022020759 W JP 2022020759W WO 2022255110 A1 WO2022255110 A1 WO 2022255110A1
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Prior art keywords
ink composition
meth
acrylate
active energy
energy ray
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Ceased
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PCT/JP2022/020759
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English (en)
French (fr)
Japanese (ja)
Inventor
直人 佐竹
怜美 藤本
直人 齊藤
啓之 福井
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DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to EP22815862.2A priority Critical patent/EP4324891A4/en
Priority to JP2022563176A priority patent/JP7298787B2/ja
Priority to CN202280032458.8A priority patent/CN117280003A/zh
Priority to US18/564,192 priority patent/US20240254354A1/en
Publication of WO2022255110A1 publication Critical patent/WO2022255110A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09D11/30—Inkjet printing inks
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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

Definitions

  • the present invention relates to an active energy ray-curable ink composition that can be used for producing various printed matter.
  • Printing by an inkjet recording apparatus is a method of printing on a recording material by ejecting ink from a nozzle without using a printing plate. Since the nozzle does not come into contact with the recording material, it is possible to print not only on paper substrates but also on substrates with curved or irregularly shaped surfaces such as plastics and metals. have Therefore, the inkjet printing method is expected to expand its use in a wide range of industrial fields.
  • active energy ray-curable inkjet inks which are cured by irradiation with active energy rays such as ultraviolet rays, have a low content of volatile organic compounds (VOCs) and consume less energy for drying in the printing process. Due to its small size, it is also attracting attention as an environmentally friendly technology.
  • Patent Documents 1 to 3 disclose ink compositions as actinic energy ray-curable inkjet inks.
  • An object of the present invention is to provide an active energy ray-curable ink composition that maintains blocking resistance at room temperature, has flexibility at low temperatures (elongation resistance), and is excellent in flexibility of printed materials and durability during stacking. is to provide
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, and X represents a single bond or a divalent linking group.
  • R 4 represents an alkylene group having 1 or more carbon atoms
  • R 5 represents an alkylene group having 1 or more carbon atoms which may be the same as or different from R 4
  • R 6 represents a hydrogen atom or an alkyl group.
  • n represents an integer of 0 or more.
  • a printed matter comprising a step of discharging the active energy ray-curable ink composition according to any one of [1] to [9] onto a recording medium and curing the composition by irradiating it with an active energy ray. manufacturing method.
  • FIG. 2 is a conceptual diagram showing a method for evaluating the tackiness of a coating film surface.
  • the present invention has the following general formula (1)
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, and X represents a single bond or a divalent linking group.
  • R 4 represents an alkylene group having 1 or more carbon atoms
  • R 5 represents an alkylene group having 1 or more carbon atoms which may be the same as or different from R 4
  • R 6 represents a hydrogen atom or an alkyl group.
  • n represents an integer of 0 or more.
  • ((meth)acrylate” is a generic term for acrylate, methacrylate, and both.
  • (Meth)acryl” is a generic term for acryl, methacryl and both.
  • a "(meth)acryloyloxy group” is a generic term for an acryloyloxy group, a methacryloyloxy group, and both of them.
  • the present ink composition contains monomer A.
  • Monomer A is a compound represented by the general formula (1).
  • alkyl groups represented by R 1 , R 2 and R 3 in general formula (1) include methyl group, ethyl group and propyl group.
  • R 1 is preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are each independently a hydrogen atom , a methyl group or an ethyl group. It is more preferable from the viewpoint of exhibiting flexibility at low temperatures, specifically elongation resistance at around 0° C. while maintaining the properties.
  • the divalent linking group represented by X is preferably a divalent hydrocarbon group or a divalent group obtained by combining a hydrocarbon group and an ether bond, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, For example, a divalent hydrocarbon group having 1 to 8 carbon atoms such as methylene group and ethylene group is more preferable.
  • Specific examples of monomer A include the following compounds.
  • the monomer A it is preferable to use cyclic trimethylolpropane formal (meth)acrylate, and it is more preferable to use cyclic trimethylolpropane formal acrylate.
  • Monomer A is contained in the range of 35 to 50% by mass, preferably in the range of 35 to 48% by mass, more preferably in the range of 35 to 45% by mass, relative to the entire ink composition. .
  • the coating film formed from the present ink composition maintains blocking resistance at room temperature while maintaining flexibility at low temperatures, specifically at around 0°C. Elongation resistance is improved.
  • the present ink composition contains monomer B.
  • Monomer B is a compound having a structure represented by the general formula (2) and a polymerizable unsaturated double bond.
  • Examples of the alkylene group having 1 or more carbon atoms represented by R 4 and R 5 in the general formula (2) include methylene group, ethylene group, propylene group, isopropylene group, butylene group and isobutylene group.
  • R 4 and R 5 may be the same or different. Among them, it is more preferable that both R 4 and R 5 are ethylene groups from the viewpoint of obtaining the present ink composition having flexibility (elongation resistance) at low temperatures while maintaining blocking resistance at room temperature. .
  • Examples of the alkyl group represented by R6 in the general formula (2) include a methyl group, an ethyl group, a propyl group and a butyl group.
  • n is preferably an integer of 0-20, more preferably in the range of 0-3.
  • monomer B examples include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, diethylene glycol mono (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate.
  • the use of 2-(2-ethoxyethoxy)ethyl (meth)acrylate as the monomer B improves the blocking resistance of the coating film formed from the present ink composition at room temperature while maintaining the blocking resistance at low temperatures. It is preferable from the viewpoint of being able to improve flexibility, specifically elongation resistance at around 0°C.
  • Monomer B is preferably contained in the range of 5 to 15% by mass with respect to the entire ink composition, and is contained in the range of 8 to 14% by mass. It is more preferable from the viewpoint of obtaining the present ink composition having flexibility (extension resistance).
  • the ink composition contains a polyfunctional polymerizable compound selected from at least one of urethane (meth)acrylates and amino (meth)acrylates.
  • polyfunctional polymerizable compounds may be monomers, oligomers or polymers.
  • the term "monomer” means a compound having a molecular weight (weight average molecular weight when having a molecular weight distribution) of 1,000 or less.
  • the molecular weight of the monomer (weight average molecular weight when it has a molecular weight distribution) is 50-1000.
  • oligomer generally means a polymer having a finite number (generally 5 to 100) of constitutional units based on monomers and having a weight average molecular weight of more than 1,000 and less than 30,000.
  • Polymer means a polymer having a weight average molecular weight of 30,000 or more.
  • the weight average molecular weight is a value obtained as a standard polystyrene conversion value measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the polyfunctional polymerizable compound contained in the present ink composition is preferably an oligomer having a weight molecular weight in the range of 1,000 to 30,000, more preferably 2,000 to 20,000.
  • urethane (meth)acrylate When urethane (meth)acrylate is used as the polyfunctional polymerizable compound, its weight average molecular weight is preferably 1,000 to 30,000, more preferably 2,000 to 20,000. When amino (meth)acrylate is used, its number average molecular weight is preferably from 2,000 to 20,000, more preferably from 2,000 to 10,000, and even more preferably from 2,000 to 5,000.
  • Urethane (meth)acrylates include aliphatic urethane (meth)acrylates and aromatic urethane (meth)acrylates.
  • Commercially available urethane (meth)acrylates can also be used, for example U-2PPA, U-4HA, U-6HA, U-6LPA, U-15HA, U-324A, UA- 122P ⁇ UA5201 ⁇ UA-512 ⁇ ;Sartomer ⁇ CN965NS ⁇ CN964A85 ⁇ CN964 ⁇ CN959 ⁇ CN962 ⁇ CN963J85 ⁇ CN965 ⁇ CN982B88 ⁇ CN981 ⁇ CN983 ⁇ CN996 ⁇ CN9002 ⁇ CN9007 ⁇ CN9009 ⁇ CN9010 ⁇ CN9011 ⁇ CN9178 ⁇ CN9788 ⁇ CN9893 EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8804, EBECRYL8807, EBECRYL9270, KRM8191 and the like manufactured by Daicel Allnex.
  • Amino (meth)acrylate is an amine-modified (meth)acrylate having an amino group.
  • Commercially available amino (meth)acrylates can be used, for example, EBECRYL7100 and EBECRYL80 manufactured by Daicel-Ornex.
  • the content of the polyfunctional polymerizable compound in the entire ink composition is preferably 2 to 12% by mass from the viewpoint of achieving both blocking resistance at room temperature and flexibility (elongation resistance) at low temperatures, and is preferably 4 to 12% by mass. More preferably, it is 8% by mass.
  • polyfunctional polymerizable compound may be used alone, or two or more types may be used in combination.
  • the present ink composition it is preferable to use urethane (meth)acrylate or contain both urethane (meth)acrylate and amino (meth)acrylate as the polyfunctional polymerizable compound. That is, the present ink composition preferably contains urethane (meth)acrylate and amino (meth)acrylate as polyfunctional polymerizable compounds.
  • the hardness of the formed coating film is improved.
  • the content of urethane (meth)acrylate in the entire ink composition is preferably 2 to 6% by mass, more preferably 2.5 to 5% by mass.
  • the content of the amino acrylate in the entire ink composition is preferably 0 to 3% by mass, more preferably 1 to 3% by mass.
  • the present ink composition may further contain other polymerizable compounds in addition to the monomer A, the monomer B, and the polyfunctional polymerizable compound.
  • Such other polymerizable compound is preferably a compound having a polymerizable double bond and being liquid at 25°C.
  • the viscosity of the other polymerizable compound is preferably 1000 mPa ⁇ s or less, more preferably 300 mPa ⁇ s or less. Such viscosity is preferably 1 mPa ⁇ s or more, more preferably 10 mPa ⁇ s or more.
  • the molecular weight of the other polymerizable compound is not particularly limited, it is preferably from 60 to 2,000, more preferably from 100 to 1,000.
  • polymerizable compounds include compounds having a heterocyclic structure, monofunctional (meth)acrylates having a linear or cyclic aliphatic group, monofunctional (meth)acrylates having an aromatic hydrocarbon group, polyfunctional (meth) ) acrylates and vinyl ether compounds.
  • N-vinylcaprolactam N-vinylpyrrolidone, (meth)acryloylmorpholine, N-(meth)acryloyloxyethylhexahydrophthalimide, tetrahydrofurfuryl (meth)acrylate, and the like.
  • N-vinylcaprolactam is preferable because it is excellent in safety, versatile and available at a relatively low cost, and provides good curability and adhesion of the cured coating film to the recording medium.
  • Monofunctional (meth)acrylates having a chain or cyclic aliphatic group include isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isomyristyl (meth)acrylate, isostearyl (meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, adamantyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, cyclohexanedimethanol di( meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethy
  • Examples of monofunctional (meth)acrylates having an aromatic hydrocarbon group include 2-phenoxyethyl (meth)acrylate and benzyl (meth)acrylate. Among them, 2-phenoxyethyl (meth)acrylate is preferable, and 2-phenoxyethyl acrylate is more preferable from the viewpoint of inkjet dischargeability, adhesiveness of the coating film obtained by curing, and flexibility at low temperatures (elongation resistance). .
  • Polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethoxylated (2) neopentyl glycol di(meth)acrylate [compound obtained by diacrylated adduct of 2 moles of neopentyl glycol ethylene oxide], propoxylated (2) neopentyl Glycol (meth)acrylates such as glycol di(meth)acrylates [compounds obtained by diacrylated a 2 mol neopentyl glycol propylene oxide adduct];
  • vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, tri Divinyl ether compounds or trivinyl ether compounds such as methylolpropane trivinyl ether; Ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, hydroxyethyl monovinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, hydroxynonyl monovin
  • the present ink composition further contains other polymerizable compounds
  • the other polymerizable compounds may be used singly or in combination of two or more.
  • the content of the other polymerizable compound is contained in the range of 15 to 60% by mass, preferably in the range of 20 to 50% by mass, and more preferably 25 to 45% by mass with respect to the entire ink composition. From the viewpoint of obtaining the present ink composition, it is more preferable to be included in the range.
  • the present ink composition may further contain a photopolymerization initiator in addition to the monomer A, the monomer B, and the polyfunctional polymerizable compound.
  • photopolymerization initiators include benzoin isobutyl ether, 2,4-diethylthioxanthone [also called 2,4-diethylthioxanthen-9-one], 2-isopropylthioxanthone, methylbenzoylformate, 2,4,6- trimethylbenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 6-trimethylbenzoyldiphenylphosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpent
  • UV-LED ultraviolet light emitting diode
  • 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)-butan-1-one 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholinophenyl)-butan-1-one ), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 2,4-diethylthioxanthone , 2,4-diethylthioxanthen-9-one, 2-isopropylthioxanthone, 1- ⁇ 4-[(4-benzo
  • a photopolymerization initiator is preferably used in combination with a sensitizer.
  • sensitizers include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N,N-dimethylbenzylamine, 4,4 Examples include amines such as '-bis(diethylamino)benzophenone, which have no reactivity with monomer A, monomer B, and polyfunctional polymerizable compounds.
  • the content of the photopolymerization initiator (the total amount of both when the photopolymerization initiator is used in combination with the sensitizer) relative to the entire ink composition is , preferably 2 to 15% by mass, and more preferably 2.5 to 10% by mass from the viewpoint of suppressing coloration of the formed coating film.
  • the present ink composition can be used by containing a colorant in addition to the monomer A, the monomer B, and the polyfunctional polymerizable compound.
  • coloring agents include pigments and dyes.
  • pigments include phthalocyanine pigments used in cyan ink, quinacridone pigments used in magenta ink, azo pigments used in yellow ink, carbon black used in black ink, and white pigments usable in white ink. etc.
  • Phthalocyanine pigments used in cyan ink include, for example, C.I. I. Pigment Blue 1, 2, 3, 15:3, 15:4, 16:6, 16, 17:1, 75, 79 and the like.
  • Examples of quinacridone-based pigments used in magenta ink include C.I. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. Pigment Red 209, C.I. I. Pigment Violet 19 and the like.
  • Examples of azo pigments used in yellow ink include C.I. I. Pigment Yellow 120, 151, 154, 175, 180, 181, 1, 65, 73, 74, 116, 12, 13, 17, 81, 83, 150, 155, 214, 128 and other monoazo and diazo pigments. be done.
  • Carbon black used for black ink includes No. 2300, No. 900, MCF88, no. 33, No. 40, No. 45, No. 52, MA7, MA8, MA11, MA100, No. 2200B, etc.; Columbia Raven 5750, 5250, 5000, 3500, 1255, 700, etc.; Cabot Regal 400R, 330R, 660R, Mogul L, 700, Monarch 800, 880, 900 , 1000, 1100, 1300, 1400, etc.; Degussa Color Black FW1, FW2, FW2V, FW18, FW200, Color Black S150, S160, S170, Printex 35, U, Same V, Same 140U, Special Black 6, Same 5, Same 4A, Same 4, etc.;
  • the volume average particle size of the various pigments described above is preferably in the range of 10 to 300 nm, and more preferably in the range of 50 to 200 nm.
  • inorganic white pigments can be used without particular limitation.
  • inorganic white pigments include sulfates or carbonates of alkaline earth metals, silicas such as finely divided silicic acid and synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like.
  • the surface of silicas etc. may be surface-treated by various surface treatment methods.
  • titanium oxide is used as the white pigment, its volume average particle diameter is preferably 100 to 500 nm. More preferably it is 400 nm.
  • the various pigments described above are preferably contained in the range of 1 to 20% by mass, and in the range of 1 to 10% by mass, based on the entire ink composition. More preferably, it is contained in the range of 1 to 5% by mass.
  • the magenta ink has a higher pigment concentration than the other color inks. Specifically, the pigment concentration is preferably 1.2 times or more, more preferably 1.2 to 4 times, that of other color inks.
  • pigment dispersants for the purpose of increasing the dispersion stability in the present ink composition, specifically the dispersion stability with respect to Monomer A, Monomer B, polyfunctional polymerizable compounds, and the like. You may use it in combination with etc.
  • a pigment dispersant for example, Ajinomoto Fine-Techno Co., Inc.
  • Ajisper (Ajisper is a registered trademark) PB821, Ajisper PB822, PB824;
  • Examples include Disparlon DA-703-50 manufactured by Kasei Co., Ltd.; EFKA (EFKA is a registered trademark) PX4701 and PX4703 manufactured by BASF.
  • pigment derivatives include sulfonic acid derivatives of pigments.
  • the amount of the pigment dispersant used is preferably in the range of 10 to 100% by mass with respect to the pigment, and from the viewpoint of obtaining an ink with even better ejection stability and pigment dispersibility, it is 20 to 60% by mass. A range is more preferred.
  • the present ink composition may further contain a surfactant as a dispersant.
  • surfactants include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts; polyoxyethylene alkyl ethers, polyoxyethylene alkylallyl ethers, acetylene glycols, polyoxyethylene - Nonionic surfactants such as polyoxypropylene block copolymers; and cationic surfactants such as alkylamine salts and quaternary ammonium salts.
  • a surfactant a compound having a silicone chain, a silicone-based surfactant having a polyether chain at the side chain or terminal and having a polysiloxane structure in the main chain; a fluorine-based surfactant having a perfluoroalkyl chain, Hydrophobic organic fluoro compounds, such as oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin), may also be used.
  • oily fluorine compounds eg, fluorine oil
  • solid fluorine compound resins eg, tetrafluoroethylene resin
  • silicone-based surfactants and fluorine-based surfactants include BYK306, 307, 310, 313, 320, 331, 333, 350, 377, and 378 from BYK Chemie; KF series and X-22 series from Shin-Etsu Chemical Co., Ltd. , X-21 series silicones with both ends substituted with organic groups, silicones with one end substituted with organic groups, silicones with both side chain ends substituted with organic groups, silicones with side chains substituted with organic groups; Megafuck F series.
  • the content of the surfactant in the present ink composition is 0.05 to 1.0% by mass relative to the entire present ink composition from the viewpoint of ensuring ejection stability and keeping the surface tension within the desired range. is preferred, and 0.1 to 0.8% by mass is more preferred.
  • the present ink composition further contains hydroquinone, di-t-butylhydroquinone, p-methoxyphenol, benzoquinone, butylhydroxytoluene, nitrosamine salts, hindered amine compounds, 2, 2, 6, if necessary. , 6-tetramethylpiperidine 1-oxyl (TEMPO) and other polymerization inhibitors may be further contained.
  • TEMPO 6-tetramethylpiperidine 1-oxyl
  • the amount thereof is preferably in the range of 0.01 to 2% by mass with respect to the total amount of the present ink composition.
  • the ink composition also contains fluorescent agents such as diaminostilbene derivatives, anthracene, sodium salicylate, diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, pyrazoline derivatives, dearylamine derivatives, ZnCdS:Ag, ZnS:Pb, and ZnS:Cu. It may further contain a compound that absorbs light energy such as radiation and ultraviolet rays and converts it into light of a different wavelength and emits it. Above all, when the present ink composition contains a white pigment, it can absorb light having a wavelength of around 300 to 450 nm, which is ultraviolet to short-wave visible, and has a wavelength of 400 to 400 nm.
  • fluorescent agents such as diaminostilbene derivatives, anthracene, sodium salicylate, diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, pyrazoline derivatives, dearylamine derivatives, ZnCdS:
  • It preferably contains a colorless or weakly colored compound capable of emitting fluorescence having a wavelength of around 500 nm.
  • a fluorescent brightener yellowing of the cured product can be suppressed, whiteness can be improved, and curability can be further improved in some cases.
  • fluorescent brightening agents include naphthalenebenzoxazolyl derivatives such as 1,4-bis-(2-benzoxazolyl)naphthalene, 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazolyl) thiophenebenzoxazolyl derivatives, stilbenebenzoxazolyl derivatives, coumarin derivatives, styrenebiphenyl derivatives, pyrazolone derivatives, stilbene derivatives, styryl derivatives of benzene and biphenyl, bis(benzazol-2-yl) derivatives, carbostyryl, sodium phthalimide, derivatives of dibenzothiophene-5,5′-dioxide, pyrene derivatives, pyridotriazole and the like.
  • naphthalenebenzoxazolyl derivatives such as 1,4-bis-(2-benzoxazolyl)naphthalene, 2,5-thioph
  • fluorescent brighteners examples include the Telalux series from Clariant Japan and the Tinopal series from BASF.
  • the content thereof is preferably 0.05 to 1.0% by mass, more preferably 0.07 to 0.7% by mass, based on the total amount of the present ink composition. is more preferable.
  • the ink composition may contain additives such as ultraviolet absorbers, antioxidants, surface tension modifiers, anti-fading agents, and conductive salts.
  • additives such as ultraviolet absorbers, antioxidants, surface tension modifiers, anti-fading agents, and conductive salts.
  • non-reactive resins such as acrylic resins, epoxy resins, terpene phenol resins, and rosin esters may be contained.
  • the viscosity of the present ink composition at 25° C. is preferably in the range of 3 to 30 mPa ⁇ s, and more preferably in the range of 5 to 20 mPa ⁇ s, from the viewpoint of enhancing ink jet ejection stability.
  • the present ink composition is prepared, for example, by adding a mixture of monomer A, monomer B, polyfunctional polymerizable compound, and optionally other polymerizable compound, colorant such as pigment, and pigment dispersant by bead mill or the like. After dispersing the pigment using a dispersing machine, a photopolymerization initiator is added, and optional additives such as polymerization inhibitors, sensitizers, and surface tension modifiers are added and stirred to dissolve. can.
  • This ink composition is also prepared by using a conventional dispersing machine such as a bead mill in advance to prepare a high-concentration pigment dispersion (mill base) containing a pigment, a pigment dispersant, a resin, etc., followed by the above-described monomer A and monomer B. , a polyfunctional polymerizable compound, a photopolymerization initiator, and an optional additive component are supplied, stirred, and mixed.
  • a conventional dispersing machine such as a bead mill in advance to prepare a high-concentration pigment dispersion (mill base) containing a pigment, a pigment dispersant, a resin, etc.
  • the dispersing machine in addition to the bead mill, for example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a nanomizer, etc., can be used. Available.
  • the ink composition is cured by exposure to light such as active energy rays, preferably ultraviolet rays.
  • light such as active energy rays, preferably ultraviolet rays.
  • light sources normally used for active energy ray-curable ink jet recording inks such as metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, UV-LED lamps, etc. can be used.
  • the ink composition preferably has a pencil hardness of F or higher when cured, and is excellent in curability and hardness.
  • the ink composition can be suitably used for printing by an inkjet recording method using an inkjet recording apparatus. That is, one of the preferred embodiments of the present ink composition is an ultraviolet-curable inkjet ink composition.
  • inkjet recording methods include a method of ejecting droplets by utilizing vibration of a piezoelectric element (a recording method using an inkjet head that forms ink droplets by mechanical deformation of an electrostrictive element), and a method of utilizing thermal energy. etc., any conventionally known method can be used.
  • a printed matter can be produced by discharging the present ink composition onto a base material, which is a recording medium, using an inkjet recording apparatus, and curing the composition by irradiating it with active energy rays.
  • Examples of the printed matter include advertisements, signboards, information boards, and promotional item printing.
  • the ink composition has excellent adhesion to various substrates that are recording media, and can be easily printed on substrates having curved surfaces or irregular shapes.
  • Materials for the substrate include acrylonitrile-butadiene-styrene (ABS) resin; ABS-based polymer alloys such as polyvinyl chloride/ABS resin, polyamide/ABS resin, polycarbonate/ABS resin, and polybutylene terephthalate/ABS resin; acrylonitrile/acrylic.
  • thermoplastic resin films for use as food packaging materials.
  • high-density polyethylene film polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like.
  • the film may be uniaxially stretched or biaxially stretched, or the surface thereof may be subjected to flame treatment, corona discharge treatment, or the like.
  • Pigments (C1, M1, Y1, K1, W1), pigment dispersants (Solsperse 32000, Solsperse 39000, EFKA PX4701) and PO-A were mixed in the compositions shown in Tables 1 and 2, and after stirring for 1 hour with a stirrer, The pigment dispersion used in each example and comparative example was obtained by treating with a bead mill for 2 hours.
  • Ink compositions 1 to 15 were prepared by placing each pigment dispersion and each component in a container and stirring and mixing according to the blending ratios shown in Tables 1 and 2.
  • Ink Composition 2-1 Production of printed material Drops of the obtained ink composition were ejected onto a substrate (polyvinyl chloride or polycarbonate), and irradiated by passing under UV-LED light to cure the ink to obtain a printed material. .
  • An ink jet recording apparatus having a piezo ink jet head was used to eject the ink.
  • the UV-LED light source for curing outputs ultraviolet light with a wavelength of 385 nm, the illuminance on the surface is fixed at 800 mW/cm 2 , and the exposure amount is 1000 mJ/cm 2 while changing the transport speed. .
  • Blocking resistance (tack feeling) A stainless petri dish ( ⁇ 75 mm) was prepared in a test room at 25° C., and a weight of 15 g was attached to the inner side surface of the petri dish. Next, the stainless petri dish to which the weight was attached was fixed by hand while standing on the surface of the coating film so that the positional relationship between the weight and the surface of the coating film was as shown in FIG. . The hand was released from the stainless petri dish, and the stainless petri dish swayed left and right on the surface of the membrane, and the number of times until it stopped was evaluated.
  • Pencil Hardness Using the resulting prints (thickness of the coating film obtained from the ink composition: 6 ⁇ m), a pencil scratch test was performed according to JIS K5600-5-4 for evaluation.
  • Tables 1 and 2 show the above evaluation results. From these results, the content of monomer A (V#200: cyclic trimethylolpropane formal acrylate) relative to the entire ink composition is within the range specified in the present invention, and monomer B (Miramer M170: 2-(2-ethoxy ethoxy)ethyl (meth)acrylate) and at least one polyfunctional polymerizable compound selected from urethane (meth)acrylate or amino (meth)acrylate exhibits blocking resistance at room temperature. It can be seen that it has flexibility (elongation resistance) at low temperatures while maintaining it.
  • the coating film is excellent in both blocking resistance, flexibility at low temperatures, and hardness. can be obtained.
  • the monomer B is contained in the range of 5 to 15% by mass with respect to the entire ink composition, both blocking resistance at room temperature and flexibility (elongation resistance) at low temperature can be achieved and obtained. Excellent hardness of coating film.
  • the active energy ray-curable ink composition of the present invention maintains blocking resistance at room temperature and has flexibility (elongation resistance) at low temperatures, and is excellent in flexibility of printed matter and durability against stacking.
  • it is useful for various applications such as signboards, signboards, display exhibitions, card printing, graphics fields such as smartphone covers, automobile interior parts, home appliances, and membrane switches.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
PCT/JP2022/020759 2021-06-01 2022-05-19 活性エネルギー線硬化性インク組成物及び印刷物の製造方法 Ceased WO2022255110A1 (ja)

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EP22815862.2A EP4324891A4 (en) 2021-06-01 2022-05-19 Actinic-ray-curable ink composition and method for producing printed matter
JP2022563176A JP7298787B2 (ja) 2021-06-01 2022-05-19 活性エネルギー線硬化性インク組成物及び印刷物の製造方法
CN202280032458.8A CN117280003A (zh) 2021-06-01 2022-05-19 活性能量射线固化性油墨组合物和印刷物的制造方法
US18/564,192 US20240254354A1 (en) 2021-06-01 2022-05-19 Active energy ray-curable ink composition and method of producing printed material

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WO2026014236A1 (ja) * 2024-07-08 2026-01-15 ａｒｔｉｅｎｃｅ株式会社 紫外線硬化型インクジェットインキ及び印刷物

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JP2023082268A (ja) * 2021-12-02 2023-06-14 セイコーエプソン株式会社 インクジェット記録方法
WO2026014236A1 (ja) * 2024-07-08 2026-01-15 ａｒｔｉｅｎｃｅ株式会社 紫外線硬化型インクジェットインキ及び印刷物

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US20240254354A1 (en) 2024-08-01
CN117280003A (zh) 2023-12-22

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