WO2021111884A1 - Encre et procédé de production d'article imprimé - Google Patents

Encre et procédé de production d'article imprimé Download PDF

Info

Publication number
WO2021111884A1
WO2021111884A1 PCT/JP2020/043115 JP2020043115W WO2021111884A1 WO 2021111884 A1 WO2021111884 A1 WO 2021111884A1 JP 2020043115 W JP2020043115 W JP 2020043115W WO 2021111884 A1 WO2021111884 A1 WO 2021111884A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
ink
mass
acrylate
pigment
Prior art date
Application number
PCT/JP2020/043115
Other languages
English (en)
Japanese (ja)
Inventor
齊藤　直人
怜美 藤本
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2021550005A priority Critical patent/JPWO2021111884A1/ja
Publication of WO2021111884A1 publication Critical patent/WO2021111884A1/fr
Priority to JP2022085918A priority patent/JP2022119898A/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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 inks that can be used in the production of various printed matter.
  • the active energy ray-curable ink is used for printing on various recording media because it has excellent curability and drying property as compared with other inks.
  • an ink composition containing, for example, a colorant, a radical polymerization initiator having a specific structure, and a radically polymerizable compound such as tetrahydrofurfuryl acrylate is known (for example, Patent Document 1). reference.).
  • Printed matter obtained by using the active energy ray-curable ink is being studied for use in a wide range of applications.
  • the ink is not easily scratched, and even if chemicals or the like adhere to the ink, it has a high hardness and excellent chemical resistance that does not easily cause deterioration of the printed image. It is required to be able to form a coating film.
  • An object to be solved by the present invention is to provide an ink capable of forming a coating film having high hardness of the coating film, excellent chemical resistance, and excellent adhesion to a recording medium.
  • the present inventor is an ink that is cured by light emitted from an LED and has a compound (A) having two or more polymerizable unsaturated double bonds and a compound (B) having one polymerizable unsaturated double bond.
  • the compound (A) contains a compound (a1) having a structure represented by the following general formula (1), and the compound (B) is a compound (b1) having a heterocyclic structure.
  • the problem was solved by an ink characterized in that the compound (A) was contained in an amount of 60% by mass or more based on the total amount of the ink.
  • R in the general formula (1) represents an alkylene group having 4 or more carbon atoms, and X represents a hydrogen atom or a methyl group.
  • the ink of the present invention it is possible to form a coating film having high hardness of the coating film, excellent chemical resistance, and excellent adhesion to the recording medium.
  • the ink of the present invention is an ink that is cured by light emitted from an LED, and is a compound (A) having two or more polymerizable unsaturated double bonds and a compound having one polymerizable unsaturated double bond (A).
  • B) the compound (A) contains a compound (a1) having a structure represented by the following general formula (1), and the compound (B) contains a compound (b1) having a heterocyclic structure. It is characterized in that it is contained and the compound (A) is contained in an amount of 60% by mass or more based on the total amount of the ink.
  • R in the general formula (1) represents an alkylene group having 4 or more carbon atoms, and X represents a hydrogen atom or a methyl group.
  • the ink of the present invention is cured by the light emitted from the LED (light emitting diode).
  • the light include ultraviolet rays having a peak emission wavelength in the wavelength range of 350 nm to 420 nm, and it is particularly preferable to use ultraviolet rays having a peak emission wavelength in the region of 360 to 400 nm.
  • the compound (A) contained in the ink of the present invention a compound having two or more polymerizable unsaturated double bonds is used.
  • the crosslink density of the cured coating film formed by using the ink of the present invention is used. Therefore, it is possible to form a cured coating film having excellent chemical resistance and high hardness.
  • the compound (A) has 2 to 6 polymerizable unsaturated double bonds from the viewpoint of achieving both good chemical resistance, high hardness, and adhesion to the recording medium. It is preferable, and it is more preferable that the number is 2 to 3.
  • the compound (A) is used in an amount of 60% by mass or more based on the total amount of the ink of the present invention.
  • the crosslink density of the cured coating film formed by using the ink of the present invention is increased, so that it is possible to form a cured coating film having excellent chemical resistance and high hardness.
  • the content of the compound (A) is less than 60% by mass with respect to the total amount of the ink, it may cause a decrease in chemical resistance and hardness.
  • the compound (A) is preferably used in the range of 65% by mass to 85% by mass, and even more excellently in the range of 70% by mass to 80% by mass, based on the total amount of the ink. It is particularly preferable to obtain an ink having chemical resistance and capable of forming a hardened coating film having high hardness.
  • R in the general formula (1) represents an alkylene group having 4 or more carbon atoms, and X represents a hydrogen atom or a methyl group.
  • the compound (a1) it is preferable to use a compound in which R in the general formula (1) is an alkylene group having 4 to 9 carbon atoms, and the R is 6 to 9 carbon atoms. It is preferable to use an alkylene group of the above, and it is preferable to use an alkylene group having R having 6 carbon atoms, which has high hardness, excellent chemical resistance, and excellent adhesion to a recording medium. It is particularly preferable to obtain an ink capable of forming a coating film, having high sensitivity to light emitted from an LED, and having a property of being rapidly cured by irradiation thereof.
  • the compound (a1) include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol di (meth) acrylate, 3.
  • 1,6-hexanediol di (meth) acrylate has high hardness and excellent chemical resistance, and adheres to the recording medium. It is particularly preferable to obtain an ink which can form a coating film having excellent properties, has high sensitivity to light emitted from an LED, and has a property of being rapidly cured by its irradiation.
  • the compound (a1) can form a coating film having excellent adhesion to a recording medium, has high sensitivity to active energy rays, and has a property of being rapidly cured by irradiation thereof. It is preferable to use 20% by mass to 70% by mass, and particularly preferably in the range of 30% by mass to 60% by mass with respect to the total amount of the ink.
  • a compound (a2) other than the compound (a1) can be used in combination with the compound (a1).
  • Examples of the compound (a2) include tricyclodecanedimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate.
  • Acrylate di (meth) acrylate such as tripropylene glycol di (meth) acrylate, polypropylene glycol, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, neopentyl glycol di (meth) acrylate, bisphenol A di (Meta) Acrylate, Bisphenol F Di (Meta) Acrylate, Hydrogenated Bisphenol A Di (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Dipentaerythritol Poly (Meta) Acrylate, And alkylene oxide modified products such as ethylene oxide and propylene oxide, caprolactone modified products, ethylene oxide modified phosphoric acid (meth) acrylate, ethylene oxide modified alkyl phosphoric acid (meth) acrylate, etc., (meth) acrylic acid 2- (2).
  • di (meth) acrylate such as trip
  • -Vinyloxyethoxy) ethyl 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 Di or trivinyl ether compounds such as methylolpropane trivinyl ether, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate and the like can be used alone or in combination of two or more.
  • the compound (a2) it is preferable to use it in the range of 60% by mass to 95% by mass, and it is preferable to use it in the range of 75% by mass to 90% by mass with respect to the total amount of the ink. It is more preferable to achieve both adhesion and chemical resistance.
  • a compound (b1) having a heterocyclic structure having one polymerizable unsaturated double bond is used alone, or the compound (b1) and the compound (b1) are polymerizable other than the compound (b1). It is used in combination with the compound (b2) having one unsaturated double bond.
  • the crosslink density formed by using the ink of the present invention is appropriately obtained as compared with the case where only the compound (A) having two or more polymerizable unsaturated double bonds is used.
  • the polymerizable unsaturated double bond of the compound (B) include a (meth) acryloyl group, and an acryloyl group is preferable.
  • the compound (B) is preferably used in the range of 1 to 39% by mass, more preferably 5% by mass to 30% by mass, and 10% by mass to the total amount of the ink. When used in the range of 20% by mass, it has good flexibility and adhesion to a recording medium without significantly impairing the high hardness of the cured coating film, excellent chemical resistance, and the sensitivity. It is particularly preferable to obtain an ink capable of forming a cured coating film.
  • the compound having a heterocyclic structure (b1) for example, a compound having a caprolactone structure, a compound having a pyridine structure, a compound having a pyrrolidone structure, a compound having a tetrahydrofuran structure, and a compound having a cyclic trimethylolpropane structure are used. be able to.
  • the compound (b1) it is preferable to use a compound having a caprolactam structure, and specifically, using N-vinylcaprolactam has high hardness and excellent chemical resistance of the cured coating film. It is particularly preferable to obtain an ink having good flexibility and adhesion to a recording medium, which can form a cured coating film without significantly impairing the above-mentioned sensitivity.
  • the compound (b1) having a heterocyclic structure including the compound having a caprolactone structure, is preferably used in a range of 15% by mass or less with respect to the total amount of the ink, and is preferably 1% by mass to 12% by mass. It is more preferable to use it in the range of%, and using it in the range of 5% by mass to 10% by mass has good flexibility without significantly impairing the high hardness and excellent chemical resistance of the cured coating film. It is particularly preferable to obtain an ink that can form a cured coating film having adhesion to a recording medium and has even higher sensitivity.
  • a known monofunctional compound can be used without particular limitation, and for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, and isooctyl acrylate can be used.
  • the compound (b2) is preferably used in the range of 5% by mass to 40% by mass, and preferably used in the range of 10% by mass to 25% by mass with respect to the total amount of the ink. It is more preferable to achieve both excellent adhesion to the ink and excellent chemical resistance.
  • the ink of the present invention contains a combination of the compound (A) and the compound (B), and further, the compound (A) and the compound (C) having one or more methacryloyl groups different from the compound (B). It is preferable to use a compound for further improving the adhesion to the recording medium.
  • Examples of the compound (C) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, nonyl methacrylate, lauryl methacrylate, tridecyl methacrylate, dodecyl methacrylate, and hexadecyl methacrylate.
  • Octadecyl methacrylate isodecyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methoxyethyl methacrylate, butoxyethyl methacrylate, phenoxyethyl methacrylate, nonylphenoxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl Monofunctional methacrylates such as methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol Dimethacrylate, 3-methyl-1,5-
  • Cyclodecane dimethanol dimethacrylate ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tris (2-hydroxyethyl) isocyanurate dimethacrylate.
  • EO ethylene oxide
  • PO propylene oxide
  • Triol trimethoxide with de or propylene oxide added dimethacrylate of diol with 4 or more moles of ethylene oxide or propylene oxide added to 1 mol of bisphenol A, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, polymethacrylate of dipentaerythritol , Ethylene oxide-modified phosphate methacrylate, ethylene oxide-modified alkyl phosphate methacrylate, etc. can be used.
  • 3 mol or more of ethylene oxide or propylene oxide is added to 1 mol of trimethylolpropane. It is preferable to use triol methacrylate or neopentyl glycol dimethacrylate added with.
  • the compound (C) is preferably in the range of 0.1% by mass to 10% by mass, and preferably in the range of 0.5% by mass to 5% by mass, based on the total amount of the ink of the present invention. , It is preferable to further improve the adhesion to the recording medium.
  • the ink of the present invention is cured by receiving the light emitted from the LED.
  • an ink containing a photopolymerization initiator can be used as the ink of the present invention.
  • photopolymerization initiator examples include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 6-trimethylbenzoyldiphenylphosphine oxide, 2-.
  • an acylphosphine oxyacid-based photopolymerization initiator as the photopolymerization initiator.
  • 2-benzyl-2-dimethylamino-1- (4-morpholino) corresponding to the wavelength of light emitted from the UV-LED light source is used.
  • the photopolymerization initiator is preferably used in combination with a sensitizer.
  • the sensitizer include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4 , 4'-bis (diethylamino) benzophenone and the like can be used.
  • an ink containing a colorant can be used if necessary.
  • a pigment or a dye can be used as the colorant.
  • the pigment include a phthalocyanine pigment used for cyan ink, a quinacridone pigment used for magenta ink, an azo pigment used for yellow ink, carbon black used for black ink, and white color that can be used for white ink. Examples include pigments.
  • Examples of the phthalocyanine pigment used in the cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15: 3, 15: 4, 16: 6, 16, 17: 1, 75, 79 and the like.
  • Examples of the quinacridone pigment 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 the azo pigment used for 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, etc., monoazo and disazo pigments included.
  • the carbon black used for black ink is No. 1 of Mitsubishi Chemical Corporation. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B and others are Raven 5750, 5250, 5000, 3500, 1255, 700, etc. manufactured by Colombia, and Regal 400R, 330R, 660R, Mogul L, 700, Monarch 800, 880, etc. manufactured by Cabot. 900, 1000, 1100, 1300, 1400, etc. are Color Black FW1, FW2, FW2V, FW18, FW200, ColorBlack S150, S160, S170, Printex 35, manufactured by Degussa. U, V, 140U, Special Black 6, 5, 4, 4A, 4 and the like can be mentioned.
  • the white pigment that can be used for white ink is not particularly limited, and a known inorganic white pigment can be used.
  • the inorganic white pigment include sulfates or carbonates of alkaline earth metals, silicas such as fine powder silicic acid and synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, and talc. , Clay, etc.
  • silicas such as fine powder silicic acid and synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, and talc. , Clay, etc.
  • the inorganic white pigment those whose surfaces such as silicas have been surface-treated by various surface treatment methods can also be used.
  • the average particle size (median diameter: 50% diameter) of the pigment is preferably in the range of 10 nm to 300 nm, more preferably 50 nm to 200 nm.
  • the white pigment is used for white ink for imparting concealing property to printed matter.
  • the white pigment has an average particle size (median diameter: 50% diameter) of 100 nm to 500 nm in order to obtain a white ink having excellent hiding power, excellent ejection stability, and high color development of a printed image. It is preferable to use one, and it is more preferable to use one having a diameter of 150 nm to 400 nm.
  • the pigment is preferably contained in the range of 1% by mass to 20% by mass, and in the range of 1% by mass to 10% by mass, based on the total amount of the ink, in order to obtain sufficient image density and light resistance of the printed image. It is more preferable that it is contained in the range of 1% by mass to 5% by mass, and most preferably.
  • the pigment may be used in combination with a pigment dispersant, a pigment derivative (synagist), or the like in order to obtain good dispersion stability in the compound (A) and the compound (B).
  • the pigment dispersant is not particularly limited, but is, for example, Ajinomoto Fine-Techno's Ajispar PB821, PB822, PB817, Abyssia's Solspurs 24000GR, 32000, 33000, 39000, and Kusumoto Kasei Co., Ltd.'s Disparon DA-703. -50, DA-705, DA-725 and the like can be used.
  • the pigment dispersant is preferably used in the range of 10% by mass to 100% by mass with respect to the pigment, and 20% by mass in order to obtain an ink having even more excellent ejection stability and pigment dispersibility. It is more preferable to use one in the range of% to 80% by mass.
  • the ink of the present invention contains, if necessary, a polymerization inhibitor such as hydroquinone, methquinone, dit-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, and nitrosamine salt, in addition to the above-mentioned components.
  • a polymerization inhibitor such as hydroquinone, methquinone, dit-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, and nitrosamine salt, in addition to the above-mentioned components.
  • a polymerization inhibitor such as hydroquinone, methquinone, dit-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, and nitrosamine salt, in addition to the above-mentioned components.
  • the polymerization inhibitor can be used in the range of 0.01% by mass to 2% by mass with respect to the total amount of the ink of the
  • the ink of the present invention contains a non-reactive resin such as an acrylic resin, an epoxy resin, a terpenphenol resin, or a rosin ester in order to further improve the adhesion to a recording medium such as a plastic base material. Can be used.
  • a non-reactive resin such as an acrylic resin, an epoxy resin, a terpenphenol resin, or a rosin ester
  • the viscosity of the ink at 25 ° C. is preferably in the range of 3 mPa ⁇ sec to 30 mPa ⁇ sec, and preferably in the range of 5 mPa ⁇ sec to 20 mPa ⁇ sec. , It is more preferable to ensure good ejection stability from the ink ejection nozzle.
  • the ink of the present invention contains, for example, the compound (A) and the compound (B), and if necessary, the compound (C), a pigment, a pigment dispersant, a resin, or the like, using a normal disperser such as a bead mill. After mixing, a photopolymerization initiator is added, and if necessary, additives such as a polymerization inhibitor, a sensitizer, and a surface tension adjusting agent are added and mixed.
  • a photopolymerization initiator is added, and if necessary, additives such as a polymerization inhibitor, a sensitizer, and a surface tension adjusting agent are added and mixed.
  • a high-concentration pigment dispersion (mill base) containing a pigment, a pigment dispersant, a resin, or the like is produced in advance using a normal disperser such as a bead mill, and a photopolymerization initiator is added to the pigment dispersion. It can also be produced by mixing, stirring and stirring the compound (A), the compound (B), the compound (C), an additive and the like.
  • disperser in addition to the bead mill, various known and commonly used dispersers such as 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, and a nanomizer are used. be able to.
  • the ink of the present invention is cured by irradiating with light emitted from an LED, preferably ultraviolet rays or the like.
  • an LED preferably ultraviolet rays or the like.
  • a light source for ultraviolet rays or the like a UV-LED lamp or the like can be used.
  • the ink of the present invention can be suitably used for printing by an inkjet recording method exclusively using an inkjet recording device.
  • any conventionally known method can be used.
  • a method of ejecting droplets by utilizing the vibration of the piezoelectric element a recording method using an inkjet head that forms ink droplets by mechanical deformation of the electrolytic strain element
  • a method of utilizing thermal energy can be mentioned.
  • a printed matter can be produced by ejecting the ink using an inkjet recording device, printing it on a recording medium, and curing it by irradiating it with light emitted from an LED.
  • Examples of the printed matter include advertisements, signboards, information boards, and promotional product printing.
  • the ink of the present invention has excellent adhesion to various types of recording media, it can be easily printed on the surface of a recording medium having a curved surface or an irregular shape having irregularities.
  • a plastic base material can be used as the recording medium.
  • the plastic base material include ABS (acrylonitrile butadiene styrene) resin, PVC (polyvinyl chloride) / ABS resin, and PA (polyamide) / ABS resin, which are used as general-purpose injection molding plastics.
  • PC polycarbonate
  • ABS polybutylene terephthalate
  • AS acrylonitrile / styrene
  • AES acrylonitrile / ethylene rubber
  • examples include a base material made of styrene) resin, MS ((meth) acrylic acid ester / styrene) resin, PC (polycarbonate) resin, acrylic resin, methacrylic resin, PP (polypropylene) resin and the like.
  • plastic base material for example, a thermoplastic resin film used for a packaging material or the like can be used.
  • thermoplastic resin film examples include those used as a thermoplastic resin film generally used for food packaging, for example, polyethylene retephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film.
  • PET polyethylene retephthalate
  • HDPE high density polyethylene film
  • polypropylene film CPP: unstretched polypropylene film
  • OPP biaxially stretched polypropylene film
  • films include films.
  • a stretched film such as uniaxially stretched or biaxially stretched, or a film whose surface is subjected to flame treatment, corona discharge treatment, or the like can also be used.
  • Cyan Pigment Dispersion (1) 10 parts by mass of Fastgen Blue TGR-G (phthalocyanine pigment CI Pigment Blue 15: 4 manufactured by DIC Corporation), 4.5 parts by mass of Solspurs 32000 (polymer pigment dispersant manufactured by Lubrizol), and MIRAMER M222. 85.5 parts by mass of (dipropylene glycol diacrylate manufactured by MIWON) was stirred and mixed with a stirrer for 1 hour, and then treated with a bead mill for 2 hours to obtain a cyan pigment dispersion (1).
  • TGR-G phthalocyanine pigment CI Pigment Blue 15: 4 manufactured by DIC Corporation
  • Solspurs 32000 polymer pigment dispersant manufactured by Lubrizol
  • MIRAMER M222 85.5 parts by mass of (dipropylene glycol diacrylate manufactured by MIWON) was stirred and mixed with a stirrer for 1 hour, and then treated with a bead mill for 2 hours to obtain a cyan pigment dispersion (1).
  • Cyan Pigment Dispersion (2) Prepared except that 85.5 parts by mass of MIRAMER M200 (1,6-hexanediol diacrylate, manufactured by MIWON) was used instead of 85.5 parts by mass of MIRAMER M222 (dipropylene glycol diacrylate manufactured by MIWON).
  • a cyan pigment dispersion (2) was obtained in the same manner as in Example 1.
  • magenta Pigment Dispersion (3) Fastgen Blue TGR-G (DIC Corporation Phthalocyanine Pigment CI Pigment Blue 15: 4) Instead of 10 parts by mass, Fastgen Super Magenta RTS (DIC Corporation Magenta Pigment CI Pigment Red 122) A magenta pigment dispersion (3) was obtained in the same manner as in Preparation Example 1 except that 10 parts by mass was used.
  • Preparation Example 4 Yellow Pigment Dispersion (4) Levascreen Yellow G01 (CI Pigment Yellow 150 manufactured by LANXESS Co., Ltd.) 10 parts by mass, Solspurs 32000 (Polymer pigment dispersant manufactured by Lubrizol) 6 parts by mass, and MIRAMER M222 (dipropylene glycol di from MIWON) 84 parts by mass of acrylate) was stirred and mixed with a stirrer for 1 hour, and then treated with a bead mill for 2 hours to obtain a yellow pigment dispersion (4).
  • Levascreen Yellow G01 CI Pigment Yellow 150 manufactured by LANXESS Co., Ltd.
  • Solspurs 32000 Polymer pigment dispersant manufactured by Lubrizol
  • MIRAMER M222 dipropylene glycol di from MIWON
  • Preparation Example 5 Black Pigment Dispersion (5) Carbon Black # 960 (Carbon Black manufactured by Mitsubishi Chemical Co., Ltd.) 10 parts by mass, Solspers 32000 (Polymer pigment dispersant manufactured by Lubrizol) 4.5 parts by mass, and MIRAMER M222 (Dipropylene glycol diacrylate manufactured by MIWON) 85
  • a black pigment dispersion (5) was obtained by stirring and mixing 5.5 parts by mass with a stirrer for 1 hour and then treating with a bead mill for 2 hours.
  • Preparation Example 6 White Pigment Dispersion (6) TITANIX JR-806 (titanium oxide manufactured by Teika Co., Ltd.) 50 parts by mass, Solspurs 24000 (polymer pigment dispersant manufactured by Lubrizol) 2.5 parts by mass, MIRAMER M222 (dipropylene glycol diacrylate manufactured by MIWON) 47.
  • the white pigment dispersion (6) was obtained by stirring and mixing 5 parts by mass with a stirrer for 1 hour and then treating with a bead mill for 2 hours.
  • Example 1 Put 9 parts by mass of MIRAMER M3130, 56 parts by mass of MIRAMER M200, 9 parts by mass of V-CAP, 0.2 parts by mass of KF-351A in a container and stir and mix, then 3.5 parts by mass of Omnirad 819 and Omnirad TPO. -H was added in an amount of 4 parts by mass and Kayace DETX-S was added in an amount of 2.5 parts by mass, and the mixture was mixed at a temperature of 60 ° C. for 30 minutes.
  • Example 2 to 12 and Comparative Examples 1 to 4 The ink was produced in the same manner as in Example 1 except that the ink composition was changed to that shown in Tables 1 to 3.
  • -MIRAMER M3130 (M3130): ethylene oxide (EO) -modified trimethylolpropane triacrylate manufactured by MIWON-MIRAMER M222 (M222): dipropylene glycol diacrylate manufactured by MIWON-MIRAMER M200 (M200): 1,6- Hexanediol diacrylate / MIRAMER M213 (M213): Neopentyl glycol dimethacrylate / V-CAP (V-CAP) manufactured by MIWON: N-vinyl-2-caprolactam / light acrylate POA (POA) manufactured by Ashland: Kyoeisha Chemical Co., Ltd.
  • EO ethylene oxide
  • MIWON-MIRAMER M222 dipropylene glycol diacrylate manufactured by MIWON-MIRAMER M200 (M200): 1,6- Hexanediol diacrylate / MIRAMER M213 (M213): Neopentyl glycol dimethacrylate /
  • Phenoxyethyl acrylate KF-351A (KF-351A) manufactured by Shin-Etsu Chemical Industry Co., Ltd .: Polysiloxane Omnirad 819 (819) manufactured by Shin-Etsu Chemical Industry Co., Ltd .: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide manufactured by IGM Co., Ltd.
  • TPO-H TPO
  • 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by IGM Kayacure DETX-S (DETX): diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.
  • the ink was applied to a polycarbonate plate (PC: manufactured by Asahi Glass Co., Ltd., Lexan, thickness 1 mm) with a spin coater so as to have a thickness of 6 ⁇ m.
  • the coated surface is irradiated with an LED irradiation device (emission wavelength: 385 nm, peak intensity: 500 mW / cm 2 ) manufactured by Hamamatsu Photonics Co., Ltd. so that the amount of one irradiation energy is 30 J / m 2.
  • the integrated value of the amount of irradiation energy until the coated surface became tack-free when touched was measured.
  • the ink capable of forming a coating film in which the integrated value of the irradiation energy amount was 400 mJ / cm 2 or less was evaluated to be excellent in curability.
  • the ink is applied to a polycarbonate plate (PC: Asahi Glass Co., Ltd., Lexan, thickness 1 mm), an acrylic plate (PMMA: Kuraray Co., Ltd., Comoglass), a vinyl chloride plate (PVC: Mitsubishi Chemical Corporation, Hishi).
  • the plate GE301 was coated with a spin coater to a thickness of 10 ⁇ m.
  • the coated surface was subjected to an LED irradiation device manufactured by Hamamatsu Photonics Co., Ltd. (emission wavelength: 385 nm, peak intensity: 500 mW / cm 2 , one irradiation energy amount of 30 J / m 2 ).
  • a cured coating film was obtained by irradiating until it became tack-free.
  • a cellophane adhesive tape manufactured by Nichiban Co., Ltd. is attached to the cured coating film, and the surface of the tape is coated. I rubbed it with my nails 10 times. Next, the tape was vigorously peeled off at a peeling speed of about 1 cm / sec, and the number of squares of the coating film remaining on the surfaces of the polycarbonate plate, the vinyl chloride plate, and the acrylic plate was confirmed.
  • Evaluation criteria Good The number of cells in the coating film is 20 or more Yes: The number of cells in the coating film is 15 or more and less than 20 No: The number of cells in the coating film is less than 15
  • the ink was applied to a polycarbonate plate (manufactured by Asahi Glass Co., Ltd., Lexan, thickness 1 mm, PC) with a spin coater to a thickness of 10 ⁇ m.
  • the coated surface was subjected to an LED irradiation device manufactured by Hamamatsu Photonics Co., Ltd. (emission wavelength: 385 nm, peak intensity: 500 mW / cm 2 , one irradiation energy amount of 30 J / m 2 ).
  • a cured coating film was obtained by irradiating until it became tack-free.
  • the obtained cured coating film was rubbed 10 times to the left and right with a width of about 2 cm with a cotton swab dipped in a mixture of ethanol and water (ethanol content ratio 70% by mass). Those having no rubbing marks on the surface of the coating film were evaluated as " ⁇ ", and those with confirmed rubbing marks were evaluated as "x".
  • the ink was applied to a polycarbonate plate (manufactured by Asahi Glass Co., Ltd., Lexan, thickness 1 mm, PC) with a spin coater to a thickness of 10 ⁇ m.
  • the coated surface was subjected to an LED irradiation device manufactured by Hamamatsu Photonics Co., Ltd. (emission wavelength: 385 nm, peak intensity: 500 mW / cm 2 , one irradiation energy amount of 30 J / m 2 ).
  • a cured coating film was obtained by irradiating until it became tack-free.
  • the pencil hardness of the obtained cured coating film was evaluated according to the test method of JIS-K5600-5-4.
  • the pencil was evaluated using MITSU-BISHI, and the test equipment was evaluated using a pencil scratch hardness tester manufactured by Toyo Seiki Seisakusho Co., Ltd.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Polymerisation Methods In General (AREA)
  • Ink Jet (AREA)

Abstract

La présente invention résout le problème que constitue la fourniture d'une encre capable de former un film de revêtement ayant une dureté de film de revêtement élevée, une excellente résistance chimique et une excellente adhérence étanche sur un support d'impression. Les inventeurs ont résolu le problème au moyen d'une encre qui est durcie par la lumière émise par une DEL, caractérisée en ce que l'encre comprend un composé (A) ayant au moins deux doubles liaisons insaturées polymérisables et un composé (B) ayant une double liaison insaturée polymérisable, le composé (A) contient un composé (a1) ayant la structure indiquée par la formule générale (1), le composé (B) contient un composé (b1) ayant une structure hétérocyclique, et la teneur du composé (A) par rapport à la quantité totale de l'encre est de 60 % en masse ou plus.
PCT/JP2020/043115 2019-12-05 2020-11-19 Encre et procédé de production d'article imprimé WO2021111884A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021550005A JPWO2021111884A1 (ja) 2019-12-05 2020-11-19 インク及び印刷物の製造方法
JP2022085918A JP2022119898A (ja) 2019-12-05 2022-05-26 インク及び印刷物の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019220325 2019-12-05
JP2019-220325 2019-12-05

Publications (1)

Publication Number Publication Date
WO2021111884A1 true WO2021111884A1 (fr) 2021-06-10

Family

ID=76222038

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/043115 WO2021111884A1 (fr) 2019-12-05 2020-11-19 Encre et procédé de production d'article imprimé

Country Status (2)

Country Link
JP (2) JPWO2021111884A1 (fr)
WO (1) WO2021111884A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009035650A (ja) * 2007-08-02 2009-02-19 Sakata Corp 光硬化型インクジェット印刷用インク組成物
WO2009148124A1 (fr) * 2008-06-05 2009-12-10 サカタインクス株式会社 Composition photodurcissable d'encre d'impression par jet d'encre et impression
JP2011241323A (ja) * 2010-05-19 2011-12-01 Seiko Epson Corp インク組成物セット、これを用いたインクジェット記録方法及び記録物
JP2012207084A (ja) * 2011-03-29 2012-10-25 Toyo Ink Sc Holdings Co Ltd 活性エネルギー線硬化型インクジェットインク組成物
JP2012255143A (ja) * 2011-05-16 2012-12-27 Seiko Epson Corp 紫外線硬化型インクジェット組成物および印刷物
WO2013031871A1 (fr) * 2011-08-29 2013-03-07 東洋インキＳｃホールディングス株式会社 Composition d'encre durcissable par des rayons énergétiques actifs pour l'impression par jet d'encre, et matériau imprimé l'utilisant
JP2013181163A (ja) * 2012-03-05 2013-09-12 Fujifilm Corp 活性光線硬化型インクセット、インクジェット記録方法、及び、印刷物
JP2014240464A (ja) * 2013-06-12 2014-12-25 富士フイルム株式会社 インクジェットインク組成物、及び、インクジェット記録方法
WO2018142819A1 (fr) * 2017-01-31 2018-08-09 富士フイルム株式会社 Procédé d'impression à jet d'encre et procédé de fabrication d'un article imprimé stratifié
WO2019189186A1 (fr) * 2018-03-30 2019-10-03 太陽インキ製造株式会社 Composition durcissable pour impression au jet d'encre, produit durci en cette dernière, et composant électronique comportant ledit produit durci
WO2020137067A1 (fr) * 2018-12-25 2020-07-02 サカタインクス株式会社 Composition d'encre photocurcissable pour impression jet d'encre

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009035650A (ja) * 2007-08-02 2009-02-19 Sakata Corp 光硬化型インクジェット印刷用インク組成物
WO2009148124A1 (fr) * 2008-06-05 2009-12-10 サカタインクス株式会社 Composition photodurcissable d'encre d'impression par jet d'encre et impression
JP2011241323A (ja) * 2010-05-19 2011-12-01 Seiko Epson Corp インク組成物セット、これを用いたインクジェット記録方法及び記録物
JP2012207084A (ja) * 2011-03-29 2012-10-25 Toyo Ink Sc Holdings Co Ltd 活性エネルギー線硬化型インクジェットインク組成物
JP2012255143A (ja) * 2011-05-16 2012-12-27 Seiko Epson Corp 紫外線硬化型インクジェット組成物および印刷物
WO2013031871A1 (fr) * 2011-08-29 2013-03-07 東洋インキＳｃホールディングス株式会社 Composition d'encre durcissable par des rayons énergétiques actifs pour l'impression par jet d'encre, et matériau imprimé l'utilisant
JP2013181163A (ja) * 2012-03-05 2013-09-12 Fujifilm Corp 活性光線硬化型インクセット、インクジェット記録方法、及び、印刷物
JP2014240464A (ja) * 2013-06-12 2014-12-25 富士フイルム株式会社 インクジェットインク組成物、及び、インクジェット記録方法
WO2018142819A1 (fr) * 2017-01-31 2018-08-09 富士フイルム株式会社 Procédé d'impression à jet d'encre et procédé de fabrication d'un article imprimé stratifié
WO2019189186A1 (fr) * 2018-03-30 2019-10-03 太陽インキ製造株式会社 Composition durcissable pour impression au jet d'encre, produit durci en cette dernière, et composant électronique comportant ledit produit durci
WO2020137067A1 (fr) * 2018-12-25 2020-07-02 サカタインクス株式会社 Composition d'encre photocurcissable pour impression jet d'encre

Also Published As

Publication number Publication date
JPWO2021111884A1 (ja) 2021-12-09
JP2022119898A (ja) 2022-08-17

Similar Documents

Publication Publication Date Title
JP5392420B2 (ja) 活性エネルギー線硬化型インクジェット記録用インク組成物及び画像形成方法
JP5252135B1 (ja) 活性エネルギー線硬化型インクジェット記録用インク組成物及び画像形成方法
JP6344633B2 (ja) 活性エネルギー線硬化型インクジェット記録用インクセット
JP2013053208A (ja) 活性エネルギー線硬化型インクジェット記録用インク組成物及び画像形成方法
JP6083484B2 (ja) 活性エネルギー線硬化型インクジェット記録用インク組成物及び画像形成方法
JP6176034B2 (ja) 活性エネルギー線硬化型インクジェットインク、インクセット及び像形成方法
JP5748103B2 (ja) 活性エネルギー線硬化型着色組成物、それを用いた活性エネルギー線硬化型インクジェット記録用インク組成物、及び画像形成方法
JP2014181281A (ja) 活性エネルギー線硬化型インクジェット記録用インク組成物及びその製造方法
JP2023080137A (ja) 活性エネルギー線硬化性インク及び印刷物の製造方法
JP6089761B2 (ja) 活性エネルギー線硬化型インクジェット記録用インクセット及び多次色の印字物の製造方法
WO2018216484A1 (fr) Encre durcissable par rayons actiniques et procédé de production de matière imprimée
JP6744360B2 (ja) 活性エネルギー線硬化性インク及び印刷物の製造方法
WO2021111884A1 (fr) Encre et procédé de production d'article imprimé
JP7067228B2 (ja) 構造体の製造方法
JP2014189754A (ja) 活性エネルギー線硬化型インクジェット記録用インク組成物及び画像形成方法
JP6255812B2 (ja) 活性エネルギー線硬化型インクジェット記録用インク及び画像形成方法
JP7381187B2 (ja) 活性エネルギー線硬化性インク及び印刷物の製造方法
JP2024077900A (ja) エネルギー線硬化性インクジェット印刷インク及び印刷物の製造方法
JP2018197309A (ja) 活性エネルギー線硬化性インク及び印刷物の製造方法
JP2022029118A (ja) エネルギー線硬化性インクジェット印刷インク及び印刷物の製造方法

Legal Events

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

Ref document number: 20895742

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021550005

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20895742

Country of ref document: EP

Kind code of ref document: A1