WO2021111884A1 - Ink and printed article production method - Google Patents

Ink and printed article production method Download PDF

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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
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Prior art keywords
compound
ink
mass
acrylate
pigment
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PCT/JP2020/043115
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French (fr)
Japanese (ja)
Inventor
齊藤　直人
怜美 藤本
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Dic株式会社
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2021550005A priority Critical patent/JPWO2021111884A1/en
Publication of WO2021111884A1 publication Critical patent/WO2021111884A1/en
Priority to JP2022085918A priority patent/JP2022119898A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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.

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Abstract

The present invention solves the problem of providing an ink capable of forming a coat film having a high coat film hardness, excellent chemical resistance, and excellent tight-adhesion to a recording medium. The inventors have solved the problem by way of an ink which is cured by light emitted from an LED, characterized in that the ink comprises 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 the structure indicated by general formula (1), the compound (B) contains a compound (b1) having a heterocyclic structure, and the content of the compound (A) relative to the total amount of the ink is 60% by mass or greater.

Description

インク及び印刷物の製造方法Manufacturing method of ink and printed matter
　本発明は、様々な印刷物の製造に使用可能なインクに関するものである。 The present invention relates to inks that can be used in the production of various printed matter.
　活性エネルギー線硬化性インクは、他のインクと比較して、硬化性や乾燥性に優れることから、様々な被記録媒体への印刷に使用されている。 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.
　前記活性エネルギー線硬化性インクとしては、例えば着色剤、特定構造のラジカル重合開始剤、及び、テトラヒドロフルフリルアクリレート等のラジカル重合性化合物を含有するインク組成物が知られている（例えば特許文献１参照。）。 As the active energy ray-curable ink, 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.).
　前記活性エネルギー線硬化性インクを用いて得られた印刷物は、広範な用途で使用することが検討されている。例えば前記印刷物を看板等として使用する場合、前記インクには、傷がつきにくく、薬品等が付着した場合であっても印刷画像の劣化等を引き起こしにくいレベルの高硬度で耐薬品性に優れた塗膜を形成できることが求められている。 Printed matter obtained by using the active energy ray-curable ink is being studied for use in a wide range of applications. For example, when the printed matter is used as a signboard or the like, 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.
　しかし、前記塗膜を高硬度化しようとすると、一般に、前記塗膜と被記録媒体との密着性が低下し、経時的に前記塗膜の剥れ等を引き起こす場合があった。 However, when an attempt is made to increase the hardness of the coating film, the adhesion between the coating film and the recording medium generally decreases, which may cause the coating film to peel off over time.
　このように、前記塗膜の高硬度化や耐薬品性と、被記録媒体への密着性とがトレードオフの関係にあるなかで、それらを両立した塗膜を形成可能なインクは未だ見出されていないのが実情である。 As described above, while there is a trade-off relationship between the high hardness and chemical resistance of the coating film and the adhesion to the recording medium, an ink capable of forming a coating film having both of them has not been found yet. The reality is that it has not been done.
特開２０１２－２０１８１５号公報Japanese Unexamined Patent Publication No. 2012-201815
　本発明が解決しようとする課題は、塗膜の硬度が高く、耐薬品性に優れ、かつ、被記録媒体への密着性に優れた塗膜を形成可能なインクを提供することである。 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.
　本発明者は、ＬＥＤから発せられる光によって硬化するインクであって、重合性不飽和二重結合を２個以上有する化合物（Ａ）と、重合性不飽和二重結合を１個有する化合物（Ｂ）とを含有し、前記化合物（Ａ）が下記一般式（１）で示される構造を有する化合物（ａ１）を含有し、前記化合物（Ｂ）が複素環式構造を有する化合物（ｂ１）、かつ、前記化合物（Ａ）が前記インクの全量に対して６０質量％以上含まれることを特徴とするインクによって、前記課題を解決した。 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.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（一般式（１）中のＲは炭素原子数４個以上のアルキレン基を表し、Ｘは水素原子またはメチル基を表す。） (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.)
　本発明のインクであれば、塗膜の硬度が高く、耐薬品性に優れ、かつ、被記録媒体への密着性に優れた塗膜を形成可能である。 With 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.
　本発明のインクは、ＬＥＤから発せられる光によって硬化するインクであって、重合性不飽和二重結合を２個以上有する化合物（Ａ）と、重合性不飽和二重結合を１個有する化合物（Ｂ）とを含有し、前記化合物（Ａ）が下記一般式（１）で示される構造を有する化合物（ａ１）を含有し、前記化合物（Ｂ）が複素環式構造を有する化合物（ｂ１）を含有し、かつ、前記化合物（Ａ）が前記インクの全量に対して６０質量％以上含まれることを特徴とする。本発明のインクであれば、塗膜の硬度が高く、耐薬品性に優れ、かつ、被記録媒体への密着性に優れた塗膜を形成することができる。 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. With 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.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
（一般式（１）中のＲは炭素原子数４個以上のアルキレン基を表し、Ｘは水素原子またはメチル基を表す。） (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.)
　本発明のインクは、ＬＥＤ（発光ダイオード）から発せられる光によって硬化する。前記光としては、例えば波長３５０ｎｍ～４２０ｎｍにピーク発光波長を持つ紫外線が挙げられ、特に３６０～４００ｎｍの領域にピーク発光波長を持つ紫外線を使用することが好ましい。 The ink of the present invention is cured by the light emitted from the LED (light emitting diode). Examples of 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.
　本発明のインクに含まれる化合物（Ａ）としては、重合性不飽和二重結合を２個以上有するものを使用する。 As the compound (A) contained in the ink of the present invention, a compound having two or more polymerizable unsaturated double bonds is used.
　前記化合物（Ａ）としては、好ましくは重合性不飽和二重結合を２個以上、より好ましくは３個以上有する化合物を使用すると、本発明のインクを用いて形成された硬化塗膜の架橋密度が高くなるため、耐薬品性に優れ高硬度な硬化塗膜を形成することが可能となる。一方、前記化合物（Ａ）としては、良好な耐薬品性と高硬度と、被記録媒体への密着性とを両立する観点から、重合性不飽和二重結合の数が２～６個であることが好ましく、２～３個であることがより好ましい。 When a compound having two or more, more preferably three or more polymerizable unsaturated double bonds is used as the compound (A), 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. On the other hand, 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.
　また、前記化合物（Ａ）は、本発明のインクの全量に対して、６０質量％以上使用する。これにより、本発明のインクを用いて形成された硬化塗膜の架橋密度が高くなるため、耐薬品性に優れ高硬度な硬化塗膜を形成することが可能となる。ここで、前記化合物（Ａ）の含有量が前記インクの全量に対して６０質量％未満である場合、耐薬品性や硬度の低下を引き起こす場合がある。 Further, 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. As a result, 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. Here, when 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.
　前記化合物（Ａ）は、前記インクの全量に対して、６５質量％～８５質量％の範囲で使用することが好ましく、７０質量％～８０質量％の範囲で使用することが、より一層優れた耐薬品性を備え高硬度な硬化塗膜を形成可能なインクを得るうえで特に好ましい。 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.
　前記化合物（Ａ）としては、前記一般式（１）で示される構造を有する化合物（ａ１）を含有するものを使用する。 As the compound (A), a compound containing the compound (a1) having the structure represented by the general formula (1) is used.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（一般式（１）中のＲは炭素原子数４個以上のアルキレン基を表し、Ｘは水素原子またはメチル基を表す。） (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.)
　前記化合物（ａ１）としては、前記一般式（１）中のＲが炭素原子数４個～９個のアルキレン基であるものを使用することが好ましく、前記Ｒが炭素原子数６個～９個のアルキレン基であるものを使用することが好ましく、Ｒが炭素原子数６個のアルキレン基であるものを使用することが、高硬度で耐薬品性に優れ、被記録媒体への密着性に優れた塗膜を形成可能で、ＬＥＤから発せられる光に対して感度が高くその照射によって速やかに硬化する性質を備えたインクを得るうえで特に好ましい。 As 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.
　前記化合物（ａ１）としては、具体的には、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）アクリレートを使用することができ、なかでも１，６－ヘキサンジオールジ（メタ）アクリレートを使用することが、高硬度で耐薬品性に優れ、被記録媒体への密着性に優れた塗膜を形成可能で、ＬＥＤから発せられる光に対して感度が高くその照射によって速やかに硬化する性質を備えたインクを得るうえで特に好ましい。 Specific examples of 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. -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-Nonandiol di (meth) acrylate can be used, and among them, 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.
　前記化合物（ａ１）は、被記録媒体への密着性に優れた塗膜を形成可能で、活性エネルギー線に対して感度が高くその照射によって速やかに硬化する性質を備えたインクを得るうえで、前記インクの全量に対して２０質量％～７０質量％使用することが好ましく、３０質量％～６０質量％の範囲で使用することが特に好ましい。 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.
　また、前記化合物（Ａ）としては、前記化合物（ａ１）以外の化合物（ａ２）を、前記化合物（ａ１）と組み合わせ使用することができる。 Further, as the compound (A), a compound (a2) other than the compound (a1) can be used in combination with the compound (a1).
　前記化合物（ａ２）としては、例えば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等のジ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートのジ（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、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＦジ（メタ）アクリレート、水添ビスフェノールＡジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート，ペンタエリスリトールトリ（メタ）アクリレート，ジペンタエリスリトールのポリ（メタ）アクリレート、及びこれらのエチレンオキサイドやプロピレンオキサイド等のアルキレンオキサイド変性物やカプロラクトン変性物、エチレンオキサイド変性リン酸（メタ）アクリレート、エチレンオキサイド変性アルキルリン酸（メタ）アクリレート等、（メタ）アクリル酸２－（２－ビニロキシエトキシ）エチル、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、トリメチロールプロパントリビニルエーテル等のジ又はトリビニルエーテル化合物、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート等を単独または２種以上組み合わせ使用することができる。
　前記化合物（ａ２）としては、前記インクの全量に対して、６０質量％～９５質量％の範囲で使用することが好ましく、７５質量％～９０質量％の範囲で使用することが、＿基材密着と耐薬品性の両立するうえでより好ましい。 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). -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.
As 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.
　次に、重合性不飽和二重結合を１個有する化合物（Ｂ）について説明する。 Next, the compound (B) having one polymerizable unsaturated double bond will be described.
　前記化合物（Ｂ）としては、重合性不飽和二重結合を１個有する複素環式構造を有する化合物（ｂ１）を単独、または、前記化合物（ｂ１）と、前記化合物（ｂ１）以外の重合性不飽和二重結合を１個有する化合物（ｂ２）とを組み合わせ使用する。前記化合物（Ｂ）を使用することによって、前記重合性不飽和二重結合を２個以上有する化合物（Ａ）のみを使用した場合よりも、本発明のインクを用いて形成された架橋密度を適度に低下させ、その結果、塗膜の硬度や耐薬品性や前記密着性や、ＬＥＤから発せられる光に対する前記感度を大幅に損なうことなく、良好な柔軟性を備えた硬化塗膜を形成可能なインクを得ることが可能となる。前記化合物（Ｂ）が有する重合性不飽和二重結合としては、（メタ）アクリロイル基が挙げられるが、アクリロイル基であることが好ましい。 As the compound (B), 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. By using the compound (B), 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. As a result, it is possible to form a cured coating film having good flexibility without significantly impairing the hardness and chemical resistance of the coating film, the adhesion, and the sensitivity to the light emitted from the LED. It becomes possible to obtain ink. Examples of the polymerizable unsaturated double bond of the compound (B) include a (meth) acryloyl group, and an acryloyl group is preferable.
　前記化合物（Ｂ）としては、前記インクの全量に対して１～３９質量％の範囲で使用することが好ましく、５質量％～３０質量％の範囲で使用することがより好ましく、１０質量％～２０質量％の範囲で使用することが、硬化塗膜の高硬度と優れた耐薬品性と前記感度とを大幅に損なうことなく、良好な柔軟性と、被記録媒体への密着性とを備えた硬化塗膜を形成可能なインクを得るうえで特に好ましい。 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.
　前記複素環式構造を有する化合物（ｂ１）としては、例えばカプロラクトン構造を有する化合物、ピリジン構造を有する化合物、ピロリドン構造を有する化合物、テトラヒドロフラン構造を有する化合物、環状トリメチロールプロパン構造を有する化合物を使用することができる。なかでも、前記化合物（ｂ１）としては、カプロラクトン構造を有する化合物を使用することが好ましく、具体的には、Ｎ－ビニルカプロラクタムを使用することが、硬化塗膜の高硬度と優れた耐薬品性とを大幅に損なうことなく、良好な柔軟性と、被記録媒体への密着性とを備えた硬化塗膜を形成可能で、かつ、前記感度がより一層高いインクを得るうえで特に好ましい。 As 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. Among them, as 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.
　また、前記カプロラクトン構造を有する化合物をはじめとする複素環式構造を有する化合物（ｂ１）は、前記インクの全量に対して１５質量％以下の範囲で使用することが好ましく、１質量％～１２質量％の範囲で使用することがより好ましく、５質量％～１０質量％の範囲で使用することが、硬化塗膜の高硬度と優れた耐薬品性とを大幅に損なうことなく、良好な柔軟性と、被記録媒体への密着性とを備えた硬化塗膜を形成可能で、かつ、前記感度がより一層高いインクを得るうえで特に好ましい。 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.
　また、前記化合物（ｂ２）としては、特に限定なく公知の単官能化合物を使用することができるが、例えばメチルアクリレート、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、アミルアクリレート、２－エチルヘキシルアクリレート、イソオクチルアクリレート、ノニルアクリレート、イソデシルアクリレート、ドデシルアクリレート、ヘキサデシルアクリレート、オクタデシルアクリレート、シクロヘキシルアクリレート、ベンジルアクリレート、メトキシエチルアクリレート、ブトキシエチルアクリレート、フェノキシエチルアクリレート、ノニルフェノキシエチルアクリレート、グリシジルアクリレート、ジメチルアミノエチルアクリレート、ジエチルアミノエチルアクリレート、イソボルニルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルアクリレート、ジシクロペンテニロキシエチルアクリレート等の置換基を有するアクリレート等が挙げられる。
　前記化合物（ｂ２）としては、前記インクの全量に対して、５質量％～４０質量％の範囲で使用することが好ましく、１０質量％～２５質量％の範囲で使用することが、被記録媒体への優れた密着性と優れた耐薬品性とを両立するうえでより好ましい。 Further, as the compound (b2), 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. , Nonyl acrylate, isodecyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, benzyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, diethylamino Examples thereof include acrylates having substituents such as ethyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and dicyclopentenyloxyethyl acrylate.
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.
　本発明のインクとしては、前記化合物（Ａ）と化合物（Ｂ）と、さらに、前記化合物（Ａ）及び前記化合物（Ｂ）とは異なるメタクリロイル基を１個以上有する化合物（Ｃ）とを組み合わせ含有するものを使用することが、被記録媒体への密着性をより一層向上させるうえで好ましい。 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.
　前記化合物（Ｃ）としては、例えばメチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、ブチルメタクリレート、アミルメタクリレート、２－エチルヘキシルメタクリレート、イソオクチルメタクリレート、ノニルメタクリレート、ラウリルメタクリレート、トリデシルメタクリレート、ドデシルメタクリレート、ヘキサデシルメタクリレート、オクタデシルメタクリレート、イソデシルメタクリレート、シクロヘキシルメタクリレート、ベンジルメタクリレート、メトキシエチルメタクリレート、ブトキシエチルメタクリレート、フェノキシエチルメタクリレート、ノニルフェノキシエチルメタクリレート、グリシジルメタクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート、イソボルニルメタクリレート、テトラヒドロフルフリルメタクリレート、ジシクロペンタニルメタクリレート、ジシクロペンテニルメタクリレート、ジシクロペンテニロキシエチルメタクリレート等の単官能メタクリレート、１，３－ブチレングリコールジメタクリレート、１，４－ブタンジオールジメタクリレート、１，５－ペンタンジオールジメタクリレート、３－メチル－１，５－ペンタンジオールジメタクリレート、１，６－ヘキサンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、１，８－オクタンジオールジメタクリレート、１，９－ノナンジオールジメタクリレート、トリシクロデカンジメタノールジメタクリレート、エチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、プロピレングリコールジメタクリレート、ジプロピレングリコールジメタクリレート、トリプロピレングリコールジメタクリレート、ポリプロピレングリコールジメタクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートのジメタクリレート、ネオペンチルグリコール１モルに４モル以上のエチレンオキサイド（EO）またはプロピレンオキサイド（PO）が付加したジオールのジメタクリレート、ビスフェノールＡ１モルに２モルのエチレンオキサイドまたはプロピレンオキサイドが付加したジオールのジメタクリレート、トリメチロールプロパン１モルに３モル以上のエチレンオキサイドまたはプロピレンオキサイドが付加したトリオールのジメタクリレート、トリメチロールプロパン１モルに３モル以上のエチレンオキサイドまたはプロピレンオキサイドが付加したトリオールのトリメタクリレート、ビスフェノールＡ１モルに４モル以上のエチレンオキサイドまたはプロピレンオキサイドが付加したジオールのジメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリメタクリレート，ジペンタエリスリトールのポリメタクリレート、エチレンオキサイド変性リン酸メタクリレート、エチレンオキサイド変性アルキルリン酸メタクリレート等を使用することができる
　前記化合物（Ｃ）としては、前記したなかでも、トリメチロールプロパン１モルに３モル以上のエチレンオキサイドまたはプロピレンオキサイドが付加したトリオールのトリメタクリレートやネオペンチルグリコールジメタアクリレートを使用することが、好ましい。 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-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,8-octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, tri. 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. Dimethacrylate, dimethacrylate of diol with 4 or more moles of ethylene oxide (EO) or propylene oxide (PO) added to 1 mol of neopentyl glycol, dimethacrylate of diol with 2 mol of ethylene oxide or propylene oxide added to 1 mol of bisphenol A , Dimethacrylate of triol in which 3 mol or more of ethylene oxide or propylene oxide is added to 1 mol of trimethylol propane, and 3 mol or more of ethylene oxide to 1 mol of trimethylol propane. 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. Among the above-mentioned compounds (C), 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.
　前記化合物（Ｃ）としては、本発明のインクの全量に対して、０．１質量％～１０質量％の範囲であることが好ましく、０．５質量％～５質量％の範囲であることが、被記録媒体への密着性をより一層向上させるうえで好ましい。 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.
　本発明のインクは、ＬＥＤから発せられる光を受けることによって硬化する。本発明のインクとしては、光重合開始剤を含有するものを使用することができる。 The ink of the present invention is cured by receiving the light emitted from the LED. As the ink of the present invention, an ink containing a photopolymerization initiator can be used.
　前記光重合開始剤としては、例えばベンゾインイソブチルエーテル、２，４－ジエチルチオキサントン、２－イソプロピルチオキサントン、ベンジル、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキシド６－トリメチルベンゾイルジフェニルフォスフィンオキシド、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタン－１－オン、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シド、１－ヒドロキシシクロヘキシルフェニルケトン、ベンゾインエチルエーテル、ベンジルジメチルケタール、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オンおよび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、ベンゾフェノン、４－フェニルベンゾフェノン、イソフタルフェノン、４－ベンゾイル－４’－メチル－ジフェニルスルフィド等を使用することができる。 Examples of the photopolymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 6-trimethylbenzoyldiphenylphosphine oxide, 2-. Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphenyl oxide, 1-hydroxycyclohexylphenyl Ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenylsulfide and the like can be used. ..
　前記光重合開始剤としては、前記したなかでもアシルホスフィンオキアシド系光重合開始剤を使用することが好ましい。 Among the above, it is preferable to use an acylphosphine oxyacid-based photopolymerization initiator as the photopolymerization initiator.
　また、前記光重合開始剤としては、ＵＶ－ＬＥＤ光源を使用する場合には、ＵＶ－ＬＥＤ光源から発せられる光の波長に対応した２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタン－１－オン、２－（ジメチルアミノ）－２－[（４－メチルフェニル）メチル]－１－（４－モルフォリノフェニル）－ブタン－１－オン）、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、フェニル（２，４，６トリメチルベンゾイル）ホスフィン酸エチル、２，４－ジエチルチオキサントン、２－イソプロピルチオキサントン等、を使用することが好ましい。 When a UV-LED light source is used 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. Phenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-morpholinophenyl) -butane-1-one), bis (2,4) , 6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, phenyl (2,4,6 trimethylbenzoyl) ethyl phosphinate, 2,4-diethylthioxanthone, 2-isopropyl It is preferable to use thioxanthone or the like.
　前記光重合開始剤は、増感剤と組み合わせ使用することが好ましい。前記増感剤としては、例えば、トリメチルアミン、メチルジメタノールアミン、トリエタノールアミン、ｐ－ジエチルアミノアセトフェノン、ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジメチルアミノ安息香酸イソアミル、Ｎ，Ｎ－ジメチルベンジルアミンおよび４，４’－ビス（ジエチルアミノ）ベンゾフェノン等を使用することができる。 The photopolymerization initiator is preferably used in combination with a sensitizer. Examples of 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.
　本発明のインクとしては、必要に応じて着色剤を含有するものを使用することができる。 As the ink of the present invention, an ink containing a colorant can be used if necessary.
　前記着色剤としては、例えば顔料や染料を使用することができる。前記顔料としては、例えばシアンインクに使用されるフタロシアニン顔料、マゼンタインクに使用されるキナクリドン系顔料、イエローインクに使用されるアゾ顔料、ブラックインクに使用されるカーボンブラック、ホワイトインクに使用可能な白色顔料等が挙げられる。 As the colorant, for example, a pigment or a dye can be used. Examples of 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.
　前記シアンインクに使用されるフタロシアニン顔料としては、例えば、Ｃ．Ｉ．ピグメントブルーの１、２、３、１５：３、１５：４、１６：６、１６、１７：１、７５、７９等が挙げられる。 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.
　マゼンタインクに使用されるキナクリドン系顔料としては、例えばＣ．Ｉ．ピグメントレッド１２２、Ｃ．Ｉ．ピグメントレッド２０２、Ｃ．Ｉ．ピグメントレッド２０９、Ｃ．Ｉ．ピグメントバイオレット１９等があげられる。 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.
　イエローインクに使用されるアゾ顔料としては、例えばＣ．Ｉ．ピグメント　イエローの１２０、１５１、１５４、１７５、１８０、１８１、１、６５、７３、７４、１１６　、１２、１３、１７、８１、８３、１５０、１５５、２１４、１２８等の、モノアゾ及びジスアゾ顔料が含まれる。 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.
　ブラックインクに使用されるカーボンブラックとしては、三菱化学株式会社のＮｏ．２３００、Ｎｏ．９００、ＭＣＦ８８、Ｎｏ．３３、Ｎｏ．４０、Ｎｏ．４５、Ｎｏ．５２、ＭＡ７、ＭＡ８、ＭＡ１００、Ｎｏ．２２００Ｂ等が、コロンビア社製のＲａｖｅｎ５７５０、同５２５０、同５０００、同３５００、同１２５５、同７００等が、キャボット社製のＲｅｇａｌ４００Ｒ、同３３０Ｒ、同６６０Ｒ、Ｍｏｇｕｌ Ｌ、同７００、Ｍｏｎａｒｃｈ８００、同８８０、同９００、同１０００、同１１００、同１３００、同１４００等が、デグッサ社製のＣｏｌｏｒ Ｂｌａｃｋ ＦＷ１、同ＦＷ２、同ＦＷ２Ｖ、同ＦＷ１８、同ＦＷ２００、ＣｏｌｏｒＢｌａｃｋ Ｓ１５０、同Ｓ１６０、同Ｓ１７０、Ｐｒｉｎｔｅｘ ３５、同Ｕ、同Ｖ、同１４０Ｕ、Ｓｐｅｃｉａｌ Ｂｌａｃｋ ６、同５、同４Ａ、同４等が挙げられる。 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.
　ホワイトインクに使用可能な白色顔料としては、特に限定はなく公知の無機白色顔料を使用できる。前記無機白色顔料としては、例えば、アルカリ土類金属の硫酸塩または炭酸塩、微粉ケイ酸や合成珪酸塩等のシリカ類、ケイ酸カルシウム、アルミナ、アルミナ水和物、酸化チタン、酸化亜鉛、タルク、クレイ等があげられる。前記無機白色顔料としては、前記したシリカ類等の表面が各種表面処理方法によって表面処理されたものを使用することもできる。 The white pigment that can be used for white ink is not particularly limited, and a known inorganic white pigment can be used. Examples of 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. As the inorganic white pigment, those whose surfaces such as silicas have been surface-treated by various surface treatment methods can also be used.
　前記顔料の平均粒径(メジアン径：５０％径）は、１０ｎｍ～３００ｎｍの範囲にあるものが好ましく、より好ましくは５０ｎｍ～２００ｎｍである。 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.
　前記顔料のうち、前記白色顔料は、印刷物に隠蔽性を付与するためのホワイトインクに使用される。前記白色顔料は、優れた隠蔽性と、優れた吐出安定性と印刷画像の高い発色性とを備えたホワイトインクを得るうえで、平均粒径(メジアン径：５０％径）が１００ｎｍ～５００ｎｍのものを使用することが好ましく、１５０ｎｍ～４００ｎｍのものを使用することがより好ましい。 Among the pigments, 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.
　前記顔料は、十分な画像濃度や印刷画像の耐光性を得るため、前記インクの全量に対して１質量％～２０質量％の範囲で含まれることが好ましく、１質量％～１０質量％の範囲で含まれることがなお好ましく、１質量％～５質量％の範囲で含まれることが最も好ましい。 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.
　前記顔料は、前記化合物（Ａ）及び前記化合物（Ｂ）中における良好な分散安定性を得るうえで、顔料分散剤や顔料誘導体（シナジスト）等と組み合せ使用してもよい。 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).
　前記顔料分散剤としては、特に限定されないが、例えば味の素ファインテクノ社製のアジスパーＰＢ８２１、ＰＢ８２２、ＰＢ８１７、アビシア社製のソルスパーズ２４０００ＧＲ、３２０００、３３０００、３９０００、楠本化成社株式会社製のディスパロンＤＡ－７０３－５０、ＤＡ－７０５、ＤＡ－７２５等を使用することができる。 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.
　前記顔料分散剤は、前記顔料に対して１０質量％～１００質量％の範囲で使用することが好ましく、より一層優れた吐出安定性と顔料分散性とを備えたインクを得るうえで、２０質量％～8０質量％の範囲であるものを使用することがより好ましい。 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.
　本発明のインクとしては、前記した成分の他に、必要に応じてハイドロキノン、メトキノン、ジ－ｔ－ブチルハイドロキノン、Ｐ－メトキシフェノール、ブチルヒドロキシトルエン、ニトロソアミン塩等の重合禁止剤を含有するものを使用することができる。前記重合禁止剤は、本発明のインクの全量に対して０．０１質量％～２質量％の範囲で使用することができる。 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. Can be used. 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 present invention.
　本発明のインクとしては、プラスチック基材等の被記録媒体への密着性をより一層向上させるうえで、アクリル樹脂、エポキシ樹脂、テルペンフェノール樹脂、ロジンエステル等の非反応性樹脂等を含有するものを使用することができる。 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.
　本発明のインクをインクジェット記録方式で吐出する場合、前記インクの２５℃の粘度は、３ｍＰａ・ｓｅｃ～３０ｍＰａ・ｓｅｃの範囲であることが好ましく、５ｍＰａ・ｓｅｃ～２０ｍＰａ・ｓｅｃの範囲であることが、インクの吐出ノズルからの良好な吐出安定性を確保するうえでより好ましい。 When the ink of the present invention is ejected by an inkjet recording method, 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.
　本発明のインクは、例えば前記化合物（Ａ）と前記化合物（Ｂ）と、必要に応じて前記化合物（Ｃ）や顔料、顔料分散剤、樹脂等を、ビーズミル等の通常の分散機を用いて混合した後、光重合開始剤を加え、必要に応じて重合禁止剤や増感剤や表面張力調整剤等の添加剤を加えて混合することで製造することができる。 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.
　前記インクは、予め、ビーズミル等の通常の分散機を用いて、顔料や顔料分散剤や樹脂等を含有する高濃度の顔料分散体（ミルベース）を製造し、前記顔料分散体に光重合開始剤や前記化合物（Ａ）や前記化合物（Ｂ）や前記化合物（Ｃ）や添加剤等を混合、攪拌、することによって製造することもできる。 For the ink, 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.
　前記分散機としては、ビーズミルの他、たとえば超音波ホモジナイザー、高圧ホモジナイザー、ペイントシェーカー、ボールミル、ロールミル、サンドミル、サンドグラインダー、ダイノーミル、ディスパーマット、ＳＣミル、ナノマイザーなど、公知慣用の各種分散機を使用することができる。 As the 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.
　本発明のインクは、ＬＥＤから発せられる光、好ましくは紫外線等の光照射をすることにより硬化する。紫外線等の光源としては、ＵＶ－ＬＥＤランプ等を使用することができる。 The ink of the present invention is cured by irradiating with light emitted from an LED, preferably ultraviolet rays or the like. As a light source for ultraviolet rays or the like, a UV-LED lamp or the like can be used.
　本発明のインクは、もっぱらインクジェット記録装置を用いたインクジェット記録方式での印刷に好適に使用することができる。 The ink of the present invention can be suitably used for printing by an inkjet recording method exclusively using an inkjet recording device.
　インクジェット記録方式としては、従来公知の方式がいずれも使用できる。例えば圧電素子の振動を利用して液滴を吐出させる方法（電歪素子の機械的変形によりインク滴を形成するインクジェットヘッドを用いた記録方法）や熱エネルギーを利用する方法が挙げられる。 As the inkjet recording method, any conventionally known method can be used. For example, 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) and a method of utilizing thermal energy can be mentioned.
　前記インクを、インクジェット記録装置を用いて吐出し、被記録媒体に印刷し、ＬＥＤから発せられる光を照射することによって硬化させることによって、印刷物を製造することができる。前記印刷物としては、例えば広告、看板、案内板、販促品印刷などが挙げられる。 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.
　本発明のインクは、様々な種類の被記録媒体に対する密着性に優れるため、曲面や凹凸した不規則な形状を有するような被記録媒体の表面にも容易に印刷することができる。 Since 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.
　前記被記録媒体としては、例えばプラスチック基材を使用することができる。前記プラスチック基材としては、具体的には、汎用の射出成形用プラスチックとして使用される、ＡＢＳ（アクリロニトリル・ブタジエン・スチレン）樹脂、ＰＶＣ（ポリ塩化ビニル）／ＡＢＳ樹脂、ＰＡ（ポリアミド）／ＡＢＳ樹脂、ＰＣ（ポリカーボネート）／ＡＢＳ樹脂、ＰＢＴ（ポリブチレンテレフタレート）／ＡＢＳ等のＡＢＳ系のポリマーアロイ、ＡＡＳ（アクリロニトリル・アクリルゴム・スチレン）樹脂、ＡＳ（アクリロニトリル・スチレン）樹脂、ＡＥＳ（アクリロニトリル・エチレンゴム・スチレン）樹脂、ＭＳ（（メタ）アクリル酸エステル・スチレン）系樹脂、ＰＣ（ポリカーボネート）系樹脂、アクリル系樹脂、メタクリル系樹脂、ＰＰ（ポリプロピレン）系樹脂等からなる基材が挙げられる。 As the recording medium, for example, a plastic base material can be used. Specific examples of 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 resin, PBT (polybutylene terephthalate) / ABS and other ABS-based polymer alloys, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, 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.
　また、前記プラスチック基材としては、例えば包装材料用に使用される熱可塑性樹脂フィルム等を使用することも可能である。 Further, as the plastic base material, for example, a thermoplastic resin film used for a packaging material or the like can be used.
　前記熱可塑性樹脂フィルムとしては、一般に食品包装用として使用される熱可塑性樹脂フィルムとして使用されるものが挙げられ、例えばポリエチレンレテフタレート（ＰＥＴ）フィルム、ポリスチレンフィルム、ポリアミドフィルム、ポリアクリロニトリルフィルム、ポリエチレンフィルム（ＬＬＤＰＥ：低密度ポリエチレンフィルム、ＨＤＰＥ：高密度ポリエチレンフィルム）やポリプロピレンフィルム（ＣＰＰ：無延伸ポリプロピレンフィルム、ＯＰＰ：二軸延伸ポリプロピレンフィルム）等のポリオレフィンフィルム、ポリビニルアルコールフィルム、エチレン－ビニルアルコール共重合体フィルム等が挙げられる。前記熱可塑性樹脂フィルムとしては、一軸延伸や二軸延伸等の延伸処理されたものや、表面に火炎処理やコロナ放電処理等が施されたものを使用することもできる。 Examples of the thermoplastic resin film 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. (LLDPE: low density polyethylene film, HDPE: high density polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film) and other polyolefin films, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer Examples include films. As the thermoplastic resin film, 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.
　以下、実施例により、本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
　［顔料分散体の調製例］
　調製例１；シアン顔料分散体（１）
　ファストゲンブルーＴＧＲ-Ｇ（ＤＩＣ株式会社製　フタロシアニン顔料Ｃ．Ｉ．ピグメントブルー１５：４）１０質量部と、ソルスパーズ　３２０００（ルーブリゾール製、高分子顔料分散剤）４．５質量部と、ＭＩＲＡＭＥＲ　Ｍ２２２（ＭＩＷＯＮ社製　ジプロピレングリコールジアクリレート）８５．５質量部とを、攪拌機で１時間撹拌混合した後、ビーズミルで２時間処理することによって、シアン顔料分散体（１）を得た。 [Example of preparation of pigment dispersion]
Preparation Example 1; 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).
　調製例２；シアン顔料分散体（２）
　ＭＩＲＡＭＥＲ　Ｍ２２２（ＭＩＷＯＮ社製　ジプロピレングリコールジアクリレート）８５．５質量部の代わりに、ＭＩＲＡＭＥＲ　Ｍ２００（ＭＩＷＯＮ社製、１，６－ヘキサンジオールジアクリレート）８５．５質量部を使用したこと以外は、調製例１と同様の方法でシアン顔料分散体（２）を得た。 Preparation Example 2; 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.
　調製例３；マゼンタ顔料分散体（３）
　ファストゲンブルーＴＧＲ-Ｇ（ＤＩＣ株式会社製　フタロシアニン顔料Ｃ．Ｉ．ピグメントブルー１５：４）１０質量部の代わりに、ファストゲンスーパーマゼンタ　ＲＴＳ（ＤＩＣ株式会社製　マゼンタ顔料Ｃ．Ｉ．ピグメントレッド　１２２）１０質量部を使用したこと以外は、調製例１と同様の方法でマゼンタ顔料分散体（３）を得た。 Preparation Example 3; 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.
　調製例４；イエロー顔料分散体（４）
　レバスクリーンイエローＧ０１（（株）ランクセス製　Ｃ．Ｉ．ピグメントイエロー１５０）１０質量部と、ソルスパーズ　３２０００（ルーブリゾール製　高分子顔料分散剤）６質量部と、ＭＩＲＡＭＥＲ　Ｍ２２２（ＭＩＷＯＮ社製　ジプロピレングリコールジアクリレート）８４質量部とを、攪拌機で１時間撹拌混合した後、ビーズミルで２時間処理することによって、イエロー顔料分散体（４）を得た。 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).
　調製例５；ブラック顔料分散体（５）
　カーボンブラック　＃９６０（三菱化学株式会社製　カーボンブラック）１０質量部と、ソルスパーズ　３２０００（ルーブリゾール製　高分子顔料分散剤）４．５質量部と、ＭＩＲＡＭＥＲ　Ｍ２２２（ＭＩＷＯＮ社製　ジプロピレングリコールジアクリレート）８５．５質量部とを、攪拌機で１時間撹拌混合した後、ビーズミルで２時間処理することによって、ブラック顔料分散体（５）を得た。 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.
　調製例６；ホワイト顔料分散体（６）
　ＴＩＴＡＮＩＸ　ＪＲ－８０６（テイカ株式会社製　酸化チタン）５０質量部と、ソルスパーズ　２４０００（ルーブリゾール製　高分子顔料分散剤）２．５質量部と、ＭＩＲＡＭＥＲ　Ｍ２２２（ＭＩＷＯＮ社製　ジプロピレングリコールジアクリレート）４７．５質量部とを、攪拌機で１時間撹拌混合した後、ビーズミルで２時間処理することによって、ホワイト顔料分散体（６）を得た。 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.
　実施例１
　容器にＭＩＲＡＭＥＲ　Ｍ３１３０を９質量部、ＭＩＲＡＭＥＲ　Ｍ２００を５６質量部、Ｖ－ＣＡＰを９質量部、ＫＦ－３５１Ａを０．２質量部を入れ攪拌混合し、次いでＯｍｎｉｒａｄ８１９を３．５質量部、Ｏｍｎｉｒａｄ　ＴＰＯ-Ｈを４質量部、Ｋａｙａｃｕｒｅ ＤＥＴＸ－Ｓを２．５質量部を加え、温度６０℃で３０分間混合した。 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.
　次に、前記混合物と前記顔料分散体（１）とを混合し１０分間攪拌することで、表１に示す配合のインクを得た。 Next, the mixture and the pigment dispersion (1) were mixed and stirred for 10 minutes to obtain inks having the formulations shown in Table 1.
　実施例２～１２及び比較例１～４
　インクの配合を表１～３に記載したものに変更したこと以外は、実施例１と同様の方法でインクを製造した。 Examples 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.
　以下に使用した原料の詳細を記載する。（）内は、表中に記載した略称である。
・ＭＩＲＡＭＥＲ　Ｍ３１３０（Ｍ３１３０）：ＭＩＷＯＮ社製　エチレンオキサイド（ＥＯ）変性トリメチロールプロパントリアクリレート
・ＭＩＲＡＭＥＲ　Ｍ２２２（Ｍ２２２）：ＭＩＷＯＮ社製　ジプロピレングリコールジアクリレート
・ＭＩＲＡＭＥＲ　Ｍ２００（Ｍ２００）：ＭＩＷＯＮ社製　1、６－ヘキサンジオールジアクリレート
・ＭＩＲＡＭＥＲ　Ｍ２１３（Ｍ２１３）：ＭＩＷＯＮ社製　ネオペンチルグリコールジメタクリレート
・Ｖ－ＣＡＰ（Ｖ－ＣＡＰ）：アッシュランド社製　Ｎ－ビニル－２－カプロラクタム
・ライトアクリレート　ＰＯＡ（ＰＯＡ）：共栄社化学株式会社製　フェノキシエチルアクリレート
・ＫＦ－３５１Ａ（ＫＦ－３５１Ａ）：信越化学工業株式会社製　ポリシロキサン
・Ｏｍｎｉｒａｄ８１９（８１９）：ＩＧＭ社製　ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド
・Ｏｍｎｉｒａｄ　ＴＰＯ-Ｈ（ＴＰＯ）：ＩＧＭ社製　２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド
・Ｋａｙａｃｕｒｅ ＤＥＴＸ－Ｓ（ＤＥＴＸ)：日本化薬株式会社製　ジエチルチオキサントン Details of the raw materials used are described below. The numbers in parentheses are the abbreviations listed in the table.
-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. 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.
　[静的表面張力]
　前記静的表面張力は、ポリ容器に入れたインクを恒温水槽に浸漬し２５℃に調整した後、協和界面科学株式会社製のウェルヘルミー型表面張力測定器：ＤＹ－３００を用いて測定した。 [Static surface tension]
The static surface tension was measured by immersing the ink in a plastic container in a constant temperature water tank to adjust the temperature to 25 ° C., and then using a well-helmy type surface tension measuring device: DY-300 manufactured by Kyowa Interface Science Co., Ltd.
　[粘度]
　インクの２５℃における粘度は、東機産業株式会社製の粘度測定器：ＴＶ－２５を用いて測定した。前記測定装置の測定回転数は２０ｒｐｍ／ｍｉｍとした。 [viscosity]
The viscosity of the ink at 25 ° C. was measured using a viscometer: TV-25 manufactured by Toki Sangyo Co., Ltd. The measurement rotation speed of the measuring device was 20 rpm / mim.
　[硬化性]
　インクを、ポリカーボネート板（ＰＣ：旭硝子（株）製、レキサン、厚さ１ｍｍ）に対し、スピンコーターにて厚さ６μｍになるように塗布した。次に、前記塗布面に浜松ホトニクス株式会社製のＬＥＤ照射装置（発光波長：３８５ｎｍ、ピーク強度：５００ｍＷ/ｃｍ２）を用いて、１回の照射エネルギー量が３０Ｊ／ｍ２となるように照射し、前記塗布面を指触した際にタックフリーになるまでの照射エネルギー量の積算値を測定した。 [Curability]
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 μm. Next, 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. Then, the integrated value of the amount of irradiation energy until the coated surface became tack-free when touched was measured.
　前記照射エネルギー量の積算値が４００ｍＪ／ｃｍ２以下であった塗膜を形成可能なインクは、硬化性に優れると評価した。 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.
［密着性］
　前記インクを、ポリカーボネート板（ＰＣ：旭硝子（株）製、レキサン、厚さ１ｍｍ）、アクリル板（ＰＭＭＡ：クラレ（株）製、コモグラス）、塩化ビニルプレート（ＰＶＣ：三菱化学（株）製、ヒシプレートＧＥ３０１）、に対し、スピンコーターにて厚さ１０μｍで塗布した。次に、前記塗布面に浜松ホトニクス株式会社製のＬＥＤ照射装置（発光波長：３８５ｎｍ、ピーク強度：５００ｍＷ/ｃｍ２、１回の照射エネルギー量が３０Ｊ／ｍ２）を用いて、前記塗布面がタックフリーとなるまで照射することによって硬化塗膜を得た。 [Adhesion]
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 μm. Next, 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.
　得られた硬化塗膜に、２ｍｍ間隔で５×５の２５マス様にカッターナイフで切り込みを入れた後、その硬化塗膜にニチバン株式会社製のセロハン粘着テープを貼り付け、前記テープの表面を１０回爪で擦った。次に、剥離速度約１ｃｍ／ｓｅｃの速度にて勢い良くテープを剥がし、前記ポリカーボネート板、塩化ビニルプレート、アクリル板の表面に残った塗膜のマス目の数を確認した。 After making cuts in the obtained cured coating film in 5 × 5 25 squares at 2 mm intervals with a cutter knife, 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.
　評価基準
　良：塗膜のマス数が２０以上
　可：塗膜のマス数が１５以上２０未満
　不可：塗膜のマス数が１５未満 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
　［耐薬品性］
　前記インクを、ポリカーボネート板（旭硝子（株）製、レキサン、厚さ１ｍｍ、ＰＣ）に対し、スピンコーターにて厚さ１０μｍで塗布した。次に、前記塗布面に浜松ホトニクス株式会社製のＬＥＤ照射装置（発光波長：３８５ｎｍ、ピーク強度：５００ｍＷ/ｃｍ２、１回の照射エネルギー量が３０Ｊ／ｍ２）を用いて、前記塗布面がタックフリーとなるまで照射することによって硬化塗膜を得た。 [chemical resistance]
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 μm. Next, 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.
　得られた硬化塗膜を、エタノール及び水の混合物（エタノールの含有割合７０質量％）を浸した綿棒で、約２ｃｍ幅で左右に１０回擦った。塗膜表面に擦り跡が無かったものを「○」と評価し、擦り跡が確認されたものを「×」と評価した。 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".
　[鉛筆硬度]
　前記インクを、ポリカーボネート板（旭硝子（株）製、レキサン、厚さ１ｍｍ、ＰＣ）に対し、スピンコーターにて厚さ１０μｍで塗布した。次に、前記塗布面に浜松ホトニクス株式会社製のＬＥＤ照射装置（発光波長：３８５ｎｍ、ピーク強度：５００ｍＷ/ｃｍ２、１回の照射エネルギー量が３０Ｊ／ｍ２）を用いて、前記塗布面がタックフリーとなるまで照射することによって硬化塗膜を得た。 [Pencil hardness]
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 μm. Next, 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.
　得られた硬化塗膜の鉛筆硬度を、に対しＪＩＳ－Ｋ５６００－５－４の試験方法に則り鉛筆硬度評価を行った。鉛筆はＭＩＴＳＵ－ＢＩＳＨＩ製を用い、試験機器は、（株）東洋精機製作所製鉛筆引っかき硬度試験機を用いて評価した。 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.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

Claims (5)

  1. ＬＥＤから発せられる光によって硬化するインクであって、重合性不飽和二重結合を２個以上有する化合物（Ａ）と、重合性不飽和二重結合を１個有する化合物（Ｂ）とを含有し、前記化合物（Ａ）が下記一般式（１）で示される構造を有する化合物（ａ１）を含有し、前記化合物（Ｂ）が複素環式構造を有する化合物（ｂ１）を含有し、かつ、前記化合物（Ａ）が前記インクの全量に対して６０質量％以上含まれることを特徴とするインク。
    Figure JPOXMLDOC01-appb-I000001
    （一般式（１）中のＲは炭素原子数４個以上のアルキレン基を表し、Ｘは水素原子またはメチル基を表す。）     An ink that is cured by light emitted from an LED and contains 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), the compound (B) contains a compound (b1) having a heterocyclic structure, and the above. An ink characterized in that the compound (A) is contained in an amount of 60% by mass or more based on the total amount of the ink.
    Figure JPOXMLDOC01-appb-I000001
    (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.)
  2. 前記化合物（ａ１）は、前記一般式（１）中のＲが炭素原子数４個～９個のアルキレン基である化合物であり、前記化合物（ａ１）は前記インクの全量に対して２０質量％～７０質量％含まれる請求項１に記載のインク。 The compound (a1) is a compound in which R in the general formula (1) is an alkylene group having 4 to 9 carbon atoms, and the compound (a1) is 20% by mass based on the total amount of the ink. The ink according to claim 1, which contains ~ 70% by mass.
  3. 前記化合物（Ｂ）が、前記複素環式構造を有する化合物（ｂ１）としてカプロラクトン構造を有する化合物を含有し、前記カプロラクトン構造を有する化合物は、前記インクの全量に対して１５質量％以下の範囲で含まれる請求項１または２に記載のインク。 The compound (B) contains a compound having a caprolactone structure as the compound (b1) having a heterocyclic structure, and the compound having a caprolactone structure is in a range of 15% by mass or less with respect to the total amount of the ink. The ink according to claim 1 or 2, which is included.
  4. 前記化合物（Ａ）及び前記化合物（Ｂ）とは構造が異なるメタクリロイル基を１個以上有する化合物（Ｃ）を含有し、前記化合物（Ｃ）の含有量が前記インクの全量に対して１０質量％以下である請求項１～３のいずれか１項に記載のインク。 The compound (A) and the compound (C) having one or more methacryloyl groups having a structure different from that of the compound (B) are contained, and the content of the compound (C) is 10% by mass with respect to the total amount of the ink. The ink according to any one of claims 1 to 3 below.
  5. 被記録媒体に請求項１～４のいずれか１項に記載のインクで印刷し、その印刷面に、ＬＥＤから発せられる光を照射し硬化させることを特徴とする印刷物の製造方法。 A method for producing a printed matter, which comprises printing on a recording medium with the ink according to any one of claims 1 to 4, and irradiating the printed surface with light emitted from an LED to cure the printed matter.
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