WO2019111895A1 - Jeu d'encres, stratifié formé à l'aide du jeu d'encres, procédé de formation d'image formant une image à l'aide du jeu d'encres, et procédé de production de stratifié - Google Patents

Jeu d'encres, stratifié formé à l'aide du jeu d'encres, procédé de formation d'image formant une image à l'aide du jeu d'encres, et procédé de production de stratifié Download PDF

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Publication number
WO2019111895A1
WO2019111895A1 PCT/JP2018/044563 JP2018044563W WO2019111895A1 WO 2019111895 A1 WO2019111895 A1 WO 2019111895A1 JP 2018044563 W JP2018044563 W JP 2018044563W WO 2019111895 A1 WO2019111895 A1 WO 2019111895A1
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WIPO (PCT)
Prior art keywords
ink
absorbance
photopolymerization initiator
substrate
wavelength
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PCT/JP2018/044563
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English (en)
Japanese (ja)
Inventor
公淳 宇▲高▼
森田　浩司
克巳 渡部
Original Assignee
株式会社Ｄｎｐファインケミカル
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Publication of WO2019111895A1 publication Critical patent/WO2019111895A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to a light-curable ink set mainly used as an inkjet ink, a laminate formed using the ink set, an image forming method of forming an image using the ink set, and a method of manufacturing the laminate About.
  • the light curable ink composition is composed of an active energy ray polymerizable monomer, a photopolymerization initiator and other additives.
  • a white ink (first ink) is first applied to the light curable ink composition on the substrate so that the color development of the ink can be obtained, for example, on a transparent sheet or a metallized sheet as a substrate.
  • first ink a white ink
  • second ink a printing method of applying various color inks on the white ink. Then, this printing method is a printing method in which the ink is cured by irradiating a light beam from the side on which the second ink is applied. Development of an ink set including such a first ink and a second ink has also been conducted.
  • Patent Document 1 discloses an ink set containing a predetermined photopolymerization initiator. According to Patent Document 1, this ink set is an ink set that is excellent in the curability to LED light and has excellent adhesion to polyvinyl chloride-based sheets.
  • the ink jet head is fixed by moving the ink jet head in the lateral direction and discharging the ink several times in the ink jet method, and the image is fixed by passing the substrate through the ink jet head once. There is a single pass method to form.
  • the single pass method has an advantage that the printing speed is high and the productivity of the printed matter (laminate) is high because an image can be formed by passing it once.
  • the first ink and the second ink are applied in this order on the substrate by a single pass method or the like, and the light beam is applied from the side on which the second ink is applied. It has been found that when irradiated, the curability of the first ink may be degraded. When the curability of the first ink is deteriorated, the adhesion between the substrate and the first ink is lowered, and it can not be said that it is preferable as a printed matter (laminated body).
  • the present invention has been made in view of the above-described circumstances, and the first ink and the second ink are applied to the substrate even when the ink set including the first ink and the second ink is applied to the substrate.
  • An object of the present invention is to provide an ink set in which the curability of the ink No. 1 is good.
  • the inventors of the present invention have found that, in absorbance measurement in which each clear ink obtained by removing the coloring material from the first ink and the second ink is irradiated with light, The inventors have found that the above problems can be solved by adjusting the absorbance curve for a wavelength of up to 420 nm within a predetermined range or adjusting the content ratio of a predetermined photopolymerization initiator, and have completed the present invention.
  • the present invention provides the following.
  • the first ink and the second ink contain an active energy ray polymerizable monomer, a photopolymerization initiator, and, if necessary, a colorant.
  • the absorbance ink of the first ink is the same as the absorbance of the clear ink in the second ink.
  • An ink set in which the area of the range where the absorbance increases is 0.5 or more.
  • first ink applied on a substrate and a second ink applied on the first ink, the light beam being irradiated from the side on which the second ink is applied
  • first ink and the second ink comprise an active energy ray polymerizable monomer, and a photopolymerization initiator.
  • the ink is applied on the substrate by a single pass method in which an image is formed on the substrate by passing the substrate once through an ink jet head which is used as an inkjet ink and fixed.
  • the ink set according to any one of (1) to (3).
  • a manufacturing method of a layered product which forms a picture and / or a concavo-convex image on a substrate using an ink set in any one of (1) to (4).
  • the ink set of the present invention is an ink set in which the curability of the first ink applied on a substrate is good.
  • FIG. 16 is an absorbance curve of the clear ink produced from the ink 1 which is the first ink in the ink set of Example 3 and the clear ink produced from the ink 2-3 which is the second ink.
  • the ink set of the present embodiment is an ink set including a first ink and a second ink.
  • the first ink is an ink to be applied on the substrate.
  • the second ink is an ink applied on the applied first ink.
  • the first ink and / or the second ink may be a single ink each containing any coloring material (for example, yellow, magenta, cyan, black), for example, a white coloring material It may be a white ink containing (white) or an ink containing no coloring material.
  • the first ink and / or the second ink may be a single ink, but may be a plurality of inks including, for example, yellow ink, magenta ink, cyan ink, and black ink.
  • the first ink may be a single ink and the second ink may be a plurality of inks.
  • the first ink may be a plurality of inks and the second ink may be a single ink.
  • the first ink and the second ink contain an active energy ray polymerizable monomer and a photopolymerization initiator.
  • the photopolymerization initiator By including the photopolymerization initiator, the polymerization reaction of the active energy ray polymerizable monomer can be promoted, and the cured film of the first ink and the second ink can be respectively formed.
  • the first ink and the second ink may contain a coloring material or may be an ink containing no coloring material. Moreover, you may contain a polymerization inhibitor, a dispersing agent, a surface conditioner, a matting agent, a plasticizer, a light stabilizer, an antioxidant etc. as needed.
  • the absorbance of the light beam for the wavelength of 350 nm to 420 nm is adjusted.
  • the first of the absorbances of the clear ink in the second ink The area of the range in which the absorbance of the clear ink in the ink is increased is 0.5 or more.
  • a ⁇ -log 10 (I / I 0 ) (Wherein ⁇ is the wavelength (in nm), A ⁇ is the absorbance at the wavelength ⁇ , I 0 is the incident light intensity at the wavelength ⁇ , and I is the transmitted light intensity at the wavelength ⁇ .)
  • each clear ink of the first ink and the second ink used for absorbance measurement is a propylene glycol monomethyl ether ink containing an identical part by mass of each component other than the coloring material contained in each ink It means ink diluted 100 times with acetate.
  • the type and addition amount of the photopolymerization initiator are adjusted. It should just be.
  • a photopolymerization initiator of an acylphosphine oxide is used as a photopolymerization initiator
  • a thioxanthone photopolymerization initiator and / or an alkylphenone is used as a photopolymerization initiator
  • the second ink may further contain a photopolymerization initiator of an acylphosphine oxide in an amount smaller than the content of a photopolymerization initiator of an acylphosphine oxide contained in the first ink.
  • the content ratio may be adjusted by using a thioxanthone photopolymerization initiator and / or an alkylphenone photopolymerization initiator in the first ink and the second ink.
  • the present embodiment also in the ink set of the present invention, X mass%, which is the content of the acylphosphine oxide-based photopolymerization initiator contained in the first ink, and the acylphosphine contained in the second ink in the total amount of the second ink It is preferable that Y / X ⁇ 100 which is a relational expression with Y mass% which is content of an oxide type photopolymerization initiator is 0 or more and 90 or less, more preferably 0 or more and 70 or less, 0 or more It is more preferably 50 or less, still more preferably 0 or more and 20 or less, and most preferably 0 or less.
  • the second ink further contains a photopolymerization initiator of an acylphosphine oxide in an amount smaller than the content of the photopolymerization initiator of an acylphosphine oxide contained in the first ink
  • a photopolymerization initiator other than the acylphosphine oxides for example, a thioxanthone photopolymerization initiator and / or an alkylphenone photopolymerization initiator
  • the area of the range in which the absorbance of the clear ink in the first ink is larger than the absorbance of the clear ink in the second ink means, for example, the range indicated by hatching in FIG. In the absorbance measurement, it is a range surrounded by the absorbance curve of the clear ink in the first ink and the absorbance curve of the clear ink in the second ink, and more than the absorbance of the clear ink in the second ink It means the area of the range (the range of oblique lines in FIG. 2) in which the absorbance of the clear ink in the first ink is large.
  • the area of absorbance means a so-called approximate area.
  • the approximate area for example, the measurement interval of the measurement wavelength when the 0.5 nm (((absorbance A lambda ink wavelength X nm) + (wavelength (X + 0.5) absorbance nm ink A ⁇ )) ⁇ 0 X means an area obtained by adding the area of a quadrangle (trapezoid) calculated from 5/2 in the range of 350 nm to 420 nm.
  • the area of the range where the absorbance of the clear ink in the first ink is larger than the absorbance of the clear ink in the second ink is the square (trapezoid) of the clear ink in the second ink
  • the distance between measurement wavelengths may be reduced. For example, absorbance may be measured at a wavelength of about 350 nm to 420 nm at an interval of about 0.5 nm.
  • the reason why the curability of the first ink is deteriorated is that the photopolymerization contained in the second ink when light is irradiated from the side on which the second ink is applied. This is because each component such as an initiator absorbs a light beam having a wavelength of 350 nm to 420 nm, and the first ink does not reach a light beam having a wavelength of 350 nm to 420 nm. If the light having a wavelength of 350 nm to 420 nm does not sufficiently reach the first ink, the curability of the first ink is degraded.
  • the clear ink in the first ink in the measurement of absorbance for irradiating the clear ink in each of the first ink and the second ink with light, the clear ink in the first ink is higher than the absorbance in the clear ink in the second ink. It is specified that the area of the range in which the absorbance of is increased is 0.5 or more. By setting the area in this range to 0.5 or more, a light beam having a wavelength of 350 nm to 420 nm, which only the first ink cures, can reach the first ink, and the curability of the first ink is improved. improves.
  • the first ink is a white ink of one color (one type)
  • the second ink is a plurality of inks of four colors (four types) such as yellow ink, magenta ink, cyan ink, and black ink.
  • the first ink and the clear ink of the second ink the relationship of the above-mentioned absorbance (the second ink) in the relation of the clear ink of at least one color (one kind) If the area of the range in which the absorbance of the clear ink in the first ink is larger than the absorbance of the clear ink is 0.5 or more), the effect of the present invention is obtained.
  • the relationship between the clear ink in the first ink and the clear ink in the second ink is at least one color (one kind) of clear ink and there is a relationship of the absorbance in each of the above clear inks, a predetermined image is formed. This is because the curability of the entire first ink layer is improved in the entire laminate.
  • the clear ink in the first ink and the second ink are preferable.
  • Clear ink in ink and at least three colors (three types) of clear ink for example, at least three colors of clear ink in four colors (four types) of yellow ink, magenta ink, cyan ink, black ink
  • at least four colors (four types) of clear ink in the second ink for example, clear inks in four colors (four types) of yellow ink, magenta ink, cyan ink, and black ink
  • the relationship of the above-mentioned absorbance is in relation to.
  • the second ink is a four-color (four-color) ink.
  • the first ink is an ink of more than four types (four colors) or less than four types (four colors)
  • the second ink is an ink of more than four types (four colors) or less than four types (four colors)
  • a certain ink set is used to a certain ink set.
  • the second ink is a four-color (four-color) ink consisting of yellow ink, magenta ink, cyan ink, and black ink
  • one ink of the second ink satisfying the relationship of absorbance described above is cyan It is preferably an ink.
  • the cyan ink is an ink that absorbs visible light of a relatively long wavelength, but contains a large amount of a photopolymerization initiator (for example, an acylphosphine oxide photopolymerization initiator) that absorbs a large amount of light having a wavelength of about 370 nm to 410 nm.
  • a photopolymerization initiator for example, an acylphosphine oxide photopolymerization initiator
  • the compound derived from the photopolymerization initiator generated by the irradiation of light may be slightly yellowed, which may cause the cured film of the cyan ink to be slightly discolored.
  • a photopolymerization initiator for example, a thioxanthone photopolymerization initiator and / or an alkylphenone photopolymerization initiator
  • the photopolymerization initiator contained in the cyan ink And the relationship between the cyan ink (second ink) and the first ink can satisfy the above-described absorbance relationship, and the cured film of the cyan ink may be discolored by a compound derived from a photopolymerization initiator Can be reduced.
  • magenta ink is an ink that absorbs visible light of a relatively medium wavelength, but when it contains a large amount of a photopolymerization initiator that absorbs a large amount of light with a wavelength of about 370 nm to 410 nm, photopolymerization initiation occurs upon irradiation with light. Depending on the compound derived from the agent, it may appear slightly yellow, which may cause the cured film of the magenta ink to slightly discolor, although not as much as the cured film of the cyan ink.
  • a photopolymerization initiator for example, a thioxanthone photopolymerization initiator and / or an alkylphenone photopolymerization initiator
  • a photopolymerization initiator which does not absorb visible light with a wavelength of about 370 nm to 410 nm so much as a photopolymerization initiator contained in magenta ink
  • the yellow ink is an ink that absorbs visible light of a relatively short wavelength
  • the black ink is an ink that absorbs visible light of the entire visible region including the short wavelength. Therefore, since the yellow ink and the black ink are already inks that absorb visible light of relatively short wavelength, even if the compound derived from the photopolymerization initiator gives a yellow color, discoloration of the cured film hardly occurs.
  • the ink is a four-color (four-color) ink consisting of yellow ink, magenta ink, cyan ink, and black ink
  • the ink is preferably a cyan ink.
  • the ink be a cyan ink and a magenta ink.
  • the ink is preferably cyan ink, magenta ink, black ink and yellow ink.
  • the ink set of the present embodiment applies a first ink and a second ink to a substrate in this order, and applies a light beam from the side on which the second ink is applied to the first ink.
  • the application method is not limited as long as it is an ink set that cures the ink of and the second ink.
  • the single pass method is a coating method in which an image is formed on a substrate by passing the substrate once with the ink jet head fixed.
  • the single pass method is a method of the following application method.
  • each inkjet head in FIG. 1, the inkjet head 21 and the inkjet head 22
  • the substrate 13 is allowed to pass through each inkjet head, and transported by roll to roll.
  • the first ink 11 is applied onto the top of the ink jet head 21.
  • the second ink 12 is applied onto the first ink 11 from the inkjet head 22.
  • the first ink 11 and the second ink 12 are simultaneously cured (mainly cured) by irradiating the light beam with the light beam 23.
  • the ink set of this embodiment be used as an ink set for applying the ink on a substrate by a single pass method.
  • the illuminance in the range of 375 to 415 nm is 1500 mW / cm 2 or more, preferably 2000 mW / cm 2 or more. It is preferable that it is a relatively strong light source capable of emitting such a light beam, for example, it is preferable to use a metal halide lamp.
  • UV POWER PUCK II manufactured by EIT can be used to measure the illuminance and integrated light quantity.
  • the first ink 11 may be irradiated with light from the light source 24 to cure (temporarily cure) the first ink 11. preferable. Even when the second ink 12 is applied by curing (temporary curing) the first ink 11, the first ink 11 is mixed with the second ink 12 by having fluidity, and the ink It is possible to prevent the occurrence of bleeding and the like due to mixing of the two.
  • the light source 24 for curing (temporary curing) the first ink 11 may be a relatively weak light source because it may be cured to such an extent that the flowability of the first ink 11 is reduced.
  • a light beam can be emitted such that the illuminance in the range of 375 to 415 nm is 1000 mW / cm 2 or more, preferably 1500 mW / cm 2 or more, and / or the illuminance outside the range of 375 to 415 nm is 10 mW / cm 2
  • the light source is a relatively weak light source such as the following, preferably 5 mW / cm 2 or less, and most preferably 0 mW / cm 2.
  • an LED lamp can be used.
  • the LED lamp is preferably an LED lamp capable of emitting light in the range of 375 to 415 nm.
  • the printer shown in FIG. 1 is an ink jet head for applying ink of a single color to the ink jet head 21 for applying the first ink, and the ink jet head 23 for applying the second ink is four colors (multicolor
  • the ink jet head is configured to apply the ink of
  • the configuration may be such that the inkjet head for applying the first ink is an inkjet head for applying multi-color ink (not shown).
  • the inkjet head for applying the second ink may be an inkjet head for applying a single color ink (not shown).
  • the ink set in which the absorbances of the clear ink in the first ink and the second ink are specified focusing on the curability of the first ink of the printed matter (laminate) is novel.
  • the area of the range in which the absorbance of the first ink is larger than the absorbance of the second ink is preferably 0.7 or more, and more preferably 1.0 or more.
  • the ink set of the present embodiment is an ink set including a first ink and a second ink.
  • the first ink is an ink to be applied on the substrate.
  • the second ink is an ink applied on the applied first ink.
  • the first ink and / or the second ink may be a single ink each containing a coloring material (for example, yellow, magenta, cyan, black), for example, a white coloring material (white). It may be a white ink containing H or an ink containing no coloring material.
  • the first ink and / or the second ink may be a single ink, but may be a plurality of inks including, for example, yellow ink, magenta ink, cyan ink, and black ink.
  • the first ink may be a single ink and the second ink may be a plurality of inks.
  • the first ink may be a plurality of inks and the second ink may be a single ink.
  • the first ink and the second ink contain an active energy ray polymerizable monomer and a photopolymerization initiator.
  • the photopolymerization initiator By including the photopolymerization initiator, the polymerization reaction of the active energy ray polymerizable monomer can be promoted, and a cured film of the first ink and the second ink can be formed.
  • the first ink and the second ink may contain a coloring material or may be an ink containing no coloring material. Moreover, you may contain a polymerization inhibitor, a dispersing agent, a surface conditioner, a matting agent, a plasticizer, a light stabilizer, an antioxidant etc. as needed.
  • the content of the acylphosphine oxide-based photopolymerization initiator is adjusted in the photopolymerization initiators in the first ink and the second ink.
  • X mass% which is the content of the acyl phosphine oxide photopolymerization initiator contained in the first ink
  • the reason why the curing properties of the first ink deteriorate is because the acyl phosph is contained in the second ink when the light is irradiated from the side on which the second ink is applied.
  • the fin oxide type photopolymerization initiator absorbs a light beam having a wavelength of 350 nm to 420 nm, the light beam having a wavelength of 350 nm to 420 nm does not reach the first ink, and the curability of the first ink is deteriorated.
  • the content of the acylphosphine oxide photopolymerization initiator contained in the first ink and the second ink is specified.
  • Y / X ⁇ 100 to be 0 or more and 90 or less, a ray of light having a wavelength of 350 nm to 420 nm that only the first ink cures can reach the first ink, and the curability of the first ink Improve.
  • a photopolymerization initiator other than the acyl phosphine oxides for example, a thioxanthone photopolymerization initiator and / or an alkylphenone light
  • a polymerization initiator for example, a thioxanthone photopolymerization initiator and / or an alkylphenone light
  • the first ink is a white ink of one color (one kind) and the second ink is a four color (four kinds) ink consisting of a yellow ink, a magenta ink, a cyan ink and a black ink
  • the second ink is a four color (four kinds) ink consisting of a yellow ink, a magenta ink, a cyan ink and a black ink
  • the curability of the entire layer of the first ink in the whole of the laminate on which the predetermined image is formed Is to improve.
  • At least two colors (two types) of the first ink and the second ink for example, at least two colors (two types out of four colors (four types) of yellow ink, magenta ink, cyan ink, and black ink
  • Relationship between the content of the acylphosphine oxide-based photopolymerization initiator contained in the first ink and the second ink in relation to the above) i.e., the ink in one kind of the first ink
  • the content of the acylphosphine oxide photopolymerization initiator contained in “Ink A” Y B-1 / X A ⁇ 100 which is a relational expression between a certain X
  • the content of the acyl phosphine oxide photopolymerization initiator contained in the first ink and the second ink described above be related, and the first ink and the fourth ink of four colors (4 Species) in An acyl phosphine oxide type photopolymerization initiator contained in the first ink and the second ink in relation to (for example, four colors (four types) of yellow ink, magenta ink, cyan ink, black ink) It is preferable that there is a relationship of the content of
  • the second ink is a four-color (four-color) ink.
  • the first ink is an ink of more than four types (four colors) or less than four types (four colors)
  • the second ink is an ink of more than four types (four colors) or less than four types (four colors)
  • a certain ink set is used to a certain ink set.
  • the second ink is a four-color (four-color) ink composed of a yellow ink, a magenta ink, a cyan ink, and a black ink
  • the second ink satisfies the relationship of the content of the acylphosphine oxide photopolymerization initiator
  • one of the two inks is cyan ink.
  • Cyan ink is an ink that absorbs visible light of relatively long wavelength, but when it contains a large amount of acylphosphine oxide photopolymerization initiator, it becomes slightly yellow due to a compound derived from the photopolymerization initiator generated by irradiation of light beam.
  • the cured film of the cyan ink may be slightly discolored.
  • a polymerization initiator which does not contain much acyl phosphine oxide type photo polymerization initiator or is other than an acyl phosphine oxide type photo polymerization initiator (for example, thioxanthone type photo polymerization initiator and / or alkyl phenone type photo polymerization initiator) It is possible to satisfy the relation of the content of the above-mentioned acyl phosphine oxide photopolymerization initiator by selecting the above, and the possibility that the cured film of cyan ink may be discolored by the compound derived from the photopolymerization initiator. It can be reduced.
  • magenta ink is an ink that absorbs visible light of a relatively medium wavelength
  • the photopolymerization initiator-derived compound generated by the irradiation of a light beam causes a slight increase. It may appear yellow, which may cause the cured film of the magenta ink itself to slightly discolor, but not as much as the cured film of the cyan ink.
  • the yellow ink is an ink that absorbs visible light of a relatively short wavelength
  • the black ink is an ink that absorbs visible light of the entire visible region including the short wavelength. Therefore, since the yellow ink and the black ink are already inks that absorb visible light of relatively short wavelength, even if the compound derived from the photopolymerization initiator gives a yellow color, discoloration of the cured film hardly occurs.
  • the second ink is a four-color (four-color) ink composed of yellow ink, magenta ink, cyan ink, and black ink
  • the relationship of the content of the above acylphosphine oxide photopolymerization initiator is
  • the ink to be filled is one color (one type)
  • the ink is preferably a cyan ink.
  • the second ink satisfying the relationship of the content of the above acylphosphine oxide photopolymerization initiator is two colors (two types), it is preferable that the ink is a cyan ink and a magenta ink.
  • the ink is a cyan ink, a magenta ink, a black ink and a yellow ink Is preferred.
  • the ink set of the present embodiment noting the curability of the first ink of the printed matter (laminate), it is an acyl phosphine oxide photopolymerization initiator contained in the first ink and the second ink.
  • the ink set for which the content ratio is specified is a new ink set.
  • the ink set of the present embodiment is used as an ink set for applying the ink on a substrate by a single pass method, as in the ink set of the first embodiment.
  • the description about the application method is the same as that of the ink set of the first embodiment.
  • Y / X ⁇ 100 is preferably 0 or more and 70 or less, more preferably 0 or more and 50 or less, still more preferably 0 or more and 20 or less, and most preferably 0.
  • the area of the range in which the absorbance of the clear ink in the first ink is larger than the absorbance of the clear ink in the second ink is preferably 0.5 or more, and 0.7 It is more preferable that it is the above, and it is still more preferable that it is 1.0 or more.
  • the photopolymerization initiator is not particularly limited as long as the photopolymerization initiator can satisfy the above-described embodiment.
  • a photopolymerization initiator which promotes the polymerization reaction of the active energy ray polymerizable monomer by irradiating a light beam containing light having a wavelength of 350 nm to 420 nm.
  • it is a photoinitiator which accelerates
  • Such a photopolymerization initiator is an excellent photopolymerization initiator in view of the curing speed, the availability of the irradiation apparatus, the price and the like.
  • photopolymerization initiator conventionally known photopolymerization initiators can be used.
  • the polymerization initiator include, for example, aromatic ketones including thioxanthone etc., ⁇ -aminoalkylphenones, ⁇ -hydroxy ketones, acyl phosphine oxides, aromatic onium salts, organic peroxides, thio compounds Hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
  • the photopolymerization initiator contained in the first ink and the photopolymerization initiator contained in the second ink have the respective absorption wavelengths.
  • the area of the range in which the absorbance of the first ink is larger than the absorbance of the second ink is 0.5 It becomes above.
  • the first ink contains a photopolymerization initiator of an acylphosphine oxide as a photopolymerization initiator
  • the second ink contains a photopolymerization initiator It is preferable to use a thioxanthone photopolymerization initiator and / or an alkylphenone photopolymerization initiator as
  • the second ink may further contain a photopolymerization initiator of an acylphosphine oxide in an amount smaller than the content of a photopolymerization initiator of an acylphosphine oxide contained in the first ink.
  • the content ratio may be adjusted by using a thioxanthone photopolymerization initiator and / or an alkylphenone photopolymerization initiator in the first ink and the second ink.
  • the alkylphenone photopolymerization initiator is contained in the first ink, there is no particular limitation as long as Y / X ⁇ 100 satisfies 0 or more and 90 or less.
  • the second ink may not contain the alkylphenone photopolymerization initiator (in this case, Y / X ⁇ 100 is 0).
  • the second ink contains a photopolymerization initiator other than the alkylphenone photopolymerization initiator.
  • photoinitiators other than an alkyl phenone type photoinitiator a thioxanthone type photoinitiator and / or an alkyl phenone type photoinitiator can be mentioned, for example.
  • the amount of the photopolymerization initiator according to the present embodiment may be an amount capable of appropriately initiating the photopolymerization reaction of the active energy ray polymerizable monomer, and is 1.0% by mass or more with respect to the entire ink composition. Preferably, it is 3.0 mass% or more. Moreover, it is preferable that it is 20.0 mass% or less with respect to the whole ink composition.
  • Each ink in the ink set of the first and second embodiments contains an active energy ray polymerizable monomer.
  • the active energy ray polymerizable monomer is not particularly limited as long as it has an ethylenically unsaturated double bond and is a monomer having a polymerizability by a photopolymerization initiator upon irradiation with an active energy ray.
  • the active energy ray polymerizable monomer may be a monofunctional monomer having one ethylenically unsaturated double bond in the compound, or a polyfunctional monomer having two or more ethylenically unsaturated double bonds in the compound It may be
  • the monomer of the "active energy ray polymerizable monomer" in this specification is the concept also including the compound also called an oligomer depending on the molecular weight.
  • monofunctional monomers are tetrahydrofurfuryl acrylate (THFA), trimethylolpropane formal acrylate (CTFA), (2-methyl-2-ethyl-1,3-dioxolan-4-yl) acrylate, (2-methyl -2-isobutyl-1,3-dioxolan-4-yl) (meth) acrylate, (cyclohexanespiro-2- (1,3-dioxolan-4-yl)) (meth) acrylate, alkyl cycloalkyl acrylate 4 -T-Butyl cyclohexyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, ⁇ -butyrolactone Cryolate, cresol acrylate, 2-acryloyl
  • polyfunctional monomers examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long chain Aliphatic di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate ) Acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, stearic acid modified pentaerythritol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate Triethylene glycol
  • content of these (meth) acrylates is an active energy ray polymerizable monomer.
  • the total amount is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99% by mass or more.
  • monofunctional (meth) acrylate and polyfunctional (meth) acrylate can be used in combination as appropriate.
  • the content ratio in the case of using the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate in combination may be appropriately adjusted according to the application, and is not particularly limited. Among them, from the viewpoint of achieving both the adhesion of the cured film and the film strength, the content of the polyfunctional (meth) acrylate is preferably 60% by mass or less and 50% by mass or less based on the total amount of monofunctional (meth) acrylates. Is more preferred.
  • the active energy ray polymerizable monomers of the first and second embodiments can be used singly or in combination of two or more.
  • the solventless type that is, the organic solvent is not contained, and therefore, the compound having the ethylenically unsaturated bond is usually used instead of the solvent or the dispersion medium. . Therefore, in addition to the curability and the film properties after curing, it is preferable to select and combine as appropriate from the viewpoint of being a solvent or a dispersion medium.
  • the active energy ray polymerizable monomer which can be a solvent or dispersion medium may be suitably selected from those which are liquid at room temperature (25.degree. C.). For example, one having a molecular weight of 150 or more or one having a molecular weight of 400 or less is suitable. Used for
  • Preferred examples of the active energy ray polymerizable monomer which can be used as a solvent or dispersion medium include, for example, phenoxyethyl acrylate, isobornyl acrylate, 4-t-butylcyclohexyl acrylate, ethyl carbitol acrylate, tetrahydrofurfuryl acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, propoxylated neopentyl glycol diacrylate Triethylene glycol divinyl ether, 2- (2-vinyloxyethoxy) ethyl acrylate, cyclohexane spiro-2- (1,3-dioxola 4-yl) (meth) acrylate, and the like.
  • the content of the active energy ray polymerizable monomer in the first and second embodiments is not particularly limited. From the viewpoint of curability in the cured film, the content of the active energy ray polymerizable monomer in the entire active energy ray curable ink composition of the present embodiment is preferably 30% by mass or more, and 45% by mass or more. Is more preferable, and 60% by mass or more is particularly preferable.
  • the ink composition in the ink set of the first and second embodiments may contain a polymerization inhibitor, as needed.
  • the polymerization inhibitor is not particularly limited.
  • diphenyl picryl hydrazide, tri-p-nitrophenylmethyl, p-benzoquinone, p-tert-butyl catechol, picric acid, copper chloride, methyl hydroquinone, methoquinone, tert- Polymerization inhibitors such as butyl hydroquinone, phenothiazines and nitrosamines can be used.
  • the ink composition in the ink set of the first and second embodiments may contain a coloring material as needed.
  • the ink composition in the ink set of the first and second embodiments may be an ink containing no coloring material.
  • a cured film can be preferably used as a cured film for decoration.
  • the coloring material may be a dye or a pigment.
  • the pigment may be any inorganic or organic pigment generally used in conventional ink compositions, for example, carbon black, cadmium red, molybdenum red, chromium yellow, cadmium yellow, titanium Yellow, titanium oxide, chromium oxide, bilizian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, diketopyrrolopyrrole, anthraquinone, benzimidazolone, anthrapyrimidine, azo pigment, phthalocyanine pigment, quinacridone pigment Isoindolinone pigments, dioxazine pigments, Sureren pigments, perylene pigments, perinone pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments, aluminum paste, silica, calcium carbonate, magnesium carbonate Clay, precipitated barium sulfate, pearl pigments.
  • inorganic or organic pigment generally used in conventional ink compositions, for example, carbon black, cadmium red,
  • the preferred dispersed particle size of the pigment is preferably 10 nm or more in volume average particle size by a laser scattering method.
  • a preferable dispersed particle size of the pigment is preferably 300 nm or less in volume average particle size by a laser scattering method.
  • the content of the pigment in the total active energy ray-curable ink composition is preferably 0.1% by mass or more, in the case of an organic pigment, from the viewpoint of achieving both dispersibility and coloring power, though it varies depending on the type of pigment. 0.2 mass% or more is more preferable.
  • 20.0% by mass or less is preferable, and 10.0% by mass or less is more preferable in terms of achieving both dispersibility and coloring power.
  • an inorganic pigment 1.0 mass% or more is preferable, and 5.0 mass% or more is more preferable, in terms of achieving both dispersibility and coloring power. Moreover, in the case of an inorganic pigment, 40.0 mass% or less is preferable, and 20.0 mass% or less is more preferable.
  • the ink composition in the ink set of the first and second embodiments may contain a dispersant, if necessary.
  • a dispersing agent a polymer dispersing agent is mentioned, for example.
  • the main chain of this polymer dispersant is polyester type, polyacrylic type, polyurethane type, polyamine type, polycaprolactone type, etc., and the polymer dispersant is composed of amino group, carboxyl group, sulfone group, hydroxyl group etc. as a side chain. It is preferable to have a polar group of
  • the active energy ray curable ink composition of the present embodiment may further contain a surface conditioner.
  • the surface conditioner is not particularly limited. Specific examples thereof include BYK-302, BYK-307, BYK-322, BYK-331, and BYK- by BYK-Chemie having dimethylpolysiloxane.
  • the active energy ray-curable ink composition of the present embodiment may contain a matting agent, if necessary.
  • a matting agent various powder particles, such as a silica, an alumina, a calcium carbonate, can be used, for example.
  • the matting agents may be used alone or in combination of two or more.
  • the active energy ray-curable ink composition of the present embodiment may contain various additives such as a plasticizer, a light stabilizer, and an antioxidant as other additives.
  • a solvent can also be added within the range which achieves the purpose of this application.
  • the surface tension of the active energy ray-curable ink composition of the present embodiment is 20 mN / m or more at 40 ° C. from the viewpoint of the dischargeability and the discharge stability of the active energy ray-curable ink composition. Is preferred.
  • the surface tension at 40 ° C. is preferably 40 mN / m or less.
  • the method for producing the ink of the present embodiment is not particularly limited, and a conventionally known method can be used.
  • a granular color material, a granular matting agent, etc. are used, they are dispersed with an active energy ray polymerizable monomer, a dispersing agent, etc. using a dispersing machine and then, if necessary, a photopolymerization initiator and An ink is obtained by adding a surface conditioner etc., stirring uniformly, and also filtering with a filter.
  • the laminate of this embodiment is produced by printing the ink set of the above embodiment onto a substrate, preferably using an inkjet method, and then curing with a light beam containing light having a wavelength of about 200 nm to 450 nm.
  • Printing can be performed by a conventionally known method such as an offset printing method, a gravure printing method, a spray method, or a brush coating method, but an inkjet method is preferable in that it can correspond to a large number of small lots.
  • the inkjet methods it is more preferable to use a single pass method in which an image is formed on a substrate by passing the substrate once while the inkjet head is fixed.
  • printing may be performed in a state where the inkjet head is heated, or printing may be performed at room temperature.
  • the ink set of the above embodiments can be used to form an image on a substrate.
  • an ink set of an active energy ray-curable ink composition containing coloring materials of various colors is prepared, and printing is performed by an inkjet method, and then the ink composition is cured to form various images on a substrate. It can be formed.
  • An ink composition for forming such a cured film and an image forming method for forming an image on a substrate are also within the scope of the present invention.
  • image refers to a decorative image that can be recognized through vision including characters, charts, figures, symbols, photographs, etc. consisting of a single color or a plurality of colors, for example, wood, Also included are patterns made of stone, grain, grain, geometric patterns, characters, etc.
  • the method for producing a laminate using the ink set of the first embodiment can include, for example, a method for producing a laminate including the following steps.
  • (1) a step of applying a first ink containing an active energy ray polymerizable monomer, a photopolymerization initiator and, if necessary, a coloring material on a substrate
  • the second ink is applied (1) in the step of curing the ink applied on the substrate by irradiating a light beam from the exposed side, and forming the cured film of the first ink and the cured film of the second ink on the substrate
  • a step of curing (temporary curing) to the extent that fluidity is lost by irradiating the first ink applied to the substrate with a light beam May be provided.
  • the ink set of the first embodiment is based on the absorbance of the clear ink in the second ink so that the light beam having a wavelength of 350 nm to 420 nm that the first ink cures can reach the first ink.
  • the area of the range in which the absorbance of the clear ink in the first ink is large is specified. Therefore, the method of manufacturing a laminate using the ink set of the first embodiment is a method of manufacturing a laminate capable of improving the curability of a cured film formed by the first ink.
  • the method for producing a laminate using the ink set of the second embodiment can include, for example, a method for producing a laminate including the following steps.
  • Step of applying a first ink containing an active energy ray polymerizable monomer and a photopolymerization initiator on a substrate (2) Activity on the first ink
  • a step of applying a second ink containing an energy beam polymerizable monomer and a photopolymerization initiator (3) applying a light beam from the side on which the second ink is applied onto the substrate This is a method for producing a laminate including the steps (1) to (3) of the steps of curing the ink and forming a cured film of the first ink and a cured film of the second ink on the substrate.
  • a step of curing to the extent that fluidity is lost by irradiating the first ink applied to the substrate with a light beam
  • the first ink and the second ink may contain a coloring material, if necessary.
  • the ink set according to the second embodiment includes the X mass% of the content of the acylphosphine oxide-based photopolymerization initiator contained in the first ink, and the second in the total amount of the second ink.
  • the Y / X ⁇ 100 which is a relational expression with the Y mass% that is the content of the acyl phosphine oxide-based photopolymerization initiator contained in the ink, is 0 or more and 90 or less.
  • a ray of light having a wavelength of 350 nm to 420 nm that the first ink cures can reach the first ink, and the curability of the first ink is improved. Therefore, the method of manufacturing a laminate using the ink set of the second embodiment is a method of manufacturing a laminate capable of improving the curability of a cured film formed by the second ink.
  • the substrate is not particularly limited, and, for example, any of an absorbent body such as coated paper, non-coated paper, fabric and the like and non-absorbent substrate can be used.
  • non-coated paper includes new paper, medium-grade paper, high-quality paper
  • coated paper includes coated paper, art paper, cast paper, lightweight coated paper, finely coated paper, fabrics, etc.
  • the body include cotton, synthetic fiber fabric, silk, hemp, cloth, non-woven fabric, leather and the like
  • non-absorptive substrates include polyester resins, polypropylene synthetic papers, vinyl chloride resins, polyimide resins, metals, metals Foil coated paper, glass, synthetic rubber, natural rubber and the like can be exemplified.
  • the substrate may be flexible or non-flexible.
  • the active energy ray for forming a cured film (hereinafter sometimes referred to as "cured film") obtained by curing the ink set of the above embodiment is a light beam containing light having a wavelength of 200 nm to 450 nm.
  • it is a light beam including light with a wavelength of 350 nm to 420 nm.
  • the light source is not particularly limited as long as it is a light source capable of irradiating a light beam including light having a wavelength of 200 nm to 450 nm, and for example, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultra high pressure mercury lamp, an ultraviolet laser, a solar Light, an LED lamp etc. are mentioned.
  • the light source 23 for simultaneously curing (main curing) the first ink 11 and the second ink 12 is preferably a relatively strong light source, and for example, a metal halide lamp is preferably used.
  • the light source 24 for curing (temporary curing) the first ink 11 may be a relatively weak light source as long as it can be cured to such an extent that the flowability of the first ink 11 is reduced, for example, an LED lamp It can be used.
  • the thickness of the cured film is preferably 1 ⁇ m or more. Moreover, it is preferable that the thickness of a cured film is 50 micrometers or less. By setting the thickness to 1 ⁇ m or more, physical properties such as design property and decorativeness, adhesion, and extensibility are improved without decreasing the color density of the cured film containing the coloring material, it is more preferable. By setting the thickness to 50 ⁇ m or less, the ink composition can be sufficiently cured in a shorter time when the ink composition is irradiated with active energy rays, which is more preferable.
  • the cured film was obtained by applying the ink composition of the above embodiment to a PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) under the same coating conditions as the produced cured film.
  • the thickness of the can be measured by a micrometer.
  • thickness of a cured film is performed ten places per sample, and the average value of these is made thickness (average thickness). The same applies to the protective layer and the primer described later.
  • the cured film formed by the ink set of the above embodiment can be used as a decorative layer, but when discharged onto the decorative layer without containing a coloring material, the cured film itself is protected. It can also be used as an overcoat layer.
  • any method may be used to form these layers, for example, spray application, application using towel, sponge, non-woven fabric, tissue, etc., dispenser, It may be any of brush coating, gravure printing, flexographic printing, silk screen printing, ink jet, thermal transfer system and the like.
  • An image can be formed on a substrate by discharging the ink set of the above embodiment and irradiating it with active energy rays such as light rays including light with a wavelength of 350 nm to 420 nm. Furthermore, by adjusting the conditions such as the ink discharge amount and the time from the discharge of the ink to the irradiation of the active energy ray, it is possible to provide the cured film with a design other than the image. For example, asperities can be provided by increasing or decreasing the amount of ejection once depending on the ejection location, or by repeating the ejection of the ink and the irradiation of the active energy ray at the same location, the unevenness difference with other locations is obtained. It can also be granted. An image forming method for forming such an image and / or a concavo-convex image is also within the scope of the present invention.
  • an overcoat layer comprising a conventionally known overcoat agent or the ink composition of the above embodiment is provided on the surface of the cured film of the ink composition of the above embodiment.
  • An overcoat layer formed by using an ink having the same composition and containing no colorant as an overcoat agent may be further formed.
  • the overcoat layer is not limited to the case where it is formed on the surface of the layer formed of the cured film of the ink composition, but may be formed directly on the surface of the substrate, or the primer formed on the surface of the substrate It may be formed on the surface of the layer.
  • the thickness of the overcoat layer is preferably 1 ⁇ m or more. It is preferable to set the thickness to 1 ⁇ m or more because the cured film can be appropriately protected.
  • the thickness of the overcoat layer is preferably 50 ⁇ m or less. Setting the thickness to 50 ⁇ m or less is preferable because the drying time for forming the overcoat layer can be shortened and the productivity can be excellent.
  • White Mill Base was produced by the following method.
  • 4 g of a polymer dispersant (“SOLSPERSE 32000" manufactured by Nippon Lubrizol Corporation) is dissolved in 56 g of 1,6-hexanediol diacrylate HDDA ("1, 6 HX-A” manufactured by Kyoeisha Chemical Co., Ltd.)
  • HDDA 1,6-hexanediol diacrylate
  • a white pigment titanium oxide JR 405, manufactured by Tayca Corporation
  • 200 g of zirconia beads having a diameter of 0.3 mm was added and dispersed by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) to prepare a white mill base.
  • cyan mill base was manufactured by the following method.
  • 6 g of a polymer dispersant (“SOLSPERSE 32000" manufactured by Nippon Lubrizol Corporation) is dissolved in 82 g of 1,6-hexanediol diacrylate HDDA ("1, 6 HX-A” manufactured by Kyoeisha Chemical Co., Ltd.)
  • HDDA 1,6-hexanediol diacrylate
  • Add 12 g of cyan pigment LIONOL BLUE FG-7400-G, manufactured by Toyo Ink Mfg. Co., Ltd.
  • HDDA means “1,6HX-A” 1,6-hexanediol diacrylate manufactured by Kyoeisha Chemical Co., Ltd.
  • VEEA means 2- (2-vinyloxyethoxy) ethyl acrylate Nippon Catalyst Co., Ltd. "VEEA”.
  • IRGACURE TPO is a 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (photopolymerization initiator manufactured by BASF and corresponds to "acyl phosphine oxide type photopolymerization initiator”) Yes).
  • IRGACURE 819 is bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide (photopolymerization initiator manufactured by BASF, and "acyl phosphine oxide type photopolymerization initiator") Corresponding to
  • DETX means 2,4-diethylthioxanthen-9-one (photopolymerization initiator manufactured by Mitsubishi Shoji Chemical Co., Ltd. and corresponds to "thioxanthone photopolymerization initiator”).
  • IRGACURE 379 is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by BASF, Inc.)
  • a photopolymerization initiator which corresponds to an "alkylphenone photopolymerization initiator”.
  • IRGACURE 127 is 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one (BASF)
  • BASF 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one
  • BASF A photopolymerization initiator manufactured by the company, which corresponds to "alkylphenone photopolymerization initiator”.
  • the absorbance was measured for Inks 1-1 to 1-6 and Inks 2-1 to 2-13. Specifically, it is manufactured by diluting an ink 1-1 to 1-6 and an ink containing the same mass parts of each component other than the coloring materials in the inks 2-1 to 2-13 with propylene glycol monomethyl ether acetate 100 times.
  • a cellophane adhesive tape is attached to the cured ink film layer in the laminate, and after the ink cured film layer and the cellophane adhesive tape are in close contact with each other, the cellophane adhesive tape is peeled off at an angle of 90 ° to the base of the cured ink film layer.
  • the adhesion of each sample was evaluated based on the following evaluation criteria.
  • the content ratio of the ink set in which the area of the range in which the absorbance of the first ink becomes large is 0.5 or more, or the content ratio of the acylphosphine oxide photopolymerization initiator contained in each ink
  • Examples 17 to 19 similarly, laminates were manufactured using inks of colors other than cyan (inks 2-11 to 2-13) as the second ink, and the adhesion test was performed. Peeling of the ink cured film layer was not observed. From this result, it can be seen that the same effect can be obtained even if the second ink is an ink other than cyan ink.
  • Example 20 a laminated body is manufactured using Ink 1-6 (yellow ink) as the first ink and Ink 2-12 (magenta ink) as the second ink, and similarly adhering As a result of the test, no peeling of the cured ink film was observed. From this result, it can be seen that the same effect can be obtained even if the first ink is an ink other than white ink.
  • Ink 1-6 yellow ink
  • Ink 2-12 magenta ink
  • the ink set of the present invention is an ink set in which the curability of the first ink applied on the substrate is good.
  • Example 21 The adhesion test of the laminate manufactured by the ink set in which the second ink is a plurality of inks was conducted. Specifically, one ink 1-1 is used as the first ink, and ink 2-11 (yellow), ink 2-12 (magenta), ink 2-3 (cyan) is used as the second ink. And ink 2-13 (black) were used. Then, the ink 1-1 is injected into one ink jet head (corresponding to the ink jet head 21 in FIG. 1) of the first ink, and the ink 2-11, the ink 2-12, the ink 2-3, the ink 2-13 Were injected into four ink jet heads (corresponding to the ink jet head 22 in FIG.
  • the first ink (ink 1-1) is applied (solid printing) on the substrate, and a light beam is irradiated by an LED lamp (irradiation wavelength 385 nm) as a light source (integrated light quantity (320 to 390 nm): 30 mJ / cm 2 )
  • Temporarily cure the second ink (Ink 2-11, Ink 2-12, Ink 2-3, Ink 2-13) 0.5 mm apart on the first ink (Ink 1-1) Apply a stripe print pattern with a width of 0.5 mm, and apply a light beam from the side coated with the second ink with a metal halide lamp as a light source (integrated light quantity (320 to 390 nm): 1850 mJ / cm 2 ),
  • the first ink and the second ink applied on the material were cured to produce a laminate.
  • Table 3 shows the relationship between the “absorbance area” determined by the absorbance curve in the absorbance measurement of each ink described above and the content ratio of the acylphosphine oxide photopolymerization initiator contained in each ink. “Y / X” "100" is shown.
  • Example 22 In the ink set of Example 21, one of the inks 1-4 is used as the first ink instead of the ink 1-1, and the ink 2-11 (yellow) and the ink 2-12 (second ink) are used as the second ink. Instead of the four types of magenta ink, ink 2-3 (cyan), and ink 2-13 (black), four types of inks 2-1 to 2-4 (all of which are cyan) were used. Then, a laminate was produced in the same manner as in Example 21 above.
  • Example 17 Ink 2-1 was injected as Ink 2 instead of Ink 2-3 in Ink 2-1 to Ink 2-4. Then, a laminate was produced in the same manner as in Example 22 above.
  • the adhesion test was conducted on the laminates produced by the ink sets of Examples 21, 22 and Comparative Example 11 in the same manner as described above.
  • the laminates produced by the ink sets of Examples 21 and 22 no peeling of the cured ink film layer was observed (corresponding to “o” in the above evaluation).
  • the laminate produced by the ink set of Comparative Example 11 most of the cured ink film layer was peeled off (corresponding to “x” in the above evaluation).
  • At least one of the clear ink in the first ink (clear ink of the ink 1-4) and the clear ink in the second ink (ink 2-3) The area of the range in which the absorbance of the clear ink in the first ink (ink 1-4) is larger than the absorbance of the clear ink in the second ink (ink 2-3) in relation to the clear ink If there is a relationship of 0.5 or more, it is understood that the ink set is good in the curability of the first ink.
  • the absorbance of the second ink in relation to the first ink is higher than that of the second ink.
  • the ratio of the area where the absorbance of the first ink is large is 0.5 or more, or Y / X ⁇ 100 which is the relation of the content of the acylphosphine oxide photopolymerization initiator is 0 or more and 90 or less It was confirmed that the ink set has high adhesion between the substrate and the first ink layer and good curability of the first ink.

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Abstract

L'invention concerne un jeu d'encres qui présente une bonne aptitude au durcissement d'une première encre appliquée sur un substrat même lorsque le jeu d'encres contient la première encre et une seconde encre et est appliqué sur le substrat. Un jeu d'encres photodurcissables contient une première encre qui est appliquée sur un substrat et une seconde encre qui est appliquée sur la première encre, et la première encre et la seconde encre contiennent un monomère polymérisable par rayonnement d'énergie active et un initiateur de photopolymérisation. Dans le cadre d'une mesure d'absorbance, dans laquelle des encres transparentes, obtenues par élimination des colorants de la première encre et de la seconde encre, sont exposées à de la lumière, sur les courbes d'absorbance indiquant les relations des absorbances respectives des encres transparentes par rapport à une lumière présentant des longueurs d'onde comprises entre 350 et 420 nm, la surface d'une plage dans laquelle l'absorbance de l'encre transparente de la première encre est supérieure à l'absorbance de l'encre transparente de la seconde encre, est supérieure ou égale à 0,5.
PCT/JP2018/044563 2017-12-06 2018-12-04 Jeu d'encres, stratifié formé à l'aide du jeu d'encres, procédé de formation d'image formant une image à l'aide du jeu d'encres, et procédé de production de stratifié WO2019111895A1 (fr)

Applications Claiming Priority (2)

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JP2017-234610 2017-12-06
JP2017234610A JP6910939B2 (ja) 2017-12-06 2017-12-06 インクセット、インクセットを使用して形成された積層体、インクセットを使用して像を形成する像形成方法及び積層体の製造方法

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WO2019111895A1 true WO2019111895A1 (fr) 2019-06-13

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