WO2016088873A1 - Image formation method - Google Patents

Image formation method Download PDF

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Publication number
WO2016088873A1
WO2016088873A1 PCT/JP2015/084128 JP2015084128W WO2016088873A1 WO 2016088873 A1 WO2016088873 A1 WO 2016088873A1 JP 2015084128 W JP2015084128 W JP 2015084128W WO 2016088873 A1 WO2016088873 A1 WO 2016088873A1
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WO
WIPO (PCT)
Prior art keywords
liquid repellent
ink
repellent ink
image
varnish
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PCT/JP2015/084128
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French (fr)
Japanese (ja)
Inventor
由佳 矢崎
高林　敏行
Original Assignee
コニカミノルタ株式会社
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Priority to JP2016562694A priority Critical patent/JPWO2016088873A1/en
Publication of WO2016088873A1 publication Critical patent/WO2016088873A1/en

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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

Definitions

  • the present invention relates to a method for forming a pseudo embossed image using an inkjet image forming method.
  • a pseudo embossed image is known as one of high value-added images.
  • the pseudo embossed image is an image having a concave portion and a convex portion by printing, the concave portion has low gloss, and the convex portion has high gloss.
  • a method for forming a pseudo-embossed image a method of applying a liquid-repellent varnish on a substrate itself or a printed material and then applying a normal varnish is known. In the portion where the liquid-repellent varnish is applied, the normal varnish applied thereon is repelled, so the portion where the liquid-repellent varnish is applied becomes the concave portion, and the portion where the normal varnish is applied is It becomes the said convex part.
  • the pseudo embossed image formed in this way looks like a portion where the high gloss portion is raised by embossing of the recording medium (base material) due to unevenness and gloss difference.
  • the above-mentioned pseudo embossed image forming method is embossed in a separate process, and a printed material having a texture equivalent to or higher than that of a normal embossed image can be obtained at a lower cost than the formation of a normal embossed image. It is widely done for the reason.
  • liquid repellent varnish a printing ink to which a phthalic diester is added as a liquid repellent, a varnish in which a paraffin wax that is solid at room temperature is dispersed, an ink containing a polyalphaolefin resin, and the like are known. (For example, see Patent Documents 1 to 3).
  • both the liquid repellent varnish and the normal varnish are performed by printing such as offset printing. Therefore, the shape of the concave portion and the degree of unevenness in the pseudo-embossed image need to be set by a plate, for example.
  • a plate for example.
  • a method that requires a plate for each image, and a method that requires such a plate may contribute to a decrease in cost performance and productivity of the pseudo-embossed image.
  • the conventional method for forming a pseudo embossed image there remains room for study from the viewpoints of, for example, manufacturing cost and productivity.
  • the present invention provides an image forming method capable of more easily setting or changing a pseudo embossed image.
  • the present inventors apply a gloss varnish to the entire surface of the substrate after image-wise applying UV ink containing a gelling agent, which forms a highly liquid-repellent film by curing, onto the substrate image-wise. Therefore, it has been found that the gloss of the concave portion in the pseudo-embossed image can be controlled in a wider range than before according to the printing rate and discharge amount of the UV ink and the type and amount of the gelling agent. Thus, the present invention has been completed.
  • a liquid repellent ink containing an actinic ray curable compound, a photoinitiator and a gelling agent is applied to at least a part of the surface of a substrate by an inkjet image forming method to form the liquid repellent ink film.
  • an image forming method for forming a pseudo embossed image comprising: a forming step; and a step of applying a varnish to the substrate so as to cover at least the liquid-repellent ink film.
  • the concave portion of the pseudo embossed image is formed by the inkjet image forming method using the liquid repellent ink, the setting or changing of the pseudo embossed image is performed as compared with the conventional method of forming the pseudo embossed image. Can be performed more easily.
  • FIG. 1A is a diagram schematically showing a substrate
  • FIG. 1B is a diagram schematically showing a substrate having an image formed on its surface
  • FIG. 1C is a partial region of the image
  • FIG. 1D schematically shows the base material in which an actinic ray gloss varnish is applied to the image and the liquid repellent ink film.
  • FIG. 1E is a diagram schematically showing a pseudo embossed image including a flat film formed by actinic ray gloss varnish and a portion repelled by the liquid repellent ink film.
  • the image forming method according to the present embodiment is a method of forming a pseudo embossed image, and the liquid repellent ink is applied to at least a part of the surface of the substrate by the ink jet image forming method to form the liquid repellent ink film. And a second step of applying a varnish to the substrate so as to cover at least the liquid-repellent ink film.
  • the liquid repellent ink is a kind of so-called inkjet ink that can be applied to an inkjet image forming method.
  • the liquid repellent ink contains an actinic ray curable compound, a photoinitiator, and a gelling agent.
  • the actinic ray curable compound is a compound that cures when irradiated with actinic rays.
  • the actinic ray curable compound may be one kind or more.
  • Examples of the actinic ray curable compound include compounds having one or more radical polymerizable unsaturated multiple bonds, and more specifically, compounds having one or more (meth) acryloyl groups.
  • Examples of compounds having one (meth) acryloyl group include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, and isomyristyl (meth) acrylate , Isostearyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meta ) Acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, pheno Siethyl (meth)
  • Examples of compounds having two (meth) acryloyl groups include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Polypropylene glycol 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, dimethylol-tricyclodecane di (meth) acrylate, bisphenol A PO adduct di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, and polytetramethyl It includes glycol di (meth) acrylate.
  • Examples of compounds having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate and caprolactam modified dipentaerythritol hexa (meth) acrylate It is.
  • the actinic ray curable compound preferably contains a compound having two or more (meth) acryloyl groups from the viewpoint of increasing the strength of the liquid repellent ink film.
  • the content of the compound having two or more (meth) acryloyl groups in the actinic ray curable compound is 30 to 100% by mass.
  • the actinic ray is an electromagnetic wave that causes a curing reaction of the actinic ray curable compound, and is, for example, an electron beam, an ultraviolet ray, an ⁇ ray, a ⁇ ray, or an X ray. Since the actinic ray is widely used in industrial applications, it is preferably ultraviolet rays or electron beams, and more preferably ultraviolet rays.
  • the content of the actinic ray curable compound in the liquid repellent ink is too small, the strength of the liquid repellent ink film may be insufficient.
  • the content is preferably 10% by mass or more, and more preferably 20% by mass or more.
  • the liquid repellency with respect to the below-mentioned actinic-light gloss varnish may become inadequate.
  • the content is preferably 97% by mass or less, and more preferably 95% by mass or less.
  • the photoinitiator is a component that causes a photocuring reaction of the actinic radiation curable compound by the actinic light, and is appropriately determined according to, for example, the type of the photocuring reaction in the actinic radiation curable compound.
  • the photoinitiator may be one kind or more.
  • Examples of the photoinitiator include a photopolymerization initiator, and more specifically, include an intramolecular bond cleavage type photopolymerization initiator and an intramolecular hydrogen abstraction type photopolymerization initiator. .
  • the actinic ray is an electron beam
  • the liquid repellent ink may not substantially contain a photoinitiator.
  • intramolecular bond cleavage type photopolymerization initiator examples include acetophenone series, benzoins, acylphosphine oxide series, benzyl, and methylphenylglyoxyester.
  • acetophenone series examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane- 1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone are included.
  • benzoins examples include benzoin, benzoin methyl ether and benzoin isopropyl ether.
  • acylphosphine oxide examples include 2,4,6-trimethylbenzoindiphenylphosphine oxide.
  • intramolecular hydrogen abstraction type photopolymerization initiator examples include benzophenone series, thioxanthone series, aminobenzophenone series, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, and 9,10-phenanthrenequinone. And camphorquinone.
  • benzophenone series examples include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylated benzophenone, 3 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and 3,3′-dimethyl-4-methoxybenzophenone.
  • Examples of the above thioxanthone series include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone.
  • aminobenzophenone series examples include Michler's ketone and 4,4'-diethylaminobenzophenone.
  • the content of the photoinitiator in the liquid repellent ink is too small, the photocuring of the liquid repellent ink may be insufficient, and if it is too large, the effect of the photoinitiator reaches a peak.
  • the content is preferably 0.01 to 10% by mass, more preferably 1 to 9% by mass, and further preferably 5 to 8% by mass.
  • the gelling agent is a component having liquid repellency with respect to the actinic ray gloss varnish described later, and is appropriately determined according to, for example, the type of component in the actinic ray gloss varnish.
  • One or more gelling agents may be used.
  • the gelling agent include fatty acid inulins such as inulin stearate, fatty acid dextrins such as dextrin palmitate and dextrin myristate, glyceryl behenate, and polyglyceryl behenate eicosane diacid.
  • the gelling agent examples include low molecular oil gelling agents described in JP-A-2005-126507, JP-A-2005-255821, JP-A 2010-1111790, and the like, N-lauroyl-L- Amide compounds such as glutamic acid dibutylamide and N-2 ethylhexanoyl-L-glutamic acid dibutylamide, and dibenzylidene sorbitols such as 1,3: 2,4-bis-O-benzylidene-D-glucitol .
  • N-lauroyl-L- Amide compounds such as glutamic acid dibutylamide and N-2 ethylhexanoyl-L-glutamic acid dibutylamide
  • dibenzylidene sorbitols such as 1,3: 2,4-bis-O-benzylidene-D-glucitol .
  • the gelling agent examples include petroleum waxes such as paraffin wax, microcrystalline wax, and petrolactam, candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, jojoba ester, etc.
  • Plant waxes, animal waxes such as beeswax, lanolin and whale wax, mineral waxes such as montan wax and hydrogenated wax, hardened castor oil or hardened castor oil derivatives and montan wax derivatives, and paraffin wax derivatives, microcrystalline Modified waxes such as wax derivatives and polyethylene wax derivatives are included.
  • the gelling agent examples include higher fatty acids such as behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid and erucic acid, stearyl alcohol and behenyl alcohol.
  • hydroxystearic acid such as 12-hydroxystearic acid or its derivatives, lauric acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12-hydroxystearic acid
  • Fatty acid amides such as amides, and N-substituted fatty acid amides such as N-stearyl stearic acid amide and N-oleyl palmitic acid amide are included.
  • the gelling agent examples include special fatty acid amides such as N, N′-ethylenebisstearylamide, N, N′-ethylenebis12-hydroxystearylamide, N, N′-xylylenebisstearylamide, Higher amines such as dodecylamine, tetradecylamine, octadecylamine, stearyl stearic acid, oleyl palmitic acid, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, polyoxyethylene fatty acid ester, etc.
  • special fatty acid amides such as N, N′-ethylenebisstearylamide, N, N′-ethylenebis12-hydroxystearylamide, N, N′-xylylenebisstearylamide, Higher amines such as dodecylamine, tetradecylamine, octadecylamine, stearyl ste
  • sucrose fatty acid esters such as sucrose stearic acid and sucrose palmitic acid
  • synthetic gelling agents such as polyethylene gelators and ⁇ -olefin maleic anhydride copolymer gelling agents, polymerizable gelling agents , Dimer And, dimer diol, contains.
  • the content of the gelling agent in the liquid repellent ink is too small, the repellent ink film described later may be insufficiently repelled in the film of the liquid repellent ink.
  • the emission stability at may be insufficient.
  • the content is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and further preferably 2 to 7% by mass.
  • the gloss of the film of the liquid repellent ink can be adjusted by the type of the gelling agent or the content of the gelling agent in the liquid repellent ink.
  • examples of gelling agents suitable for setting the gloss of the liquid repellent ink to 1 to 30 include distearyl ketone, behenyl behenate, behenyl stearate, stearyl stearate and ethylene glycol distearate. Is included.
  • the content of the gelling agent in the liquid repellent ink suitable for setting the gloss of the liquid repellent ink film to 1 to 30 is, for example, 0.1 to 10% by mass, 0.5% It is more preferably ⁇ 7% by mass, and further preferably 1 ⁇ 5% by mass.
  • the liquid repellent ink may further contain components other than those described above as long as the effects of the present invention are obtained.
  • the other component may be one kind or more. Examples of the other components include a polymerization inhibitor, a coloring material, and a surfactant.
  • the polymerization inhibitor is added to the liquid repellent ink, for example, from the viewpoint of improving the stability of the liquid repellent ink.
  • One or more polymerization inhibitors may be used.
  • the polymerization inhibitor include quinone compounds such as hydroquinone, methylhydroquinone, and t-butylhydroquinone, and N-oxyl groups such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical or derivatives thereof.
  • the content of the polymerization inhibitor in the liquid-repellent ink is too small, the storage stability of the liquid-repellent ink may be insufficient, and if it is too large, photocuring of the liquid-repellent ink may be insufficient.
  • the content is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and further preferably 0.05 to 1% by mass. preferable.
  • the color material may be added to the liquid repellent ink from the viewpoint of the design of a pseudo embossed image to be formed, for example.
  • the color material may be one kind or more.
  • the color material include pigments and dyes that are known to be usable as color materials for inkjet inks.
  • the pigment include organic pigments and inorganic pigments described in the color index.
  • the dye include oil-soluble dyes.
  • the surfactant may be added to the liquid repellent ink from the viewpoint of decreasing the surface tension of the liquid repellent ink and promoting the wetting and spreading to the substrate.
  • One or more surfactants may be used.
  • surfactants include compounds that are known to be usable as surfactants for inkjet inks. More specifically, fluorine-based surfactants, silicone-based surfactants, higher alcohol-based surfactants are included. Includes all non-ionic surfactants such as surfactants.
  • the liquid repellent ink does not substantially or simply contain the color material.
  • the content is, for example, From the viewpoint of sufficient adhesion and design, 0.5 to 10% by mass is preferable, 0.5 to 7% by mass is more preferable, and 1 to 5% by mass is preferable. More preferably.
  • substantially does not contain the color material also means that it does not contain any color material, but in such an amount that the function of the color material such as coloring is not sufficiently expressed in the liquid repellent ink, It means that the liquid repellent ink can contain a color material.
  • the substrate is an object on which the liquid repellent ink can be applied by an inkjet image forming method.
  • the form of the substrate is usually a sheet, but may be other forms as long as ink can be applied in the present embodiment.
  • Examples of the substrate include coated paper, vapor-deposited paper, aluminum foil paper, polyethylene terephthalate (PET) sheet, polypropylene (PP) sheet, fine paper, cardboard, art paper, corrugated paper, coated cardboard and embossed paper. Is included.
  • the liquid repellent ink can be adjusted, for example, by mixing the material components described above, or by adding a gelling agent to an existing inkjet ink containing an actinic ray curable compound and a photoinitiator. It is possible to prepare.
  • the image of the ink may be formed on the surface of the base material from the viewpoint of design, for example. Further, from the viewpoint of improving the adhesion of the liquid repellent ink film to the base material, the image formed on the surface of the base material is preferably an image of an actinic ray curable inkjet ink, The image is more preferably an inkjet gel ink.
  • the actinic ray curable inkjet ink is an inkjet ink having a property of being cured by irradiation with the actinic ray such as ultraviolet rays, and includes, for example, the actinic ray curable compound, the photoinitiator, and the coloring material.
  • the actinic radiation curable inkjet gel ink is a composition further containing a gelling agent in the actinic radiation curable inkjet ink.
  • the actinic radiation curable compound, the photoinitiator, the coloring material, and the gelation. Contains agents.
  • the types and contents of the actinic ray curable compound, the photoinitiator, the coloring material, and the gelling agent in the actinic ray curable inkjet ink or the actinic ray curable inkjet gel ink are the same as those of the liquid repellent ink. It may be different or different. Moreover, the actinic ray may be the same as or different from the actinic ray that cures the liquid repellent ink.
  • the content of the gelling agent in the actinic ray curable inkjet gel ink is preferably 0.1% by mass or more from the viewpoint of enhancing the adhesion of the liquid repellent ink film to the substrate. % Or more, more preferably 1.5% by mass or more.
  • the content of the gelling agent in the actinic ray curable inkjet ink or the actinic ray curable inkjet gel ink is 10% by mass or less from the viewpoint of achieving the desired design in the pseudo-embossed image. Preferably, it is 7 mass% or less, More preferably, it is 5 mass% or less.
  • the above-mentioned actinic ray curable inkjet ink comprises 80 to 97% by mass of an actinic ray curable compound, 0.01 to 10% by mass of a photoinitiator, and 0.5 to 10% by mass. It is a composition containing these coloring materials.
  • the actinic ray curable inkjet gel ink includes 70 to 97% by mass of an actinic ray curable compound, 0.01 to 10% by mass of a photoinitiator, and 0.1 to 10% by mass of a gelling agent. And 0.5 to 10% by mass of a coloring material.
  • the actinic radiation curable inkjet ink or the actinic radiation curable inkjet gel ink may be, for example, a commercially available UV curable inkjet ink as it is, or can be prepared by mixing the above material components. Alternatively, it can be prepared by adding an appropriate amount of a gelling agent to the UV curable inkjet ink.
  • the liquid repellent to the film (image) of the actinic radiation curable inkjet ink wherein the actinic radiation curable inkjet ink containing the gelling agent further contains a silicone surfactant or a fluorine surfactant.
  • a silicone surfactant or a fluorine surfactant is preferable from the viewpoint of improving the adhesion of the ink film. This is because the surface of the film of the actinic radiation curable inkjet ink is within an appropriate range in which the liquid repellent ink exhibits better coating properties by adding the surfactant to the actinic radiation curable inkjet ink. This is probably because the tension is adjusted.
  • the actinic ray curable inkjet ink contains a silicone surfactant or a fluorosurfactant in addition to the gelling agent
  • the liquid repellent ink has the effect of improving the adhesion and coating properties.
  • one or both of the silicone-based surfactant and the fluorine-based surfactant may be contained.
  • the silicone It is preferable not to contain one or both of a surfactant and a fluorosurfactant.
  • the content of the silicone surfactant in the actinic radiation curable inkjet ink containing the gelling agent is 0.01 to 10% by mass.
  • the content is 0.01 to 5% by mass, and more preferably 0.01 to 1% by mass.
  • the content of the fluorosurfactant in the actinic ray curable inkjet ink containing the gelling agent is preferably 0.01 to 10% by mass, and 0.01 to 5% by mass. % Is more preferable, and 0.01 to 1% by mass is even more preferable.
  • the fluorine-based surfactant is preferably a nonionic surfactant having a perfluoroalkyl group having 6 or less carbon atoms (also referred to as “C6PNS”).
  • the “perfluoroalkyl group” refers to a hydrocarbon group in which at least one carbon atom is bonded to a fluorine atom, and the “perfluoroalkyl group having 6 or less carbon atoms” means the number of carbon atoms.
  • 1 represents a perfluoroalkyl group having a straight chain portion of 1 to 6.
  • a perfluoroalkyl group having 6 or less carbon atoms may have a branched structure.
  • the C6PNS has higher orientation on the surface of an actinic ray curable inkjet ink film (hereinafter also referred to as “cured film”) than a gelling agent. Therefore, it is considered that the C6PNS covers the hydrophobic component of the gelling agent crystal deposited on the surface of the cured film, and as a result, the surface energy of the cured film is higher than that due to the gelling agent crystal. .
  • the adhesion of the liquid repellent ink may be insufficient. This is thought to be because when the number of carbon atoms of the perfluoroalkyl group exceeds 6, the C6PNS oriented on the surface of the cured film aggregates and crystallizes, and the surface energy of the surface of the cured film decreases. It is done. It is considered that the perfluoroalkyl group having 6 or less carbon atoms is preferable from the viewpoint of preventing the aggregation and crystallization and effectively increasing the surface energy of the cured film.
  • the C6PNS perfluoroalkyl group may have a linear structure or a branched structure, but preferably has a linear structure from the viewpoint of adhesion.
  • C6PNS having a branched structure examples include a footage 212M, 215M, FTX-218, 208G, 212P, 250, 251, 245F, 602A, 681, 710FM, 730FM, and 730LM (manufactured by Neos Corporation, “ “Factent” is a registered trademark of the same company.
  • C6PNS having a linear structure include Capstone FS-22, FS-30, FS031, FS-34, FS-35, and FS-3100 (manufactured by DuPont, “Capstone” Registered trademark), MegaFuck F-559, F-477, F-556, F-554, F-569, F-553, F-557, F-552, F-563, R-40, RS-76- NS, F-444 (manufactured by DIC Corporation, “Megafuck” is a registered trademark of the company), Surflon S-241, S-386, S-611, S-651, S-242, S-243 and S-420 (AGC Seimi Chemical Co., Ltd., “Surflon” is a registered trademark of the same company).
  • the weight average molecular weight of the C6PNS is preferably 500 or more and 100,000 or less, more preferably 3000 or more and 100,000 or less, and further preferably 10,000 or more and 80,000 or less, from the viewpoint of adhesion of the liquid repellent ink.
  • the weight average molecular weight is 3000 or more, the nonionic surfactant having a perfluoroalkyl group having 6 or less carbon atoms oriented on the surface of the cured film is difficult to volatilize and can exist stably, and the adhesion of the liquid repellent ink It is considered that the property becomes better.
  • the weight average molecular weight of the C6PNS can be measured by gel permeation chromatography (GPC). It is a weight average molecular weight in terms of polystyrene.
  • GPC gel permeation chromatography
  • the C6PNS preferably has a higher surface orientation from the viewpoint of the adhesion of the liquid repellent ink, and the height of the surface orientation can be determined by measuring the dynamic surface tension.
  • the dynamic surface tension can be measured by a known method. For example, it can be measured by the maximum bubble pressure method.
  • the number of carbon atoms in the perfluoroalkyl group may be a catalog value, and can also be measured by a known analysis method such as 13 CNMR or 19 FNMR.
  • the silicone surfactant is preferably a polyether-modified silicone surfactant.
  • examples thereof include X22-4272, KF-352 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF4452 (manufactured by MOMENTIVE), BYK- 361N, BYK-3455, BYK348 (all manufactured by BYK, “BYK” is a registered trademark of the company).
  • the liquid-repellent ink film is formed by, for example, applying the liquid-repellent ink (landing of the liquid-repellent ink droplets) to the substrate by an inkjet image forming method and applying the liquid-repellent ink. It can be produced by solidifying the liquid ink.
  • the film of the liquid repellent ink is not limited as long as it can apply the actinic ray gloss varnish described later on the film, and may be a dried product of the liquid repellent ink coating, or the liquid repellent ink by actinic ray irradiation. It may be a semi-cured product of the coating film (in a state where the photocuring reaction is not completed) or a cured product of the liquid repellent ink coating film (in a state where the photocuring reaction is completed).
  • the gloss of the liquid repellent ink film can also be adjusted by the printing rate of the liquid repellent ink in the inkjet image forming method.
  • the printing rate suitable for setting the gloss of the liquid repellent ink film to 1 to 30 is, for example, 60 to 100%, more preferably 70 to 100%, and more preferably 80 to 100%. More preferably it is.
  • the surface energy of the liquid-repellent ink film can be appropriately determined from the viewpoint of the design property relating to the embossed tone in the pseudo-embossed image, and is preferably 45 mN / m or less, for example, 40 mN / m or less. More preferably, it is more preferably 35 mN / m or less.
  • the surface energy can be determined, for example, by measuring the contact angles of water, nonane, and propylene carbonate with respect to the substrate, for example, depending on the amount of gelling agent added, the amount of surfactant added, etc. It is possible to adjust.
  • the contact angle of the surface of the base material with respect to the liquid repellent ink is too high, it becomes difficult to form an intended image with the liquid repellent ink by a normal printing method. Since the ink is formed by the ink jet image forming method and the ink contains a gelling agent, it is possible to use a substrate having a larger contact angle than that of a substrate applied to a normal printing method.
  • the contact angle with respect to the liquid-repellent ink described above may be 10 to 15 °, 15 to 25 °, or 25 to 35 °.
  • the contact angle is measured with the measurement ink obtained by removing the gelling agent from the liquid-repellent ink, for example, the measurement with respect to the base material 5 seconds after the measurement ink droplet has landed on the base material. It can be determined by the contact angle of the ink for use, and can be adjusted, for example, by the amount of surfactant added.
  • the contact angle of the actual liquid repellent ink to the surface of the substrate can be adjusted by the addition amount of the gelling agent in addition to the addition amount of the surfactant in the liquid repellent ink. Wetting and spreading on the substrate surface of the liquid repellent ink can be confirmed.
  • varnish is applied to the substrate so as to cover at least the liquid-repellent ink film.
  • the method for applying the varnish is not particularly limited.
  • the application method of the varnish can be appropriately determined from a known application method of ink, and may be, for example, an inkjet image forming method or an offset printing method.
  • the varnish may be applied to the substrate so as to cover at least the film of the liquid repellent ink, but is preferably applied to the entire surface of the substrate from the viewpoints of designability and productivity.
  • the above varnish is a paint that exhibits liquid repellency to a film of liquid repellent ink and can form a glossy cured film.
  • the varnish can be appropriately selected from known varnishes exhibiting a desired liquid repellency with respect to the liquid repellent ink film according to the composition of the liquid repellent ink.
  • the varnish is preferably an actinic ray gloss varnish.
  • the actinic ray gloss varnish is a composition that exhibits liquid repellency with respect to the film of the liquid repellent ink and forms a cured film that exhibits gloss upon irradiation with actinic rays such as ultraviolet rays.
  • the actinic ray gloss varnish may be one kind or more.
  • As the actinic ray gloss varnish a known varnish applied on the liquid-repellent varnish in forming a pseudo-embossed image can be used as it is.
  • the glossiness of the cured film of the actinic ray gloss varnish can be determined from the viewpoint of the design of the pseudo-embossed image to be formed, and is preferably 50 to 100, for example, 60 to 100. Is more preferable, and 70 to 100 is even more preferable.
  • Examples of the actinic ray gloss varnish include the ultraviolet curable overprint varnish composition described in Patent Document 2, the overprint varnish described in Patent Document 3, a high gloss aqueous varnish, and other actinic light gloss varnishes.
  • an appropriate method can be selected from known methods, and examples thereof include offset printing, gravure printing, and flexographic printing.
  • the image forming method may further include other steps other than the first step and the second step as long as the effects of the present embodiment can be obtained.
  • an image of the actinic ray curable inkjet ink or the actinic ray curable inkjet gel ink is applied to a portion or the entire surface of the substrate where the liquid repellent ink film is to be formed.
  • a step of forming by a forming method, a step of performing a surface treatment such as corona treatment on a substrate on which an image is formed or the substrate itself, and by semi-curing the actinic ray curable inkjet ink applied to the substrate Obtaining a substrate on which an image is formed.
  • FIG. 1A to 1E schematically show how pseudo embossed images are formed by the above image forming method.
  • the actinic ray curable inkjet ink or the actinic ray curable inkjet gel ink is applied to the surface of a substrate 100 such as aluminum foil paper as shown in FIG. 1A by, for example, an inkjet image forming method.
  • a substrate 100 such as aluminum foil paper as shown in FIG. 1A
  • an inkjet image forming method As a result, an image 101 is formed.
  • FIG. 1C the liquid repellent ink 102 is applied to a partial region of the image 101 by the inkjet image forming method.
  • the applied liquid repellent ink 102 is quickly dried.
  • the applied liquid repellent ink 102 is further irradiated with actinic rays such as ultraviolet rays as necessary, and thus, for example, a semi-cured product of the liquid repellent ink 102 is formed as a film of the liquid repellent ink 102.
  • the actinic ray gloss varnish 103 is applied by, for example, an offset printing method so as to cover at least the film of the liquid repellent ink 102 (for example, the entire surface in the planar direction of the substrate 100).
  • the actinic ray gloss varnish 103 applied to the film of the liquid repellent ink 102 is repelled by the film because the liquid repellent ink 102 contains a gelling agent, and is scattered in the film shape.
  • the applied actinic ray gloss varnish 103 is irradiated with ultraviolet rays, and the actinic ray gloss varnish 103 is cured.
  • the irradiation of the ultraviolet rays causes a photoreaction of an unreacted actinic ray curable compound in the film of the liquid repellent ink 102, and the film of the liquid repellent ink 102 becomes a cured product of the liquid repellent ink 102.
  • a pseudo-embossed image is formed by flat portions of the cured product of the actinic ray gloss varnish 103 and scattered portions.
  • the image forming method includes the first step and the second step, the liquid repellent ink film is formed by the ink jet image forming method. It is possible to easily set the liquid ink film to a desired shape. Therefore, in the above image forming method, it is possible to set or change the pseudo embossed image more easily than the method of forming a pseudo embossed image consisting only of the conventional printing method.
  • the content of the gelling agent in the liquid repellent ink is 20% by mass or less, both the emission stability of the liquid repellent ink and the adhesion of the liquid repellent ink film to the base material are sufficiently expressed. It is more effective from the viewpoint, and it is more effective from the above viewpoint that the content is 10% by mass or less.
  • the liquid repellent ink containing a color material is more effective from the viewpoint of enhancing the design of the pseudo embossing, and the liquid repellent ink does not contain a color material. This is more effective from the viewpoint of improving the adhesion to the substrate.
  • step of applying the varnish applying the varnish to the entire surface of the substrate on which the liquid repellent ink film is formed is more effective from the viewpoint of increasing the productivity of the pseudo embossed image.
  • actinic ray gloss varnish for the varnish is more effective from the viewpoint of enhancing the productivity of embossed images having good gloss.
  • an image of the actinic ray curable inkjet ink is formed on the base material, and the formation of the liquid repellent ink film on the image means that the liquid repellent ink film is applied to the base material. It is more effective from the viewpoint of improving the adhesion, and it is more effective from the above viewpoint that the image is an image by the actinic ray curable inkjet gel ink.
  • the actinic ray curable inkjet ink containing the gelling agent is a silicone-based surfactant or a fluorine-based surfactant. It is more effective to contain the agent, and it is even more effective that the liquid repellent ink does not contain the silicone surfactant or the fluorine surfactant.
  • liquid-repellent ink to the base material at a printing rate corresponding to the desired gloss of the liquid-repellent ink film in the final image is further enhanced from the viewpoint of easily realizing the desired embossed tone. It is effective.
  • the image forming method it is possible to set the glossiness of the liquid-repellent ink film from a wider control range as compared to the conventional pseudo embossed image forming method described above.
  • the glossiness of the liquid repellent ink film can be set from a wider range of 1 to 30.
  • both the ink and the varnish can be applied to the substrate by the ink jet image forming method.
  • the shape of any of the color image of the lowermost layer to which the liquid-repellent ink should be applied, the film of the liquid-repellent ink, and the image of the varnish of the uppermost layer can be easily compared with the conventional method using only the offset printing method Adjustment and change are possible. Therefore, the image formation by the ink jet image forming method as described above is more effective from the viewpoint of realizing the desired design and realizing high productivity even in the production of a small variety of products.
  • “Monomer 1” is polypropylene glycol # 700 diacrylate
  • “Monomer 2” is 4EO-modified pentaerythritol tetraacrylate (SR494, manufactured by SARTOMER)
  • “Monomer 3” is 6EO. It is a modified trimethylolpropane triacrylate (SR499, manufactured by SARTOMER).
  • “Monomer 4” is polyethylene glycol diacrylate (NK ester A-400: Shin-Nakamura Chemical Co., Ltd.)
  • “Monomer 5” is tripropylene glycol diacrylate (APG-200: Shin-Nakamura Chemical Co., Ltd.).
  • “Monomer 6” is tricyclodecane dimethanol diacrylate (A-DCP: Shin-Nakamura Chemical Co., Ltd.).
  • polymerization initiator is DAROCUR TPO (manufactured by BASF, “DAROCUR” is a registered trademark of the company)
  • polymerization inhibitor is IRGASTAB UV10 (manufactured by BASF, “IRGASTAB” is a registered trademark of the company) ).
  • gelling agent 1 is behenyl stearate
  • “gelling agent 2” is distearyl ketone
  • “gelling agent 3” is behenyl behenate
  • gelling agent 4 Is stearyl stearate.
  • the “pigment dispersion” was prepared as follows. First, the following components were charged in a stainless beaker in the following amounts, dissolved by heating and stirring for 1 hour while heating on a 65 ° C. hot plate, and the resulting solution was cooled to room temperature. After cooling the resulting solution to room temperature, 21 parts by mass of the following magenta pigment 1 was added, sealed in a glass bottle together with 200 g of zirconia beads having a diameter of 0.5 mm, and dispersed for 8 hours with a paint shaker. Thereafter, the zirconia beads were removed to prepare a pigment dispersion 1 having the following composition.
  • the “dispersing agent” is Ajisper PB824 (manufactured by Ajinomoto Fine Techno Co., Ltd., “Ajisper” is a registered trademark of Ajinomoto Co., Inc.), and the “active ray curable compound” is tripropylene glycol diacrylate (APG-200).
  • “Magenta pigment” is Pigment Red 122 (chromofine red 6112JC, manufactured by Dainichi Seika Kogyo Co., Ltd.).
  • “Substrate 1” is aluminum foil paper
  • “Substrate 2” is a PET sheet
  • “Substrate 3” is a coated paper having an image of aqueous ink.
  • the “substrate 4” is an aluminum foil paper having a UV curable ink image
  • the “substrate 5” is a coated paper having a UV curable gel ink image
  • the “substrate 6” is a coated cardboard having an image of UV curable gel ink
  • the “substrate 7” is an aluminum foil paper having an image of UV curable gel ink.
  • the “substrate 8” is a coated paper having a UV curable gel ink image containing 0.5% by mass of a fluorosurfactant (Megafac F-559, manufactured by DIC Corporation).
  • Base material 9 is a coated cardboard having an image of a UV curable gel ink containing 0.5% by mass of a silicone surfactant (BYK-361N, manufactured by BYK). The images on the substrates 3 to 9 are all formed by the inkjet image forming method.
  • liquid repellent ink 4 was obtained in the same manner as the liquid repellent ink 1 except that the addition amount of the monomer 3 was changed to 25.85 parts by mass and the addition amount of the gelling agent 1 was changed to 8.0 parts by mass. It was. Further, 19 parts by mass of the pigment dispersion was added to the liquid repellent ink 4 to obtain a liquid repellent ink 5.
  • liquid repellent inks 6 and 7 The same as liquid repellent ink 1 except that the amount of monomer 3 added was changed to 30.85 parts by mass and 3.0 parts by mass of gelling agent 2 was used instead of 20.0 parts by mass of gelling agent 1. Thus, a liquid repellent ink 6 was obtained. Further, 19 parts by mass of the pigment dispersion was added to the liquid repellent ink 6 to obtain a liquid repellent ink 7.
  • a liquid repellent ink 9 was obtained in the same manner as the liquid repellent ink 1 except that the addition amount of the monomer 3 was changed to 30.85 parts by mass and the addition amount of the gelling agent 1 was changed to 3.0 parts by mass. It was.
  • a liquid repellent ink 11 was obtained in the same manner as the liquid repellent ink 1 except that the amount of the monomer 3 added was changed to 33.85 parts by mass and the gelling agent 1 was not added.
  • liquid repellent ink 12 The liquid repellent ink 12 was obtained in the same manner as the liquid repellent ink 11 except that each of the monomers 4 to 6 was used in place of each of the monomers 1 to 3 and 3.0 parts by mass of the gelling agent 4 was further added. It was.
  • compositions of the liquid repellent inks 1 to 12 are shown in Table 1.
  • Example 1 Using a line type ink jet recording apparatus with the liquid repellent ink 1 and the temperature of the ink jet head set to 80 ° C., a solid image of 5 cm ⁇ 5 cm (an image having a printing rate (DR) of 100%) is formed on the substrate 1. Pre-image 1 was formed.
  • a piezo head having a nozzle diameter of 20 ⁇ m and a number of nozzles of 512 (256 nozzles ⁇ 2 rows, staggered arrangement, 1 row nozzle pitch is 360 dpi) was used.
  • the ejection conditions were such that the volume of one droplet was 2.5 pl, and the pre-image 1 was formed at a resolution of 1440 dpi ⁇ 1440 dpi by emitting at a droplet velocity of about 6 m / s.
  • the image forming speed (recording speed) was 500 mm / s.
  • the image formation was performed in an environment of 23 ° C. and 55% RH.
  • dpi represents the number of dots per 2.54 cm.
  • the pre-image 1 is irradiated with ultraviolet rays by an LED lamp (Phoseon Technology 395 nm, water-cooled LED) disposed on the downstream side of the substrate transport direction in the recording apparatus, thereby curing the liquid repellent ink 1 and repelling it.
  • a liquid ink image 1 was obtained.
  • the thickness of the liquid repellent ink image 1 (the layer of the cured product of the liquid repellent ink 1) was 15 ⁇ m. *
  • a UV varnish coater (model: DKSH SP-5, UV varnish using a UV varnish coater (UV gloss varnish for DKSH ⁇ ⁇ ⁇ overcoat, UV gloss varnish TEC series) is applied on the base material 1 from above the liquid repellent ink image 1. ) was applied to the coating film of the varnish, and a cured film of varnish with a thickness of 5 ⁇ m was formed on the liquid repellent ink image 1 to obtain an embossed image 1 as shown in FIG. 1E, for example. .
  • Embossed images 2 and 3 were obtained in the same manner as embossed image 1 except that liquid repellent inks 2 and 3 were used in place of liquid repellent ink 1, respectively.
  • An embossed image 4 was obtained in the same manner as the embossed image 1 except that the substrate 2 was used instead of the substrate 1 and the liquid repellent ink 4 was used instead of the liquid repellent ink 1. Further, an embossed image 5 was obtained in the same manner as the embossed image 4 except that the printing rate (DR) was changed to 75%. Further, embossed images 6 to 8 were obtained in the same manner as the embossed image 4 except that the printing rate was changed to 50%, 25%, and 5%, respectively. Further, an embossed image 9 was obtained in the same manner as the embossed image 8 except that the liquid repellent ink 5 was used instead of the liquid repellent ink 4.
  • An embossed image 10 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 6 was used instead of the liquid repellent ink 1 and the substrate 3 was used instead of the substrate 1. Further, embossed images 11, 12, 13, and 14 were obtained in the same manner as the embossed image 10 except that the printing ratio was changed to 75%, 50%, 25%, and 5%, respectively.
  • An embossed image 15 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 6 was used instead of the liquid repellent ink 1 and the substrate 4 was used instead of the substrate 1. Further, embossed images 16, 17, 18, and 19 were obtained in the same manner as the embossed image 15 except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively. Further, an embossed image 20 was obtained in the same manner as the embossed image 19 except that the liquid repellent ink 7 was used instead of the liquid repellent ink 6.
  • An embossed image 21 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 8 was used instead of the liquid repellent ink 1 and the substrate 5 was used instead of the substrate 1. Further, embossed images 22, 23, 24, and 25 were obtained in the same manner as the embossed image 21, except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
  • An embossed image 26 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 9 was used instead of the liquid repellent ink 1 and the substrate 6 was used instead of the substrate 1. Further, embossed images 27, 28, 29, and 30 were obtained in the same manner as the embossed image 21, except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
  • An embossed image 31 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 10 was used instead of the liquid repellent ink 1 and the base material 7 was used instead of the base material 1. Further, embossed images 32, 33, 34, and 35 were obtained in the same manner as the embossed image 31 except that the printing ratio was changed to 75%, 50%, 25%, and 5%, respectively.
  • Example 36 to 40 In the same manner as each of the embossed images 31 to 35 except that a water-based varnish (Aqua Pack Varnish F-22, manufactured by T & K TOKA Co., Ltd.) is applied over the liquid repellent ink image instead of the UV curable varnish. Embossed images 36 to 40 were obtained.
  • a water-based varnish Aqua Pack Varnish F-22, manufactured by T & K TOKA Co., Ltd.
  • An embossed image 41 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 12 was used instead of the liquid repellent ink 1 and the substrate 8 was used instead of the substrate 1. Further, embossed images 42, 43, 44, and 45 were obtained in the same manner as the embossed image 41, except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
  • An embossed image 46 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 12 was used instead of the liquid repellent ink 1 and the substrate 9 was used instead of the substrate 1. Further, embossed images 47, 48, 49, and 50 were obtained in the same manner as the embossed image 46, except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
  • An embossed image C1 which is a pseudo-embossed image only by conventional printing is formed on the substrate 1 by forming an image by UV printing with a printing machine, then printing a liquid repellent varnish, and then coating the entire surface with a gloss UV varnish with a coater. Got.
  • An embossed image C2 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 11 was used instead of the liquid repellent ink 1. Further, embossed images C3, C4, C5, and C6 were obtained in the same manner as the embossed image 1 except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
  • Adhesiveness A 10 mm x 10 mm cross cut of 1 mm square was formed on each liquid repellent ink image of embossed images 1 to 50 and C1 to C6 (solid image after 5 cm x 5 cm curing with liquid repellent ink). The cellophane tape was peeled off after being applied thereto, and the cut portions (1 mm square portions) peeled from the substrate were counted, and the adhesion of the liquid repellent ink image to the substrate was evaluated according to the following criteria.
  • the number of peeled cut parts is 0
  • A The number of peeled cut parts is more than 0 and less than 5
  • B The number of peeled cut parts is more than 5 and less than 20
  • C The number of peeled cut parts is More than 20 and less than 40
  • D The number of peeled cut parts exceeds 40
  • Embossed degree (rough feeling) A value of a difference ⁇ G (Gn ⁇ Ge) between Gn and Ge was obtained as an index representing the rough appearance of the embossed tone in the embossed images 1 to 50 and C1 to C6, and evaluated according to the following criteria. “5” has the largest roughness, and the smaller the number, the smaller the roughness. “0” is almost not rough. 5: ⁇ G is 70 or more and less than 100 4: ⁇ G is 50 or more and less than 70 3: ⁇ G is 40 or more and less than 50 2: ⁇ G is 20 or more and less than 40 1: ⁇ G is 5 or more and less than 20 0: ⁇ G is 0 or more and less than 5
  • the embossed images 1 to 50 are sufficient in any of gloss controllability, emission stability, adhesion, and variable properties. For example, as apparent from Examples 1 and 2, 8 and 9, or 19 and 20, the above characteristics are sufficiently exhibited even when the liquid repellent ink contains a pigment.
  • the printing rate of the liquid repellent ink It is possible to change the gloss controllability (the degree of embossing) by changing. That is, in these examples, the liquid repellent ink having the same composition is used, and the gloss Ge of the liquid repellent ink image portion differs depending on the printing rate between the embossed images when the printing rate is changed. . Then, in response to the change in the printing rate of the liquid repellent ink, the rough feeling between the embossed images represented by ⁇ G also changes.
  • the printing rate of the liquid repellent ink or the glossiness of the liquid repellent ink image portion substantially corresponds to the embossed appearance of the obtained pseudo embossed image, so the pseudo embossed image depends on the printing rate of the liquid repellent ink. It can be seen that the degree of embossing is controlled.
  • the surface of the substrate is constituted by the image of the UV curable ink, so that the liquid repellent ink can be used.
  • the adhesion of the film is further improved, and the adhesion of the film of the liquid repellent ink is further enhanced by forming the surface of the substrate with the image of the UV curable gel ink.
  • the UV curable ink containing the gelling agent further contains a fluorine-based surfactant, so that the adhesion of the liquid repellent ink film is further increased. Enhanced.
  • the adhesion of the liquid repellent ink film is further increased. Increased further.
  • the embossed image C1 is at least insufficiently variable. Further, as apparent from the fact that the printing rate of the liquid repellent part cannot be controlled, the gloss controllability is insufficient. This is considered because the liquid repellent ink image portion is not formed by the ink jet image forming method. In addition, since none of the embossed images C2 to C6 has a difference between Ge and Gn, the conditions for pseudo embossing are not satisfied, and the gloss controllability is insufficient. This is presumably because the liquid repellent ink does not contain a gelling agent.
  • the design, glossiness, unevenness, etc. of the embossed image can be freely controlled according to the type and content of the gelling agent in the liquid repellent ink, the printing rate of the liquid repellent ink, and the like. It is possible to adjust to. Therefore, the present invention is suitable for forming a small amount or a small amount of various types of pseudo-embossed images having high added value such as high-grade feeling, and is expected to contribute to further spread of such images having high added value.
  • Substrate 101 Image 102 Liquid repellent ink 103 Actinic ray gloss varnish

Abstract

The present invention: coats, on to at least part of a surface of a base material, a liquid-repellent ink containing an active light curable compound, a photoinitiator, and a gelling agent, using an inkjet image formation method; coating varnish on at least an area including the section of the surface of the base material that has the liquid-repellent ink coated thereupon; and forms a pseudo-embossed image.

Description

画像形成方法Image forming method
　本発明は、インクジェット画像形成方法を利用して擬似エンボス画像を形成する方法に関する。 The present invention relates to a method for forming a pseudo embossed image using an inkjet image forming method.
　付加価値の高い画像の一つとして、擬似エンボス画像が知られている。擬似エンボス画像とは、印刷による凹部と凸部とを有する画像であり、凹部は低い光沢を有し、凸部は高い光沢を有する。擬似エンボス画像を形成する方法としては、基材そのものや印刷物などの上に撥液性ニスを塗布し、その後に通常のニスを塗布する方法が知られている。上記撥液性ニスが塗布された部分では、その上に塗られる通常のニスが弾かれるので、上記撥液性ニスが塗布された部分が上記凹部となり、上記通常のニスが塗布された部分は上記凸部となる。こうして形成された擬似エンボス画像は、凹凸と光沢差とにより、上記高光沢の部分が、記録媒体（基材）の型押しによって浮き出た部分のように見える。上記の擬似エンボス画像の形成方法は、別工程で型押しを行う、通常のエンボス画像の形成よりも低コストでありながら、通常のエンボス画像と同等かそれ以上の質感の高い印刷物が得られるなどの理由から、広く行われている。 A pseudo embossed image is known as one of high value-added images. The pseudo embossed image is an image having a concave portion and a convex portion by printing, the concave portion has low gloss, and the convex portion has high gloss. As a method for forming a pseudo-embossed image, a method of applying a liquid-repellent varnish on a substrate itself or a printed material and then applying a normal varnish is known. In the portion where the liquid-repellent varnish is applied, the normal varnish applied thereon is repelled, so the portion where the liquid-repellent varnish is applied becomes the concave portion, and the portion where the normal varnish is applied is It becomes the said convex part. The pseudo embossed image formed in this way looks like a portion where the high gloss portion is raised by embossing of the recording medium (base material) due to unevenness and gloss difference. The above-mentioned pseudo embossed image forming method is embossed in a separate process, and a printed material having a texture equivalent to or higher than that of a normal embossed image can be obtained at a lower cost than the formation of a normal embossed image. It is widely done for the reason.
　上記撥液性ニスには、撥液剤としてフタル酸ジエステルが添加された印刷インキや、常温で固体であるパラフィンワックスが分散されたワニス、ポリアルファオレフィン樹脂を含有するインク、などが知られている（例えば、特許文献１～３参照）。 As the liquid repellent varnish, a printing ink to which a phthalic diester is added as a liquid repellent, a varnish in which a paraffin wax that is solid at room temperature is dispersed, an ink containing a polyalphaolefin resin, and the like are known. (For example, see Patent Documents 1 to 3).
特開昭４８－５８０６８号公報Japanese Patent Laid-Open No. 48-58068 特開２００７－１６１９９８号公報JP 2007-161998 A 特開２０１０－１８５０５８号公報JP 2010-185058 A
　従来の擬似エンボス画像の形成方法では、上記撥液性ニスおよび上記通常のニスのいずれもが、オフセット印刷などの印刷によって行われている。したがって、上記凹部の形状や擬似エンボス画像における凹凸の程度などは、例えば、版によって設定する必要がある。しかしながら、従来の擬似エンボス画像の形成方法では、小ロットの擬似エンボス画像の形成であっても、また、図柄の軽微な変更による種々のバリエーションを有する複数種の擬似エンボス画像の形成であっても、画像ごとの版を必要とし、このような版を必要とする方法は、擬似エンボス画像のコストパフォーマンスや生産性などを低下させる一因となることがある。このように、従来の擬似エンボス画像の形成方法では、例えば製造コストや生産性などの観点から検討の余地が残されている。 In the conventional method for forming a pseudo embossed image, both the liquid repellent varnish and the normal varnish are performed by printing such as offset printing. Therefore, the shape of the concave portion and the degree of unevenness in the pseudo-embossed image need to be set by a plate, for example. However, in the conventional pseudo embossed image forming method, even if a small lot pseudo embossed image is formed or a plurality of types of pseudo embossed images having various variations due to slight changes in the design are formed. A method that requires a plate for each image, and a method that requires such a plate may contribute to a decrease in cost performance and productivity of the pseudo-embossed image. Thus, in the conventional method for forming a pseudo embossed image, there remains room for study from the viewpoints of, for example, manufacturing cost and productivity.
　本発明は、擬似エンボス画像の設定または変更をより容易に可能な画像形成方法を提供する。 The present invention provides an image forming method capable of more easily setting or changing a pseudo embossed image.
　本発明者らは、硬化によって撥液性の高い膜を形成する、ゲル化剤を含有するＵＶインクをインクジェットで像様に基材に塗布した後に、グロスニスを当該基材の全面に塗布することによって、当該ＵＶインクの印字率や吐出量、ゲル化剤の種類や量などに応じて、擬似エンボス画像における上記凹部の光沢を従来よりも広い範囲でコントロールすることができることを見出し、鋭意検討して、本発明を完成させた。 The present inventors apply a gloss varnish to the entire surface of the substrate after image-wise applying UV ink containing a gelling agent, which forms a highly liquid-repellent film by curing, onto the substrate image-wise. Therefore, it has been found that the gloss of the concave portion in the pseudo-embossed image can be controlled in a wider range than before according to the printing rate and discharge amount of the UV ink and the type and amount of the gelling agent. Thus, the present invention has been completed.
　すなわち、本発明は、活性光線硬化性化合物、光開始剤およびゲル化剤を含有する撥液インクをインクジェット画像形成方法によって基材の表面の少なくとも一部に塗布して前記撥液インクの膜を形成する工程と、少なくとも前記撥液インクの膜を覆うようにニスを前記基材に塗布する工程と、を含む、擬似エンボス画像を形成する画像形成方法、を提供する。 That is, in the present invention, a liquid repellent ink containing an actinic ray curable compound, a photoinitiator and a gelling agent is applied to at least a part of the surface of a substrate by an inkjet image forming method to form the liquid repellent ink film. There is provided an image forming method for forming a pseudo embossed image, comprising: a forming step; and a step of applying a varnish to the substrate so as to cover at least the liquid-repellent ink film.
　本発明によれば、上記撥液性インクを用いるインクジェット画像形成方法によって擬似エンボス画像の上記凹部が形成されることから、従来の擬似エンボス画像の形成方法に比べて、擬似エンボス画像の設定または変更をより容易に行うことができる。 According to the present invention, since the concave portion of the pseudo embossed image is formed by the inkjet image forming method using the liquid repellent ink, the setting or changing of the pseudo embossed image is performed as compared with the conventional method of forming the pseudo embossed image. Can be performed more easily.
図１Ａは、基材を模式的に示す図であり、図１Ｂは、その表面に形成された画像を有する基材を模式的に示す図であり、図１Ｃは、当該画像の一部の領域に形成された撥液インクの膜を有する上記基材を模式的に示す図であり、図１Ｄは、上記画像および上記撥液インクの膜に活性光線グロスニスが塗布された上記基材を模式的に示す図であり、図１Ｅは、活性光線グロスニスによる平坦な膜と撥液インクの膜に弾かれた部分とを含む擬似エンボス画像を模式的に示す図である。FIG. 1A is a diagram schematically showing a substrate, FIG. 1B is a diagram schematically showing a substrate having an image formed on its surface, and FIG. 1C is a partial region of the image FIG. 1D schematically shows the base material in which an actinic ray gloss varnish is applied to the image and the liquid repellent ink film. FIG. 1E is a diagram schematically showing a pseudo embossed image including a flat film formed by actinic ray gloss varnish and a portion repelled by the liquid repellent ink film.
　以下、本発明の実施の形態を説明する。本実施の形態に係る画像形成方法は、擬似エンボス画像を形成する方法であり、撥液インクをインクジェット画像形成方法によって基材の表面の少なくとも一部に塗布して上記撥液インクの膜を形成する第１の工程と、少なくとも上記撥液インクの膜を覆うようにニスを上記基材に塗布する第２の工程と、を含む。 Hereinafter, embodiments of the present invention will be described. The image forming method according to the present embodiment is a method of forming a pseudo embossed image, and the liquid repellent ink is applied to at least a part of the surface of the substrate by the ink jet image forming method to form the liquid repellent ink film. And a second step of applying a varnish to the substrate so as to cover at least the liquid-repellent ink film.
　上記撥液インクは、インクジェット画像形成方法に適用可能な、いわゆるインクジェットインクの一種である。当該撥液インクは、活性光線硬化性化合物、光開始剤およびゲル化剤を含有する。 The liquid repellent ink is a kind of so-called inkjet ink that can be applied to an inkjet image forming method. The liquid repellent ink contains an actinic ray curable compound, a photoinitiator, and a gelling agent.
　上記活性光線硬化性化合物は、活性光線に照射されて硬化する化合物である。当該活性光線硬化性化合物は、一種でもそれ以上でもよい。当該活性光線硬化性化合物の例には、一以上のラジカル重合性の不飽和多重結合を有する化合物が含まれ、より具体的には、一以上の（メタ）アクリロイル基を有する化合物が含まれる。 The actinic ray curable compound is a compound that cures when irradiated with actinic rays. The actinic ray curable compound may be one kind or more. Examples of the actinic ray curable compound include compounds having one or more radical polymerizable unsaturated multiple bonds, and more specifically, compounds having one or more (meth) acryloyl groups.
　一つの（メタ）アクリロイル基を有する化合物の例には、イソアミル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、イソミルスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、２－エチルヘキシル－ジグリコール（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－アクリロイロキシエチルヘキサヒドロフタル酸、ブトキシエチル（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシプロピレングリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－アクリロイロキシエチルコハク酸、２－アクリロイロキシエチルフタル酸、２－アクリロイロキシエチル－２－ヒドロキシエチル－フタル酸、ラクトン変性（メタ）アクリレートおよびｔ－ブチルシクロヘキシル（メタ）アクリレートが含まれる。 Examples of compounds having one (meth) acryloyl group include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, and isomyristyl (meth) acrylate , Isostearyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meta ) Acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, pheno Siethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, lactone-modified (meth) acrylate and t-butylcyclohexyl (meth) acrylate included.
　二つの（メタ）アクリロイル基を有する化合物の例には、トリエチレングリコールジ（メタ）アクリレート、テトラ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、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（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、１，９－ノナンジオールジ（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、ジメチロール－トリシクロデカンジ（メタ）アクリレート、ビスフェノールＡのＰＯ付加物ジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレートおよびポリテトラメチレングリコールジ（メタ）アクリレートが含まれる。 Examples of compounds having two (meth) acryloyl groups include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Polypropylene glycol 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, dimethylol-tricyclodecane di (meth) acrylate, bisphenol A PO adduct di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, and polytetramethyl It includes glycol di (meth) acrylate.
　三つ以上の（メタ）アクリロイル基を有する化合物の例には、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、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、グリセリンプロポキシトリ（メタ）アクリレート、カプロラクトン変性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エトキシテトラ（メタ）アクリレートおよびカプロラクタム変性ジペンタエリスリトールヘキサ（メタ）アクリレートが含まれる。 Examples of compounds having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate and caprolactam modified dipentaerythritol hexa (meth) acrylate It is.
　上記活性光線硬化性化合物は、二以上の（メタ）アクリロイル基を有する化合物を含有することが、撥液インクの膜の強度を高める観点から好ましい。たとえば、上記活性光線硬化性化合物における上記二以上の（メタ）アクリロイル基を有する化合物の含有量は、３０～１００質量％である。 The actinic ray curable compound preferably contains a compound having two or more (meth) acryloyl groups from the viewpoint of increasing the strength of the liquid repellent ink film. For example, the content of the compound having two or more (meth) acryloyl groups in the actinic ray curable compound is 30 to 100% by mass.
　上記活性光線は、上記活性光線硬化性化合物の硬化反応を生じさせる電磁波であり、例えば、電子線、紫外線、α線、γ線またはエックス線である。上記活性光線は、工業上の用途で広く普及されていることから、紫外線または電子線であることが好ましく、紫外線であることがより好ましい。 The actinic ray is an electromagnetic wave that causes a curing reaction of the actinic ray curable compound, and is, for example, an electron beam, an ultraviolet ray, an α ray, a γ ray, or an X ray. Since the actinic ray is widely used in industrial applications, it is preferably ultraviolet rays or electron beams, and more preferably ultraviolet rays.
　上記撥液インクにおける上記活性光線硬化性化合物の含有量は、少なすぎると撥液インクの膜の強度が不十分となることがある。このような観点から、当該含有量は、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましい。また、上記撥液インクにおける上記活性光線硬化性化合物の含有量は、多すぎると後述の活性光線グロスニスに対する撥液性が不十分となることがある。このような観点から、当該含有量は、９７質量％以下であることが好ましく、９５質量％以下であることがより好ましい。 If the content of the actinic ray curable compound in the liquid repellent ink is too small, the strength of the liquid repellent ink film may be insufficient. From such a viewpoint, the content is preferably 10% by mass or more, and more preferably 20% by mass or more. Moreover, when there is too much content of the said actinic-light curable compound in the said liquid repellent ink, the liquid repellency with respect to the below-mentioned actinic-light gloss varnish may become inadequate. From such a viewpoint, the content is preferably 97% by mass or less, and more preferably 95% by mass or less.
　上記光開始剤は、上記活性光線による上記活性光線硬化性化合物の光硬化反応を生じさせる成分であり、例えば、当該活性光線硬化性化合物における光硬化反応の種類に応じて適宜に決められる。当該光開始剤は、一種でもそれ以上でもよい。上記光開始剤の例には、光重合開始剤が含まれ、より具体的には、分子内結合開裂型の光重合開始剤、および、分子内水素引き抜き型の光重合開始剤、が含まれる。なお、活性光線が電子線である場合では、上記撥液インクは、光開始剤を実質的に含有していなくてもよいことがある。 The photoinitiator is a component that causes a photocuring reaction of the actinic radiation curable compound by the actinic light, and is appropriately determined according to, for example, the type of the photocuring reaction in the actinic radiation curable compound. The photoinitiator may be one kind or more. Examples of the photoinitiator include a photopolymerization initiator, and more specifically, include an intramolecular bond cleavage type photopolymerization initiator and an intramolecular hydrogen abstraction type photopolymerization initiator. . When the actinic ray is an electron beam, the liquid repellent ink may not substantially contain a photoinitiator.
　上記分子内結合開裂型の光重合開始剤の例には、アセトフェノン系、ベンゾイン類、アシルホスフィンオキシド系、ベンジルおよびメチルフェニルグリオキシエステルが含まれる。 Examples of the intramolecular bond cleavage type photopolymerization initiator include acetophenone series, benzoins, acylphosphine oxide series, benzyl, and methylphenylglyoxyester.
　上記アセトフェノン系の例には、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、ベンジルジメチルケタール、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、４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、１－ヒドロキシシクロヘキシル－フェニルケトン、２－メチル－２－モルホリノ（４－チオメチルフェニル）プロパン－１－オン、および、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン、が含まれる。 Examples of the acetophenone series include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane- 1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone are included.
　上記ベンゾイン類の例には、ベンゾイン、ベンゾインメチルエーテルおよびベンゾインイソプロピルエーテルが含まれる。 Examples of the above benzoins include benzoin, benzoin methyl ether and benzoin isopropyl ether.
　上記アシルホスフィンオキシド系の例には、２，４，６－トリメチルベンゾインジフェニルホスフィンオキシドが含まれる。 Examples of the above acylphosphine oxide include 2,4,6-trimethylbenzoindiphenylphosphine oxide.
　上記分子内水素引き抜き型の光重合開始剤の例には、ベンゾフェノン系、チオキサントン系、アミノベンゾフェノン系、１０－ブチル－２－クロロアクリドン、２－エチルアンスラキノン、９，１０－フェナンスレンキノンおよびカンファーキノンが含まれる。 Examples of the intramolecular hydrogen abstraction type photopolymerization initiator include benzophenone series, thioxanthone series, aminobenzophenone series, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, and 9,10-phenanthrenequinone. And camphorquinone.
　上記ベンゾフェノン系の例には、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル－４－フェニルベンゾフェノン、４，４’－ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチル－ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３’，４，４’－テトラ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、および、３，３’－ジメチル－４－メトキシベンゾフェノンが含まれる。 Examples of the benzophenone series include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylated benzophenone, 3 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and 3,3′-dimethyl-4-methoxybenzophenone.
　上記チオキサントン系の例には、２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、および、２，４－ジクロロチオキサントン、が含まれる。 Examples of the above thioxanthone series include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone.
　上記アミノベンゾフェノン系の例には、ミヒラーケトンおよび４，４’－ジエチルアミノベンゾフェノンが含まれる。 Examples of the aminobenzophenone series include Michler's ketone and 4,4'-diethylaminobenzophenone.
　上記撥液インクにおける上記光開始剤の含有量は、少なすぎると撥液インクの光硬化が不十分となることがあり、多すぎると当該光開始剤による効果が頭打ちになる。このような観点から、当該含有量は、０．０１～１０質量％であることが好ましく、１～９質量％であることがより好ましく、５～８質量％であることがさらに好ましい。 If the content of the photoinitiator in the liquid repellent ink is too small, the photocuring of the liquid repellent ink may be insufficient, and if it is too large, the effect of the photoinitiator reaches a peak. From such a viewpoint, the content is preferably 0.01 to 10% by mass, more preferably 1 to 9% by mass, and further preferably 5 to 8% by mass.
　上記ゲル化剤は、後述の活性光線グロスニスに対する撥液性を有する成分であり、例えば当該活性光線グロスニス中の成分の種類に応じて適宜に決められる。当該ゲル化剤は、一種でもそれ以上でもよい。上記ゲル化剤の例には、ステアリン酸イヌリンなどの脂肪酸イヌリン、パルミチン酸デキストリンやミリスチン酸デキストリンなどの脂肪酸デキストリン、ベヘン酸エイコサン二酸グリセリル、および、ベヘン酸エイコサン二酸ポリグリセリル、が含まれる。 The gelling agent is a component having liquid repellency with respect to the actinic ray gloss varnish described later, and is appropriately determined according to, for example, the type of component in the actinic ray gloss varnish. One or more gelling agents may be used. Examples of the gelling agent include fatty acid inulins such as inulin stearate, fatty acid dextrins such as dextrin palmitate and dextrin myristate, glyceryl behenate, and polyglyceryl behenate eicosane diacid.
　また、上記ゲル化剤の例には、特開２００５－１２６５０７号公報や特開２００５－２５５８２１号公報、特開２０１０－１１１７９０号公報などに記載の低分子オイルゲル化剤、Ｎ－ラウロイル－Ｌ－グルタミン酸ジブチルアミドやＮ－２エチルヘキサノイル－Ｌ－グルタミン酸ジブチルアミドなどのアミド化合物、および、１，３：２，４－ビス－Ｏ－ベンジリデン－Ｄ－グルシトールなどのジベンジリデンソルビトール類、が含まれる。 Examples of the gelling agent include low molecular oil gelling agents described in JP-A-2005-126507, JP-A-2005-255821, JP-A 2010-1111790, and the like, N-lauroyl-L- Amide compounds such as glutamic acid dibutylamide and N-2 ethylhexanoyl-L-glutamic acid dibutylamide, and dibenzylidene sorbitols such as 1,3: 2,4-bis-O-benzylidene-D-glucitol .
　また、上記ゲル化剤の例には、パラフィンワックスやマイクロクリスタリンワックス、ペトロラクタムなどの石油系ワックス、キャンデリラワックスやカルナウバワックス、ライスワックス、木ロウ、ホホバ油、ホホバ固体ロウ、ホホバエステルなどの植物系ワックス、ミツロウやラノリン、鯨ロウなどの動物系ワックス、モンタンワックスや水素化ワックスなどの鉱物系ワックス、硬化ヒマシ油または硬化ヒマシ油誘導体やモンタンワックス誘導体、および、パラフィンワックス誘導体、マイクロクリスタリンワックス誘導体、ポリエチレンワックス誘導体などの変性ワックス、が含まれる。 Examples of the gelling agent include petroleum waxes such as paraffin wax, microcrystalline wax, and petrolactam, candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, jojoba ester, etc. Plant waxes, animal waxes such as beeswax, lanolin and whale wax, mineral waxes such as montan wax and hydrogenated wax, hardened castor oil or hardened castor oil derivatives and montan wax derivatives, and paraffin wax derivatives, microcrystalline Modified waxes such as wax derivatives and polyethylene wax derivatives are included.
　また、上記ゲル化剤の例には、ベヘン酸やアラキジン酸、ステアリン酸、パルミチン酸、ミリスチン酸、ラウリン酸、オレイン酸、エルカ酸などの高級脂肪酸、ステアリルアルコ－ルやベヘニルアルコ－ルなどの高級アルコ－ル、１２－ヒドロキシステアリン酸などのヒドロキシステアリン酸またはその誘導体、ラウリン酸アミドやステアリン酸アミド、ベヘン酸アミド、オレイン酸アミド、エルカ酸アミド、リシノ－ル酸アミド、１２－ヒドロキシステアリン酸アミドなどの脂肪酸アミド、および、Ｎ-ステアリルステアリン酸アミドやＮ-オレイルパルミチン酸アミドなどのＮ－置換脂肪酸アミド、が含まれる。 Examples of the gelling agent include higher fatty acids such as behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid and erucic acid, stearyl alcohol and behenyl alcohol. Higher alcohol, hydroxystearic acid such as 12-hydroxystearic acid or its derivatives, lauric acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12-hydroxystearic acid Fatty acid amides such as amides, and N-substituted fatty acid amides such as N-stearyl stearic acid amide and N-oleyl palmitic acid amide are included.
　また、上記ゲル化剤の例には、Ｎ，Ｎ’－エチレンビスステアリルアミドやＮ，Ｎ’－エチレンビス１２－ヒドロキシステアリルアミド、Ｎ，Ｎ’－キシリレンビスステアリルアミドなどの特殊脂肪酸アミド、ドデシルアミンやテトラデシルアミン、オクタデシルアミンなどの高級アミン、ステアリルステアリン酸やオレイルパルミチン酸、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、プロピレングリコ－ル脂肪酸エステル、エチレングリコ－ル脂肪酸エステル、ポリオキシエチレン脂肪酸エステルなどの脂肪酸エステル化合物、ショ糖ステアリン酸やショ糖パルミチン酸などのショ糖脂肪酸エステル、ポリエチレンゲル化剤やα－オレフィン無水マレイン酸共重合体ゲル化剤などの合成ゲル化剤、重合性ゲル化剤、ダイマー酸、および、ダイマージオール、が含まれる。 Examples of the gelling agent include special fatty acid amides such as N, N′-ethylenebisstearylamide, N, N′-ethylenebis12-hydroxystearylamide, N, N′-xylylenebisstearylamide, Higher amines such as dodecylamine, tetradecylamine, octadecylamine, stearyl stearic acid, oleyl palmitic acid, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, polyoxyethylene fatty acid ester, etc. Fatty acid ester compounds, sucrose fatty acid esters such as sucrose stearic acid and sucrose palmitic acid, synthetic gelling agents such as polyethylene gelators and α-olefin maleic anhydride copolymer gelling agents, polymerizable gelling agents , Dimer And, dimer diol, contains.
　上記撥液インクにおける上記ゲル化剤の含有量は、少なすぎると撥液インクの膜における後述の活性光線グロスニスの弾きが不十分となることがあり、多すぎると撥液インクのインクジェット画像形成方法における出射安定性が不十分となることがある。このような観点から、当該含有量は、１～２０質量％であることが好ましく、１～１０質量％であることがより好ましく、２～７質量％であることがさらに好ましい。 If the content of the gelling agent in the liquid repellent ink is too small, the repellent ink film described later may be insufficiently repelled in the film of the liquid repellent ink. The emission stability at may be insufficient. From such a viewpoint, the content is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and further preferably 2 to 7% by mass.
　上記撥液インクの膜の光沢は、上記ゲル化剤の種類または上記撥液インクにおける上記ゲル化剤の含有量によって調整することが可能である。たとえば、上記撥液インクの膜の光沢度を１～３０とするのに好適なゲル化剤の例には、ジステアリルケトン、ベヘン酸ベヘニル、ステアリン酸ベヘニル、ステアリン酸ステアリルおよびジステアリン酸エチレンングリコールが含まれる。また、上記撥液インクの膜の光沢度を１～３０とするのに好適な、上記撥液インクにおける上記ゲル化剤の含有量は、例えば０．１～１０質量％であり、０．５～７質量％であることがより好ましく、１～５質量％であることがさらに好ましい。 The gloss of the film of the liquid repellent ink can be adjusted by the type of the gelling agent or the content of the gelling agent in the liquid repellent ink. For example, examples of gelling agents suitable for setting the gloss of the liquid repellent ink to 1 to 30 include distearyl ketone, behenyl behenate, behenyl stearate, stearyl stearate and ethylene glycol distearate. Is included. Further, the content of the gelling agent in the liquid repellent ink suitable for setting the gloss of the liquid repellent ink film to 1 to 30 is, for example, 0.1 to 10% by mass, 0.5% It is more preferably ˜7% by mass, and further preferably 1˜5% by mass.
　上記撥液インクは、本発明の効果が得られる範囲において、上記以外の他の成分をさらに含有していてもよい。当該他の成分は、一種でもそれ以上でもよい。当該他の成分の例には、重合禁止剤、色材、界面活性剤が含まれる。 The liquid repellent ink may further contain components other than those described above as long as the effects of the present invention are obtained. The other component may be one kind or more. Examples of the other components include a polymerization inhibitor, a coloring material, and a surfactant.
　上記重合禁止剤は、例えば、上記撥液インクの安定性を高める観点から当該撥液インクに添加される。上記重合禁止剤は、一種でもそれ以上でもよい。当該重合禁止剤の例には、ハイドロキノンやメチルハイドロキノン、ｔ－ブチルハイドロキノンなどのキノン系化合物、２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカルまたはその誘導体などのＮ－オキシル基を有するピペリジン系化合物、および、ニトロソアミノアルミキレート、が含まれる。 The polymerization inhibitor is added to the liquid repellent ink, for example, from the viewpoint of improving the stability of the liquid repellent ink. One or more polymerization inhibitors may be used. Examples of the polymerization inhibitor include quinone compounds such as hydroquinone, methylhydroquinone, and t-butylhydroquinone, and N-oxyl groups such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical or derivatives thereof. A piperidine-based compound having a nitrosoaminoaluminum chelate.
　上記撥液インクにおける上記重合禁止剤の含有量は、少なすぎると撥液インクの保存安定性が不十分となることがあり、多すぎると撥液インクの光硬化が不十分となることがある。このような観点から、当該含有量は、０．０１～１０質量％であることが好ましく、０．０５～５質量％であることがより好ましく、０．０５～１質量％であることがさらに好ましい。 If the content of the polymerization inhibitor in the liquid-repellent ink is too small, the storage stability of the liquid-repellent ink may be insufficient, and if it is too large, photocuring of the liquid-repellent ink may be insufficient. . From such a viewpoint, the content is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and further preferably 0.05 to 1% by mass. preferable.
　上記色材は、例えば、形成されるべき擬似エンボス画像の意匠性の観点から上記撥液インクに添加されてもよい。上記色材は、一種でもそれ以上でもよい。当該色材の例には、インクジェットインクの色材として利用可能であることが公知の顔料および染料が含まれる。上記顔料の例には、カラーインデックスに記載されている有機顔料および無機顔料が含まれる。上記染料の例には、油溶性染料が含まれる。 The color material may be added to the liquid repellent ink from the viewpoint of the design of a pseudo embossed image to be formed, for example. The color material may be one kind or more. Examples of the color material include pigments and dyes that are known to be usable as color materials for inkjet inks. Examples of the pigment include organic pigments and inorganic pigments described in the color index. Examples of the dye include oil-soluble dyes.
　上記界面活性剤は、撥液インクの表面張力を低下させ、基材に対する濡れ広がりを促進する観点から上記撥液インクに添加されていてもよい。上記界面活性剤は、一種でもそれ以上でもよい。当該界面活性剤の例には、インクジェットインクの界面活性剤として利用可能であることが公知の化合物が含まれ、より具体的には、フッ素系界面活性剤やシリコーン系界面活性剤、高級アルコール系界面活性剤などの非イオン系界面活性剤全般を含む。 The surfactant may be added to the liquid repellent ink from the viewpoint of decreasing the surface tension of the liquid repellent ink and promoting the wetting and spreading to the substrate. One or more surfactants may be used. Examples of such surfactants include compounds that are known to be usable as surfactants for inkjet inks. More specifically, fluorine-based surfactants, silicone-based surfactants, higher alcohol-based surfactants are included. Includes all non-ionic surfactants such as surfactants.
　上記撥液インクにおける上記色材の含有量は、多すぎると撥液インクの膜の上記基材への密着性が不十分となることがある。このような観点から、上記撥液インクは当該色材を実質的にあるいは単に含有しないことが好ましいが、当該撥液インクが当該色材を含有する場合では、その含有量は、例えば、上記の密着性が十分に発現される観点および意匠性の観点から、０．５～１０質量％であることが好ましく、０．５～７質量％であることがより好ましく、１～５質量％であることがさらに好ましい。 If the content of the color material in the liquid repellent ink is too large, the adhesion of the liquid repellent ink film to the substrate may be insufficient. From such a viewpoint, it is preferable that the liquid repellent ink does not substantially or simply contain the color material. However, when the liquid repellent ink contains the color material, the content is, for example, From the viewpoint of sufficient adhesion and design, 0.5 to 10% by mass is preferable, 0.5 to 7% by mass is more preferable, and 1 to 5% by mass is preferable. More preferably.
　なお、色材を「実質的に含有しない」とは、色材を全く含有しないことも意味するが、呈色などの当該色材の機能が撥液インクにおいて十分に発現されない程度の量で、撥液インクが色材を含有し得ることを意味する。 Incidentally, "substantially does not contain" the color material also means that it does not contain any color material, but in such an amount that the function of the color material such as coloring is not sufficiently expressed in the liquid repellent ink, It means that the liquid repellent ink can contain a color material.
　上記基材は、上記撥液インクをインクジェット画像形成方法によって塗布可能な物体である。上記基材の形態は、通常はシートであるが、本実施の形態におけるインクの塗布が可能な範囲において、他の形態であってもよい。当該基材の例には、コート紙、蒸着紙、アルミホイル紙、ポリエチレンテレフタラート（ＰＥＴ）シート、ポリプロピレン（ＰＰ）シート、上質紙、ボール紙、アート紙、段ボール紙、コートボール紙およびエンボス紙が含まれる。 The substrate is an object on which the liquid repellent ink can be applied by an inkjet image forming method. The form of the substrate is usually a sheet, but may be other forms as long as ink can be applied in the present embodiment. Examples of the substrate include coated paper, vapor-deposited paper, aluminum foil paper, polyethylene terephthalate (PET) sheet, polypropylene (PP) sheet, fine paper, cardboard, art paper, corrugated paper, coated cardboard and embossed paper. Is included.
　上記撥液インクは、例えば、上記の材料成分の混合によって調整することが可能であり、あるいは、活性光線硬化性化合物および光開始剤を含有する既存のインクジェットインクにゲル化剤を添加することによって調製することが可能である。 The liquid repellent ink can be adjusted, for example, by mixing the material components described above, or by adding a gelling agent to an existing inkjet ink containing an actinic ray curable compound and a photoinitiator. It is possible to prepare.
　上記基材の表面には、例えば意匠性の観点から、インクによる画像が形成されていてもよい。さらに上記撥液インクの膜の上記基材への密着性を高める観点から、当該基材の表面に形成された画像は、活性光線硬化性インクジェットインクによる画像であることが好ましく、活性光線硬化性インクジェットゲルインクによる画像であることがより好ましい。 The image of the ink may be formed on the surface of the base material from the viewpoint of design, for example. Further, from the viewpoint of improving the adhesion of the liquid repellent ink film to the base material, the image formed on the surface of the base material is preferably an image of an actinic ray curable inkjet ink, The image is more preferably an inkjet gel ink.
　上記活性光線硬化性インクジェットインクは、紫外線などの前述の活性光線の照射によって硬化する性質を有するインクジェットインクであり、例えば、上記活性光線硬化性化合物、上記光開始剤および上記色材を含有する。上記活性光線硬化性インクジェットゲルインクは、上記活性光線硬化性インクジェットインクにさらにゲル化剤を含有した組成物であり、例えば、上記活性光線硬化性化合物、上記光開始剤、上記色材および上記ゲル化剤を含有する。上記活性光線硬化性インクジェットインクまたは上記活性光線硬化性インクジェットゲルインクにおける活性光線硬化性化合物、光開始剤、色材、およびゲル化剤の種類および含有量は、上記撥液インクのそれらと同じであってもよいし、異なっていてもよい。また、活性光線は、撥液インクを硬化させる活性光線と同じであってもよいし、異なっていてもよい。 The actinic ray curable inkjet ink is an inkjet ink having a property of being cured by irradiation with the actinic ray such as ultraviolet rays, and includes, for example, the actinic ray curable compound, the photoinitiator, and the coloring material. The actinic radiation curable inkjet gel ink is a composition further containing a gelling agent in the actinic radiation curable inkjet ink. For example, the actinic radiation curable compound, the photoinitiator, the coloring material, and the gelation. Contains agents. The types and contents of the actinic ray curable compound, the photoinitiator, the coloring material, and the gelling agent in the actinic ray curable inkjet ink or the actinic ray curable inkjet gel ink are the same as those of the liquid repellent ink. It may be different or different. Moreover, the actinic ray may be the same as or different from the actinic ray that cures the liquid repellent ink.
　上記活性光線硬化性インクジェットゲルインクにおける上記ゲル化剤の含有量は、上記撥液インクの膜の上記基材への密着性を高める観点から、０．１質量％以上であることが好ましく、１質量％以上であることがより好ましく、１．５質量％以上であることがさらに好ましい。また、上記活性光線硬化性インクジェットインクまたは上記活性光線硬化性インクジェットゲルインクにおける上記ゲル化剤の含有量は、擬似エンボス画像における所期の意匠性を達成する観点から、１０質量％以下であることが好ましく、７質量％以下であることがより好ましく、５質量％以下であることがさらに好ましい。 The content of the gelling agent in the actinic ray curable inkjet gel ink is preferably 0.1% by mass or more from the viewpoint of enhancing the adhesion of the liquid repellent ink film to the substrate. % Or more, more preferably 1.5% by mass or more. In addition, the content of the gelling agent in the actinic ray curable inkjet ink or the actinic ray curable inkjet gel ink is 10% by mass or less from the viewpoint of achieving the desired design in the pseudo-embossed image. Preferably, it is 7 mass% or less, More preferably, it is 5 mass% or less.
　より具体的には、例えば、上記活性光線硬化性インクジェットインクは、８０～９７質量％の活性光線硬化性化合物と、０．０１～１０質量％の光開始剤と、０．５～１０質量％の色材とを含有する組成物である。また、例えば、上記活性光線硬化性インクジェットゲルインクは、７０～９７質量％の活性光線硬化性化合物と、０．０１～１０質量％の光開始剤と、０．１～１０質量％のゲル化剤と、０．５～１０質量％の色材とを含有する組成物である。 More specifically, for example, the above-mentioned actinic ray curable inkjet ink comprises 80 to 97% by mass of an actinic ray curable compound, 0.01 to 10% by mass of a photoinitiator, and 0.5 to 10% by mass. It is a composition containing these coloring materials. Also, for example, the actinic ray curable inkjet gel ink includes 70 to 97% by mass of an actinic ray curable compound, 0.01 to 10% by mass of a photoinitiator, and 0.1 to 10% by mass of a gelling agent. And 0.5 to 10% by mass of a coloring material.
　上記活性光線硬化性インクジェットインクまたは上記活性光線硬化性インクジェットゲルインクは、例えば、市販のＵＶ硬化性インクジェットインクをそのまま用いることが可能であり、あるいは上記の材料成分を混合することによって調製することが可能であり、あるいは当該ＵＶ硬化性インクジェットインクにゲル化剤を適量添加することによって調製することが可能である。 The actinic radiation curable inkjet ink or the actinic radiation curable inkjet gel ink may be, for example, a commercially available UV curable inkjet ink as it is, or can be prepared by mixing the above material components. Alternatively, it can be prepared by adding an appropriate amount of a gelling agent to the UV curable inkjet ink.
　上記ゲル化剤を含有する上記活性光線硬化性インクジェットインクは、シリコーン系界面活性剤またはフッ素系界面活性剤をさらに含有することが、当該活性光線硬化性インクジェットインクの膜（画像）に対する上記撥液インクの膜の密着性を高める観点から好ましい。これは、上記の界面活性剤の上記活性光線硬化性インクジェットインクへの添加によって、上記撥液インクがより良好な塗布性を発現する適切な範囲に、当該活性光線硬化性インクジェットインクの膜の表面張力が調整されるため、と考えられる。 The liquid repellent to the film (image) of the actinic radiation curable inkjet ink, wherein the actinic radiation curable inkjet ink containing the gelling agent further contains a silicone surfactant or a fluorine surfactant. This is preferable from the viewpoint of improving the adhesion of the ink film. This is because the surface of the film of the actinic radiation curable inkjet ink is within an appropriate range in which the liquid repellent ink exhibits better coating properties by adding the surfactant to the actinic radiation curable inkjet ink. This is probably because the tension is adjusted.
　上記活性光線硬化性インクジェットインクが上記ゲル化剤に加えてシリコーン系界面活性剤またはフッ素系界面活性剤を含有する場合には、上記撥液インクは、上記の密着性および塗布性の向上効果を十分に発現させる範囲において、当該シリコーン系界面活性剤およびフッ素系界面活性剤の一方または両方を含有してもよいが、上記の密着性および塗布性の十分な向上効果を得る観点から、当該シリコーン系界面活性剤およびフッ素系界面活性剤の一方または両方を含有しないことが好ましい。 When the actinic ray curable inkjet ink contains a silicone surfactant or a fluorosurfactant in addition to the gelling agent, the liquid repellent ink has the effect of improving the adhesion and coating properties. In the range of sufficient expression, one or both of the silicone-based surfactant and the fluorine-based surfactant may be contained. From the viewpoint of obtaining a sufficient improvement effect on the adhesion and coating properties, the silicone It is preferable not to contain one or both of a surfactant and a fluorosurfactant.
　上記画像に対する撥液インクの膜の十分な密着性を発現させる観点では、上記ゲル化剤を含有する活性光線硬化性インクジェットインクにおけるシリコーン系界面活性剤の含有量は、０．０１～１０質量％であることが好ましく、０．０１～５質量％であることがより好ましく、０．０１～１質量％であることがさらに好ましい。また、上記の観点から、上記ゲル化剤を含有する活性光線硬化性インクジェットインクにおけるフッ素系界面活性剤の含有量は、０．０１～１０質量％であることが好ましく、０．０１～５質量％であることがより好ましく、０．０１～１質量％であることがさらに好ましい。 From the viewpoint of expressing sufficient adhesion of the liquid repellent ink film to the image, the content of the silicone surfactant in the actinic radiation curable inkjet ink containing the gelling agent is 0.01 to 10% by mass. Preferably, the content is 0.01 to 5% by mass, and more preferably 0.01 to 1% by mass. From the above viewpoint, the content of the fluorosurfactant in the actinic ray curable inkjet ink containing the gelling agent is preferably 0.01 to 10% by mass, and 0.01 to 5% by mass. % Is more preferable, and 0.01 to 1% by mass is even more preferable.
　フッ素系界面活性剤は、炭素原子数６以下のパーフルオロアルキル基を有するノニオン性界面活性剤（「Ｃ６ＰＮＳ」とも言う）が好ましい。本発明において「パーフルオロアルキル基」とは、炭素原子の少なくとも一つがフッ素原子と結合している炭化水素基を示し、「炭素原子数６以下のパーフルオロアルキル基」とは、炭素原子数が１以上６以下の直鎖部分を有するパーフルオロアルキル基を示す。炭素原子数６以下のパーフルオロアルキル基は、分岐構造を有していてもよい。 The fluorine-based surfactant is preferably a nonionic surfactant having a perfluoroalkyl group having 6 or less carbon atoms (also referred to as “C6PNS”). In the present invention, the “perfluoroalkyl group” refers to a hydrocarbon group in which at least one carbon atom is bonded to a fluorine atom, and the “perfluoroalkyl group having 6 or less carbon atoms” means the number of carbon atoms. 1 represents a perfluoroalkyl group having a straight chain portion of 1 to 6. A perfluoroalkyl group having 6 or less carbon atoms may have a branched structure.
　上記Ｃ６ＰＮＳは、ゲル化剤よりも活性光線硬化型インクジェットインクの膜（以下、「硬化膜」とも言う）の表面への配向性が高い。よって、当該Ｃ６ＰＮＳは、硬化膜の表面に析出するゲル化剤の結晶の疎水性成分を覆い、その結果、上記硬化膜の表面エネルギーがゲル化剤の結晶によるそれよりも高くなる、と考えられる。 The C6PNS has higher orientation on the surface of an actinic ray curable inkjet ink film (hereinafter also referred to as “cured film”) than a gelling agent. Therefore, it is considered that the C6PNS covers the hydrophobic component of the gelling agent crystal deposited on the surface of the cured film, and as a result, the surface energy of the cured film is higher than that due to the gelling agent crystal. .
　パーフルオロアルキル基の炭素原子数が６を超えてしまうと、撥液インクの密着性が不十分となることがある。これは、パーフルオロアルキル基の炭素原子数が６を超えると、硬化膜の表面に配向したＣ６ＰＮＳが凝集し、結晶化してしまい、硬化膜の表面の表面エネルギーが低くなってしまうため、と考えられる。パーフルオロアルキル基の炭素原子数が６以下であることは、上記の凝集および結晶化を防止し、上記硬化膜の表面エネルギーを効果的に高くする観点から好ましい、と考えられる。 If the number of carbon atoms in the perfluoroalkyl group exceeds 6, the adhesion of the liquid repellent ink may be insufficient. This is thought to be because when the number of carbon atoms of the perfluoroalkyl group exceeds 6, the C6PNS oriented on the surface of the cured film aggregates and crystallizes, and the surface energy of the surface of the cured film decreases. It is done. It is considered that the perfluoroalkyl group having 6 or less carbon atoms is preferable from the viewpoint of preventing the aggregation and crystallization and effectively increasing the surface energy of the cured film.
　上記Ｃ６ＰＮＳのパーフルオロアルキル基は、直鎖構造を有していてもよいし、分岐構造を有していてもよいが、密着性の観点から、直鎖構造を有することが好ましい。 The C6PNS perfluoroalkyl group may have a linear structure or a branched structure, but preferably has a linear structure from the viewpoint of adhesion.
　分岐構造を有しているＣ６ＰＮＳの具体例には、フタージェント２１２Ｍ、２１５Ｍ、ＦＴＸ－２１８、２０８Ｇ、２１２Ｐ、２５０、２５１、２４５Ｆ、６０２Ａ、６８１、７１０ＦＭ、７３０ＦＭおよび７３０ＬＭ（株式会社ネオス製、「フタージェント」は同社の登録商標）が含まれる。 Specific examples of the C6PNS having a branched structure include a footage 212M, 215M, FTX-218, 208G, 212P, 250, 251, 245F, 602A, 681, 710FM, 730FM, and 730LM (manufactured by Neos Corporation, “ "Factent" is a registered trademark of the same company.
　直鎖構造を有しているＣ６ＰＮＳの具体例には、キャップストーンＦＳ－２２、ＦＳ－３０、ＦＳ０３１、ＦＳ－３４、ＦＳ－３５、ＦＳ－３１００（デュポン社製、「キャップストーン」は同社の登録商標）、メガファックＦ－５５９、Ｆ－４７７、Ｆ－５５６、Ｆ－５５４、Ｆ－５６９、Ｆ－５５３、Ｆ－５５７、Ｆ－５５２、Ｆ－５６３、Ｒ－４０、ＲＳ－７６－ＮＳ、Ｆ－４４４（ＤＩＣ株式会社製、「メガファック」は同社の登録商標）、サーフロンＳ－２４１、Ｓ－３８６、Ｓ－６１１、Ｓ－６５１、Ｓ－２４２、Ｓ－２４３およびＳ－４２０（ＡＧＣセイミケミカル株式会社製、「サーフロン」は同社の登録商標）が含まれる。 Specific examples of C6PNS having a linear structure include Capstone FS-22, FS-30, FS031, FS-34, FS-35, and FS-3100 (manufactured by DuPont, “Capstone” Registered trademark), MegaFuck F-559, F-477, F-556, F-554, F-569, F-553, F-557, F-552, F-563, R-40, RS-76- NS, F-444 (manufactured by DIC Corporation, “Megafuck” is a registered trademark of the company), Surflon S-241, S-386, S-611, S-651, S-242, S-243 and S-420 (AGC Seimi Chemical Co., Ltd., “Surflon” is a registered trademark of the same company).
　上記Ｃ６ＰＮＳの重量平均分子量は、撥液インクの密着性の観点から、５００以上１０００００以下が好ましく、３０００以上１０００００以下がより好ましく、１００００以上８００００以下がさらに好ましい。重量平均分子量が３０００以上であると、硬化膜の表面に配向した炭素原子数６以下のパーフルオロアルキル基を有するノニオン性界面活性剤が揮発しづらく、安定して存在でき、撥液インクの密着性がより良好になると考えられる。 The weight average molecular weight of the C6PNS is preferably 500 or more and 100,000 or less, more preferably 3000 or more and 100,000 or less, and further preferably 10,000 or more and 80,000 or less, from the viewpoint of adhesion of the liquid repellent ink. When the weight average molecular weight is 3000 or more, the nonionic surfactant having a perfluoroalkyl group having 6 or less carbon atoms oriented on the surface of the cured film is difficult to volatilize and can exist stably, and the adhesion of the liquid repellent ink It is considered that the property becomes better.
　上記Ｃ６ＰＮＳの重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定することができる。ポリスチレン換算重量平均分子量である。下記校正曲線における１３のサンプルの間隔は、ほぼ等間隔である。 The weight average molecular weight of the C6PNS can be measured by gel permeation chromatography (GPC). It is a weight average molecular weight in terms of polystyrene. The intervals of 13 samples in the calibration curve below are substantially equal.
　溶媒　　　：　テトラヒドロフラン
　カラム　　：　東ソー製ＴＳＫｇｅｌ　Ｇ４０００＋２５００＋２０００ＨＸＬ
　カラム温度：　４０℃
　注入量　　：　１０μＬ
　検出器　　：　Ｌ２４５５（日立製作所（株）製）
　ポンプ　　：　Ｌ６０００（日立製作所（株）製）
　流量　　　：　１．０ｍｌ／ｍｉｎ
　校正曲線　：　標準ポリスチレンＳＴＫ　ｓｔａｎｄａｒｄ　ポリスチレン（東ソー（株）製）重量平均分子量＝１００００００～５００迄の１３のサンプルによる校正曲線 Solvent: Tetrahydrofuran Column: Tosoh TSKgel G4000 + 2500 + 2000HXL
Column temperature: 40 ° C
Injection volume: 10 μL
Detector: L2455 (manufactured by Hitachi, Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Weight average molecular weight = Calibration curve with 13 samples from 1000000 to 500
　上記Ｃ６ＰＮＳは、撥液インクの密着性の観点から、その表面配向性が高い方が好ましく、表面配向性の高さは、動的表面張力を測定することでわかる。動的表面張力の測定方法としては、公知の方法により測定することができる。たとえば、最大泡圧法により測定することができる。 The C6PNS preferably has a higher surface orientation from the viewpoint of the adhesion of the liquid repellent ink, and the height of the surface orientation can be determined by measuring the dynamic surface tension. The dynamic surface tension can be measured by a known method. For example, it can be measured by the maximum bubble pressure method.
　パーフルオロアルキル基の炭素原子数は、カタログ値でよく、また、１３ＣＮＭＲ、１９ＦＮＭＲ等の公知の分析法により測定することもできる。 The number of carbon atoms in the perfluoroalkyl group may be a catalog value, and can also be measured by a known analysis method such as 13 CNMR or 19 FNMR.
　シリコーン系界面活性剤は、ポリエーテル変性シリコーン系界面活性剤が好ましく、その例には、Ｘ２２－４２７２、ＫＦ－３５２（いずれも信越化学工業株式会社製）、ＴＳＦ４４５２（ＭＯＭＥＮＴＩＶＥ社製）、ＢＹＫ－３６１Ｎ、ＢＹＫ－３４５５、ＢＹＫ３４８（いずれもＢＹＫ社製、「ＢＹＫ」は同社の登録商標）が含まれる。 The silicone surfactant is preferably a polyether-modified silicone surfactant. Examples thereof include X22-4272, KF-352 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF4452 (manufactured by MOMENTIVE), BYK- 361N, BYK-3455, BYK348 (all manufactured by BYK, “BYK” is a registered trademark of the company).
　上記第１の工程において、上記撥液インクの膜は、例えば、インクジェット画像形成方法による上記基材への上記撥液インクの塗布（当該撥液インクの液滴の着弾）と、塗布された撥液インクの固化と、によって作製することが可能である。上記撥液インクの膜は、当該膜の上に後述の活性光線グロスニスを塗布可能であればよく、撥液インクの塗膜の乾燥物であってもよいし、活性光線の照射による撥液インクの塗膜の半硬化物（光硬化反応が完了しない状態）であってもよいし、撥液インク塗膜の硬化物（光硬化反応が完了した状態）であってもよい。 In the first step, the liquid-repellent ink film is formed by, for example, applying the liquid-repellent ink (landing of the liquid-repellent ink droplets) to the substrate by an inkjet image forming method and applying the liquid-repellent ink. It can be produced by solidifying the liquid ink. The film of the liquid repellent ink is not limited as long as it can apply the actinic ray gloss varnish described later on the film, and may be a dried product of the liquid repellent ink coating, or the liquid repellent ink by actinic ray irradiation. It may be a semi-cured product of the coating film (in a state where the photocuring reaction is not completed) or a cured product of the liquid repellent ink coating film (in a state where the photocuring reaction is completed).
　上記撥液インクの膜の光沢は、上記撥液インクのインクジェット画像形成方法における印字率によっても調整することが可能である。たとえば、上記撥液インクの膜の光沢度を１～３０とするのに好適な上記印字率は、例えば６０～１００％であり、７０～１００％であることがより好ましく、８０～１００％であることがさらに好ましい。 The gloss of the liquid repellent ink film can also be adjusted by the printing rate of the liquid repellent ink in the inkjet image forming method. For example, the printing rate suitable for setting the gloss of the liquid repellent ink film to 1 to 30 is, for example, 60 to 100%, more preferably 70 to 100%, and more preferably 80 to 100%. More preferably it is.
　上記撥液インクの膜の表面エネルギーは、擬似エンボス画像におけるエンボス調に係る意匠性の観点から適宜に決めることが可能であり、例えば４５ｍＮ／ｍ以下であることが好ましく、４０ｍＮ／ｍ以下であることがより好ましく、３５ｍＮ／ｍ以下であることがさらに好ましい。当該表面エネルギーは、例えば、基材に対する水、ノナン、炭酸プロピレンの接触角をそれぞれ測定することによって求めることが可能であり、例えば、ゲル化剤の添加量や、界面活性剤の添加量などによって調整することが可能である。 The surface energy of the liquid-repellent ink film can be appropriately determined from the viewpoint of the design property relating to the embossed tone in the pseudo-embossed image, and is preferably 45 mN / m or less, for example, 40 mN / m or less. More preferably, it is more preferably 35 mN / m or less. The surface energy can be determined, for example, by measuring the contact angles of water, nonane, and propylene carbonate with respect to the substrate, for example, depending on the amount of gelling agent added, the amount of surfactant added, etc. It is possible to adjust.
　上記基材の表面の上記撥液インクに対する接触角は、高すぎると、通常の印刷方法による当該撥液インクによる所期の画像の形成が困難になるが、本実施の形態では、上記画像がインクジェット画像形成方法によって形成され、かつインクにゲル化剤を含有することから、通常の印刷方法に適用される基材よりも、上記接触角がより大きな基材を用いることが可能である。たとえば、当該記載の上記撥液インクに対する接触角は、１０～１５°であってよく、また１５～２５°であってよく、さらに２５～３５°であってよい。 If the contact angle of the surface of the base material with respect to the liquid repellent ink is too high, it becomes difficult to form an intended image with the liquid repellent ink by a normal printing method. Since the ink is formed by the ink jet image forming method and the ink contains a gelling agent, it is possible to use a substrate having a larger contact angle than that of a substrate applied to a normal printing method. For example, the contact angle with respect to the liquid-repellent ink described above may be 10 to 15 °, 15 to 25 °, or 25 to 35 °.
　上記接触角は、上記の撥液インクからゲル化剤を除いた測定用インクによって、例えば、当該測定用インクの液滴が基材に着弾してから５秒後の、当該基材に対する上記測定用インクの接触角によって求めることが可能であり、例えば、界面活性剤の添加量によって調整することが可能である。なお、実際の撥液インクの基材の表面に対する接触角は、上記撥液インク中の界面活性剤の添加量に加えて、ゲル化剤の添加量によって調整することが可能であり、併せて当該撥液インクの基材表面における濡れ広がりが確認され得る。 The contact angle is measured with the measurement ink obtained by removing the gelling agent from the liquid-repellent ink, for example, the measurement with respect to the base material 5 seconds after the measurement ink droplet has landed on the base material. It can be determined by the contact angle of the ink for use, and can be adjusted, for example, by the amount of surfactant added. The contact angle of the actual liquid repellent ink to the surface of the substrate can be adjusted by the addition amount of the gelling agent in addition to the addition amount of the surfactant in the liquid repellent ink. Wetting and spreading on the substrate surface of the liquid repellent ink can be confirmed.
　上記第２の工程では、少なくとも上記撥液インクの膜を覆うようにニスを上記基材に塗布する。当該ニスの塗布方法は、特に限定されない。たとえば、当該ニスの塗布方法は、インクの公知の塗布方法から適宜に決めることが可能であり、例えば、インクジェット画像形成方法であってもよいし、オフセット印刷方法であってもよい。 In the second step, varnish is applied to the substrate so as to cover at least the liquid-repellent ink film. The method for applying the varnish is not particularly limited. For example, the application method of the varnish can be appropriately determined from a known application method of ink, and may be, for example, an inkjet image forming method or an offset printing method.
　上記ニスは、少なくとも上記撥液インクの膜を覆うように上記基材に塗布されればよいが、意匠性や生産性などの観点から、上記基材の全面に塗布されることが好ましい。 The varnish may be applied to the substrate so as to cover at least the film of the liquid repellent ink, but is preferably applied to the entire surface of the substrate from the viewpoints of designability and productivity.
　上記ニスは、撥液インクの膜に対する撥液性を呈し、かつ光沢を呈する硬化膜を形成可能な塗料である。上記ニスは、上記撥液インクの組成に応じて、当該撥液インクの膜に対して所望の撥液性を呈する公知のニスの中から適宜に選ぶことができる。上記撥液インクがゲル化剤を含有する場合には、上記ニスは、活性光線グロスニスであることが好ましい。 The above varnish is a paint that exhibits liquid repellency to a film of liquid repellent ink and can form a glossy cured film. The varnish can be appropriately selected from known varnishes exhibiting a desired liquid repellency with respect to the liquid repellent ink film according to the composition of the liquid repellent ink. When the liquid repellent ink contains a gelling agent, the varnish is preferably an actinic ray gloss varnish.
　上記活性光線グロスニスは、撥液インクの膜に対する撥液性を呈し、かつ紫外線などの活性光線の照射によって光沢を呈する硬化膜を形成する組成物である。当該活性光線グロスニスは、一種でもそれ以上でもよい。当該活性光線グロスニスには、擬似エンボス画像の形成において撥液性のニスの上に塗られる公知のニスをそのまま用いることが可能である。また、当該活性光線グロスニスの硬化膜の光沢度は、形成されるべき擬似エンボス画像の意匠性などの観点から決めることができ、例えば、５０～１００であることが好ましく、６０～１００であることがより好ましく、７０～１００であることがさらに好ましい。 The actinic ray gloss varnish is a composition that exhibits liquid repellency with respect to the film of the liquid repellent ink and forms a cured film that exhibits gloss upon irradiation with actinic rays such as ultraviolet rays. The actinic ray gloss varnish may be one kind or more. As the actinic ray gloss varnish, a known varnish applied on the liquid-repellent varnish in forming a pseudo-embossed image can be used as it is. The glossiness of the cured film of the actinic ray gloss varnish can be determined from the viewpoint of the design of the pseudo-embossed image to be formed, and is preferably 50 to 100, for example, 60 to 100. Is more preferable, and 70 to 100 is even more preferable.
　上記活性光線グロスニスの例には、特許文献２に記載の紫外線硬化型オーバープリントワニス組成物、特許文献３に記載の上刷りワニス、高光沢水性ニス、および、その他の活性光線グロスニス、を含む。当該活性光線グロスニスを上記撥液インクの膜に塗布する方式は、例えば公知の方法から適当な方法を選ぶことができ、その例には、オフセット印刷、グラビア印刷およびフレキソ印刷が含まれる。 Examples of the actinic ray gloss varnish include the ultraviolet curable overprint varnish composition described in Patent Document 2, the overprint varnish described in Patent Document 3, a high gloss aqueous varnish, and other actinic light gloss varnishes. As a method for applying the actinic ray gloss varnish to the liquid repellent ink film, for example, an appropriate method can be selected from known methods, and examples thereof include offset printing, gravure printing, and flexographic printing.
　上記画像形成方法は、本実施の形態の効果が得られる範囲において、上記第１の工程および第２の工程以外の他の工程をさらに含んでいてもよい。当該他の工程の例には、上記基材における上記撥液インクの膜が形成されるべき部分または表面全体に、上記活性光線硬化性インクジェットインクまたは上記活性光線硬化性インクジェットゲルインクによる画像をインクジェット画像形成方法によって形成する工程、画像が形成された基材または基材そのものにコロナ処理などの表面処理を行う工程、および、上記基材に塗布された活性光線硬化型インクジェットインクを半硬化させることによって画像が形成された基材を得る工程、が含まれる。 The image forming method may further include other steps other than the first step and the second step as long as the effects of the present embodiment can be obtained. In another example of the process, an image of the actinic ray curable inkjet ink or the actinic ray curable inkjet gel ink is applied to a portion or the entire surface of the substrate where the liquid repellent ink film is to be formed. A step of forming by a forming method, a step of performing a surface treatment such as corona treatment on a substrate on which an image is formed or the substrate itself, and by semi-curing the actinic ray curable inkjet ink applied to the substrate Obtaining a substrate on which an image is formed.
　上記画像形成方法によって擬似エンボス画像が形成される様子を模式的に図１Ａ～１Ｅに示す。図１Ａに示されるようなアルミホイル紙などの基材１００の表面に、図１Ｂに示されるように、例えばインクジェット画像形成方法によって上記活性光線硬化性インクジェットインクまたは上記活性光線硬化性インクジェットゲルインクが塗布され、画像１０１が形成される。そして、図１Ｃに示されるように、画像１０１の一部の領域に撥液インク１０２がインクジェット画像形成方法によって塗布される。塗布された撥液インク１０２は、速やかに乾燥する。塗布された撥液インク１０２には、必要に応じて紫外線などの活性光線がさらに照射され、こうして、例えば撥液インク１０２の半硬化物が撥液インク１０２の膜として形成される。 1A to 1E schematically show how pseudo embossed images are formed by the above image forming method. As shown in FIG. 1B, the actinic ray curable inkjet ink or the actinic ray curable inkjet gel ink is applied to the surface of a substrate 100 such as aluminum foil paper as shown in FIG. 1A by, for example, an inkjet image forming method. As a result, an image 101 is formed. Then, as shown in FIG. 1C, the liquid repellent ink 102 is applied to a partial region of the image 101 by the inkjet image forming method. The applied liquid repellent ink 102 is quickly dried. The applied liquid repellent ink 102 is further irradiated with actinic rays such as ultraviolet rays as necessary, and thus, for example, a semi-cured product of the liquid repellent ink 102 is formed as a film of the liquid repellent ink 102.
　さらに、図１Ｄに示されるように、少なくとも撥液インク１０２の膜を覆うように（例えば基材１００の平面方向における全面）に、活性光線グロスニス１０３が、例えばオフセット印刷方法によって塗布される。撥液インク１０２の膜に塗布された活性光線グロスニス１０３は、撥液インク１０２がゲル化剤を含有することから、当該膜に弾かれ、当該膜状に点在する。そして、塗布された活性光線グロスニス１０３に紫外線が照射され、活性光線グロスニス１０３が硬化する。また、上記の紫外線の照射によって、撥液インク１０２の膜中の未反応の活性光線硬化性化合物の光反応が生じ、撥液インク１０２の膜は、撥液インク１０２の硬化物となる。その結果、図１Ｅに示されるように、活性光線グロスニス１０３の硬化物による平坦な部分と、点在する部分とによる擬似エンボス画像が形成される。 Further, as shown in FIG. 1D, the actinic ray gloss varnish 103 is applied by, for example, an offset printing method so as to cover at least the film of the liquid repellent ink 102 (for example, the entire surface in the planar direction of the substrate 100). The actinic ray gloss varnish 103 applied to the film of the liquid repellent ink 102 is repelled by the film because the liquid repellent ink 102 contains a gelling agent, and is scattered in the film shape. Then, the applied actinic ray gloss varnish 103 is irradiated with ultraviolet rays, and the actinic ray gloss varnish 103 is cured. Further, the irradiation of the ultraviolet rays causes a photoreaction of an unreacted actinic ray curable compound in the film of the liquid repellent ink 102, and the film of the liquid repellent ink 102 becomes a cured product of the liquid repellent ink 102. As a result, as shown in FIG. 1E, a pseudo-embossed image is formed by flat portions of the cured product of the actinic ray gloss varnish 103 and scattered portions.
　以上の説明から明らかなように、上記画像形成方法は、上記第１の工程と上記第２の工程とを含むことから、撥液インクの膜がインクジェット画像形成方法によって形成されるので、当該撥液インクの膜を所期の形状に容易に設定することが可能である。よって、上記画像形成方法では、従来の印刷方法のみからなる擬似エンボス画像の形成方法に比べて、擬似エンボス画像をより容易に設定または変更することが可能である。 As is clear from the above description, since the image forming method includes the first step and the second step, the liquid repellent ink film is formed by the ink jet image forming method. It is possible to easily set the liquid ink film to a desired shape. Therefore, in the above image forming method, it is possible to set or change the pseudo embossed image more easily than the method of forming a pseudo embossed image consisting only of the conventional printing method.
　上記撥液インクにおける上記ゲル化剤の含有量が２０質量％以下であることは、撥液インクの出射安定性と撥液インクの膜の基材への密着性との両方を十分に発現させる観点からより効果的であり、当該含有量が１０質量％以下であることは、上記の観点からより一層効果的である。 When the content of the gelling agent in the liquid repellent ink is 20% by mass or less, both the emission stability of the liquid repellent ink and the adhesion of the liquid repellent ink film to the base material are sufficiently expressed. It is more effective from the viewpoint, and it is more effective from the above viewpoint that the content is 10% by mass or less.
　また、上記撥液インクが色材を含有することは、上記擬似エンボスの意匠性を高める観点からより一層効果的であり、上記撥液インクが色材を含有しないことは、撥液インクの膜の基材への密着性を高める観点からより一層効果的である。 The liquid repellent ink containing a color material is more effective from the viewpoint of enhancing the design of the pseudo embossing, and the liquid repellent ink does not contain a color material. This is more effective from the viewpoint of improving the adhesion to the substrate.
　また、上記ニスを塗布する工程では、撥液インクの膜が形成された上記基材の全面に上記ニスを塗布することは、擬似エンボス画像の生産性を高める観点からより一層効果的である。 In the step of applying the varnish, applying the varnish to the entire surface of the substrate on which the liquid repellent ink film is formed is more effective from the viewpoint of increasing the productivity of the pseudo embossed image.
　また、上記ニスに活性光線グロスニスを用いることは、良好な光沢を有するエンボス画像の生産性を高める観点からより一層効果的である。 In addition, the use of actinic ray gloss varnish for the varnish is more effective from the viewpoint of enhancing the productivity of embossed images having good gloss.
　また、上記基材には、上記活性光線硬化性インクジェットインクによる画像が形成されており、上記撥液インクの膜が当該画像上に形成されることは、撥液インクの膜の基材への密着性を高める観点からより効果的であり、上記画像が上記活性光線硬化性インクジェットゲルインクによる画像であることは、上記の観点からより一層効果的である。 In addition, an image of the actinic ray curable inkjet ink is formed on the base material, and the formation of the liquid repellent ink film on the image means that the liquid repellent ink film is applied to the base material. It is more effective from the viewpoint of improving the adhesion, and it is more effective from the above viewpoint that the image is an image by the actinic ray curable inkjet gel ink.
　また、撥液インクの塗布性を高める観点、および撥液インクによる画像の密着性を高める観点から、上記ゲル化剤を含有する活性光線硬化性インクジェットインクがシリコーン系界面活性剤またはフッ素系界面活性剤を含有していることがより効果的であり、当該撥液インクが上記シリコーン系界面活性剤またはフッ素系界面活性剤を含有しないことがより一層効果的である。 In addition, from the viewpoint of enhancing the applicability of the liquid repellent ink and enhancing the adhesion of the image with the liquid repellent ink, the actinic ray curable inkjet ink containing the gelling agent is a silicone-based surfactant or a fluorine-based surfactant. It is more effective to contain the agent, and it is even more effective that the liquid repellent ink does not contain the silicone surfactant or the fluorine surfactant.
　また、最終画像における上記撥液インクの膜の所期の光沢に応じた印字率で上記撥液インクを上記基材に塗布することは、所期のエンボス調を容易に実現する観点からより一層効果的である。 In addition, applying the liquid-repellent ink to the base material at a printing rate corresponding to the desired gloss of the liquid-repellent ink film in the final image is further enhanced from the viewpoint of easily realizing the desired embossed tone. It is effective.
　また、上記画像形成方法によれば、前述した従来の擬似エンボス画像の形成方法に比べて、撥液インクの膜における光沢度をより一層広い制御幅から設定することが可能である。たとえば、上記画像形成方法によれば、撥液インクの膜における光沢度を１～３０というより広い幅から設定することが可能である。 Further, according to the image forming method, it is possible to set the glossiness of the liquid-repellent ink film from a wider control range as compared to the conventional pseudo embossed image forming method described above. For example, according to the image forming method, the glossiness of the liquid repellent ink film can be set from a wider range of 1 to 30.
　また、上記画像形成方法によれば、上記のインクおよびニスのいずれをも、インクジェット画像形成方法によって基材に塗布することも可能である。この場合、撥液インクが塗布されるべき最下層の色画像、撥液インクの膜、および最上層のニスによる画像、のいずれもの形状を、従来のオフセット印刷方法のみによる方法に比べて容易に調整、変更することが可能となる。よって、上記のようなインクジェット画像形成方法による画像の形成は、所期の意匠性を実現し、かつ少量多品種の生産であっても高い生産性を実現する観点からより一層効果的である。 Further, according to the image forming method, both the ink and the varnish can be applied to the substrate by the ink jet image forming method. In this case, the shape of any of the color image of the lowermost layer to which the liquid-repellent ink should be applied, the film of the liquid-repellent ink, and the image of the varnish of the uppermost layer can be easily compared with the conventional method using only the offset printing method Adjustment and change are possible. Therefore, the image formation by the ink jet image forming method as described above is more effective from the viewpoint of realizing the desired design and realizing high productivity even in the production of a small variety of products.
　以下、本発明の実施例を説明する。下記の実施例において、「モノマー１」は、ポリプロピレングリコール＃７００ジアクリレートであり、「モノマー２」は、４ＥＯ変性ペンタエリスリトールテトラアクリレート（ＳＲ４９４、ＳＡＲＴＯＭＥＲ社製）であり、「モノマー３」は、６ＥＯ変性トリメチロールプロパントリアクリレート（ＳＲ４９９、ＳＡＲＴＯＭＥＲ社製）である。そして、「モノマー４」はポリエチレングリコールジアクリレート（ＮＫエステルＡ－４００：新中村化学工業株式会社製）であり、「モノマー５」はトリプロピレングリコールジアクリレート（ＡＰＧ－２００：新中村化学工業株式会社製）であり、「モノマー６」はトリシクロデカンジメタノールジアクリレート（Ａ－ＤＣＰ：新中村化学工業株式会社製）である。また、「重合開始剤」は、ＤＡＲＯＣＵＲ　ＴＰＯ（ＢＡＳＦ社製、「ＤＡＲＯＣＵＲ」は同社の登録商標）であり、「重合禁止剤」は、ＩＲＧＡＳＴＡＢ ＵＶ１０（ＢＡＳＦ社製、「ＩＲＧＡＳＴＡＢ」は同社の登録商標）である。また、「ゲル化剤１」は、ステアリン酸ベヘニルであり、「ゲル化剤２」は、ジステアリルケトンであり、「ゲル化剤３」は、ベヘン酸ベヘニルであり、「ゲル化剤４」は、ステアリン酸ステアリルである。 Hereinafter, examples of the present invention will be described. In the following examples, “Monomer 1” is polypropylene glycol # 700 diacrylate, “Monomer 2” is 4EO-modified pentaerythritol tetraacrylate (SR494, manufactured by SARTOMER), and “Monomer 3” is 6EO. It is a modified trimethylolpropane triacrylate (SR499, manufactured by SARTOMER). “Monomer 4” is polyethylene glycol diacrylate (NK ester A-400: Shin-Nakamura Chemical Co., Ltd.), and “Monomer 5” is tripropylene glycol diacrylate (APG-200: Shin-Nakamura Chemical Co., Ltd.). “Monomer 6” is tricyclodecane dimethanol diacrylate (A-DCP: Shin-Nakamura Chemical Co., Ltd.). In addition, “polymerization initiator” is DAROCUR TPO (manufactured by BASF, “DAROCUR” is a registered trademark of the company), “polymerization inhibitor” is IRGASTAB UV10 (manufactured by BASF, “IRGASTAB” is a registered trademark of the company) ). Further, “gelling agent 1” is behenyl stearate, “gelling agent 2” is distearyl ketone, “gelling agent 3” is behenyl behenate, and “gelling agent 4”. Is stearyl stearate.
　また、下記の実施例において、「顔料分散液」は、以下のように作製した。まず、下記の成分を下記の量でステンレスビーカーに投入し、６５℃のホットプレート上で加熱しながら１時間加熱攪拌して溶解させ、得られた溶液を室温まで冷却した。得られた溶液を室温まで冷却後、下記のマゼンタ顔料１を２１質量部加えて、直径０．５ｍｍのジルコニアビーズ２００ｇとともにガラス瓶に入れて密栓し、ペイントシェーカーにて８時間分散処理した。その後、ジルコニアビーズを除去して、下記組成の顔料分散液１を調製した。なお、「分散剤」は、アジスパーＰＢ８２４（味の素ファインテクノ株式会社製、「アジスパー」は味の素株式会社の登録商標）であり、「活性線硬化性化合物」は、トリプロピレングリコールジアクリレート（ＡＰＧ－２００、新中村化学工業株式会社製）であり、「マゼンタ顔料」は、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２（クロモファインレッド６１１２ＪＣ、大日精化工業株式会社製）である。
　分散剤　　　　　　　　　　　　　　　　　　　　９質量部
　活性線硬化性化合物　　　　　　　　　　　　　７０質量部
　重合禁止剤　　　　　　　　　　　　　　　０．０２質量部
　マゼンタ顔料　　　　　　　　　　　　　　　　２１質量部 In the following examples, the “pigment dispersion” was prepared as follows. First, the following components were charged in a stainless beaker in the following amounts, dissolved by heating and stirring for 1 hour while heating on a 65 ° C. hot plate, and the resulting solution was cooled to room temperature. After cooling the resulting solution to room temperature, 21 parts by mass of the following magenta pigment 1 was added, sealed in a glass bottle together with 200 g of zirconia beads having a diameter of 0.5 mm, and dispersed for 8 hours with a paint shaker. Thereafter, the zirconia beads were removed to prepare a pigment dispersion 1 having the following composition. The “dispersing agent” is Ajisper PB824 (manufactured by Ajinomoto Fine Techno Co., Ltd., “Ajisper” is a registered trademark of Ajinomoto Co., Inc.), and the “active ray curable compound” is tripropylene glycol diacrylate (APG-200). “Magenta pigment” is Pigment Red 122 (chromofine red 6112JC, manufactured by Dainichi Seika Kogyo Co., Ltd.).
Dispersant 9 parts by weight Actinic radiation curable compound 70 parts by weight Polymerization inhibitor 0.02 part by weight Magenta pigment 21 parts by weight
　次いで、得られた溶液に、２１質量部のマゼンタ顔料を添加し、直径０．５ｍｍのジルコニアビーズ２００ｇとともにガラス瓶に投入して当該ガラス瓶を密栓し、ペイントシェーカーにて８時間分散処理した。その後、ジルコニアビーズを除去して、顔料分散液を得た。 Next, 21 parts by mass of a magenta pigment was added to the obtained solution, put into a glass bottle together with 200 g of zirconia beads having a diameter of 0.5 mm, the glass bottle was sealed, and dispersed with a paint shaker for 8 hours. Thereafter, the zirconia beads were removed to obtain a pigment dispersion.
　また、下記の実施例において、「基材１」は、アルミホイル紙であり、「基材２」は、ＰＥＴシートであり、「基材３」は、水性インクの画像を有するコート紙である。また、「基材４」は、ＵＶ硬化性インクの画像を有するアルミホイル紙であり、「基材５」は、ＵＶ硬化性ゲルインクの画像を有するコート紙である。さらに、「基材６」は、ＵＶ硬化性ゲルインクの画像を有するコートボール紙であり、「基材７」は、ＵＶ硬化性ゲルインクの画像を有するアルミホイル紙である。また、「基材８」は、フッ素系界面活性剤（メガファックＦ－５５９、ＤＩＣ株式会社製）を０．５質量％含有するＵＶ硬化性ゲルインクの画像を有するコート紙である。「基材９」は、シリコーン系界面活性剤（ＢＹＫ－３６１Ｎ、ＢＹＫ社製）を０．５質量％含有するＵＶ硬化性ゲルインクの画像を有するコートボール紙である。基材３～９における画像は、いずれもインクジェット画像形成方法により形成される。 Further, in the following examples, “Substrate 1” is aluminum foil paper, “Substrate 2” is a PET sheet, and “Substrate 3” is a coated paper having an image of aqueous ink. . The “substrate 4” is an aluminum foil paper having a UV curable ink image, and the “substrate 5” is a coated paper having a UV curable gel ink image. Further, the “substrate 6” is a coated cardboard having an image of UV curable gel ink, and the “substrate 7” is an aluminum foil paper having an image of UV curable gel ink. The “substrate 8” is a coated paper having a UV curable gel ink image containing 0.5% by mass of a fluorosurfactant (Megafac F-559, manufactured by DIC Corporation). “Base material 9” is a coated cardboard having an image of a UV curable gel ink containing 0.5% by mass of a silicone surfactant (BYK-361N, manufactured by BYK). The images on the substrates 3 to 9 are all formed by the inkjet image forming method.
　［撥液インク１の調製］
　下記の成分の下記の量で混合し、８０℃に加熱して撹拌し、当該温度で＃３０００の金属メッシュフィルタで熱濾過し、冷却して、撥液インク１を得た。
　モノマー１　　　　　　　　　　　　　　　３０．０質量部
　モノマー２　　　　　　　　　　　　　　　３０．０質量部
　モノマー３　　　　　　　　　　　　　　１３．８５質量部
　重合開始剤　　　　　　　　　　　　　　　　６．０質量部
　重合禁止剤　　　　　　　　　　　　　　　０．１５質量部
　ゲル化剤１　　　　　　　　　　　　　　　２０．０質量部 [Preparation of liquid repellent ink 1]
The following components were mixed in the following amounts, heated to 80 ° C. and stirred, filtered hot with a # 3000 metal mesh filter at that temperature, and cooled to obtain liquid repellent ink 1.
Monomer 1 30.0 parts by weight Monomer 2 30.0 parts by weight Monomer 3 13.85 parts by weight Polymerization initiator 6.0 parts by weight Polymerization inhibitor 0.15 parts by weight Gelling agent 1 20.0 parts by weight
　［撥液インク２、３の調製］
　１９質量部の顔料分散液を撥液インク１に添加して、撥液インク２を得た。また、モノマー３の添加量を１８．８５質量部に、そしてゲル化剤１の添加量を１５．０質量部に、それぞれ変更した以外は、撥液インク１と同様にして、撥液インク３を得た。 [Preparation of liquid repellent inks 2 and 3]
19 parts by mass of the pigment dispersion was added to the liquid repellent ink 1 to obtain a liquid repellent ink 2. Further, the liquid repellent ink 3 was changed in the same manner as the liquid repellent ink 1 except that the addition amount of the monomer 3 was changed to 18.85 parts by mass and the addition amount of the gelling agent 1 was changed to 15.0 parts by mass. Got.
　［撥液インク４、５の調製］
　モノマー３の添加量を２５．８５質量部に、そしてゲル化剤１の添加量を８．０質量部に、それぞれ変更した以外は、撥液インク１と同様にして、撥液インク４を得た。また、１９質量部の顔料分散液を撥液インク４に添加して、撥液インク５を得た。 [Preparation of liquid repellent inks 4 and 5]
The liquid repellent ink 4 was obtained in the same manner as the liquid repellent ink 1 except that the addition amount of the monomer 3 was changed to 25.85 parts by mass and the addition amount of the gelling agent 1 was changed to 8.0 parts by mass. It was. Further, 19 parts by mass of the pigment dispersion was added to the liquid repellent ink 4 to obtain a liquid repellent ink 5.
　［撥液インク６、７の調製］
　モノマー３の添加量を３０．８５質量部に変更し、２０．０質量部のゲル化剤１に代えて３．０質量部のゲル化剤２を用いた以外は、撥液インク１と同様にして、撥液インク６を得た。また、１９質量部の顔料分散液を撥液インク６に添加して、撥液インク７を得た。 [Preparation of liquid repellent inks 6 and 7]
The same as liquid repellent ink 1 except that the amount of monomer 3 added was changed to 30.85 parts by mass and 3.0 parts by mass of gelling agent 2 was used instead of 20.0 parts by mass of gelling agent 1. Thus, a liquid repellent ink 6 was obtained. Further, 19 parts by mass of the pigment dispersion was added to the liquid repellent ink 6 to obtain a liquid repellent ink 7.
　［撥液インク８の調製］
　モノマー３の添加量を３１．５５質量部に変更し、２０．０質量部のゲル化剤１に代えて１．５質量部のゲル化剤２と０．８質量部のゲル化剤３とを用いた以外は、撥液インク１と同様にして、撥液インク８を得た。 [Preparation of liquid repellent ink 8]
The addition amount of monomer 3 is changed to 31.55 parts by mass, and instead of 20.0 parts by mass of gelling agent 1, 1.5 parts by mass of gelling agent 2 and 0.8 parts by mass of gelling agent 3 A liquid repellent ink 8 was obtained in the same manner as the liquid repellent ink 1 except that was used.
　［撥液インク９の調製］
　モノマー３の添加量を３０．８５質量部に、そしてゲル化剤１の添加量を３．０質量部に、それぞれ変更した以外は、撥液インク１と同様にして、撥液インク９を得た。 [Preparation of liquid repellent ink 9]
A liquid repellent ink 9 was obtained in the same manner as the liquid repellent ink 1 except that the addition amount of the monomer 3 was changed to 30.85 parts by mass and the addition amount of the gelling agent 1 was changed to 3.0 parts by mass. It was.
　［撥液インク１０の調製］
　モノマー３の添加量を３０．５５質量部に変更し、２０．０質量部のゲル化剤１に代えて２．８質量部のゲル化剤１と０．５質量部のゲル化剤３とを用いた以外は、撥液インク１と同様にして、撥液インク１０を得た。 [Preparation of liquid repellent ink 10]
The addition amount of monomer 3 is changed to 30.55 parts by mass, and instead of 20.0 parts by mass of gelling agent 1, 2.8 parts by mass of gelling agent 1 and 0.5 parts by mass of gelling agent 3 A liquid repellent ink 10 was obtained in the same manner as the liquid repellent ink 1 except that was used.
　［撥液インク１１の調製］
　モノマー３の添加量を３３．８５質量部に変更し、ゲル化剤１を添加しなかった以外は、撥液インク１と同様にして、撥液インク１１を得た。 [Preparation of liquid repellent ink 11]
A liquid repellent ink 11 was obtained in the same manner as the liquid repellent ink 1 except that the amount of the monomer 3 added was changed to 33.85 parts by mass and the gelling agent 1 was not added.
　［撥液インク１２の調製］
　モノマー１～３のそれぞれに代えてモノマー４～６のそれぞれを用い、３．０質量部のゲル化剤４をさらに添加した以外は、撥液インク１１と同様にして、撥液インク１２を得た。 [Preparation of liquid repellent ink 12]
The liquid repellent ink 12 was obtained in the same manner as the liquid repellent ink 11 except that each of the monomers 4 to 6 was used in place of each of the monomers 1 to 3 and 3.0 parts by mass of the gelling agent 4 was further added. It was.
　撥液インク１～１２の組成を表１に示す。 The compositions of the liquid repellent inks 1 to 12 are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　［実施例１］
　撥液インク１で、インクジェットヘッドの温度を８０℃に設定したライン型インクジェット記録装置を用いて、基材１に、５ｃｍ×５ｃｍのベタ画像（印字率（ＤＲ）が１００％の画像）であるプレ画像１を形成した。 [Example 1]
Using a line type ink jet recording apparatus with the liquid repellent ink 1 and the temperature of the ink jet head set to 80 ° C., a solid image of 5 cm × 5 cm (an image having a printing rate (DR) of 100%) is formed on the substrate 1. Pre-image 1 was formed.
　吐出用記録ヘッドには、ノズル径が２０μｍ、ノズル数が５１２（２５６ノズル×２列、千鳥配列、１列のノズルピッチが３６０ｄｐｉ）のピエゾヘッドを用いた。吐出条件は、１滴の液滴量が２．５ｐｌとなる条件で、液滴速度約６ｍ／ｓで出射させて、１４４０ｄｐｉ×１４４０ｄｐｉの解像度でプレ画像１を形成した。画像形成速度（記録速度）は、５００ｍｍ／ｓとした。当該画像形成を、２３℃、５５％ＲＨの環境下で行った。なお、ｄｐｉとは、２．５４ｃｍ当たりのドット数を表す。 As the ejection recording head, a piezo head having a nozzle diameter of 20 μm and a number of nozzles of 512 (256 nozzles × 2 rows, staggered arrangement, 1 row nozzle pitch is 360 dpi) was used. The ejection conditions were such that the volume of one droplet was 2.5 pl, and the pre-image 1 was formed at a resolution of 1440 dpi × 1440 dpi by emitting at a droplet velocity of about 6 m / s. The image forming speed (recording speed) was 500 mm / s. The image formation was performed in an environment of 23 ° C. and 55% RH. In addition, dpi represents the number of dots per 2.54 cm.
　次いで、上記記録装置における基材の搬送方向のより下流側に配置したＬＥＤランプ（Ｐｈｏｓｅｏｎ　Ｔｅｃｈｎｏｌｏｇｙ社製３９５ｎｍ、水冷ＬＥＤ）によってプレ画像１に紫外線を照射して、撥液インク１を硬化し、撥液インク画像１を得た。撥液インク画像１（撥液インク１の硬化物の層）の厚さは、１５μｍであった。　 Next, the pre-image 1 is irradiated with ultraviolet rays by an LED lamp (Phoseon Technology 395 nm, water-cooled LED) disposed on the downstream side of the substrate transport direction in the recording apparatus, thereby curing the liquid repellent ink 1 and repelling it. A liquid ink image 1 was obtained. The thickness of the liquid repellent ink image 1 (the layer of the cured product of the liquid repellent ink 1) was 15 μm. *
　次いで、撥液インク画像１の上から、基材１に、下記の条件で、ＵＶニスコーター（型式：ＤＫＳＨ　ＳＰ－５　ＵＶニスコーターを用いてＵＶ硬化性を有するニス（ＤＫＳＨ オーバーコート用　ＵＶグロスニス ＴＥＣシリーズ）を塗布し、当該ニスの塗膜に紫外線を照射し、膜厚５μｍのニスの硬化膜を撥液インク画像１の上に形成し、例えば図１Ｅに示されるようなエンボス画像１を得た。 Next, a UV varnish coater (model: DKSH SP-5, UV varnish using a UV varnish coater (UV gloss varnish for DKSH コ ー ト overcoat, UV gloss varnish TEC series) is applied on the base material 1 from above the liquid repellent ink image 1. ) Was applied to the coating film of the varnish, and a cured film of varnish with a thickness of 5 μm was formed on the liquid repellent ink image 1 to obtain an embossed image 1 as shown in FIG. 1E, for example. .
　［実施例２、３］
　撥液インク１に代えて撥液インク２、３をそれぞれ用いる以外はエンボス画像１と同様にして、エンボス画像２、３をそれぞれ得た。 [Examples 2 and 3]
Embossed images 2 and 3 were obtained in the same manner as embossed image 1 except that liquid repellent inks 2 and 3 were used in place of liquid repellent ink 1, respectively.
　［実施例４～９］
　基材１に代えて基材２を用い、撥液インク１に代えて撥液インク４を用いる以外はエンボス画像１と同様にしてエンボス画像４を得た。また、印字率（ＤＲ）を７５％に変更する以外はエンボス画像４と同様にして、エンボス画像５を得た。さらに印字率を５０％、２５％、および５％にそれぞれ変更した以外はエンボス画像４と同様にして、エンボス画像６～８をそれぞれ得た。さらに、撥液インク４に代えて撥液インク５を用いる以外はエンボス画像８と同様にして、エンボス画像９を得た。 [Examples 4 to 9]
An embossed image 4 was obtained in the same manner as the embossed image 1 except that the substrate 2 was used instead of the substrate 1 and the liquid repellent ink 4 was used instead of the liquid repellent ink 1. Further, an embossed image 5 was obtained in the same manner as the embossed image 4 except that the printing rate (DR) was changed to 75%. Further, embossed images 6 to 8 were obtained in the same manner as the embossed image 4 except that the printing rate was changed to 50%, 25%, and 5%, respectively. Further, an embossed image 9 was obtained in the same manner as the embossed image 8 except that the liquid repellent ink 5 was used instead of the liquid repellent ink 4.
　［実施例１０～１４］
　撥液インク１に代えて撥液インク６を、そして基材１に代えて基材３を用いる以外は、エンボス画像１と同様にして、エンボス画像１０を得た。また、印字率を７５％、５０％、２５％および５％にそれぞれ変更する以外はエンボス画像１０と同様にして、エンボス画像１１、１２、１３、１４をそれぞれ得た。 [Examples 10 to 14]
An embossed image 10 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 6 was used instead of the liquid repellent ink 1 and the substrate 3 was used instead of the substrate 1. Further, embossed images 11, 12, 13, and 14 were obtained in the same manner as the embossed image 10 except that the printing ratio was changed to 75%, 50%, 25%, and 5%, respectively.
　［実施例１５～２０］
　撥液インク１に代えて撥液インク６を、そして基材１に代えて基材４を用いる以外は、エンボス画像１と同様にして、エンボス画像１５を得た。また、印字率を７５％、５０％、２５％および５％にそれぞれ変更する以外はエンボス画像１５と同様にして、エンボス画像１６、１７、１８、１９をそれぞれ得た。さらに、撥液インク６に代えて撥液インク７を用いる以外はエンボス画像１９と同様にして、エンボス画像２０を得た。 [Examples 15 to 20]
An embossed image 15 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 6 was used instead of the liquid repellent ink 1 and the substrate 4 was used instead of the substrate 1. Further, embossed images 16, 17, 18, and 19 were obtained in the same manner as the embossed image 15 except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively. Further, an embossed image 20 was obtained in the same manner as the embossed image 19 except that the liquid repellent ink 7 was used instead of the liquid repellent ink 6.
　［実施例２１～２５］
　撥液インク１に代えて撥液インク８を、そして基材１に代えて基材５を用いる以外は、エンボス画像１と同様にして、エンボス画像２１を得た。また、印字率を７５％、５０％、２５％および５％にそれぞれ変更する以外はエンボス画像２１と同様にして、エンボス画像２２、２３、２４、２５をそれぞれ得た。 [Examples 21 to 25]
An embossed image 21 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 8 was used instead of the liquid repellent ink 1 and the substrate 5 was used instead of the substrate 1. Further, embossed images 22, 23, 24, and 25 were obtained in the same manner as the embossed image 21, except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
　［実施例２６～３０］
　撥液インク１に代えて撥液インク９を、そして基材１に代えて基材６を用いる以外は、エンボス画像１と同様にして、エンボス画像２６を得た。また、印字率を７５％、５０％、２５％および５％にそれぞれ変更する以外はエンボス画像２１と同様にして、エンボス画像２７、２８、２９、３０をそれぞれ得た。 [Examples 26 to 30]
An embossed image 26 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 9 was used instead of the liquid repellent ink 1 and the substrate 6 was used instead of the substrate 1. Further, embossed images 27, 28, 29, and 30 were obtained in the same manner as the embossed image 21, except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
　［実施例３１～３５］
　撥液インク１に代えて撥液インク１０を、そして基材１に代えて基材７を用いる以外は、エンボス画像１と同様にして、エンボス画像３１を得た。また、印字率を７５％、５０％、２５％および５％にそれぞれ変更する以外はエンボス画像３１と同様にして、エンボス画像３２、３３、３４、３５をそれぞれ得た。 [Examples 31 to 35]
An embossed image 31 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 10 was used instead of the liquid repellent ink 1 and the base material 7 was used instead of the base material 1. Further, embossed images 32, 33, 34, and 35 were obtained in the same manner as the embossed image 31 except that the printing ratio was changed to 75%, 50%, 25%, and 5%, respectively.
　［実施例３６～４０］
　ＵＶ硬化性を有するニスに代えて、撥液インク画像の上から水性ニス（アクアパックワニス　Ｆ－２２、株式会社Ｔ＆Ｋ　ＴＯＫＡ製）を塗布する以外は、エンボス画像３１～３５のそれぞれと同様にして、エンボス画像３６～４０をそれぞれ得た。 [Examples 36 to 40]
In the same manner as each of the embossed images 31 to 35 except that a water-based varnish (Aqua Pack Varnish F-22, manufactured by T & K TOKA Co., Ltd.) is applied over the liquid repellent ink image instead of the UV curable varnish. Embossed images 36 to 40 were obtained.
　［実施例４１～４５］
　撥液インク１に代えて撥液インク１２を、そして基材１に代えて基材８を用いる以外は、エンボス画像１と同様にして、エンボス画像４１を得た。また、印字率を７５％、５０％、２５％および５％にそれぞれ変更する以外はエンボス画像４１と同様にして、エンボス画像４２、４３、４４、４５をそれぞれ得た。 [Examples 41 to 45]
An embossed image 41 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 12 was used instead of the liquid repellent ink 1 and the substrate 8 was used instead of the substrate 1. Further, embossed images 42, 43, 44, and 45 were obtained in the same manner as the embossed image 41, except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
　［実施例４６～５０］
　撥液インク１に代えて撥液インク１２を、そして基材１に代えて基材９を用いる以外は、エンボス画像１と同様にして、エンボス画像４６を得た。また、印字率を７５％、５０％、２５％および５％にそれぞれ変更する以外はエンボス画像４６と同様にして、エンボス画像４７、４８、４９、５０をそれぞれ得た。 [Examples 46 to 50]
An embossed image 46 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 12 was used instead of the liquid repellent ink 1 and the substrate 9 was used instead of the substrate 1. Further, embossed images 47, 48, 49, and 50 were obtained in the same manner as the embossed image 46, except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
　［比較例１］
　基材１に、印刷機によるＵＶ印刷で画像を形成し、次いで撥液ワニスを印刷し、次いでコーターにより光沢ＵＶニスを全面塗布することにより、従来の印刷のみによる擬似エンボス画像であるエンボス画像Ｃ１を得た。 [Comparative Example 1]
An embossed image C1 which is a pseudo-embossed image only by conventional printing is formed on the substrate 1 by forming an image by UV printing with a printing machine, then printing a liquid repellent varnish, and then coating the entire surface with a gloss UV varnish with a coater. Got.
　［比較例２～６］
　撥液インク１に代えて撥液インク１１を用いる以外はエンボス画像１と同様にして、エンボス画像Ｃ２を得た。また印字率を７５％、５０％、２５％、５％にそれぞれ変更した以外はエンボス画像１と同様にしてエンボス画像Ｃ３、Ｃ４、Ｃ５、Ｃ６を得た。 [Comparative Examples 2 to 6]
An embossed image C2 was obtained in the same manner as the embossed image 1 except that the liquid repellent ink 11 was used instead of the liquid repellent ink 1. Further, embossed images C3, C4, C5, and C6 were obtained in the same manner as the embossed image 1 except that the printing rate was changed to 75%, 50%, 25%, and 5%, respectively.
　［評価］
　（１）表面エネルギー（ＳＥ）
　エンボス画像１～５０、Ｃ１～Ｃ６の各撥液インク画像（撥液インクによる５ｃｍ×５ｃｍの硬化後のベタ画像）における、水、炭酸プロピレン、ノナンのそれぞれの接触角を、接触角計（共和界面科学株式会社製接触角計、型版：ＤＭ-５００）を用いて求め、求められた接触角の値とＹｏｕｎｇ－Ｆｏｗｋｅｓ式とに基づき、当該撥液インク画像の表面エネルギーの値を求めた。 [Evaluation]
(1) Surface energy (SE)
The contact angles of water, propylene carbonate, and nonane in each of the liquid-repellent ink images of Embossed images 1 to 50 and C1 to C6 (solid image after 5 cm × 5 cm curing with liquid-repellent ink) The surface energy value of the liquid-repellent ink image was obtained based on the obtained contact angle value and Young-Fowkes equation. .
　（２）光沢度（Ｇ）
　エンボス画像１～５０、Ｃ１～Ｃ６のそれぞれにおける、撥液インク画像部の６０°光沢度Ｇｅおよび上記ニスの硬化膜部の６０°光沢度Ｇｎを、光沢計（日本電色工業株式会社製ＰＧ－１Ｍ）を用いて測定した。当該光沢度は、それぞれ、各エンボス画像における任意の３箇所の測定値の平均値である。 (2) Glossiness (G)
In each of the embossed images 1 to 50 and C1 to C6, the 60 ° glossiness Ge of the liquid repellent ink image portion and the 60 ° glossiness Gn of the cured film portion of the varnish were measured with a gloss meter (PG manufactured by Nippon Denshoku Industries Co., Ltd.). -1M). The glossiness is an average value of measured values at arbitrary three locations in each embossed image.
　（３）出射安定性
　エンボス画像１～５０、Ｃ１～Ｃ６を形成する条件で各撥液インクを上記インクジェット記録装置でインクジェットヘッドから出射し、ノズル欠および出射曲がりの有無について目視で観察し、下記の基準により出射安定性を評価した。
　Ａ：ノズル欠の発生が全く認められなかった。
　Ｂ：全ノズル（５１２ノズル）中、１～４個のノズルでノズル欠が認められた。
　Ｃ：全ノズル（５１２ノズル）中、５個以上のノズルでノズル欠が認められた。 (3) Output stability Each liquid-repellent ink is output from the inkjet head with the above-described inkjet recording device under the conditions for forming the embossed images 1 to 50 and C1 to C6, and is visually observed for the presence or absence of nozzle missing and output bending. Outgoing stability was evaluated according to the criteria.
A: No nozzle missing was observed at all.
B: Nozzle missing was observed in 1 to 4 nozzles among all nozzles (512 nozzles).
C: Nozzle missing was observed in 5 or more nozzles among all nozzles (512 nozzles).
　（４）密着性
　エンボス画像１～５０、Ｃ１～Ｃ６の各撥液インク画像（撥液インクによる５ｃｍ×５ｃｍの硬化後のベタ画像）に、１ｍｍ角の１０×１０のクロスカットを形成し、そこにセロハンテープを貼り付けた後に剥がし、基材から剥離したカット部（１ｍｍ角の部分）を数え、下記の基準による当該撥液インク画像の基材に対する密着性を評価した。
　ＡＡ：剥離したカット部の数が０個
　Ａ：剥離したカット部の数が０個超５個以下
　Ｂ：剥離したカット部の数が５個超２０個以下
　Ｃ：剥離したカット部の数が２０個超４０個以下
　Ｄ：剥離したカット部の数が４０個超 (4) Adhesiveness A 10 mm x 10 mm cross cut of 1 mm square was formed on each liquid repellent ink image of embossed images 1 to 50 and C1 to C6 (solid image after 5 cm x 5 cm curing with liquid repellent ink). The cellophane tape was peeled off after being applied thereto, and the cut portions (1 mm square portions) peeled from the substrate were counted, and the adhesion of the liquid repellent ink image to the substrate was evaluated according to the following criteria.
AA: The number of peeled cut parts is 0 A: The number of peeled cut parts is more than 0 and less than 5 B: The number of peeled cut parts is more than 5 and less than 20 C: The number of peeled cut parts is More than 20 and less than 40 D: The number of peeled cut parts exceeds 40
　（５）バリアブル性
　エンボス画像１～５０、Ｃ１～Ｃ６におけるエンボスのパターン（撥液インク画像部の形状や撥液の程度など）の変更の容易さ（バリアブル性）を、下記の基準により評価した。
　Ａ：エンボスのパターンをインクジェット記録方法により変更することが可能。
　Ｂ：エンボスのパターンをインクジェット記録方法では変更できない。 (5) Variable property Ease of changing the emboss pattern (shape of liquid repellent ink image portion, degree of liquid repellency, etc.) in embossed images 1 to 50 and C1 to C6 was evaluated according to the following criteria. .
A: The emboss pattern can be changed by an ink jet recording method.
B: The embossed pattern cannot be changed by the ink jet recording method.
　（６）エンボス調の程度（ざらざら感）
　エンボス画像１～５０、Ｃ１～Ｃ６におけるエンボス調の見た目のざらざら感を表す指標としてＧｎとＧｅの差ΔＧ（Ｇｎ－Ｇｅ）の値を求め、下記の基準により評価した。「５」は最もざらざら感が大きく、数字が小さくなるほどざらざら感は小さくなる。「０」はほぼざらざらは見られない。
　５：ΔＧが７０以上１００未満
　４：ΔＧが５０以上７０未満
　３：ΔＧが４０以上５０未満
　２：ΔＧが２０以上４０未満
　１：ΔＧが５以上２０未満
　０：ΔＧが０以上５未満 (6) Embossed degree (rough feeling)
A value of a difference ΔG (Gn−Ge) between Gn and Ge was obtained as an index representing the rough appearance of the embossed tone in the embossed images 1 to 50 and C1 to C6, and evaluated according to the following criteria. “5” has the largest roughness, and the smaller the number, the smaller the roughness. “0” is almost not rough.
5: ΔG is 70 or more and less than 100 4: ΔG is 50 or more and less than 70 3: ΔG is 40 or more and less than 50 2: ΔG is 20 or more and less than 40 1: ΔG is 5 or more and less than 20 0: ΔG is 0 or more and less than 5
　結果を表２～４にそれぞれ示す。 The results are shown in Tables 2 to 4, respectively.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表２～４に示されるように、エンボス画像１～５０は、光沢制御性、出射安定性、密着性およびバリアブル性のいずれにおいても十分である。また、例えば、実施例１と２、８と９、あるいは１９と２０から明らかなように、撥液インクが顔料を含有していても、上記の特性が十分に発現される。 As shown in Tables 2 to 4, the embossed images 1 to 50 are sufficient in any of gloss controllability, emission stability, adhesion, and variable properties. For example, as apparent from Examples 1 and 2, 8 and 9, or 19 and 20, the above characteristics are sufficiently exhibited even when the liquid repellent ink contains a pigment.
　また、例えば、実施例４～８や１０～１４、１５～１９、２１～２５、２６～３０、３１～３５、４１～４５、４６～５０などから明らかなように、撥液インクの印字率を変えることによって、光沢制御性（エンボスの度合い）を変えることが可能である。すなわち、これらの実施例では、同一な組成の撥液インクを用い、そして印字率を変えたときのエンボス画像間で、撥液インク画像部の光沢度Ｇｅが上記印字率に応じて異なっている。そして、撥液インクの印字率の変化に対応して、ΔＧで表されるエンボス画像間のざらざら感も変化している。このように、撥液インクの印字率または撥液インク画像部の光沢度は、得られる擬似エンボス画像のエンボス調の外観に実質的に対応するので、撥液インクの印字率によって、擬似エンボス画像のエンボス調の程度が制御されることがわかる。 Further, as is clear from, for example, Examples 4 to 8, 10 to 14, 15 to 19, 21 to 25, 26 to 30, 31 to 35, 41 to 45, 46 to 50, etc., the printing rate of the liquid repellent ink It is possible to change the gloss controllability (the degree of embossing) by changing. That is, in these examples, the liquid repellent ink having the same composition is used, and the gloss Ge of the liquid repellent ink image portion differs depending on the printing rate between the embossed images when the printing rate is changed. . Then, in response to the change in the printing rate of the liquid repellent ink, the rough feeling between the embossed images represented by ΔG also changes. Thus, the printing rate of the liquid repellent ink or the glossiness of the liquid repellent ink image portion substantially corresponds to the embossed appearance of the obtained pseudo embossed image, so the pseudo embossed image depends on the printing rate of the liquid repellent ink. It can be seen that the degree of embossing is controlled.
　また、例えば、実施例１５～１９や２１～２５、２６～３０、３１～３５などから明らかなように、基材の表面を上記ＵＶ硬化性インクの画像によって構成することによって、撥液インクの膜の密着性がより高められ、基材の表面を上記ＵＶ硬化性ゲルインクの画像によって構成することによって、撥液インクの膜の密着性がより一層高められる。 Further, as is clear from, for example, Examples 15 to 19, 21 to 25, 26 to 30, 31 to 35, etc., the surface of the substrate is constituted by the image of the UV curable ink, so that the liquid repellent ink can be used. The adhesion of the film is further improved, and the adhesion of the film of the liquid repellent ink is further enhanced by forming the surface of the substrate with the image of the UV curable gel ink.
　また、例えば、実施例３６～４０から明らかなように、水性ニスを用いても、ＵＶ硬化性ニスと同様のエンボス画像が得られることがわかる。 Further, for example, as is clear from Examples 36 to 40, it can be seen that an embossed image similar to the UV curable varnish can be obtained even when an aqueous varnish is used.
　また、例えば、実施例４１～４５から明らかなように、ゲル化剤を含有する上記ＵＶ硬化性インクがフッ素系界面活性剤をさらに含有することによって、撥液インクの膜の密着性がさらに一層高められる。 For example, as is clear from Examples 41 to 45, the UV curable ink containing the gelling agent further contains a fluorine-based surfactant, so that the adhesion of the liquid repellent ink film is further increased. Enhanced.
　また、例えば、実施例４６～５０から明らかなように、ゲル化剤を含有する上記ＵＶ硬化性インクがシリコーン系界面活性剤をさらに含有することによっても、撥液インクの膜の密着性がさらに一層高められる。 For example, as is clear from Examples 46 to 50, when the UV curable ink containing a gelling agent further contains a silicone surfactant, the adhesion of the liquid repellent ink film is further increased. Increased further.
　これに対して、エンボス画像Ｃ１は、少なくともバリアブル性が不十分である。さらに撥液部の印字率が制御できないことから明らかなように、上記光沢制御性も不十分である。これは、インクジェット画像形成方法によって撥液インク画像部が形成されないため、と考えられる。また、エンボス画像Ｃ２～Ｃ６は、いずれもＧｅとＧｎとの差がないことから、疑似エンボスの条件を満たしておらず、上記光沢制御性の観点からも不十分である。これは、撥液インクがゲル化剤を含有していないため、と考えられる。 In contrast, the embossed image C1 is at least insufficiently variable. Further, as apparent from the fact that the printing rate of the liquid repellent part cannot be controlled, the gloss controllability is insufficient. This is considered because the liquid repellent ink image portion is not formed by the ink jet image forming method. In addition, since none of the embossed images C2 to C6 has a difference between Ge and Gn, the conditions for pseudo embossing are not satisfied, and the gloss controllability is insufficient. This is presumably because the liquid repellent ink does not contain a gelling agent.
　本出願は、２０１４年１２月５日出願の特願２０１４－２４６７３８号に基づく優先権を主張する。当該出願明細書および図面に記載された内容は、すべて本願明細書に援用される。 This application claims priority based on Japanese Patent Application No. 2014-246738 filed on Dec. 5, 2014. The contents described in the application specification and the drawings are all incorporated herein.
　本発明に係る画像形成方法によれば、撥液インク中のゲル化剤の種類や含有量、当該撥液インクの印字率などによって、擬似エンボス画像のデザインや光沢度、凹凸の粗密などを自在に調整することが可能である。よって、本発明は、高級感などの高い付加価値を有する擬似エンボス画像の少量または少量多品種の形成に好適であり、このような高い付加価値を有する画像のさらなる普及に寄与することが期待される。 According to the image forming method of the present invention, the design, glossiness, unevenness, etc. of the embossed image can be freely controlled according to the type and content of the gelling agent in the liquid repellent ink, the printing rate of the liquid repellent ink, and the like. It is possible to adjust to. Therefore, the present invention is suitable for forming a small amount or a small amount of various types of pseudo-embossed images having high added value such as high-grade feeling, and is expected to contribute to further spread of such images having high added value. The
　１００　基材
　１０１　画像
　１０２　撥液インク
　１０３　活性光線グロスニス 100 Substrate 101 Image 102 Liquid repellent ink 103 Actinic ray gloss varnish

Claims (10)

  1. 　活性光線硬化性化合物、光開始剤およびゲル化剤を含有する撥液インクをインクジェット画像形成方法によって基材の表面の少なくとも一部に塗布して前記撥液インクの膜を形成する工程と、
    　少なくとも前記撥液インクの膜を覆うようにニスを前記基材に塗布する工程と、を含む、
    　擬似エンボス画像を形成する画像形成方法。     Applying a liquid repellent ink containing an actinic ray curable compound, a photoinitiator and a gelling agent to at least a part of the surface of the substrate by an inkjet image forming method to form the liquid repellent ink film;
    Applying a varnish to the substrate so as to cover at least the film of the liquid repellent ink,
    An image forming method for forming a pseudo embossed image.
  2. 　前記撥液インクにおける前記ゲル化剤の含有量は、２０質量％以下である、請求項１に記載の画像形成方法。 The image forming method according to claim 1, wherein the content of the gelling agent in the liquid repellent ink is 20% by mass or less.
  3. 　前記撥液インクにおける前記ゲル化剤の含有量は、１０質量％以下である、請求項１または２に記載の画像形成方法。 The image forming method according to claim 1 or 2, wherein the content of the gelling agent in the liquid repellent ink is 10% by mass or less.
  4. 　前記撥液インクは、色材をさらに含有する、請求項１～３のいずれか一項に記載の画像形成方法。 The image forming method according to any one of claims 1 to 3, wherein the liquid repellent ink further contains a color material.
  5. 　前記ニスを塗布する工程では、前記撥液インクの膜が形成された前記基材の全面に前記ニスを塗布する、請求項１～４のいずれか一項に記載の画像形成方法。 5. The image forming method according to claim 1, wherein, in the step of applying the varnish, the varnish is applied to the entire surface of the base material on which the liquid repellent ink film is formed.
  6. 　前記ニスには、活性光線グロスニスを用いる、請求項１～５のいずれか一項に記載の画像形成方法。 6. The image forming method according to claim 1, wherein an actinic ray gloss varnish is used as the varnish.
  7. 　前記基材には、活性光線硬化性インクジェットインクによる画像が形成されており、
    　前記撥液インクの膜は、前記画像上に形成される、請求項１～６のいずれか一項に記載の画像形成方法。     The substrate is formed with an image of actinic ray curable inkjet ink,
    The image forming method according to any one of claims 1 to 6, wherein the liquid repellent ink film is formed on the image.
  8. 　前記基材には、ゲル化剤を含有する活性光線硬化性インクジェットインクによる画像が形成されており、
    　前記撥液インクの膜は、前記画像上に形成される、請求項１～６のいずれか一項に記載の画像形成方法。     The substrate is formed with an image of an actinic ray curable inkjet ink containing a gelling agent,
    The image forming method according to any one of claims 1 to 6, wherein the liquid repellent ink film is formed on the image.
  9. 　前記ゲル化剤を含有する活性光線硬化性インクジェットインクは、シリコーン系界面活性剤またはフッ素系界面活性剤を含有している、請求項８に記載の画像形成方法。 The image forming method according to claim 8, wherein the actinic ray curable inkjet ink containing the gelling agent contains a silicone surfactant or a fluorine surfactant.
  10. 　最終画像における前記撥液インクの膜の所期の光沢に応じた印字率で、前記撥液インクを前記基材に塗布する、請求項１～９のいずれか一項に記載の画像形成方法。 The image forming method according to any one of claims 1 to 9, wherein the liquid repellent ink is applied to the substrate at a printing rate corresponding to an intended gloss of the liquid repellent ink film in the final image.
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