WO2016021655A1 - Composition d'encre type durcissable par rayonnement d'énergie active, stratifié mettant en œuvre cette composition d'encre, et procédé de formation d'image formant une image sur un matériau de base - Google Patents

Composition d'encre type durcissable par rayonnement d'énergie active, stratifié mettant en œuvre cette composition d'encre, et procédé de formation d'image formant une image sur un matériau de base Download PDF

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Publication number
WO2016021655A1
WO2016021655A1 PCT/JP2015/072272 JP2015072272W WO2016021655A1 WO 2016021655 A1 WO2016021655 A1 WO 2016021655A1 JP 2015072272 W JP2015072272 W JP 2015072272W WO 2016021655 A1 WO2016021655 A1 WO 2016021655A1
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WIPO (PCT)
Prior art keywords
active energy
energy ray
monomer
ink composition
molecular weight
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PCT/JP2015/072272
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English (en)
Japanese (ja)
Inventor
保真 齋藤
岳 森山
公淳 宇高
敏男 古高
Original Assignee
株式会社Ｄｎｐファインケミカル
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Publication of WO2016021655A1 publication Critical patent/WO2016021655A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks

Definitions

  • the present invention relates to an active energy ray-curable ink composition, a laminate obtained by printing the ink composition on a substrate having high flexibility at room temperature by an inkjet method, and an image formed on the substrate using the ink composition.
  • the present invention relates to an image forming method for forming an uneven image, or an image and an uneven image.
  • the active energy ray-curable ink composition is composed of a polymerizable monomer, a polymerization initiator, a pigment and other additives.
  • the base material is plastic, glass, coated paper, etc., but also when the base material is flexible, such as polyethylene terephthalate resin, vinyl chloride resin, and elastomer.
  • the cured ink is required to have characteristics such as flexibility.
  • Examples of such an active energy ray-curable ink composition include (A) an acrylate monomer having a glass transition point of 0 ° C.
  • the active energy ray-curable ink formed on the polycarbonate substrate satisfies the relationship between the predetermined elongation at break and the molecular weight between crosslinks in a 190 ° C. environment.
  • An active energy ray curable ink has been proposed (see Patent Document 2).
  • JP 2011-162703 A Japanese Patent No. 4923523
  • an active energy ray curable type suitable for a flexible base material that can be stretched from a low temperature to a high temperature, such as rubber, and that has a high elastic modulus (hereinafter sometimes simply referred to as an elastic base material).
  • the active energy ray curable ink according to Patent Document 2 is an active energy ray curable ink suitable for polycarbonate having lower flexibility and elasticity than an elastic base material such as rubber. Cannot be necessarily used for an elastic base material such as rubber. This is because the cured film used for the elastic base material having stretchability needs to be stretched following the same manner as the elastic base material, and it is necessary to use an active energy ray-curable ink that forms a highly stretchable cured film. .
  • the present invention has been made in view of the above circumstances, and the object of the present invention is that it can be applied to an elastic substrate such as an elastomer substrate, and has stretchability and scratch resistance. Is to provide an excellent active energy ray-curable ink composition.
  • the present inventor has conducted intensive studies, and in the active energy ray-curable ink composition containing the active energy ray polymerizable monomer, examines the composition of the active energy ray polymerizable monomer.
  • the present invention provides the following.
  • the monomer A) a monofunctional monomer having a cyclic structure
  • a monomer B) a trifunctional or higher functional monomer having a molecular weight / number of functional groups ⁇ 200
  • the active energy ray In the total amount of polymerizable monomers, the total content of all monofunctional monomers including the monomer A) is 85.0 mol% or more, and the content of the monomer B) is 0.5 mol% or more and 10.0 mol% or less.
  • the monomer A) is benzyl acrylate, phenoxyethyl acrylate, isobornyl acrylate, 4-tert-butylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, ⁇ -butyrolactone acrylate , Cresol acrylate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, paracumylphenoxyethylene glycol acrylate, Nonylphenoxy polyethylene glycol acrylate, 1-adamantyl acrylate, cyclohexyl acrylate, Tet Group consisting of hydrofurfuryl acrylate, 3-3-5-trimethylcyclohexanol acrylate, 2-hydroxy-3
  • the active energy ray-curable ink composition is formed as a cured film having a thickness of 10 ⁇ m on a nitrile rubber (hereinafter referred to as “NBR”) sheet having a thickness of 1 mm, and the cured film is formed.
  • NBR nitrile rubber
  • a film-forming substrate is tested as a dumbbell-shaped No. 6 (JIS K6251-5) test piece according to JIS K7161 method at 25 ° C. and a tensile rate of 100 mm / min, the cured film is cracked.
  • the active energy ray-curable ink composition according to any one of (1) to (14), wherein the elongation at break of the film is 50% or more.
  • the active energy ray-curable ink composition is formed as a cured film having a thickness of 10 ⁇ m on an NBR sheet having a thickness of 1 mm, and the elongation percentage of the cured film-forming substrate on which the cured film is formed is from 0%.
  • the expansion / contraction of the cured film-forming substrate is repeated 10 times at a strain rate of 100 mm / min so as to repeat the range up to 30%, cracks in the cured film are 3 or less (1) to (14 The active energy ray-curable ink composition according to any one of 1).
  • an active energy ray-curable ink composition capable of achieving both stretchability and scratch resistance when formed as a cured film on a substrate.
  • the active energy ray-curable ink composition of the present invention contains a monofunctional monomer A) having a cyclic structure and a tri- or higher functional monomer B) having “molecular weight / number of functional groups ⁇ 200”. And the monofunctional monomer in the total amount of the active energy ray polymerizable monomer: 85.0 mol% or more, and the monomer B in the total amount of the active energy ray polymerizable monomer): 0.5 mol% or more and 10.0 mol% or less .
  • mol% means the percentage of the number of moles of a substance divided by the sum of the number of moles of all substances.
  • (Monofunctional monomer) [Monomer A): Monofunctional monomer having a cyclic structure]
  • the monofunctional monomer is also referred to as monomer A) (hereinafter “monomer A)”.
  • monomer A) affects the curing by active energy rays, and has a cyclic structure, so that the curing rate can be increased more than when a non-cyclic monofunctional monomer having no cyclic structure is used. Become.
  • the scratch resistance can be further improved.
  • the cyclic structure may be an aromatic ring, an aliphatic ring, or a heterocyclic ring.
  • aromatic monofunctional monomers such as benzyl acrylate and phenoxyethyl acrylate, isobornyl acrylate, 4-t-butylcyclohexyl acrylate, cyclohexyl acrylate, and dicyclohexane.
  • monofunctional monomers having an alicyclic structure such as pentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl acrylate, 3-3-5-trimethylcyclohexanol acrylate
  • Any one or more monomers are preferable, and more preferable are aromatic monomers such as benzyl acrylate, isobornyl acrylate, and 4-t-butyl cyclohexyl.
  • the composition can have a low viscosity while having an appropriate composition.
  • a compound having an alicyclic structure it is possible to improve the adhesion with a substrate described later.
  • the combined use of benzyl acrylate and a monofunctional monomer having an alicyclic structure is particularly preferable because it can have both low viscosity and appropriate curability while also having good adhesion to a substrate.
  • the molecular weight of monomer A) is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less.
  • the molecular weight of the monomer A) is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less.
  • the monofunctional monomer of the present invention if the total of the monofunctional monomers contained in the active energy ray-curable ink composition is in the range of 85.0 mol% or more, isooctyl acrylate, tridecyl acrylate, lauryl are used as necessary.
  • Acyclic monofunctional such as acrylate, 2-hydroxyethyl acrylate, stearyl acrylate, isodecyl acrylate, caprolactone acrylate, methoxypolyethylene glycol acrylate, methoxypolypropylene glycol acrylate, 2-methoxyethyl acrylate, ethyl carbitol acrylate, 2-ethylhexyl acrylate Monomers can also be added.
  • the total of monofunctional monomers is less than 85.0 mol%, there are too many polyfunctional monomers, the crosslink density is increased, the stretchability is lowered, and the viscosity of the active energy ray-curable ink itself is increased. This is not preferable because it becomes difficult when printing by this method.
  • the content of the monomer A) is a content ratio in the whole monofunctional monomer, and the monomer A) is 60.0 mol% or more and 100.0 mol% or less, and more preferably 80.0 mol% or more and 100.0 mol% or less. preferable.
  • the monomer A) having a cyclic structure is 60.0 mol% or more and 100.0 mol% or less, the curing rate can be further improved as compared with a non-cyclic monofunctional monomer. Therefore, the deterioration of scratch resistance due to insufficient curing can be prevented, and an excellent curable ink composition with improved scratch resistance can be obtained.
  • Monomer B Monofunctional or higher-functional monomer with “molecular weight / number of functional groups ⁇ 200”
  • the active energy ray-polymerizable polyfunctional monomer is also referred to as monomer B): a tri- or higher functional monomer (hereinafter referred to as “monomer B)” having “molecular weight / number of functional groups ⁇ 200”. ).
  • monomer B) contributes to improving scratch resistance while maintaining stretchability.
  • the coating film becomes tough and repeatability is improved.
  • the scratch resistance can be improved by crosslinking, and a sufficient distance is secured between the crosslinking points. Can also be flexible. Therefore, by using the monomer B), both stretchability and scratch resistance can be improved.
  • the molecular weight / number of functional groups of the monomer B) is preferably 230 or more and 600 or less, more preferably 250 or more and 600 or less, further preferably 259 or more and 600 or less, and 380 or more and 600 or less. Is even more preferred.
  • the stretchability and repeated stretchability of the cured film of the active energy ray-curable ink composition of the present invention can be improved. Since the molecular weight / number of functional groups is 600 or less, a sufficient crosslinking point in the cured film of the active energy ray-curable ink of the present invention can be secured, so that the scratch resistance of the cured film can be improved. .
  • the molecular weight of the monomer B) is preferably 640 or more and 3000 or less, more preferably 750 or more and 3000 or less, further preferably 776 or more and 3000 or less, and even more preferably 1100 or more and 3000 or less. .
  • the upper limit of the molecular weight of monomer B) is preferably 2659 or less.
  • the crosslinking points in the cured film of the active energy ray-curable ink composition of the present invention can be sufficiently secured, and thus the scratch resistance of the cured film is improved. be able to.
  • the content of the monomer B) is 0.5 mol% or more and 10.0 mol% or less, more preferably 1.0 mol% or more and 7.0 mol% or less, based on the total amount of the active energy ray-curable monomer. Most preferably, it is 1.5 mol% or more and 5.0 mol% or less. If the amount is less than 0.5 mol%, the crosslinking density is not within the appropriate range due to the small number of crosslinking points or the short distance between the crosslinking points, making it difficult to balance stretchability and scratch resistance. Moreover, since crosslinking density will become high when it exceeds 10.0 mol%, stretchability falls and it becomes easy to enter a crack.
  • other monomers may be contained as long as the object of the present invention can be achieved.
  • examples of other monomers include polyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and the like.
  • Active energy ray-curable ink compositions containing monomers having a relatively high viscosity such as these acrylates have high overall ink viscosity. For example, when ejected using an ink jet apparatus, depending on the ejection pressure May be difficult to discharge.
  • these acrylates when these acrylates are contained, it is preferable that these acrylates are included in an amount of 10.0% by mass or less, and more preferable that 5.0% by mass or less are included with respect to the total amount of monomers. More preferably, it is not included in. “Substantially not included” means that other monomers are 1.0% by mass or less based on the total amount of monomers.
  • the monomer in the present invention is a concept including a compound also called an oligomer or a prepolymer depending on the molecular weight.
  • a conventionally known bifunctional monomer or a trifunctional or higher monomer other than the monomer B) having a molecular weight / functional group number of less than 200 may be included as other monomers.
  • bifunctional monomers satisfying “molecular weight / number of functional groups ⁇ 200” are used as the third component in addition to the monomers A) and B), so that the crosslinking density is reduced and stretchability (especially stretch at 0 ° C. or lower). Is particularly preferable in that it can be further improved.
  • the monomer in this invention is the concept also including the compound also called an oligomer depending on the molecular weight.
  • the total amount of all monofunctional monomers, monomer B, and other monomers is preferably 80.0% by mass or more based on the total amount of monomers, 90.0 More preferably, it is more than 10 mass%, and it is preferable that it is substantially 100.0 mass%.
  • substantially 100.0 mass% means that the total amount of monomer A, monomer B and other monomers is 99.0 mass% or more with respect to the total amount of monomers.
  • the monomer C) of “molecular weight / functional group ⁇ 200” is 0.5 mol% or more and less than 5.0 mol%, more preferably 1.3 mol% or more and 3.0 mol% or less, More preferably, the active energy ray-polymerizable curable ink composition contained in an amount of 1.5 mol% or more and 2.6 mol% or less can relax the crosslink density within a range in which scratch resistance can be maintained, and thus more stretched. Can be improved. In particular, it can be preferably used in a use environment that requires stretchability.
  • the molecular weight / functional group number of the monomer C) is preferably 1750 or less.
  • the molecular weight of the monomer C is preferably 400 or more and 3500 or less. When the molecular weight of the monomer C) is 400 or more, the stretchability and repeated stretchability of the cured film of the active energy ray-curable ink composition of the present invention can be improved.
  • the molecular weight of the monomer C) is 3500 or less, a sufficient crosslinking point in the cured film of the active energy ray-curable ink composition of the present invention can be secured, and the scratch resistance of the cured film is maintained. Can do.
  • the active energy ray curable ink composition having a specific amount of monomers A) and B) according to the present invention has a trifunctional or higher polyfunctional monomer component compared to the conventional ink composition as compared with the conventional active energy ray curable ink. Many are included in comparison.
  • the monomer has a high molecular weight / number of functional groups and is cured, the polyfunctional monomers having a long distance between double bonds are polymerized and crosslinked. As a result, the distance between crosslinks is increased as compared with the conventional active energy ray curable ink. Therefore, it is possible to obtain an active energy ray-curable ink excellent in stretchability that follows and stretches the elastic substrate during stretching.
  • polymer components include acrylic resins and cellulose acetate butyrate resins.
  • the active energy ray-curable ink composition may contain an active energy ray polymerization initiator as necessary.
  • Active energy rays are energy rays that can trigger polymerization reactions such as radicals, cations, and anions.
  • electromagnetic waves such as X-rays and ⁇ rays, electron beams Any of proton beam, neutron beam and the like may be used, but curing by ultraviolet irradiation is preferable from the viewpoints of curing speed, availability of an irradiation apparatus, price, and the like.
  • the active energy ray polymerization initiator is not particularly limited as long as it accelerates the polymerization reaction of the compound having an ethylenically unsaturated double bond in the active energy ray-curable ink composition by irradiation with active energy rays, Conventionally known active energy ray polymerization initiators can be used.
  • active energy ray polymerization initiator examples include, for example, aromatic ketones containing thioxanthone, ⁇ -aminoalkylphenones, ⁇ -hydroxyketones, acylphosphine oxides, aromatic onium salts, organic peroxides Thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
  • the amount of the active energy ray polymerization initiator may be an amount capable of appropriately starting the polymerization reaction of the active energy ray polymerizable monomer, and is 1% by mass or more and 20% by mass or less based on the entire active energy ray curable ink composition. It is preferable that it is 3 mass% or more and 20 mass% or less.
  • the active energy ray polymerization initiator is not necessarily required. For example, when an electron beam is used as the active energy ray, the active energy ray polymerization initiator may not be used.
  • the active energy ray-curable ink composition of the present invention may contain a coloring material as necessary.
  • a coloring material By containing a coloring material, a cured film can be preferably used as a cured film (decorative layer) for decoration.
  • the coloring material may be any inorganic pigment or organic pigment that is usually used in conventional oil-based ink compositions, such as carbon black, cadmium red, molybdenum red, chrome yellow, and cadmium yellow.
  • the preferable dispersed particle diameter of the pigment of the active energy ray-curable ink composition is preferably 10 nm or more and 300 nm or less in terms of a volume average particle diameter by a laser scattering method.
  • the volume average particle size is 10 nm or more and 300 nm or less, light resistance can be maintained, dispersion can be stabilized, and pigment sedimentation or when inkjet ink is ejected by an inkjet recording apparatus. Since it is possible to reduce the possibility of occurrence of head clogging or ejection bending, a more preferable curable ink can be obtained.
  • the content of the pigment in the entire inkjet ink composition is preferably 0.1% by mass or more and 20% by mass or less in the case of an organic pigment from the viewpoint of achieving both dispersibility and coloring power. 0.2 mass% or more and 10 mass% or less are more preferable. Moreover, from the point which balances dispersibility and coloring power, in the case of an inorganic pigment, 1 mass% or more and 40 mass% or less are preferable, and 5 mass% or more and 20 mass% or less are more preferable.
  • the active energy ray-curable ink composition of the present invention may contain a matte material, if necessary.
  • a matte material for example, various powders such as silica, alumina, calcium carbonate and the like can be used. Matting agents may be used alone or in combination of two or more.
  • the active energy ray-curable ink composition may contain a dispersant as necessary.
  • the dispersant include a polymer dispersant.
  • the main chain of this polymer dispersant is made of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and the polymer dispersant has amino groups, carboxyl groups, sulfone groups, hydroxyl groups, etc. as side chains. It is preferable to have a polar group or a salt thereof.
  • a preferred polymer dispersant is a polyester-based dispersant. Specific examples thereof include “SOLPERSE 33000” and “SOLPERSE 32000” and “SOLPERSE 24000” manufactured by Lubrizol Japan; “Dispersbyk 168” manufactured by BYK Chemie; Etc.
  • the active energy ray-curable ink composition may further contain a surface conditioner.
  • the surface conditioning agent is not particularly limited, but specific examples include “BYK-306”, “BYK-333”, “BYK-371”, “BYK-377”, Evonik Degussa Japan, manufactured by BYK Chemie having dimethylpolysiloxane. “TegoRad2100”, “TegoRad2200N”, “TegoRad2300” and the like manufactured by the company can be mentioned.
  • the content of the surface conditioner is preferably 0.1% by mass or more and 5.0% by mass or less with respect to the total amount of the ink composition.
  • the ink composition has preferable wettability with respect to the thermoplastic resin substrate and the like, and the active energy ray curable type is used when printing on the substrate. Since the ink composition can spread and spread without causing repelling, a particularly preferable active energy ray-curable ink composition can be obtained.
  • the active energy ray-curable ink composition may contain various additives such as a plasticizer, a polymerization inhibitor, a light stabilizer, and an antioxidant as other additives.
  • the solvent can be added within a range that achieves the object of the present application.
  • the viscosity of the active energy ray-curable ink composition is preferably 5 mPa ⁇ s to 30 mPa ⁇ s at 40 ° C., more preferably 5 mPa ⁇ s to 20 mPa ⁇ s.
  • the ejection property means the frequency of occurrence of missing ink dots during continuous printing, the accuracy of printing due to the occurrence of ejection disturbance, and the like.
  • the surface tension of the active energy ray-curable ink composition of the present invention is such that the surface tension at 40 ° C. is 20 mN / m or more and 40 mN / m or less from the viewpoint of inkjet dischargeability and discharge stability. preferable.
  • the method for producing the active energy ray-curable ink composition of the present invention is not particularly limited, and a conventionally known method can be used. Moreover, when using a granular coloring material, a granular matting agent, etc., it disperse
  • the active energy ray-curable ink composition of the present invention is obtained by adding a surface conditioner and the like, stirring uniformly, and further filtering through a filter.
  • the laminate of the present invention is produced by printing the active energy ray-curable ink composition on a substrate, preferably by an ink jet method, and then curing with an active energy ray.
  • the printing can be performed by a conventionally known method such as an offset printing method, a gravure printing method, a spray method, or a brush coating method, but an inkjet method is preferable in that it can cope with a wide variety of small lots.
  • An image can be formed on the substrate using the active energy ray-curable ink composition.
  • an ink set of an active energy ray-curable ink composition prepared using dispersions in which color materials of various shades are dispersed and printing by an ink jet method, the ink composition is cured, Various images can be formed on the substrate.
  • An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming an image on a substrate are also within the scope of the present invention.
  • the substrate is not particularly limited, but a substrate having elasticity is desirable.
  • rubber or elastomer resin can be preferably used.
  • elastomer resin for example, a thermoplastic elastomer (hereinafter also referred to as “TPE”) can be preferably used.
  • TPE refers to a polymer material that is plasticized at a high temperature and can be injection-molded and processed like a plastic and exhibits properties of a rubber elastic body (elastomer) at room temperature.
  • the TPE molecule may be a block polymer type in which a hard segment (plastic component) and a soft segment (elastic component) are chemically bonded in a single polymer, or a blend in which a hard segment and a soft segment are physically mixed. It may be a mold.
  • TPE molecules include styrene, olefin, polyurethane and the like.
  • styrene-based materials include NBR (nitrile rubber), SBS (styrene / butadiene / styrene block copolymer), SEBS (styrene / ethylene / butylene styrene block copolymer), and SEPS (styrene / ethylene / propylene / styrene block copolymer). Polymer) and the like.
  • An example of the olefin type is TPO (thermoplastic olefin) in which ethylene-propylene rubber is finely dispersed in polypropylene.
  • examples of the polyurethane system include thermoplastic polyurethane (hereinafter also referred to as “TPU”). Among them, it is preferable to use NBR (nitrile rubber) from the viewpoint of wear resistance and aging resistance.
  • the present invention is an active energy ray-curable ink that forms a cured film having excellent scratch resistance and stretchability even if the substrate is an elastic substrate, even if the substrate is repeatedly expanded and contracted Further, it is characterized in that cracking or peeling of the cured film formed on the surface can be effectively suppressed.
  • the active energy ray is preferably light having a wavelength range of 200 nm to 450 nm, and more preferably light having a wavelength range of 250 nm to 430 nm.
  • the light source is not particularly limited, and examples thereof include a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, sunlight, and an LED lamp.
  • the thickness of the cured film obtained by curing the active energy ray-curable ink composition of the present invention is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the thickness is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the cured film thickness is measured by applying an ink composition to a PET film (A4300, manufactured by Toyobo Co., Ltd.) under the same coating conditions as the prepared cured film, and measuring the thickness of the obtained cured film with a micrometer. did. The measurement was performed at 10 points per sample, and the average value of these was taken as the average film thickness. The same applies to the protective layer and primer described later.
  • the active energy ray-curable ink composition of the present invention is formed as a cured film having a thickness of 10 microns on an NBR sheet having a thickness of 1 mm, and a cured film-forming substrate on which the cured film is formed is dumbbell-shaped No. 6.
  • a test piece of the shape JIS K6251-5
  • the minimum elongation when cracking of the cured film occurs when a tensile test is performed at 25 ° C. and a tensile speed of 100 mm / min according to JIS K7161 method is the elongation at break of the cured film.
  • the elongation at break of the cured film is preferably 50% or more (for example, the elongation when the base material is stretched twice the original is expressed as 100%) or more, and preferably 100% or more. More preferably, it is preferably 1000% or less.
  • the elongation at break of the cured film is 50% or more, so that it can sufficiently follow the elongation of the substrate, and even when the substrate expands and contracts, the cured film formed on the surface is cracked or peeled off. Can be further suppressed.
  • the elongation at break of the cured film exceeds 1000%, it is difficult to increase the strength of the cured film.
  • the active energy ray-curable ink composition of the present invention is formed as a cured film having a thickness of 10 ⁇ m on a 1 mm thick NBR sheet, and the elongation percentage of the cured film-forming substrate on which the cured film is formed is 0%. Even if the expansion / contraction of the cured film-forming substrate is repeated 10 times at a strain rate of 100 mm / min so as to repeat the range from 1 to 30%, the cured film does not crack. Therefore, it is possible to sufficiently follow the expansion and contraction of the base material, and even when the base material expands and contracts, cracking and peeling of the cured film formed on the surface can be suppressed.
  • the cured film formed from the active energy ray-curable ink composition of the present invention can be used as a decorative layer as long as it contains a coloring material as described above, but it can be added without adding a coloring material. If it discharges on a decoration layer, this cured film itself can also be utilized as an overcoat layer which protects a cured film. Furthermore, it can utilize also as a primer layer for improving both adhesiveness by forming between a base-material surface and a cured film. An active energy ray-curable ink composition that forms such a cured film is also within the scope of the present invention.
  • the active energy ray-curable ink composition of the present invention may be used to form a decorative layer, an overcoat layer, or a primer layer independently only with a cured film formed by the active energy ray-curable ink composition of the present invention. Or a combination of these layers.
  • the active energy ray-curable ink composition of the present invention in which a coloring material is added to the active energy ray-curable ink composition of the present invention to form a decorative layer, and no coloring material is added on the decorative layer.
  • An overcoat layer can also be formed by discharging.
  • the cured film formed with the active energy ray-curable ink composition of the present invention can also be used in combination with a decorative layer, overcoat layer or primer layer formed with a conventionally known ink composition.
  • a decorative layer e.g., an overcoat layer can be formed on the decorative layer using a conventionally known overcoat composition.
  • the thickness of the decorative layer is preferably 1 ⁇ m or more and 100 ⁇ m or less. By setting the thickness to 1 ⁇ m or more, the color density of the decorative layer becomes appropriate, the design properties and decorative properties are improved, and physical properties such as adhesion and extensibility are improved. A thickness of 100 ⁇ m or less is preferable because the ink composition can be sufficiently cured in a short time when the ink composition is irradiated with active energy rays.
  • any method may be used to form these layers, for example, spray coating, towel, sponge, non-woven fabric, tissue-based coating, etc. , Dispenser, brush coating, gravure printing, flexographic printing, silk screen printing, ink jet, thermal transfer method, etc. may be used.
  • an overcoat layer comprising a conventionally known overcoat agent or the ink composition of the present invention is used as an overcoat agent on the surface of the cured film of the ink composition of the present invention.
  • An overcoat layer formed by use may be further formed.
  • the overcoat layer is not limited to being formed on the surface of the layer made of the cured film of the ink composition, but may be directly formed on the surface of the substrate, or may be formed on the surface of the substrate. You may form in the surface of the primer layer mentioned later.
  • the active energy ray-curable ink composition of the present invention can be preferably used.
  • the active energy ray-curable ink composition of the present invention By using the active energy ray-curable ink composition of the present invention, excellent stretchability and scratch resistance can be realized.
  • an overcoat layer is formed with an overcoat agent using the active energy ray-curable ink composition of the present invention on a cured film using the active energy ray-curable ink composition of the present invention, the curing is performed. Since the film and the overcoat layer have the same composition, their adhesion is extremely high. Therefore, it is particularly preferable to use the active energy ray-curable ink composition of the present invention as an overcoat agent for the cured film of the active energy ray-curable ink composition of the present invention.
  • the thickness of the overcoat layer is preferably 1 ⁇ m or more and 100 ⁇ m or less. Since it can protect a decoration layer appropriately by setting it as 1 micrometer or more, it is preferable. Moreover, it is preferable for the thickness to be 100 ⁇ m or less because the drying time can be shortened to form an overcoat layer and the productivity can be improved.
  • the Tg which made the active ingredient amount 20% or more and less than 60% is 50 ° C. or less.
  • a composition containing a modified (meth) acrylic emulsion can also be used.
  • OP-11, OP-13, OP-39, OP-53, OP-55 are commercially available resin compositions for forming an overcoat layer containing a silicone-modified (meth) acrylic emulsion. Is mentioned. Since the Tg of the silicone-modified (meth) acrylic emulsion containing any of these is 50 ° C. or less, the elongation of the cured film is good. Moreover, it has a high followability to the substrate even under conditions where repeated stress is applied.
  • the design property is imparted to the overcoat layer by adjusting the discharge amount of the ink composition and the conditions such as the time from the discharge of the ink composition to the irradiation of the active energy ray.
  • the surface after discharging the ink composition, the surface can be made glossy by irradiating active energy rays after a predetermined time has elapsed, and the surface can be quickly irradiated by irradiating active energy rays after discharging. It can be matte.
  • unevenness can be imparted by increasing / decreasing the discharge amount per time depending on the discharge location, and unevenness difference from other locations by repeating the ejection of the ink composition and the irradiation of the active energy ray at the same location. Can also be given.
  • An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming an uneven image are also within the scope of the present invention.
  • Such an overcoat layer is desirably formed by an ink jet method from the viewpoint of easy condition adjustment.
  • a primer formed with a conventionally known primer for the purpose of improving the adhesion between layers for example, a base layer and a decorative layer, a base layer and an overcoat layer, and a decorative layer and an overcoat layer).
  • a layer or a cured film formed from the ink composition of the present invention may be provided as a primer layer.
  • a cured film using the active energy ray-curable ink composition of the present invention is formed as a primer layer with the active energy ray-curable ink composition of the present invention when a decorative layer and / or an overcoat layer is formed.
  • the active energy ray-curable ink composition of the present invention since the cured film and the primer layer have the same composition, their adhesion is extremely high. Therefore, it is particularly preferable to use the active energy ray-curable ink composition of the present invention as a primer agent.
  • 10 mass% or more and less than 80 mass% are preferable as an active ingredient amount of a silicone modified (meth) acrylic-type emulsion with respect to the whole primer agent, 20 mass% or more and less than 60 mass% are preferable. More preferred.
  • 10 mass% or more in order to form a primer layer, it is preferable at the point which productivity improves from the point of drying time.
  • 80 mass% By making it less than 80 mass%, it is preferable at the point which becomes easy to apply
  • the curing agent examples include polyisocyanate. It is preferable that content of a hardening
  • a primer agent having a concealing property can be obtained by adding a concealing pigment to the primer agent.
  • a primer agent having a concealing property for example, when the base material is colored, the base material color can be concealed, so that the design and color development can be improved when the decorative layer is formed.
  • Conventionally known hiding pigments can be used as the hiding pigment, and for example, white pigments such as titanium oxide, hiding pigments such as aluminum paste and pearl pigments can be used.
  • a primer agent containing titanium oxide is preferable in order to improve the designability and color developability of the decorative layer.
  • the content of titanium oxide is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the primer agent. By setting it as 1 mass part or more, the designability and coloring property after printing improve significantly. By setting it to 50 parts by mass or less, the followability of the cured film is improved.
  • the thickness of the primer layer is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the thickness 1 ⁇ m or more By making the thickness 1 ⁇ m or more, the adhesion between the tire surface and the decorative layer is significantly improved, and in the case of a primer layer containing a concealing pigment, the design and color development properties after printing the decorative layer are significantly improved. This is preferable because it can be performed.
  • the thickness it is preferable for the thickness to be 100 ⁇ m or less because the drying time can be shortened to form an overcoat layer and the productivity can be improved.
  • primer agents examples include PR-12 and PR-13 (both manufactured by DNP Fine Chemical Co.) containing titanium oxide and silicone-modified (meth) acrylic emulsion.
  • Table 1 shows the number of moles of each monomer in 100 g of the ink composition in Examples
  • Table 2 shows mol% of each monomer in the total amount of monomers of the ink composition in Examples.
  • Table 3 shows the mol number of each monomer in 100 g of the ink composition in the comparative example
  • Table 4 shows mol% of each monomer in the total amount of the monomer in the ink composition in the comparative example.
  • Table 5 and Table 5 show the mol% of the total amount of monomer A, the mol% of the total amount of monomer B, and the mol% of the total amount of monomer A in all monofunctional monomers in the total amount of all the monomers of the ink compositions in Examples and Comparative Examples. It is shown in FIG.
  • a dispersion is prepared by dispersing 12% by mass of titanium oxide as a pigment and a polymer dispersant in the monomer so that the active ingredient is 8% by mass with respect to the pigment, and the ratio is as shown in Tables 1 to 6.
  • a monomer was further mixed with 10% by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photoinitiator, and 0.05% by mass of phenothiazine as a polymerization inhibitor. The mixture was stirred for 1 hour while warming. Then, after confirming that there was no undissolved residue and returning to room temperature, a dispersion prepared in advance was added and stirred for 1 hour. Thereafter, filtration was performed using a membrane filter, and ink compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were prepared.
  • Examples 1 to 10, Comparative Examples 1 to 4 A laminate was produced using NBR as a base material. Each sample was produced on the surface of the substrate by the inkjet method. Then, using a SubZero system (UV lamp system, manufactured by Integration Technology, D bulb, output 100 W / cm), ink is used under the conditions of an integrated light quantity of 900 mJ / cm2, a peak illuminance of 640 mW / cm2, and a conveyance speed of 18 m / min. The composition was cured. The accumulated light amount and peak illuminance were measured using an ultraviolet light meter UV-351 (manufactured by Oak Manufacturing Co., Ltd.). Thereby, the decoration layer was produced.
  • UV-351 ultraviolet light meter UV-351
  • the substantial crack means a crack in which a crack (crack) has progressed by 50% or more with respect to the length of the sample piece width.
  • the substantial crack means a crack in which a crack (crack) has progressed by 50% or more with respect to the length of the sample piece width.
  • Monomer A) a monofunctional monomer having a cyclic structure
  • monomer B) a trifunctional or higher functional monomer having “molecular weight / number of functional groups ⁇ 200”.
  • the cured film made from an active energy ray-curable ink having a total of 85.0 mol% or more and monomer B of 0.5 mol% or more and 10.0 mol% or less has stretchability, repeated stretchability, scratch resistance and tackiness. Since it is excellent in the balance of performance, it was confirmed that it is an excellent active energy ray-curable ink that can be used even for a substrate having elasticity like an elastomer resin.
  • the active energy ray-curable inks according to Example 1 and Examples 3 to 10 have a monomer B) content of 1.0 mol% or more and 7.0 mol% or less. It was confirmed that the ink was an active energy ray-curable ink having an excellent balance of repeated stretchability, scratch resistance and tack performance.
  • the monomer C) of “molecular weight / functional group ⁇ 200” is 1.3 mol% or more. Since it was contained in an amount of less than 0 mol%, it was confirmed that the ink was an active energy ray-curable ink having scratch resistance and excellent extensibility.
  • the evaluation criteria in Examples 7 and 8 and Table 7 in Example 10 indicate that the extensibility evaluation is “ ⁇ ”.
  • the monomer C) is also superior to Example 10 having excellent extensibility. It was confirmed that Examples 7 and 8 containing 1.5 mol% or more and less than 2.6 mol% are active energy ray-curable ink compositions that form a cured film having further excellent stretchability.
  • the laminated body which concerns on an Example is the evaluation of "(circle)” or “(double-circle)” in the extending
  • Comparative Example 1 in which the total of monofunctional monomers is not contained in an amount of 85.0 mol% or more, the ratio of polyfunctional monomers is higher than that in Examples, and the crosslink density is high.
  • the stretchability was inferior, and it was confirmed that a cured film was formed that could not be said to have an excellent balance of stretchability, repeated stretchability, scratch resistance, and tack performance.
  • the comparative example 2 which does not contain the monomer B) 0.5 mol% or more has a low ratio of a polyfunctional monomer compared with an Example. Therefore, although the crosslink density is low and the stretchability is good, the cured film has poor scratch resistance and cannot be said to have excellent balance of stretchability, repeated stretchability, scratch resistance, and tack performance. It was confirmed that it was formed.
  • Comparative Example 3 in which the total amount of monomers B) exceeds 10.0 mol%, the ratio of the polyfunctional monomer is higher than that in Examples, so that the crosslinking density is high, and the scratch resistance is Although it was good, the stretchability was inferior, and it was confirmed that a cured film that could not be said to have an excellent balance of stretchability, repeated stretchability, scratch resistance, and tack performance was formed.
  • Comparative Example 4 which does not contain the monomer B) and includes a polyfunctional monomer having a Mw / functional group number of less than 200 has a high crosslinking density due to a short crosslinking point distance. Although the properties were good, the stretchability was inferior, and it was confirmed that a cured film that could not be said to have an excellent balance of stretchability, repeated stretchability, scratch resistance and tack performance was formed.
  • Articles for which the active energy ray-curable ink composition of the present invention can be used include automobile members, household appliance members, electronic device members, battery members, information office equipment members, optical members, household goods, industrial members It can be widely used for building materials, flooring materials, packaging materials, etc. Specifically, it can be used for rubber and plastics, hoses, packaging films, packaging materials, tubes, synthetic leather, electronic device exterior materials, and the like.

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

Abstract

L'invention fournit une composition d'encre qui présente d'excellentes propriétés de suivi vis-à-vis d'un matériau de base souple. La composition d'encre type durcissable par rayonnement d'énergie active comprend, en tant que monomères polymérisables par rayonnement, des monomères A) qui sont des monomères monofonctionnels possédant une structure cyclique, et des monomères B) qui sont des monomères trifonctionnels ou plus tels que leur masse moléculaire / leur nombre de groupes fonctionnels ≥ 200. La somme des monomères monofonctionels inclus par les monomères A) est supérieure ou égale à 85.0% en moles, et les monomères B) représentent 0,5% en moles ou plus à 10,0% en moles ou moins.
PCT/JP2015/072272 2014-08-08 2015-08-05 Composition d'encre type durcissable par rayonnement d'énergie active, stratifié mettant en œuvre cette composition d'encre, et procédé de formation d'image formant une image sur un matériau de base WO2016021655A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018094787A (ja) * 2016-12-13 2018-06-21 株式会社フェクト 銀鏡膜層が形成されたゴム弾性体及びその製造方法
JP2018111211A (ja) * 2017-01-06 2018-07-19 株式会社ミマキエンジニアリング 印刷装置、印刷方法及び装飾物の製造方法
EP3608372A1 (fr) * 2018-08-10 2020-02-12 Agfa Nv Fabrication de cuir décoré
WO2022145137A1 (fr) * 2020-12-28 2022-07-07 凸版印刷株式会社 Feuille décorative et procédé de fabrication d'une feuille décorative
WO2022239270A1 (fr) * 2021-05-12 2022-11-17 凸版印刷株式会社 Feuille décorative et procédé de production d'une feuille décorative

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201821555A (zh) * 2016-11-09 2018-06-16 日商迪愛生股份有限公司 噴墨印墨組成物
JP6209690B1 (ja) * 2017-01-20 2017-10-04 太陽インキ製造株式会社 インクジェット用硬化性組成物、硬化物、およびプリント配線板

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008179810A (ja) * 2006-12-28 2008-08-07 Dic Corp 活性エネルギー線硬化型インクジェット記録用インク組成物
JP2008266560A (ja) * 2007-03-23 2008-11-06 Fujifilm Corp インク組成物、インクジェット記録方法、及び印刷物
JP2013057043A (ja) * 2011-09-09 2013-03-28 Fujifilm Corp インクジェットインク組成物、及び、インクジェット記録方法
JP2013193288A (ja) * 2012-03-19 2013-09-30 Ricoh Co Ltd インクジェット記録方法、インクジェット記録装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008179810A (ja) * 2006-12-28 2008-08-07 Dic Corp 活性エネルギー線硬化型インクジェット記録用インク組成物
JP2008266560A (ja) * 2007-03-23 2008-11-06 Fujifilm Corp インク組成物、インクジェット記録方法、及び印刷物
JP2013057043A (ja) * 2011-09-09 2013-03-28 Fujifilm Corp インクジェットインク組成物、及び、インクジェット記録方法
JP2013193288A (ja) * 2012-03-19 2013-09-30 Ricoh Co Ltd インクジェット記録方法、インクジェット記録装置

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018094787A (ja) * 2016-12-13 2018-06-21 株式会社フェクト 銀鏡膜層が形成されたゴム弾性体及びその製造方法
JP2018111211A (ja) * 2017-01-06 2018-07-19 株式会社ミマキエンジニアリング 印刷装置、印刷方法及び装飾物の製造方法
EP3608372A1 (fr) * 2018-08-10 2020-02-12 Agfa Nv Fabrication de cuir décoré
WO2020030699A1 (fr) * 2018-08-10 2020-02-13 Agfa Nv Fabrication de cuir décoré
CN112534005A (zh) * 2018-08-10 2021-03-19 爱克发有限公司 经装饰皮革制造
CN112534005B (zh) * 2018-08-10 2022-11-11 爱克发有限公司 经装饰皮革制造
US11981155B2 (en) 2018-08-10 2024-05-14 Agfa Nv Decorated leather manufacturing
WO2022145137A1 (fr) * 2020-12-28 2022-07-07 凸版印刷株式会社 Feuille décorative et procédé de fabrication d'une feuille décorative
EP4101640A4 (fr) * 2020-12-28 2023-10-25 Toppan Inc. Feuille décorative et procédé de fabrication d'une feuille décorative
WO2022239270A1 (fr) * 2021-05-12 2022-11-17 凸版印刷株式会社 Feuille décorative et procédé de production d'une feuille décorative

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