JP2018083343A - Production method of printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a printed matter capable of forming a printed matter excellent in interlayer adhesive property between a ground layer and a printed layer.SOLUTION: There is provided a production method of a printed matter comprising a ground layer and a printed layer arranged on the ground layer, comprising a first step in which printing by an active energy ray hardening type ink is performed to the ground layer for forming a printed layer, then, an active energy ray is radiated to the printed layer for hardening the printed layer, in which, the active energy ray hardening type ink has a compound expressed by the following formula (1), in the formula (1), Ris a hydrogen atom or an alkyl group having C1-C8, and Ris a hydrogen atom or methyl group, in the first step, the ground layer contains a functional group which can react with the compound expressed by the formula (1), and a second step for heating the printed matter.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a printed material including an underlayer and a printed layer, and more particularly to a method for producing a printed material capable of forming a printed material excellent in interlayer adhesion between the underlayer and the printed layer.

  In recent years, decoration has been performed using an active energy ray-curable ink. Active energy ray curable inks are cured by irradiation with active energy rays, and as in the case of conventional organic solvent inks and water-based inks, ejection failures such as nozzle clogging due to volatilization and drying of water and organic solvents occur. It is difficult and quick-drying, so there is an advantage that productivity can be improved.

  Active energy ray curable ink cures the ink composition by irradiating active energy rays immediately after ink ejection, so it is not necessary to provide an ink receiving layer on the substrate, but suitable for printing with active energy ray curable ink Proposals have also been made for ink receiving layers.

  JP-A-2006-068405 (Patent Document 1) is an ink-receiving layer-forming paint containing at least an acrylic resin and fine particles, and the calculated Tg of the acrylic resin is in the range of −5 to 30 ° C. The ink-receiving layer-forming coating material is characterized in that the content of the fine particles with respect to the nonvolatile components in the coating material is 20 to 50% by mass, and without being affected by the substrate surface temperature, An image having good image quality can be formed.

  JP 2010-188309 A (Patent Document 2) discloses a crosslinking agent composed of a polyester resin and / or an epoxy resin having a hydroxyl group, a thermoplastic resin, and an amino resin and / or a blocked polyisocyanate compound. A primer coating having a ratio of the total amount of the crosslinkable resin and the crosslinker to the thermoplastic resin of 97: 3 to 70:30, calculated by solid content mass, is applied to the surface of the metal plate. A method for producing a pre-coated metal is described, wherein a coating layer is formed, and then a pattern is provided on the undercoat layer partially or entirely on the undercoat layer using an ink-jet printer using a colored ink, followed by drying. Therefore, it is possible to form a pattern coating film with excellent workability, accuracy, and reproducibility in a small number of steps, without causing bleeding, and with excellent design and corrosion resistance. It is set to kill.

  Japanese Patent Application Laid-Open No. 2007-283627 (Patent Document 3) is a primer for a photocurable inkjet ink, which contains an acid generator and an acid polymerizable compound, and has an amine value of 5.0 mgKOH / g or less. This makes it possible to improve the adhesion between an ink layer formed on a medium using a photocurable inkjet ink and the medium, and to form a high quality image. It is said.

Japanese Patent Laid-Open No. 2006-068405 JP 2010-188309 A JP 2007-283627 A

  Patent Documents 1 to 3 propose an ink receiving layer suitable for printing with an active energy ray-curable ink, but the adhesion between the ink receiving layer and the printing layer has not been sufficiently studied. The active energy ray curable ink has a problem that the interlaminar adhesion between the ink receiving layer and the printing layer tends to be lower than the organic solvent-based ink and the water-based ink which easily penetrate into the base material and the ink receiving layer.

  Accordingly, an object of the present invention is to solve the above-described problems of the prior art and to provide a printed material manufacturing method capable of forming a printed material having excellent interlayer adhesion between a base layer and a printed layer.

  As a result of intensive studies to achieve the above object, the present inventor can react with an active energy ray-curable ink containing a compound having a specific structure as a monomer having an ethylenically unsaturated group, and the compound. By using an underlayer containing various functional groups, even in a printing layer formed from an active energy ray-curable ink, the portion derived from the compound present in the printing layer and the functional group contained in the underlayer It has been found that the interlayer adhesion between the printed layer and the underlayer can be improved by reacting with a group, and the present invention has been completed.

〔式（１）中、Ｒ^１は、水素原子又は炭素数が１〜８のアルキル基である。Ｒ^２は、水素原子又はメチル基である。〕で表される化合物を含み、前記下地層が、前記式（１）で表される化合物と反応することが可能な官能基を含む第１の工程と、
印刷物を加熱する第２の工程と
を含むことを特徴とする。 That is, the method for producing a printed material according to the present invention is a method for producing a printed material comprising an underlayer and a printed layer disposed on the underlayer,
A first step of performing printing with an active energy ray-curable ink on an underlayer to form a print layer, and then irradiating the print layer with an active energy ray to cure the print layer, the active energy ray The curable ink has the following formula (1):

[Equation (1), ^{R 1} is a hydrogen atom or a carbon number of 1 to 8 alkyl group. R ² is a hydrogen atom or a methyl group. A first step including a functional group capable of reacting with the compound represented by the formula (1),
And a second step of heating the printed matter.

  In the suitable example of the manufacturing method of the printed matter of this invention, content of the compound represented by the said Formula (1) in the said active energy ray hardening-type ink exists in the range of 1-50 mass%.

  In another preferred embodiment of the method for producing a printed matter of the present invention, the functional group contained in the underlayer is at least one selected from the group consisting of a hydroxyl group, an amino group, an amide group, an imide group, and an alkoxymethyl group. It is.

  In another preferred embodiment of the method for producing a printed matter of the present invention, the underlayer contains at least one resin selected from the group consisting of an epoxy resin, a polyester resin, an acrylic resin, an alkyd resin, and a fluorine resin.

  In another preferred embodiment of the method for producing a printed material of the present invention, in the second step, the heating temperature of the printed material is in the range of 70 to 300 ° C.

  In another preferred embodiment of the method for producing a printed matter of the present invention, the method further includes a third step of forming a surface protective layer so as to cover the cured printed layer before the second step.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the printed matter which can form the printed matter which is excellent in the interlayer adhesiveness of a base layer and a printed layer can be provided.

〔式（１）中、Ｒ^１は、水素原子又は炭素数が１〜８のアルキル基である。Ｒ^２は、水素原子又はメチル基である。〕で表される化合物を含み、前記下地層が、前記式（１）で表される化合物と反応することが可能な官能基を含む第１の工程と、印刷物を加熱する第２の工程とを含むことを特徴とする。 Below, the manufacturing method of the printed matter of this invention is demonstrated in detail. The method for producing a printed material according to the present invention is a method for producing a printed material including an underlayer and a printed layer disposed on the underlayer, and printing the active energy ray-curable ink on the underlayer to form a printed layer. Then, in the first step of irradiating the print layer with active energy rays to cure the print layer, the active energy ray curable ink is represented by the following formula (1):

[Equation (1), ^{R 1} is a hydrogen atom or a carbon number of 1 to 8 alkyl group. R ² is a hydrogen atom or a methyl group. A first step including a functional group capable of reacting with the compound represented by the formula (1), and a second step of heating the printed material. It is characterized by including.

  In the method for producing a printed matter of the present invention, first, printing with an active energy ray-curable ink is performed on the underlayer to form a printing layer, and then the printing layer is cured by irradiating the printing layer with active energy rays. (Also referred to as the first step or the printing step).

  The base layer means a layer that is a base for performing printing with an active energy ray-curable ink, and may be a base material itself, or a coating film or a print layer that can be formed on the base material. There may be.

The underlayer includes a functional group capable of reacting with the compound represented by the formula (1). For this reason, the part derived from the compound represented by the above formula (1) present in the cured printed layer (specifically, CONHCH ₂ OR ¹ site of the formula (1)) and the functional group contained in the underlayer Can be reacted in the second step to be described later, and the adhesion between the printed layer and the underlayer can be improved.

More specifically, the functional group capable of reacting with the compound represented by the formula (1) is a compound represented by the formula (1) present in the printed layer cured in the first step. It can also be expressed as a functional group capable of reacting with the derived part (specifically, the CONHCH ₂ OR ¹ site of the formula (1)) through the second step described below. Preferable examples include hydroxyl group, amino group, amide group, imide group, and alkoxymethyl group. Among these, a hydroxyl group is the most preferable. In addition, although the said foundation | substrate layer may be 1 type, these functional groups may contain 2 or more types.

  The underlayer preferably contains at least one resin selected from the group consisting of epoxy resins, polyester resins, acrylic resins, alkyd resins, and fluorine resins. If the material of the underlayer is an organic material such as resin (preferably epoxy resin, polyester resin, acrylic resin, alkyd resin or fluorine resin), it can react with the compound represented by the above formula (1). An underlayer containing possible functional groups can be easily prepared.

  When the underlayer is a base material itself, examples of the base material preferably include a resin molded body containing a functional group capable of reacting with the compound represented by the formula (1), and a resin. Preferred examples of the resin that can be used for the molded body include epoxy resins, polyester resins, acrylic resins, alkyd resins, and fluorine resins. Moreover, as a shape of a base material, there exist plate shape etc., for example.

  Moreover, when the said foundation | substrate layer is a coating film or a printing layer formed on the base material, this coating film or a printing layer has the functional group which can react with the compound represented by the said Formula (1). It is preferable to contain the resin to contain. Preferred examples of the resin that can be used for the coating film and the printed layer include epoxy resins, polyester resins, acrylic resins, alkyd resins, and fluorine resins.

  The paint used for forming the coating film as the underlayer and the ink used for forming the printing layer as the underlayer include organic solvent-based paints and inks using an organic solvent as a main solvent, water-based paints using water as a main solvent, and Various conventionally known paints and inks such as inks, active energy ray-curable paints and inks, and powder paints can be used. In the paint and ink, as components other than the resin, a curing agent component, a colorant, an ultraviolet absorber, a light stabilizer, a rheology modifier, a leveling agent, a surface tension modifier, an antioxidant, a plasticizer, and a rust inhibitor , Solvent, filler, pH adjuster, antifoaming agent, charge control agent, active energy ray curable monomer and oligomer, photopolymerization initiator, photosensitizer, polymerization inhibitor, stress relaxation agent, penetrating agent, light guide Materials, glittering materials, magnetic materials, phosphors, waxes and the like may be used as necessary. The paint and ink can be prepared by mixing various components appropriately selected as necessary.

  The coating method of the paint used for forming the coating film which is the base layer can use various conventionally used coating means such as air spray, airless spray, roll coater, flow coater and electrostatic coating. Various printing means conventionally used, such as screen printing, gravure printing, and ink jet printer, can be used as a printing method of the ink used for forming the printing layer that is the base layer.

It is preferable to dry the coating film and the printing layer, which are the base layer, together with curing by irradiation with active energy rays such as normal temperature, heating, or ultraviolet rays. The drying / curing conditions for heating are preferably 60 to 250 ° C. and 30 seconds to 1 hour. When curing is performed by irradiation with active energy rays, the integrated light amount is preferably in the range of 100 to 2000 mJ / cm ² .

  Moreover, when the said base layer is the coating film and printing layer which were formed on the base material, this base material is although it does not specifically limit, The base material used by an industrial line is mentioned suitably. Examples of the shape of the substrate include a plate shape. Examples of the material of the base material include plastics such as epoxy resin, ABS resin, polycarbonate, polyvinyl chloride, polystyrene, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), and polypropylene (PP), iron, stainless steel, and aluminum. And metals such as wood, glass and the like.

  The active energy ray-curable ink is an ink composition that can be cured by irradiation with active energy rays such as ultraviolet rays, and is preferably an ink composition for an ink jet printer. In the method for producing a printed matter of the present invention, the active energy ray-curable ink contains a monomer having an ethylenically unsaturated group, and particularly contains at least a compound represented by the above formula (1). In the present invention, the monomer having an ethylenically unsaturated group means an ethylenically unsaturated group (for example, a carbon-carbon double bond constituting an acryloyl group, a methacryloyl group, a vinyl group or an allyl group) by irradiation with active energy rays. A monomer that undergoes a polymerization reaction via the active energy ray, specifically, a monofunctional monomer (monofunctional monomer having one ethylenically unsaturated group) in which the number of functional groups exhibiting reactivity when irradiated with active energy rays is 1, Bifunctional monomer having two functional groups (bifunctional monomer having two ethylenically unsaturated groups), polyfunctional monomer having three or more functional groups (polyfunctional having three or more ethylenically unsaturated groups) Monomer) and the like. In the present invention, the monomer has a molecular weight of less than 2000.

  When the compound represented by the above formula (1) is used among the monomers having these ethylenically unsaturated groups, the inventor reacts with the functional group contained in the above-described underlayer in the second step described later. It was found that the adhesion between the printed layer and the underlayer can be improved. Moreover, the compound represented by the said Formula (1) can further improve the interlayer adhesiveness of a printing layer and a base layer by the hydrogen bond in an amide bond part.

  In the active energy ray-curable ink, the content of the compound represented by the formula (1) is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, It is more preferable that it is 9 mass%, and it is most preferable that it is 5-9 mass%. If the content of the compound represented by the formula (1) is less than 1% by mass, the effect of improving the interlayer adhesion may be lowered, and the performance of the printed layer such as water resistance, boiling water resistance, weather resistance, etc. Tend to decrease. On the other hand, if it exceeds 50% by mass, the ink ejection may be adversely affected.

In the above formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In the above formula (1), R ² is a hydrogen atom or a methyl group, and is preferably hydrogen.

  Preferable examples of the compound represented by the above formula (1) include Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methylolacrylamide and the like. In addition, the compound represented by the said Formula (1) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Other monomers having an ethylenically unsaturated group (hereinafter referred to as other monomers) that can be used in the active energy ray-curable ink will be described. In the active energy ray-curable ink, the content of the other monomer having an ethylenically unsaturated group is, for example, 50 to 90% by mass.

  Among other monomers, the monofunctional monomer preferably has a molecular weight of 1000 or less. Specific examples include 4-hydroxybutyl acrylate, stearyl acrylate, acryloylmorpholine, tridecyl acrylate, lauryl acrylate, N, N- Dimethylacrylamide, decyl acrylate, phenoxyethyl acrylate, isodecyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, isooctyl acrylate, octyl acrylate, dicyclopentenyloxyethyl acrylate, cyclohexyl acrylate, N-vinyl Caprolactam, isoamyl acrylate, 2-ethylhexyl-diglycol acrylate, EO (ethylene oxide) modification 2-ethylhexyl acrylate, neopentyl glycol acrylic acid benzoate, N-vinyl-2-pyrrolidone, N-vinylimidazole, tetrahydrofurfuryl acrylate, methoxydipropylene glycol acrylate, (2-methyl-2-ethyl-1,3 -Dioxolan-4-yl) methyl acrylate, cyclic trimethylolpropane formal acrylate, and ethoxy-diethylene glycol acrylate. Among these, 4-hydroxybutyl acrylate, ethoxy-diethylene glycol acrylate, isobornyl acrylate, phenoxyethyl acrylate, methoxydipropylene glycol acrylate, cyclohexyl acrylate, and tetrahydrofurfuryl acrylate are preferable from the viewpoint of the viscosity of the ink. In addition, these monofunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the other monomers, the bifunctional monomer preferably has a molecular weight of 1000 or less. Specific examples include 1,10-decanediol diacrylate, 2-methyl-1,8-octanediol diacrylate, 2 -Butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol diacrylate, 1,7-heptanediol diacrylate, 1,6-hexanediol diacrylate Acrylate, 1,4-butanediol diacrylate, polytetramethylene glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, hydroxypivalate neopentyl glycol diacrylate, neopentyl glycol diacrylate, PO (propyleneoxy) ) Modified neopentyl glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, and dipropylene glycol diacrylate, and the like. Among these, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and neopentyl glycol diacrylate are preferable from the viewpoint of the viscosity of the ink. In addition, these bifunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the other monomers, the trifunctional or higher polyfunctional monomer preferably has a molecular weight of 2000 or less. Specific examples thereof include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane. Triacrylate, ethoxylated glycerin triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, EO modified diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, EO modified dipentaerythritol hexaacrylate, etc. Can be mentioned. Among these, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate are preferable. In addition, these polyfunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

The active energy ray curable ink may contain an acrylate oligomer in order to increase the strength of the printed layer. An acrylate oligomer is an oligomer having one or more acryloyloxy groups (CH ₂ ═CHCOO—), and preferably has 2 to 6 functional groups. The acrylate oligomer preferably has a molecular weight of 2000 to 20000. In addition, this molecular weight is a weight average molecular weight of polystyrene conversion. Specific examples of the acrylate oligomer include aminoacrylate oligomer [acrylate oligomer having a plurality of amino groups (-NH ₂ )], urethane acrylate oligomer [acrylate oligomer having a plurality of urethane bonds (-NHCOO-)], epoxy acrylate oligomer [ Acrylate oligomer having a plurality of epoxy groups], silicone acrylate oligomer [acrylate oligomer having a plurality of siloxane bonds (—SiO—)], ester acrylate oligomer [acrylate oligomer having a plurality of ester bonds (—COO—)] and butadiene acrylate oligomer [butadiene Acrylate oligomer having a plurality of units] and the like. Among these, urethane acrylate oligomers are preferable from the viewpoint of weather resistance and adhesiveness, and aliphatic urethane acrylate oligomers having no aromatic ring in the structure are more preferable. In addition, content of an acrylate oligomer is 1-20 mass% in the total mass of an ink, for example.

Specific examples of the acrylate oligomer include the following. In addition, these acrylate oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.
Beam set 502H, beam set 505A-6, beam set 550B, beam set 575, beam set AQ-17 (manufactured by Arakawa Chemical Industries),
UA-306H, UA-306I, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.),
CN929, CN940, CN944B85, CN959, CN961E75, CN961H81, CN962, CN963A80, CN963B80, CN963E75, CN963E80, CN963J75, CN964, CN964A85, CN964E75, CN965, CN965A80, CN966A80, CN966B85, CN966H90, CN966J75, CN966R60, CN968, CN980, CN981, CN981A75, CN981B88, CN982A75, CN982B88, CN982E75, CN982P90, CN983, CN985B88, CN989, CN991, CN996, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007 CN9009, CN9010, CN9011, CN9014, CN9178, CN9788, CN9893 (manufactured by Sartomer Co., Ltd.),
U-4HA, U-6HA, U-6LPA, UA-1100H, UA-53H, UA-33H, U-200PA, UA-4200, UA-122P (manufactured by Shin-Nakamura Chemical Co., Ltd.),
New Frontier R-1214, New Frontier R-1301, New Frontier R-1304, New Frontier R-1306X, New Frontier R-1150D (Daiichi Kogyo Seiyaku Co., Ltd.),
EBECRYL230, EBECRYL244, EBECRYL245, EBECRYL264, EBECRYL265, EBECRYL270, EBECRYL284, EBECRYL285, EBECRYL294, EBECRYL1290, EBECRYL1290, EBECRYL1290, EBECRYL1290, EBECRYL1290, EBECRYL1290
UV-1700B, UV-7600B, UV-7605B, UV-6630B, UV-7000B, UV-7461TE, UV-3000B, UV-3310B, UV-3520TL, UV-3700B (manufactured by Nippon Synthetic Chemical),
Art Resin UN-333, UN-1255, UN-2600, UN-2700, UN-5500, UN-5507, UN-6060P, UN-6200, UN-6300, UN-6301, UN-7600, UN-7700, UN-9000PEP, UN-9200A, UN-3320HA, UN-3320HC, UN-904 (manufactured by Negami Kogyo Co., Ltd.)

  In the active energy ray curable ink, the ratio of the compound having two or more ethylenically unsaturated groups (hereinafter referred to as bifunctional or higher polyfunctional compound) to the total of the compounds having ethylenically unsaturated groups is: It is preferably 10 to 90% by mass, more preferably 30 to 90% by mass, and still more preferably 40 to 80% by mass. By blending a bifunctional or higher polyfunctional compound with the active energy ray-curable ink, the hardness of the printed layer is increased and the odor can be reduced. When a large amount of a bifunctional or higher polyfunctional compound is blended, the internal stress of the printing layer generally increases and the adhesion of the printing layer tends to be reduced. Since it is excellent in property, it becomes possible to mix | blend a polyfunctional compound more than bifunctional. Specific examples of the bifunctional or higher polyfunctional compound include the bifunctional monomer and trifunctional or higher polyfunctional monomer described above, and an oligomer having two or more acryloyloxy groups among the acrylate oligomers.

  The active energy ray curable ink preferably contains a photopolymerization initiator. A photoinitiator has the effect | action which starts superposition | polymerization of the monomer and oligomer mentioned above by irradiating an active energy ray. Further, the content of the photopolymerization initiator is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and more preferably 3 to 15% by mass in the total mass of the ink. preferable. When the content of the photopolymerization initiator is less than 1% by mass, the printed layer may be poorly cured. When the content exceeds 25% by mass, precipitates are generated at low temperatures and ink ejection becomes unstable. There is. Furthermore, in order to accelerate the initiation reaction of the photopolymerization initiator, an auxiliary such as a photosensitizer can be used in combination.

  Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, thioxanthone compounds, phosphine oxide compounds, etc. From the viewpoint of curability, the wavelength of the active energy ray to be irradiated and the photopolymerization initiator It is preferable that the absorption wavelengths overlap as much as possible.

As a specific example of the photopolymerization initiator,
2,2-dimethoxy-1,2-diphenylethane-1-one,
1-hydroxy-cyclohexyl-phenyl-ketone,
2-hydroxy-2-methyl-1-phenylpropan-1-one,
Benzophenone,
1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one,
2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methyl-propan-1-one,
Phenylglyoxylic acid methyl ester,
2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one,
2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone,
2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one,
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide,
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)],
Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime),
2,4-diethylthioxanthone,
2-isopropylthioxanthone,
Examples include 2-chlorothioxanthone. Among these, from the viewpoint of ink curability, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4-diethylthioxanthone are preferred, and 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide is particularly preferred. In addition, these photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  The active energy ray curable ink may further contain a light stabilizer. The light stabilizer has an action of absorbing ultraviolet rays and preventing deterioration due to ultraviolet rays. Examples of the light stabilizer include cyanoacrylate compounds, benzophenone compounds, benzoate compounds, benzotriazole compounds, hydroxyphenyl triazine compounds, benzylidene camphor compounds, inorganic fine particles, etc. Among them, ultraviolet absorption has a shorter wavelength. The hydroxyphenyltriazine compound is preferably from the viewpoint of the curability of the ink. From the viewpoint of curability, it is preferable that the wavelength of the active energy ray to be irradiated and the absorption wavelength of the light stabilizer do not overlap as much as possible. In addition, the content of the light stabilizer is preferably 0.1 to 15% by mass, and more preferably 0.2 to 5% by mass in the total mass of the ink. When the content of the light stabilizer is less than 0.1% by mass, a sufficient ultraviolet ray absorbing effect cannot be obtained, and when it exceeds 15% by mass, the curability of the printed layer may be lowered.

As a specific example of the light stabilizer,
2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid,
2-hydroxy-4-octoxybenzophenone,
2-hydroxy-4-dodecyloxybenzophenone-2-hydroxy-4-benzyloxybenzophenone,
Bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane,
2,2′-dihydroxy-4-methoxybenzophenone,
2,2′-dihydroxy-4,4′-dimethoxybenzophenone,
2,2 ′, 4,4′-tetrahydroxybenzophenone,
2-hydroxy-4-methoxy-2′-carboxybenzophenone,
2- (2′-hydroxy-5′-methylphenyl) benzotriazole 2- [2′-hydroxy-3 ′, 5′-bis (α, α- (dimethylbenzyl) phenyl] benzotriazole,
2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole,
2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole,
2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole,
2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole,
2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole,
2,2′-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol],
A condensate of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol;
2- (2-hydroxyphenyl) benzotriazole,
2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
2,6-di-tert-butylphenyl-3 ′, 5′-di-tert-butyl-4′-hydroxybenzoate,
And hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. In addition, these light stabilizers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The active energy ray curable ink may further contain a polymerization inhibitor. The polymerization inhibitor has a function of reacting with active radicals generated in the ink and preventing the polymerization reaction from occurring. Further, it has been found that the storage stability can be further improved by adding a polymerization inhibitor to the active energy ray curable ink. The content of the polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.001 to 1% by mass, based on the total mass of the ink. When the content of the polymerization inhibitor is less than 0.001% by mass, the effect of improving the storage stability is not sufficiently obtained, and when it exceeds 5% by mass, the curability of the printed layer cannot be maintained and is lowered.

  Examples of the polymerization inhibitor include hydroquinone compounds, phenol compounds, phenothiazine compounds, nitroso compounds, and N-oxyl compounds.

  Specific examples of the polymerization inhibitor include phenol, o-, m- or p-cresol, 2-t-butyl-4-methylphenol, 6-t-butyl-2,4-dimethylphenol, 2,6- Di-t-butyl-4-methylphenol, 2-t-butylphenol, 4-t-butylphenol, 2,4-di-t-butylphenol, 2-methyl-4-t-butylphenol, 4-t-butyl-2 Phenol compounds such as 1,6-dimethylphenol, hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, 2,5-di-t-butyl hydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethyl hydroquinone, trimethyl hydroquinone 4- Methylbenzcatechin, t-butylhydroquinone, 3-methylbenzcatechin, 2-me Hydroquinone compounds such as ru-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, benzoquinone, t-butyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and phenothiazines such as phenothiazine Compounds, nitroso compounds such as N-nitroso-N-phenylhydroxylamine ammonium, N-nitroso-N-phenylhydroxylamine aluminum salt, 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N- N-oxyl compounds such as oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl Etc. Among these, hydroquinone monomethyl ether, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, and N-nitroso-N-phenylhydroxylamine aluminum salt are preferable from the viewpoint of improving storage stability and maintaining curability. In addition, these polymerization inhibitors may be used individually by 1 type, and may be used in combination of 2 or more type.

  The active energy ray-curable ink may contain a colorant such as a dye or a pigment, but preferably contains a pigment from the viewpoint of weather resistance. In addition, content of a coloring agent is 0.1-10 mass% in the total mass of an ink, for example. Moreover, a coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.

As a specific example of the colorant,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 24, 32, 34, 35, 36, 37, 41, 42, 43, 49, 53, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 128, 129, 130, 133, 138, 139, 150, 151, 152, 153, 154, 155, 165, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 91,193,194,199,205,206,209,212,213,214,215,219,
C. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 20, 21, 24, 31, 34, 36, 38, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 38, 41, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 52, 52: 1, 52: 2, 53: 1, 54, 57: 1, 58, 60: 1, 63, 64: 1, 68, 81: 1, 83, 88, 89, 95, 101, 104, 105, 108, 112, 114, 119, 122, 123, 136, 144, 146, 147, 149, 150, 164, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 20 208, 209, 210, 211, 213, 214, 216, 220, 220, 221, 224, 226, 237, 238, 239, 242, 245, 247, 248, 251, 253, 254, 255, 256, 257 258, 260, 262, 263, 264, 266, 268, 269, 270, 271, 272, 279,
C. I. Pigment Violet 1, 2, 3, 3: 1, 3: 3, 5: 1, 13, 15, 16, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 42, 50,
C. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 24, 24: 1, 25, 26, 27, 28, 29, 36, 56, 60, 61, 62, 63, 75, 79, 80,
C. I. Pigment Green 1, 4, 7, 8, 10, 15, 17, 26, 36, 50,
C. I. Pigment Brown 5, 6, 23, 24, 25, 32, 41, 42,
C. I. Pigment Black 1, 6, 7, 9, 10, 11, 20, 31, 32, 34,
C. I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28,
Examples include aluminum flakes, glass flakes, and hollow particles.

Among these, from the viewpoint of weather resistance and color reproducibility of the printed layer,
C. I. Pigment Black 7,
C. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 28,
C. I. Pigment Red 101, C.I. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. Pigment Red 254, C.I. I. Pigment Red 282,
C. I. Pigment Violet 19,
C. I. Pigment White 6,
C. I. Pigment Yellow 42, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 213 is preferable.

  When a pigment is used as the colorant, the pigment particles dispersed in the ink have a volume average particle diameter of 0.05 to 0.4 μm and a volume maximum particle diameter of 0.2 from the viewpoint of ejection stability. It is preferably ˜1 μm. When the volume average particle diameter is larger than 0.4 μm and the volume maximum particle diameter is larger than 1 μm, it tends to be difficult to stably eject ink. The volume average particle diameter and the volume maximum particle diameter can be measured by a measuring instrument using a dynamic light scattering method.

  The active energy ray-curable ink may further contain a pigment dispersant as needed in order to disperse the pigment. In addition, content of a pigment dispersant is 0.1-5 mass% in the total mass of an ink, for example. Moreover, a pigment dispersant may be used individually by 1 type, and may be used in combination of 2 or more type.

Specific examples of the pigment dispersant include
ANTI-TERRA-U, ANTI-TERRA-U100,
ANTI-TERRA-204, ANTI-TERRA-205,
DISPERBYK-101, DISPERBYK-102,
DISPERBYK-103, DISPERBYK-106,
DISPERBYK-108, DISPERBYK-109,
DISPERBYK-110, DISPERBYK-111,
DISPERBYK-112, DISPERBYK-116,
DISPERBYK-130, DISPERBYK-140,
DISPERBYK-142, DISPERBYK-145,
DISPERBYK-161, DISPERBYK-162,
DISPERBYK-163, DISPERBYK-164,
DISPERBYK-166, DISPERBYK-167,
DISPERBYK-168, DISPERBYK-170,
DISPERBYK-171, DISPERBYK-174,
DISPERBYK-180, DISPERBYK-182,
DISPERBYK-183, DISPERBYK-184,
DISPERBYK-185, DISPERBYK-2000,
DISPERBYK-2001, DISPERBYK-2008,
DISPERBYK-2009, DISPERBYK-2020,
DISPERBYK-2025, DISPERBYK-2050,
DISPERBYK-2070, DISPERBYK-2096,
DISPERBYK-2150, DISPERBYK-2155,
DISPERBYK-2163, DISPERBYK-2164,
BYK-P104, BYK-P104S, BYK-P105,
BYK-9076, BYK-9077, BYK-220S, BYKJET-9150, BYKJET-9151 (above, manufactured by Big Chemie Japan),
Solsperse 3000, Solsperse 5000,
Solsperse 9000, Solsperse 11200,
Solsperse 13240, Solsperse 13650,
Solsperse 13940, Solsperse 16000,
Solsperse 17000, Solsperse 18000,
Solsperse 20000, Solsperse 21000,
Solsperse 24000SC, Solsperse 24000GR,
Solsperse 26000, Solsperse 27000,
Solsperse 28000, Solsperse 32000,
Solsperse 32500, Solsperse 32550,
Solsperse 32600, Solsperse 33000,
Solsperse 34750, Solsperse 35100,
Solsperse 35200, Solsperse 36000,
Solsperse 36600, Solsperse 37500,
Solsperse 38500, Solsperse 39000,
Solsperse 41000, Solsperse 54000,
Solsperse 55000, Solsperse 56000,
Solsperse 71000, Solsperse 76500,
Solsperse X300 (above, manufactured by Lubrizol),
Disparon DA-7301, Disparon DA-325, Disparon DA-375, Disparon DA-234 (above, manufactured by Enomoto Kasei Co., Ltd.)
FLOREN AF-1000, FLOREN DOPA-15B, FLOREN DOPA-15BHFS, FLOREN DOPA-17HF, FLOREN DOPA-22, FLOREN DOPA-33, FLOREN G-600, FLOREN G-700, FLOREN G-700AMP, FLOREN G-700DMEA, Floren G-820, Floren G-900, Floren GW-1500, Floren KDG-2400, Floren NC-500, Floren WK-13E, (manufactured by Kyoeisha Chemical Co., Ltd.)
TEGO Dispers 610, TEGO Dispers 610S,
TEGO Dispers 630, TEGO Dispers 650,
TEGO Dispers 652, TEGO Dispers 655,
TEGO Dispers 662C, TEGO Dispers 670,
TEGO Dispers 685, TEGO Dispers 700,
TEGO Dispers 710, TEGO Dispers 740W,
LIPOTIN A, LIPOTIN BL,
LIPOTIN DB, LIPOTIN SB (above, manufactured by Evonik Degussa),
PB821, PB822, PN411, PA111 (above, manufactured by Ajinomoto Fine Techno Co.),
Texahole 963, Texahole 964, Texahole 987, Texahole P60, Texahole P61, Texahole P63, Texahole SF71, Texahole UV20, Texahole UV21 (above, manufactured by Cognis),
BorchiGen SN88, BorchiGen 0451 (above, manufactured by Bochas) and the like.

  The active energy ray-curable ink includes, as other components, a polymerization inhibitor, an antioxidant, a surface tension adjuster, a plasticizer, a rust preventive agent, a solvent, a non-reactive polymer, a filler, a pH adjuster, an eraser. Additives such as a foaming agent, a charge control agent, a stress relaxation agent, a penetrating agent, a light guide material, a bright material, a magnetic material, and a phosphor may be used as necessary.

  The active energy ray-curable ink is prepared by mixing a monomer having an ethylenically unsaturated group and various components appropriately selected as necessary, and, if necessary, about 1 of the nozzle diameter of an inkjet print head to be used. It can be prepared by filtering the resulting mixture using a filter with a pore size of / 10 or less.

  The active energy ray-curable ink preferably has a viscosity at 40 ° C. of 5 to 25 mPa · s, and more preferably 5 to 20 mPa · s. If the ink viscosity at 40 ° C. is within the above specified range, good ejection stability can be obtained. The ink viscosity can be measured using a cone plate viscometer.

  The active energy ray-curable ink preferably has a surface tension at 25 ° C. of 20 to 35 mN / m. If the ink surface tension at 25 ° C. is within the above specified range, good ejection stability can be obtained. The ink surface tension can be measured by a plate method.

  In the method for producing a printed matter of the present invention, printing with an active energy ray-curable ink is performed on a base layer by a normal printing means to form a printed layer. Here, as the printing unit, a printing unit using an ink jet printer is preferable. Examples of the ink jet printer include an ink jet printer that discharges ink by a charge control method or a piezo method, and particularly a large ink jet printer, specifically, an ink jet printer intended for printing on articles produced on an industrial line. Preferably mentioned.

In the method for producing a printed matter of the present invention, the printing layer formed with the active energy ray-curable ink is cured by irradiation with active energy rays such as ultraviolet rays. As a light source for the active energy ray, a high-pressure mercury lamp, a metal halide lamp, an LED lamp, or the like can be used. Further, the wavelength of the active energy ray irradiated for curing the printed layer preferably overlaps with the absorption wavelength of the photopolymerization initiator. For the active energy ray-curable ink, the active energy ray The dominant wavelength is preferably 360 to 425 nm. In addition, it is preferable that the integrated light quantity of an active energy ray exists in the range of 100-2000mJ / cm < ² >.

In the method for producing a printed material of the present invention, the printed material including the cured printed layer and the base layer formed in the first step is then heated (also referred to as a second step or a heating step). Thereby, the part derived from the compound represented by the formula (1) present in the printing layer and the functional group contained in the underlayer capable of reacting with the part can be reacted, and the printing layer and the lower layer can be reacted. Interlayer adhesion of the formation can be improved.
In the active energy ray-curable ink, a small amount of water contained in the blended pigment and other components is present and remains in the cured printed layer. For this reason, the portion derived from the compound represented by the above formula (1) existing in the printed layer cured in the first step (specifically, the CONHCH ₂ OR ¹ site of the formula (1)) is not present in the underlayer. It is considered that the reaction with the functional group contained is possible, and the interlayer adhesion can be improved.

  In the second step, the heating temperature of the printed material is preferably in the range of 70 to 300 ° C, more preferably in the range of 90 to 250 ° C, and in the range of 150 to 190 ° C. Most preferred. In addition, in this invention, the heating temperature of the said printed matter refers to the surface temperature of a base layer or a base material. As for the heating time, for example, about 20 minutes is sufficient if it is within the specified range.

  The printed matter manufacturing method of the present invention may further include a third step (also referred to as a surface protective layer forming step) in which a surface protective layer is formed so as to cover the cured printed layer formed in the first step. preferable.

  The said surface protective layer means the layer for protecting the surface (especially printing layer) of printed matter. Here, as the resin that can be used for the surface protective layer, an epoxy resin, a polyester resin, an acrylic resin, an alkyd resin, a fluorine resin, and the like can be preferably cited. These resins may be used alone or in combination of two kinds. A combination of the above may also be used.

  For the formation of the surface protective layer, conventionally known organic solvent-based paints and inks using an organic solvent as a main solvent, water-based paints and inks using water as a main solvent, active energy ray-curable paints and inks, and the like. Various paints and inks are available. In the paint and ink, as components other than the resin, a curing agent component, a colorant, an ultraviolet absorber, a light stabilizer, a rheology modifier, a leveling agent, a surface tension modifier, an antioxidant, a plasticizer, and a rust inhibitor , Solvent, filler, pH adjuster, antifoaming agent, charge control agent, active energy ray curable monomer and oligomer, photopolymerization initiator, photosensitizer, polymerization inhibitor, stress relaxation agent, penetrating agent, light guide Materials, glittering materials, magnetic materials, phosphors, waxes and the like may be used as necessary. The paint and ink can be prepared by mixing various components appropriately selected as necessary.

  As the coating method of the paint used for forming the surface protective layer, various conventionally used coating means such as air spray, airless spray, roll coater and flow coater can be used, and also used for forming the surface protective layer. Various printing means conventionally used such as an ink jet printer can be used as the ink printing method.

  The surface protective layer may be formed before or after the second step, but it is preferable to perform the second step after forming the surface protective layer in terms of productivity. In particular, when heating is necessary for forming the surface protective layer, it is more preferable because the second step and the step of forming the surface protective layer can be performed simultaneously.

  The printed matter obtained by the production method of the present invention comprises a base layer and a printed layer disposed on the base layer, and is excellent in interlayer adhesion between the base layer and the print layer. Here, the base layer may be the base material itself, but when the base layer is a coating film or a printing layer, the coating film or the printing layer is formed on the base material. Moreover, it is preferable that the said printed matter is further provided with the surface protective layer arrange | positioned on this printing layer so that the said printing layer may be covered.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Ink preparation method>
Mixtures according to the formulation shown in Table 1 were obtained and kneaded with a bead mill to make homogeneous, and active energy ray-curable inkjet inks 1 to 9 were prepared.

<Underlayer paint>
According to the formulation shown in Table 2, the raw materials were mixed with stirring, and sufficiently homogenized to prepare an undercoat coating material.
The coating materials 1 to 5 and 9 were applied to a stainless steel plate (base material) by spray coating at 15 μm and heated at 160 ° C. for 20 minutes to obtain a base layer.
The coating materials 6-8 apply | coated 80 micrometers by electrostatic coating to the stainless steel plate (base material), and obtained the base layer by heating at 180 degreeC for 20 minutes.

Regarding the base layer obtained from the paints 1 to 9, the functional group capable of reacting with the compound represented by the formula (1) contained in the base layer and the resin contained in the base layer are shown below. .
Paint 1: (functional group) amide, (resin) acrylic resin paint 2: (functional group) hydroxyl group, (resin) acrylic resin paint 3: (functional group) hydroxyl group, (resin) polyester resin paint 4: (functional group) hydroxyl group , (Resin) acrylic resin paint 5: (functional group) hydroxyl group, (resin) fluorine resin paint 6: (functional group) hydroxyl group, (resin) polyester resin paint 7: (functional group) hydroxyl group, (resin) polyester resin paint 8 : (Functional group) hydroxyl group, (resin) polyester resin paint 9: (functional group) none, (resin) acrylic resin

<Coating for surface protective layer>
Duracron CW Clear (Dainippon Paint Co., Ltd.), which is a clear paint, was used as the surface protective layer paint. The cured printed layer was applied with a spray coating of 15 μm to form a surface protective layer.

  In order to evaluate adhesiveness and pencil hardness, printed materials were produced using the inks and the undercoat layer paints in the combinations shown in Table 3. In addition, when producing printed matter provided with a surface protective layer, it is shown as "Yes" in the item of the surface protective layer of Table 3.

<Adhesiveness>
A solid image (thickness: about 8 μm) is printed on the underlayer by an ink jet printer using an active energy ray curable ink jet ink, and then an active energy ray having a main wavelength of 380 to 390 nm is applied with an ultraviolet LED lamp to 2000 mJ. The image (printed layer) was cured by irradiation with / cm ² . When the surface protective layer was necessary, the surface protective layer was formed before heating. Next, the surface temperature of the base material was raised to the temperature shown in Table 3, and heating was performed for 20 minutes in this state to produce a printed matter.
When “no heating” is shown in the item of heating temperature in Table 3, the heating test was not performed, and an evaluation test was performed on the printed matter when the printing layer was completely cured.
The printed layer of the printed material was subjected to a cross cut of 1 mm width and 100 squares (when the surface protective layer was provided, from the surface protective layer to the printed layer), and the cellophane tape was sufficiently adhered, and then peeled off. Adhesion was evaluated according to the following criteria.
(Double-circle): Peeling is not confirmed in a cut part.
○: Peeling of less than 10% can be confirmed at the cut part.
(Triangle | delta): The peeling of 10% or more and less than 25% can be confirmed in a cut part.
X: Exfoliation of 25% or more can be confirmed in the cut part.

<Pencil hardness>
A printed matter was produced in the same manner as in the above adhesion evaluation. The printed matter was evaluated for pencil hardness by scratch hardness (pencil method) according to JIS K-5600-5-4.

<Discharge stability>
The ejection stability of the prepared active energy ray-curable inkjet ink was evaluated. Specifically, a nozzle check image was printed on a copy sheet by an inkjet printer using an active energy ray-curable inkjet ink, and the ejection stability was visually evaluated according to the following criteria.
○: An image can be printed at a predetermined position without causing nozzle clogging.
Δ: No nozzle clogging occurs, but slight flight bending occurs.
X: Nozzle clogging occurs, the image is missing, and the ink cannot adhere to a predetermined position, so that a beautiful image cannot be printed.

Claims (6)

A method for producing a printed matter comprising an underlayer and a printed layer disposed on the underlayer,
A first step of performing printing with an active energy ray-curable ink on an underlayer to form a print layer, and then irradiating the print layer with an active energy ray to cure the print layer, the active energy ray The curable ink has the following formula (1):

[Equation (1), ^{R 1} is a hydrogen atom or a carbon number of 1 to 8 alkyl group. R ² is a hydrogen atom or a methyl group. A first step including a functional group capable of reacting with the compound represented by the formula (1),
And a second step of heating the printed material.   2. The method for producing a printed material according to claim 1, wherein the content of the compound represented by the formula (1) in the active energy ray-curable ink is in the range of 1 to 50 mass%.   The functional group contained in the underlayer is at least one selected from the group consisting of a hydroxyl group, an amino group, an amide group, an imide group, and an alkoxymethyl group. Manufacturing method of printed matter.   The said foundation | substrate layer contains at least 1 sort (s) of resin chosen from the group which consists of an epoxy resin, a polyester resin, an acrylic resin, an alkyd resin, and a fluorine resin. Manufacturing method for printed materials.   In the said 2nd process, the heating temperature of the said printed matter exists in the range of 70-300 degreeC, The manufacturing method of the printed matter as described in any one of Claims 1-4 characterized by the above-mentioned.   The printed material according to any one of claims 1 to 5, further comprising a third step of forming a surface protective layer so as to cover the cured printed layer before the second step. Production method.