JP2019043140A - Printed matter and method for producing printed matter - Google Patents

Abstract

To provide a printed matter in which, by an inkjet system, formed is an inkjet image layer showing excellent weather resistance even when not top coat is provided, and a method for producing a printed matter.SOLUTION: A printed matter contains a base material, and an inkjet image layer formed on the base material, the inkjet image layer containing a colorant and a fluororesin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a print and a method of manufacturing the print. More particularly, the present invention relates to prints and methods of making prints that exhibit excellent weatherability even when the ink jet imaging layer is not provided with a topcoat.

  In recent years, a composition containing a fluorocarbon resin has attracted attention as a composition for producing a print having excellent weather resistance. For example, Patent Document 1 discloses a fluorine coating composition comprising a main agent comprising a copolymer containing fluoroolefin and the like, and a curing agent containing a polyisocyanate compound.

Patent No. 5481859 gazette

  However, there is no known technique for obtaining a print having excellent weatherability by a method other than the method of applying the coating composition. Also, conventionally, after forming an image, a top coat may be provided to impart weather resistance. However, when the top coat is provided by coating after the composition is provided by a method other than coating (for example, inkjet method), the manufacturing process becomes complicated.

  The present invention was made in order to solve such problems, and a printed matter in which an inkjet image layer showing excellent weatherability even when not provided with a top coat is formed by an inkjet method and It aims at providing the manufacturing method of a printed matter.

  The following configurations are mainly included in the printed matter and the printed matter production method of the present invention for solving the above-mentioned problems.

  (1) A printed matter comprising a substrate and an inkjet image layer formed on the substrate, wherein the inkjet image layer comprises a coloring material and a fluorine resin.

  According to such a configuration, the printed matter may form an inkjet image layer by an inkjet method. The print also includes an inkjet imaging layer comprising a fluoroplastic. Such an inkjet image layer exhibits sufficient weatherability even without a topcoat. Therefore, the printed matter exhibits the desired color over a long period of time.

  (2) The inkjet image layer includes a first layer containing the coloring material, and a second layer covering the first layer and not containing the coloring material, and the fluorine resin may be the first layer or the first layer or the second layer. The printed matter according to (1), which is included in at least one of the second layer.

  According to such a configuration, the desired ink jet image can be formed by the first layer containing the coloring material. Also, the first layer may be covered by the second layer not containing a colorant. Since at least one of the first layer and the second layer contains a fluorine resin, the resulting inkjet image layer exhibits excellent weatherability.

  (3) The printed matter according to (2), wherein the first layer contains an antioxidant.

  According to such a configuration, the printed matter can suppress the deterioration of the first layer.

  (4) The printed matter according to (2) or (3), wherein the second layer contains an ultraviolet light absorber or a light stabilizer.

  According to such a configuration, the printed matter can exhibit further excellent weatherability. Therefore, the printed matter can exhibit a desired color for a longer period of time.

  (5) The first layer further includes a first layer curing agent, the second layer further includes a second layer curing agent, and the crosslinking reaction initiation temperature of the first layer curing agent is The printed matter in any one of (2)-(4) which is below the crosslinking reaction start temperature of the hardening agent for 2nd layers.

  According to such a configuration, in the printed matter, the second layer can be formed on the more rigidly formed first layer. As a result, in the printed matter obtained, the ink jet image layer is unlikely to cause bleeding or the like.

  (6) The printed matter according to any one of (1) to (5), further comprising a base layer between the substrate and the inkjet image layer.

  According to such a configuration, the printed matter can form an inkjet image layer on the base layer by an inkjet method. The print also includes an inkjet imaging layer comprising a fluoroplastic. Such an inkjet image layer exhibits sufficient weatherability even without a topcoat. Therefore, the printed matter exhibits the desired color over a long period of time.

  (7) A base layer is further included between the substrate and the inkjet image layer, and the base layer further includes a base layer curing agent, and the crosslinking reaction initiation temperature of the base layer curing agent is The crosslinking reaction initiation temperature of the first layer curing agent is equal to or lower than the crosslinking reaction initiation temperature, and the crosslinking reaction initiation temperature of the first layer curing agent is equal to or lower than the crosslinking reaction initiation temperature of the second layer curing agent. Printed matter.

  According to such a configuration, the printed matter may form an inkjet image layer on the more firmly formed base layer. As a result, in the printed matter obtained, the ink jet image layer is unlikely to cause bleeding or the like.

  (8) The printed matter according to (6) or (7), wherein the base layer contains a fluorocarbon resin.

  According to such a configuration, excellent weather resistance is imparted not only to the ink jet image layer but also to the base layer. Therefore, the printed matter exhibits excellent weatherability not only in the area where the ink jet image layer is formed but also throughout.

  (9) The printed matter according to any one of (1) to (8), wherein the coloring material contains an inorganic pigment.

  According to such a configuration, the printed matter is less likely to be discolored due to the deterioration of the coloring material.

  (10) The printed matter according to any one of (1) to (9), wherein a top coat is further formed on the ink jet image layer.

  According to such a configuration, the printed matter can be imparted with further excellent weather resistance.

  (11) A method for producing a printed matter, comprising: applying an inkjet ink by an inkjet method on a substrate to form an inkjet image layer containing a coloring material and a fluorine resin.

  According to such a configuration, the present manufacturing method can manufacture a print having an ink jet image layer formed thereon by the ink jet method. The resulting printed matter comprises an inkjet imaging layer comprising a fluoroplastic. Such an inkjet image layer exhibits sufficient weatherability even without a topcoat. Therefore, according to the present manufacturing method, it is possible to manufacture a print exhibiting a desired color over a long period of time.

  (12) The inkjet ink includes a first inkjet ink containing the coloring material and a second inkjet ink containing no coloring material, and the fluorine resin includes the first inkjet ink and the second ink. The ink jet process includes a first layer forming process of applying the first ink jet ink onto the base material, and the ink jet process including the first layer being covered in the ink jet ink. (12) The method for producing a printed matter according to (11), including the step of forming a second layer by applying the inkjet ink of No.

  According to such a configuration, the present manufacturing method can form a desired inkjet image by the first layer containing the colorant. In addition, according to the present manufacturing method, the first layer can be covered by the second layer not containing the coloring material. According to this manufacturing method, the fluorocarbon resin is contained in at least one of the first layer and the second layer, so that the obtained inkjet image layer can be provided with excellent weather resistance.

  (13) The method for producing a printed matter according to (12), wherein the surface tension of the first inkjet ink is equal to or higher than the surface tension of the second inkjet ink.

  According to such a configuration, in the present manufacturing method, the second layer can be applied more uniformly.

  (14) The method further includes a base layer forming step of forming a base layer on the base, and the inkjet step is performed on the base on which the base layer is formed, (11) to (13) The manufacturing method of the printed matter in any one of-.

  According to such a configuration, the production method can produce a print having an inkjet image layer formed on the base layer by an inkjet method. The resulting printed matter comprises an inkjet imaging layer comprising a fluoroplastic. Such an inkjet image layer exhibits sufficient weatherability even without a topcoat. Therefore, according to the present manufacturing method, it is possible to manufacture a print exhibiting a desired color over a long period of time.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the printed matter and printed matter which formed the inkjet image layer which shows the outstanding weather resistance even when it is not provided with a topcoat by the inkjet system can be provided.

FIG. 1 is a schematic cross-sectional view for explaining the case where the ink jet image layer is a single layer in the printed matter according to the embodiment of the present invention. FIG. 2 is a schematic cross-sectional view for explaining the case where the inkjet image layer is two layers in the printed matter according to the embodiment of the present invention.

<Printed material>
The print of an embodiment of the present invention comprises a substrate and an inkjet imaging layer formed on the substrate. The inkjet image layer contains a colorant and a fluorine resin. Thus, in the printed matter of the present embodiment, an inkjet image layer is formed by the inkjet method. The print also includes an inkjet imaging layer comprising a fluoroplastic. Such an inkjet image layer exhibits sufficient weatherability even without a topcoat. Therefore, the printed matter exhibits the desired color over a long period of time. In the printed matter of the present embodiment, a base layer may be further included between the substrate and the inkjet image layer. Moreover, although the printed matter of this embodiment exhibits sufficient weather resistance even when the top coat is not provided, the top coat may be further provided so as to exhibit more excellent weather resistance. Each of these will be described below.

(Base material)
The substrate of the printed matter is not particularly limited. For example, the substrate is a steel plate, a metal plate such as aluminum or stainless steel, a plastic plate or film such as acrylic, polycarbonate, ABS, polypropylene, polyester, vinyl chloride or the like, a ceramic plate, concrete, wood, glass or the like. In addition, the base material includes cationic dyeable polyester (CDP) fiber, polyethylene terephthalate (PET) fiber, polybutylene terephthalate (PBT) fiber, polytrimethylene terephthalate (PTT) fiber, wholly aromatic polyester fiber, polylactic acid fiber, etc. Polyester fibers, acetate fibers, triacetate fibers, polyurethane fibers, nylon fibers, etc. or fabrics made of these composite fibers may be used. These may be suitably selected according to a use. When the substrate is a fabric, the fabric is preferably treated with a pretreatment agent before printing. As the pretreatment agent, water-soluble polymers, water-insoluble inert organic compounds, flame retardants, UV absorbers, reduction inhibitors, antioxidants, pH adjusters, hydrotropes, antifoaming agents, penetrants, microporous A forming agent etc. are illustrated. Examples of methods for applying these pretreatment agents to the fabric include a pad method, a spray method, an immersion method, a coating method, a laminating method, a gravure method, an inkjet method and the like.

(Base layer)
The base layer is a layer suitably provided between the substrate and the inkjet image layer. The base layer may be provided to make the surface of the substrate uniform or to improve the adhesion between the substrate and the inkjet image layer. The base layer can be formed by applying a base composition on a substrate.

  The resin composition which comprises a base composition is not specifically limited. As an example, the resin composition constituting the base composition is a polyester resin, a polyurethane resin, an acrylic resin, a silicone resin, an epoxy resin, an alkyd resin, an amino alkyd resin, a fluorine resin or the like. These may be used in combination. Among these, the base layer preferably contains a fluorine resin as a resin composition so as to impart excellent weather resistance. As the fluorine resin, one similar to the fluorine resin contained in the inkjet image layer described later can be used.

  When the base composition contains a fluorine resin, the content of the fluorine resin in the resin composition is preferably 5% by mass or more, and more preferably 10% by mass or more. Moreover, it is preferable to be contained so that it may be 80 mass% or less in a resin composition, and it is more preferable to be contained so that it may be 50 mass% or less in a resin composition. By containing the fluorine resin in the above range, the printed matter provided with the obtained base layer exhibits excellent weatherability not only in the ink jet image layer described later but also over the whole.

  The base composition is, if necessary, a curing agent, a dispersing agent, a slip agent, a thickener, an antisettling agent, an antifoaming agent, an antistatic agent, an antioxidant, a curing catalyst, an antiglare agent, a leveling agent, and a smooth An agent, an ultraviolet absorber, etc. may be blended.

  The method for forming the base layer on the substrate is not particularly limited. As an example, the base layer can be formed by applying the base composition on a substrate by a spray, roll coater, hand coating, inkjet method or the like.

  In the case where the base layer is provided, the thickness of the base layer is not particularly limited. As one example, the thickness of the base layer is preferably 5 μm or more in dry thickness, and more preferably 10 μm or more in dry thickness. The thickness of the base layer is preferably 100 μm or less in dry thickness, and more preferably 50 μm or less in dry thickness.

(Inkjet image layer)
The ink jet image layer is a layer formed on the above-described base material by the ink jet method, and mainly contains a color material and a fluorine resin. When the base layer is provided on the substrate, the inkjet image layer may be provided on the base layer. Such an inkjet image layer exhibits sufficient weatherability even without a topcoat. Hereinafter, each component mix | blended with the inkjet ink used for formation of an inkjet image layer is demonstrated. In the present embodiment, the inkjet image layer may be formed by a single inkjet ink, and is formed by a plurality of inkjet inks (for example, a first inkjet ink and a second inkjet ink described later) having different compositions. May be In the case where an inkjet image layer is formed by a plurality of inkjet inks, the coloring material may be contained in either one, and the fluorocarbon resin may be contained in at least one of them.

Color Material The color material may be various inorganic pigments or organic pigments. As the inorganic pigment, oxides, complex oxides, hydroxides, sulfides, ferrocyanides, chromates, carbonates, silicates, phosphates, carbons (carbon black), Metal powder etc. are illustrated. As organic pigments, nitroso, dyed lakes, azo lakes, insoluble azos, monoazos, disazos, condensed azos, benzimidazolones, phthalocyanines, anthraquinones, perylenes, quinacridones, dioxazines, Examples are isoindolines, azomethines, pyrrolopyrroles and the like. These may be used in combination. Among these, the printed matter of the present embodiment preferably contains an inorganic pigment as a coloring material, from the viewpoint of being less likely to cause fading due to deterioration of the coloring material.

  The content of the colorant is not particularly limited. As an example, the content of the coloring material in the inkjet ink is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. In addition, the content of the coloring material is preferably 30% by mass or less, and more preferably 20% by mass or less, in the inkjet ink. When the content of the colorant is less than 0.01% by mass, sufficient coloring tends not to be given. On the other hand, when the content of the coloring material exceeds 30% by mass, the viscosity of the inkjet ink tends to be high, and the ejection stability at the time of inkjet printing tends to be lowered.

-Fluorine resin Fluorine resin is blended in order to provide weather resistance to printed matter. The fluorine resin is not particularly limited. As an example, the fluorine resin is a copolymer of various fluorine-containing monomers and a vinyl monomer. Among these, among the vinyl monomers, the fluorine resin is preferably a copolymer with a vinyl ether monomer. The fluorine resin is more preferably a copolymer of fluoroethylene described later and a vinyl ether monomer.

  Examples of the fluorine-containing monomer include tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyl trifluoroethylene and the like. Among these, from the viewpoint of obtaining a printed product having excellent weather resistance, the fluorine-containing monomer is preferably fluoroethylene, and more preferably tetrafluoroethylene or chlorotrifluoroethylene.

  Examples of vinyl monomers include nonionic monoethylenically unsaturated monomers and difunctional vinyl monomers. Examples of nonionic monoethylenically unsaturated monomers include styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth) acrylamide, (meth) acrylic acid ester and the like. As (meth) acrylic acid ester, methyl acrylate, methyl methacrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl Examples include (meth) acrylate, oleyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate and the like. Examples of difunctional vinyl monomers include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butane-diol dimethacrylate, diethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate.

  As vinyl ethers, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane trivinyl ether Di or tri vinyl ether compounds such as vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-propyl vinyl Ether, isopropyl vinyl ether, isopropenyl ether -o- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether are exemplified.

  The copolymerization ratio of the fluorine-containing monomer and the vinyl monomer is not particularly limited. As an example, the copolymerization ratio is fluorine-containing monomer: vinyl monomer = 3 to 1 to 2 (weight ratio). When the copolymerization ratio is in such a range, the resulting printed matter is likely to exhibit excellent weatherability. The polymerization method is not particularly limited. As an example, the polymerization method is solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization and the like.

The obtained fluorocarbon resin may be any of an alternating copolymer, a block copolymer, a random copolymer, and a graft copolymer. Among these, the fluorine resin is preferably an alternating copolymer of fluoroethylene and a vinyl monomer. An inkjet ink containing such a fluorocarbon resin is likely to obtain a printed matter having further excellent weather resistance. In the present embodiment, “alternating copolymer” refers to a combination of a fluoroethylene unit and a vinyl monomer unit, a bond of a fluoroethylene unit and a fluoroethylene unit, and a vinyl monomer unit and a vinyl monomer unit. It means a copolymer containing much more than the sum of bonds of Specifically, it is preferable that the alternating copolymer of the present embodiment contains 90 to 100% by mole of a bond of a fluoroethylene unit and a vinyl monomer unit. In the present embodiment, the alternating copolymer may contain a small number of random bonding portions or block bonding portions. Also, the bonds can be distinguished by, for example, ¹ H NMR measurement and ²⁹ Si NMR measurement. In addition, for the analysis method of alternating copolymerizability, for example, Journal of Applied Polymer Science, Vol. 106, 1007-1013 (2007), etc. can be referred to.

  The fluorine resin of the present embodiment preferably has a hydroxyl value of 20 mg KOH / g or more, and more preferably 30 mg KOH / g or more. The fluorine resin preferably has a hydroxyl value of 100 mg KOH / g or less, more preferably 80 mg KOH / g or less. When the hydroxyl value is within the above range, the ink-jet ink is excellent in curability and more excellent in ejection stability at the time of ink jet printing. If the hydroxyl value is less than 20 mg KOH / g, it tends to be difficult to react with the curing agent. On the other hand, when the hydroxyl value exceeds 100 mg KOH / g, the dispersion system of the ink-jet ink tends to be unstable, and the ejection stability tends to decrease. In the present embodiment, the hydroxyl value means the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of the sample (solid content of the resin) is acetylated, It is a value measured by a method according to the method described in JIS K 0070.

  The fluorine resin preferably has an acid value of 5 mg KOH / g or less, more preferably 4 mg KOH / g or less. When the acid value is 5 mgKOH / g or less, the dispersion system of the ink-jet ink tends to be stable, and the ejection stability is excellent. On the other hand, when the acid value exceeds 5 mgKOH / g, the dispersion system of the ink jet ink tends to be unstable, and the discharge stability tends to decrease. In the present embodiment, the acid value refers to the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the sample (solid content of resin), as described in JIS K 0070. It is a value measured by a method according to the method.

  The fluororesin of the present embodiment is preferably of the solvent-soluble type. Specifically, in terms of solid content, the fluorine resin preferably has a solubility in diethylene glycol diethyl ether of 500 (g / L) or more, and more preferably 1000 (g / L) or more. When the solubility with respect to a glycol ether solvent is within the above range, repositioning of the fluorocarbon resin is unlikely to occur in the long term in the fluorocarbon resin, and the ejection stability at the time of inkjet printing is more excellent.

  Further, the fluorine resin of the present embodiment preferably has a solubility in water of 50 (g / L) or less, more preferably 30 (g / L) or less, in terms of solid content. Thereby, the printed matter obtained using such an inkjet ink becomes favorable in water resistance, and is further excellent in weather resistance. On the other hand, when the solubility in water exceeds 50 (g / L), the printed matter obtained using such an inkjet ink tends to have reduced water resistance.

  The fluorine resin of the present embodiment may be used in a state of being dispersed or dissolved in a predetermined solvent, or may be used in a solvent-free state (that is, solid to semi-solid state). However, depending on the type of solvent, the fluorine resin dispersed or dissolved in the solvent may damage the head during ink jet printing if it is contained in the ink jet ink. Therefore, it is preferable that the fluorine resin of the present embodiment does not contain such a poor solvent for head suitability, and it is more preferable to be in a non-solvent state. Such a non-solvent fluorine resin originally does not contain a solvent which is not excellent in head suitability, and therefore, the head of the ink jet recording apparatus is less likely to be damaged at the time of ink jet printing.

  The weight average molecular weight (Mw) of the fluorine resin is not particularly limited. If an example is given, it is preferable that Mw is 5000 or more, and it is more preferable that it is 8000 or more. The Mw is preferably 50,000 or less, more preferably 40,000 or less. When Mw is in the above range, the fluorine resin is easily soluble in the solvent. In addition, the drying property of the inkjet ink is improved, and the ejection stability at the time of inkjet printing is excellent. Furthermore, the printed matter obtained has less stickiness on the surface of the image layer, and is excellent in the blocking prevention property when the printed matter is overlapped. If the Mw is less than 5,000, the resulting printed matter tends to stick and the antiblocking properties tend to be reduced. On the other hand, when the Mw exceeds 50,000, the solubility of the fluorine resin tends to decrease, and the discharge stability of the inkjet ink at the time of inkjet printing tends to decrease. In the present embodiment, Mw is, for example, a value measured by GPC (gel permeation chromatography), and can be measured using a high-speed GPC apparatus (HLC-8120 GPC, manufactured by Tosoh Corp.).

  The content of the fluorine resin is not particularly limited. For example, in terms of solid content, the fluorocarbon resin in the inkjet ink is preferably 2% by mass or more, and more preferably 5% by mass or more. Further, the content of the fluorine resin in the ink-jet ink is preferably 40% by mass or less, and more preferably 30% by mass or less. When the content of the fluorine resin is 2% by mass or more, the discharge stability at the time of ink jet printing tends to be excellent. On the other hand, when the content of the fluorine resin exceeds 40% by mass, the viscosity of the inkjet ink tends to be high, and the ejection stability at the time of inkjet printing tends to be lowered.

(Optional ingredient)
The ink-jet ink can contain optional components well known in the field of ink-jet ink in addition to the above-mentioned color material and fluorine resin. For example, optional components include various binder resins (but excluding fluorine resin), various solvents, curing agents, curing catalysts, slip agents (leveling agents), dispersants, polymerization accelerators, polymerization inhibitors, permeation accelerators. Wetting agents (humectants), fixing agents, fungicides, preservatives, antioxidants, chelating agents, thickeners and the like.

Binder Resin A binder resin may be contained, for example, to adjust the viscosity of the ink-jet ink, or to adjust the hardness and control the shape of the resulting printed matter.

  The type of binder resin is not particularly limited. For example, the binder resin may be epoxy resin, diallyl phthalate resin, silicone resin, phenol resin, unsaturated polyester resin, polyimide resin, polyurethane resin, melamine resin, urea resin, ionomer resin, ionomer resin, ethylene ethyl acrylate resin, acrylonitrile acrylate styrene Copolymer resin, acrylonitrile styrene resin, acrylonitrile chloride polyethylene styrene copolymer resin, ethylene vinyl acetate resin, ethylene vinyl alcohol copolymer resin, acrylonitrile butadiene styrene copolymer resin, vinyl chloride resin, chlorinated polyethylene resin, polyvinylidene chloride resin, acetic acid Cellulose resin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyether ether Ton resin, polyether sulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene, polystyrene maleic acid copolymer resin, polystyrene acrylic acid copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin, acrylic resin, Examples thereof include methacrylic resin, methyl pentene resin, polylactic acid, polybutylene succinate resin, butyral resin, formal resin, polyvinyl alcohol, polyvinyl pyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and copolymer resins of these. The binder resin may be appropriately selected in consideration of film strength, viscosity, remaining viscosity of ink jet ink, dispersion stability of color material, thermal stability, non-coloring property, water resistance, and chemical resistance. The binder resin may be used in combination.

  Among these, the binder resin is preferably an acrylic resin, a vinyl chloride resin, or a silicone resin, from the viewpoint of excellent heat resistance and weather resistance.

  The acrylic resin is not particularly limited. As an example, the acrylic resin is exemplified by a polymer of acrylic acid ester (acrylate) or methacrylic acid ester (methacrylate). More specifically, acrylic resins include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, etc .; methyl methacrylate, methacrylic Alkyl esters of methacrylic acid such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate and 2-ethylhexyl methacrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, etc. Hydroxy group-containing acrylic acid esters; polymers such as hydroxy group-containing methacrylic acid esters such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and the like; . These may be used in combination.

  The weight average molecular weight (Mw) of the acrylic resin is not particularly limited. If an example is given, it is preferable that Mw is 5000 or more, and it is more preferable that it is 10000 or more. Mw is preferably 100,000 or less, more preferably 50,000 or less. When Mw is in the above range, the inkjet ink containing such an acrylic resin is excellent in the ejection stability at the time of inkjet printing.

  The vinyl chloride resin is not particularly limited. As an example, the vinyl chloride resin is exemplified by a copolymer of vinyl chloride and other monomers such as vinyl acetate, vinylidene chloride, acrylic acid, maleic acid, vinyl alcohol and the like. Among these, the vinyl chloride resin is preferably a copolymer (salt-and-pepper copolymer) containing a constituent unit derived from vinyl chloride and vinyl acetate.

  The salt-and-pepper copolymer can be obtained, for example, by suspension polymerization. It is preferable that a salt-and-vinegar copolymer contains 70 to 90% by mass of a vinyl chloride unit. If it is the said range, in order that it may melt | dissolve in a inkjet ink stably, a salt vinegar copolymer will be excellent in long-term storage stability. In addition, the inkjet ink is excellent in ejection stability.

  In addition to the vinyl chloride unit and the vinyl acetate unit, the salt-and-vinegar copolymer may have other structural units as needed. As an example, the other structural unit is exemplified by a carboxylic acid unit, a vinyl alcohol unit, a hydroxyalkyl acrylate unit and the like. Among these, the other structural unit is preferably a vinyl alcohol unit.

  The number average molecular weight (Mn) of the vinyl chloride resin is not particularly limited. If an example is given, it is preferable that Mn of a vinyl chloride resin is 10000 or more, and it is more preferable that it is 12000 or more. Further, Mn is preferably 50000 or less, more preferably 42000 or less. Mn can be measured by GPC and can be determined as a relative value in terms of polystyrene.

  The silicone resin is not particularly limited. As an example, silicone resins include methyl-based straight silicone resin (polydimethylsiloxane), methylphenyl-based straight silicone resin (polydimethylsiloxane in which a part of methyl group is substituted with phenyl group), acrylic resin-modified silicone resin, polyester Examples include resin-modified silicone resins, epoxy resin-modified silicone resins, alkyd resin-modified silicone resins, and rubber-based silicone resins. These may be used in combination. Among these, as the silicone resin, methyl-based straight silicone resin, methylphenyl-based straight silicone resin, and acrylic resin-modified silicone resin are preferable.

  The silicone resin may be dissolved in an organic solvent or the like. Examples of the organic solvent include xylene, toluene and the like.

  The number average molecular weight (Mn) of the silicone resin is not particularly limited. As an example, Mn of the silicone resin is preferably 10000 or more, and more preferably 20000 or more. Further, Mn is preferably 5,000,000 or less, and more preferably 3,000,000 or less. Mn can be measured by GPC and can be determined as a relative value in terms of polystyrene.

  Returning to the description of the entire binder resin, the content of the binder resin is not particularly limited. As an example, the binder resin is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more in terms of solid content in the inkjet ink. In addition, the binder resin is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less in the inkjet ink. When the content of the binder resin is less than 1% by mass, desired performance as a binder is difficult to be obtained, and adhesion to a substrate (or a base layer provided on the substrate) tends to be reduced. On the other hand, when the content of the binder resin exceeds 40% by mass, the viscosity of the inkjet ink tends to be high, and the ejection stability at the time of inkjet printing tends to be lowered.

Solvent The solvent is a liquid component for dissolving the binder resin in the inkjet ink. The type of solvent is not particularly limited. Examples of the solvent include water, glycol ether solvents, acetate solvents, alcohol solvents, ketone solvents, ester solvents, hydrocarbon solvents, fatty acid ester solvents, aromatic solvents and the like. These may be used in combination. Among these, the solvent of the present embodiment preferably contains at least one of a glycol ether solvent and an acetate solvent. Both glycol ether solvents and acetate solvents have a low viscosity and a relatively high boiling point. Therefore, the drying property is further improved and the inkjet ink containing these as a solvent is more excellent in discharge stability at the time of inkjet printing.

  Glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono (iso) propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n -Butyl ether, triethylene glycol monomethyl ether Ter, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono- n-Butyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, tri Chi glycol butyl methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether and the like.

  Acetate solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-sec-butyl ether acetate, Ethylene glycol monoisobutyl ether acetate, ethylene glycol mono-tert-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol Mono-n-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-ethoxybutyl Acetate, 3-Methyl-3-propoxybutyl acetate, 3-Methyl-3-isopropoxybutyl acetate, 3-Methyl-3-n-butoxyethyl acetate, 3-Methyl-3-isobutoxybutyl acetate, 3-Methyl Alkylene glycol monoalkyl ether acetates such as -3-sec-butoxycyclohexyl, 3-methyl-3-tert-butoxycyclohexyl, ethylene glycol Diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, and the like.

  The solvent of the present embodiment preferably has a boiling point of 150 ° C. or more, more preferably 180 ° C. or more. The solvent preferably has a boiling point of 300 ° C. or less, more preferably 280 ° C. or less. When the boiling point is in the above range, the drying property is further improved in the inkjet ink, and the ejection stability at the time of inkjet printing is more excellent. In addition, according to the inkjet ink, a clear printed matter with less bleeding is easily formed. When the boiling point of the solvent is less than 150 ° C., the inkjet ink tends to be dried in the vicinity of the head nozzle, and the ejection stability tends to be lowered. On the other hand, when the boiling point of the solvent exceeds 300 ° C., the ink-jet ink becomes difficult to dry, and the drying step at the time of formation of a print tends to take a long time. Also, the printed matter obtained tends to blur the image.

  The content of the solvent is not particularly limited. If an example is given, it is preferable that it is 50 mass% or more in an inkjet ink, and, as for a solvent, it is more preferable that it is 60 mass% or more. The solvent is preferably 99% by mass or less, and more preferably 80% by mass or less, in the inkjet ink. When the content of the solvent is less than 50% by mass, the viscosity of the inkjet ink tends to be high, and the ejection stability at the time of inkjet printing tends to be lowered. On the other hand, when the content of the solvent exceeds 99% by mass, the proportion of the binder resin which can be added to the ink-jet ink tends to be low, and it may be difficult to obtain desired performance.

Curing Agent A curing agent may be formulated to cure the inkjet ink. The curing agent is not particularly limited. For example, the curing agent may be a carbodiimide compound, an aziridine compound, a metal chelate compound, an isocyanate compound, a melamine compound, an epoxy compound, an oxazoline compound, a urea compound, a polyamine compound, a polyethyleneimine compound , Acrylamide compounds and the like. Curing agents may be used in combination. Among these, the curing agent preferably contains an isocyanate resin. Thereby, the printed matter obtained using such an inkjet ink is more excellent in a weather resistance.

  As the isocyanate resin, any compound having two or more isocyanate groups in one molecule may be used, and any of general-purpose type, light yellowing type, non-yellowing type and the like can be used. Examples of the general-purpose type include tolylene diisocyanate (TDI), isocyanurate which is a trimer of TDI, 4,4-diphenylmethane diisocyanate (MDI), and polymeric diphenylmethane diisocyanate (polymeric MDI). Xylylenediamine (XDI) etc. are illustrated as a non-yellowing type. Examples of the non-yellowing type include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI and the like. Among these, the curing agent preferably contains a non-yellowing blocked isocyanate, and more preferably a non-yellowing blocked isocyanate having an isocyanurate structure. An inkjet ink containing such a curing agent is more excellent in curability. Moreover, the printed matter obtained by using such an inkjet ink is further excellent in a weather resistance. Therefore, the printed matter tends to exhibit the desired color for a longer period of time.

  The content of the curing agent is not particularly limited. Since it changes also with the addition amount of a fluororesin, a hydroxyl value, and an acid value, it is not decided uniquely. As an example, the content of the curing agent in the ink-jet ink is preferably 0.1% by mass or more, and more preferably 1% by mass or more. The content of the curing agent is preferably 20% by mass or less, more preferably 10% by mass or less, in the inkjet ink. When the content of the curing agent is less than 0.1% by mass, the resin does not react sufficiently with the fluorine resin, and there is a tendency that desired performance can not be obtained. On the other hand, when the content of the curing agent exceeds 20% by mass, there is a possibility of excessive addition to the fluorocarbon resin, and the weather resistance of the resulting printed matter tends to decrease.

-Curing catalyst As a curing catalyst, organic acid salts of metal such as tin, titanium, zirconium, iron, antimony, bismuth, manganese, zinc, aluminum, alcoholates and chelate compounds; amines such as hexylamine and dodecylamine; hexyl acetate Examples thereof include amines, amine salts such as dodecylamine phosphate; quaternary ammonium salts such as benzyltrimethylammonium acetate; salts of alkali metals such as potassium acetate and the like. More specifically, organic bismuth compounds such as bismuth octylate, bismuth neodecanoate, dibutyltin dilaurate, dibutyltin dioctylate, dimethyltin dineodecanoate, organic tin compounds such as stannous octoate, tetrabutyl titanate, tetraisopropyl titanate, Examples include organic titanium compounds such as isopropoxy bis (acetylacetone) titanium and diisopropoxy bis (ethyl acetoacetate) titanium. These may be used in combination. In the present embodiment, the curing catalyst is preferably a tin-based compound, more preferably a dialkyltin-based compound such as dibutyltin dilaurate or dimethyltin dineodecanoate, and still more preferably dibutyltin dilaurate. When dibutyltin dilaurate is contained as a curing catalyst, the obtained inkjet ink has excellent curability.

  The content in the case where the curing catalyst is blended is not particularly limited. For example, the content of the curing catalyst in the ink-jet ink is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more. In addition, the content of the curing catalyst is preferably 5% by mass or less, and more preferably 3% by mass or less in the inkjet ink. When the content of the curing catalyst is less than 0.001% by mass, the performance as the curing catalyst tends not to be sufficiently exhibited. On the other hand, when the content of the curing catalyst exceeds 5% by mass, the curability of the inkjet ink tends to be high, and the ejection stability at the time of inkjet printing tends to be lowered.

Dispersant The dispersant is suitably contained to disperse the coloring material. The dispersant is not particularly limited. For example, the dispersant is an anionic surfactant, a nonionic surfactant, a polymer dispersant or the like. Dispersants may be used in combination.

  Anionic surfactants include fatty acid salts, alkyl sulfates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, lignin sulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalene sulfonate formalin condensates, poly Examples thereof include oxyethylene alkyl sulfates and substituted derivatives thereof.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethyleneoxy Propylene block polymers and their substituted derivatives are exemplified.

  The polymer dispersant preferably has both an acid value and a base value, and one having an acid value larger than the base value is preferable from the viewpoint of obtaining more stable dispersion characteristics. For example, polymer dispersants include PB series manufactured by Ajinomoto Fine Techno Co., Ltd., Hinoakt series manufactured by Kawaken Fine Chemicals Co., Ltd., Solsperse series manufactured by Nippon Lubrizol Co., Ltd., Kushimoto Kasei And the like, and Efka (registered trademark) series manufactured by BASF Japan Ltd. and the like.

  The content of the dispersant is appropriately determined depending on the type and the content of the colorant to be dispersed. If an example is given, it is preferable that it is 5 mass parts or more with respect to 100 mass parts of coloring materials, and, as for content of a dispersing agent, it is more preferable that it is 10 mass parts or more. Further, the content of the dispersing agent is preferably 150 parts by mass or less, and more preferably 80 parts by mass or less, with respect to 100 parts by mass of the coloring material. When the content of the dispersant is less than 5 parts by mass, the colorant tends to be difficult to be dispersed. On the other hand, when the content of the dispersant exceeds 150 parts by mass, the raw material cost tends to increase and the dispersion of the coloring material tends to be inhibited.

  Returning to the description of the entire inkjet ink, the viscosity of the inkjet ink is not particularly limited. The viscosity of the inkjet ink at 30 ° C. is preferably 5 mPa · s or more, and more preferably 6 mPa · s or more. The viscosity of the inkjet ink is preferably 30 mPa · s or less at 30 ° C., and more preferably 20 mPa · s or less. When the viscosity is in the above range, the inkjet ink is excellent in ejection stability. When the viscosity of the inkjet ink is less than 5 mPa · s, the ejection stability at the time of inkjet printing tends to be reduced. On the other hand, when the viscosity exceeds 30 mPa · s, the ink jet ink can not be successfully discharged from the head nozzle, and the discharge stability at the time of ink jet printing tends to be lowered. In the present embodiment, the viscosity can be measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., model number: TVB-20LT).

  In addition, the method of adjusting a viscosity in the said range is not specifically limited. As an example, the viscosity can be adjusted by the amount of addition of the fluorocarbon resin to be used, and the type and amount of addition of the solvent to be used. The viscosity may be adjusted using a viscosity modifier such as a thickener, if necessary.

  The surface tension of the inkjet ink is not particularly limited. The surface tension of the inkjet ink is preferably 20 dyne / cm or more at 25 ° C., and more preferably 22 dyne / cm or more. The surface tension of the ink-jet ink is preferably 40 dyne / cm or less at 25 ° C., and more preferably 38 dyne / cm or less. When the surface tension is within the above range, the inkjet ink is excellent in ejection stability. When the surface tension is less than 20 dyne / cm, the ink jet ink tends to be too wet and easy to be wet. On the other hand, when the surface tension exceeds 40 dyne / cm, the ink-jet ink tends to be easily repelled on the surface of the substrate (or the base layer if provided on the substrate), and the printed matter tends to be unclear. is there. In addition, in this embodiment, surface tension can be measured using a static surface tension meter (plate method) (seller: Kyowa Interface Science Co., Ltd. product, model number: CBVP-A3).

  In addition, the method of adjusting surface tension in the said range is not specifically limited. For example, the surface tension can be adjusted by adding an acrylic surface conditioner, a silicone surface conditioner, a fluorine surface conditioner, and the like.

  The wetting index of the ink jet image layer is not particularly limited. As an example, the wetting index of the inkjet image layer is preferably 20 dyne / cm or more, and more preferably 25 dyne / cm or more. The wetting index of the ink jet image layer is preferably 50 dyne / cm or less, more preferably 40 dyne / cm or less. When the wetting index is in the above range, the printed matter has an advantage that a uniform coating film can be easily obtained even when another ink, a paint, or the like is further applied on the ink jet image layer. In the present embodiment, the wetting index can be measured in accordance with the method described in JIS K 6768.

<Layer Configuration of Inkjet Image Layer>
Returning to the description of the entire inkjet image layer, the inkjet image layer of the present embodiment may be composed of a single layer or multiple layers. FIG. 1 is a schematic cross-sectional view of a print 1 on which a single-layer ink jet image layer 4 is formed. FIG. 2 is a schematic cross-sectional view of the printed matter 1a on which the inkjet image layers 4a of a plurality of layers (the first layer 41a and the second layer 42a) are formed. In the following description, the printed matter includes the case where the base layer is included. The base layer may be omitted as appropriate. If the base layer is omitted, an inkjet imaging layer may be formed on the substrate.

(When a single layer ink jet image layer is formed)
As shown in FIG. 1, the printed matter 1 includes a substrate 2, a base layer 3 formed on the substrate 2, and a single-layer inkjet image layer 4 formed on the base layer 3. The ink jet image layer 4 contains the coloring material and the fluorine resin as described above. Such an inkjet image layer contains a fluorine resin, and therefore exhibits sufficient weatherability even when no top coat is provided.

(When a plurality of inkjet image layers are formed)
On the other hand, the inkjet image layer may be composed of a plurality of layers. In FIG. 2, the printed matter 1a on which the two-layered inkjet image layer 4a is formed is illustrated. In this case, the printed matter 1 a includes a substrate 2, a base layer 3 formed on the substrate 2, and a plurality of inkjet image layers 4 a formed on the base layer 3. The ink jet image layer can be, for example, a layer containing a coloring material for one layer and a layer not containing a coloring material for the other layer. FIG. 2 exemplifies the case where the inkjet image layer 4a is composed of a first layer 41a containing a coloring material, and a second layer 42a covering the first layer 41a and not containing a coloring material. . As described above, when the ink jet image layer is composed of a plurality of layers, the printed matter is less likely to cause the dropout of the color material due to the deterioration of the resin as compared with the case where it is composed of a single layer. The printed matter can also be provided with a layer not containing a colorant so as to be interlocked with the first layer containing a colorant. Therefore, the printed matter in which the ink jet image layer is composed of a plurality of layers can be more easily expressed as a concavo-convex expression, and can be processed into an appearance with excellent designability. Furthermore, such a printed matter can be provided with functionality only where it is necessary, for example, by adding a functional pigment or the like to the second layer. The second layer 42a may be provided so as to cover the entire surface of the first layer 41a, or may be provided so as to cover a part thereof.

  In the embodiment, when the ink jet image layer is composed of a plurality of layers (for example, two layers), the fluorine resin may be contained in at least one of the first layer and the second layer. More preferably, the fluorine resin is contained in both the first layer and the second layer. Hereinafter, as an example, the case where a fluorine resin is included in both the first layer and the second layer will be described in detail.

First Layer The first layer can be formed by applying the first inkjet ink on the base layer by an inkjet method. The first inkjet ink has the same configuration as the above-described inkjet ink, and contains the above-described color material, a fluorine resin, and an optional component as appropriate.

  Among the optional components, the first inkjet ink of the present embodiment preferably contains an antioxidant. The antioxidant is not particularly limited. As an example, the antioxidant is a phenol-based antioxidant, a phosphorus-based antioxidant or the like.

  The phenolic antioxidant is preferably a hindered phenolic antioxidant. Hindered phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, C2-10 alkylenebis (tert-butylphenol) [eg, 2,2'-methylenebis (4-methyl-6-t) -Butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), etc.], tris (di-t-butyl-hydroxybenzyl) benzene [eg, 1,3,5-trimethyl-2,4 , 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene etc.], C 2-10 alkanediol-bis [(di-t-butyl-hydroxyphenyl) propionate] [eg, 1, 6 -Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], etc.], di- or trioxy C2- Alkanediol-bis (t-butyl-hydroxyphenyl) propionate [eg, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] etc., C3-8 alkanetriol -Bis [(di-t-butyl-hydroxyphenyl) propionate], C 4-8 alkanetetraol tetrakis [(di-t-butyl-hydroxyphenyl) propionate] [eg, pentaerythritol tetrakis [3- (3,5-, [Di-t-butyl-4-hydroxyphenyl) propionate], etc.], long-chain alkyl (di-t-butylphenyl) propionate [eg, n-octadecyl-3- (4 ′, 5′-di-t-butylphenyl)] ) Propionate, Stearyl-2- (3,5-di) t-Butyl-4-hydroxyphenyl) propionate and the like], 2-t-butyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenyl acrylate, 4,4′-thiobis (3-methyl-6-t-butylphenol) and the like are exemplified.

  The phosphorus antioxidant is a mono- to tris (branched C3-6 alkyl-phenyl) such as tris (2,4-di-t-butylphenyl) phosphite, bis (2-t-butylphenyl) phenyl phosphite and the like ) Phosphites; Aliphatic polymers such as bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite Branched compounds such as (branched C3-6 alkyl-aryl) phosphite of tetrahydric alcohol; tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite; Tris (2) Triphenyl phosphate compounds such as 4-di-t-butylphenyl) phosphate; metal salts of phosphoric acid, eg, primary phosphorus Calcium, alkali or alkaline earth metal phosphates such as monobasic sodium phosphate monohydrate (or its hydrate) and the like.

  When the antioxidant is contained, the content of the antioxidant is preferably 0.1% by mass or more based on the total amount of the first inkjet ink. The content of the antioxidant is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on the total amount of the first inkjet ink. When the content of the antioxidant is in the above range, deterioration of the first layer, particularly yellowing, of the resulting printed matter is easily prevented.

Second Layer The second layer may be formed by applying a second inkjet ink on the first layer by an inkjet method. The second inkjet ink has the same configuration as the above-described first inkjet ink except that the second inkjet ink does not contain a coloring material, and includes the above-described fluorocarbon resin and an optional component as appropriate.

  In the present embodiment, the second inkjet ink containing no coloring material means that the above-mentioned various inorganic pigments and organic pigments (that is, pigments mainly intended for coloring) are not contained. Therefore, the second inkjet ink may contain a pigment not mainly intended for coloring (for example, an extender pigment), various matting agents, and the like. Examples of extender pigments include calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide and talc. The matting agent is exemplified by silica, resin beads and the like. Thereby, the second layer may be formed as a layer exhibiting appropriate gloss. In addition, the second layer can be formed as a layer having a matte feeling. In addition, the second inkjet ink containing no colorant may contain a pigment for imparting various functionalities to the inkjet layer. Examples of such a pigment include silver nanoparticles for imparting an antimicrobial effect and the like, gold nanoparticles for imparting a deodorizing effect and the like, and metal particles such as zinc sulfide particles for imparting a light emitting effect and the like. .

  It is preferable that the 2nd inkjet ink of this embodiment contains a ultraviolet absorber or a light stabilizer among arbitrary components. These may be used in combination. UV absorbers or light stabilizers are preferably formulated to improve the weatherability of the print. That is, the second layer can reduce the amount of ultraviolet light transmitted to the first layer by containing the ultraviolet absorber. This prevents the deterioration of the first layer in the printed matter, and particularly reduces the delamination between the first layer and the second layer and the discoloration. As a result, the printed matter can exhibit a desired color for an even longer time.

  Examples of the UV absorber include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine derivatives, and salicylic acid derivatives. The benzotriazole-based UV absorbers are 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-) Hydroxy-5'-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3) '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4') Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, 2-{(2'-hydroxy-3 ', 3' ', 4' ', 5 '', 6 ''-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole and the like are exemplified. Benzophenone-based UV absorbers include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy -4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4 -Methoxy-5-sulfobenzophenone and the like are exemplified. The triazine derivative is 2- [4-{(2-hydroxy-3-dodecyloxy-propyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-. Triazine, 2- [4-{(2-hydroxy-3-tridecyloxy-propyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- {4- (Octyl-2-methylethanoate) oxy-2-hydroxyphenyl-4,6- {bis (2,4-dimethylphenyl)}-1,3,5-triazine [BASF Japan KK] Manufactured by trade name Tinuvin 479], tris [2,4,6- [2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl}]]-1,3,5-triadien Like it is exemplified. Examples of salicylic acid derivatives include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, p- (1,1,3,3-tetramethylbutyl) phenyl salicylate and the like. These may be used in combination. Among these, from the viewpoint of having an excellent ability to absorb ultraviolet light, the ultraviolet light absorber is selected from the group consisting of 2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl-4,6- {bis (2,4) It is preferable that it is -dimethylphenyl)}-1,3,5-triazine.

  The content of the ultraviolet absorber in the case where the ultraviolet absorber is blended is not particularly limited. As an example, the content of the ultraviolet light absorber in the second inkjet ink is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. The content of the ultraviolet light absorber in the second inkjet ink is preferably 10% by mass or less, and more preferably 5% by mass or less. When the content of the ultraviolet absorber is less than 0.01% by mass, the effect as the ultraviolet absorber tends not to be sufficiently exhibited. On the other hand, when the content of the ultraviolet absorber exceeds 10% by mass, no further effect can be obtained, and the cost tends to be high as the second inkjet ink.

-Light stabilizer A light stabilizer is suitably mix | blended in order to improve the weather resistance of printed matter. As a result, the printed matter can exhibit the desired color over a longer period of time.

  Examples of light stabilizers include hindered amine light stabilizers. The hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6- Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1 Undecyloxy-2,2,6,6-tetramethyl-4-piperidyl) carbonate, tetrakis (2,2,6,6-tetramethyl-4-piperidylbutane tetracarboxylate, tetrakis (1,2,2) 6,6,6-Pentamethyl-4-piperidylbutanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tri) Syl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) · di (tridecyl) -1,2,3,4-butanetetra Carboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2- (2-) Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / Dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6 -Bis ( 2,2,6,6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tertiary octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4 -Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1 , 5, 8, 12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl]- 1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -S-Triazin-6-ylaminoundecane, 1,6,11-to Squirrel [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylaminoundecane, bis (1-octyloxy Examples are -2,2,6,6- tetramethyl-4-piperidyl) -decanedioate and the like. These may be used in combination. Among these, a light stabilizer is bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) in that it is liquid and stable without reacting with other materials. Preferably it is decangioart.

  The content of the light stabilizer in the case where the light stabilizer is blended is not particularly limited. As an example, the content of the light stabilizer is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more in the second inkjet ink. In addition, the content of the light stabilizer is preferably 10% by mass or less, and more preferably 5% by mass or less in the second inkjet ink. When the content of the light stabilizer is less than 0.01% by mass, the effect as the light stabilizer tends not to be sufficiently exhibited. On the other hand, when the content of the light stabilizer exceeds 10% by mass, no further effect can be obtained, and the cost tends to be high as the second inkjet ink.

  The thickness of the second layer is not particularly limited. The thickness of the second layer may be, for example, a thickness required to sufficiently block ultraviolet rays transmitted to the first layer. When the ultraviolet absorber is contained in the second layer, the thickness of the second layer also varies depending on the content of the ultraviolet absorber. Therefore, the thickness of the second layer is not uniquely determined. As an example, the thickness of the second layer can be adjusted to 5 to 20 μm when a UV absorber (for example, Tinuvin 479) is blended at 2% by mass. Thereby, the ultraviolet light can be reduced by 70% or more by the second layer. Here, the ultraviolet light refers to a wavelength of 360 nm. As a result, in the printed matter, the deterioration of the first layer is prevented, and the delamination between the first layer and the second layer and the discoloration are particularly reduced. The extent to which the ultraviolet light has been reduced can be measured, for example, by an infrared visible spectrophotometer (UV-1700, manufactured by Shimadzu Corporation).

  The wetting indices of the first and second layers are both similar to the wetting index of the inkjet imaging layer described above. In the printed matter of the present embodiment, when an inkjet image layer comprising a plurality of layers is formed, the wetting index of the first layer is preferably equal to or higher than the wetting index of the second layer, and higher preferable. Thus, the printed matter can be uniformly applied without the second layer being flipped because the wetting index of the first layer is equal to or higher than the wetting index of the second layer.

  The first inkjet ink forming the first layer and the second inkjet ink forming the second layer may contain the same curing agent as the base layer and the inkjet ink described above. In the printed matter of the present embodiment, when the base layer, the first layer and the second layer contain a curing agent, the crosslinking initiation temperature (T1) of the curing agent (base layer curing agent) contained in the base layer, The crosslinking initiation temperature (T2) of the curing agent (first layer curing agent) contained in the first layer and the crosslinking initiation temperature (T3) of the curing agent (second layer curing agent) contained in the second layer are It is preferable that T1 ≦ T2 ≦ T3, and more preferably T1 <T2 ≦ T3. This allows the first layer to cure at the same or lower temperature as the second layer. Also, the base layer can be cured at the same or lower temperature as the first layer. As a result, the resulting print has an ink jet image layer formed on the more firmly formed base layer. Thus, the ink jet image is unlikely to cause bleeding or the like.

  Further, in the printed matter of the present embodiment, the crosslinking initiation temperature (T2) of the first layer curing agent and the crosslinking initiation temperature (T3) of the second layer curing agent satisfy T2 ≦ T3. preferable. This allows the first layer to cure at the same or lower temperature as the second layer. As a result, in the resulting printed matter, the second layer is formed on the more rigidly formed first layer. Thus, the ink jet image is unlikely to cause bleeding or the like.

  It is preferable that the above-mentioned fluorine resin is contained in a total amount of 4 to 40% by mass in the first inkjet ink constituting the first layer and the second inkjet ink constituting the second layer. In this case, the fluorocarbon resin is preferably contained in the first inkjet ink constituting the first layer so as to be 2 to 15% by mass. When the first inkjet ink contains the above-described content of the fluorine resin, the pigment is easily held by the coating film and is unlikely to be detached. The fluorine resin is preferably contained in the second inkjet ink constituting the second layer so as to be 2 to 25% by mass. By containing the fluorine resin having the above content in the second inkjet ink, the viscosity becomes appropriate, and the resulting printed matter tends to exhibit sufficient weather resistance.

  As mentioned above, the printed matter of this embodiment can form an inkjet image layer by an inkjet system. The print also includes an inkjet imaging layer comprising a fluoroplastic. Such an image layer exhibits sufficient weatherability even when no top coat is provided. Therefore, the printed matter exhibits the desired color over a long period of time.

<Production method of printed matter>
The method for producing a printed matter according to an embodiment of the present invention mainly includes an ink jet process of applying an ink jet ink by an ink jet method on a substrate to form an ink jet image layer containing a coloring material and a fluorine resin. According to the method of producing a printed matter of the present embodiment, the printed matter obtained is excellent in weather resistance. Therefore, the printed matter can exhibit a desired color over a long period of time. In addition, the method for producing a printed matter of the present embodiment may further include a base layer forming step of forming a base layer on a substrate. In this case, the above-described inkjet process may be performed on the base layer on which the base layer is formed. In the present embodiment, the case where the base layer forming step is performed and the inkjet step is performed on the base on which the base layer is formed will be illustrated. The details of the substrate, the base layer and the inkjet ink are the same as those described above in the embodiment of the printed matter.

(Base layer formation process)
In the base layer forming step, the method of applying the base composition on the substrate to form the base layer is not particularly limited. The base layer can be formed by applying the base composition onto the substrate by a spray, roll coater, hand coating, inkjet method or the like.

(Inkjet process)
In the inkjet process, the system for applying the inkjet ink on the base layer by the inkjet recording system is not particularly limited. Such methods include charge modulation method, micro dot method, charge injection control method, continuous method such as ink mist method, piezo method, pulse jet method, bubble jet (registered trademark) method, electrostatic suction method and the like. The demand system etc. are illustrated.

  In the case of forming an inkjet image layer comprising a plurality of layers (for example, the first layer and the second layer described above), the inkjet process comprises the first layer forming process of applying a first inkjet ink containing a coloring material onto the base layer And a second layer forming step of applying a second inkjet ink containing no coloring material so as to cover the first layer. The fluorine resin may be contained in at least one of the first inkjet ink and the second inkjet ink. The details of the first inkjet ink and the second inkjet ink are the same as those described above in the embodiment of the printed matter. According to such a manufacturing method, the desired ink jet image is formed by the first layer containing the colorant, and then the first layer is covered by the second layer not containing the colorant. Since the printed matter obtained contains a fluorine resin in at least one of the first layer and the second layer, excellent weatherability is imparted.

  In addition, when forming an inkjet image layer comprising a plurality of layers (for example, the first layer and the second layer described above), the surface tension of the first inkjet ink is adjusted to be equal to or higher than the surface tension of the second inkjet ink. Is preferred. Thereby, the second inkjet ink can be uniformly applied without being repelled.

  The substrate to which the inkjet ink has been applied is then dried. The drying conditions are not particularly limited. As an example, drying may be heat-treated at 50 to 250 ° C. for 1 to 60 minutes. Such drying can remove the solvent in the inkjet ink. Drying is preferably performed at the same time or immediately after application of the inkjet ink to the substrate in order to prevent bleeding of the inkjet image.

  The embodiments of the present invention have been described above with reference to the drawings. For example, the following modified embodiments can be adopted for the printed matter and the method for producing the printed matter according to the present invention.

  (1) In the said embodiment, it illustrated about the printed matter in which the top coat was not provided. Alternatively, the present invention may be provided with a topcoat to cover the inkjet imaging layer. In this case, the resulting printed matter may be further imparted with excellent weatherability.

  (2) In the said embodiment, it illustrated about the case where an inkjet image layer consists of two layers. Alternatively, in the present invention, the inkjet imaging layer may be composed of three or more layers. In this case, at least one of the layers constituting the ink jet image layer may contain a fluorine resin.

  (3) In the above embodiment, in the case where the ink jet image layer is composed of the first layer and the second layer, the case where the first layer and the second layer contain a fluorine resin is exemplified. Alternatively, in the present invention, the fluorine resin may be contained only in the first layer, or may be contained only in the second layer. If the fluorocarbon resin is contained only in the first layer, the printed matter can be produced relatively inexpensively. On the other hand, when the fluorocarbon resin is contained only in the second layer, the printed matter can reduce the reduction in surface gloss.

  (4) In the above-described embodiment (the method of producing a printed matter), the case where the base layer forming step is performed and the inkjet step is performed on the substrate on which the base layer is formed is illustrated. Alternatively, in the present invention, the base layer forming step may be omitted. In this case, the inkjet process is a process of applying an inkjet ink on the substrate by an inkjet method to form an inkjet image layer containing a color material and a fluorine resin.

  Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited to these examples.

The raw materials used are shown below.
(Fluororesin)
LF-200F: Trifluoroethylene / vinyl monomer alternating copolymer, manufactured by Asahi Glass Co., Ltd., hydroxyl value: 50 mg KOH / g, acid value: 0 mg KOH / g, Mw: 20000, nonvolatile content: 100%
Acrylic resin: BR-105: manufactured by Mitsubishi Rayon Co., Ltd., Mw: 50000
(Dispersant)
Solsparse 33000: Polymeric dispersant, 41.6 mg KOH / g base number, manufactured by Nippon Lubrizol (pigment)
Hostaperm Blue BT 617 D: Cyan organic pigment, manufactured by Clariant Dipyroxide Blue # 9410: Cyan inorganic pigment, manufactured by Dainichi Seika Kogyo Co., Ltd. (solvent)
DEDG: diethylene glycol diethyl ether, glycol ether solvents, boiling point: 189 ° C., Nippon Emulsifier MTEM: tetraethylene glycol dimethyl ether, glycol ether solvents, boiling point: 275 ° C., Toho Chemical Industries, Ltd. (curing agent)
X2252-2: block isocyanate, crosslinking reaction start temperature: 110 ° C., manufactured by Asahi Kasei Chemicals Corporation (catalyst)
Dibutyltin dilaurate: Metal compound catalyst (light stabilizer)
Tinuvin 123: HALS, manufactured by BASF Japan Ltd. (ultraviolet absorber)
Tinuvin 479: UVA, manufactured by BASF Japan Ltd. (wetting agent)
F-556: Fluorinated surfactant, manufactured by DIC Corporation (antioxidant)
IRGANOX 1010: manufactured by BASF Japan KK IRGAFOS 168: manufactured by BASF Japan KK

<Base composition>
The following were used as a base composition for forming a base layer.
Base composition 1: Super coat DB 5000 line (white polyester thermosetting paint, crosslinking reaction start temperature: 110 ° C., made by Taiho Paint Co., Ltd.)
Base composition 2: Bonflon # 1000 SR top coat (white fluorine-based thermosetting coating, crosslinking reaction initiation temperature: 90 ° C., AGC Cortec Co., Ltd.)

<First inkjet ink and second inkjet ink>
As the first inkjet ink for forming the first layer and the second inkjet ink for forming the second layer, the first inkjet inks 1 to 4 and the first inkjet ink on the basis of the formulations described in the following table, respectively Two inkjet inks 1 to 4 were prepared.

<Composition for top coat>
The second inkjet ink 4 was used as a topcoat composition for forming a topcoat.

(viscosity)
It measured on 30 degreeC conditions using a Brookfield viscometer (Toki Sangyo Co., Ltd. product, TVB-20LT).
(surface tension)
The surface tension was measured using a static surface tension meter (plate method) (CBVP-A3, manufactured by Kyowa Interface Science Co., Ltd.).

(Examples 1 to 11, Comparative Examples 1 to 4)
Each layer (base layer, ink jet image layer, top coat as needed) was formed by the following method according to the formulation shown in Table 2 below, and a print was produced. In Examples 1 to 3 and Comparative Example 1, a single-layer ink jet image layer was formed using only the first ink jet ink. Others formed an inkjet imaging layer consisting of multiple layers (two layers). The top coat was provided only in Example 11 and Comparative Example 4.

(Example 12)
A print was produced in the same manner as in Example 1 except that the base layer was not formed, and the inkjet image layer was formed directly on the substrate.

(Formation of base layer)
In the case of using the base composition 1, the base composition 1 is applied about 150 g / m ² (dry film thickness is about 25 μm) to the base material (aluminum steel plate subjected to chromate treatment) by air spray. Drying for a minute was performed.
In the case of using the base composition 2, the base composition 2 is applied about 150 g / m ² (dry film thickness is about 25 μm) to the base material (aluminum steel sheet subjected to chromate treatment) by air spray. Drying for a minute was performed.

(Formation of inkjet image layer)
An inkjet image layer was formed on a substrate (or a substrate on which a base layer was formed) according to the following inkjet conditions.
<Ink jet conditions>
Ink jet recording device: Piezo method Nozzle diameter: 40 μm
Driving voltage: 70V
Ink dot size: 30 pl
Frequency: 12kHz
Resolution: 400 x 800 dpi
Substrate temperature: 60 ° C (warming)
Evaluation pattern: 100 mm square solid pattern <drying conditions>
Heat drying (200 ° C environment, 1 minute)

(Formation of top coat)
As a top coat composition, the second inkjet ink 4 was applied by air spray at about 150 g / m ² (dry film thickness of about 30 μm), and dried for 1 minute in a 200 ° C. environment.

  The prints obtained in Examples 1 to 12 and Comparative Examples 1 to 4 were evaluated based on the following evaluation method and evaluation criteria. The results are shown in Table 2.

<Discoloration ΔE>
After performing UV irradiation for 6 hours (UV condition 100 mW / cm ² , temperature 63 ° C., humidity 50%) as a super accelerated weathering test using a super UV tester (SUV-W161 manufactured by Iwasaki Electric Co., Ltd.) on printed matter Then, after 30 seconds of showering, condensation was carried out for 2 hours, and a cycle of 2 hours was carried out for a total of 1000 hours. The ΔE before and after the test was taken as the color difference. The color difference was measured using a spectrophotometer (CM-3700, manufactured by Konica Minolta Co., Ltd.).
(Evaluation criteria)
A: color difference was ΔE ≦ 3 ○: color difference was 3 <ΔE ≦ 8 Δ: color difference was 8 <ΔE ≦ 16 C: color difference was ΔE> 16 <gloss retention>
The gloss retention was the ratio of the gloss after the test to that before the super accelerated weathering of the print. The glossiness was measured using a gloss checker (IG-410, manufactured by Horiba, Ltd.).
(Evaluation criteria)
A: Gloss retention was 50% or more B: Gloss retention was 30% or more and less than 50% C: Gloss retention was 10% or more and less than 30% C: Gloss retention Rate was less than 10% <Peeling of coating film>
According to JIS K 5400, the sample after super accelerated weathering test was subjected to cross-cut tape peeling (1 mm width, 100 mass) test to confirm peeling of the coating film.
(Evaluation criteria)
○: The coating did not peel off Δ: The coating was partially peeled off ×: The coating was entirely peeled off

  As shown in Table 2, the printed matter of Examples 1 to 12 is less likely to discolor any of the formed inkjet image layers and less likely to lose gloss, as compared to the printed matter of Comparative Examples 1 to 4, And it was hard to peel off. In particular, as can be seen from Example 1 and Example 12, the printed matter of the present invention has an ink jet image layer formed on the base material on which the ink jet image layer is formed directly on the base material and on the base layer. In both cases, it was found that an ink jet image layer was formed which was less likely to discolor, less likely to lose gloss, and less likely to come off. In addition, since the printed matter of Example 9 exhibited excellent weather resistance comparable to that of the printed matter of Example 11 provided with a top coat, the present invention relates to the case where no top coat is provided. It was also found that they exhibit excellent weatherability.

1, 1a Printed matter 2 base material 3 base layer 4, 4a inkjet image layer 41a first layer 42a second layer

Claims (14)

A substrate, and an inkjet imaging layer formed on the substrate,
The inkjet image layer contains a color material and a fluorine resin. The inkjet image layer includes a first layer containing the coloring material, and a second layer covering the first layer and containing no coloring material.
The printed matter according to claim 1, wherein the fluorine resin is included in at least one of the first layer and the second layer.   The printed matter according to claim 2, wherein the first layer contains an antioxidant.   The printed matter according to claim 2, wherein the second layer contains a UV absorber or a light stabilizer. The first layer further comprises a first layer curing agent,
The second layer further comprises a second layer curing agent,
The printed matter according to any one of claims 2 to 4, wherein a crosslinking reaction initiation temperature of the first layer curing agent is equal to or lower than a crosslinking reaction initiation temperature of the second layer curing agent.   The printed matter according to any one of claims 1 to 5, further comprising a base layer between the substrate and the ink jet image layer. A base layer is further included between the substrate and the inkjet imaging layer,
The base layer further comprises a base layer curing agent,
The crosslinking reaction initiation temperature of the base layer curing agent is not higher than the crosslinking reaction initiation temperature of the first layer curing agent,
The printed matter according to claim 5, wherein a crosslinking reaction initiation temperature of the first layer curing agent is equal to or lower than a crosslinking reaction initiation temperature of the second layer curing agent.   The printed matter according to claim 6, wherein the base layer contains a fluorocarbon resin.   The printed matter according to any one of claims 1 to 8, wherein the colorant contains an inorganic pigment.   The printed matter according to any one of claims 1 to 9, wherein a top coat is further formed on the ink jet image layer.   A method for producing a printed matter, comprising: an inkjet step of applying an inkjet ink by an inkjet method on a substrate to form an inkjet image layer containing a coloring material and a fluorine resin. The inkjet ink includes a first inkjet ink containing the coloring material and a second inkjet ink containing no coloring material.
The fluorine resin is included in at least one of the first inkjet ink and the second inkjet ink.
The ink jet process includes a first layer forming process for applying the first ink jet ink onto the substrate, and a second layer forming process for applying the second ink jet ink so as to cover the first layer. A method of producing a printed matter according to claim 11, comprising   The method for producing a print according to claim 12, wherein the surface tension of the first inkjet ink is equal to or higher than the surface tension of the second inkjet ink. Further comprising a base layer forming step of forming a base layer on the substrate,
The method for producing a print according to any one of claims 11 to 13, wherein the inkjet process is performed on the substrate on which the base layer is formed.

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