阅读说明：本技术 印刷物和印刷物的制造方法 (Printed matter and method for producing printed matter ) 是由 河村明广 于 2018-02-13 设计创作，主要内容包括：一种印刷物,其包含基材和形成在基材上的喷墨图像层,喷墨图像层包含色材和氟树脂。(A printed matter includes a substrate and an inkjet image layer formed on the substrate, the inkjet image layer including a coloring material and a fluororesin.)

1. A printed matter comprising a substrate and an inkjet image layer formed on the substrate, the inkjet image layer comprising a coloring material and a fluororesin.

2. The printed matter according to claim 1,

the inkjet image layer includes a first layer containing the color material, and a second layer covering the first layer and containing no color material,

the fluororesin is contained in at least either one of the first layer or the second layer.

3. The printed matter according to claim 2, wherein the first layer comprises an antioxidant.

4. A printed matter according to claim 2 or 3, wherein the second layer comprises an ultraviolet absorber or light stabilizer.

5. The printed matter according to any one of claims 2 to 4,

the first layer further comprises a curing agent for the first layer,

the second layer further comprises a curing agent for the second layer,

the crosslinking reaction initiation temperature of the curing agent for the first layer is not higher than the crosslinking reaction initiation temperature of the curing agent for the second layer.

6. A printed article according to any one of claims 1 to 5, further comprising a matrix layer between the substrate and the inkjet image layer.

7. The printed matter according to claim 5,

further comprising a matrix layer between the substrate and the ink jet image layer,

the base layer further comprises a base layer curing agent,

the crosslinking reaction initiation temperature of the curing agent for the base layer is not higher than the crosslinking reaction initiation temperature of the curing agent for the first layer,

the crosslinking reaction initiation temperature of the curing agent for the first layer is not higher than the crosslinking reaction initiation temperature of the curing agent for the second layer.

8. The printed matter according to claim 6 or 7, wherein the base layer contains a fluororesin.

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

10. A printed matter according to any one of claims 1 to 9, wherein a top coat layer is further formed on the inkjet image layer.

11. A method for producing a printed matter, comprising the following ink-jet step: an inkjet image layer containing a coloring material and a fluororesin is formed by applying an inkjet ink to a substrate by an inkjet method.

12. The method for manufacturing a printed matter according to claim 11,

the inkjet ink contains a first inkjet ink containing the color material and a second inkjet ink containing no color material,

the fluororesin is contained in at least either one of the first inkjet ink and the second inkjet ink,

the inkjet process includes: a first layer forming step of applying the first inkjet ink to the substrate, and a second layer forming step of applying the second inkjet ink so as to cover the first layer.

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

14. The method for producing a printed matter according to any one of claims 11 to 13,

further comprising a base layer forming step of forming a base layer on the base material,

the ink jet process is performed on the base material on which the base layer is formed.

Technical Field

The present invention relates to a printed matter and a method for manufacturing the printed matter. More specifically, the present invention relates to a printed matter exhibiting excellent weather resistance even when a topcoat layer is not provided on an inkjet image layer, and a method for producing the printed matter.

Background

In recent years, a composition containing a fluororesin has attracted attention as a composition for producing a printed matter having excellent weather resistance. For example, patent document 1 discloses a fluorine coating composition comprising: a main agent comprising a copolymer containing a fluoroolefin or the like, and a curing agent comprising a polyisocyanate compound.

Disclosure of Invention

However, a technique for obtaining a printed matter having excellent weather resistance by a method other than the method of applying the coating composition is not known. In addition, conventionally, after forming an image, a topcoat layer is sometimes provided in order to impart weather resistance. However, when the top coat layer is applied by coating after the composition is applied by a method other than coating (for example, an ink jet method), the production process becomes complicated.

The present invention has been made to solve the above problems, and an object thereof is to provide a printed matter on which an inkjet image layer exhibiting excellent weather resistance is formed by an inkjet method even when a topcoat layer is not provided, and a method for producing the printed matter.

A printed matter according to an embodiment of the present invention to solve the above problems includes a base material and an inkjet image layer formed on the base material, and the inkjet image layer includes a coloring material and a fluororesin.

In addition, a method for manufacturing a printed matter according to an embodiment of the present invention for solving the above problems includes an inkjet step of: an inkjet image layer containing a coloring material and a fluororesin is formed by applying an inkjet ink to a substrate by an inkjet method.

Drawings

Fig. 1 is a schematic cross-sectional view for explaining a case where an inkjet image layer is a single layer in a printed matter according to an embodiment of the present invention.

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

Detailed Description

< printed matter >

A printed matter according to one embodiment of the present invention includes a substrate and an inkjet image layer formed on the substrate. The inkjet image layer includes a coloring material and a fluororesin. As described above, in the printed matter of the present embodiment, the inkjet image layer is formed by the inkjet method. In addition, the printed matter includes an inkjet image layer containing a fluororesin. Such an inkjet image layer exhibits sufficient weatherability even when the topcoat layer is not provided. Therefore, the printed matter displays a desired color for a long period of time. The printed matter of the present embodiment may further include a base layer between the base material and the inkjet image layer. In addition, although the printed matter of the present embodiment exhibits sufficient weather resistance even when the topcoat layer is not provided, a topcoat layer may be further provided to exhibit more excellent weather resistance. The following describes various aspects.

(substrate)

The base material of the printed matter is not particularly limited. Examples of the substrate include metal plates such as steel plate, aluminum, and stainless steel; plastic plates or films such as acryl, polycarbonate, ABS, polypropylene, polyester, vinyl chloride, etc.; ceramic plates, concrete, wood, glass, etc. The base material may be polyester fibers such as Cationic Dyeable Polyester (CDP) fibers, polyethylene terephthalate (PET) fibers, polybutylene terephthalate (PBT) fibers, polytrimethylene terephthalate (PTT) fibers, wholly aromatic polyester fibers, and polylactic acid fibers; and a fabric made of acetate fibers, triacetate fibers, polyurethane fibers, nylon fibers, or a composite fiber thereof. These may be appropriately selected depending on the purpose. When the base material is a fabric, the fabric is preferably treated with a pretreatment agent before printing. Examples of the pretreatment agent include a water-soluble polymer, a water-insoluble inactive organic compound, a flame retardant, an ultraviolet absorber, an anti-reducing agent, an antioxidant, a pH adjuster, a water solubility promoter, an antifoaming agent, a penetrant, and a pore-forming agent. Examples of the method for applying these pretreatment agents to the fabric include a filling method, a spraying method, a dipping method, a coating method, a laminating method, a gravure method, an ink jet method, and the like.

(substrate layer)

The base layer is preferably a layer disposed between the substrate and the ink jet image layer. The base layer may be provided to make the surface of the base material uniform or to improve the adhesion between the base material and the inkjet image layer. The matrix layer may be formed by imparting a matrix composition on the substrate.

The resin composition constituting the matrix composition is not particularly limited. Examples of the resin composition constituting the matrix composition include polyester resins, polyurethane resins, acrylic resins, silicone resins, epoxy resins, alkyd resins, aminoalkyd resins, fluorine resins, and the like. These may be used in combination. Of these, the base layer preferably contains a fluororesin as a resin composition in order to impart excellent weather resistance. As the fluororesin, the same fluororesin as that contained in the inkjet image layer described later can be used.

In the case where the fluorine-containing resin is contained in the base composition, the fluorine-containing resin is contained in the resin composition preferably at 5% by mass or more, more preferably at 10% by mass or more. The fluororesin is preferably contained in the resin composition in an amount of 80% by mass or less, more preferably 50% by mass or less. By including the fluororesin in the above range, the printed matter including the obtained base layer exhibits excellent weather resistance not only in the inkjet image layer described later but also in the whole.

The base composition may contain a curing agent, a dispersant, a slip agent, a thickener, a sedimentation preventing agent, an antifoaming agent, an antistatic agent, an antioxidant, a curing catalyst, an antiglare agent, a leveling agent, a smoothing agent, an ultraviolet absorber, and the like as required.

The method for forming the base layer on the base material is not particularly limited. For example, the base layer can be formed by applying the base composition to the base material by spray coating, roll coating, manual coating, ink jet method, or the like.

When the base layer is provided, the thickness of the base layer is not particularly limited. For example, the thickness of the base layer is preferably 5 μm or more in terms of dry film thickness, and more preferably 10 μm or more in terms of dry film thickness. The thickness of the base layer is preferably 100 μm or less in terms of dry film thickness, and more preferably 50 μm or less in terms of dry film thickness.

(ink-jet image layer)

The inkjet image layer is a layer formed on the substrate by an inkjet method, and mainly includes a coloring material and a fluororesin. In the case where the base layer is provided on the base material, the ink jet image layer may be provided on the base layer. Such an inkjet image layer exhibits sufficient weatherability even when the topcoat layer is not provided. The components to be mixed in the inkjet ink used for forming the inkjet image layer will be described below. In the present embodiment, the inkjet image layer may be formed of a single inkjet ink or may be formed of a plurality of inkjet inks having different compositions (for example, a first inkjet ink and a second inkjet ink described later). In the case where the inkjet image layer is formed by a plurality of inkjet inks, the colorant may be contained in any one, and the fluororesin may be contained in at least any one.

Color material

The color material may be various inorganic pigments or organic pigments. Examples of the inorganic pigment include oxides, composite oxides, hydroxides, sulfides, ferrocyanides, chromates, carbonates, silicates, phosphates, carbons (carbon black), and metal powders. Examples of the organic pigment include nitroso-based pigments, dye lakes (dye レー キ), azo lakes, insoluble azo pigments, monoazo pigments, bisazo pigments, condensed azo pigments, benzimidazolone pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindoline pigments, azomethine pigments, pyrrolopyrrole pigments, and the like. These may be used in combination. Among these, it is preferable to include an inorganic pigment as the color material from the viewpoint that the printed matter of the present embodiment is less likely to suffer discoloration due to deterioration of the color material.

The content of the color material is not particularly limited. For 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. The content of the coloring material in the inkjet ink is preferably 30% by mass or less, and more preferably 20% by mass or less. When the content of the color material is less than 0.01% by mass, sufficient coloring tends not to be performed. On the other hand, when the content of the color material exceeds 30% by mass, the viscosity of the inkjet ink tends to be high, and the discharge stability during inkjet printing tends to be low.

Fluorine resin

The fluororesin is compounded for imparting weather resistance to the printed matter. The fluororesin is not particularly limited. For example, the fluororesin is a copolymer of various fluorine-containing monomers and a vinyl monomer. Of these, the fluororesin is preferably a copolymer of a fluorine-containing monomer and a vinyl ether monomer among vinyl monomers. The fluororesin is more preferably a copolymer of vinyl fluoride and a vinyl ether monomer described later.

Examples of the fluorine-containing monomer include tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, and trifluoromethyltrifluoroethylene. Among these, the fluorine-containing monomer is preferably vinyl fluoride, and more preferably tetrafluoroethylene or chlorotrifluoroethylene, from the viewpoint of obtaining a printed matter exhibiting excellent weather resistance.

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

Examples of the vinyl ether include: di-or trivinyl ether compounds such as 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, cyclohexanedimethanol divinyl ether, and trimethylolpropane trivinyl ether; and monovinyl ether compounds such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol 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.

The copolymerization ratio of the fluorine-containing monomer and the vinyl monomer is not particularly limited. For example, the copolymerization ratio is the fluorine-containing monomer: 3-1% of vinyl monomer: 1 to 2 (by weight). When the copolymerization ratio is within such a range, the resulting printed matter tends to exhibit excellent weather resistance. The polymerization method is not particularly limited. As an example, the polymerization method is solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization or the like.

The fluororesin obtained may be any of an alternating copolymer, a block copolymer, a random copolymer, and a graft copolymer. Of these, the fluororesin is preferably an alternating copolymer of vinyl fluoride and a vinyl monomer. An inkjet ink containing such a fluororesin can easily provide a printed matter having further excellent weather resistance. In the present embodiment, the "alternating copolymer" means: a copolymer containing a bond between a vinyl fluoride unit and a vinyl monomer unit which is far more than the total of a bond between a vinyl fluoride unit and a bond between a vinyl monomer unit and a vinyl monomer unit. Specifically, the alternating copolymer of the present embodiment preferably contains 90 to 100 mol% of a bond between a vinyl fluoride unit and a vinyl monomer unit. In the present embodiment, the alternating copolymer may contain a small amount of a random bonding portion or a block bonding portion. In addition, the above-mentioned bond may be, for example, formed by¹H NMR determination and²⁹si NMR measurement, etc. For the method of analyzing the alternating copolymerization, for example, Journal of Applied Polymer Science, Vol.106,1007-1013(2007) and the like can be referred to.

The hydroxyl value of the fluororesin of the present embodiment is preferably 20mgKOH/g or more, and more preferably 30mgKOH/g or more. The hydroxyl value of the fluororesin is preferably 100mgKOH/g or less, more preferably 80mgKOH/g or less. When the hydroxyl value is within the above range, the inkjet ink has excellent curability and further has excellent ejection stability during inkjet printing. When the hydroxyl value is less than 20mgKOH/g, the reaction with the curing agent tends to be difficult. On the other hand, when the hydroxyl value exceeds 100mgKOH/g, the dispersion system of the ink-jet ink tends to be unstable, and the ejection stability tends to be lowered. In the present embodiment, the hydroxyl value represents the number of mg of potassium hydroxide required for neutralizing acetic acid bonded to a hydroxyl group when 1g of a sample (solid content of a resin) is acetylated, and is a value measured by a method according to the method described in JIS K0070.

The acid value of the fluororesin is preferably 5mgKOH/g or less, more preferably 4mgKOH/g or less. When the acid value is 5mgKOH/g or less, the dispersion system of the ink-jet ink is easily stabilized, and the ejection stability is excellent. On the other hand, when the acid value exceeds 5mgKOH/g, the dispersion system of the ink-jet ink tends to be unstable, and the ejection stability tends to be lowered. In the present embodiment, the acid value represents the mass (mg) of potassium hydroxide required for neutralizing the acidic component contained in 1g of the sample (solid component of the resin), and is a value measured by a method according to the method described in JIS K0070.

The fluororesin of the present embodiment is preferably solvent-soluble. Specifically, the solubility of the fluororesin in diethylene glycol diethyl ether is preferably 500(g/L) or more, more preferably 1000(g/L) or more, in terms of solid content. When the solubility of the fluororesin in the glycol ether solvent is within the above range, the inkjet ink is less likely to cause reprecipitation of the fluororesin over a long period of time, and the ejection stability during inkjet printing is more excellent.

The solubility of the fluororesin of the present embodiment in terms of solid content in water is preferably 50(g/L) or less, and more preferably 30(g/L) or less. As a result, a printed material obtained using such an inkjet ink has good water resistance and excellent weather resistance. On the other hand, if the solubility to water exceeds 50(g/L), the water resistance of a printed matter obtained using such an inkjet ink tends to decrease.

The fluororesin 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 (i.e., solid to semisolid state) containing no solvent. However, if the fluororesin dispersed or dissolved in the solvent is contained in the inkjet ink depending on the kind of the solvent, the inkjet head may be damaged in the inkjet printing. Therefore, the fluororesin of the present embodiment preferably does not contain such a solvent having insufficient ink jet compatibility, and more preferably is in a solvent-free state. Such a solvent-free fluororesin does not inherently contain a solvent having an insufficient ink-jet head suitability, and therefore, is less likely to damage the ink-jet head of an ink-jet recording apparatus during ink-jet printing.

The weight average molecular weight (Mw) of the fluororesin is not particularly limited. For example, Mw is preferably 5000 or more, and more preferably 8000 or more. Mw is preferably 50000 or less, more preferably 40000 or less. When Mw is within the above range, the fluororesin is easily dissolved in the solvent. Further, the drying property of the inkjet ink is improved, and the ejection stability at the time of inkjet printing is excellent. Further, the obtained printed matter had less stickiness on the surface of the image layer, and was excellent in blocking prevention property when the printed matters were stacked. When Mw is less than 5000, the resulting printed matter tends to be sticky or have reduced blocking resistance. On the other hand, when Mw exceeds 50000, the solubility of the fluororesin tends to be lowered, or the discharge stability of the inkjet ink tends to be lowered at the time of inkjet printing. In the present embodiment, Mw is a value measured by GPC (gel permeation chromatography), for example, and can be measured by using a high performance GPC apparatus (HLC-8120 GPC, manufactured by Tosoh corporation).

The content of the fluororesin is not particularly limited. For example, the fluororesin is preferably 2% by mass or more, more preferably 5% by mass or more in the inkjet ink in terms of solid content. The fluororesin is preferably 40% by mass or less, more preferably 30% by mass or less in the inkjet ink. When the content of the fluororesin is 2% by mass or more, the discharge stability in the ink jet printing tends to be excellent. On the other hand, if the content of the fluororesin exceeds 40% by mass, the viscosity of the inkjet ink tends to be high, and the discharge stability during inkjet printing tends to be low.

(optional Components)

The inkjet ink may contain any component known in the field of inkjet inks, in addition to the above color material and fluororesin. As an example, the optional components include various binder resins (excluding fluorine resins), various solvents, curing agents, curing catalysts, slip agents (leveling agents), dispersing agents, polymerization promoters, polymerization inhibitors, permeation promoters, wetting agents (humectants), fixing agents, antifungal agents, preservatives, antioxidants, chelating agents, and thickening agents.

Binder resin

The binder resin may be contained for adjusting the viscosity of the inkjet ink, or adjusting the hardness and controlling the shape of the obtained printed matter, for example.

The kind of the binder resin is not particularly limited. As an example, the binder resin may be exemplified by: epoxy resin, diallyl phthalate resin, silicone resin, phenol resin, unsaturated polyester resin, polyimide resin, polyurethane resin, melamine resin, urea resin, ionomer resin, ethylene-ethyl acrylate resin, acrylonitrile-acrylate-styrene copolymer resin, acrylonitrile styrene resin, acrylonitrile chlorinated 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, cellulose acetate resin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyether ether ketone resin, polyether sulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene-maleic acid copolymer resin, poly (ethylene-co-vinyl acetate copolymer resin, poly (ethylene-co-vinyl acetate-styrene copolymer resin), poly (ethylene-co-vinyl acetate-styrene copolymer resin), poly (ethylene-vinyl acetate-, Polystyrene acrylic copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin, acrylic resin, methacrylic resin, methylpentene resin, polylactic acid, polybutylene succinate resin, butyral resin, methylal resin, polyvinyl alcohol, polyvinyl pyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and copolymer resins thereof, and the like. The binder resin may be appropriately selected in consideration of film strength, viscosity, residual viscosity of the inkjet ink, dispersion stability of the coloring material, thermal stability, non-coloring property, water resistance, and chemical resistance. Binder resins 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. For example, the acrylic resin may be a polymer of Acrylate or Methacrylate. More specifically, the acrylic resin may be exemplified by: alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate; hydroxyl-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate; hydroxyl group-containing polymers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. These may be used in combination.

The weight average molecular weight (Mw) of the acrylic resin is not particularly limited. For example, Mw is preferably 5000 or more, and more preferably 10000 or more. Mw is preferably 100000 or less, more preferably 50000 or less. When Mw is within the above range, the inkjet ink containing such an acrylic resin has excellent discharge stability during inkjet printing.

The vinyl chloride resin is not particularly limited. Examples of the vinyl chloride resin include copolymers of vinyl chloride and other monomers such as vinyl acetate, vinylidene chloride, acrylic acid, maleic acid, and vinyl alcohol. Of these, the vinyl chloride resin is preferably a copolymer (vinyl chloride-vinyl acetate copolymer) containing constituent units derived from vinyl chloride and vinyl acetate.

Vinyl chloride-vinyl acetate copolymers can be obtained, for example, by suspension polymerization. The vinyl chloride-vinyl acetate copolymer preferably contains 70 to 90 mass% of vinyl chloride units. When the amount is within the above range, the vinyl chloride-vinyl acetate copolymer is stably dissolved in the ink-jet ink, and therefore, the long-term storage stability is excellent. Further, the ejection stability of the inkjet ink is excellent.

The vinyl chloride-vinyl acetate copolymer may contain other constituent units as necessary in addition to the vinyl chloride unit and the vinyl acetate unit. Examples of the other constituent units include a carboxylic acid unit, a vinyl alcohol unit, and a hydroxyalkyl acrylate unit. Of these, the other constituent unit is preferably a vinyl alcohol unit.

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

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

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

The number average molecular weight (Mn) of the silicone resin is not particularly limited. For example, Mn of the silicone resin is preferably 10000 or more, and more preferably 20000 or more. Further, Mn is preferably 5000000 or less, more preferably 3000000 or less. Mn can be measured by GPC and can be obtained 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. For example, the binder resin is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more in the inkjet ink in terms of solid content. 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, it tends to be difficult to obtain desired performance as a binder, adhesion to a substrate (or a base layer provided on the substrate), and the like. On the other hand, if the content of the binder resin exceeds 40 mass%, the viscosity of the inkjet ink tends to increase, and the discharge stability during inkjet printing tends to decrease.

Solvent(s)

The solvent is a liquid component for dissolving the binder resin in the inkjet ink. The kind of the 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, and aromatic solvents. These may be used in combination. The solvent of the present embodiment preferably contains at least one of the glycol ether solvent and the acetate solvent. Both the glycol ether solvent and the acetate solvent have low viscosity and high boiling point. Therefore, the drying property of the inkjet ink containing these solvents is further improved, and the ejection stability at the time of inkjet printing is further improved.

Examples of the glycol ether solvent 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, 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, Triethylene glycol butyl methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and the like.

The acetate-based solvent may be exemplified by: 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 mono-isobutyl 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, n-butyl acetate, n-, Alkylene glycol monoalkyl ether acetates such as 3-methyl-3-isobutoxybutyl acetate, 3-methyl-3-sec-butoxybutyl acetate, and 3-methyl-3-tert-butoxybutyl acetate; ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, and the like.

The boiling point of the solvent of the present embodiment is preferably 150 ℃ or higher, and more preferably 180 ℃ or higher. The boiling point of the solvent is preferably 300 ℃ or lower, and more preferably 280 ℃ or lower. When the boiling point is within the above range, the drying property of the inkjet ink is further improved, and the ejection stability at the time of inkjet printing is further excellent. Further, 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 ℃, the inkjet ink tends to be easily dried in the vicinity of the inkjet head nozzle, and the discharge stability tends to be lowered. On the other hand, if the boiling point of the solvent exceeds 300 ℃, the inkjet ink is not easily dried, and the drying step for forming a printed material tends to take a long time. In addition, the image of the obtained printed matter is easily discolored.

The content of the solvent is not particularly limited. For example, the solvent is preferably 50% by mass or more, and more preferably 60% by mass or more in the inkjet ink. 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 discharge stability during inkjet printing tends to be low. On the other hand, if the content of the solvent exceeds 99% by mass, the proportion of the binder resin that can be added to the inkjet ink tends to be low, and it tends to be difficult to obtain desired performance.

Curing agents

The curing agent may be blended for curing the inkjet ink. The curing agent is not particularly limited. Examples of the curing agent include carbodiimide compounds, aziridine compounds, metal chelate compounds, isocyanate compounds, melamine compounds, epoxy compounds, oxazoline compounds, urea compounds, polyamine compounds, polyethyleneimine compounds, and acrylamide compounds. Curing agents may be used in combination. Of these, the curing agent preferably contains an isocyanate resin. Thus, a printed matter obtained using such an inkjet ink is more excellent in weather resistance.

As the isocyanate resin, any of general-purpose type, hard-to-yellow modification, non-yellow modification and the like may be used as long as it is a compound having 2 or more isocyanate groups in1 molecule. Examples of the general-purpose type include Toluene Diisocyanate (TDI), isocyanurate which is a trimer of TDI, 4-diphenylmethane diisocyanate (MDI), and polymeric diphenylmethane diisocyanate (polymeric MDI). Examples of the hard yellow modification include Xylylenediamine (XDI) and the like. As the non-yellow modification, Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, and the like can be exemplified. Of these, the curing agent preferably contains a blocked isocyanate having no yellow modification, and more preferably a blocked isocyanate having an isocyanurate structure and having no yellow modification. The inkjet ink containing such a curing agent is more excellent in curability. Further, by using such an inkjet ink, the obtained printed matter is more excellent in weather resistance. Therefore, the printed matter is likely to display a desired color for a longer period of time.

The content of the curing agent is not particularly limited. The amount of the fluororesin varies depending on the amount, hydroxyl value and acid value, and therefore cannot be determined in a lump. For example, the content of the curing agent is preferably 0.1% by mass or more, and more preferably 1% by mass or more in the inkjet ink. The content of the curing agent in the inkjet ink is preferably 20% by mass or less, and more preferably 10% by mass or less. If the content of the curing agent is less than 0.1% by mass, the reaction with the fluororesin may be insufficient, and desired performance may not be obtained. On the other hand, if the content of the curing agent exceeds 20 mass%, the curing agent may be excessively added to the fluororesin, and the weather resistance of the resulting printed matter tends to be deteriorated.

Curing catalysts

Examples of the curing catalyst include: organic acid salts, alkoxides and chelate compounds of metals such as tin, titanium, zirconium, iron, antimony, bismuth, manganese, zinc and aluminum; amines such as hexylamine, dodecylamine; amine salts such as hexylamine acetate, dodecylamine phosphate; quaternary ammonium salts such as benzyltrimethylammonium acetate; and salts of alkali metals such as potassium acetate. More specifically, the following can be exemplified: organic bismuth compounds such as bismuth octoate and bismuth neodecanoate; organotin compounds such as dibutyltin dilaurate, dibutyltin dioctoate, dimethyltin dineodecanoate and stannous octoate; and organic titanium compounds such as tetrabutyl titanate, tetraisopropyl titanate, diisopropoxy bis (acetylacetonato) titanium, and diisopropoxy bis (ethylacetoacetate) 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 of the curing catalyst is not particularly limited. For example, the content of the curing catalyst is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more in the inkjet ink. The content of the curing catalyst in the inkjet ink is preferably 5% by mass or less, and more preferably 3% by mass or less. When the content of the curing catalyst is less than 0.001% by mass, the performance as a curing catalyst tends to be not sufficiently exhibited. On the other hand, if the content of the curing catalyst exceeds 5% by mass, the curing properties of the inkjet ink tend to be high, and the discharge stability during inkjet printing tends to be low.

Dispersing agent

The dispersant is preferably contained for dispersing the color material. The dispersant is not particularly limited. Examples of the dispersant include anionic surfactants, nonionic surfactants, and polymeric dispersants. The dispersants may be used in combination.

Examples of the anionic surfactant include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonate salts, alkylnaphthalene sulfonate salts, lignin sulfonate salts, dialkyl sulfosuccinate salts, alkyl phosphate ester salts, naphthalenesulfonic acid formalin condensates, polyoxyethylene alkyl sulfate ester salts, and substituted derivatives thereof.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, ethylene oxide-propylene oxide block polymers, and substituted derivatives thereof.

The polymer dispersant preferably has both an acid value and a base value, and the acid value is larger than the base value, from the viewpoint of obtaining more stable dispersion characteristics. Examples of the polymer dispersant include PB series manufactured by Wako pure chemical industries, HINACT series manufactured by Chun Kagaku K.K., Solsperse series manufactured by Nippon Rakazu K.K., DISPARLON series manufactured by Nakekuwa Kabushiki Kaisha, and Efka (registered trademark) series manufactured by BASF Nippon K.K.

The content of the dispersant can be determined appropriately according to the kind and content of the color material to be dispersed. For example, the content of the dispersant is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the color material. The content of the dispersant is preferably 150 parts by mass or less, and more preferably 80 parts by mass or less, per 100 parts by mass of the color material. When the content of the dispersant is less than 5 parts by mass, it tends to be difficult to disperse the color material. On the other hand, when the content of the dispersant exceeds 150 parts by mass, the raw material cost tends to increase, and dispersion of the color material tends to be suppressed.

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 is preferably 5mPa · s or more, and more preferably 6mPa · s or more at 30 ℃. The viscosity of the inkjet ink is preferably 30mPa · s or less, and more preferably 20mPa · s or less at 30 ℃. When the viscosity is within the above range, the ejection stability of the inkjet ink is excellent. When the viscosity of the inkjet ink is less than 5mPa · s, the discharge stability during inkjet printing tends to decrease. On the other hand, if the viscosity exceeds 30mPa · s, the inkjet ink cannot be discharged satisfactorily from the inkjet head nozzle, and the discharge stability during inkjet printing tends to decrease. In the present embodiment, the viscosity can be measured using a B-type viscometer (model TVB-20LT, manufactured by Toyobo industries Co., Ltd.).

The method for adjusting the viscosity to the above range is not particularly limited. For example, the viscosity can be adjusted by the amount of the fluororesin to be used, the kind of the solvent to be used, or the amount of the solvent to be used. The viscosity may be adjusted by using a viscosity adjuster 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 20dyne/cm or more, and more preferably 22dyne/cm or more at 25 ℃. The surface tension of the inkjet ink is preferably 40dyne/cm or less, and more preferably 38dyne/cm or less at 25 ℃. When the surface tension is within the above range, the ejection stability of the inkjet ink is excellent. When the surface tension is less than 20dyne/cm, the wettability of the ink-jet ink tends to be excessively good, and bleeding tends to occur easily. On the other hand, if the surface tension exceeds 40dyne/cm, the ink jet ink tends to pop open on the surface of the substrate (or the substrate layer when the substrate is provided with the substrate layer), and the resulting printed matter tends to be unclear. In the present embodiment, the surface tension can be measured by using a static surface tension meter (plate method) (product of Kagaku corporation, model: CBVP-A3, trade name).

The method for adjusting the surface tension to be within the above range is not particularly limited. For example, the surface tension can be adjusted by adding an acrylic surface conditioner, a silicone surface conditioner, a fluorine surface conditioner, or the like.

The wetting index of the ink-jet image layer is not particularly limited. For example, the ink-jet image layer preferably has a wetting index of 20dyne/cm or more, more preferably 25dyne/cm or more. The ink-jet image layer preferably has a wetting index of 50dyne/cm or less, more preferably 40dyne/cm or less. By making the wetting index within the above range, the printed matter has the following advantages: even when other inks, paints, and the like are further applied to the inkjet image layer, a uniform coating film can be easily obtained. In the present embodiment, the wet index can be measured according to the method described in JIS K6768.

< layer constitution concerning ink-jet 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 may be composed of a plurality of layers. Fig. 1 is a schematic cross-sectional view showing a printed matter 1 formed with a single inkjet image layer 4. Fig. 2 is a schematic cross-sectional view of a printed matter 1a on which an inkjet image layer 4a of a plurality of layers (a first layer 41a and a second layer 42a) is formed. In the following description, the case where the printed matter includes the base layer is exemplified. The base layer may also be omitted as appropriate. In the case where the base layer is omitted, the ink-jet image layer may be formed on the substrate.

(case of forming a single-layer ink-jet image layer)

As shown in fig. 1, the printed matter 1 includes a base material 2, a base layer 3 formed on the base material 2, and a single-layer inkjet image layer 4 formed on the base layer 3. As described above, the inkjet image layer 4 contains the coloring material and the fluororesin. Since such an inkjet image layer contains a fluororesin, sufficient weather resistance is exhibited even when a topcoat layer is not provided.

(case of forming a multilayered ink-jet image layer)

Alternatively, the ink jet image layer can be comprised of multiple layers. Fig. 2 shows an example of a printed matter 1a on which an inkjet image layer 4a composed of two layers is formed. In this case, the printed matter 1a includes a base 2, a base layer 3 formed on the base 2, and a plurality of inkjet image layers 4a formed on the base layer 3. The ink-jet image layer may be, for example, a layer containing a color material in one layer and a layer containing no color material in the other layer. Fig. 2 illustrates a case where the inkjet image layer 4a is composed of a first layer 41a containing a color material and a second layer 42a covering the first layer 41a and not containing a color material. When such an inkjet image layer is formed of a plurality of layers, the printed matter is less likely to suffer color material dropout due to resin deterioration than when it is formed of a single layer. In addition, a layer containing no color material may be provided to the printed matter in conjunction with the first layer containing a color material. Therefore, a printed matter having an ink jet image layer composed of a plurality of layers can more easily exhibit an uneven form and can be processed into an appearance having excellent design properties. Further, in such a printed matter, if a pigment having a functionality or the like is added to the second layer, for example, the functionality can be provided only at a necessary position. 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 of the first layer 41 a.

In addition, in the present embodiment, in the case where the inkjet image layer is composed of a plurality of layers (for example, two layers), the above-mentioned fluororesin may be contained in at least either one of the first layer or the second layer. The fluororesin is more preferably contained in both the first layer and the second layer. Hereinafter, a case where the fluorine-containing resin is contained in both the first layer and the second layer will be described in detail as an example.

First layer

The first layer may be formed by imparting a first inkjet ink on the substrate layer in an inkjet manner. The first inkjet ink has the same configuration as the inkjet ink described above, and contains the above color material, fluororesin, and appropriate optional components.

In the first inkjet ink of the present embodiment, an antioxidant is preferably contained in any of the components. The antioxidant is not particularly limited. Examples of the antioxidant include a phenol-based antioxidant and a phosphorus-based antioxidant.

The phenolic antioxidant is preferably a hindered phenolic antioxidant. Examples of the hindered phenol-based antioxidant include 2, 6-di-t-butyl-p-cresol and C2-10 alkylenebis (t-butylphenol) [ e.g., 2,2 '-methylenebis (4-methyl-6-t-butylphenol) and 4, 4' -methylenebis (2, 6-di-t-butylphenol) ], tris (di-t-butyl-hydroxybenzyl) benzene [ e.g., 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene ], C2-10 alkanediol-bis [ (di-t-butyl-hydroxyphenyl) propionate ] [ e.g., 1, 6-hexanediol-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], dioxy or trioxo C2-4 alkanediol-bis (t-butyl-hydroxyphenyl) propionate [ e.g., triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], C3-8 alkanetriol-bis [ (di-tert-butyl-hydroxyphenyl) propionate ], C4-8 alkanetetraol tetrakis [ (di-tert-butyl-hydroxyphenyl) propionate ] [ e.g., pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], long-chain alkyl (di-tert-butylphenyl) propionate [ e.g., n-octadecyl-3- (4 ', 5' -di-tert-butylphenyl) propionate, stearyl-2- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-tert-butyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-hydroxy-ethyl -methyl phenyl acrylate, 4' -thiobis (3-methyl-6-tert-butylphenol), and the like.

Examples of the phosphorus-containing antioxidant include: mono-to tri (branched C3-6 alkyl-phenyl) phosphites such as tris (2, 4-di-tert-butylphenyl) phosphite and bis (2-tert-butylphenyl) phenyl phosphite; (branched C3-6 alkyl-aryl) phosphites of aliphatic polyhydric alcohols such as bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite; phosphonite-based compounds such as tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylene diphosphonite; triphenyl phosphate compounds such as tris (2, 4-di-t-butylphenyl) phosphate; examples of the metal phosphate include alkali metal or alkaline earth metal phosphates (or hydrates thereof) such as calcium hydrogen phosphate and sodium hydrogen phosphate monohydrate.

When the antioxidant is contained, the content of the antioxidant is preferably 0.1% by mass or more with respect to the total amount of the first inkjet ink. The content of the antioxidant is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less, relative to the total amount of the first inkjet ink. When the content of the antioxidant is in the above range, the obtained printed matter is easily prevented from deterioration, particularly yellowing, of the first layer.

Second layer

The second layer may be formed by imparting a second inkjet ink on the first layer in an inkjet manner. The second inkjet ink has the same configuration as the first inkjet ink except that it does not contain a coloring material, and contains the fluororesin and an optional component as appropriate.

In the present embodiment, the second inkjet ink containing no color material means that the ink does not contain the above-described various inorganic pigments and organic pigments (i.e., pigments for coloring as a main purpose). Therefore, the second inkjet ink may contain a pigment (e.g., an extender pigment) not mainly intended for coloring, various matting agents, and the like. Examples of the extender pigment include calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, talc and the like. Examples of the matting agent include silica and resin beads. Thus, the second layer can be formed as a layer suitably exhibiting gloss. In addition, the second layer may be formed as a layer having a matte feeling. Further, the second inkjet ink containing no color material may contain a pigment for imparting various functionalities to the inkjet layer. Examples of such pigments include silver nanoparticles for imparting an antibacterial effect or the like, gold nanoparticles for imparting a deodorizing effect or the like, and metal particles such as zinc sulfide particles for imparting a light-emitting effect or the like.

The second inkjet ink of the present embodiment preferably contains an ultraviolet absorber or a light stabilizer among arbitrary components. These may be used in combination. The ultraviolet absorber or light stabilizer is preferably blended to improve the weather resistance of the printed matter. That is, the second layer can reduce the amount of ultraviolet rays transmitted to the first layer by including an ultraviolet absorber. This prevents the first layer from deteriorating, and particularly reduces interlayer peeling and discoloration between the first layer and the second layer. As a result, the printed matter can further display a desired color for a long period of time.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine derivatives, and salicylic acid derivatives. Examples of the benzotriazole-based ultraviolet absorber include 2- (2 ' -hydroxy-5 ' -methylphenyl) 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 '-methacryloyloxyethylphenyl) -2H-benzotriazole, 2- { (2' -hydroxy-3 ', 3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5' -methylphenyl } benzotriazole and the like. Examples of the benzophenone-based ultraviolet absorber 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 ' -dihydroxy-4-methoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, and 2-hydroxy-4-methoxy-5-sulfobenzophenone. Examples of triazine derivatives include 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-methyl acetate) oxy-2-hydroxyphenyl-4, 6- { bis (2, 4-dimethylphenyl) } -1,3, 5-triazine [ BASF, Japan K.K.; product of BASF, Trade name TINUVIN479], tris [2,4,6- [2- {4- (octyl-2-methyl acetate) oxy-2-hydroxyphenyl } ] ] -1,3, 5-triazine, and the like. Examples of the salicylic acid derivative 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. Of these, from the viewpoint of having excellent ultraviolet absorbing ability, the ultraviolet absorber is preferably 2- {4- (octyl-2-methyl acetate) oxy-2-hydroxyphenyl-4, 6- { bis (2, 4-dimethylphenyl) } -1,3, 5-triazine.

The content of the ultraviolet absorber when the ultraviolet absorber is blended is not particularly limited. For example, the content of the ultraviolet 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 absorber in the second inkjet ink is preferably 10% by mass or less, and more preferably 5% by mass or less. If the content of the ultraviolet absorber is less than 0.01% by mass, the effect as an ultraviolet absorber tends to be not sufficiently exhibited. On the other hand, when the content of the ultraviolet absorber exceeds 10% by mass, further effects cannot be obtained, and the cost of the second inkjet ink tends to increase.

Light stabilizers

The light stabilizer is preferably blended to improve the weather resistance of the printed matter. This allows the printed matter to display a desired color for a longer period of time.

Examples of the light stabilizer include hindered amine light stabilizers. Examples of the hindered amine-based light stabilizer include 2,2,6, 6-tetramethyl-4-piperidyl stearate, 1,2,2,6, 6-pentamethyl-4-piperidyl stearate, 2,2,6, 6-tetramethyl-4-piperidyl benzoate, 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-piperidyl butane tetraformate, tetrakis (1,2,2,6, 6-pentamethyl-4-piperidyl butane tetraformate), Bis (2,2,6, 6-tetramethyl-4-piperidyl) ditridecyl-1, 2,3, 4-butanetetracarboxylate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) -2-butyl-2- (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (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-tert-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-piperidinyl) 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-piperidinyl) amino) -s-triazin-6-ylaminoaundecane, 1,6, 11-tris [2, 4-bis (N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylaminoaundecane, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) -sebacate, and the like. These may be used in combination. Among these, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) -sebacate is preferable from the viewpoint of stability in a liquid state without reacting with other materials.

The content of the light stabilizer in the case of blending the light stabilizer is not particularly limited. For 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. The content of the light stabilizer 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 light stabilizer is less than 0.01% by mass, the effect as a light stabilizer tends not to be exhibited. On the other hand, when the content of the light stabilizer exceeds 10 mass%, no further effect is obtained, and the cost of the second inkjet ink tends to increase.

The thickness of the second layer is not particularly limited. The thickness of the second layer may be, for example, a thickness necessary for blocking ultraviolet rays transmitted through the first layer. When the second layer contains an ultraviolet absorber, the thickness of such second layer also varies depending on the content of the ultraviolet absorber. Therefore, the thickness of the second layer cannot be determined globally. For example, when 2 mass% of an ultraviolet absorber (e.g., TINUVIN479) is added, the thickness of the second layer can be adjusted to 5 to 20 μm. This reduces the ultraviolet radiation by 70% or more by the second layer. The ultraviolet ray referred to herein means a wavelength of 360 nm. As a result, the printed matter can prevent deterioration of the first layer, and particularly, can reduce interlayer peeling and discoloration between the first layer and the second layer. The amount of reduction of the ultraviolet light can be measured, for example, by an infrared-visible spectrophotometer (UV-1700, manufactured by Shimadzu corporation).

The wetting index of both the first and second layers is the same as that of the ink-jet image layer described above. In the case where the printed matter of the present embodiment is formed with an inkjet image layer composed of a plurality of layers, the wetting index of the first layer is preferably equal to or higher than the wetting index of the second layer, and more preferably higher. By setting the wet index of the first layer to be equal to or greater than the wet index of the second layer in this way, the second layer of the printed matter can be uniformly coated without being flicked.

The first inkjet ink constituting the first layer and the second inkjet ink constituting the second layer may contain the same curing agent as the above-described base layer and inkjet ink. When the base layer, the first layer, and the second layer of the printed material of the present embodiment contain the curing agent, the crosslinking start temperature (T1) of the curing agent (curing agent for base layer) contained in the base layer, the crosslinking start temperature (T2) of the curing agent (curing agent for first layer) contained in the first layer, and the crosslinking start temperature (T3) of the curing agent (curing agent for second layer) contained in the second layer are preferably T1 ≦ T2 ≦ T3, and more preferably T1 < T2 ≦ T3. Thus, the first layer may be cured at the same or lower temperature as the second layer. In addition, the matrix layer may be cured at the same or lower temperature as the first layer. As a result, the ink jet image layer is formed on the base layer formed more firmly with respect to the obtained printed matter. This makes the ink-jet image less likely to cause bleeding and the like.

In the printed matter of the present embodiment, the crosslinking start temperature (T2) of the curing agent for the first layer and the crosslinking start temperature (T3) of the curing agent for the second layer are preferably T2 ≦ T3. Thus, the first layer may be cured at the same or lower temperature as the second layer. As a result, the second layer is formed on the first layer, which is formed more firmly, in the obtained printed matter. This makes the ink-jet image less likely to cause bleeding and the like.

The first inkjet ink constituting the first layer and the second inkjet ink constituting the second layer preferably contain the fluororesin in a total amount of 4 to 40 mass%. In this case, the first inkjet ink constituting the first layer preferably contains 2 to 15 mass% of a fluororesin. When the fluororesin is contained in the first inkjet ink in the above amount, the pigment is easily retained in the coating film and is less likely to fall off. Preferably, the second inkjet ink constituting the second layer contains 2 to 25 mass% of a fluororesin. When the fluororesin is contained in the second inkjet ink in the above content, the viscosity becomes appropriate and the obtained printed matter easily exhibits sufficient weather resistance.

As described above, in the printed matter of the present embodiment, the inkjet image layer can be formed by the inkjet method. In addition, the printed matter includes an inkjet image layer containing a fluororesin. Such an image layer exhibits sufficient weather resistance even without providing a topcoat layer. Therefore, the printed matter displays a desired color for a long period of time.

< method for producing printed matter >

A method for producing a printed matter according to an embodiment of the present invention mainly includes the following ink-jet steps: an inkjet image layer containing a coloring material and a fluororesin is formed by applying an inkjet ink to a substrate by an inkjet method. According to the method for producing a printed matter of the present embodiment, the obtained printed matter is excellent in weather resistance. Therefore, the printed matter can display a desired color for a long period of time. The method for producing a printed matter according to the present embodiment may further include a base layer forming step of forming a base layer on the base material. In this case, the ink-jet process may be performed on the base material on which the base layer is formed. In the present embodiment, a case where the base material on which the base layer is formed by performing the base layer forming step is subjected to the ink jet step is exemplified. The details of the substrate, the base layer, and the inkjet ink are the same as those described in the embodiment of the printed matter.

(base layer Forming step)

In the base layer forming step, a method of applying the base composition to the base material to form the base layer is not particularly limited. The base layer can be formed by applying the base composition to the base material by spray coating, roll coating, manual coating, inkjet method, or the like.

(ink-jet Process)

In the ink jet step, the method of applying the ink jet ink to the base layer by the ink jet recording method is not particularly limited. As such a system, a continuous system such as a charge control system, a micro-dot system, a charged jet control system, and an ink mist system; an on-demand system such as a piezoelectric system, a pulse jet system, a bubble jet (registered trademark) system, and an electrostatic attraction system.

In the case of forming an inkjet image layer composed of a plurality of layers (for example, the first layer and the second layer described above), the inkjet process may include: a first layer forming step of applying a first inkjet ink containing a color material to the base layer; and a second layer forming step of applying a second inkjet ink containing no color material so as to cover the first layer. In addition, the fluororesin may be contained in at least either one of the first inkjet ink or the second inkjet ink. The details of the first inkjet ink and the second inkjet ink are the same as those described in the embodiment of the printed matter. According to such a manufacturing method, a desired inkjet image is formed by a first layer containing a color material, and then the first layer is covered by a second layer not containing a color material. The obtained printed matter is imparted with excellent weather resistance by including a fluorine resin in at least either one of the first layer and the second layer.

In the case of forming an inkjet image layer composed of a plurality of layers (for example, the first layer and the second layer described above), the surface tension of the first inkjet ink is preferably adjusted to be equal to or higher than the surface tension of the second inkjet ink. Thus, the second inkjet ink does not pop up and can be uniformly applied.

Next, the substrate to which the inkjet ink was applied was dried. The drying conditions are not particularly limited. For example, the drying may be performed at 50 to 250 ℃ for 1 to 60 minutes. By this drying, the solvent in the inkjet ink can be removed. In order to prevent bleeding of the inkjet image, drying is preferably performed simultaneously with or immediately after the inkjet ink is imparted onto the substrate.

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

(1) The above embodiment exemplifies a printed matter without a top coat layer. Instead of this, the present invention may provide a topcoat layer in such a manner as to cover the inkjet image layer. In this case, the resulting printed matter can be imparted with more excellent weather resistance.

(2) The above embodiment exemplifies a case where the inkjet image layer is composed of two layers. In place of this, in the present invention, the inkjet image 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 fluororesin.

(3) In the above embodiment, the case where the fluorine resin is contained in both the first layer and the second layer when the inkjet image layer is composed of the first layer and the second layer is exemplified. In the present invention, the fluorine-containing resin may be contained only in the first layer or only in the second layer, instead of this embodiment. When the fluorine-containing resin is contained only in the first layer, a printed matter can be produced at a relatively low cost. On the other hand, when the fluorine-containing resin is contained only in the second layer, the decrease in the glossiness of the surface of the printed matter can be reduced.

(4) In the above-described embodiment (method for producing printed matter), the case where the base layer forming step is performed and the ink jet step is performed on the base material on which the base layer is formed is exemplified. In place of this, the present invention can omit the base layer forming step. In this case, the ink-jet process is a process including: an inkjet image layer containing a coloring material and a fluororesin is formed by applying an inkjet ink to a substrate by an inkjet method.

One embodiment of the present invention has been described above. The present invention is not limited to the above-described embodiments. The above embodiments mainly explain the invention having the following configurations.

(1) A printed matter comprising a substrate and an ink jet image layer formed on the substrate, wherein the ink jet image layer comprises a coloring material and a fluororesin.

With this configuration, the inkjet image layer can be formed on the printed matter by an inkjet method. In addition, the printed matter includes an inkjet image layer containing a fluororesin. Such an inkjet image layer exhibits sufficient weatherability even when the topcoat layer is not provided. Therefore, the printed matter displays a desired color for a long period of time.

(2) The printed matter according to (1), wherein the inkjet image layer includes a first layer containing the color material and a second layer covering the first layer and containing no color material, and the fluororesin is contained in at least either one of the first layer and the second layer.

According to such a configuration, a desired ink jet image can be formed by the first layer containing the color material. In addition, the first layer may be covered by a second layer that does not contain a color material. Since at least either one of the first layer or the second layer contains a fluorine-containing resin, the resulting inkjet image layer exhibits excellent weatherability.

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

With this configuration, the printed matter can be inhibited from deteriorating the first layer.

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

With such a configuration, the printed matter can exhibit more excellent weather resistance. Therefore, the printed matter can further display a desired color for a long period of time.

(5) The printed matter according to any one of (2) to (4), wherein the first layer further contains a first-layer curing agent, the second layer further contains a second-layer curing agent, and a crosslinking reaction initiation temperature of the first-layer curing agent is not higher than a crosslinking reaction initiation temperature of the second-layer curing agent.

With this configuration, the second layer can be formed on the first layer which is formed more firmly in the printed matter. As a result, the ink-jet image layer is less likely to cause bleeding and the like in the obtained printed matter.

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

With this configuration, the ink-jet image layer can be formed on the base layer by an ink-jet method in the printed matter. In addition, the printed matter includes an inkjet image layer containing a fluororesin. Such an inkjet image layer exhibits sufficient weatherability even when the topcoat layer is not provided. Therefore, the printed matter displays a desired color for a long period of time.

(7) The printed matter according to (5), further comprising a base layer between the base material and the inkjet image layer, wherein the base layer further comprises a curing agent for a base layer, wherein a crosslinking reaction start temperature of the curing agent for a base layer is not higher than a crosslinking reaction start temperature of the curing agent for a first layer, and a crosslinking reaction start temperature of the curing agent for a first layer is not higher than a crosslinking reaction start temperature of the curing agent for a second layer.

With this configuration, the ink-jet image layer can be formed on the base layer formed more firmly in the printed matter. As a result, the ink-jet image layer is less likely to cause bleeding and the like in the obtained printed matter.

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

With such a configuration, not only the inkjet image layer but also the base layer is provided with excellent weather resistance. Therefore, the printed matter exhibits excellent weather resistance not only at the portion where the ink jet image layer is formed but also over the entire portion.

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

With this configuration, the printed matter is less likely to be discolored due to deterioration of the color material.

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

With such a configuration, the printed matter can be provided with more excellent weather resistance.

(11) A method for producing a printed matter, comprising the following ink-jet step: an inkjet image layer containing a coloring material and a fluororesin is formed by applying an inkjet ink to a substrate by an inkjet method.

With such a configuration, in the present manufacturing method, a printed matter on which an inkjet image layer is formed can be manufactured by an inkjet method. The resulting print comprises an inkjet image layer comprising a fluororesin. Such an inkjet image layer exhibits sufficient weatherability even when the topcoat layer is not provided. Therefore, according to the present manufacturing method, a printed matter that displays a desired color for a long period of time can be manufactured.

(12) The method for producing a printed matter according to item (11), wherein the inkjet ink includes a first inkjet ink containing the color material and a second inkjet ink containing no color material, the fluororesin is included in at least either one of the first inkjet ink and the second inkjet ink, and the inkjet step includes: a first layer forming step of applying the first inkjet ink to the substrate, and a second layer forming step of applying the second inkjet ink so as to cover the first layer.

With such a configuration, the manufacturing method can form a desired inkjet image with the first layer containing the color material. In addition, the present manufacturing method may cover the first layer with the second layer not containing the color material. According to the present production method, since the fluorine-containing resin is contained in at least either one of the first layer or the second layer, excellent weather resistance can be imparted to the resulting inkjet image layer.

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

With such a configuration, the second layer can be provided more uniformly in the present manufacturing method.

(14) The method for producing a printed matter according to any one of (11) to (13), further comprising a base layer forming step of forming a base layer on the base material, wherein the inkjet step is performed on the base material on which the base layer is formed.

With such a configuration, the present manufacturing method can manufacture a printed matter having an ink-jet image layer formed on a base layer by an ink-jet method. The resulting print comprises an inkjet image layer comprising a fluororesin. Such an inkjet image layer exhibits sufficient weatherability even when the topcoat layer is not provided. Therefore, according to the present manufacturing method, a printed matter that displays a desired color for a long period of time can be manufactured.