JP5891712B2 - Recorded matter - Google Patents

Description

  The present invention relates to a recorded matter.

  In recent years, there has been an increasing demand for recorded matter in which an image having glitter is formed on a recording surface. As a method for forming an image having glitter, there has been proposed a technique capable of recording a glitter image by an ink jet method capable of on-demand recording at a low cost (Patent Document 1). In order to achieve the same image quality as conventional multicolor recording and color photographic methods, and to increase the recording speed, this ink jet recording is improved with inks aimed at high color development, multiple colors, and high weather resistance, As for the recording material, many techniques have been proposed particularly for the ink receiving layer in order to realize stable fixing of the color material, improvement of weather resistance, excellent absorption of the ink solvent, and the like (Patent Document 2, Patents). Reference 3).

  On the other hand, as an ink for forming an image having glossiness, Patent Document 1 proposes a glittering ink containing aluminum. However, as a metal having excellent glossiness, for example, it is known as a photosensitive material for a silver salt film. Thus, an image having a glittering property is formed by an ink containing silver.

JP 2008-174712 A JP 2006-263951 A Japanese Examined Patent Publication No. 7-121609

  However, many recording materials for recording images having glitter using a glittering ink containing silver often contain chlorine. For example, in order to achieve excellent fixability of the color material, it is a recording material intentionally added with an aluminum chloride cation fixing agent, or chlorine is an additive material in the production process of fine alumina particles constituting the receiving layer. In the case where chlorine is unintentionally mixed into the receiving layer, and further, bleaching of pulp as a raw material for paper generally uses a chlorine bleach, and chlorine as an impurity. In many cases, the recording material contains chlorine or a chlorine compound.

  The chlorine concentration in the recording material differs from the ppm order to about 1% depending on whether it is intentionally added or unintentionally mixed. In other words, dyes and pigments for reproducing cyan, magenta, yellow, black, etc. have poor reactivity with chlorine, so there are no quality issues such as discoloration of colorants and reduced light resistance due to chlorine. It was. However, when a glittering image is recorded using a water-based ink containing silver particles, a very excellent metallic luster is obtained immediately after recording, but the existing color ink (cyan, magenta, As compared with yellow, black, etc.), it was found that the gloss deteriorates very quickly. Furthermore, it was also found that the deterioration of gloss occurs more remarkably in the colored image portion having the glitter.

  The gloss deterioration is caused when free chlorine is first generated and dissolved in water used as a solvent for the ink when water-based ink containing silver particles is recorded on the recording material. The free chlorine may be released from the aluminum chloride cation fixing agent as an anion or may be generated from chlorine contained as an impurity in the recording material. Here, it is known as a general chemistry that chlorine and silver directly react to form silver chloride in each of a nonionic state and an ionic state, and a part of silver particles used as a bright pigment is silver chloride. It becomes. As is apparent from the fact that silver chloride formed in a glittering image is suitably used as a light-sensitive material in a silver salt photographic film, it is supposed to have photosensitivity to ultraviolet rays. Although the detailed reaction process is omitted, the gloss deterioration of the glitter image due to light is caused by the fact that the silver chloride formed in the glitter image is exposed to light, and as a result, the partially recrystallized silver recrystallized. Formed on the image surface, the surface scattering of visible light becomes strong and manifests as gloss degradation.

  Furthermore, silver chloride is exposed to ultraviolet rays of about 370 nm or less to form silver, but the reason is not clear because the color material contained in the color ink (cyan, magenta, yellow) is in contact with silver chloride. It was found that the photosensitivity of silver increased. As a result, the gloss deterioration at the image recording portion having the glittering property occurred more remarkably.

  Therefore, even when a glittering image is formed on a recording medium (recording material) containing chlorine or a chlorine compound by using silver-containing ink for forming a glittering image, it has excellent light resistance, Provided is a recorded matter on which an image having a glitter property which maintains the glossiness of silver is recorded.

  The present invention can be realized as the following forms or application examples so as to solve at least one of the above-described problems.

  [Application Example 1] The recorded matter of this application example is a recorded matter in which an image is formed on at least one recording surface of a recording medium, and the recording medium contains chlorine or a chlorine compound, and the image Is a silver pigment layer on the recording surface, a resin layer is formed on the surface of the silver pigment layer, the film thickness of the silver pigment layer is 50 nm or more and 280 nm or less, and the film thickness of the resin layer is 40 nm or more, It is 450 nm or less.

  According to the recorded matter of this application example, it is possible to suppress transmission of ultraviolet rays that sensitize silver chloride, which is a compound of silver contained in the silver pigment layer and chlorine contained in the recording medium, to the silver pigment layer. Therefore, the gloss of the formed glittering image can be maintained for a long time. Furthermore, the resin layer can suppress the penetration of moisture into the silver pigment layer that promotes the formation of silver chloride, which is a compound of silver contained in the silver pigment layer and chlorine contained in the recording medium. It is possible to reduce the amount of silver chloride itself that lowers the properties, and to maintain the gloss of the formed glitter image for a long period of time.

  Application Example 2 In the above application example, a colored layer is formed on the surface of the resin layer, and the thickness of the colored layer is 500 nm or more and 5500 nm or less.

  According to the application example described above, it is possible to obtain a recorded matter that suppresses the reduction in glitter and is excellent in color reproducibility.

  Application Example 3 In the application example described above, the silver pigment layer is formed of a first ink composition containing water and silver.

  According to the above application example, the dispersion stability of the silver particles contained in the silver pigment layer can be excellent, and when a droplet discharge device is used as a recording device, the ink near the slip Therefore, it is possible to quickly perform drying on a recording medium to which ink is applied while preventing drying due to evaporation of the dispersion medium. Therefore, high-speed recording of a desired image can be suitably performed over a long period of time. it can.

  Application Example 4 In the application example described above, the resin layer is formed of a second ink composition containing 0.1% by mass or more of a resin and substantially not containing a color material.

  According to the application example described above, excellent light resistance can be imparted to the glitter image.

  Application Example 5 In the application example described above, the resin of the second ink composition is one or more of urethane resin, polyester resin, fluorene resin, and paraffin wax.

  According to the application example described above, excellent light resistance and gloss can be imparted to the glitter image.

  Application Example 6 In the application example described above, the colored layer contains at least a quinacridone color material or a copper phthalocyanine color material as a color material.

  According to the application example described above, the photosensitivity of silver chloride produced in the silver pigment layer is suppressed, and a recorded matter with little deterioration in glossiness can be obtained.

  Application Example 7 In the application example described above, the film thickness ratio between the silver pigment layer and the resin layer is 1: 9 to 7: 1.

  According to the application example described above, it is possible to reduce the amount of silver chloride itself that lowers the glitter, and to maintain the gloss of the formed glitter image over a long period of time.

  Application Example 8 A recording apparatus according to this application example forms the recorded matter described in the application example described above.

  According to the application example described above, it is possible to obtain a recorded matter excellent in glitter.

  Application Example 9 According to the application example described above, an ink jet recording unit is provided.

  According to the application example described above, it is possible to accurately control the layer thickness of the silver pigment layer, the resin layer, and the colored layer, and also to accurately realize the image forming position of each layer and to have excellent glitter. Can be obtained.

FIG. 3 is a schematic cross-sectional view of a recorded matter according to the first embodiment. FIG. 2A is a structural skeleton diagram of a quinacridone-based color material, and FIG. 2B is a structural skeleton diagram of a copper phthalocyanine-based color material, which is a part of the composition contained in the colored layer ink. FIG. 6 is a schematic perspective view of a recording apparatus according to a second embodiment. The table | surface which shows the composition of silver pigment layer ink and resin layer ink. The table | surface which shows a composition of an example of a colored layer ink. The table | surface which shows Examples 1-4, Comparative Examples 1-8, and Reference Examples 1 and 2. FIG. The table | surface which shows Examples 5-7.

  Embodiments according to the present invention will be described below with reference to the drawings.

(First embodiment)
FIG. 1 is an enlarged view schematically showing a cross section of an image forming portion of a recorded matter having glitter as a first embodiment. As shown in FIG. 1A, a recorded product 100 includes a recording medium 10, and a silver pigment layer 20 having a glitter property containing silver or a silver compound formed on the surface of a recording surface 10a of the recording medium 10. And a resin layer 30 formed on the surface of the silver pigment layer 20. Further, the recorded matter 200 shown in FIG. 1B includes a recording medium 10, a silver pigment layer 20 having a glitter property containing silver or a silver compound formed on the surface of the recording surface 10 a of the recording medium 10, and The resin layer 30 formed on the surface of the silver pigment layer 20 and the colored layer 40 formed on the surface of the resin layer 30 are configured. That is, the recorded matter 200 has a configuration in which the colored layer 40 is formed on the surface of the resin layer 30 of the recorded matter 100.

[Recording medium]
Examples of the recording medium 10 include plain paper, special paper having an ink receiving layer, and a substrate whose image recording surface is made of plastic, ceramics, metal, and a composite material thereof. A recording medium on which an ink receiving layer is formed is preferable. Examples of the ink receiving layer include a void layer and a swelling layer. The void layer has a resin ratio of less than 30%, is mainly composed of inorganic particles such as silica and alumina, and is configured such that the solvent penetrates between the inorganic particles or between the pores provided in the inorganic particles. Indicates a layer. The swelling layer is a resin composed of 70% or more of the components constituting the layer, and the resin layer is swollen by the solvent of the ink so that the solvent penetrates into the open pores. Show. Some recording media having an ink receiving layer contain several percent or less of chlorine (Cl).

[Bright ink]
In the recorded materials 100 and 200 according to the present embodiment, a silver pigment layer is formed using a bright pigment containing silver particles, which has high glossiness (brightness) and low reactivity with water and various organic solvents used as a solvent. 20 is formed. Hereinafter, the glitter ink as the first ink composition containing the silver pigment forming the silver pigment layer 20 will be described.

[1] Silver Particles The recorded matter 100, 200 according to the present embodiment is formed using glitter ink containing silver particles. When the glitter ink contains silver particles, an image having excellent metallic luster can be formed. In particular, an image having excellent metallic luster can be formed by including silver particles together with wax that satisfies a predetermined condition. Silver is a metal having the highest visible light reflectance among various metals, and therefore, various metal colors such as gold and copper can be expressed by superimposing them with inks of other colors. The average particle size of the silver particles contained in the glitter ink is preferably 3 nm or more and 100 nm or less, and more preferably 15 nm or more and 65 nm or less. Thereby, the glossiness (brightness) and abrasion resistance of the image formed using the silver ink can be made particularly excellent. Further, ink ejection stability (landing position accuracy, ejection amount stability, etc.) by the ink jet method can be made particularly excellent, and an image with a desired image quality can be more reliably formed over a long period of time. . In the present specification, the “average particle size” means a volume-based average particle size unless otherwise specified. The average particle diameter can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. As the laser diffraction type particle size distribution measuring device, for example, a particle size distribution meter (for example, “Microtrack UPA” manufactured by Nikkiso Co., Ltd.) having a dynamic light scattering method as a measurement principle can be used.

  The content of silver particles in the glitter ink is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 5.0% by mass or more and 15% by mass or less. Thereby, the discharge stability by the ink jet system of ink and the storage stability of ink can be made particularly excellent. In addition, even when the density of silver particles (content per unit area) on the recording medium when the recording material is recorded is low to high, it has good image quality and scratch resistance. Can be realized. The silver particles may be prepared by any method. For example, the silver particles can be suitably formed by preparing a solution containing silver ions and reducing the silver ions in the presence of a dispersant. .

[2] Dispersant Since the specific gravity of silver is as high as 10.49 g / cm ³ , when the particle size of the silver particles is 100 nm or more, the precipitation of the silver particles in the ink becomes remarkable. On the other hand, if the silver particles have a particle size of 100 nm or less, the sedimentation in the ink is reduced due to the increase in Brownian motion, but the surface activity increases, so that aggregates are easily formed by contact of the particles. Then, sedimentation as the formed aggregate occurs. Therefore, it is preferable that a dispersant is applied to the surface of the silver particles in order to suppress the formation of aggregates.

  The dispersant is not particularly limited, but a polymer compound capable of coordinating with silver such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, citric acid, malic acid, trisodium citrate, tripotassium citrate, trilithium citrate, Hydroxy acids or salts thereof capable of coordinating with silver, such as triammonium citrate, disodium malate, tannic acid, gallotannic acid, pentaploid tannin, mercaptoacetic acid, mercaptopropionic acid, thiodipropionic acid, mercaptosuccinic acid, thio Acetic acid, sodium mercaptoacetate, sodium mercaptopropionate, sodium thiodipropionate, disodium mercaptosuccinate, potassium mercaptoacetate, potassium mercaptopropionate, potassium thiodipropionate, dimercaptosuccinate Such as helium, such as mercapto acid or a salt thereof can be mentioned having a silver allow coordinated thiol group and hydroxy group may be used singly or in combination of two or more of them. Among them, a polymer compound capable of multipoint coordination with silver such as polyvinyl alcohol, polyacrylamine, and polyvinylpyrrolidone is more preferable from the viewpoint of aggregation suppression, and polyvinylpyrrolidone is most preferable from the viewpoint of storage stability of the ink. .

[3] Resin The glittering ink according to the present embodiment may contain a resin, and by containing this, the fixability and the scratch resistance are improved. Resins include polyacrylic acid, polymethacrylic acid, polymethacrylic acid ester, polyethylacrylic acid, styrene-butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer, chloroprene copolymer, fluororesin, fluoride resin Vinylidene, polyolefin resin, cellulose, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, polystyrene, styrene-acrylamide copolymer, polyisobutyl acrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl acetal, polyvinyl pyrrolidone, polyamide , Rosin resin, fluorene resin, polyethylene, polycarbonate, vinylidene chloride resin, cellulose resin such as cellulose acetate butyrate, vinyl acetate resin, ethylene-vinegar Vinyl copolymer, vinyl acetate - acrylic copolymer, vinyl chloride resin, polyurethane, and rosin esters, and the like is not limited thereto.

[4] Water The glittering ink according to the present invention may be a water-based ink containing 50% by mass or more of water or a non-aqueous ink having a water content of less than 50% by mass. A water-based ink containing 50% by mass or more of water is more preferable because the fixability of the silver pigment is improved by rapidly reducing the solvent on the recording medium. The water contained in the ink mainly functions as a dispersion medium for dispersing the silver particles and the resin emulsion. By containing water in the ink, the dispersion stability of silver particles and the like can be improved, and the ink dispersion medium in the vicinity of a nozzle of a droplet discharge device as a recording device as described later Since drying on a recording medium to which ink is applied can be performed quickly while preventing drying due to evaporation of the ink, high-speed recording of a desired image can be suitably performed over a long period of time. When water is contained in the ink, the content of the water is not particularly limited, but is preferably 20% by mass or more and 80% by mass or less, and more preferably 50% by mass or more and 70% by mass or less. preferable.

[5] Polyhydric alcohol The glittering ink according to the present embodiment preferably contains a polyhydric alcohol. When the ink according to the present embodiment is applied to an ink jet recording apparatus, the polyhydric alcohol can suppress drying of the ink and prevent clogging by the ink in the ink jet recording head portion.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, and trimethylolethane. , Trimethylolpropane, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,2-octanediol, and the like. . Especially, a C4-C8 alkanediol is preferable and a C6-C8 alkanediol is more preferable.

  Thereby, the permeability to a recording medium can be made particularly high. The content of polyhydric alcohol in the ink is not particularly limited, but is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less. Among the polyhydric alcohols, an ink containing 1,2-hexanediol and trimethylolpropane is preferable. Thereby, the dispersion stability of the silver particles in the ink and the storage stability of the ink can be made particularly excellent, and the ink ejection stability can be made particularly excellent.

[6] Glycol ether The glittering ink according to this embodiment preferably contains glycol ether. By containing the glycol ether, it is possible to improve the wettability of the recording surface such as a recording medium and the ink permeability.

  As glycol ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol Mention may be made of lower alkyl ethers of polyhydric alcohols such as monomethyl ether, triethylene glycol monobutyl ether and tripropylene glycol monomethyl ether. Among these, when triethylene glycol monobutyl ether is used, good recording quality can be obtained. The content of glycol ether in the ink is not particularly limited, but is preferably 0.2% by mass or more and 20% by mass or less, and more preferably 0.3% by mass or more and 10% by mass or less.

[7] Surfactant The glittering ink according to the present embodiment may contain a surfactant. Although it does not specifically limit as a kind of surfactant, It is preferable to contain an acetylene glycol type surfactant or a polysiloxane type surfactant. Acetylene glycol surfactants or polysiloxane surfactants can increase the wettability of a recording surface such as a recording medium and improve the ink permeability.

  Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, 5-dimethyl-1-hexyn-3-ol, 2,4-dimethyl-5-hexyn-3-ol and the like can be mentioned. Moreover, a commercial item can also be utilized for acetylene glycol type-surfactant, for example, Orphine E1010, STG, Y (above, Nissin Chemical Co., Ltd.), Surfinol 104, 82, 465, 485, TG (above , Air Products and Chemicals Inc.).

  A commercially available product can be used as the polysiloxane surfactant. For example, BYK-347, BYK-348 (manufactured by Big Chemie Japan) and the like can be mentioned. Furthermore, the glittering ink according to this embodiment may contain other surfactants such as an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. The content of the surfactant described above in the glitter ink is not particularly limited, but is preferably 0.01% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass or more and 0.5% by mass. % Or less is more preferable.

[8] Other components The glittering ink according to this embodiment may contain components other than the above (other components). Examples of such components include pH regulators, penetrants, organic binders, urea compounds, saccharides, drying inhibitors such as alkanolamines (such as triethanolamine), and bright layer slipping agents such as paraffin. Can be mentioned.

[9] Ink physical properties When the surface tension is S (mN / m) and the viscosity is V (Pa · s), the surface of the glitter ink appropriately containing the components shown in [1] to [8] above, the surface The tension is preferably 20 ≦ S ≦ 40, and the viscosity is preferably 1.5 ≦ V ≦ 10. More preferably, the surface tension is 25 ≦ S ≦ 35, and the viscosity is 2.5 ≦ V ≦ 8. Thereby, the brightness (glossiness) and scratch resistance of an image formed using the glitter ink can be made particularly excellent. Further, the ink ejection stability (landing position accuracy, ejection volume stability, etc.) by the ink jet method can be made particularly excellent, and an image that can maintain a desired image quality over a long period of time can be more reliably formed. Can do.

  In this specification, “surface tension” and “viscosity” indicate measured values when the ink temperature is 23 ° C. unless otherwise specified. The surface tension can be measured by the Wilhelmy method (plate method). As the Wilhelmy method surface tension meter, for example, “fully automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.)” or the like can be used. The viscosity can be measured with a vibration viscometer. The vibration viscometer can calculate the viscosity from the amount of torque for keeping the vibration constant when the vibrator is immersed in the liquid. As the vibration viscometer, for example, “vibration viscometer VM-100A” or the like can be used.

[Resin layer ink]
The resin layer ink as the second ink composition for forming the resin layer 30 according to the present embodiment is an ink that does not substantially contain a color material and contains a resin. The resin layer ink may be either water-based ink (water content is 50% or more) or non-water-based ink (water content is less than 50%). Note that “substantially no colorant” means, for example, that the content of the colorant in the ink is less than 0.5% by mass, more preferably less than 0.1% by mass, Preferably it is less than 0.01% by mass, and most preferably less than 0.005% by mass. The “coloring material” refers to pigments and dyes used for the purpose of coloring.

[1] Resin The resin layer ink according to the present embodiment may contain a resin similar to the resin contained in the above-described glitter ink. Among these, polyurethane and fluorene-based resin are more preferable from the viewpoint of light resistance, and polyurethane is most preferable from the viewpoint of glossiness after adhesion of the protective ink. By including a resin component in the resin layer ink, excellent light resistance can be imparted to the glitter image. The resin is preferably contained in the resin layer ink in the range of 0.1% by mass to 30% by mass in terms of solid content, and more preferably in the range of 0.5% by mass to 15% by mass. preferable.

[3] Polyhydric alcohol The resin layer ink according to the present embodiment may contain a polyhydric alcohol similar to the polyhydric alcohol contained in the above-described glitter ink. When the resin layer ink according to the present embodiment is applied to an ink jet recording apparatus, polyhydric alcohol can suppress ink drying and prevent clogging by ink in the ink jet recording head portion. It is preferable to contain a monohydric alcohol.

[4] Glycol ether The resin layer ink according to the present embodiment may contain a glycol ether similar to the glycol ether contained in the glitter ink. By containing the glycol ether, it is possible to improve the wettability of the recording surface such as a recording medium and the ink permeability. The content of glycol ether in the ink is not particularly limited, but is preferably 0.2% by mass or more and 20% by mass or less, and more preferably 0.3% by mass or more and 10% by mass or less.

[4] Surfactant The type of the resin layer ink according to the present embodiment is not particularly limited, but preferably contains a surfactant such as an acetylene glycol surfactant or a polysiloxane surfactant. Typical examples of the acetylene glycol surfactant and the polysiloxane surfactant are the same as the surfactant contained in the glitter ink. The acetylene glycol surfactant or the polysiloxane surfactant can increase the wettability of the recording medium to the recording surface and increase the ink permeability. The content of the surfactant in the ink is not particularly limited, but is preferably 0.01% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less. Is more preferable.

[5] Other components The resin layer ink according to the present embodiment may include other components as components other than those described above. Examples of other components include a pH adjusting agent, a penetrating agent, an organic binder, a urea compound, a saccharide, a drying inhibitor such as alkanolamine (such as triethanolamine), and a slipping property imparting agent such as paraffin.

[Colored layer ink]
The colored layer ink that forms the colored layer 40 in the recorded matter 200 according to the present embodiment is an ink containing a color material. The colored layer ink may be an aqueous ink having a water content of 50% by mass or more, or a non-aqueous ink having a water content of less than 50% by mass.

[1] Resin The colored layer ink according to the present embodiment may contain a resin similar to the resin contained in the above-described glitter ink. By using a color ink containing a resin component, strong scratch resistance can be obtained. The resin is preferably contained in the color ink in a range of 4% by mass to 50% by mass in terms of solid content, and more preferably in the range of 6% by mass to 25% by mass.

[2] Color Material [2-1] Pigment The pigment that can be used in the colored layer ink according to the present embodiment is not particularly limited, and examples thereof include inorganic pigments and organic pigments. As the inorganic pigment, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black and channel black, iron oxide, and titanium oxide can be used. Organic pigments include insoluble azo pigments, condensed azo pigments, azo lakes, chelate azo pigments and other azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, A daylight fluorescent pigment is mentioned. The said pigment may be used individually by 1 type, and may use 2 or more types together. Hereinafter, an example of a pigment is given.

  As the inorganic pigment used for black, the following carbon black, for example, No. manufactured by Mitsubishi Chemical Corporation is used. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, or No2200B, etc .; Columbia-made Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc .; 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc .; or Color Black FW1, Color Black FW2, Clk Black FW2C, Decksa's Color Black FW2 FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, and Special Black 5S.

  Examples of yellow organic pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180 and the like.

  Examples of magenta organic pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 192, 202, 207, 209, 219, 224, 245, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 42, 43, 50 and the like.

  Examples of cyan organic pigments include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 15:34, 16, 18, 22, 25, 60, 65, 66, 75, C. I. Bat Blue 4, 60, C.I. I. Pigment green 7, 36, 37, and the like.

[2-2] Dyes As dyes, direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, and the like are used for normal inkjet recording. Various dyes can be used. Hereinafter, an example of a dye is given.

  Examples of yellow dyes include C.I. I. Acid Yellow 1, 3, 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 59, 61, 70, 72, 75, 76, 78, 79, 98, 99, 110, 111, 127, 131, 135, 142, 162, 164, 165, C.I. I. Direct Yellow 1, 8, 11, 12, 24, 26, 27, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 110, 132, 142, 144, C.I. I. Reactive Yellow 1, 2, 3, 4, 6, 7, 11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37, 42, C.I. I. Food Yellow 3, 4, C.I. I. Solvent yellow 15, 19, 21, 30, 109 etc. are mentioned.

  Examples of magenta dyes include C.I. I. Acid Red 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 37, 42, 51, 52, 57, 75, 77, 80, 82, 85, 87, 88, 89, 92, 94, 97, 106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, 180, 183, 184, 186, 194, 198, 209, 211, 215, 219, 249, 252, 254, 262, 265, 274, 282, 289, 303, 317, 320, 321, 322, C.I. I. Direct Red 1, 2, 4, 9, 11, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230, 231, C.I. I. Reactive Red 1, 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 28, 29, 31, 32 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 49, 50, 58, 59, 63, 64, C.I. I. Sorbize red 1, C.I. I. Food red 7, 9, 14 etc. are mentioned.

  Examples of cyan dyes include C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78, 80, 82, 83, 90, 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167, 168, 170, 171, 182, 183, 184, 187, 192, 199, 203, 204, 205, 229, 234, 236, 249, C.I. I. Direct Blue 1, 2, 6, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, C.I. I. Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20, 21, 25, 26, 27, 28, 29, 31, 32, 33 , 34, 37, 38, 39, 40, 41, 43, 44, 46, C.I. I. Solvize Bat Blue 1, 5, 41, C.I. I. Bat Blue 4, 29, 60, C.I. I. Food Blue 1, 2, C.I. I. Basic blue 9, 25, 28, 29, 44 etc. are mentioned.

  The content of the color material in the colored layer ink according to the present embodiment is not particularly limited, but is preferably 1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less with respect to the total mass of the ink. It is.

[3] Polyhydric alcohol The color ink of the present invention may contain a polyhydric alcohol similar to the polyhydric alcohol contained in the above-described glitter ink. By including polyhydric alcohol in the colored layer ink according to the present embodiment, when applied to an ink jet recording apparatus, drying of the ink is suppressed and clogging by ink in the ink jet recording head portion can be prevented. Therefore, it is preferable to contain a polyhydric alcohol.

[4] Glycol ether The color ink of the present invention may contain a glycol ether similar to the glycol ether contained in the glitter ink. By containing glycol ether, the wettability to the recording surface of the recording medium or the like can be improved and the permeability of the colored layer ink can be increased. The content of glycol ether in the colored layer ink is not particularly limited, but is preferably 0.2% by mass or more and 20% by mass or less, and more preferably 0.3% by mass or more and 10% by mass or less.

[5] Surfactant The type of the surfactant contained in the colored layer ink according to the present embodiment is not particularly limited, but includes a fluorine-based surfactant, an acetylene glycol-based surfactant, a polysiloxane-based surfactant, and the like. It is preferable to contain the surfactant. Typical examples of the acetylene glycol surfactant and the polysiloxane surfactant are the same as the surfactant contained in the glitter ink. Acetylene glycol surfactants or polysiloxane surfactants can increase the wettability of a recording surface such as a recording medium and improve the ink permeability. Although the content rate of the said surfactant in colored layer ink is not specifically limited, It is preferable that they are 0.01 mass% or more and 5.0 mass% or less, and they are 0.1 mass% or more and 0.5 mass% or less. More preferably.

[6] Other components The color ink according to the present invention may contain components other than the above (other components). Examples of such components include pH inhibitors, penetrants, organic binders, urea compounds, sugars, drying inhibitors such as alkanolamines (such as triethanolamine), and the like.

  By forming the recorded matter 100 and 200 according to the present embodiment with the ink described above, the silver contained in the silver pigment layer 20 having brilliant properties is generated by reacting with chlorine contained in the recording medium 10. The resin layer 30 prevents contact between the silver chloride, which is a compound to be obtained, and the color material contained in the colored layer 40 that promotes the sensitivity of silver chloride to ultraviolet rays. As a result, it is possible to suppress the photosensitivity of the silver chloride generated in the silver pigment layer 20 and to obtain a recorded matter that can maintain the gloss of the formed glittering image over a long period of time.

  Further, by forming the resin layer 30 on the surface of the silver pigment layer 20, ultraviolet rays that sensitize silver chloride, which is a compound of silver contained in the silver pigment layer 20 and chlorine contained in the recording medium, are exposed to the silver pigment layer. Since transmission to 20 can be suppressed, a recorded matter capable of maintaining the gloss of the formed glittering image for a long time can be obtained. Furthermore, the resin layer 30 can suppress the penetration of moisture into the silver pigment layer 20 that promotes the formation of silver chloride, which is a compound of silver contained in the silver pigment layer 20 and chlorine contained in the recording medium. Therefore, it is possible to obtain a recorded matter in which the amount of silver chloride itself that lowers the glitter is reduced, and the gloss of the formed glitter image can be maintained over a long period of time.

In order to suppress the deterioration of the glitter (gloss) of the silver pigment layer 20, it is desirable to form the recorded material 100 and the recorded material 200 under the following conditions. Assuming that the layer thickness t _A of the silver pigment layer 20 shown in FIG. 1, the layer thickness t _P of the resin layer 30, and the layer thickness t _C of the colored layer 40,
50 nm ≦ t _A ≦ 280 nm
40 nm ≦ t _P ≦ 450 nm
500 nm ≦ t _C ≦ 5500 nm
It is preferable that

When the layer thickness t _A of the silver pigment layer 20 is less than 50 nm, the glossiness indicating glossiness decreases, and the silver contained in the silver pigment layer 20 absorbs and transmits visible light so that the silver pigment layer 20 is yellowish. May lead to discoloration. On the other hand, when the layer thickness t _A exceeds 280 nm, cracks are likely to occur in the silver pigment layer 20 and the quality of the recorded image is degraded. Furthermore, it consumes more silver than necessary and increases the printing cost.

When the layer thickness t _P of the resin layer 30 is less than 40 nm, functions for protecting the silver pigment layer 20 such as scratch resistance and water resistance are deteriorated. On the other hand, if the layer thickness t _P exceeds 450 nm, the absorption of visible light increases or the surface of the resin layer 30 becomes uneven and wavy, resulting in a decrease in glossiness.

When the layer thickness t _C of the colored layer 40 is less than 500 nm, good saturation cannot be obtained, and a good color metallic image cannot be obtained. Further, when the layer thickness t _C exceeds 5500 nm, a color metallic image with good saturation can be obtained. However, since a large amount of color ink is applied onto the resin layer 30, the ink from a predetermined recording image forming area is not coated. Overflow occurs and incident light that is regularly reflected by the silver pigment layer is absorbed by the colored layer. That is, the metallic feeling is lowered and a good recorded image cannot be obtained.

Therefore, the layer thicknesses t _A , t _P and t _C are
80 nm ≦ t _A ≦ 220 nm
80 nm ≦ t _P ≦ 400 nm
600 nm ≦ t _C ≦ 5000 nm
It is still more preferable that the recorded image is formed under the above conditions.

The layer thicknesses t _A , t _P , and t _C of each layer are preferably in the following relationship.
t _A : t _P = 1: 9 to t _A : t _P = 7: 1
t _A : t _C = 1: 11 to t _A : t _C = 7: 12
t _A + t _P + t _C ≦ 5500 nm

When t _P is larger than 9 times with respect to t _A , the function of protecting the silver pigment layer 20 can be sufficiently secured, but a good metallic space cannot be obtained due to light absorption by the resin layer 30. To The t _P is t _A, in the case of less than 1/7, lowering of the protection of the silver pigment layer 20, and thicker than necessary t _A, cracks are likely to occur in the silver pigment layer 20, the image The quality will be degraded. Furthermore, since the amount of silver used is large, the printing cost is increased. When t _C is larger than 11 times as much as t _A , sufficient color saturation is obtained, but incident light that is regularly reflected by the silver pigment layer is absorbed by the colored layer 40, that is, it has a metallic feeling. A decrease occurs. On the other hand, when t _C is less than 12/7 with respect to t _A , the metallic feeling is excellent, but only a color metallic with a light tint, that is, low saturation can be expressed. Further, the sum of the film thicknesses of t _A , t _P and t _C is preferably 5500 nm or less in order to prevent overflow of ink from a predetermined recording image forming area.

  As described above, since the photosensitivity is promoted by the color material contained in the colored layer 40 and the gloss is lowered due to the silver chloride generated in the silver pigment layer 20, the configuration of the recorded matter 200 according to the embodiment is as follows. The quinacridone color material having the structural skeleton shown in FIG. 2A and the copper phthalocyanine color material having the structural skeleton shown in FIG. Therefore, it is effective to apply the present invention to at least the colored layer 40 formed of these color materials. Note that the present invention is not limited to a recorded matter in which the resin layer 30 is formed only on the colored layer 40 formed of a copper phthalocyanine color material or a quinacridone color material.

  The quinacridone color material may be a pigment or a dye, but is preferably a pigment. Although not limited as a quinacridone pigment, C.I. I. Pigment violet 19, 42, C.I. I. Pigment red 122, 192, 202, 207, and 209, and preferably C.I. I. Pigment violet 19, C.I. I. Pigment Red 122, 202, and De 209.

  The copper phthalocyanine color material may be a dye or a pigment, but is preferably a pigment. Although it does not specifically limit as a copper phthalocyanine dye, C.I. I. Acid Blue 249, C.I. I. Direct blue 86, 87, 199 etc. are mentioned. Among them, C.I. I. Direct blue 199 is preferred. Although it does not specifically limit as a copper phthalocyanine pigment, C.I. I. Pigment green 7, 36, 37, C.I. I. Pigment blue 16, 75, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, and the like. I. Pigment green 7, 36, C.I. I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, and most preferably C.I. I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, and 15: 6.

(Second Embodiment)
FIG. 3 is a perspective view illustrating a schematic configuration of an ink jet printer as an example of a recording apparatus that forms the recorded matter 100 and the recorded matter 200 according to the first embodiment as the second embodiment.

  As shown in FIG. 3, an ink jet printer 1000 (hereinafter referred to as a printer 1000) as a recording apparatus has a frame 1100. A platen 1200 is provided on the frame 1100, and the recording medium 10 is fed onto the platen 1200 by driving a recording medium feed motor 1300. The frame 1100 is provided with a rod-shaped guide member 1400 in parallel with the longitudinal direction of the platen 1200. A carriage 1500 is supported on the guide member 1400 so as to be capable of reciprocating in the axial direction of the guide member 1400. The carriage 1500 is connected to a carriage motor 1700 via a timing belt 1600 provided in the frame 1100. The carriage 1500 is reciprocated along the guide member 1400 by driving the carriage motor 1700.

  The carriage 1500 is provided with a head 1800 and an ink cartridge 1900 for supplying ink as a liquid to the head 1800 is detachably disposed. The ink in the ink cartridge 1900 is supplied from the ink cartridge 1900 to the head 1800 by driving a piezoelectric element (not shown) provided in the head 1800, and from a plurality of nozzles formed on the nozzle formation surface of the head 1800, the platen 1200. The ink is discharged to the recording medium 10 fed upward. This makes it possible to produce recorded matter. As a discharging method, a thermal jet (bubble jet (registered trademark)) method may be used. In addition, any conventionally known method can be used.

[1] Brilliant ink Polyvinylpyrrolidone (PVP, weight average molecular weight 10,000) was heated at 70 ° C. for 15 hours and then cooled at room temperature. The PVP 1000g was added to the ethylene glycol solution 500ml, and the PVP solution was adjusted. In another container, 500 ml of ethylene glycol was added, 128 g of silver nitrate was added, and the mixture was sufficiently stirred with a magnetic stirrer to prepare a silver nitrate solution. While stirring the PVP solution using an overhead mixer at 120 ° C., the silver nitrate solution was added and the reaction was allowed to proceed by heating for about 80 minutes. And it was made to cool at room temperature after that. The obtained solution was centrifuged for 10 minutes with a centrifuge at 2200 rpm. Thereafter, the separated silver particles were taken out and added to 500 ml of an ethanol solution in order to remove excess PVP. Then, further centrifugation was performed to take out silver particles. Furthermore, the taken-out silver particle was dried on 35 degreeC and 1.3 Pa conditions with the vacuum dryer, and the predetermined | prescribed silver particle was obtained. In preparing the glittering ink composition containing the silver pigment, a silver particle dispersion liquid in which silver particles were previously dispersed with water was used. Specifically, the silver particles obtained by the above method were stirred in pure water for 3 hours and redispersed to obtain a silver particle aqueous dispersion adjusted to a solid content of 20%.

  As shown in the glitter ink composition of FIG. 4, 8% by mass of the silver particles produced as described above, 3% by mass of 1,6-hexanediol, 1.0% by mass of triethanolamine, and 5% of trimethylolpropane. 5% by mass, polyvinyl pyrrolidone (PVP, k-15) 5% by mass, nonionic surfactant (Orphine (R) E1010 manufactured by Nissin Chemical Industry Co., Ltd.) 0.5% by mass, paraffin wax (BIC Chemie Japan) AQUACER (R) 539) manufactured by the company was added to 0.1% by mass, and ion exchange water for adjusting the concentration was further added to obtain a glittering ink. The average particle diameter of the silver particles is “Microtrac UPA” (manufactured by Nikkiso Co., Ltd.), and the measurement conditions are a refractive index of 0.2-3.9i, a solvent (water) refractive index of 1.333, It was 20 nm when the shape of the measurement particles was spherical.

[2] Adjustment of Resin Layer Ink As shown in the resin layer ink formulation of FIG. 4, 1,2-hexanediol is 8% by mass, trimethylolpropane is 25% by mass, nonionic surfactant (Nisshin Chemical Industries) Olufin (R) E1010 manufactured by Co., Ltd. is 0.5% by mass, pH adjuster (triethanolamine) is 0.3% by mass, and paraffin wax (AQUACER (R) 539 manufactured by Big Chemie Japan) is 0.1. It was adjusted so that the mass%, the urethane resin emulsion (W6061 manufactured by Mitsui Chemicals, Inc.) was 1.5 mass%, and the remaining water.

[3] Adjustment of colored layer ink As the colored layer ink, magenta ink 1 (ICM37 manufactured by Seiko Epson Corporation) and the following colored layer ink adjusted as shown in the recipe of FIG. 5 were used.

Magenta ink 2:
6.0% by mass of 1,2-hexanediol, 25% by mass of trimethylolpropane, 1.0% by mass of nonionic surfactant (Orphine (R) E1010 manufactured by Nissin Chemical Industry Co., Ltd.), pH adjustment Agent (triethanolamine) is 1.0 mass%, C.I. I. Pigment violet 19 was adjusted to 4.0% by mass, urethane resin emulsion (W6061 manufactured by Mitsui Chemicals) was adjusted to 3.0% by mass, and water was left as a residue.

Cyan ink:
6.0% by mass of 1,2-hexanediol, 25% by mass of trimethylolpropane, 1.0% by mass of nonionic surfactant (Orphine (R) E1010 manufactured by Nissin Chemical Industry Co., Ltd.), pH adjustment Agent (triethanolamine) is 1.0 mass%, C.I. I. Pigment Blue 15: 3 was adjusted to 4.0% by mass, urethane resin emulsion (W6061 manufactured by Mitsui Chemicals, Inc.) was adjusted to 3.0% by mass, and water was left as a residue.

Yellow ink:
6.0% by mass of 1,2-hexanediol, 25% by mass of trimethylolpropane, 1.0% by mass of nonionic surfactant (Orphine (R) E1010 manufactured by Nissin Chemical Industry Co., Ltd.), pH adjustment Agent (triethanolamine) is 1.0 mass%, C.I. I. Pigment Yellow 74 was adjusted to 4.0% by mass, urethane resin emulsion (W6061 manufactured by Mitsui Chemicals, Inc.) was 3.0% by mass, and water was left as a residue.

[4] Preparation of recorded matter Commercially available glossy paper containing the above-mentioned glitter ink, resin layer ink, and colored layer ink in a dedicated cartridge of an ink jet printer (“PX-G930” manufactured by Seiko Epson Corporation) and containing chlorine. (Photo paper <Glossy> manufactured by Seiko Epson Corporation) was set in an ink jet printer, and recorded materials of the following Examples and Comparative Examples and Reference Examples were formed.

(Examples 1-3, Comparative Examples 1-6)
As shown in FIG. 6, the ink was ejected on the glossy paper so that a predetermined recording image was formed in the order of the colored layer ink using the glitter ink, the resin layer ink, and the magenta 1 ink. The thickness of the silver pigment layer, the thickness of the resin layer, and the thickness of the colored layer formed by the glitter ink in the recorded image are recorded as in Examples 1 to 3 and Comparative Examples 1 to 6 shown in FIG. It was created.

(Example 4, Comparative Example 8)
As shown in FIG. 6, ink was ejected so as to form a predetermined image in the order of glitter ink and resin layer ink on glossy paper. In the recorded image, the thickness of the silver pigment layer formed by the glitter ink and the thickness of the resin layer were recorded as in Example 4 and Comparative Example 8 shown in FIG.

(Examples 5-7)
As shown in FIG. 7, ink was ejected so that a predetermined image was formed in the order of glitter ink, resin layer ink, and colored layer ink on glossy paper. For the colored layer, magenta 2 ink, cyan ink, and yellow ink shown in FIG. 5 were used. With respect to the thickness of the silver pigment layer, the thickness of the resin layer, and the thickness of the colored layer formed by the glitter ink in the recorded image, recorded materials as shown in Examples 5 to 7 shown in FIG.

(Reference Examples 1 and 2)
As shown in FIG. 6, the ink was ejected on the glossy paper so as to form a predetermined image in the order of the colored layer ink using the glitter ink, the resin layer ink, and the magenta 1 ink. In the recorded image, the recorded matter as shown in Reference Examples 1 and 2 shown in FIG. 4 was prepared for the thickness of the silver pigment layer, the thickness of the resin layer, and the thickness of the colored layer formed by the glitter ink.

[5] Evaluation of initial gloss The initial gloss of a recorded product is evaluated according to the following criteria by measuring the gloss at a turning angle of 60 ° using a “MULTI GLOSS 268 gloss meter” (trade name, manufactured by Konica Minolta). did.
A: Gloss value is 200 or more B: Gloss value is 150 or more and less than 200% C: Gloss value is 100 or more and less than 150% D: Gloss value is less than 100 These results are shown in FIG.

[6] Saturation Using a colorimeter “SPECTROLINO” (manufactured by Gretag Macbeth), the determination was made as follows.
Determination A: Saturation C * 7 or higher (colorful)
Determination B: Saturation C * 3.5 or more and less than 7 (there is color)
Determination C: Saturation C * 1 or more and less than 3.5 (there is almost no color)

[7] Metallic feeling The metallic feeling (metallic luster) by the silver pigment layer was determined as follows.
Judgment A: Clear metallic luster Judgment B: Metallic luster Judgment C: Slight metallic luster Judgment D: No metallic luster

[8] Light resistance evaluation The light resistance test was performed using a xenon light resistance tester according to the JEITA CP-3901 method. Following exposure for 20 years, the following determinations were made.
Judgment A: No discoloration Judgment B: Slight discoloration Judgment C: Discoloration present

[9] Overflow after printing “Overflow after printing” refers to a state where ink protrudes from a predetermined image forming area. Therefore, the recorded material without overflow was determined as “◯”, and the recorded material with overflow was determined as “x”.

[10] Comprehensive Judgment of Recorded Items The comprehensive judgment in the tables shown in FIGS. 6 and 7 is “◯” when any of the above evaluation items is the following evaluation result, and any of the evaluation items is the following evaluation result. When it was not, it was set as "x".
Initial gloss evaluation: A or B
Saturation: A or B
Metallic feeling: A or B
Light resistance: A
Overflow after printing: No overflow “○”

  As is apparent from FIG. 6, according to the recorded matter according to the above-described embodiment, a recorded image having excellent gloss and light resistance can be obtained. On the other hand, satisfactory results could not be obtained with the recorded material shown in the comparative example. Further, as is apparent from FIG. 7, C.I. of the quinacridone pigment which deteriorates the light resistance. I. Pigment Violet 19, a copper phthalocyanine pigment C.I. I. Pigment Blue 15: 3, an azo pigment C.I. I. Even when CI Pigment Yellow 72 or the like is used as the colored layer ink, a recorded matter on which a recorded image having good light resistance is formed can be obtained.

  DESCRIPTION OF SYMBOLS 10 ... Recording medium, 20 ... Silver pigment layer, 30 ... Resin layer, 40 ... Colored layer, 100 ... Recorded matter.

Claims (6)

A recorded matter in which an image is formed on at least one recording surface of a recording medium,
The recording medium contains chlorine or a chlorine compound,
In the image, a silver pigment layer is formed on the recording surface, and a resin layer is formed on the surface of the silver pigment layer.
The film thickness of the silver pigment layer is 50 nm or more and 280 nm or less,
The film thickness of the resin layer is 40 nm or more and 450 nm or less ,
A colored layer is formed on the surface of the resin layer,
The recorded matter, wherein the colored layer has a thickness of 500 nm or more and 5500 nm or less . The silver pigment layer, the recording material according to claim 1, characterized in that that will be formed by the first ink composition comprising water and silver. The resin layer includes a resin 0.1 mass% or more, coloring material according to any one of claims 1 or 2, characterized in that that will be formed by the second ink composition is substantially free Recorded matter. Wherein the resin of the second ink composition, urethane resins, polyester resins, fluorene resins, recorded matter according to claim 3, wherein the Ru Der any one or more paraffin waxes. The colored layer, the recording material according to claim 1, any one of 4, characterized in that you at least quinacridone colorant or copper phthalocyanine-colored colorant. The silver pigment layer and the film thickness ratio between the resin layer is 1: 9 to 7: recorded matter according to any one of claims 1 to 5, characterized in that Ru 1 der.

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