JP5942333B2 - Thermal transfer medium, thermal transfer medium manufacturing method and image forming method - Google Patents

Description

The present invention is a thermal transfer medium, relates to the manufacturing method and the image forming method of the thermal transfer medium.

  Conventionally, a thermal transfer sheet (thermal transfer medium) having a configuration in which an image layer that can be thermally transferred is provided on a sheet such as paper or a plastic film is known. Generally, image layers such as characters and symbols are formed on the sheet by silk screen printing, gravure printing, offset printing or the like by the thermal transfer sheet. The thermal transfer sheet can record an image on a recording medium by thermally transferring the image layer to a recording medium (transfer target medium).

By the way, as a method for forming such an image layer, an attempt is made to produce a thermal transfer sheet by ejecting ink onto a sheet by an ink jet method to form an image. By using the inkjet method, a thermal transfer sheet corresponding to various images can be easily manufactured.
However, in a thermal transfer sheet manufactured by a conventional ink jet method, the adhesion between the image layer and the sheet is increased due to the influence of the resin for dispersing the colorant in the ink, and the peelability of the image layer is reduced. There was a problem such as. For this reason, there has been a problem that the image is not sufficiently transferred to the recording medium. In particular, when a transfer sheet having a void layer as an ink receiving layer was used, such a tendency was remarkable.

JP 2000-168250 A

  An object of the present invention is to provide a thermal transfer medium having excellent image transferability, a method for producing a thermal transfer medium capable of easily producing such a thermal transfer medium, an image forming method using such a thermal transfer medium, and such a method. An object of the present invention is to provide a recorded matter in which an image is recorded using a thermal transfer medium.

Such an object is achieved by the present invention described below.
The thermal transfer medium of the present invention has a void layer as an ink receiving layer, and a transfer sheet provided with a silicon resin on the surface on which the void layer is formed,
Wherein the surface on which the gap layer is the silicone resin is provided has been granted the transfer sheet, the color material and having and an image layer formed by the dispersed ink.
Thereby, a thermal transfer medium having excellent image transferability can be provided.

In the thermal transfer medium of the present invention, the ink is preferably at least one selected from a color ink in which a colorant is dispersed as a color material and a glitter ink in which a glitter pigment is dispersed as a color material.
Accordingly, it is possible to provide a thermal transfer medium having an image layer that has an excellent image transferability and can form an image with excellent color developability.

In the thermal transfer medium of the present invention, the content of the resin component in the color ink is preferably 0.1% by mass or more and 10% by mass or less.
Thereby, the image layer can be more easily peeled from the transfer sheet at the time of transferring the image layer of the thermal transfer medium while preventing the image layer from being unintentionally peeled off from the transfer sheet.
In the thermal transfer medium of the present invention, the colorant is preferably dispersed using a resin.
Thereby, the dispersibility of a coloring agent can be made excellent. This also makes it possible to more easily peel the image layer from the transfer sheet during transfer of the image layer of the thermal transfer medium, and to prevent the image layer from being unintentionally peeled off from the transfer sheet during storage.

In the thermal transfer medium of the present invention, the image layer includes a colored layer provided with the color ink on the surface provided with the silicon resin, and a glitter layer provided with the glitter ink on the colored layer. It is preferable to have.
Thereby, the image transferability can be further improved.
In the thermal transfer medium of the present invention, it is preferable that an adhesive layer is applied to the image layer with a material containing an adhesive compound.
Thereby, the image transferability can be further improved.

The image forming method of the present invention includes a transfer step of transferring the image layer of the thermal transfer medium of the present invention to a recording medium different from the transfer sheet.
Thereby, an image excellent in color developability can be formed.
The recorded matter of the present invention is formed by the image forming method of the present invention,
It has the recording medium, the adhesive layer, and the image layer.
Thereby, it is possible to provide a recorded matter provided with an image having excellent color developability.

The method for producing a thermal transfer medium of the present invention is a method for producing a thermal transfer medium using a transfer sheet having a void layer as an ink-receiving layer and having a silicone resin applied to the surface on which the void layer is formed .
A step of forming an image layer by applying an ink in which a coloring material is dispersed to a surface of the transfer sheet on which the void layer is formed and the silicon resin is applied, by an inkjet method. To do.
Thereby, the manufacturing method of the thermal transfer medium which can manufacture easily the thermal transfer medium which has the outstanding image transferability can be provided.

It is sectional drawing which shows an example of the thermal transfer medium of this invention. It is a perspective view which shows schematic structure of an inkjet apparatus. It is a schematic diagram which shows an example of the manufacturing method of the thermal transfer medium of this invention. It is a schematic diagram which shows an example of the image forming method of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<Thermal transfer medium>
First, a preferred embodiment of the thermal transfer medium of the present invention will be described.
FIG. 1 is a cross-sectional view showing an example of the thermal transfer medium of the present invention.
As shown in FIG. 1, the thermal transfer medium 100 is configured by a laminate in which a transfer sheet 11, an image layer 12, and an adhesive layer 13 are sequentially laminated.

The transfer sheet 11 has a function of supporting the image layer 12 and the adhesive layer 13 and is removed at the time of image formation.
The transfer sheet 11 is obtained by applying a silicon resin to a surface (a surface in contact with the image layer 12) of the base sheet having a void layer as an ink receiving layer.
By the way, in the thermal transfer sheet manufactured by the conventional inkjet method, the adhesiveness between the image layer and the transfer sheet is increased due to the influence of the resin for dispersing the colorant in the ink, and the peelability of the image layer is increased. There was a problem of a drop. For this reason, there has been a problem that the image is not sufficiently transferred to the recording medium. In particular, when a transfer sheet having a void layer as an ink receiving layer was used, such a tendency was remarkable.

  On the other hand, in the thermal transfer medium of the present invention, the transfer sheet is obtained by adding a silicone resin to the surface of the base sheet having the void layer as the ink receiving layer. It has characteristics. By having such characteristics, it is possible to prevent the image layer due to the resin derived from the ink contained in the image layer and the transfer sheet from being excessively adhered, and the image layer is excellently peelable from the transfer sheet. Can be. As a result, a thermal transfer medium having excellent image transferability can be provided.

  Examples of the silicone resin used in the present invention include Polyflow KL-401, Polyflow KL-402 (trade name of Kyoeisha Chemical Co., Ltd.), BYK-322 (trade name of Big Chemie Japan Co., Ltd.), BYK-331 (Bic Chemie Product name of Japan Co., Ltd.). The silicone resin is more preferably silicone oil that is liquid at room temperature.

Note that the range to which the silicon resin is applied may be the entire surface of the transfer sheet 11 or only the portion where the image layer is formed. Further, the silicon resin may be applied to the entire thickness direction of the transfer sheet 11 or may be applied to a part near the surface.
The material of the base sheet constituting the transfer sheet 11 is not particularly limited as long as it is provided with a void layer as an ink receiving layer. For example, the substrate sheet includes a void layer in a region including the surface to which ink is applied. In addition, examples include various plastics, ceramics, glass, metal, and base materials composed of these composite materials. The “void layer” means that the proportion of the resin is less than 30% of the components constituting the layer, and the liquid is mainly formed between the inorganic particles or in the pores provided in the inorganic particles. A layer configured to penetrate. When a sheet having such a void layer is used, it is possible to form an image with excellent color developability, but an image was formed by applying ink to the sheet having such a void layer by an inkjet method. In such a case, there is a problem that a decrease in peelability of the image layer 12 becomes remarkable due to the resin contained in the ink. However, the peelability of the image layer 12 can be made excellent by using the transfer sheet 11 provided with a silicon resin. Examples of inorganic particles include heavy calcium carbonate, light calcium carbonate, kaolin, purified natural mineral pigments such as talc, composite synthetic pigments of calcium carbonate and other hydrophilic organic compounds, satin white, lithopone. , Titanium dioxide, silica, alumina, aluminum hydroxide, zinc oxide, magnesium carbonate, and organic pigments.

The image layer 12 is a layer formed on the transfer sheet 11 and is a layer formed by evaporating at least a part of an ink dispersion medium as described later. The image layer 12 may be formed on the entire surface of the transfer sheet 11 or may be formed on a part of the transfer sheet 11. The image layer 12 becomes an image on the transfer destination recording medium when it is transferred from the thermal transfer medium 100 to the transfer destination recording medium. The image layer may be formed by any one of the color ink and the glitter ink described later. Preferably, the image layer has a colored layer in which a color ink is applied to a surface on which a void layer is formed and a silicon resin is applied, and a glittering layer in which a glittering ink is applied to the colored layer. It is. With such an image layer, even when a thermal transfer medium having a void layer is used, a glittering image colored on the transfer destination recording medium can be obtained.

The ink will be described in detail later.
The adhesive layer 13 is formed on at least the image layer 12, and has a function of adhering the image layer 12 and the recording medium when the image layer 12 is transferred from the thermal transfer medium 100 to a recording medium as a transfer destination. Yes. Note that the adhesive layer 13 may be formed on a region other than on the image layer 12. Further, the adhesive layer 13 may be formed on the image layer 12 by being formed on the transfer destination recording medium, and the recording medium being disposed so as to face the image layer 12.

  Although the thickness of the contact bonding layer 13 is not specifically limited, For example, it can be 0.2 micrometer or more and 10 micrometers or less. The thickness of the adhesive layer 13 can be appropriately set according to the property of the recording medium that is the transfer destination of the image layer 12. For example, when the unevenness of the surface of the transfer destination recording medium is large, the thickness of the adhesive layer 13 is such that the influence of the unevenness does not occur on the surface of the image layer 12 (the surface in contact with the transfer sheet 11 before transfer). Can be set as appropriate. Further, when the recording medium of the transfer destination has permeability, the thickness can be set in consideration of the permeability.

The adhesive layer 13 has adhesiveness. Here, adhesiveness refers to the property of adhering the image layer 12 and the transfer destination recording medium. In the present invention, the adhesiveness is manifested when a temperature (heat) stimulus is applied to the adhesive layer 13.
The degree of adhesiveness of the adhesive layer 13 is greater than the adhesive force (adhesive force) between the transfer sheet 11 and the protective layer, and the adhesion between the image layer 12 and the transfer destination recording medium via the adhesive layer 13. It is sufficient if the force (adhesion) is greater. In the case where no protective layer is provided, the adhesion between the image layer 12 and the transfer destination recording medium via the adhesive layer 13 is higher than the adhesive force (adhesion force) between the transfer sheet 11 and the image layer 12. It is sufficient if the adhesive force (adhesion force) is larger. Note that it is not necessary to transfer all of the bright pigment constituting the image layer 12 for the image, and an adhesive layer 13 having an adhesive force to be partially transferred may be formed.
The adhesive layer 13 is made of a material containing an adhesive compound.

  Examples of such adhesive compounds include monomers, oligomers, polyester resins, polyacrylic ester resins, polyacrylic esters, acrylic resins, urethane-based, vinyl chloride-based, and vinyl acetate-based adhesives. Vinyl acetate resins, polyvinyl chloride resins such as polyvinyl chloride resins and polyvinyl alcohol resins, polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral, polyether resins, polyurethane resins, styrene acrylate resins, polyacrylamide resins And resins such as polyamide resins, polystyrene resins, polyethylene resins, polypropylene resins, and polyvinylpyrrolidone resins. In this case, additives such as a polymerization initiator, a reaction aid, and a filler may be contained as necessary. Examples of the compound having adhesive properties include thermoplastic resins such as polyolefins, polyamides, and modified products thereof. In this case, additives such as an antioxidant, an ultraviolet absorber and a filler may be contained as necessary. In addition, examples of the compound having adhesiveness include sticky substances such as rosin, gelatinized starch, glue, natural resins such as various sugars, and modified products thereof.

"ink"
Next, the ink used for forming the image layer of the thermal transfer medium of the present invention will be described.
As the ink used in the present invention, a color ink in which a colorant is dispersed as a color material and a glitter ink in which a glitter pigment is dispersed as a color material can be used. By using such an ink, the image layer 12 capable of forming an image with excellent color developability can be easily formed.

[Color ink]
The color ink is an ink used for forming the image layer 12 alone or together with the glitter ink described later.
Color ink contains a colorant. Color inks include cyan, magenta, yellow, light cyan, light magenta, dark yellow, red, green, blue, orange, violet, etc., black ink, light black And ink.

Examples of the colorant include pigments and dyes, and any colorant that can be used in ordinary inks can be used without particular limitation.
Although it does not restrict | limit especially as a pigment which can be used for this embodiment, Various well-known pigments are mentioned.
Examples of yellow 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, 155, 167, 172, 180, 185, 213 and the like. Pigment yellow 74, 155, and 213 are preferable.

  Examples of magenta 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, 202, 209, 219, 224, 245, 254, 264 or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like. Pigment Red 122, Red 202, and Pigment Violet 19 are preferable.

Examples of cyan 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, C.I. I. Bat Blue 4, 60 and the like. Pigment blue 15: 3 and 15: 4 are preferable.
Examples of organic pigments other than magenta, cyan and yellow include C.I. I. Pigment green 7, 10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, and the like.

The pigment preferably has an average particle size in the range of 10 nm to 200 nm, more preferably about 50 nm to 150 nm. The addition amount of the pigment in the present embodiment is preferably in the range of about 1% by mass to 25% by mass, and more preferably in the range of 3% by mass to 20% by mass.
Examples of the dye that can be used in this embodiment include acridine dyes, aniline dyes, anthraquinone dyes, azine dyes, azomethine dyes, benzo- and naphthoquinone dyes, indigoid dyes, indophenol dyes, indoaniline dyes, indamine dyes, leuco dyes, Naphthalimide dyes, nigrosine dyes, indulin dyes, nitro and nitroso dyes, oxazine and dioxazine dyes, oxidation dyes, phthalocyanine dyes, polymethine dyes, quinophthalone dyes, sulfur dyes, tri and diacrylmethane dyes, thiazine dyes, thiazole dyes, xanthene dyes, And cyanine dyes.

  Specific 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.

  Specific examples of the magenta dye 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.

  Specific 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.

  Specific dyes of other color systems include, for example, C.I. I. Acid Green 7, 12, 25, 27, 35, 36, 40, 43, 44, 65, 79, C.I. I. Direct Green 1, 6, 8, 26, 28, 30, 31, 37, 59, 63, 64, C.I. I. Reactive Green 6, 7, C.I. I. Acid Violet 15, 43, 66, 78, 106, C.I. I. Direct violet 2, 48, 63, 90, C.I. I. Reactive violet 1, 5, 9, 10 etc. are mentioned.

A plurality of these dyes can be selected from the group of dyes of each color system described above and between groups.
The addition amount of the dye in the present embodiment is preferably in the range of about 1% by mass to 25% by mass, more preferably in the range of 3% by mass to 20% by mass.
The color ink preferably contains a resin component. Thereby, the dispersibility of a coloring agent can be made excellent. This also makes it possible to more easily peel the image layer 12 from the transfer sheet 11 when transferring the image layer 12 of the thermal transfer medium 100, and to prevent the image layer 12 from being unintentionally peeled from the transfer sheet 11 during storage. Can be prevented.

  Resin components include polyacrylic acid, polymethacrylic acid, polymethacrylic acid ester, polyethylacrylic acid, styrene-butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer, chloroprene copolymer, fluororesin, fluorine resin, Vinylidene chloride, polyolefin resin, cellulose, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, polystyrene, styrene-acrylamide copolymer, polyisobutyl acrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl acetal, polyamide, rosin Resin, polyethylene, polycarbonate, vinylidene chloride resin, cellulose resin such as cellulose acetate butyrate, vinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic Copolymers, vinyl chloride resin, polyurethane, and rosin esters, and the like is not limited thereto.

Among the above, it is preferable to use at least one selected from the group consisting of a styrene-acrylic resin and polyurethane as the resin component.
The content of the resin component in the color ink is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less. Thereby, the image layer 12 can be more easily peeled from the transfer sheet 11 when the image layer 12 of the thermal transfer medium 100 is transferred while preventing the image layer 12 from being unintentionally peeled off from the transfer sheet 11.

[Bright ink]
The glitter ink is an ink used to form the image layer 12 alone or together with the color ink. When such glitter ink is used together with the color ink, the color ink is applied to the transfer sheet 11 and then applied onto the layer formed of the color ink. Thereby, while being able to make the outstanding image transfer property excellent, color property and brightness can be provided to the formed image.

As the glitter pigment contained in the glitter ink, any pigment can be used as long as the ink droplets can be ejected by the ink jet recording method. The glitter pigment has a function of imparting glitter when the glitter ink is deposited on the resin ink layer, and can also impart glitter to the deposit. Examples of such bright pigments include pearl pigments and metal particles. Representative examples of pearl pigments include pigments having pearly luster and interference gloss such as titanium dioxide-coated mica, fish scale foil, and bismuth oxychloride. On the other hand, examples of the metal particles include particles of aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, copper, etc., and are selected from these simple substances or alloys thereof and mixtures thereof. At least one kind can be used.
The glitter pigment used in the present embodiment is preferably silver particles from the viewpoint of high glossiness (brightness). Hereinafter, a silver ink will be described as a specific example of the glitter ink.

(1) Silver particle As mentioned above, the silver ink which concerns on this embodiment contains a silver particle. As described above, when the silver ink contains silver particles, an image having excellent metallic luster can be formed. Moreover, since silver is a metal having high whiteness among various metals, various metal colors such as gold and copper can be expressed by overlapping with other color inks.

  The average particle diameter of the silver particles is preferably 3 nm or more and 100 nm or less, and more preferably 10 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 silver particle content in the silver 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, it achieves good image quality and abrasion resistance in a wide density range from low to high density of silver particles (content per unit area) on the recording medium when it is recorded. be able to.
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.

(2) Resin The glitter ink according to the present invention may contain a resin, and by containing this, fixability and abrasion 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, polyamide, rosin Resin, polyethylene, polycarbonate, vinylidene chloride resin, cellulose resin such as cellulose acetate butyrate, vinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer Coalescence, vinyl chloride resin, polyurethane, and rosin esters, and the like is not limited thereto.

(3) 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.
When water is contained in the ink, it functions mainly as a dispersion medium for dispersing silver particles. When the ink contains water, the dispersion stability of silver particles and the like can be improved. Further, it is possible to quickly dry on the transfer sheet to which ink is applied while preventing unintentional drying (evaporation of the dispersion medium) of the ink in the vicinity of the nozzle of the droplet discharge device as will be described later. Therefore, high-speed recording of a desired image can be suitably performed over a long period. Further, it is possible to form an image having excellent image transferability and particularly excellent in glitter. When water is contained in the ink, the content of the water is not particularly limited, but is preferably 20% by mass to 80% by mass, and more preferably 25% by mass to 70% by mass. preferable.

(4) Polyhydric alcohol The glittering ink according to the present invention 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, 1,2-heptanediol, 1,2-octanediol, 1,6-hexanediol and the like. . Especially, a C4-C8 alkanediol is preferable and a C6-C8 alkanediol is more preferable. Thereby, the permeability to the 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 above polyhydric alcohols, the ink preferably contains 1,2-hexanediol and trimethylolpropane. As a result, the dispersion stability of the silver particles in the ink can be made particularly excellent, the storage stability of the ink can be made particularly excellent, and the ink ejection stability is particularly excellent It can be.

(5) Glycol ether The glittering ink according to the present invention preferably contains glycol ether. By including the glycol ether, the wettability to the recording surface such as a transfer sheet can be improved and the ink permeability can be increased.
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.

(6) Surfactant The glitter ink according to the present invention preferably contains an acetylene glycol surfactant or a polysiloxane surfactant. Acetylene glycol surfactants or polysiloxane surfactants can increase the wettability of a recording surface such as a transfer sheet to increase 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.).

Commercially available products can be used as the polysiloxane surfactant, and examples thereof include BYK-347, BYK-348 (manufactured by BYK Japan).
Furthermore, the ink according to the present invention can also contain other surfactants such as an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
The content of the surfactant in the glitter ink is not particularly limited, but is preferably 0.01% by mass or more and 5.0% by mass or less, and preferably 0.1% by mass or more and 0.5% by mass or less. More preferably.

(7) Other components The glittering ink according to the present invention may contain components other than those described above (other components). Examples of such components include pH regulators, penetrants, organic binders, urea compounds, drying inhibitors such as alkanolamines (such as triethanolamine), and thiourea.

<Inkjet device>
Next, a preferred embodiment of the ink jet apparatus (droplet discharge apparatus) will be described. FIG. 2 is a perspective view illustrating a schematic configuration of the ink jet apparatus according to the present embodiment. As shown in FIG. 2, an ink jet printer 1 (hereinafter referred to as a printer 1) as a recording apparatus has a frame 2. A platen 3 is provided on the frame 2, and a medium P is fed onto the platen 3 by driving a medium feed motor 4. The frame 2 is provided with a rod-shaped guide member 5 in parallel with the longitudinal direction of the platen 3.

A carriage 6 is supported on the guide member 5 so as to be capable of reciprocating in the axial direction of the guide member 5. The carriage 6 is connected to a carriage motor 8 via a timing belt 7 provided in the frame 2. The carriage 6 is reciprocated along the guide member 5 by driving the carriage motor 8.
The carriage 6 is provided with a head 9 and an ink cartridge 10 for supplying ink as liquid to the head 9 is detachably disposed. The ink in the ink cartridge 10 is supplied from the ink cartridge 10 to the head 9 by driving a piezoelectric element (not shown) provided in the head 9, and from the plurality of nozzles formed on the nozzle forming surface of the head 9, the platen 3 The ink is discharged to the medium P fed upward. Thereby, an image (image layer) can be formed.
As a discharging method, a thermal jet (bubble jet (registered trademark)) method may be used. In addition, any conventionally known method can be used.

<< Method for producing thermal transfer medium >>
Next, a method for manufacturing a thermal transfer medium using the ink as described above will be described in detail.
FIG. 3 is a schematic view showing an example of a method for producing a thermal transfer medium of the present invention.
The thermal transfer medium manufacturing method of the present embodiment includes a transfer sheet forming step of forming a transfer sheet 11 by applying silicon resin to one surface of a base sheet, and an ink as described above by an inkjet method on the transfer sheet 11. The image layer forming step for forming the image layer 12, the drying step for drying the formed image layer 12, and the material containing an adhesive compound are applied to the image layer 12 to form the adhesive layer 13. An adhesive layer forming step.

Hereinafter, each step will be described in detail.
First, as shown in FIG. 3A, a transfer sheet 11 is prepared.
The transfer sheet 11 can be formed by applying a silicon resin to one surface of the base sheet.
As the base sheet and the silicon resin, those described above are used.

Next, as shown in FIG. 3B, the above-described ink is applied to the transfer sheet 11 using the above-described ink jet apparatus to form the image layer 12 (image layer forming step).
Next, the formed image layer 12 is dried (drying process).
In the drying step, at least a part of the water contained in the image layer 12 immediately after formation is removed.

Next, as shown in FIG.3 (c), the material containing the compound which has adhesiveness is provided on the image layer 12, and the contact bonding layer 13 is formed (adhesion layer formation process). Thereby, the thermal transfer medium 100 (the thermal transfer medium of the present invention) can be obtained.
The method for applying a material containing an adhesive compound is not particularly limited, and is an ink jet method, a dipping method (including application by a brush, a squeegee, etc.), a bar coating method, a stencil printing method (screen printing method), a relief printing plate. Examples thereof include a printing method and an intaglio printing method. Among these methods, the inkjet method does not require a step such as preparing a plate, and can be selectively applied onto the image layer 12, thereby suppressing waste of a material containing an adhesive compound. It is more preferable in that
In addition, after providing the material containing the compound which has adhesiveness, you may provide the drying process which dries the contact bonding layer 13 as needed.

<Image forming method>
Next, an image forming method using the thermal transfer medium 100 as described above will be described.
FIG. 4 is a schematic diagram showing an example of the image forming method of the present invention.
First, as shown in FIG. 4A, a recording medium 15 is prepared, the recording medium 15 and the adhesive layer 13 of the thermal transfer medium 100 are arranged to face each other, and the image layer 12 and the recording medium 15 are arranged. Bonding is performed via the bonding layer 13 (bonding step).

  The recording medium 15 is not particularly limited, and examples thereof include various papers, cloths, films, and sheets. More specifically, papers described in Japanese Industrial Standard JIS-P0001, textiles described in JIS-L0206, nonwoven fabrics described in JIS-L0222, and polyethylene terephthalate (PET), Polybutylene terephthalate (PBT), polycarbonate, polyethylene naphthalate, polyester, polyethylene, polypropylene, acrylic resin, polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyether ether ketone, polyamide, polyether sulfone, polydiacetate, triacetate And films and sheets of materials such as polyimide, wood, metal, ceramics, and glass. The recording medium 15 may be coated paper such as coated paper or art paper.

The image layer 12 and the recording medium 15 are bonded by heating. Thereby, the adhesiveness (adhesiveness) between the image layer 12 (adhesive layer 13) and the recording medium 15 can be made higher.
Next, as shown in FIG. 4B, the transfer sheet 11 and the image layer 12 are peeled off, and the image layer 12 is transferred to the recording medium 15 (transfer process). Thereby, a recorded matter 200 (recorded matter of the present invention) provided with the image layer 12, the adhesive layer 13, and the recording medium 15 can be obtained.
According to the image forming method as described above, it is possible to easily form a recorded matter provided with an image having excellent color developability.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.

Next, specific examples of the present invention will be described.
[1] Ink (1) Color ink As color ink, yellow ink (ICY37, manufactured by Seiko Epson Corporation) and magenta ink (ICM37, manufactured by Seiko Epson Corporation) were prepared.

(2) Glossy ink 17 g of trisodium citrate dihydrate and 0.36 g of tannic acid were dissolved in 50 mL of water made alkaline by adding 3 mL of 10N-NaOH aqueous solution. To the obtained solution, 3 mL of 3.87 mol / L silver nitrate aqueous solution was added and stirred for 2 hours to obtain a silver colloid solution.
The obtained silver colloid solution was desalted by dialysis until the electrical conductivity was 30 μS / cm or less. After dialysis, the coarse metal colloid particles were removed by centrifugation at 3000 rpm for 10 minutes. The average particle size was 20 nm. In this example, the average particle diameter of silver particles is “Microtrac UPA” (manufactured by Nikkiso Co., Ltd.), and the measurement conditions are a refractive index of 0.2-3.9i and a refractive index of solvent (water) Was 1.333 and the measured particle shape was spherical.
Silver colloid liquid produced as described above: 10 parts by mass, nonionic surfactant (Orphine (R) E1010 manufactured by Nissin Chemical Industry Co., Ltd.): 1 part by mass, trimethylolpropane: 10 parts by mass, 1 , 2-hexanediol: 5 parts by mass and ion-exchanged water: 74 parts by mass were added to obtain a glittering ink.

[2] Preparation of material containing adhesive compound (adhesive layer forming ink) Vinyl chloride emulsion (vinyl chloride adhesive, manufactured by Nissin Chemical Industry Co., Ltd.): 10 parts by mass and nonionic surfactant (Orshin (R) E1010 manufactured by Nissin Chemical Industry Co., Ltd.): 1 part by mass, propylene glycol: 11 parts by mass, 1,2-hexanediol: 5 parts by mass, 2-pyrrolidone: 2 parts by mass, ion exchange Water: 71 parts by mass were mixed to obtain an adhesive layer forming ink.

[3] Production of thermal transfer medium (Example 1)
A base sheet having a void layer (manufactured by Seiko Epson Corporation, trade name “Epson Photographic Paper <Glossy>”) is prepared, and a silicone resin (Polyflow KL-401, Kyoeisha Chemical Co., Ltd.) was applied with a # 2 bar coater to a film thickness of about 4.5 μm to form a transfer sheet.

On the obtained transfer sheet, yellow ink was applied at 50% duty with PX-G930 (manufactured by Seiko Epson) to form an image layer.
Thereafter, the formed image layer was dried.
Next, an adhesive layer forming ink was applied at 50% duty on the image layer by PX-G930 (manufactured by Seiko Epson Corporation) and dried to form an adhesive layer.

(Example 2)
A thermal transfer medium was manufactured in the same manner as in Example 1 except that magenta ink was used as the ink.
(Example 3)
A thermal transfer medium was produced in the same manner as in Example 1 except that glittering ink was used as the ink.

Example 4
A base sheet having a void layer (manufactured by Seiko Epson Corporation, trade name “Epson Photographic Paper” <Glossy>) is prepared, and a silicone resin (Polyflow KL-401, Kyoeisha Chemical Co., Ltd.) was applied with a # 2 bar coater to a film thickness of about 4.5 μm to form a transfer sheet.

On the obtained transfer sheet, PX-G930 (manufactured by Seiko Epson) applied yellow ink at 50% duty, and then applied glitter ink at 50% duty on the yellow ink layer. Formed.
Thereafter, the formed image layer was dried.
Next, an adhesive layer forming ink was applied at 50% duty on the image layer by PX-G930 (manufactured by Seiko Epson Corporation) and dried to form an adhesive layer.
(Examples 5 to 12)
Except for using the silicon resin shown in Table 1 and applying the ink shown in Table 1, when one type of ink is used, it is the same as in Example 1 above, and when two types are used, the above example is used. In the same manner as in No. 4, a thermal transfer medium was produced.

(Comparative Examples 1-20)
The material shown in Table 1 was used in place of the silicone resin, and the ink shown in Table 1 was used, except that one type of ink was used in the same manner as in Example 1 above, and when two types were used, the above type was used. A thermal transfer medium was produced in the same manner as in Example 4.
(Comparative Examples 21-24)
In the case of using one kind of ink except that the base sheet is used as it is as a transfer sheet without applying the silicon resin to the base sheet, and the ink shown in Table 1 is used, When two types were used, a thermal transfer medium was produced in the same manner as in Example 4 above.

In Table 1, Polyflow KL-401 (manufactured by Kyoeisha Chemical Co., Ltd.) is K401, Polyflow KL-402 (manufactured by Kyoeisha Chemical Co., Ltd.) is K402, BYK-322 (manufactured by Big Chemie Japan Co., Ltd.) is BYK, silicon emulsion (SM7001EX, manufactured by Toray Dow Corning Co., Ltd.) SM, fluororesin (AGE060, manufactured by AGC Asahi Glass Co., Ltd.), AGE060, fluorine emulsion (AGE400, manufactured by AGC Asahi Glass Co., Ltd.), AGE400, polyethylene wax (AQUACER515, Big Chemie Japan Co., Ltd.) Company) was designated as A515, and paraffin wax (AQUACER 539, produced by Big Chemie Japan Co., Ltd.) as A539. The yellow ink was indicated as Y, the magenta ink as M, and the glitter ink as Me.
In this specification, “duty” is a value calculated by the following equation.
duty (%) = number of actual printing dots / (vertical resolution × horizontal resolution) × 100
(In the formula, “number of actual printing dots” is the number of actual printing dots per unit area, and “vertical resolution” and “horizontal resolution” are resolutions per unit area, respectively.)

[5] Evaluation of image transferability A recording medium of paper media (super fine paper: manufactured by Seiko Epson Corporation) is prepared, and image transfer processing is performed on each recording medium using the thermal transfer media of the respective examples and comparative examples. The recorded matter was obtained, and the image transferability was evaluated according to the following criteria.
A: The transfer surface is smooth and no peeling unevenness is observed. ○: A peeling unevenness of 5% or less is observed.
Δ: Peeling unevenness of more than 5% and 20% or less is observed.
X: Peeling unevenness exceeding 20% is observed.
These results are shown in Table 1.
As is apparent from Table 1, the thermal transfer medium of each example was excellent in image transferability. In contrast, the thermal transfer media of the comparative examples did not provide satisfactory results.

  DESCRIPTION OF SYMBOLS 1 ... Inkjet printer (printer) 2 ... Frame 3 ... Platen 4 ... Medium feed motor 5 ... Guide member 6 ... Carriage 7 ... Timing belt 8 ... Carriage motor 9 ... Head 10 ... Ink cartridge P ... Medium 11 ... Transfer sheet 12 ... Image layer 13 ... Adhesive layer 15 ... Recording medium 100 ... Thermal transfer medium 200 ... Recorded matter

Claims (7)

It has a void layer as an ink receiving layer, and the void layer has a resin ratio of less than 30% of the components constituting the layer, and is mainly composed of inorganic particles and provided between inorganic particles or between inorganic particles. A layer configured to allow liquid to permeate into the voids of the holes, and a transfer sheet provided with a silicone resin on the surface on which the void layer is formed;
A thermal transfer medium comprising: an image layer formed of an inkjet ink in which a color material is dispersed on a surface of the transfer sheet on which the void layer is formed.   2. The ink for forming the image layer is at least one selected from a color ink in which a colorant is dispersed as a color material or a glitter ink in which a glitter pigment is dispersed as a color material. The thermal transfer medium described.   The thermal transfer medium according to claim 2, wherein a resin component is contained in the color ink forming the image layer.   The image layer includes a colored layer formed of the color ink on a surface on which the void layer is formed and the silicon resin is provided, and a glittering layer made of the glittering ink provided on the colored layer. The thermal transfer medium according to claim 2, wherein the thermal transfer medium is provided.   5. The thermal transfer medium according to claim 1, further comprising an adhesive layer formed of a material containing an adhesive compound on the image layer. An image formed on the recording medium using a transfer step of transferring the image layer of the thermal transfer medium according to any one of claims 1 to 5 to a recording medium different from the transfer sheet. Forming method. It has a void layer as an ink receiving layer, and the void layer has a resin ratio of less than 30% of the components constituting the layer, and is mainly composed of inorganic particles and provided between inorganic particles or between inorganic particles. It is a layer configured to allow liquid to permeate into the voids of the holes, and a method for producing a thermal transfer medium using a transfer sheet provided with a silicon resin on the surface on which the void layer is formed,
A thermal transfer comprising a step of forming an image layer by applying an ink in which a coloring material is dispersed to a surface of the transfer sheet on which the void layer is formed and the silicon resin is applied by an inkjet method. A method for producing a medium.

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