TWI701159B - Combination of heat transfer film and transferred material, method for forming printed matter, and heat transfer film - Google Patents

Abstract

The invention provides a combination of thermal transfer film and transfer material or thermal transfer film that can form highly creative printed matter. In addition, it provides a method for forming printed matter that can form highly creative printed matter.

A combination of a thermal transfer film (10) and an object to be transferred (100), characterized in that: the thermal transfer film (10) is present on the side of the substrate (1), and is provided with the substrate in the order of the surface. Composition of the invisible light absorbing material layer (2), the first transfer layer (5), and the color material layer (3); the transferred object (100) and the laminate containing the invisible light absorbing material layer (2) , The color difference (△E*ab) with the transfer material (100) is 10 or less.

Description

Combination of heat transfer film and transferred material, method for forming printed matter, and heat transfer film

The present invention relates to a combination of a thermal transfer film and a transfer material, a method for forming a printed matter, and a thermal transfer film.

One of the game machines installed and used in game centers or commercial facilities. Known ones are large game machines that read barcode information printed on cards and use the read barcode information to execute games. The cards used in these large game machines are printed with the image, name, and status of the character reproduced in the large game machine, as well as barcode information such as a two-dimensional bar code. The barcode information has a function to define the character News.

Recently, it is known that there is a printer inside the printer, and the status of the character changes according to the progress of the game. After the game is over, the card of the character reflecting the changed status during the game can be used as Large game consoles that are distributed on-demand. According to this large-scale game machine, game players can use newly issued cards in the next game to strengthen or nurture characters, etc., and increase the player's interest in cards. For example, in Patent Document 1, a game card printing device is proposed, which It is equipped with: the game is executed by the user's operation, and the communication unit that receives game result information from the portable terminal that saves the result of the executed game; and the memory unit that memorizes the data of a plurality of character images; And according to the received game result information, the character image is selected and combined with the state information contained in the game result information to generate the image data generating part of the card image data; and using the card image data, the card image A printer that prints on printing paper and outputs game cards; and proposes a large-scale game machine system, which has: the game card printing device, an input unit that accepts operations, and a display unit that displays the game screen, and The reading part that reads the barcode information printed on the game card, the charging part that recognizes and calculates the inserted currency, and the reproduction part that reproduces the character in the game based on the read barcode information; and is accompanied by A predetermined amount of investment is used to execute the game.

Recently, the use of large-scale game consoles has also become diversified, and a large-scale game console with built-in infrared scanners and the like has been proposed. In this large game machine, it is used: a card printed with a viewable image showing the character and the like, and a non-viewable image as bar code information for defining the character and the like.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2016-22208

The present invention was created in view of this situation. The main subject is to provide a combination of a thermal transfer film and a transfer material or a thermal transfer film that can form highly creative printed matter. In addition, it is to provide a creative The method of forming high-quality printed matter.

The combination of the thermal transfer film and the transfer material of the embodiment of the present disclosure to solve the above-mentioned problems is characterized in that the thermal transfer film is on one side of the substrate, and is provided with invisible light in the order of the surface. The heat transfer film containing the invisible light absorbing material layer, the first transfer layer, and the color material layer of the absorbing material; the aforementioned transferred object and the aforementioned laminate containing the invisible light absorbing material layer, and the aforementioned transferred The color difference (△E*ab) of the object is 10 or less.

In addition, the combination of the thermal transfer film and the transferred material of the embodiment of the present disclosure is characterized in that the thermal transfer film is on one side of the substrate, and is provided with an invisible light absorbing material in the order of the surface. The invisible light absorbing material layer, the first transfer layer, and the color material layer; the first transfer layer is a single layer composed of only the receiving layer, or the receiving layer is located closest to the substrate The layered structure of the position; the color material layer contains sublimation dye; the color difference (△E*ab) between the transferred material and the laminate containing the invisible light absorbing material layer and the transferred material is 10 the following.

In addition, the aforementioned layer containing invisible light absorbing material may further contain There are pigments or organic dyes. In addition, the aforementioned invisible light absorbing material-containing layer may have a laminated structure of a layer containing an invisible light absorbing material and a layer containing a pigment or an organic dye. In addition, among the layers constituting the layer containing the invisible light absorbing material, the layer located closest to the substrate may be the layer containing the invisible light absorbing material, or the layer containing the pigment or organic dye. In addition, the first transfer layer may be a single layer composed of only a receiving layer, or a transfer layer composed of a laminate in which the receiving layer is located closest to the substrate.

In addition, the method of forming a printed matter of the embodiment of the present disclosure to solve the above-mentioned problems is a method of forming a printed matter using a thermal transfer film and a transferred object, and is characterized by including: preparing the transferred object The printing preparation step; and the heat transfer film preparation step of preparing the heat transfer film. The heat transfer film is provided on one side of the substrate with invisible light absorbing material containing invisible light absorbing material layer, And the first transfer layer, and the color material layer; and transfer the invisible light absorbing material-containing layer of the thermal transfer film to one side of the transfer object to form a special image containing the invisible light absorbing material The special image forming step; and the first transfer layer transfer step of transferring the first transfer layer of the thermal transfer film to the special image; and the color material layer of the thermal transfer film , The thermal transfer image forming step of thermal transfer to the first transfer layer after the transfer to form a thermal transfer image; the transfer object formed in the special image forming step and The color difference (ΔE*ab) between the aforementioned special image laminate and the aforementioned object to be transferred prepared in the aforementioned step of preparing the aforementioned object to be transferred is 10 or less.

In addition, the first transfer layer transfer step may be a step of transferring the first transfer layer so as to cover the entire surface of the special image and one surface of the object to be transferred.

In addition, the thermal transfer film of the embodiment of the present disclosure for solving the above-mentioned problems is a thermal transfer film used when a thermal transfer image is formed on a transfer object, and is characterized by: Yu Ji On one side of the material, an invisible light absorbing material-containing layer containing an invisible light absorbing material, a first transfer layer, and a color material layer are arranged in the order of the surface; the aforementioned to-be-transferred object and the aforementioned layer containing the invisible light absorbing material layer The color difference (ΔE*ab) between the compound and the aforementioned object to be transferred is 10 or less.

In addition, the thermal transfer film of the embodiment of the present disclosure is a thermal transfer film used when a thermal transfer image is formed on a transfer object, and is characterized in that the aforementioned thermal transfer film is On one side of the substrate, an invisible light absorbing material-containing layer containing an invisible light absorbing material, a first transfer layer, and a color material layer are arranged in the order of the surface; the aforementioned first transfer layer appears to be composed of only the receiving layer Single layer structure or laminated structure in which the receiving layer is located closest to the substrate; the color material layer contains sublimable dye; the transfer material and the laminate containing the invisible light absorption material layer , The color difference (△E*ab) from the aforementioned transfer material is 10 or less.

According to the combination of the thermal transfer film and the transfer material, the thermal transfer film, and the method of forming printed matter according to the embodiment of the present disclosure, it can be formed Creative prints.

1‧‧‧Substrate

2‧‧‧Containing invisible light absorbing material layer

2A‧‧‧Layer containing invisible light absorbing material

2B‧‧‧Layer containing pigment or organic dye

3‧‧‧Color material layer

5‧‧‧First transfer layer

5A‧‧‧Reception layer

5B‧‧‧Pin layer

5C‧‧‧Heat Sealing Layer

7‧‧‧Second transfer layer

7A‧‧‧Protection layer

10‧‧‧Heat Transfer Film

20‧‧‧Laminate

50A‧‧‧Image with invisible light absorbing material (special image)

50B‧‧‧Thermal transfer image

100‧‧‧Subject to be transferred

200‧‧‧Prints

Figure 1 is a schematic cross-sectional view of a thermal transfer film according to an embodiment.

Figure 2 is a schematic cross-sectional view of a thermal transfer film according to an embodiment.

Figure 3 is a schematic cross-sectional view of a thermal transfer film of an embodiment.

Figure 4 is a schematic cross-sectional view of a thermal transfer film according to an embodiment.

Figure 5 is a schematic cross-sectional view of a thermal transfer film of an embodiment.

Figure 6 is a step diagram for explaining the printing method of an embodiment, (a) ~ (e) are schematic cross-sectional views.

Figure 7 is a schematic cross-sectional view of a thermal transfer film according to an embodiment.

"Combination of Thermal Transfer Film and Substrate"

The following describes the combination of the thermal transfer film and the transfer material of the present invention with reference to the drawings. The present invention can be implemented in a variety of different forms, and should not be interpreted as being limited to the description of the embodiments exemplified below. In addition, in order to make the description clearer, the drawing sometimes schematically shows the width, thickness, shape, etc. of each part compared with the mode of implementation, but this is only an example and should not be used to limit the interpretation of the present invention. In addition, in the specification of this application and each drawing, the same reference numerals are attached to the same elements as those described in the already-shown drawings, and detailed descriptions are appropriately omitted. For the printed matter of the invention described later The forming method and thermal transfer film are also the same.

<Thermal transfer film>

The thermal transfer film used in the combination of the thermal transfer film and the transfer material of the embodiment of the present disclosure (hereinafter sometimes referred to as the combination of one embodiment) is shown in the base material One side of 1 is provided with an invisible light absorbing material layer 2, a first transfer layer (5), and a color material layer 3 in the order of the surface. The base material 1, the invisible light-absorbing material-containing layer 2, the first transfer layer (5), and the color material layer 3 are essential components of the thermal transfer film 10 used in the combination of one embodiment.

The thermal transfer film 10 of the form shown in Figure 1 is presented on one side of the substrate 1, and is provided with an invisible light absorbing material layer 2, and a first transfer layer (5), and color materials in the order of the surfaces. The structure of the layer 3 is not limited to the order in which the invisible light absorbing material-containing layer 2, the first transfer layer (5), and the color material layer 3 are provided on one side of the substrate 1. Each configuration will be described in detail below.

(Substrate)

The base material 1 is not particularly limited, and those generally known in the field of using thermal transfer films can be appropriately selected. As an example, tissue paper such as cellophane, capacitor paper, or paraffin paper; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyphenylene sulfide, polyether Polyester with high heat resistance such as ketone or polyether; polypropylene, polycarbonate, cellulose acetate, polyethylene derivatives, polyvinyl chloride, polyvinylidene chloride, polyphenylene Stretched or unstretched films of plastics such as ethylene, polyamide, polyimide, polymethylpentene, or ionomers. In addition, a composite film in which two or more layers of these materials are laminated can also be used.

In addition, the substrate 1 can be subjected to corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also known as anchor coating, adhesion promoter, easy adhesion agent) coating treatment, and pre-heat treatment , Dust removal treatment, evaporation treatment, alkali treatment, imparting anti-static layer and other easy bonding treatments. In addition, the base material 1 may optionally contain fillers, plasticizers, colorants, antistatic agents, and other additives. The thickness of the substrate 1 is not particularly limited, but is preferably 2 μm or more and 10 μm or less.

(Invisible light absorbing material layer included)

As shown in Figure 1, on one side of the substrate 1 (the upper surface of the substrate 1 in the form of the figure), the first transfer layer (5) and the color material layer 3 are arranged in the order of the surfaces. There is a layer 2 containing invisible light absorbing material. The layer 2 containing invisible light absorbing material contains no visible light absorbing material as an essential component. The invisible light absorbing material in the specification of this application refers to a material that absorbs infrared rays or ultraviolet rays. According to the combination of one embodiment, the thermal transfer film 10 is overlapped with the object to be transferred 100, and the layer 2 containing the invisible light absorbing material is melt-transferred onto the object to be transferred 100. On the top, an image 50A that can be recognized under infrared light or ultraviolet light is formed (refer to Figure 6). In addition, the invisible light absorbing material-containing layer may be constituted as an invisible light absorbing material containing layer that does not absorb or hardly absorbs visible light but absorbs infrared rays or ultraviolet rays. At this time, the thermal transfer film 10 is overlapped with the object to be transferred 100, and the layer 2 containing the invisible light absorbing material is melt-transferred onto the object to be transferred 100, thereby forming a layer on the object to be transferred 100. An image 50A that cannot be viewed or easily viewed under visible light and can be recognized under infrared or ultraviolet light. Hereinafter, an image containing an invisible light absorbing material is sometimes referred to as a "special image".

Examples of invisible light absorbing materials include infrared absorbing materials and ultraviolet absorbing materials. In the specification of this application, the term "infrared rays" means the wavelength region with the maximum absorption wavelength (λ max) from 750 nm to 2000 nm, and the so-called "ultraviolet rays" means the wavelength region with the maximum absorption wavelength (λ max) from 280 nm to 400 nm. Wavelength region.

Infrared absorbing materials, for example, Diimonium compounds, aluminum compounds, phthalocyanine compounds, dithiol organometallic compounds, anthocyanin compounds, azo compounds, polymethine Based compounds, quinone based compounds, diphenylmethane based compounds, triphenylmethane based compounds, Oxole based compounds, carbon black, etc. The invisible light absorbing material-containing layer 2 may contain one kind of these infrared absorbing materials alone or two or more kinds of them. Among these, anthocyanin-based compounds and diamine-based compounds can be preferably used as infrared absorbing materials.

The ultraviolet absorbing materials include organic ultraviolet absorbing materials such as benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, and benzoate-based compounds; or titanium oxide, zinc oxide, cerium oxide, Inorganic ultraviolet absorbing materials such as iron oxide and barium sulfate. Does not contain The visible light absorbing material layer 2 may contain one kind of ultraviolet absorbing material alone or two or more kinds.

In addition, the layer 2 containing the invisible light absorbing material may contain both an infrared absorbing material and an ultraviolet absorbing material.

In addition, the layer 2 containing the invisible light absorbing material may contain a binder resin together with the above invisible light absorbing material. Binder resins, for example, polyester resins, polyvinyl resins, fluorine resins, polystyrene resins, polyacrylic resins, cellulose resins, polycarbonate resins, polyamide resins , Polyolefin resins such as polypropylene resins; commonly known resins such as polyvinyl alcohol resins, polyimide resins, phenol resins, and polyurethane resins.

The thermal transfer film 10 used in the combination of one embodiment is provided with an invisible light absorbing material-containing layer 2 containing an invisible light absorbing material as described above. The invisible light absorbing material-containing layer 2 can be used on the transfer object On 100, a special image 50A that can be recognized under infrared or ultraviolet light is formed. The invisible light absorbing material or binder resin contained in the invisible light absorbing material layer 2 sometimes absorbs all or part of visible light. When using the invisible light absorbing material or binder resin containing the invisible light absorbing material Material layer 2, when the special image 50A is formed on the transfer object 100, due to the difference in the hue of the transfer object 100, the special image 50A is unexpectedly viewed under visible light, and sometimes it The problem of reduced creativity under visible light.

Therefore, in the combination of one embodiment, it is characterized by: the transfer object 100 and the laminate 20 containing the invisible light absorbing material layer 2, The color difference (ΔE*ab) from the transfer target 100 is 10 or less. In other words, it is characterized by: the special image 50A formed by transferring the invisible light absorbing material-containing layer 2 of the thermal transfer film 10 to the transfer object 100 and the laminate 20 of the transfer object 100 ( Referring to Fig. 6(a)), the color difference (ΔE*ab) from the transfer target 100 is 10 or less. Hereinafter, sometimes the laminate of the object to be transferred 100 and the layer 2 containing the invisible light absorbing material, in other words, the laminate of the object to be transferred 100 and the special image 50A is simply referred to as the laminate.

According to the combination of the embodiment having one of the above-mentioned features, by making the color difference (ΔE*ab) between the laminate 20 and the transfer material 100 to be 10 or less, it is possible to sufficiently suppress the formation of special features on the transfer material 100. The image 50A is viewed unexpectedly under visible light. In addition, it is possible to form highly creative prints on-demand. In the combination of one embodiment, the color difference (△E*ab) between the laminate 20 and the transferred object 100 is specified to be 10 or less, because when the color difference between the laminate 20 and the transferred object 100 (△E *ab) When it exceeds 10, the special image 50A can be easily recognized under visible light, and the creativity of the printed matter cannot be improved sufficiently. The combination of a preferred embodiment is that the color difference (ΔE*ab) between the transferred object 100 and the laminate 20 containing the invisible light absorbing material layer 2 and the transferred object 100 is 8 or less.

The so-called chromatic aberration (△E*ab) in the specification of this application refers to the difference or distance between two colors and is based on JIS-Z-8730 (2009). Color difference (△E*ab), for example, can be measured using a spectrophotometer (manufactured by i1 X-rite), and defined by the value in the L*a*b* color system of the International Certification Committee. It is the value represented by △E*ab=((△L*) ² +(△a*) ² +(△b*) ² ) ^1/2 . The larger the value, the more significant the difference in color when visually observed. (△L*), (△a*), (△b*) are the difference between the L*, a*, and b* values of the laminate 20 and the transferred object 100. The color measurement of the laminate 20 is performed where the thermal transfer film 10 and the special image 50A overlap in the thickness direction.

The means for making the color difference (ΔE*ab) between the laminate 20 and the transfer target 100 10 or less is not particularly limited, and can be achieved by including various additives in the invisible light absorbing material-containing layer 2. An example of the additive material is a compound having a hue, etc., for example, organic pigments, inorganic pigments, etc. can be cited. Examples of organic pigments include colored pigments such as yellow, magenta, and indigo, or hollow particles. Examples of inorganic pigments include silicon dioxide, titanium oxide, titanium dioxide, zinc oxide, cerium oxide, titanium mica, muscovite, white carbon, calcium carbonate, barium sulfate, aluminum white, and talc. In addition, it is also possible to use a core-shell pigment in which the outer shell composed of an organic pigment coats the periphery of the middle core composed of an inorganic pigment. In addition, organic dyes such as yellow dye, magenta dye, and indigo dye can also be used.

Generally speaking, the transfer material 100 is preferably white, so it is used to form the color difference (△E*ab) to an additive material below 10, preferably white compounds such as titanium oxide and calcium carbonate . Among them, titanium oxide is particularly preferred.

In addition, as an alternative to containing pigments or organic dyes in the layer 2 containing invisible light absorbing material, as shown in Figure 7(a)~ As shown in (c), the layer 2 containing the invisible light absorbing material can also be configured as a layered structure of a layer 2A containing an invisible light absorbing material and a layer 2B containing a pigment, so that the laminate 20 and the transfer material 100 The color difference (△E*ab) becomes 10 or less.

When the invisible light absorbing material-containing layer 2 is constructed as a laminated structure, the invisible light absorbing material-containing layer 2A, as shown in Figure 7(a), can be located at the position closest to the substrate 1, or as shown in Figure 7. As shown in (b), it is located at the farthest position from the substrate 1, or as shown in Fig. 7 (c), (d), the invisible light absorbing material-containing layer 2 is formed as a layer 2A containing invisible light absorbing material , And a layer 2B containing a pigment, and any layer 2C containing two or more layers, and the layer 2A containing an invisible light absorbing material is located between any layers. The same applies to the pigment-containing layer 2B.

The pigment-containing layer 2B may contain at least one of the above-exemplified organic pigments, inorganic pigments, and optional binders and other additives. The binder includes, for example, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, polyethylene, polystyrene, polypropylene, polybutene, petroleum resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer Materials, polyvinyl alcohol, vinylidene chloride resin, acrylic resin, methacrylic resin, polyamide, polycarbonate, fluororesin, polyvinyl formaldehyde, polyvinyl butyral, cellulose acetate, nitrocellulose, Polyvinyl acetate, polyisobutylene, ethyl cellulose or polyacetal, etc. In addition, the adhesives include microcrystalline wax, carnauba wax, paraffin wax and so on. Furthermore, Fischer-Tropsch synthetic wax, various low molecular weight polyethylene, wood wax, beeswax, whale Wax, insect wax, wool wax, shellac wax, candelilla wax, petroleum amide, polyester wax, partially modified wax, fatty acid ester, fatty acid amide and other waxes.

The thickness of the pigment-containing layer 2B is not particularly limited, but is preferably in the range of 0.1 μm to 5 μm, and particularly preferably in the range of 0.5 μm to 1.5 μm.

In addition, the above-mentioned pigment-containing layer 2B may be configured as an organic dye-containing layer 2B. For the layer containing organic dyes, the color material layer 3 described later can be appropriately selected and used.

The thermal transfer film 10 used in the combination of one embodiment is presented on one side of the substrate 1, and in the order of the surface, a first transfer layer containing an invisible light absorbing material layer 2 and a receiving layer 5A ( 5) and the composition of the color material layer 3, when it contains the hue of the invisible light absorbing material layer 2 and the first transfer layer (5) containing the receiving layer, or the hue of the invisible light absorbing material layer 2 and the color material layer 3 When the hues are similar, the invisible light-absorbing material layer 2 cannot be detected correctly in the printer, which may cause the problem of incorrect positioning during printing. On the other hand, as described above, when the invisible light absorbing material-containing layer 2 contains pigments, etc., the hue of the invisible light absorbing material-containing layer 2 and other layers can be different, and the printer can accurately detect whether it contains Visible light absorbing material layer 2.

In addition, as will be described later, the color material layer 3 as an example may contain sublimable dyes. Therefore, the invisible light absorbing material-containing layer 2 contains pigments, so that the invisible light absorbing material layer 2 and the color material layer 3 The visible light transmittance is different, and the detection accuracy of the layer 2 containing invisible light absorbing material can be improved in the printer. In addition, due to the invisible light absorption The material layer 2 contains organic dyes with different hue from the color material layer 3, which can improve the detection accuracy of the invisible light absorbing material layer 2 in the printer. In addition, as an alternative to containing pigments and organic dyes in the layer 2 containing the invisible light absorbing material, the layer 2 containing the invisible light absorbing material can be constructed as the layer 2A containing the invisible light absorbing material, and the layer 2 containing the pigment or the color material The laminated structure of the layer 2B of organic dyes with different hues of the layer 3 can improve the detection accuracy of the layer 2 containing the invisible light absorbing material in the printer.

The content of the above-mentioned additive material is not particularly limited, and can be appropriately set within a range in which the color difference (ΔE*ab) between the laminate 20 and the transfer target 100 is 10 or less. In addition, the content of the invisible light absorbing material is not particularly limited. As an example, relative to the total mass of the solid content of the layer 2 containing the invisible light absorbing material, it is in the range of 0.1% by mass to 80% by mass, preferably 5% by mass or more The range of 40% by mass or less.

The thickness of the invisible light absorbing material-containing layer 2 is not particularly limited, but is preferably in the range of 0.1 μm to 5 μm, and particularly preferably in the range of 0.5 μm to 1.5 μm. By configuring the thickness of the invisible light-absorbing material-containing layer 2 in a preferable range, a special image 50A that can be sufficiently recognized under infrared or ultraviolet rays can be formed. In other words, the detection performance when detecting the special image 50A formed by using the layer 2 containing the invisible light absorbing material can be improved. In addition, it is also possible to suppress the occurrence of tailing or text collapse when transferring the invisible light absorbing material-containing layer 2 to the transfer object. The so-called tailing in the specification of this application means that when the transfer layer is transferred to the object to be transferred, the starting point is the boundary between the transfer area and the non-transfer area of the transfer layer, and the The transfer layer is transferred by the way of exudation on the transfer area side Elephant. In addition, the word collapse in the specification of this application means that the non-transfer area surrounded or sandwiched by the transfer area expressed as the text is transferred with the same phenomenon as the tail, and the original text cannot be reproduced. The phenomenon.

The method for forming the layer 2 containing the invisible light absorbing material is not particularly limited. The invisible light absorbing material, the binder resin, and various additives added as necessary can be dispersed or dissolved in toluene, methyl ethyl ketone, ethanol, or isopropyl. Alcohol, cyclohexane, dimethylformamide, etc. are used to prepare a coating solution for a layer containing an invisible light absorbing material, and this is applied to the substrate 1 or any layer provided on the substrate 1 And dry to form. The coating method of the coating liquid for an invisible light absorbing material-containing layer is not particularly limited, and a conventionally known coating method can be appropriately selected and used. The coating method includes, for example, a gravure printing method, a screen printing method, and a reverse printing method using gravure. In addition, other coating methods can also be used. The same applies to the application of various coating liquids described later.

(Release layer)

In order to improve the transferability (releasing property) of the invisible light absorbing material-containing layer 2, a release layer (not shown in the figure) may be provided between the substrate 1 and the invisible light absorbing material-containing layer 2. The release layer is a layer that remains on the side of the base material 1 when the invisible light absorbing material-containing layer 2 is moved onto the object 100 to be transferred. The material of the release layer includes, for example, various waxes such as silicone wax; water-soluble resins such as silicone resin, modified silicone resin, fluororesin, acrylic resin, and polyvinyl alcohol resin; cellulose derivatives Resins, urethane-based resins, silicone vinyl acetate resins, acrylic vinyl ether-based resins, maleic Various resins such as acid anhydride resins, etc. or mixtures of these. The thickness of the release layer is usually in the range of 0.5 μm or more and 5 μm or less.

(1st transfer layer)

As shown in Fig. 1, on the substrate 1, an invisible light absorbing material-containing layer 2, a color material layer 3, and a first transfer layer (5) are arranged in the order of the surface. The first transfer layer (5) is a layer that can be peeled off from the base material 1, and is transferred to (moved to) the transfer object 100 on which the special image 50A is formed by thermal transfer .

In the formation of a printed matter using the combination of one embodiment, a special image 50A is formed on the transfer object 100 by the invisible light absorbing material-containing layer 2 of the thermal transfer film 10, and then the special image 50A A first transfer layer (5) is formed. That is, according to the combination of one embodiment, the combination can be used to cover the special image 50A formed on the thermal transfer film 10 with the first transfer layer (5). Thereby, various problems caused when the special image 50A is exposed on the surface, such as the disappearance of the special image 50A due to impact from the outside, etc., can be suppressed.

As an example, the first transfer layer (5) contains at least the receiving layer 5A, and exhibits a single layer structure consisting of only the receiving layer 5A, or the receiving layer 5A and other layers are sequentially laminated from the substrate 1 side Layered layered composition. When the first transfer layer (5) containing the receiving layer 5A is constituted, among the layers constituting the first transfer layer (5), the layer located closest to the substrate 1 becomes the receiving layer 5A. This is because when the first transfer layer (5) is transferred to the object to be transferred, the receiving layer 5A is located on the outermost surface of the transfer layer 100. Because of the face.

[Receiving layer]

The material of the receiving layer 5A is not particularly limited, and it is preferable to use a binder resin that can easily dye the sublimable dye contained in the color material layer 3. Examples of the binder resin include polyolefin resins such as polypropylene; halogenated resins such as polyvinyl chloride and polyvinylidene chloride; vinyl resins such as polyvinyl acetate and polyacrylate; and polyparaphenylene Polyester resins such as ethylene dicarboxylate and polybutylene terephthalate; polystyrene resins; polyamide resins; copolymers of olefins such as ethylene or propylene and other vinyl monomers; Ionic polymer; cellulose resin, etc. The receiving layer 5A may contain one type of these binder resins alone or two or more types. In addition, copolymers obtained by copolymerizing two or more of these binder resins can also be used. Among them, the cellulosic resin can sufficiently satisfy the transferability of the receiving layer 5A of the layer located at the transfer interface, and even when the energy applied to the thermal transfer film 10 is increased, it can also satisfy the requirement of the receiving layer 5A. 1 The transferability of the transfer layer (5), in this regard, can be preferably used as the material of the receiving layer 5A. In addition, the vinyl chloride-vinyl acetate copolymer can improve the dyeability of the receiving layer 5A or the releasability of the receiving layer 5A and the color material layer 3. In this regard, it can be preferably used as the receiving layer 5A. material.

Examples of the cellulose resin include cellulose acetate resin, cellulose acetate butyrate resin, cellulose acetate propionate resin, nitrocellulose resin, and cellulose acetate.

Receiving layer 5A, in order to prevent the color material layer 3 Heat fusion, may contain release agent. The release agent includes, for example, solid waxes such as polyethylene wax, amide wax, Teflon (registered trademark) powder; fluorine-based or phosphate ester-based surfactants; silicone oil, reactive silicone oil, Various modified silicone oils such as hardened silicone oil; and various silicone resins, etc.

The receiving layer 5A can be prepared by dissolving or dispersing the above-mentioned binder resin and optional release agent and other additives in a suitable solvent to prepare a coating solution for receiving layer, and applying this to the substrate 1 or formed on any layer on the substrate 1 and dried. The thickness of the receiving layer 5A is not particularly limited, but is usually in the range of 0.3 μm or more and 10 μm or less.

"Heat Sealing Layer"

In order to improve the adhesion between the transferred object 100 and the first transfer layer (5), as shown in Figure 2, the first transfer layer (5) can also be configured to be sequentially laminated from the substrate 1 side The receiving layer 5A and the heat-sealing layer 5C are laminated. The material of the heat-sealing layer 5C is preferably a material that has good adhesion with the object to be transferred 100. Examples of this material include cellulose derivatives such as ethyl cellulose and cellulose acetate butyrate; styrene copolymers such as polystyrene and polyα-methylstyrene; polymethyl methacrylate, poly Acrylic resins such as ethyl methacrylate and polyethyl acrylate; vinyl resins such as polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, etc.; polyester resins, Synthetic resins such as nylon resins, epoxy resins, polyurethane resins, ionomers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, etc., or as an adhesive agent Incense and rosin modified maleic acid resin, ester rubber, polyisobutylene rubber, butyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, polyamide resin, polychlorinated olefin, etc. The thickness of the heat-sealing layer 5C is preferably in the range of 0.1 μm or more and 20 μm or less.

"Pin layer"

As shown in Fig. 2, a primer layer 5B may be provided between the receiving layer 5A and the heat-sealing layer 5C. By providing the primer layer 5B, the adhesion between the receiving layer 5A and the heat sealing layer 5C can be improved, and the releasability of the receiving layer 5A and the color material layer can be improved. In addition, the heat transfer formed on the receiving layer 5A can be suppressed. Bleeding may occur on the printed image, or it can impart anti-charge properties.

As an example, the primer layer 5B may contain binder resins such as urethane resin, polyester resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone resin, and polyvinyl alcohol resin; As well as inorganic particles such as alumina, silicon dioxide, titanium oxide, carbon black, etc. as required. According to the primer layer 5B containing the binder resin and inorganic particles, the foil cutting property of the first transfer layer (5) containing the primer layer 5B can be improved. The preferred form of the primer layer 5B contains a binder resin, and alumina particles or silica particles. The primer layer 5B of a particularly good form contains a binder resin, and alumina particles from alumina sol or silica particles from colloidal silica. In addition, the primer layer 5B may be formed of inorganic fine particles without using a binder resin.

In addition, when focusing mainly on the improvement of the dye releasability, it is preferable to provide a primer layer 5B containing a water-based resin on the receiving layer 5A. In other words, it is preferable to use a primer layer coating solution obtained by dispersing or dissolving an aqueous resin in an aqueous solvent to provide the primer layer 5B on the receiving layer 5A. The term "aqueous resin" in the specification of this application refers to a water-soluble resin, or a resin that is insoluble in water-based solvents but can be dispersed in water-based solvents like emulsions or dispersions. Examples of the aqueous solvent include water, or a mixed solvent of water and alcohol.

Water-soluble resins, for example, polyvinylpyrrolidone resin, polyvinyl alcohol resin, polyacrylic acid, polyhydroxyethyl methacrylate, water-soluble (or water-dispersed) polyester resin, water-soluble (or water-dispersed) Polyurethane resin, water-dispersible vinyl chloride resin, water-dispersible chlorinated acrylic resin, water-dispersible epoxy resin, gelatin, hydroxyethyl cellulose resin, hydroxypropyl cellulose resin, carboxymethyl cellulose Resin etc. Among them, polyvinylpyrrolidone resin and water-soluble (or water-dispersible) polyurethane resin can further improve the adhesion between the receiving layer 5A and the heat-sealing layer 5C, or the receiving layer 5A and the color material layer. Releasability is better in this regard.

The method of forming the primer layer 5B is not particularly limited, and the binder resin and optional additives can be dissolved or dispersed in a suitable solvent to prepare a coating solution for the primer layer, and this can be applied to the receiver. It is formed on the layer 5A and dried.

The thickness of the primer layer 5B is not particularly limited, but is preferably in the range of 0.01 μm to 5 μm, and particularly preferably in the range of 0.02 μm to 3 μm.

When the color material layer described later is formed as a color material layer containing hot melt ink, it may be configured as a first transfer layer (5) that does not include the receiving layer 5A. For example, it can also be configured as a first transfer layer (5) (not shown in the figure) containing a protective layer (sometimes called a release layer) instead of the first transfer layer (5) containing the receiving layer 5A. . In addition, it may be configured as any layer other than the protective layer. In this case, the description of the receiving layer 5A explained above may be replaced with a protective layer or an arbitrary layer.

The material of the protective layer includes, for example, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, maleic acid modified vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin , Polyethylene resin, ethylene-isobutyl methacrylate copolymer, butyraldehyde resin, polyvinyl acetate and the copolymer, ionic polymer resin, acid-modified polyolefin resin, acrylic-methacrylic acid, etc. Of (meth)acrylic resins, acrylate resins, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylate copolymers, polymethylmethacrylate resins, cellulose resins, poly Vinyl ether resins, polyurethane resins, polycarbonate resins, polypropylene resins, epoxy resins, phenol resins, vinyl resins, maleic acid resins, alkyd resins, polyethylene oxide Resin, urea resin, melamine resin, melamine-alkyd resin, polysiloxane resin, rubber-based resin, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene Block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), etc. One type of these materials may be contained alone or two or more types may be contained.

The thickness of the protective layer is not particularly limited, preferably 1 μm or less The upper 5μm range.

(Color material layer)

As shown in Fig. 1, on one side of the substrate 1, the invisible light-containing absorbing material layer 2, the first transfer layer (5), and the color material layer 3 are provided in the order of the surface. As an example, the color material layer 3 contains sublimable dyes. When the thermal transfer image formed by the combination of an embodiment is a single color, as shown in Figure 1, only one of the appropriate selections can be formed. The color layer, when the desired image is a full-color image, as shown in Figure 2, the yellow color material layer 3Y containing the yellow sublimation dye can be repeatedly formed on the same surface of the substrate in the order of the surface. And the magenta color material layer 3M containing magenta sublimation dye, and the indigo color material layer 3C containing indigo sublimation dye. In addition, it can also be formed into a configuration in which two types of color material layers are provided among the yellow color material layer 3Y, the magenta color material layer 3M, and the indigo color material layer 3C.

As an example, the sublimable dye contained in the color material layer 3 is not particularly limited, but it is preferably one having a sufficient color density and not being discolored or fading due to light, heat, temperature, or the like. This sublimable dye includes, for example, diarylmethane dyes, triarylmethane dyes, Thiazole dyes, Merocyanine dyes; Pyrazolone dyes; Base dyes; Indoaniline dyes; Pyrazolmethine dyes; Acetophenone azomethine, pyrazole azomethine, imidazolyl azomethine, imidazole azomethine Azomethine dyes such as methyl and pyridone azomethine; Xanthene dyes; Oxazine dyes; dicyanide Cyanostyrene dyes such as styrene and tricyanostyrene; Thiazine dyes; Azine dyes; Acridine dyes; phenylazo dyes; pyridone Azo dyes such as azo, thiophene azo, isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazo, triazole azo, diazo and other azo dyes; Spiropyran ( Spiropyran dyes; Indospiropyran dyes; Fluoran dyes; Rose bengal endoamide dyes; Naphthoquinone dyes; Anthraquinone dyes; Quinophthalone Department of dyes and so on. Specifically, red dyes such as MSRedG (manufactured by Mitsui Togaki Chemical Co., Ltd.), Macrolex Red Violet R (manufactured by Bayer), CeresRed 7B (manufactured by Bayer), and Samaron Red F3BS (manufactured by Mitsubishi Chemical Corporation) can be cited; Foron Brilliant Yellow 6GL (manufactured by Clariant), PTY-52 (manufactured by Mitsubishi Chemical Corporation), Macrolex Yellow 6G (manufactured by Bayer), etc.; Kayaset (registered trademark) Blue714 (manufactured by Nippon Kayaku Co., Ltd.) , Foron Brilliant Blue SR (manufactured by Clariant), MS Blue 100 (manufactured by Mitsui Token Chemical Co., Ltd.), CISolvent Blue 63, etc.

The content of the sublimable dye is preferably in the range of 50% by mass to 350% by mass, and more preferably in the range of 80% by mass to 300% by mass relative to the total solid content of the binder resin described later. By setting the content of the sublimable dye within the above range, the printing density and storage properties can be improved.

The binder resin contained in the color material layer 3 as an example and used to carry the sublimable dye is also not particularly limited, and one having a certain degree of heat resistance and a moderate affinity with the sublimable dye can be used. Examples of the binder resin include cellulose resins such as nitrocellulose, cellulose acetate butyrate resin, and cellulose acetate propionate resin; polyvinyl acetate, polyvinyl butyral, and polyvinyl acetal. Vinyl resins such as aldehydes; acrylic resins such as poly(meth)acrylate and poly(meth)acrylamide; polyurethane resins; polyamide resins; polyester resins, etc.

The content of the binder resin is not particularly limited, but it is preferably 20% by mass or more with respect to the total solid content of the color material layer 3. By setting the content of the binder resin to 20% by mass or more, the sublimable dye can be sufficiently maintained in the color material layer 3, and the storage properties can be improved. The upper limit of the content of the binder resin is not particularly limited, and can be appropriately set in accordance with the content of the sublimable dye or optional additive material.

In addition, the color material layer 3 may contain additives such as inorganic particles and organic fine particles. Examples of the inorganic particles include talc, carbon black, aluminum, and molybdenum disulfide, and examples of the organic particles include polyethylene wax, silicone resin particles, and the like. The color material layer 3 may contain a release agent. The mold release agent includes modified or modified polysiloxane oil (also referred to as polysiloxane resin), phosphate ester, and fatty acid ester.

The method of forming the color material layer 3 containing the sublimable dye is not particularly limited, and the binder resin, sublimable dye, and optional additives or release agents can be dissolved or dispersed in a suitable solvent. The coating liquid for the excellent material layer is prepared, and this is applied to the substrate 1 or any layer provided on the substrate 1 and dried to form it. The thickness of the color material layer 3 is not particularly limited, but is generally in the range of 0.2 μm or more and 2.0 μm or less.

(Dye primer layer)

Between the base material 1 and the color material layer 3, a dye primer layer for improving the adhesion between the base material 1 and the color material layer 3 may be provided.

The dye primer layer is not particularly limited, and a dye primer layer generally known in the field of thermal transfer film can be appropriately selected and used. As an example, the dye primer layer is made of resin material. The resin material constituting the dye primer layer includes, for example, polyester resin, polyvinylpyrrolidone resin, polyvinyl alcohol resin, polyacrylate resin, polyvinyl acetate resin, and polyurethane resin , Styrene acrylate resin, polypropylene amide resin, polyamide resin, polyvinyl acetal or polyvinyl butyral resin. In addition, the dye primer layer may contain various additives such as organic particles or inorganic particles together with these resin components.

The method of forming the dye primer layer is also not particularly limited. The resin components exemplified above and the additional materials added as necessary can be dissolved or dispersed in an appropriate solvent to prepare a coating solution for the dye primer layer. It is formed by coating on the substrate 1 and drying. The thickness of the dye primer layer is not particularly limited, but it is usually in the range of 0.02 μm or more and 1 μm or less.

In addition, the color material layer 3 containing hot melt ink may be configured to replace the color material layer 3 containing the sublimable dye. In addition, the color material layer 3 containing sublimation dye and the hot melt The color material layer 3 of the melted ink is formed. The color material layer 3 containing the hot-melt ink contains a binder resin and a coloring agent as the hot-melt ink. The coloring agent may be appropriately selected from conventionally known organic or inorganic pigments or dyes, and is preferably, for example, one having a sufficient color density and not being discolored or fading due to light, heat, etc. In addition, it may be a substance that develops color by heating, or a substance that develops color by contact with a component coated on the surface of the object to be transferred. The color of the coloring agent is not limited to indigo, magenta, yellow, and black, and coloring agents of various colors can be used. For example, fluorescent raw materials can also be used. Fluorescent raw materials, mainly inorganic phosphor materials, are mainly composed of Ca, Ba, Mg, Zn, Cd and other oxides, sulfides, silicates, phosphates, tungstates and other crystals. The pigment is obtained by adding metal elements such as Mn, Zn, Ag, Cu, Sb, Pb, or rare earth elements such as lanthanum elements as an active agent and firing. Specific compounds of such inorganic phosphor materials include, for example, oxides such as calcium tungstate and magnesium tungstate; or calcium sulfide-bismuth, zinc sulfide-silver, zinc sulfide-copper, zinc sulfide-gold- Sulfide series such as aluminum; zinc oxide-zinc, yttrium vanadate-europium, yttrium oxide-europium, yttrium sulfate-europium, yttrium sulfate-porcium, sulfated gyrium-porcium, lanthanum sulfate-porcium, lanthanum oxybromide -Phosphor materials such as oxide series, etc.

(Second transfer layer)

As shown in Figure 2, it is also possible to provide a protective layer on one side of the substrate 1, along with the above-mentioned invisible light-absorbing material-containing layer 2, the first transfer layer (5), and the color material layer 3 in the order of the surface. The second transfer layer (7) of layer 7A. The second transfer layer (7) can present a single layer composed of only the protective layer 7A The structure may be a laminate structure in which the release layer 7B and the protective layer 7A are sequentially laminated from the base material 1 side as shown in FIG. 2. In addition, other configurations may be presented.

"The protective layer"

The binder resin constituting the protective layer 7A includes, for example, polyester resin, polyester urethane resin, polycarbonate resin, acrylic resin, ultraviolet absorbing resin, epoxy resin, acrylic urethane resin, and Polysiloxane modified resins, mixtures of these resins, active energy ray curable resins, etc. The term “active energy ray” means light that chemically acts on the active energy ray-curable resin to promote polymerization, and specifically means visible light, ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays.

The content of the binder resin constituting the protective layer 7A is not particularly limited. The binder resin is preferably 20% by mass or more, and more preferably 30% by mass or more with respect to the total solid content of the protective layer 7A. The upper limit of the binder resin content is not particularly limited, but the upper limit is 100% by mass. In addition, the protective layer 7A, in addition to the binder resin, may also contain various fillers or fluorescent whitening agents, ultraviolet absorbers for improving weather resistance, and other materials.

The method of forming the protective layer 7A is not particularly limited, and the binder resin exemplified above and the additives added as necessary can be dissolved or dispersed in an appropriate solvent to prepare a coating liquid for the protective layer, and This is coated on the substrate 1 or any layer set on the substrate 1 and dried to form. The thickness of the protective layer 7A is not particularly limited, but is generally in the range of 2 μm or more and 15 μm or less.

"Peeling layer"

In order to improve the transferability of the second transfer layer (7), the second transfer layer (7) can also be configured as a laminate in which the release layer 7B and the protective layer 7A are sequentially laminated from the side of the substrate 1 constitute. The binder resin constituting the release layer 7B includes, for example, cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate; polymethyl methacrylate, polyethyl methacrylate, and polyacrylic acid. Acrylic resins such as butyl ester; thermoplastic resins such as vinyl copolymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, etc.; or saturated or unsaturated polyester resins, polyurethane Thermosetting resins such as ester resins, thermally cross-linkable epoxy-amino resins, amino alkyd resins; polysiloxane waxes, polysiloxane resins, polysiloxane modified resins, fluororesins, fluorine modified resins, poly Vinyl alcohol and so on. In addition, in order to improve the foil cutting property of the second transfer layer (7), fillers such as micro silica or polyethylene wax may be contained in the peeling layer 7B. In addition, the release layer may be formed using a catalyst such as a crosslinking agent such as an isocyanate compound, a tin-based catalyst, and an aluminum-based catalyst in addition to the resins exemplified above.

The method of forming the peeling layer 7B is also not particularly limited. The binder resin exemplified above and the additives added as necessary can be dissolved or dispersed in a suitable solvent to prepare a coating solution for the peeling layer, and This is formed by coating on the substrate 1 and drying. The thickness of the peeling layer 7B is not particularly limited, but is usually in the range of 0.1 μm or more and 5 μm or less.

(Back layer)

In addition, a back layer (not shown in the figure) may be provided on the other side of the substrate 1. The back layer is an arbitrary structure in the thermal transfer film 10 used in the combination of one embodiment.

The material of the back layer is not limited, and examples include cellulose resins such as cellulose acetate butyrate resin and cellulose acetate propionate resin, and vinyl resins such as polyvinyl butyral and polyvinyl acetal. ; Acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, acrylonitrile-styrene copolymer, etc.; polyamide resin, polyamide imide resin, polyester resin, poly Monomers or mixtures of natural or synthetic resins such as urethane resin, silicone modified or fluorine modified urethane.

In addition, the back layer may contain a solid or liquid lubricant. Lubricants include, for example, various waxes such as polyethylene wax and paraffin wax; higher aliphatic alcohols, organopolysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Surfactants, fluorine-based surfactants, organic carboxylic acids and their derivatives, metal soaps, fluorine-based resins, silicone resins, fine particles of inorganic compounds such as talc, and mica. The mass of the lubricant relative to the total mass of the back layer is in the range of 5% by mass to 50% by mass, preferably in the range of 10% by mass to 40% by mass.

The method of forming the back layer is also not particularly limited. The resin and the lubricant added as necessary can be dissolved or dispersed in an appropriate A coating liquid for the back layer is prepared in a solvent, and this is applied to the base material 1 and dried to form it. The thickness of the back layer is not particularly limited, but is preferably in the range of 1 μm or more and 10 μm or less.

(A thermal transfer film in a deformed form used in the combination of the embodiment)

The above is based on the heat transfer film composed of the invisible light absorbing material layer 2, and the first transfer layer (5), and the color material layer 3 are arranged in the order of the surface of the substrate 1. The thermal transfer film used in the combination of one embodiment will be described, but the following combination of thermal transfer film may be configured as a thermal transfer film combined with the transfer object, instead of the thermal transfer film of the above configuration.

For example, on one side of the first substrate, any one or two of the invisible light absorbing material layer 2, the first transfer layer (5), and the color material layer 3 may be provided in the order of the surface The combination of the first thermal transfer film (not shown in the figure) and the second thermal transfer film (not shown in the figure) with another 1 or 2 layers on one side of the second substrate. , And the transferred material to form a thermal transfer film. The layer of the first thermal transfer film and the layer of the second thermal transfer film can be arbitrarily selected to contain the invisible light absorbing material layer 2, the first transfer layer (5), and the color material layer 3 Either one or two floors. For example, a first thermal transfer film containing an invisible light absorbing material layer 2 can be provided on one side of the first substrate, and a first transfer layer (5 ), and the combination of the second thermal transfer film of the color material layer 3, and the transferred material to form a thermal transfer film. In addition, you can add: on the first substrate The first heat transfer film containing the invisible light absorbing material layer 2 and the first transfer layer (5) is arranged in the order of the faces, and the second heat transfer film is arranged on the second substrate with the color material layer 3 The combination of printing film and the transferred material form a heat transfer film.

In addition, it is also possible to combine: a first thermal transfer film containing an invisible light absorbing material layer on the first substrate, and a second thermal transfer film with the first transfer layer (5) on the second substrate The printing film is a combination of the third thermal transfer film provided with the color material layer 3 on the third substrate, and the transfer material to form the thermal transfer film. Furthermore, when the thermal transfer film having the color material layer 3 is a thermal transfer film having multiple color material layers, for example, it is a thermal transfer film having a yellow color material layer, a magenta material layer, and an indigo color material layer. It can be configured as a thermal transfer film with a yellow color material layer, a magenta color material layer, and an indigo color material layer arranged in the order of the surface on the third substrate, or a thermal transfer film with only a yellow color material layer. A combination of printing film, thermal transfer film with only magenta material layer, and thermal transfer film with only indigo material layer. In addition, these thermal transfer films can be appropriately combined to form a structure.

The first substrate, the second substrate, and the third substrate can be appropriately selected and used for the thermal transfer film described above.

In addition, a thermal transfer film containing an invisible light absorbing material layer 2 can be provided on at least one side of the substrate and combined with the transferred material to form a thermal transfer film to replace one side of the substrate 1. A thermal transfer film composed of an invisible light absorbing material layer 2, a first transfer layer (5), and a color material layer 3 is arranged in the order of. In this combination, the color difference between the transferred object and the laminate containing the invisible light absorbing material layer 2 and the transferred object (△E*ab) is 10 or less.

〈Subject to transfer〉

Next, the transfer target 100 used in the combination of one embodiment will be described. The transfer material 100 used in the combination of one embodiment is not particularly limited. It can be composed of natural fiber paper, coated paper, tracing paper, plastic film, glass, metal, ceramic, wood, cloth, etc., and can be a single unit. Those composed of layers or composed of multiple layers.

When the transfer material 100 is composed of a plastic film, the plastic film may, for example, include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate Ester (PEN), polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyethylene terephthalate/poly Polyester resins such as co-extruded films of ethylene naphthalate; polyamide resins such as nylon 6, nylon 66; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polychlorine Vinyl resins such as ethylene; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl methacrylate, etc.; imine resins such as polyimine and polyether imine; polyarylate, Polycarbonate, polyether sulfide, polyphenylene ether, polyphenylene sulfide (PPS), polyaromatic polyamide, polyether ketone, polyether nitrile, polyether ether ketone, polyether sulfide and other engineering resins; polycarbonate , Polystyrene, high-impact polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin) and other styrene resins; cellophane, cellulose Cellulose films such as acetate, nitrocellulose, etc. Plastic film can also be Copolymers or mixtures (including alloys) containing the above resin as the main component.

The thermal transfer film 10 used in the combination of one embodiment is provided with the first transfer layer (5) containing the receiving layer 5A. The transfer object 100 itself may not have the receiving layer, but it is desirable for the transfer object 100 When a thermal transfer image is formed on both sides of an embodiment, the thermal transfer film 10 used in the combination of an embodiment adopts a method of transferring the first transfer layer (5) only on one side of the object 100 In the configuration, the transfer target 100 is preferably provided with a receiving layer on one side. When the thermal transfer film 10 used in the combination of one embodiment adopts a configuration in which the first transfer layer (5) is transferred to both sides of the transfer object 100 as described later, the transfer object 100 may not be required With a receiving layer.

In addition, in the above, various additives are contained in the invisible light absorbing material-containing layer 2 and the color difference (ΔE*ab) between the invisible light absorbing material-containing layer 2 and the transfer object 100 is 10 or less. However, due to the different viewpoints from the side of the transferred object 100, specifically, various additives may be contained in the transferred object 100, and the invisible light absorbing material layer 2 and the transferred object may be included. The color difference of 100 (△E*ab) is 10 or less. In addition, various additives may be contained in both the invisible light absorbing material-containing layer 2 and the transfer target 100. When an additive material is contained in both the invisible light absorbing material-containing layer 2 and the transfer material 100, the additive material that may be contained in the invisible light absorption material-containing layer 2 and the additive material that may be contained in the transfer material 100, Can be of the same type or different types. At this time, the additive material contained in the invisible light absorbing material-containing layer 2 and the additive material contained in the transfer target 100 are preferably the same kind of additive material. borrow By using the same type of additive material, the color difference (△E*ab) can be easily adjusted.

The thickness of the object 100 to be transferred is not particularly limited, but is preferably in the range of 3 μm or more and 800 μm or less, and particularly preferably in the range of 100 μm or more and 600 μm or less.

<Configuration example of thermal transfer film>

Figures 3 to 5 are schematic cross-sectional views showing an example of the structure of the thermal transfer film used in the combination of an embodiment.

The thermal transfer film 10 of the form shown in Fig. 3(a) is on one side of the substrate 1. In the order of the surface, a layer 2 containing an invisible light absorbing material and a first transfer layer (5) are arranged in sequence , And yellow color material layer 3Y, and magenta color material layer 3M, and indigo color material layer 3C, and the second transfer layer (7), and yellow color material layer 3Y, and magenta color material layer 3M, and indigo color material Layer 3C, and the second transfer layer (7). The thermal transfer film 10 of the form shown in Figure 3, when each layer is set to "1 plate", the "6 plates" from the upstream side of printing (the left side of the drawing in the form of the figure) , Is used to form an image on one side of the transfer material 100 (form the image of the first screen), the remaining "4 plates" are used to form the image on the transferred A drawing board on the other side of the printed matter 100 (forming the image of the second screen). When the object to be transferred 100 does not have a receiving layer, the first transfer layer (5) can also be provided between the second transfer layer (7) and the yellow color material layer 3Y, and by using the first transfer layer (5), and the yellow color material layer 3Y, the magenta color material layer 3M, and the indigo color material layer 3C, and the second transfer layer (7) constitute the "5 plate", the image is formed on the transferred Print 100 The other side. In addition, as shown in Figure 3(b), the "6-panel" and "4-panel" in Figure 3(a) can also be interchanged. In addition, it can also be formed by subtracting the second transfer layer (7) (not shown in the figure). In addition, in the form shown in Figure 3 (c), the invisible light absorbing material layer 2, and the first transfer layer (5), and the yellow color material layer 3Y, the magenta material layer 3M, and indigo Color material layer 3C, second transfer layer (7), yellow color material layer 3Y, magenta color material layer 3M, indigo color material layer 3C, and second transfer layer (7) When "is set to "1 unit", the "1 unit" is set repeatedly. Hereinafter, the image formed on one side of the object to be transferred 100 is sometimes referred to as the "image of the first screen", and the image formed on the other side of the object to be transferred 100 is sometimes referred to as the "second screen". Image".

The alignment or prompting during printing is performed in units of "1 unit" when the assembly of each "board" is set to "1 unit", "1 unit", and other "1 unit" , The arrangement of the "boards" that constitute "1 unit" must be the same. That is, in the form shown in Figure 3, it is impossible to form the "image of the first screen" on one side of the object to be transferred 100. The image of "" is formed on the other side of the transfer material 100. Each "plate" of the "4 plate" used is set to "1 unit", and the "6 plate" and "4 plate" must be combined Set the "10 board" to "1 unit". However, as the number of "boards" constituting "1 unit" increases, there is also a problem that the design load of the printer for detecting each layer increases. The number of "boards" constituting "1 unit" decreases. The better.

Therefore, the thermal transfer film 10 in the form shown in Figure 4, On one side of the substrate 1, a layer 2 containing an invisible light absorbing material, a first transfer layer (5), a yellow color material layer 3Y, a magenta color material layer 3M, and an indigo color material layer 3C, and When the aggregate constituted by the "six plates" of the second transfer layer (7) is set to "1 unit", the "1 unit" is repeatedly installed. That is, in the form shown in Fig. 3, a "six plate" is used to form a plate used to form the "image of the first screen" on one side of the object to be transferred 100, and The "4 pattern board" constitutes a pattern board used to form the "image of the second screen" on the other side of the transfer object 100. In contrast, in the form shown in FIG. 4, The boards that form the "image of the first screen" and the "image of the second screen" are all composed of "6 boards". By setting this "6 boards" to "1 unit", it can be reduced The number of boards that constitute "1 unit".

On the other hand, in the form shown in Fig. 4, even if the "image on the first screen" is set to include the special image 50A, the "image on the second screen" is set to not include the special image. For an image like 50A, in order to reduce the number of plates that constitute "1 unit", the "1 unit" must also contain the invisible light absorbing material layer 2, which may cause increased waste.

Therefore, the thermal transfer film 10 of the form shown in Fig. 5 consists of a layer 2 containing an invisible light absorbing material, a first transfer layer (5), and a yellow color material layer 3Y on one side of the substrate 1. , And the magenta material layer 3M, the indigo material layer 3C, and the second transfer layer (7) of the "6 plate" assembly constituted when set to "1 unit", it is provided to the first screen The formation of the image of the image and the image of the second screen are integrated, and the structure It becomes a "graphic board" with 2 screens long. In the form shown in the figure, each color material layer of the yellow color material layer 3Y, the magenta color material layer 3M, and the indigo color material layer 3C becomes a "plate" with a length of 2 screens. That is, the color material layer of one layer is used as a configuration for forming the image on the first screen and the image on the second screen. According to the thermal transfer film 10 of this aspect, the "plate" of the layer used for the image formed on one side and the other side of the object to be transferred is set to a length of 2 screens, and the film is formed on any The "drawing board" of the layer used for the image on one side is set to the length of one screen, so that waste caused by the unused "drawing board" can be suppressed. For example, according to the thermal transfer film 10 of the form shown in Figure 5, "1 unit" can be used to form a first screen image on one surface of the transfer object 100, and then the front and back of the transfer object 100 Reverse and roll back the thermal transfer film 10, and then use the previously used "1 unit" again to form a second screen image on the other side of the transfer object 100. In the form shown in Fig. 5, in order to use the yellow color material layer 3Y, the magenta color material layer 3M, and the indigo color material layer 3C to form the image on the first screen and the image on the second screen, The length of the "plate" is set to the length of 2 screens, but other layers can also be used, such as the "plate" of the first transfer layer (5) or the second transfer layer (7) Set the length to the length of 2 screens. In addition, "1 unit" can be set repeatedly.

"Method of Formation of Printed Matter"

Next, referring to FIG. 6, the method of forming a printed matter according to the embodiment of the present disclosure (hereinafter referred to as the method of forming a printed matter of an embodiment) will be described.

One embodiment of the method of forming printed matter, which uses The method for forming a printed matter of a thermal transfer film and a transfer object is characterized by comprising: a transfer article preparation step of preparing the transfer article 100; and a thermal transfer film preparation step of preparing the thermal transfer film 10. The thermal transfer film is provided with an invisible light absorbing material-containing layer 2 containing an invisible light absorbing material on one side of the substrate 1 in the order of the surface, and a single layer composed of only the receiving layer 5A, or a receiving layer 5A is the first transfer layer (5) of laminated structure located closest to the substrate 1 and the color material layer 3 containing sublimation dye; and as shown in Figure 6(a), the thermal transfer film 10, the invisible light absorbing material-containing layer 2 is transferred to one side of the transfer object 100 to form a special image 50A containing the invisible light absorbing material; and as shown in Figure 6(b) , The transfer step of the first transfer layer (5) containing the receiving layer 5A of the thermal transfer film 10 onto the special image 50A; and as shown in Figure 6(c), The thermal transfer image forming step of thermally transferring the color material layer 3 of the thermal transfer film 10 to the first transfer layer (5) after the transfer to form a thermal transfer image 50B; special image The color difference (△E*ab) between the transferred object 100 formed in the forming step and the laminate 20 of the special image 50A and the transferred object 100 prepared in the transferred object preparation step is 10 or less .

In addition, the method of forming a printed matter of an embodiment is a method of forming a printed matter using a thermal transfer film and a transferred object, which is characterized by including: a step of preparing the transferred object 100 for preparing the transferred object; and preparation The heat transfer film preparation step of the heat transfer film. The heat transfer film is provided on one side of the substrate 1 with an invisible light absorbing material containing layer 2 containing an invisible light absorbing material in the order of the surface, and a first transfer Layer (5), to And the color material layer 3; and as shown in Figure 6(a), the invisible light absorbing material layer 2 of the thermal transfer film 10 is transferred to the side of the transfer object 100 to form an invisible light absorbing material The special image forming step of the special image 50A; and as shown in Figure 6(b), the first transfer layer (5) of the thermal transfer film 10 containing the receiving layer 5A is transferred to the special image 50A The first transfer layer transfer step above; and as shown in Figure 6(c), the color material layer 3 of the thermal transfer film 10 is thermally transferred to the transferred first transfer layer (5 ) To form the thermal transfer image forming step of the thermal transfer image 50B; the special image forming step is formed in the transfer object 100 and the special image 50A laminate 20, and the transfer object preparation The color difference (ΔE*ab) of the transferred material 100 prepared in the step is 10 or less.

According to the method of forming a printed matter according to an embodiment, it is possible to prevent the special image 50A from being unexpectedly viewed under visible light, and to form a highly creative printed matter. The steps are described in detail below.

(Steps to prepare the transfer material)

For the transfer object 100 prepared in this step, the transfer object 100 described in the combination of the above-mentioned embodiment can be used directly, and the detailed description is omitted here. In the illustrated form, a receiving layer is provided on the surface of the thermal transfer film 10 on the opposite side to the surface on which the special image 50A is formed, but the transfer target 100 may not have the receiving layer.

(Steps to prepare thermal transfer film)

The thermal transfer film 10 prepared in this step can be used directly The transfer target 100 described in the combination of one embodiment will not be described in detail here.

(Special image forming step)

In this step, the thermal transfer film 10 and the object to be transferred 100 are overlapped so that the invisible light-containing absorbing material layer 2 of the thermal transfer film 10 and the surface of the object to be transferred 100 face each other, and as in the sixth Figure (a) shows the step of melting and transferring the invisible light absorbing material-containing layer 2 of the thermal transfer film 10 to one side of the transfer object 100 to form a special image 50A. The special image 50A is not particularly limited. For example, a two-dimensional bar code including image information of the thermal transfer image 50B described later can be cited. The printer used for the formation of the special image 50A, the transfer of the first transfer layer (5), and the formation of the thermal transfer image 50B can be appropriately selected to use conventional heating means such as a heating head Known printers.

(The first transfer layer transfer step)

In this step, the thermal transfer film 10 and the object to be transferred 100 on which the special image 50A is formed so that the first transfer layer (5) of the thermal transfer film 10 and the object to be transferred 100 face each other The method overlaps, and as shown in Fig. 6(b), the first transfer layer (5) of the thermal transfer film 10 is melt-transferred to the transfer target 100 on which the special image 50A is formed. The first transfer layer (5) may be transferred on the area where the thermal transfer image 50B described later is formed. The transfer area may be the entire surface of the object 100 or the object 100. Part of one side (in the form of the figure, it is The entire surface of the transfer material).

In addition, the first transfer layer (5) can also be transferred at a position that does not overlap with the special image 50A. From the viewpoint of protecting the special image 50A, it is preferable to transfer the first transfer layer (5) so as to cover the special image 50A.

(Thermal transfer image forming step)

In this step, the thermal transfer film 10 is formed with the special image 50A and the first transfer layer (5) to be transferred 100, so that the color material layer 3 of the thermal transfer film 10 One side of the object 100 is overlapped in such a manner that the sublimable dye contained in the color material layer 3 is diffused and moved, and as shown in Figure 6(c), a thermal transfer image 50B is formed on the first transfer layer ( 5) The above steps. Or, when the color material layer 3 contains hot melt ink, the color material layer is melted or softened, and the melted or softened color material layer 3 is transferred with each layer, and as shown in Figure 6(c) As shown, the step of forming a thermal transfer image 50B on the first transfer layer (5). After this step, a printed matter 200 with a special image 50A and a thermal transfer image 50B formed on one surface of the object to be transferred 100 can be obtained.

(Second transfer layer transfer step)

In addition, as shown in Figure 6(d), after the formation of the thermal transfer image 50B, a second transfer layer (7) may be included to transfer the second transfer layer (7) to the thermal transfer image 50B. Layer transfer step. The second transfer layer transfer step is an arbitrary step in the method of forming a printed matter of one embodiment. Second transfer The transfer of the layer (7), as shown in Figures 2 to 5, can be carried out by using a thermal transfer film 10 with a second transfer layer (7), or by using a thermal transfer film prepared separately from the above The printing film 10 is different from a thermal transfer film (protective layer transfer film, etc.).

(Additional thermal transfer image forming step)

In addition, the thermal transfer film 10 shown in Figures 3 to 5 can also be used before or after the above various steps, as shown in Figure 6(e), on the transfer material 100 On the other side, another thermal transfer image 50C is formed. At this time, when the other side of the transfer object 100 does not have a receiving layer, it may include transferring the first transfer layer (5) to the transfer object 100 before forming the thermal transfer image 50C. The other side of the step. In addition, it may include a step of transferring the second transfer layer (7) to the thermal transfer image 50C (not shown in the figure). According to the method of forming a printed matter in one of the embodiments including an additional thermal transfer image forming step, a printed matter with thermal transfer images formed on both sides can be obtained. In addition, a special image 50A may also be formed on the other side of the object 100 to be transferred.

In addition, the thermal transfer film of the modified form described in the combination of the above-mentioned one embodiment can be appropriately selected and used instead of the substrate 1 having invisible light absorbing material containing invisible light absorbing material arranged in the order of the surface. The material layer 2, the first transfer layer (5), and the thermal transfer film 10 of the color material layer 3 are used to form printed matter.

"Heat Transfer Film"

Next, the thermal transfer film of the embodiment of the present disclosure (hereinafter referred to as the thermal transfer film of one embodiment) will be described. The thermal transfer film 10 of one embodiment is a thermal transfer film used when the thermal transfer image (50A, 50B) is formed on the object to be transferred, as shown in Figures 1 to 5 , Characterized in that: on one side of the substrate 1, a layer containing an invisible light absorbing material 2, and a first transfer layer (5), and a color material layer 3 are arranged in the order of the surface; the first transfer layer (5) , Showing a single-layer structure composed of only the receiving layer 5A, or a laminated structure in which the receiving layer 5A is located closest to the substrate 1; the color material layer 3 contains sublimable dyes; the transferred material 100 and contains no The color difference (ΔE*ab) between the laminate 20 of the visible light absorbing material layer 2 and the transfer target 100 is 10 or less.

In addition, the thermal transfer film 10 of one embodiment is a thermal transfer film used when forming a thermal transfer image (50A, 50B) on an object to be transferred, and is characterized in that: On one side, the invisible light absorbing material-containing layer 2, and the first transfer layer (5), and the color material layer 3 containing the invisible light absorbing material are arranged in the order of the faces; the transferred object 100 and the invisible light absorbing material The color difference (ΔE*ab) between the laminate 20 of the layer 2 and the object to be transferred 100 is 10 or less.

According to the thermal transfer film 10 of the aforementioned embodiment, the use of the thermal transfer film 10 can prevent the image 50A (special image 50A) containing the invisible light absorbing material from being unexpectedly viewed under visible light. Can form highly creative prints. For the thermal transfer film 10 of one embodiment, the thermal transfer film 10 of various embodiments described in the combination of the above-mentioned one embodiment can be appropriately selected and used, and the detailed description is omitted here. Bright.

Example

Next, examples are given to illustrate the present invention more specifically. Hereinafter, unless otherwise stated, parts are the basis of mass.

(Production of thermal transfer film 1)

A PET film with a thickness of 4.5 μm was used as a substrate, and a coating liquid for a back layer having the following composition was applied to one side of the substrate and dried to form a back layer so that the thickness during drying became 1 μm. In addition, the coating liquid 1 for an invisible light absorbing material-containing layer having the following composition was applied to the other surface of the base material and dried to form an invisible light absorbing material-containing layer so that the thickness during drying became 1 μm. In addition, in accordance with the order of the surfaces along with the layer containing the invisible light absorbing material, the coating solution for a receiving layer having the following composition is applied to the other surface of the substrate and dried to form the substrate so that the thickness during drying becomes 1 μm. Receptive layer. In addition, along with the invisible light-absorbing material-containing layer and the receiving layer, in the order of the surfaces, the primer layer coating solution of the following composition was applied to the other surface of the substrate so that the thickness during drying became 0.2 μm And dried to form a primer layer, and by a gravure printing machine, the coating solution for the yellow color material layer and the magenta material layer with the following composition were applied so that the thickness of each layer when dried became 0.7μm. The cloth liquid and the coating liquid for the indigo color material layer are applied on the primer layer and dried to form the color material layer. Then, with the invisible light absorbing material layer, the receiving layer, and the yellow color material layer, the magenta color material layer, and the indigo color material layer in accordance with the surface order In order to make the thickness when drying becomes 1μm, the coating solution for release layer of the following composition is applied to the other side of the substrate and dried to form a release layer, and the thickness when dried becomes 1μm In this way, a coating solution for a protective layer with the following composition is applied to the release layer and dried to form a protective layer, whereby a back layer is provided on one side of the substrate and on the other side of the substrate. In accordance with the order of the surface, a thermal transfer film containing a laminate of an invisible light absorbing material layer, a receiving layer, a yellow color material layer, a magenta color material layer, and an indigo color material layer, a peeling layer, and a protective layer is provided 1 .

(Coating liquid for back layer)

●Polyvinyl butyral 1.8 parts

(S-Lec (registered trademark) BX-1 Sekisui Chemical Industry Co., Ltd.)

●Polyisocyanate 5.5 parts

(Burnock (registered trademark) D750 DIC Co., Ltd.)

●Phosphate ester surfactant 1.6 parts

(Plysurf (registered trademark) A208N First Industrial Pharmaceutical Co., Ltd.)

●Talc 0.35 parts

(Micro Ace (registered trademark) P-3 Nippon Talc Co., Ltd.)

●Toluene 18.5 parts

●Butanone 18.5 parts

(Coating liquid 1 for layer containing invisible light absorbing material)

●Acrylic resin 6.7 parts

(Dianal (registered trademark) BR-87 Mitsubishi Rayon Co., Ltd.)

●Diaminium salt 0.3 parts

(CIR-RL Japan Carlit Co., Ltd.)

●Titanium oxide 2.9 parts

(TCA-888 Sakai Chemical Industry Co., Ltd.)

●Toluene 20 parts

●Butanone 20 parts

(Coating liquid for receiving layer)

●Vinyl chloride-vinyl acetate copolymer 15.8 parts

(Solbin (registered trademark) CNL Nissin Chemical Industry Co., Ltd.)

●Vinyl chloride-vinyl acetate copolymer 1 part

(Solbin (registered trademark) C Nissin Chemical Industry Co., Ltd.)

●Organic modified polysiloxane oil 1.2 parts

(X-22-3000T Shin-Etsu Chemical Industry Co., Ltd.)

●Organic modified polysiloxane oil 1.2 parts

(X-24-510T Shin-Etsu Chemical Industry Co., Ltd.)

●Organic modified polysiloxane oil 0.8 parts

(KF-352A Shin-Etsu Chemical Industry Co., Ltd.)

●Toluene 40 parts

●Butanone 40 parts

(Coating liquid for primer layer)

●Alumina sol 2.5 parts

(Alumina Sol 200 Nissan Chemical Industry Co., Ltd.)

●Polyvinylpyrrolidone resin 2.5 parts

(PVP K-60 ISP Japan Co., Ltd.)

● Water 47.5 parts

●47.5 parts of isopropyl alcohol

(Coating liquid for yellow color material layer)

●Solvent Yellow 93 2.5 copies

●Solvent Yellow 201 2.5 copies

●Polyvinyl acetal resin 5 parts

(KS-5 Sekisui Chemical Industry Co., Ltd.)

●Toluene 50 parts

●Butanone 50 parts

(Coating liquid for magenta material layer)

●Disperse Red 60 3 copies

● Disperse Violet 26 4 copies

●Polyvinyl acetal resin 5 parts

(KS-5 Sekisui Chemical Industry Co., Ltd.)

●Toluene 50 parts

●Butanone 50 parts

(Coating liquid for indigo color material layer)

●Solvent Blue 63 4 copies

● Disperse Blue 354 4 copies

●Polyvinyl acetal resin 5 parts

(KS-5 Sekisui Chemical Industry Co., Ltd.)

●Toluene 50 parts

●Butanone 50 parts

(Coating liquid for release layer)

●Acrylic resin 20 parts

(Dianal (registered trademark) BR-87 Mitsubishi Rayon Co., Ltd.)

●Toluene 40 parts

●Butanone 40 parts

(Coating liquid for protective layer)

●24 parts of polyester resin

(Vylon (registered trademark) 700 Toyobo Co., Ltd.)

●Ultraviolet absorber 6 parts

●35 parts of toluene

●Butanone 35 parts

(Production of Thermal Transfer Film 2)

The invisible light absorbing material-containing layer coating liquid 2 of the following composition is used instead of the invisible light absorbing material-containing layer coating liquid 1 to form an invisible light absorbing material layer. In addition, other methods are used with thermal transfer The thermal transfer film 2 was obtained by the same manufacturing method as the film 1.

(Coating liquid 2 for layer containing invisible light absorbing material)

●Acrylic resin 6.7 parts

(Dianal (registered trademark) BR-87 Mitsubishi Rayon Co., Ltd.)

●Diaminium salt 0.3 parts

(CIR-RL Japan Carlit Co., Ltd.)

●Calcium carbonate 2.9 parts

(Homocal D Shiraishi Industrial Co., Ltd.)

●Toluene 20 parts

●Butanone 20 parts

(Production of Thermal Transfer Film 3)

The coating liquid 3 for a layer containing invisible light absorbing material of the following composition was used instead of the coating liquid 1 for a layer containing invisible light absorbing material to form a layer containing an invisible light absorbing material. In addition, other methods are used with thermal transfer The thermal transfer film 3 was obtained by the same manufacturing method as the film 1.

(Coating liquid 3 for layer containing invisible light absorbing material)

●Acrylic resin 6.7 parts

(Dianal (registered trademark) BR-87 Mitsubishi Rayon Co., Ltd.)

●Diaminium salt 0.3 parts

(CIR-RL Japan Carlit Co., Ltd.)

●Propionic acid fine particles 2.9 parts

(MA1004 Nippon Shokubai Co., Ltd.)

●Toluene 20 parts

●Butanone 20 parts

(Production of Thermal Transfer Film 4)

The coating liquid 4 for a layer containing an invisible light absorbing material with the following composition was used instead of the coating liquid 1 for a layer containing an invisible light absorbing material to form a layer containing an invisible light absorbing material. In addition, other methods were used with thermal transfer The thermal transfer film 4 was obtained by the same manufacturing method as the film 1.

(Coating liquid 4 for layer containing invisible light absorbing material)

●Acrylic resin 6.7 parts

(Dianal (registered trademark) BR-87 Mitsubishi Rayon Co., Ltd.)

●Diaminium salt 0.3 parts

(CIR-RL Japan Carlit Co., Ltd.)

●Titanium oxide 3.3 parts

(TCA-888 Sakai Chemical Industry Co., Ltd.)

●Toluene 20 parts

●Butanone 20 parts

(Production of Thermal Transfer Film 5)

The invisible light absorbing material-containing layer coating solution 5 of the following composition is used instead of the invisible light absorbing material-containing layer coating solution 1 to form an invisible light absorbing material layer. In addition, other methods are used with thermal transfer The thermal transfer film 5 was obtained by the same manufacturing method as the film 1.

(Coating solution 5 for layer containing invisible light absorbing material)

●Acrylic resin 8.5 parts

(Dianal (registered trademark) BR-87 Mitsubishi Rayon Co., Ltd.)

●Diaminium salt 1.5 parts

(CIR-RL Japan Carlit Co., Ltd.)

●Titanium oxide 2.4 parts

(TCA-888 Sakai Chemical Industry Co., Ltd.)

●Toluene 20 parts

●Butanone 20 parts

(Production of heat transfer film 6)

The coating liquid 6 for a layer containing an invisible light absorbing material of the following composition was used instead of the coating liquid 1 for a layer containing an invisible light absorbing material to form an invisible light containing layer: The thermal transfer film 6 is obtained by the same manufacturing method as the thermal transfer film 1 except for the absorbent material layer.

(Coating liquid 6 for layer containing invisible light absorbing material)

●Acrylic resin 6.7 parts

(Dianal (registered trademark) BR-87 Mitsubishi Rayon Co., Ltd.)

●Diaminium salt 0.3 parts

(CIR-RL Japan Carlit Co., Ltd.)

●Toluene 20 parts

●Butanone 20 parts

(Production of Thermal Transfer Film 7)

The invisible light absorbing material-containing layer coating liquid 7 of the following composition is used instead of the invisible light absorbing material-containing layer coating liquid 1 to form an invisible light absorbing material layer. In addition, other methods are used with thermal transfer The thermal transfer film 7 was obtained by the same manufacturing method as the film 1.

(Coating liquid 7 for layer containing invisible light absorbing material)

●Acrylic resin 6.7 parts

(Dianal (registered trademark) BR-87 Mitsubishi Rayon Co., Ltd.)

●Diaminium salt 0.7 parts

(CIR-RL Japan Carlit Co., Ltd.)

●Toluene 20 parts

●Butanone 20 parts

(Production of Thermal Transfer Film 8)

The invisible light absorbing material-containing layer coating liquid 8 of the following composition is used instead of the invisible light absorbing material-containing layer coating liquid 1 to form an invisible light absorbing material layer. In addition, other methods are used with thermal transfer The thermal transfer film 8 was obtained by the same manufacturing method as the film 1.

(Coating liquid 8 for layer containing invisible light absorbing material)

●Acrylic resin 6.7 parts

(Dianal (registered trademark) BR-88 Mitsubishi Rayon Co., Ltd.)

●Diaminium salt 0.3 parts

(CIR-RL Japan Carlit Co., Ltd.)

●Solvent Yellow 93 0.4 copies

●Toluene 20 parts

●Butanone 20 parts

(Production of transfer material 1)

Using a bar coater, the primer layer coating solution 1 of the following composition was applied to a 35μm thick porous polyolefin membrane (SP-U Mitsui Chemicals Tohcello Co., Ltd.) so that the thickness during drying became 1.5μm. Co., Ltd.) and dried (110°C, 1 minute) to form a primer layer. Then, by using a bar coater, the coating solution for receiving layer with the following composition was applied so that the thickness during drying became 4μm It is coated on the primer layer and dried (110° C., 1 minute) to form a receiving layer to obtain a laminate in which a porous polyolefin film, a primer layer, and a receiving layer are sequentially laminated. Next, the adhesive layer coating liquid of the following composition was applied to the core paper (OKL Card Oji Paper Co., Ltd.) with a thickness of 400 μm (basis weight 310 g/m ² ) so that the thickness during drying became 4 μm. An adhesive layer is formed on both one side and the other side of the core material, and then the adhesive layer is maintained in a wet state, and the obtained laminate is attached to one side and the other side of the core paper through the adhesive layer On both of them, the next layer is dried. Thereby, an intermediary layer can be obtained, and a laminate in which a porous polyolefin film, a primer layer, and a receiving layer are laminated in sequence on one side and the other side of the core paper is transferred. Printed matter 1.

(Coating liquid for primer layer 1)

●Polyester resin 4.2 parts

(Polyester (registered trademark) WR-905 Nippon Synthetic Chemical Industry Co., Ltd.)

●Titanium oxide 8.4 parts

(TCA-888 Sakai Chemical Industry Co., Ltd.)

●Fluorescent brightener 0.07 parts

(Uvitex (registered trademark) BAC BASF company)

●Isopropyl alcohol 7.2 parts

● 21 parts water

(Coating liquid for receiving layer)

●10 parts of vinyl chloride-vinyl acetate copolymer

(Solbin (registered trademark) C Nissin Chemical Industry Co., Ltd.)

●Polysiloxane oil 1 part

(X-22-3000T Shin-Etsu Chemical Industry Co., Ltd.)

●Toluene 20 parts

●20 parts of ethyl acetate

(Coating liquid for adhesive layer)

● 30 parts of urethane resin

(Takelac (registered trademark) A-969V Mitsui Chemicals Co., Ltd.)

●Isocyanate 10 parts

(Takenate (registered trademark) A-5 Mitsui Chemicals Co., Ltd.)

●60 parts of ethyl acetate

(Production of transfer material 2)

The coating liquid 1 for a primer layer was changed to the coating liquid 2 for a primer layer mentioned below, and other than the same as that of the to-be-transferred object 1, the to-be-transferred object 2 was obtained.

(Coating liquid for primer layer 2)

●Polyester resin 10 parts

(MD-1480 Toyobo Co., Ltd.)

●Synthetic magnesium lithium silicate clay 10 parts

(Laponite JS Rockwood Additives)

●Defoamer 0.05 parts

(Dynol 604 Nissin Chemical Industry Co., Ltd.)

●10 parts of isopropyl alcohol

● 80 parts of water

(Combination of thermal transfer film and transferred material)

The thermal transfer film and the object to be transferred prepared as described above were constituted in the combination shown in Table 1 below, and used as a combination of each of the examples and comparative examples. The laminate is formed by forming a special image on the transfer object formed by the method of forming a printed matter described below, and the color difference (△E*ab) of the transfer object is 10 or less. For example, a combination with a color difference (ΔE*ab) exceeding 10 is constituted as a comparative example. The color difference (△E*ab) used a spectrometer (manufactured by i1 X-rite).

(Formation of printed matter) 〈Formation of image (special image) containing layer containing invisible light absorbing material〉

With the combination of Table 1 below, using the following test printer, the layer containing the invisible light absorbing material was melted and transferred to the transfer object to form a special image. The thickness of the special image is 1.0 μm.

(Test printer)

Heating head: KEE-57-12GAN2-STA (manufactured by Kyocera Co., Ltd.)

Average resistance value of heating element: 3303 (Ω)

Print density in main scanning direction: 300 (dpi)

Print density in the sub-scanning direction: 300 (dpi)

Printing voltage: 18 (V)

Line period: 1.5(msec./line)

Printing start temperature: 35(℃)

Pulse duty ratio: 85 (%)

<Transfer of receiving layer>

Using the above-mentioned test printer, transfer the receiving layer on the special image formed above.

<Transfer of Thermal Transfer Image>

Using the above-mentioned test printer, a 128/256-tone gray image was formed on the above-mentioned transfer-receiving layer to obtain printed matter of each embodiment and comparative example.

(Printed Material Evaluation)

Visually confirm the printed matter of each embodiment and comparative example formed by the combination of each embodiment and comparative example, and perform the following evaluation criteria Evaluate whether the bar code pattern of a particular image can be recognized. The evaluation results are shown in Table 1.

"Assessment criteria"

A: Even when someone who knows the location of a special image in advance watches it, the location and shape cannot be recognized.

B: Although a person who knows the location of a special image in advance can recognize the location and shape when viewing it, a person who does not know the location in advance cannot recognize the location and shape.

NG: Even people who have not known the location of the special image in advance can recognize the location and shape.

(Printer testing and evaluation)

According to the following evaluation criteria, evaluate whether it is possible to use the color sensor (CZ-H35S Keyence Co., Ltd.) to combine the invisible light absorbing material layer of the thermal transfer film used in the combination of each embodiment and comparative example , Distinguished from each color material layer (yellow color material layer, magenta color material layer, indigo color material layer), and the protective layer and detected. The evaluation results are shown in Table 1.

"Assessment criteria"

A: It can be detected without problems, and the possibility of false detection is extremely low.

B: It can be detected, and the possibility of false detection is low.

C: Although it can be detected, the possibility of false detection is high.

1‧‧‧Substrate

2‧‧‧Containing invisible light absorbing material layer

3‧‧‧Color material layer

5‧‧‧First transfer layer

5A‧‧‧Reception layer

10‧‧‧Heat Transfer Film

Claims (5)

A combination of a thermal transfer film and a transfer material, which is characterized in that the thermal transfer film is on one side of a substrate, and a layer containing invisible light absorbing materials and pigments is arranged in the order of the surfaces. , And a thermal transfer film containing a first transfer layer containing a sublimable dye-receiving layer, and a color material layer containing sublimable dye; by the aforementioned pigment contained in the aforementioned layer containing invisible light absorbing material, and the aforementioned The visible light transmittance of the layer containing invisible light absorbing material is different from that of the aforementioned color material layer, and the color difference (△E*ab) between the aforementioned transferred material and the aforementioned laminate containing the aforementioned non-visible light absorbing material layer and the aforementioned transferred material, It is 10 or less. The combination of the thermal transfer film and the transfer material of claim 1, wherein the first transfer layer is a single layer composed of the receiving layer only, or the receiving layer is located closest to the substrate The position of the transfer layer composed of lamination. A method for forming a printed matter, which is a method for forming a printed matter using a thermal transfer film and an object to be transferred, is characterized by including: a step of preparing the transferred object for preparing the transferred object; and the heat for preparing the thermal transfer film The transfer film preparation step. The thermal transfer film is provided on one side of the substrate with an invisible light absorbing material layer containing an invisible light absorbing material and a pigment and a receiving layer containing an acceptable sublimation dye in the order of the surface. The first transfer layer and the color material layer containing sublimable dye; and the invisible light absorption material-containing layer of the thermal transfer film is transferred A special image forming step of printing on one side of the aforementioned object to be transferred to form a special image containing an invisible light absorbing material; and transferring the first transfer layer of the aforementioned thermal transfer film to the aforementioned special image The first transfer layer transfer step; and the sublimation dye contained in the color material layer of the thermal transfer film is transferred onto the receiving layer of the first transfer layer after the transfer is formed The thermal transfer image forming step of the thermal transfer image; and by the pigment contained in the invisible light absorbing material layer, the visible light transmittance of the invisible light absorbing material layer and the color material layer are different, The aforementioned object to be transferred prepared in the step of preparing the object to be transferred and the aforementioned heat transfer film prepared in the step of preparing the aforementioned thermal transfer film are the aforementioned object to be transferred formed in the aforementioned special image forming step The color difference (ΔE*ab) between the laminate of the aforementioned special image and the aforementioned object to be transferred prepared in the aforementioned step of preparing the object to be transferred is the object to be transferred and the thermal transfer film of 10 or less. The method for forming a printed matter according to claim 3, wherein the first transfer layer transfer step is to transfer the first transfer layer in a manner that covers the entire surface of the special image and the object to be transferred的步。 The steps. A thermal transfer film, which is a thermal transfer film used when a thermal transfer image is formed on a transfer object. It is characterized in that: on one side of the substrate, invisible light is provided in the order of the surface. The first transfer layer containing the invisible light absorbing material layer of the absorbing material and the pigment and the receiving layer containing the sublimable dye, and the first transfer layer containing the sublimable dye Color material layer; and by the pigment contained in the invisible light absorbing material-containing layer, the visible light transmittance of the invisible light absorbing material layer and the color material layer are different.

Images