JP2009274290A - Intermediate transfer recording medium and forgery prevention medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intermediate transfer recording medium which can print an image by an ink jet system, is free from the blotting of image upon printing, is fast in drying, and is excellent in endurance such as scuffing resistance, solvent resistance and Launderability with respect to the image transferred to a medium, and to provide a forgery prevention medium. <P>SOLUTION: The intermediate transfer recording medium 10 is prepared by laminating a releasing layer 13, a protective layer 15 and a receptive layer 21 on a base 11, wherein the receptive layer 21 comprises: a cationic urethane resin; a cationic fixing agent; filler; and an aziridine derivative having at least two aziridinyl groups in a molecule, the receptive layer 21 can be printed by an inkjet method and a rate of the cationic urethane resin in the receptive layer 21 to the aziridine derivative having at least two aziridinyl groups in a molecule is in the range of 100/1 to 100/15. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an intermediate transfer recording medium, and more specifically, an image can be printed by an ink jet method that does not use an ink ribbon that leaves traces of personal information or the like, and when the image is printed, the image does not blur and dries quickly, The printed image after transfer relates to an intermediate transfer recording medium and a forgery prevention medium having excellent durability such as scratch resistance, solvent resistance, and fastness to washing, and high security.

  In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated. In addition, “PET” is “polyethylene terephthalate”, “UV” is “ultraviolet”, “ionizing radiation curable resin” is “a general term for uncured ionizing radiation curable resin and cured ionizing radiation curable resin”, “Print” is an abbreviation, functional expression, common name, or industry term for “print”.

(Main application) As the main application of the transfer layer (forgery prevention medium) on which the image is transferred to the transfer layer (medium) using the intermediate transfer recording medium of the present invention, for example, banknotes, Stock certificates, securities, certificates, gift certificates, checks, bills, admission tickets, passbooks, gift certificates, boarding tickets, car horse tickets, stamps, stamps, appreciation tickets, admission cards, passports, ticket tickets, cash cards, credits Cards such as cards, ID cards, prepaid cards, members cards, IC cards, optical cards, greeting cards, postcards, business cards, driver's licenses, passports, etc. and their ID photos, cartons, cases, flexible packaging Packaging materials such as materials, bags, cosmetics, wristwatches, brand accessories such as lighters, envelopes, tags, bookmarks, calendars, posters, brochures, name plates Stationery such as report paper, a building material, panel, emblem, key, cloth, clothing, footwear, radio, television, calculators, and devices such as OA equipment.
However, it is possible to print an image by an ink jet method that does not use an ink ribbon that leaves traces of personal information, etc., and the image transferred to the medium is required to have durability such as scratch resistance, solvent resistance, and washing fastness. If it is a use, it will not specifically limit.

(Background Art) Conventionally, forgery prevention media such as gold vouchers, cards, and various certificates have qualifications and certain economic values and effects, so the owner's personal information is displayed. It is necessary to prevent leakage of information and to withstand external forces during use. As a display method of personal information, printing (display) by a thermal transfer method is widely used. In these thermal transfer methods, various images are easily formed, and therefore, the thermal transfer method is used to create a printed material that requires a relatively small number of prints, for example, an ID card such as an identification card. Further, when a color image is preferable such as a face photograph, a large number of colored thermal transfer layers of, for example, yellow, magenta, and cyan (and black if necessary) are repeatedly provided in the surface sequence on a continuous base film. A thermal transfer method using a long thermal transfer film has been performed. There are two types of such thermal transfer films: a melt transfer type and a sublimation type thermal transfer film, both of which print using a dedicated ink ribbon. The missing portion of the discharged ink ribbon is personal information to be kept secret, and there is a risk that the personal information is easily known from the discarded ink ribbon.
Also, when creating ID cards such as identification cards with the above-mentioned thermal transfer film, it is easy to form images such as letters and numbers in the case of a melt transfer type thermal transfer film, but these images are durable. There is a drawback that the properties, particularly the friction resistance, are inferior. On the other hand, in the case of a sublimation transfer type thermal transfer film, a gradation image such as a face photograph can be formed, but unlike a normal printing ink, the formed image has no vehicle, so There exists a problem that it is inferior to durability, such as a weather resistance and friction resistance. As a method of solving the above problem, after forming an image, a protective layer (corresponding to a hard coat layer or a protective layer of the present invention) such as a transparent resin layer or a cured resin layer is further stacked on the surface of the image. There is a way to transfer. However, since the image transfer and the protective layer transfer are performed twice, it is complicated and inefficient.
Therefore, there are intermediate transfer recording media that do not use an ink ribbon and form an image by an ink jet method. However, an image by an ink jet method is slow to dry, so the image forming speed is slow, the print is blurred, and the image is further formed. Since the subsequent drying is slow, there is also a problem in that it cannot be immediately transferred to the transfer target.
Furthermore, since cards and various certificates have credential and certain economic value and effect, the owner cannot be easily identified, and impersonation can be used by anyone other than the owner through counterfeiting. There were also drawbacks.
Therefore, the intermediate transfer recording medium does not use an ink ribbon that leaves traces of personal information or the like. When an image is printed on the intermediate transfer recording medium, the image does not bleed and dries quickly, and the intermediate transfer recording medium is used. In addition, after transferring an image to a transfer target, durability such as abrasion resistance and solvent resistance is required, and further, security for preventing forgery, alteration and spoofing is also required.

(Prior Art) Conventionally, a card is known in which an image is formed on an image receiving layer by sublimation thermal transfer, melt thermal transfer, ink jet, or electrophotography, and transferred onto a substrate by thermal transfer (see, for example, Patent Document 1). ). However, there is a problem that an image by ink jet is an image such as a character and does not have special security.
Further, the applicant of the present invention is a thermal transfer sheet (corresponding to the intermediate transfer recording medium of the present invention) in which a thermal transfer sheet substrate, a release layer, a water-resistant resin layer, a water-based ink receiving layer, and an inkjet printing layer are formed in order. A card manufacturing method for thermally transferring the thermal transfer sheet to a card material is disclosed (for example, see Patent Document 2). However, although it is possible to form a clear original image composed of a personal photograph of an individual possessed or a design or design of the user's preference, there is a drawback in that security is low to prevent forgery, alteration and spoofing.

Japanese Patent Laid-Open No. 10-244788 JP 2006-2054889 A

  Accordingly, the present invention has been made to solve such problems. The purpose is to be able to print an image with an ink jet method that does not use an ink ribbon that leaves traces of personal information, etc., and when printing an image on the receiving layer of the intermediate transfer recording medium, the image does not blur, dries quickly, and An image transferred to a medium is excellent in durability such as scratch resistance, solvent resistance and fastness to washing, and provides an intermediate transfer recording medium and anti-counterfeit medium having high security.

In order to solve the above problems, an intermediate transfer recording medium according to the invention of claim 1 is formed by laminating a base material and at least a release layer, a protective layer, and a receiving layer on one surface of the base material. An intermediate transfer recording medium, wherein the receiving layer includes a cationic urethane resin, a cationic fixing agent, a filler, and an aziridine derivative having two or more aziridinyl groups in the molecule, and the receiving layer is an inkjet method It was made so that it could be printed.
The intermediate transfer recording medium according to the invention of claim 2 is a cationic urethane-based resin in which the blending ratio of an aziridine derivative having two or more aziridinyl groups in the molecule to the cationic urethane-based resin of the receiving layer is on a mass basis: Aziridine derivatives having two or more aziridinyl groups in the molecule = 100: 1-15.
An anti-counterfeit medium according to a third aspect of the invention uses the intermediate transfer recording medium according to any one of the first and second aspects, and after printing an image on the receiving layer of the intermediate transfer recording medium by an ink jet method, The protective layer and the receiving layer on which an image has been formed are transferred onto the surface of the transfer body.

According to the first aspect of the present invention, an image can be printed by an ink jet method that does not use an ink ribbon that leaves traces of personal information or the like, and the image does not blur when the image is printed on the receiving layer of the intermediate transfer recording medium. An image that is quickly dried and transferred to the medium is excellent in durability such as scratch resistance, solvent resistance, and fastness to washing, and an intermediate transfer recording medium having high security is provided.
According to the second aspect of the present invention, in addition to the effect of the first aspect, an intermediate transfer recording medium is provided which is more excellent in durability such as scratch resistance, solvent resistance, and fastness to washing.
According to the third aspect of the present invention, an image printed by an inkjet method that does not use an ink ribbon that leaves traces of personal information or the like, and an image transferred to a transfer target (medium) is scratch-resistant, An anti-counterfeit medium having excellent durability such as solvent resistance and fastness to washing and high security is provided.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of an intermediate transfer recording medium showing one embodiment of the present invention.
FIG. 2 is an explanatory diagram for explaining the image forming method on the intermediate transfer recording medium of the present invention.
FIG. 3 is a cross-sectional view of an anti-counterfeit medium showing one embodiment of the present invention.

(Intermediate transfer recording medium) As shown in FIG. 1, the intermediate transfer recording medium 10 of the present invention has a base material 11, a release layer 13, a protective layer 15, and a receiving layer 21 on one surface of the base material 11. Have You may provide other layers, such as a primer layer 16 and a printing layer, in these interlayers and / or the layer surface as needed. The receiving layer 21 contains a cationic urethane resin, a cationic fixing agent, a filler, and an aziridine derivative having two or more aziridinyl groups in the molecule, and can be printed on the receiving layer 21 by an ink jet method. Preferably, the proportion of the aziridine derivative having two or more aziridinyl groups in the molecule relative to the cationic urethane resin of the receiving layer 21 is based on mass, and the cationic urethane resin: two or more aziridinyl in the molecule. Aziridine derivative having a group = 100: 1 to 15. Further, FIG. 2 shows a state in which the image 103 is printed on the receiving layer 21 by the ink jet method.
By transferring the intermediate transfer recording medium 10 of the present invention on which the image 103 is printed to the transfer target 101, a forgery prevention medium 100 as shown in FIG. 3 is obtained.

  (Substrate) The substrate 11 is not particularly limited. Specific examples of the preferred substrate 11 include polyester, polypropylene, polycarbonate, cellulose acetate, and polyethylene derivatives having high heat resistance such as polyethylene terephthalate and polyethylene naphthalate. And stretched or unstretched films of plastics such as polyamide and polymethylpentene. Moreover, the composite film which laminated | stacked 2 or more types of these materials can also be used. Although the thickness of a base film can be suitably selected according to material so that the intensity | strength, heat resistance, etc. may become appropriate, the thing about 1-100 micrometers is normally used normally.

  (Release layer) A release layer 13 may be provided to improve the releasability during transfer, and a release layer may be provided instead of the release layer 13 as necessary. If both are provided, the transferability can be further improved.

  (Release layer) As the release layer 13, there are usually a release resin, a resin containing a release agent, a curable resin which is cross-linked by ionizing radiation, etc., preferably a melamine-based resin, which will be described later. By combining with the hard coat layer 14, the releasability from the release layer 13 is stabilized, and the transferability during transfer can be improved. The release layer 13 is formed by dispersing or dissolving the resin in a solvent, applying and drying the resin by a known coating method such as roll coating or gravure coating, and baking at a temperature of about 150 ° C to 200 ° C. The thickness of the release layer 13 is usually about 0.01 μm to 5.0 μm, preferably about 0.5 μm to 3.0 μm.

  (Peeling layer) As a peeling layer provided as needed, generally cellulose derivatives such as ethyl cellulose, nitrocellulose, cellulose acetate, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, It is formed using thermoplastic resins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, etc., and thermosetting resins such as unsaturated polyester resin, polyurethane resin, and amino alkyd resin. be able to. The release layer preferably contains a filler such as microsilica or polyethylene wax in order to improve the foil breakability. The release layer may be prepared by dispersing or dissolving the above resin in a solvent and applying at least one part by a known coating method such as roll coating, gravure coating, bar coating, etc. and drying to form a coating film. good. The thickness of the release layer is usually about 0.1 μm to 5 μm, preferably about 0.5 μm to 2 μm. When both the release layer 13 and the release layer are provided, they may be used in combination as appropriate. In this case, the release layer is transferred to the transfer target after transfer, and has a function as a protective layer. .

  (Protective layer) The protective layer 15 may include a cured product of an ionizing radiation curable resin, a silicone oil, a silicone such as a reactive silicone, or a filler of micro silica or polyethylene wax. Good.

  (Formation of protective layer) The protective layer 15 may be, for example, an epoxy-modified acrylate resin, a urethane-modified acrylate resin, an acrylic-modified polyester, etc., preferably an ionizing radiation curable resin such as a urethane-modified acrylate resin, and as required. The additive is dispersed or dissolved in a solvent, and is applied to at least a part by a known coating method such as roll coating, gravure coating, comma coating, etc., and then irradiated with ionizing radiation such as ultraviolet rays or electron beams. When cured (reacted), it becomes an ionizing radiation curable resin (protective layer 15). The thickness of the protective layer 15 is usually about 1 μm to 30 μm, preferably about 2 μm to 20 μm. It may be applied several times.

  (Receiving layer) A receiving layer 21 is provided on the surface of the protective layer 15 through a primer layer 16 as necessary. The receiving layer 21 becomes the outermost surface of the intermediate transfer recording medium 10, and an image is printed on the receiving layer 21 by an ink jet method. The inkjet receiving layer 21 is obtained by applying an inkjet receiving layer composition. The inkjet receiving layer composition includes at least a cationic urethane-based resin, a cationic fixing agent, a filler, and two or more aziridinyl in a molecule. And an aziridine derivative having a group.

  Polycationic polyurethane resins with cationic groups, polytetramethylene ether glycol polyurethane, polyester ether polyurethane, polybutylene adipate polyurethane, polymethylpentane adipate polyurethane, polynonanediol adipate / polyoctane adipate Polyurethane resins such as polyurethane and polymethylpentane adipate polyurethane, preferably self-emulsifying or aqueous, and a reaction product of a polycarbonate or polyester polyol having a cationic hydrophilic group and an aliphatic isocyanate. Examples of cationic groups include primary to tertiary amines or quaternary ammonium bases.

  (Cationic Fixing Agent) Examples of the cationic fixing agent include dye fixing agents such as polyamine derivatives and quaternary ammonium salts.

  (Filler) As the filler, micro-silica is preferable because it contains fine particles such as silica, alumina, calcium carbonate, and plastic pigment, wax, and the like so as to improve foil cutting properties and not to impair transparency.

（式中、Ｒ₁は水素原子、炭素数１〜３のアルキル基、又はＲ₂−ＯＣＨ₂−で、Ｒ₂〜₅は水素原子、塩素原子、アルキル基、ハロゲン化アルキル基、アルキルアルコール基、アクリル酸アルキル基、アルキルフェノール基で、同一でも異なってもよい。）

（式中、Ｒ₆〜₁₀は水素原子、塩素原子、アルキル基、ハロゲン化アルキル基、アルキルアルコール基、アクリル酸アルキル基、アルキルフェノール基で、同一でも異なってもよい。ｎは１〜３の整数）
一般式１におけるＲ₃〜₅のうち２個以上が一般式２の構造を有する化合物、即ち、分子内に２個以上のアジリジニル基を有するアジリジル誘導体である。 (Aziridinine derivative) As the aziridyl derivative, a compound having two or more aziridinyl groups in the molecule is used.

(In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or R ₂ —OCH ₂ —, and R ₂ to ₅ are a hydrogen atom, a chlorine atom, an alkyl group, a halogenated alkyl group, or an alkyl alcohol group. An alkyl acrylate group or an alkylphenol group, which may be the same or different.)

(Wherein R ₆ to ₁₀ are a hydrogen atom, a chlorine atom, an alkyl group, a halogenated alkyl group, an alkyl alcohol group, an alkyl acrylate group or an alkylphenol group, and may be the same or different. N is an integer of 1 to 3) )
Two or more of R ₃ to ₅ in the general formula 1 are compounds having the structure of the general formula 2, that is, aziridyl derivatives having two or more aziridinyl groups in the molecule.

  Aziridine derivatives having two or more aziridinyl groups in the molecule, such as trimethylolpropane-tris- (α-methyl-α-aziridinyl acetate), trimethylolpropane-tris- (α-ethyl-α-aziridinini) Acetate), trimethylolmethane-tris- (β- (1-aziridinylpropionate)), trimethylolethane-tris- (β- (1-aziridinylpropionate)), trimethylolbutane- Tris- (β- (1-aziridinylpropionate)), monoethoxytrimethylolmethane-tris- (β- (1-aziridinylpropionate)), trimethylolethane-tris- (β- ( 2-methyl-1-aziridinylpropionate)), tetramethylolmethane-tris- (α-methyl-α-aziridinyl a) Tate), tetramethylolethane-tris- (β- (1-aziridinylpropionate)), ditrimethylolpropane-hexakis- (β-aziridinylpropionate), ditrimethylolpropane-pentakis- (β- (2-methylaziridinyl propionate) and the like.

  Preferably, trimethylolmethane-tris- (β- (1-aziridinylpropionate)), trimethylolethane-tris- (β- (1-aziridinylpropionate)), trimethylolpropane-tris -(Β- (1-aziridinylpropionate)), trimethylolbutane-tris- (β- (1-aziridinylpropionate)), trimethylolethane-tris- (β- (2-methyl -1-aziridinylpropionate)), trimethylolpropane-tris- (β- (2-methyl-1-aziridinylpropionate)), trimethylolpropane-tris- (β- (2,2 -Dimethyl-1-aziridinylpropionate)), trimethylolpropane-tris- (α-methyl-β- (1-aziridinylpropionate), trimethylo Propane-tris- (β-methyl-β- (1-aziridinylpropionate), tetramethylolmethane-tris- (α-methyl-α-aziridinyl acetate), tetramethylolmethane-tris- (β- (1-aziridinylpropionate), tetramethylolethane-tris- (β- (1-aziridinylpropionate)), tetramethylolmethane-tris- (β- (2-propyl-1-aziridini) Lupropionate)), tetramethylolmethane-tris- (β- (2-methyl-1-aziridinylpropionate)), tetramethylolmethane-tris- (β- (2,2-dimethyl-1-) Aziridinylpropionate), tetramethylolmethane-tris- (β- (2,2-diethyl-1-aziridinylpropionate) tetramethylo Rumethane-tetrakis-β- (1-aziridinylpropionate), tetramethylolmethane-tetrakis-β-methyl-β- (1-aziridinylpropionate), tetramethylolmethane-tetrakis-β- (2 -Methyl-1-aziridinylpropionate), ditrimethylolpropane-hexakis- (β-aziridinylpropionate), ditrimethylolpropane-pentakis- (β- (2-methylaziridinylpropionate) Are preferred, trimethylolpropane-tris- (β- (1-aziridinylpropionate), tetramethylolmethane-tris- (β- (1-aziridinylpropionate), tetramethylolmethane-tetrakis- ( β-aziridinylpropionate).

  Examples of commercially available aziridine derivatives having two or more aziridinyl groups in the molecule include TAZM (trimethylolpropane-tris- (β-aziridinylpropionate), TAZO, manufactured by Mutual Yakuhin Co., Ltd.). (Tetramethylolmethane-tris- (β- (1-aziridinylpropionate))) Nippon Shokubai Chemite PZ-33 (trimethylolpropane-tris- (β-aziridinylpropionate)) and the like An aziridine derivative having three aziridinyl groups is particularly preferable because of its high reactivity and a high network durability after curing.

  The ratio of cationic urethane resin, cationic fixing agent, microsilica, and aziridine derivative having two or more aziridinyl groups in the molecule is based on mass. Cationic urethane resin: cationic fixing agent: microsilica: intramolecular The aziridine derivative having two or more aziridinyl groups in the group is 100: 5 to 20: 1 to 10: 1 to 15. If the content of the cationic fixing agent is less than the above range, the fixing property is poor, and if it exceeds the above range, it elutes during washing and lowers the fastness. If the content ratio of the microsilica is less than the above range, the ink fixing property is poor, and if it exceeds the above range, the transparency is lowered and the image becomes difficult to see.

  The addition amount of the aziridine derivative is not particularly limited as long as it does not inhibit the effect of the present invention, but the blending ratio of the aziridine derivative having two or more aziridinyl groups in the molecule with respect to the cationic urethane resin is usually on a mass basis. Cationic urethane resin: Aziridine derivative having two or more aziridinyl groups in the molecule = 100: 1 to 15 is preferable, and 100: 3 to 10 is more preferable. Since the aziridine derivative functions as a water-soluble curing agent, if the content ratio of the aziridine derivative is less than the above range, since the curing is insufficient, durability such as water resistance and alcohol resistance is not sufficient, If it exceeds the above range, the transparency is lowered and the image becomes difficult to see.

  The receiving layer 21 for inkjet is formed by dispersing or dissolving the above materials in a solvent, adding an additive as necessary, and applying corona treatment or a primer layer to at least one surface of the medium 101 as necessary. May be applied and dried by a known coating method such as roll coating, gravure coating, comma coating or die coating. The thickness thereof is usually about 1 μm to 15 μm, preferably about 2 μm to 10 μm.

  (Other layers) The layers provided on the interlayer and / or the layer surface as needed include a primer layer, a printing layer, an antistatic layer, a back-sliding layer, etc., and each may be a known layer. In particular, the printing layer may be printed by a known screen printing or gravure printing method using colored ink or fluorescent ink.

  (Primer layer) It is preferable to provide the primer layer 16 in order to improve the adhesive force as required. Examples of the primer layer 16 include polyurethane resins, polyester resins, polyamide resins, epoxy resins, phenol resins, polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, Acid-modified polyolefin resins, copolymers of ethylene and vinyl acetate or acrylic acid, (meth) acrylic resins, polyvinyl alcohol resins, polyvinyl acetal resins, polybutadiene resins, rubber compounds, etc. can be used. Preferably, those having oxygen or nitrogen, or those having a reactive isocyanate compound, such as those known as conventional adhesives such as acrylic resins, urethane resins, amide resins, epoxy resins, ionomer resins, rubber resins, etc. is there. The primer layer is not necessarily contained since it has a thin film thickness, but it is preferable to contain a filler such as microsilica or polyethylene wax.

  (Inkjet) The image 103 may be formed by printing on the inkjet receiving layer 21 of the intermediate transfer recording medium 10 by the inkjet method. The ink jet method includes a thermal impact method, but is not particularly limited. The ink jet ink includes water-based and oil-based inks, but is not particularly limited. Also, the image 103 formed by the ink jet method may be a spot shape such as a circle or a star, or any shape such as letters, numbers, illustrations, and photographs, and the color tone is not limited to a single color, a plurality of colors, or a full color image. Absent. Preferably, the variable information is printed by an inkjet method on demand. In the ink jet method, when the image 103 is printed, an ink ribbon that leaves traces of personal information or the like is not used, and when the image 103 is printed, the image does not blur and dries quickly, so that the image is printed efficiently. be able to.

  (Fixability) As an image by a conventional ink jet method, when creating an ID card such as an ID card, it is easy to form an image. However, these images have a drawback that they are inferior in durability, particularly in abrasion resistance. is there. Conventional ink-receiving layers are mainly composed of water-soluble resins such as polyvinyl alcohol, and the water resistance is remarkably poor. Also, porous fillers are used, and good and poor solvents are used as the solvent for the receiving layer coating solution. Although a solvent is used to separate the phases and gel during drying to form a porous network structure, there is a problem that the image is not sufficiently fixed and the image becomes light during washing.

  On the other hand, if the image 103 is printed on the receiving layer 21 of the intermediate transfer recording medium of the present invention by an ink jet method, the image is printed with a high image quality and good fixability. Excellent durability such as solvent resistance such as alcohol resistance and fastness to washing. Although coexistence of fixing property and fastness to washing is not certain, by including a cationic urethane resin, a cationic fixing agent, a filler, and an aziridine derivative having two or more aziridinyl groups in the molecule, The surface has fine irregularities, the cohesive state of the coating itself is not very dense but rather rough, and an aziridine derivative having two or more aziridinyl groups in the molecule reacts with other components. As a result, the network and the aggregated state are stabilized, so that the adhesion with the image components is improved, and in particular, the alcohol resistance can be improved. In addition, it is presumed that a dye constituting an image interacts with or reacts with a cationic urethane resin, a cationic fixing agent, an aziridine derivative having two or more aziridinyl groups in the molecule and curing.

  (Durability of image) The vinyl chloride credit card (inkjet image recording medium) having the ink jet receiving layer 21 of the intermediate transfer recording medium of the present invention has the chemical immersion resistance of the card according to JIS X6301. Passed, details are given in the examples. Further, even in an exposure test for 240 hours in an atmosphere of 80 ° C., it has heat resistance without peeling from the interlayer and / or the adherend. Even in a 96-hour immersion test in hot water at 40 ° C., it has hot water resistance without peeling from the interlayer and / or the adherend. It has friction resistance that does not cause significant scratches in 100 wiping tests at room temperature while applying pressure at 20 kPa using a sheet cleaner. The conditions of low temperature (−40 ° C.), high temperature (80 ° C.) and high humidity (40 ° C. and 90% RH) are set to 1 cycle (1 day) every 8 hours, and even in a 5 cycle (5 days) thermal cycle test, It has cold and heat resistance without peeling.

  (Transfer) As shown in FIG. 2, in the transfer process to the transfer target 101, the surface of the intermediate transfer recording medium 10 on which the image 103 is formed is superimposed on the surface of the transfer target 101 and heated. Is peeled off and transferred. The receiving layer 21 / primer layer 16 (if necessary) / protective layer 15 on which the image 103 is formed are transferred to the transfer target 101 to form the forgery prevention medium 100. The transfer method may be a known transfer method, for example, hot stamping by hot stamping (foil stamping), whole surface or stripe transfer by a thermal roll, thermal printer (also called thermal transfer printer) by a thermal head (thermal printing head), etc. These known methods can be applied. The shape may be a spot shape such as a circle, rectangle, or star shape, or an arbitrary shape such as a letter or a number.

  (Inline operation) Image printing and transfer may be separate offline operations or continuously inline operations. Preferably, even in-line operation, the image 103 does not bleed and dries quickly, so that the transfer operation can be performed immediately after the image 103 is printed.

  (Transfer to be transferred) The transfer target (medium) 101 is not particularly limited. For example, natural fiber paper, coated paper, tracing paper, plastic film that is not deformed by heat during transfer, glass, metal, ceramics, wood, Any of cloth and the like may be used, and a plurality of layers thereof may be used. In addition, at least a part of the medium of the transfer target 101 may be colored, printed, or otherwise decorated.

  The transfer to the transfer target 101 is usually performed through a layer having an adhesive function. However, the binder contained in the receiving layer 21 of the intermediate transfer recording medium 10 of the present invention has thermal adhesiveness, and is heated by the heat during transfer. Since they are in close contact and integrated, a strongly adhered transfer can be performed.

  In addition, for transfer to the transfer target 101, an adhesion function is provided by an ink jet method or another coating process, or the receiving layer 21 is softened and / or melted and adhered to the surface of the transfer target 101 by heat and pressure during transfer. Then, an integrated deposition layer may be provided. The adherent layer is not particularly limited as long as it is softened and / or melted by heat and pressure during transfer with the binder contained in the receiving layer so as to be closely integrated. For example, polyester resins, ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, polystyrene resins, acrylic resins, polyurethane resins, acrylic urethane resins, modified resins of these resins, and these resins Preferably, it is the same resin as the binder resin of the receiving layer 21, and a polyurethane resin is particularly preferable.

  (Durability of Protective Layer) When an ID card such as an ID card is created as the image 103 by the ink jet method, it is easy to form an image, but these images are inferior in durability, particularly in abrasion resistance. There are drawbacks. After the image is printed on the receiving layer 21 of the intermediate transfer recording medium 10 of the present invention, the image is transferred to the surface of the transfer target 101 so that the protective layer 15 is positioned on the outermost surface as shown in FIG. Protect and increase durability. The pencil hardness test of the protective layer 15 is measured according to JIS-K5400, and a hardness of H or higher is preferable. The scratch strength is 150 g or more, preferably 200 g or more, from the viewpoint of sufficient friction resistance on the surface. The scratch strength was measured using a wear resistance tester (HEIDON-18) on a sample conditioned at 23 ° C. and 55% RH for 24 hours, with a 0.8 mmφ sapphire needle at a right angle. As a result, the load applied to the sapphire needle was gradually increased from 0 g to 200 g, and the load when the surface began to be scratched was measured while sliding and moving the sample surface at 60 cm / min. The larger the load, the better.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this. In addition, except a solvent, each composition of each layer is a mass part of solid content conversion.

Example 2 Using a PET film having a thickness of 25 μm as the base material 11, the following release layer resin composition (coating liquid) was dried on one surface of the base material 11 by gravure coating, and then 2 μm. It was applied and dried, and baked at 180 ° C. for 20 seconds to form a release layer 13.
・ <Resin layer resin composition>
TCM01 medium (Dainippon Ink Co., Ltd., melamine resin trade name) 25 parts Solvent (MEK: toluene = 1: 1) 75 parts The following ionizing radiation curable resin composition is applied to the surface of the release layer 13 with a gravure reverse coater. After coating and drying at 100 ° C. so that the thickness after drying was 5 μm, the protective layer 15 was formed by irradiating with ultraviolet rays using a high-pressure mercury lamp and curing.
・ <Ionizing radiation curable resin composition of protective layer>
Iupimer UV-V3031 (Mitsubishi Chemical Corporation, UV curable resin trade name) 100 parts Reactive silicone (Shin-Etsu Chemical Co., trade name X-22-1602) 0.5 part Polyethylene wax (average particle size 3-5 μm, Spherical) 2 parts Photopolymerization initiator (trade name Irgacure 184, manufactured by Ciba) 5 parts Ethyl acetate 300 parts The following primer layer composition is applied to the surface of the protective layer 15 by a gravure coater, and the coating amount is 0.5 μm. The primer layer 16 was formed by coating and drying at 100 ° C.
・ <Primer layer composition working solution>
Polyester resin 20 parts Microsilica (average particle size 0.5 μm) 1 part Solvent (toluene: methyl ethyl ketone = 1: 1) 80 parts Thickness after drying the following receiving layer composition on the surface of the primer layer 16 with a gravure reverse coater Was applied to a thickness of 4 μm and dried to form a receiving layer 21 to obtain an intermediate transfer recording medium 10 on which no image was formed.
・ <Receptive layer composition>
Quaternary ammonium salt type polycarbonate-based polyurethane 20 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative agent) 2 parts Microsilica (average particle size 0.5 μm) 1 part Chemite PZ-33 (manufactured by Nippon Shokubai, Aziridine) Product name of derivative) 3 parts Solvent (water) 80 parts

(Example 2) An intermediate transfer recording medium 10 of Example 2 was obtained in the same manner as Example 1 except that the following receiving layer composition was used.
・ <Receptive layer composition>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative agent) 10 parts Microsilica (average particle size 0.5 μ) 5 parts Chemitite PZ-33 (manufactured by Nippon Shokubai Co., Ltd.) Aziridine derivative) 5 parts Solvent (water) 300 parts

Example 3 An intermediate transfer recording medium 10 of Example 3 was obtained in the same manner as in Example 1 except that the following receiving layer composition was used.
・ <Receptive layer composition for inkjet>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative agent) 10 parts Microsilica (average particle size 0.5 μ) 5 parts Chemitite PZ-33 (manufactured by Nippon Shokubai Co., Ltd.) Aziridine derivative) 10 parts Solvent (water) 300 parts

Comparative Example 1 An intermediate transfer recording medium 10 of Comparative Example 1 was obtained in the same manner as in Example 1 except that the following receiving layer composition was used.
・ <Receptive layer composition for inkjet>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative) 10 parts Microsilica (average particle size 0.5 μ) 5 parts Solvent (water) 300 parts

Comparative Example 2 An intermediate transfer recording medium 10 of Comparative Example 2 was obtained in the same manner as in Example 1 except that the following receiving layer composition was used.
・ <Receptive layer composition for inkjet>
Quaternary ammonium salt type polycarbonate-based polyurethane 100 parts Dunfix 505RE (manufactured by Nitto Boseki Co., Ltd .; polycationic fixative agent) 10 parts Microsilica (average particle size 0.5 μ) 5 parts Chemitite PZ-33 (manufactured by Nippon Shokubai Co., Ltd.) Aziridine derivative) 20 parts Solvent (water) 300 parts

  (Examples 4 to 6, Comparative Examples 3 to 4) A known aqueous inkjet ink was applied to the receiving layer 21 of the intermediate transfer recording medium 10 of Examples 1 to 3 and Comparative Examples 1 and 2 with a 600 dpi color inkjet printer. Using the on-demand method, after printing a name and a color face photograph as an image 103, a heated roll method is applied to a sheet surface made of 4-layer polyvinyl chloride having a thickness of 0.76 mm for a transfer object 101 for a credit card. It transferred with the transfer apparatus, the base material 11 was peeled with the release layer 13, and it left away, and the forgery prevention medium 100 of Examples 4-6 and Comparative Examples 3-4 was obtained.

(Evaluation test)
About the anti-counterfeit medium 100 of Examples 4-6 and Comparative Examples 3-4, based on JISX6301, it evaluated by the chemical-dipping resistance of a card | curd. Images were visually observed after being immersed in 5% saline, 5% acetic acid, 5% aqueous sodium carbonate solution, 10% sugar water, 50% ethylene glycol, and 60% ethanol for 24 hours.
Table 1 shows the results of chemical immersion resistance of the anti-counterfeit media 100 of Examples 4 to 6 and Comparative Examples 3 to 4. “◎” indicates almost no change in the image 103, “○” indicates that no significant change is observed and passes without any practical trouble, and “×” indicates that the image 103 is distorted, missing, or lost. And rejected. In addition, there was no problem in printing by the inkjet method on the receiving layer 21 of the intermediate transfer recording medium 10 of Examples 1 to 3 and Comparative Examples 1 and 2.

  (Evaluation result) As shown in Table 1, in Example 4, 5% acetic acid water, 10% sugar water, 50% ethylene glycol, 60% ethanol is “◯”, and others are “「 ”. In Example 6, “◯” in 60% ethanol, “◎” in the other, and “◎” in Example 6, all satisfying the credit card standard. Further, in Comparative Example 3, the image was lost with 10% sugar water for “x” and 60% ethanol for “xx”, which did not satisfy the standard. In Comparative Example 4, all are “◎”, but the performance is excessive and the cost is high.

  Furthermore, the anti-counterfeit medium 100 of Examples 4 to 6 and Comparative Examples 3 to 4 had heat resistance without peeling from the interlayer and / or the adherend even in an exposure test for 240 hours in an atmosphere of 80 ° C. . Even in a 96-hour immersion test in warm water at 40 ° C., it had warm water resistance without peeling from the interlayer and / or the adherend. It had friction resistance that did not cause significant scratches in 100 wiping tests at room temperature while applying pressure at 20 kPa using a sheet cleaner. The conditions of low temperature (−40 ° C.), high temperature (80 ° C.) and high humidity (40 ° C. and 90% RH) are set to 1 cycle (1 day) every 8 hours, and even in a 5 cycle (5 days) thermal cycle test, It had cold-heat repeatability without peeling.

1 is a cross-sectional view of an intermediate transfer recording medium showing one embodiment of the present invention. FIG. 3 is an explanatory diagram for explaining an image forming method on an intermediate transfer recording medium of the present invention. It is sectional drawing of the to-be-transferred to-be-transferred body which shows one Example of this invention.

Explanation of symbols

10: Intermediate transfer recording medium 11: Base material 13: Release layer 15: Protective layer 16: Primer layer 21: Receptive layer 101: Transfer object 103: Image

Claims (3)

An intermediate transfer recording medium comprising a substrate and at least a release layer, a protective layer, and a receiving layer laminated on one surface of the substrate, wherein the receiving layer is a cationic urethane resin, a cationic fixing agent An intermediate transfer recording medium comprising a filler and an aziridine derivative having two or more aziridinyl groups in the molecule, and wherein the receiving layer can be printed by an ink jet method. The mixing ratio of the aziridine derivative having 2 or more aziridinyl groups in the molecule to the cationic urethane resin of the receptor layer is based on mass, and the cationic urethane resin: the aziridine derivative having 2 or more aziridinyl groups in the molecule The intermediate transfer recording medium according to claim 1, wherein = 100: 1 to 15. Using the intermediate transfer recording medium according to any one of claims 1 to 2, an image is printed on the receiving layer of the intermediate transfer recording medium by an inkjet method, and then a protective layer and an image are formed on the surface of the transfer target. An anti-counterfeit medium, wherein the received receiving layer is transferred.

Images