JP2007290250A - Manufacturing method of information recording medium, information recording medium, and manufacturing equipment of information recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture an information recording medium being capable of preventing forgery and excellent in durability at an inexpensive manufacturing cost. <P>SOLUTION: This manufacturing method of the information recording medium for forgery prevention has a recording process wherein an image 4 for forgery prevention is recorded on the information recording medium by an inkjet method using photosetting type ink for forgery prevention and a light irradiation process wherein the ink for forgery prevention is irradiated with light after the recording process. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an information recording medium manufacturing method for manufacturing an anti-counterfeit information recording medium, an information recording medium manufactured by the manufacturing method, and an information recording medium manufacturing apparatus used in the manufacturing method.

In recent years, there are increasing cases of recording an image on an information recording medium such as an ID card (IDentity card) using an ink jet method. Since the inkjet method is highly versatile for ejecting ink as droplets, an image can be recorded at a low cost, but the personal information can be easily rewritten and it is difficult to prevent forgery. It has become. An anti-counterfeiting technique using an inkjet method is disclosed in Patent Document 1. In the technique described in Patent Document 1, a special image-receiving layer is provided on a base material, and an ink jet image is formed thereon to prevent counterfeiting of the information recording medium (paragraph numbers 0032, 0033, and 0041). reference).
JP 2002-226740 A

However, as in the technique described in Patent Document 1, a special image receiving layer is provided on a substrate and an image is formed thereon by an ink jet method. It is necessary to take two steps of formation and image formation by the ink jet method, and this technology cannot sufficiently bring out the advantage of the low cost inherent in the ink jet method. Furthermore, in the ink jet system, it is necessary to reduce the viscosity of the ink by containing a large amount of water, a solvent, or the like because of discharging ink from a fine discharge port, but as in the technique described in Patent Document 1. An information recording medium having a special image-receiving layer is easily affected by water or a solvent in the ink and has poor durability.
An object of the present invention is to manufacture an information recording medium that can prevent counterfeiting and has excellent durability at a low manufacturing cost.

In order to solve the above problems, the first invention is
A method of manufacturing an information recording medium for manufacturing an information recording medium for preventing forgery,
A recording step of recording an anti-counterfeit image on an information recording medium by an ink jet method using a photocurable anti-counterfeit ink;
A light irradiation step of irradiating the anti-counterfeit ink with light after the recording step;
It is characterized by having.

In the method for manufacturing the information recording medium according to the first invention,
It is preferable to provide a surface protection step of forming a surface protective layer for protecting the surface of the information recording medium after the recording step and before the light irradiation step.

In the method for manufacturing the information recording medium according to the first invention,
It is preferable to provide a surface protection step of forming a surface protection layer for protecting the surface of the information recording medium before the recording step.

  In the surface protection step, it is preferable that the surface protection layer is formed by an inkjet method using a surface protection ink composed of a photocurable resin and having a transmittance of 90% or more.

In the method for manufacturing the information recording medium according to the first invention,
It is preferable to provide a surface protection step of forming a surface protection layer for protecting the surface of the information recording medium after the light irradiation step.

  In the surface protection step, it is preferable to transfer the transfer foil including the photocurable resin layer to the surface of the information recording medium to form the surface protection layer.

  The forgery-preventing ink contains a photocurable compound, a photocuring accelerator, and a forgery-preventing material.

  The anti-counterfeiting material is an infrared absorber, a scale pigment, a phosphor, metal fine particles, a high refractive index material or a low refractive index material.

  The anti-counterfeit image is preferably a unique image that is different for each information recording medium.

  The information recording medium is preferably an ID card.

The second invention is
An information recording medium manufactured by the method for manufacturing an information recording medium according to the first invention.

The third invention is
In the information recording medium manufacturing apparatus used for the information recording medium manufacturing method according to the first invention,
An anti-counterfeit recording head for recording an anti-counterfeit image by ejecting a photocurable anti-counterfeit ink onto an information recording medium by an ink jet method;
A light irradiation mechanism for irradiating the anti-counterfeit ink with light;
A surface protection mechanism for forming a surface protective layer for protecting the surface of the information recording medium;
It is characterized by having.

  According to the present invention, an information recording medium that can prevent counterfeiting and has excellent durability can be manufactured (see the following examples). In addition, since the forgery prevention image is recorded by the ink jet method, an information recording medium can be manufactured at a low manufacturing cost.

  The best mode for carrying out the present invention will be described below with reference to the drawings. However, although various technically preferable limitations for carrying out the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.

[First Embodiment]
The information recording medium according to the present invention can be used for cash cards, employee cards, employee cards, membership cards, student cards, alien registration cards, various licenses, IC cards and other important documents such as securities and bills. Applicable.

In the first embodiment, an example in which the information recording medium is applied to the ID card 1 is shown.
FIG. 1 is a perspective view showing a schematic configuration of the ID card 1.
As shown in FIG. 1, the ID card 1 has a rectangular base 2.

  The substrate 2 is made of, for example, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polyolefin resin such as polyethylene, polypropylene, polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoride. Polyethylene resin such as ethylene, ethylene-tetrafluoroethylene copolymer, polyamide such as nylon 6, nylon 6.6, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, Ethylene / vinyl alcohol copolymer, vinyl polymer such as polyvinyl alcohol and vinylon, biodegradable aliphatic polyester, biodegradable polycarbonate, biodegradable polylactic acid, biodegradable polyvinyl alcohol, biodegradable cellulose Biodegradable resins such as cetate, biodegradable polycaprolactone, cellulose resins such as cellulose triacetate and cellophane, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, ethyl polyacrylate, and polybutyl acrylate Synthetic resin sheets such as resin, polystyrene, polycarbonate, polyarylate, polyimide, ABS, AES, etc., or paper such as fine paper, thin paper, glassine paper, sulfuric acid paper, metal foil, etc., or a laminate of these two or more layers It is composed of.

  A white pigment such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay, calcium carbonate or the like is added to the substrate 2 in advance in order to enhance the sharpness of an image formed in a later step. May be.

  The base body 2 may be configured by laminating a plurality of base materials or supports having different thicknesses depending on the case and bonding them. The substrate 2 may be subjected to an easy-to-contact treatment if necessary, and may be formed with a resin layer such as a coupling agent, latex, hydrophilic resin, antistatic resin, corona treatment, plasma treatment, etc. The easy-contact process may be performed. Further, in order to enhance the function of the base 2, layers and components such as an emboss, a sign, an IC memory, an optical memory, a magnetic recording layer, a falsification preventing layer, an IC chip, and an infrared absorption layer are interposed in the base 2. May be.

  The substrate 2 may have a thickness of about 50 to 1200 μm, and preferably 50 to 1000 μm. A writing layer may be provided on the back side of the substrate 2.

A normal image 3 and an anti-counterfeit image 4 are recorded on the surface of the substrate 2.
The normal image 3 is a face image of the owner of the ID card 1 recorded with photocurable image recording ink.
The anti-counterfeit image 4 is a face image of the owner of the ID card 1 recorded with photocurable anti-counterfeit ink, and is a unique image that is different for each ID card 1.

  1, only the face image is illustrated as the normal image 3 and the anti-counterfeit image 4, but the normal image 3 and the anti-counterfeit image 4 include a ruled line, a company name, a card name, Notes, issuer phone number, address, name, date of birth, personal information such as ID card 1, unique number, unique symbol, unique display section, etc. are included.

  A surface protective layer 5 is formed on the substrate 2. The surface protective layer 5 protects the surface of the substrate 2 and is formed so as to cover the entire surface of the substrate 2 including the normal image 3 and the anti-counterfeit image 4. The surface protective layer 5 is mainly for the purpose of improving the surface strength, chemical resistance, etc. of the ID card 1, and is formed of a surface protective ink so as not to deteriorate the appearance of the anti-counterfeiting functional layer. (See below).

  The surface protective layer 5 may not be formed so as to cover the entire surface of the substrate 2, and may be formed so as to cover the normal image 3 and the anti-counterfeit image 4, or simply the normal image 3. It may be formed so as to cover the top, or may be formed so as to simply cover the forgery prevention image 4.

FIG. 2 is a side view showing a schematic configuration of the information recording medium manufacturing apparatus 100.
As shown in FIG. 2, the information recording medium manufacturing apparatus 100 according to the present invention is an apparatus for manufacturing an ID card 1, and a platen 12 transported in the direction A in FIG. 2 while supporting a base 2 of the ID card 1. Have. The platen 12 is of a known belt conveyor type (details are not shown), and the surface thereof is made of a resin having light absorption.

  Above the platen 12, an image recording unit 13 for recording the normal image 3 and the anti-counterfeit image 4 on the base 2 is provided. The image recording unit 13 includes four recording heads 14 to 17 that record the normal image 3 on the base 2 and a second recording head 18 as a forgery-preventing recording head that records the anti-counterfeit image 4 on the base 2. And have.

The recording heads 14 to 17 and the second recording head 18 have known piezo elements and ejection openings.
In the recording heads 14 to 17, when the piezo element is driven, yellow (Y), magenta (M), cyan (C), and black (K) image recording inks are directed downward from the ejection openings. It is designed to discharge. On the other hand, in the second recording head 18, when the piezo element is driven, the forgery prevention ink is ejected downward from the ejection port. The image recording ink and the anti-counterfeit ink are photo-curing inks that are cured by light irradiation, and the types (compositions) thereof are different from each other (see later).

  On the upstream side of the image recording unit 13 in the conveyance direction A of the substrate 2, an accumulation unit 20 in which a plurality of substrates 2 are accumulated is provided. The stacking unit 20 is provided with a supply roller 21, and when the supply roller 21 is driven, the substrates 2 are supplied to the platen 12 one by one from the plurality of substrates 2 at a predetermined timing. ing.

  A surface protection mechanism 30 is provided on the downstream side of the image recording unit 13 in the transport direction A of the substrate 2. The surface protection mechanism 30 has the same configuration as the recording heads 14 to 18 and the second recording head 18 and protects the surface of the normal image 3 and the anti-counterfeit image 4 recorded on the base 2. Therefore, the surface protecting ink is discharged downward (toward the base 2). The surface protecting ink is also a photocurable ink, similar to the image recording ink and the anti-counterfeit ink, and is different in type (composition) from these inks (see later).

  A light irradiation mechanism 40 is provided on the downstream side of the surface protection mechanism 30 in the transport direction A of the substrate 2. The light irradiation mechanism 40 has a light source 41 and a reflector 42 (reflector). The reflector 42 is a box that is open at the bottom and is provided with a reflection plate or a reflection film on its inner surface. In the light irradiation mechanism 40, when the light source 41 is turned on, the light is reflected by the reflector 42, and light can be irradiated below the light irradiation mechanism 40.

  The “light” in the present embodiment is, for example, an electron beam, an ultraviolet ray, an α ray, a β ray, a γ ray, an X ray, and the like, which is easy to handle and is widely used industrially. Is preferably used. In the present embodiment, it is preferable to use light having the highest illuminance in the wavelength region of 280 to 320 nm. Specific examples of the light source 41 include a fluorescent tube, a cold cathode tube, and an LED (Light Emitting Diode). It is not limited to.

  As a light irradiation method, the basic method is disclosed in Japanese Patent Laid-Open No. 60-132767. According to this, the light source is provided on both sides of the head unit, and the head and the light source are scanned by the shuttle method. Irradiation is performed after a certain period of time after ink landing. Further, the curing is completed by another light source that is not driven. In US Pat. No. 6,145,979, as an irradiation method, a method using an optical fiber or a method of applying a collimated light source to a mirror surface provided on the side surface of the head unit and irradiating the recording unit with light is disclosed. . Any of these irradiation methods may be used in the first embodiment.

  Further, it is also preferable to divide the light irradiation into two stages, and first irradiate light by the above-described method within 0.001 to 2.0 seconds after ink landing, and further irradiate light after completion of all recording. This is one aspect. By dividing the light irradiation into two stages, the shrinkage of the substrate 2 that occurs during ink curing can be further suppressed.

  A pair of unloading rollers 51 and 52 and a stacker 53 are provided below the light irradiation mechanism 40 in the transport direction A of the base 2. The carry-out rollers 51 and 52 rotate in opposite directions, and the base 2 is carried out from the platen 12 to the stacker 53. The stacker 53 stocks (accumulates) the substrate 2 that has passed through the carry-out rollers 51 and 52.

  Next, “image recording ink” will be described.

  The image recording ink contains (A.1) a photocurable compound, (A.2) a photocuring accelerator, (A.3) a colorant, and the like.

(A.1) Photocurable Compound A photocurable compound is a compound that forms a polymer by polymerization upon irradiation with light. As the polymerizable compound, a photo-radical polymerizable compound that is polymerized by a radical reaction at the time of light irradiation and a cationic polymerizable compound that is polymerized with a cationic chemical species as a reactive species are known. For example, they are described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-7-231444, and the like.

  Recently, photo-cationic polymerization type photo-curing resins sensitized to a long wavelength region longer than visible light are also disclosed in, for example, JP-A-6-43633 and JP-A-8-324137. Japanese Patent Application Laid-Open No. 2005-153386 discloses a photocured polyvinyl alcohol derivative polymer. As maleimide derivatives, JP-A-61-250064, JP-A-62-79243, JP-A-6-298817, JP-A-11-124403 and the like are disclosed. Any material can be applied to the image recording ink.

  In the image recording ink, it is preferable to use a cationically polymerizable compound, a photocurable polyvinyl alcohol derivative, a maleimide derivative, or the like as the photocurable compound because the material has little influence on the human body (skin irritation and the like). More preferably, a low viscosity is essential for inkjet applications, and it is difficult to receive polymerization inhibition by oxygen, and it is expected to have high chemical resistance, water resistance, and high surface strength, so that cationically polymerizable compounds and photocurable polyvinyl alcohol derivatives can be expected. Is preferably used as a photocurable compound.

  In the following, (A.1.1) a radical polymerizable compound, (A.1.2) a cationic polymerizable compound, (A.1.3) a photocurable polyvinyl alcohol derivative applicable as a photocurable compound, and (A A.1.4) Maleimide derivatives will be described respectively.

(A.1.1) Radical polymerizable compound The radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. Any one may be used as long as it has a chemical form such as a monomer, oligomer, or polymer. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties.

  Examples of compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, urethanes, amides. And radically polymerizable compounds such as unsaturated monomers, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate More specifically, Yamashita Junzo, “Crosslinker Handbook”, (1981 Taiseisha); Kato Kiyomi, “UV / EB Curing Handbook (Materials)” (1985, Polymer Publication) ); Rad-Tech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Commercially available products described in the above, or radically polymerizable or crosslinkable monomers known in the industry Oligomers and polymers can be used.

  Examples of other radical polymerizable compounds include derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate. More specifically, Shinzo Yamashita, “Crosslinker Handbook”, (1981 Taiseisha); Kato Kiyosumi, “UV / EB Curing Handbook (Materials)” (1985, Polymer Publications); Radtech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); written by Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Also known radically polymerizable or crosslinkable monomers, oligomers and polymers can be used.

  The addition amount of the radical polymerizable compound to the image recording ink is preferably 1 to 97% by mass.

(A.1.2) Cationic polymerizable compound The cationic polymerizable compound is a type in which polymerization occurs by cationic polymerization. As the cationic polymerizable compound, for example, an epoxy-type photocurable prepolymer or a monomer containing two or more epoxy groups in one molecule can be applied. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyls of aromatic polyols. Examples include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. These prepolymers and monomers can be used alone or in a mixture of two or more.

  Other examples of the cationically polymerizable compound include the following (A.1.1.2.1) styrene derivatives, (A.1.2.2.2) vinylnaphthalene derivatives, (A.1.1.2.3) vinyl ethers, ( A. 1.2.4) N-vinyl compounds, (A. 1.2.5) oxetane compounds and the like.

(A.1.2.2.1) Styrene derivatives Examples of styrene derivatives include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p. -Methoxy-β-methylstyrene or the like is applicable.

(A.1.2.2.2) Vinyl naphthalene derivatives Examples of vinyl naphthalene derivatives include 2-vinyl naphthalene, α-methyl-2-vinyl naphthalene, β-methyl-2-vinyl naphthalene, 4-methyl-2-vinyl. Naphthalene, 4-methoxy-2-vinylnaphthalene and the like are applicable.

(A.1.2.2.3) Vinyl ethers Examples of vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexane. Di- or trivinyl ether compounds such as diol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane Dimethano And monovinyl ether compounds such as vinyl monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-O-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

(A.1.2.4) N-vinyl compounds As N-vinyl compounds, for example, N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, N-vinylphenothiazine, N -Vinylacetanilide, N-vinylethylacetamide, N-vinylsuccinimide, N-vinylphthalimide, N-vinylcaprolactam, N-vinylimidazole, etc. are applicable.

(A.1.2.5) Oxacene compounds Oxetane compounds mean compounds having an oxetane ring. As the oxetane compounds, for example, known oxetane compounds such as those described in JP-A Nos. 2001-220526 and 2001-310937 can be used. When a compound having 5 or more oxetane rings is used as the oxetane compounds, the viscosity of the image recording ink becomes high, making it difficult to handle, and the curing obtained by increasing the glass transition temperature of the image recording ink The stickiness of things will not be sufficient. As the oxetane compounds, compounds having 1 to 4 oxetane rings are preferable.

  Specific examples of the oxetane compounds will be described below, but are not limited thereto. An example of the compound having one oxetane ring is a compound represented by the following general formula (1).

  In the general formula (1), “R1” is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group or an aryl group. Group, furyl group or thienyl group. "R2" is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl -2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like alkenyl groups having 2 to 6 carbon atoms, phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group, etc. A group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group, or a butylcarbonyl group, an alkylcarbonyl group such as an ethoxycarbonyl group, a propoxycarbonyl group, or a butoxycarbonyl group. Alkoxycarbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, pentylcarbamo Carbon atoms, such as Le group 2-6 is N- alkylcarbamoyl group.

  As the oxetane compounds used in the image recording ink, it is particularly preferable to use a compound having one oxetane ring because the obtained image recording ink has excellent adhesiveness, low viscosity and excellent workability. .

  An example of a compound having two oxetane rings includes a compound represented by the following general formula (2).

  In the general formula (2), “R1” is the same group as that in the general formula (1). “R3” is, for example, a linear or branched poly (alkylene) such as a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, a poly (ethyleneoxy) group or a poly (propyleneoxy) group. Oxy) group, propenylene group, methylpropenylene group, butenylene group or other linear or branched unsaturated hydrocarbon group, alkylene group containing carbonyl group or carbonyl group, alkylene group containing carboxyl group, carbamoyl group An alkylene group and the like;

  Moreover, as R3, the polyvalent group selected from the group shown by the following general formula (3), (4) and (5) can also be mentioned.

  In the general formula (3), “R4” represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. An alkoxy group having 1 to 4 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.

In the general formula (4), “R5” represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .

  In the general formula (5), “R6” is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. n is an integer of 0-2000. “R7” is a methyl group, an ethyl group, a propyl group, a butyl group having 1 to 4 carbon atoms, or an aryl group. As R7, the group further selected from the group shown by following General formula (6) can also be mentioned.

  In the general formula (6), “R8” is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. “M” is an integer of 0 to 100.

  Specific examples of the compound having two oxetane rings include the following exemplified compounds 1 and 2.

  Exemplary compound 1 is a compound in which R1 is an ethyl group and R3 is a carbonyl group in the general formula (2). Exemplary compound 2 is a compound in which, in the general formula (2), R1 is an ethyl group, R3 is the general formula (5), R6 and R7 are methyl groups, and n is 1.

  Among the compounds having two oxetane rings, preferred examples other than the above compounds include compounds represented by the following general formula (7). In the general formula (7), “R1” has the same meaning as R1 in the general formula (1).

  An example of a compound having 3 to 4 oxetane rings includes a compound represented by the following general formula (8).

  In the general formula (8), “R1” has the same meaning as R1 in the general formula (1). “R9” includes, for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly (alkyleneoxy) group such as a group represented by the following D, or the following E And branched polysiloxy groups such as the group represented by “J” is 3 or 4.

  In the above A, “R10” is a lower alkyl group such as a methyl group, an ethyl group or a propyl group. In the above D, “p” is an integer of 1 to 10.

  Illustrative compound 3 is an example of a compound having four oxetane rings.

  Furthermore, examples of the compound having 1 to 4 oxetane rings other than those described above include compounds represented by the following general formula (9).

  In the general formula (9), “R8” has the same meaning as R8 in the general formula (6). “R11” is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group or a trialkylsilyl group, and “r” is 1 to 4. “R1” has the same meaning as R1 in formula (6).

  Preferable specific examples of the oxetane compound used in the image recording ink include Exemplified Compounds 4, 5, and 6 shown below.

  The production method of each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method, for example, Pattison (DB Pattison, J. Am. Chem. Soc., 3455, 79). (1957)) discloses a method for synthesizing an oxetane ring from a diol. In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also included. Examples of these specific compounds include the following compounds.

  The addition amount of the cationic polymerizable compound to the image recording ink is preferably 1 to 97% by mass.

(A.1.3) Photocurable polyvinyl alcohol derivative A photocurable polyvinyl alcohol derivative is a saponified product of polyvinyl acetate, polyvinyl acetal, polyethylene oxide, polyalkylene oxide, polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, methylcellulose, Hydroxypropyl cellulose, or a derivative of the hydrophilic resin, and at least one selected from the group consisting of these copolymers, or a photodimerization type, a photodecomposition type, a photopolymerization type, a light It is modified with a modifying group such as a modified type or a photodepolymerization type.

  As the photodimerization-type modifying group, those having a diazo group, a cinnamoyl group, a styrylpyridinium group, or a stilquinolium group introduced are preferable, and a resin dyed with a water-soluble dye such as an anionic dye after photodimerization is preferable. Examples of such resins include resins having a cationic group such as a primary amino group or a quaternary ammonium group, such as JP-A Nos. 62-283339, 1-198615, and 60-252341. Photosensitive resins (compositions) described in JP-A-56-67309, JP-A-60-129742, etc., resins that become cationic after curing, such as azide groups that become amino groups by curing treatment, such as Examples thereof include photosensitive resins (compositions) described in JP-A-56-67309.

  The addition amount of the photocurable polyvinyl alcohol derivative to the image recording ink is preferably 1 to 97% by mass.

(A.1.4) Maleimide Derivatives Known compounds can be used as maleimide derivatives. For example, JP 61-250064, JP 62-64813, JP 62-79243, JP 6-298817, JP 11-124403, JP 11-292874, JP 11-11 -302278, JP 2000-264922, "Polymer Materials Science and Engineering" Vol. 72, 470-472 (1995), "Polymer Preprints" Vol. 37, 348-349 (1996), "The 4th Fusion UV Technology Seminar", pages 43-77 (1996), "Polymer Letters", Volume 6, pages 883-888 (1998), "The 9th Fusion UV Technology Seminar", pages 5-20 (2001) etc. are used Kill.

  The amount of maleimide derivative added to the image recording ink is preferably 1 to 97% by mass.

  In the image recording ink, the cationic polymerizable compound and the radical polymerizable compound may be used alone or in combination.

(A.2) Photocuring accelerator A photocuring accelerator means a photopolymerization initiator, an initiation assistant, and an acceleration assistant for initiating a polymerization reaction of a polymerizable compound mainly by light irradiation. . As the photocuring accelerator, those suitable for each of a radically polymerizable compound, a cationically polymerizable compound, a polymerizable compound made of a photocurable polyvinyl alcohol derivative, and a polymerizable compound made of a maleimide derivative are applied.

  In the following, (A.2.1) photopolymerization initiator, (A.2.2) initiation assistant and (A.2.3) acceleration assistant which can be applied as a photocuring accelerator will be described.

(A.2.1) Photopolymerization initiator The photopolymerization initiator is not particularly limited, but as an example, benzophenone, hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, bis-N, N-diethylaminobenzophenone, 4- Benzophenones such as methoxy-4′-dimethylaminobenzophenone, and thioxanthones such as thioxatone, 2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, and isopropoxychlorothioxanthone. Anthraquinones such as ethyl anthraquinone, benzanthraquinone, aminoanthraquinone and chloroanthraquinone, and acetophenones. Benzoin ethers such as benzoin methyl ether, 2,4,6-trihalomethyltriazines, 1-hydroxycyclohexyl phenyl ketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o- Chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Phenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2, -di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2, 2,4,5-triarylimidazole dimer of 4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, N-dimethylketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1- Propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one , Phenanthrenequinone, 9,10-phenanthrenequinone, methylbenzoin, benzoins such as ethylbenzoin, 9-phenylacridine, acridine derivatives such as 1,7-bis (9,9'-acridinyl) heptane, titanocene, bisacyl Phosphine oxide, diazonium, ammonium, iodonium, sulfonium, phosphonium, etc. Comprising onium salts, benzophenone ammonium salts, sulfonated, halides, iron Aalen compounds, titanocene compounds, and the like. The above substances may be used alone or in combination.

  As photopolymerization initiators, in addition to the above-mentioned compounds, “Application and Market of UV / EB Curing Technology” (CMC Publishing Co., Ltd., edited by Yoneho Tabata, edited by Radtech Study Group), “Organic Materials for Imaging” ( It is good also as applying the compound known by literature, such as an organic electronics material study group edited by Bunshin publication, and pp. 187-192 of 1993.

  Initiating aids and accelerating aids can be used to advance the photocuring reaction.

(A.2.2) Initiating aid An initiating aid is a radical or acid of a photopolymerization initiator that provides energy to the photopolymerization initiator by electron irradiation, electron attraction, heat generation, etc. by light irradiation. It is a substance that acts as a sensitizing dye that improves the generation efficiency of, and is applied in combination with a photopolymerization initiator.

  Examples of the initiator include xanthene, thioxanthone dye, ketocoumarin, thioxanthene dye, cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane , Triphenylmethane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbituric acid derivative and the like can be applied.

In addition to the above-mentioned compounds, it is well known that the initiator acts as a sensitizing dye in documents such as “Development technology of polymer additives” (CMC Publishing Co., Ltd., supervised by Junichi Daikatsu). The substance may be applied.
The initiation assistant can also be regarded as a component that forms part of the photopolymerization initiator.

(A.2.3) Acceleration aid In addition to these photopolymerization initiators, an acceleration aid that accelerates the photocuring acceleration reaction may be added to the image recording ink.
Examples of the accelerator aid include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethanolamine, diethanolamine, triethanolamine and the like.

  The acceleration aid is preferably added in an addition amount of 0.1 to 10% by mass. When the addition amount of the acceleration aid is less than 0.1% by mass, the ink for image recording that has landed on the ID card 1 (base 2) is not quickly cured, so that it is difficult to control the dot diameter and the dot shape. A point arises. On the other hand, when the addition amount exceeds 10% by mass, there are problems such as local polymerization at the time of the polymerization reaction, resulting in unevenness and a decrease in strength variation and chemical resistance.

(A.3) Colorant In the image recording ink, a colorant can be used in addition to the photocurable compound and the photocuring accelerator.
Examples of the colorant include various chromatic organic pigments such as phthalocyanine, azo, quinacridone, dioxazine, and diketopyrrolopyrrole, and inorganic pigments such as carbon black, titanium white, silica, mica, and zinc oxide. Etc.

  Specifically, as the colorant, a colorant that can be dissolved or dispersed in the main component of a polymerizable compound of a photocurable compound is applicable, and a pigment is preferable in terms of light resistance. The amount of the color material added to the image recording ink is determined by the color developability after dispersion, but is preferably 0.1 to 15% by mass. When the addition amount of the color material is less than 0.1% by mass, the color material is not sufficiently colored, and there is a problem that the color reproducibility of the normal image 3 recorded on the ID card 1 (base 2) is lowered. . Further, when the coloring material is added in an amount exceeding 15% by mass, there is a problem that the ink dots are not quickly cured by light irradiation or the image quality of the normal image 3 is deteriorated.

  Next, “counterfeit prevention ink” will be described.

  The anti-counterfeit ink contains (B.1) a photocurable compound, (B.2) a photocuring accelerator, (B.3) an anti-counterfeiting material, and the like.

(B.1) (B.2) Photo-curable compound, photo-curing accelerator The photo-curable compound and the photo-curing accelerator are the same as those described in the item of the image recording ink.
The anti-counterfeit ink may contain the colorant described in the item of the image recording ink.

(B.3) Anti-counterfeiting materials For anti-counterfeiting inks, for the purpose of preventing forgery and alteration, anti-counterfeiting materials include infrared absorbers, flake pigments, phosphors, fine metal particles, high refractive index materials, and low refractive indexes. It is preferable to contain at least any one of the materials. The anti-counterfeiting ink is more preferably a scaly pigment, metal fine particles, high refractive index material, or low refractive index material that can be visually confirmed without using the second jig when the ink is formed with the material. .

  In the following, (B.3.1) infrared absorbers, (B.3.2) scale pigments, (B3.3) phosphors, (B.3.4) metals applicable as anti-counterfeiting materials The fine particles, (B.3.5) high refractive index material and (B.3.6) low refractive index material will be described.

(B.3.1) Infrared Absorber As an infrared absorber, an infrared absorbing inorganic material, an infrared absorbing pigment, an infrared absorbing organic material, an infrared absorbing dye, an infrared phosphor, and the like are absorbed by infrared light. If it is a substance which has this, there will be no restriction | limiting in particular.

  Examples of the infrared absorbing inorganic material include the aforementioned metals such as Nd, Yb, In and Sn, and compounds such as oxides, sulfides and halides, and composites thereof. In particular, ITO, which is a conductive oxide, has high infrared light absorption. Specifically, examples of the infrared absorbing inorganic material include compounds described in JP-A Nos. 7-113072, 7-310072, 8-113776, and the like.

  Examples of infrared absorbing dyes include cyanine dyes, squalium dyes, croconium dyes, azurenium dyes, phthalocyanine dyes, naphthalocyanine dyes, polymethine dyes, naphthoquinone dyes, thiopyrylium dyes, dithiol metal complex dyes, And anthraquinone dyes, indoaniline metal complex dyes, and intermolecular CT dyes. Examples of the infrared absorbing dye include JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, JP-A-2-2074, and JP-A-3-2074. No. 26593, No. 3-30991, No. 3-34891, No. 3-36093, No. 3-36094, No. 3-36095, No. 3-42281, No. 3-103476, No. 5-201140, etc. And the compounds described in the above.

(B.3.2) Scale pigment A scale pigment is a thin film coating that gives mica reflectivity (high iris reflection), such as a metal oxide or metal sulfide that is transparent in the visible range and has a refractive index of 2.0 or more. For example, Sb ₂ S ₃ , Fe ₂ O ₃ , PbO, ZnSe, CdS, Bi ₂ O ₃ , TiO ₂ , PbCl ₂ , CeO ₂ , Ta ₂ O ₅ , ZnS, ZnO, CdO, Nd ₂ It is formed by coating a single layer of O ₃ , Sb ₂ O ₃ , SiO and InO ₃ , or by coating two layers.

  When a mica and a metal oxide film are combined, the difference in refractive index of the scale pigment is greater than 0.4. Therefore, the amount of incident white light is large, and at the same time, the interface between the mica and the metal oxide film. Due to the secondary refraction, it becomes highly iris reflective and works to promote the discoloration effect more effectively.

  At this time, by controlling the film thickness of the metal oxide film covering the mica, the film thickness can be a scale pigment having high rainbow reflectivity of an arbitrary color, and the film thickness is 10 to 10000 angstrom, preferably 200 to 5000 angstrom. A film thickness in the range is desirable because it is highly iris reflective to the visible range. Specifically, as scale pigments, JP-A-6-145553, JP-A-8-209024, JP-A-8-269358, JP-A-10-101957, JP-A-11-273932, JP-A-11-315219, JP-A-2000- The pigments described in 1628, JP-A 2000-44834, JP-A 1-158077 and the like can be used. Examples of commercially available scale pigments include “Iriodin” (trade name, manufactured by MERCK).

  “Iriodin” is a stable inorganic scale pigment with the surface of natural mica coated with a metal oxide with a high refractive index such as titanium oxide and iron oxide, a layer of titanium oxide with a high refractive index, a mica with a low refractive index and the surroundings. The light reflected at the boundary with the medium brings about pearl luster. In this “Iriodin”, a specific iris color can be emphasized by changing the film thickness of the coated titanium oxide.

  The scaly pigment used in the color change printing layer may be the above-described scaly pigment as long as it is different from the scaly pigment used in the reflective layer. In addition, there are gold type and silver type.

(B.3.3) Phosphor The phosphor is described in, for example, JP-A Nos. 50-6410, 61-65226, 64-22987, 64-60671, and JP-A-1-168911. The phosphor is not particularly limited, but metal oxides such as Y ₂ O ₂ S, Zn ₂ SiO ₄ , Ca ₅ (PO ₄ ) ₃ Cl, etc., which are crystal bases, and ZnS, In sulfides represented by SrS, CaS, etc., ions of rare earth metals such as Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ag, Al, Mn, A combination of metal ions such as Sb as an activator or coactivator is preferred. In addition, when a nanophosphor such as JP-T-2002-533291, 2006-28354 or the like is used, the coloring efficiency is good even with a small addition amount, and this can be used as the phosphor. There are no particular restrictions on the use of the anti-counterfeit ink.

Preferable examples of the crystal matrix of the phosphor include, for example, ZnS, Y ₂ O ₂ S, Y ₃ Al ₅ O ₁₂ , Y ₂ SiO ₅ , Zn ₂ SiO ₄ , Y ₂ O ₃ , BaMgAl ₁₀ O ₁₇ , BaAl _12. O ₁₉ , (Ba, Sr, Mg) O · aAl ₂ O ₃ , (Y, Gd) BO ₃ , YO ₃ , (Zn, Cd) S, SrGa ₂ S ₄ , SrS, GaS, SnO ₂ , Ca ₁₀ ( PO ₄ ) ₆ (F, Cl) ₂ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ , (La, Ce) PO ₄ , CeMgAl ₁₁ O ₁₉ , GdMgB ₅ O ₁₀ , Sr ₂ P ₂ O ₇ , Sr ₄ Al ₁₄ O _{25 and the} like.

  The above crystal matrix and activator or coactivator may be partially replaced with elements of the same family, and the element composition is not particularly limited.

(B.3.4) Metal fine particles As the metal of the metal fine particles, platinum, gold, silver, nickel, chromium, copper, iron, tin, tantalum, indium, cobalt, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, Germanium, molybdenum, tungsten, zinc, or the like can be used. As a method for producing such a dispersion of fine metal particles, metal ions are reduced in the liquid phase, such as a physical generation method such as gas evaporation method, sputtering method, metal vapor synthesis method, colloidal method, coprecipitation method, etc. And a chemical production method for producing metal fine particles. The metal fine particles are preferably colloidal methods disclosed in JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, JP-A-2000-239853, JP-A-2001-254185, JP-A-2001-53028, It may be produced by a gas evaporation method described in JP 2001-35255, 2000-124157, 2000-123634, etc.

(B.3.5) High Refractive Index Material High refractive index materials include metal alkoxides described in JP-A-2000-266908, specifically titanium alkoxides, titanium polymers described in JP-A-2004-50810, and metal oxide fine particles. and so on. Although there is no restriction | limiting in particular as a high refractive index material, It is preferable to use the metal oxide fine particle and titanium alkoxide whose refractive index is 1.60 or more. Examples of such metal oxide fine particles include titanium oxide, zinc oxide, zirconium oxide, cerium oxide, tin oxide, thallium oxide, barium titanate, aluminum oxide, magnesium oxide, yttrium oxide, antimony oxide, and indium oxide. . Among these, fine particles such as titanium oxide, cerium oxide, tin oxide, antimony oxide, zirconium oxide, and indium oxide are preferable. Furthermore, these fine particles may be doped, and specifically, may be doped with a different element such as antimony, tin, or fluorine.

(B.3.6) Low Refractive Index Material Examples of the low refractive index material include fluorine compounds and silica compounds. Although there is no restriction | limiting in particular as a low refractive index material, Preferably it is a material below 1.4. Specifically, examples of low refractive index materials include silica fine particles described in JP-A-2001-233611, fluorine-containing resins described in JP-A-2000-266908, compounds formed from silicate oligomers, and SiO ₂ sol and reactive organic silicon. At least one compound selected from compounds formed from compounds is used. Examples of the fluorine-containing resin include a polymer mainly containing a fluorine-containing unsaturated ethylenic monomer component and a fluorine-containing epoxy compound, and further includes magnesium fluoride.

  It is preferable to add the infrared absorbent, the scaly pigment, the phosphor, the metal fine particles, the high refractive index material, and the low refractive index material described above at a ratio of 5 to 50% by weight in the anti-counterfeit ink. Addition should just contain at least 1 material, and may mix 2 or more types depending on the case. When the addition amount is less than 5% by weight, it cannot be determined, and the forgery prevention function is lost, which is problematic. If it is greater than 50% by weight, the anti-counterfeiting function is improved, but the ink viscosity is increased and the ink-jet ink does not function.

  A polymer dispersant, a viscosity modifier, a polymerization inhibitor, an antioxidant, a surfactant, a leveling additive, water, an organic solvent, and the like may be added to the anti-counterfeit ink as necessary. The addition amount is preferably 0.000 to 10% by weight in the anti-counterfeit ink.

  In addition, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes, and elastomers are added to the anti-counterfeit ink as necessary. I can do it. The addition amount is preferably 0.1 to 30% by weight in the anti-counterfeit ink.

  A ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, etc. may be used to disperse the anti-counterfeiting material in the anti-counterfeit ink. it can.

  Further, it is possible to add a dispersant to the anti-counterfeit ink when dispersing the pigment. Since the anti-counterfeit ink is a special material, it is preferable to use a polymer dispersant.

  Since the anti-counterfeit ink uses a forgery-preventing material, it is important that it can be identified. Factors that determine discrimination are the amount and particle size of the anti-counterfeiting material contained in the prepared anti-counterfeit ink.

  The maximum particle size should be 0.5 to 30 μm when using scale-like powder, phosphors, and metal fine particles, which are used as anti-counterfeiting inks, except when nanoparticles with specific coloring efficiency are used. The pigment, the dispersant, the selection of the dispersion medium, the dispersion conditions, and the filtration conditions are set so that the thickness is preferably 0.5 to 20 μm. By controlling the particle size, clogging of the head nozzle (discharge port) can be suppressed. When the average particle diameter is larger than 30 μm, problems such as head clogging occur. If it is less than 0.5 μm, in the case of a normal material, the visual distinctiveness is lowered and the forgery prevention effect is deteriorated.

  The anti-counterfeiting ink is preferably discharged in the range of 30 to 80 ° C. with heating and low viscosity.

  The anti-counterfeit ink preferably has a viscosity of 1 to 1000 mPa · s at 30 ° C., more preferably 3 to 500 mPa · s. When the viscosity is higher than 1000 mPa · s, there is a problem in supplying the anti-counterfeit ink. Moreover, when the viscosity is low, unevenness or the like occurs, and the forgery prevention function decreases.

  In addition, in order to obtain a desired refractive index, the high refractive index material is not used, and the photocurable compound described above is used for the high refractive index layer, which is an aromatic, alicyclic, halogen, or titanium-containing system. The refractive index may be controlled using a photocurable material.

  Even in a low refractive index material, the low refractive index material may not be used, and the refractive index may be controlled by using the photocurable compound described above for the low refractive index layer and a silicone-based fluorine-based photocurable material. .

  The anti-counterfeit ink needs to have a surface strength of 120 g or more (scratch hardness based on JIS K 5600 (0.8 mmφ sapphire needle scratch strength)). If it is 120 g or less, it may be scraped off by a third party and easily altered.

  In the measurement of the surface strength, first, a layer made of anti-counterfeit ink (layer thickness: 20 μm) is formed on 188 μ-white PET (U298W) to prepare a sample, and then an abrasion resistance tester (HEIDON-18) is used. Use a 0.1 mmφ sapphire needle to change the load at 0 to 300 g, slide the sample surface, and measure the load when the anti-counterfeit image or the like starts to be damaged. The greater the load, the better the surface strength.

  Next, the “surface protecting ink” will be described.

  The surface protecting ink is an ink having a transmittance of 90% or more made of a photocurable resin. “Surface protecting ink having a transmittance of 90% or more” means that when a surface protecting ink layer having a thickness of 20 μm is formed on a transparent PET having a thickness of 25 μm and the layer is cured with light of 500 mJ, Hitachi This means that the transmittance with respect to light having a wavelength of 400 nm measured using a spectrophotometer U-3200 manufactured by Seisakusho is 90% or more.

  As the surface protecting ink, it is more preferable to use a photocurable resin comprising the above-described photocurable compound and a photocuring accelerator. When the surface protective layer 5 is composed of the surface protective ink, it is convenient because the number of steps is small and the printer price is low because the ink is recorded and formed by the ink jet method.

  Next, the “information recording medium manufacturing method” according to the present invention will be described.

  In a state where the supply roller 21, the platen 12, and the carry-out rollers 51 and 52 are operated, the base 2 is supplied to the platen 12 from the stacking unit 20 one by one. The lower part of the protection mechanism 30 and the light irradiation mechanism 40 are transported in this order along the transport direction A, and are transported from the transport rollers 51 and 52 to the stacker 53.

  In this state, when the substrate 2 passes under the image recording unit 13, the recording heads 13 to 17 eject the image recording ink to record the normal image 3 on the substrate 2 (first recording step). Thereafter, the second recording head 18 discharges the anti-counterfeit ink to record the anti-counterfeit image 4 on the substrate 2 (second recording step).

  When the substrate 2 passes under the surface protection mechanism 30, the surface protection mechanism 30 discharges the surface protection ink to form the surface protection layer 5 on the surface of the substrate 2 (surface protection step).

When the substrate 2 passes under the light irradiation mechanism 40, the light source 41 is turned on to irradiate the substrate 2 with light, and the normal image 3, the anti-counterfeit image 4, and the surface protective layer 5 on the substrate 2 are cured. (Light irradiation process).
The ID card 1 as the information recording medium according to the present invention can be manufactured by performing each process from the above recording process to the light irradiation process through the surface protection process.

  In the first embodiment described above, since the anti-counterfeit image 4 is recorded with the special anti-counterfeit ink, the ID card 1 can be prevented from being counterfeited and the durability can be improved. Further, when recording the anti-counterfeit image 4 with the anti-counterfeit ink, since it is recorded by an ink jet method, it is possible to record a unique anti-counterfeit image 4 for each ID card 1 on demand and at a low cost. ID card 1 can be manufactured at a low manufacturing cost. From the above, it is possible to manufacture the ID card 1 that can prevent counterfeiting and has excellent durability at a low manufacturing cost.

  The present invention is not limited to the first embodiment, and various improvements and design changes may be made without departing from the spirit of the present invention.

  As one improvement / design change matter, as shown in FIG. 4, a second recording head 19 for discharging anti-counterfeit ink may be additionally provided in the image recording unit 13. In this case, the second recording head 18 and the second recording head 19 may eject anti-counterfeit inks having different compositions, or eject anti-counterfeit inks having the same composition. You may do it.

  As another improvement / design change matter, the arrangement of the second recording head 18 (including the second recording head 19) and the surface protection mechanism 30 is reversed, as shown in FIG. The anti-counterfeit image 4 may be formed on the surface protective layer 5 formed thereon.

[Second Embodiment]
In the second embodiment, an example in which the information recording medium according to the present invention is applied to an ID card 10 is shown.
FIG. 6 is a perspective view showing a schematic configuration of the ID card 10.
As shown in FIG. 6, the ID card 10 is the same as the ID card 1 except that a surface protective layer 6 is formed in place of the surface protective layer 5 in the ID card 1 (see FIG. 1). It has the composition of.

  The surface protective layer 6 is made of a transfer foil and has the same function as the surface protective layer 5. The surface protective layer 6 is provided with a release layer as the lowermost layer and an adhesive layer as the uppermost layer on one side of the support, and an optical layer between the release layer and the adhesive layer as necessary. A curable resin layer, a pattern layer, an intermediate layer, and the like are provided.

  In the surface protective layer 6, an antistatic layer and an uneven layer may be formed as necessary. An uneven | corrugated layer means the anti-blocking layer by mat agent kneading, sandblasting, hairline processing, mat coating, or chemical etching.

  In the following, (C.1) support, (C.2) release layer, (C.3) photo-curable resin layer, (C.4) intermediate layer and (C.1) applicable as anti-counterfeiting materials. 5) Each adhesive layer will be described.

(C.1) Support As the support, plastic films such as heat-resistant polyester, polyethylene terephthalate, polyethylene naphthalate, and ABS resin are applicable. The thickness of a support body is 3-50 micrometers normally, Preferably it is 10-30 micrometers.

(C.2) Release layer As the release layer, resins such as acrylic resin having a high glass transition temperature, polyvinyl acetal resin, poly vinyl butyral resin, waxes, silicone oils, fluorine compounds, water-soluble polyvinyl pyrrolidone Resin, polyvinyl alcohol resin, Si-modified polyvinyl alcohol, methyl cellulose resin, hydroxy cellulose resin, silicone resin, paraffin wax, acrylic modified silicone, polyethylene wax, ethylene vinyl acetate, etc. Modified products such as polyester modified silicone, acrylic modified silicone, urethane modified silicone, alkyd modified silicone, amino modified silicone, epoxy modified silicone, polyether modified silicone, etc. Yl, resin, or a cured product thereof. Other fluorinated compounds include fluorinated olefins and perfluorophosphate ester compounds. Preferred olefin compounds include dispersions such as polyethylene and polypropylene, and long-chain alkyl compounds such as polyethyleneimine octadecyl. These release agents having poor solubility can be used after being dispersed. Moreover, it is also possible to add to other polymers like a silicone compound. In addition, fine particles (micron or submicron order) such as silica particles and boron nitride are also effective.

But the layer thickness of the release layer is particularly limited, but is preferably 0.000~3.00g / ^{m 2,} more preferably from 0.000005~2.00g / ^{m 2,} 0.00001~2 More preferably, it is 0.000 g / m ² .

(C.3) Photocurable resin layer The photocurable resin layer is a layer composed of a photocurable resin, and is preferably provided adjacent to the release layer. The photocurable resin has addition polymerization property or ring-opening polymerization property.

  Addition polymerizable compounds are radical polymerizable compounds such as JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, and JP-A-7-231444. And a photocurable material using a photopolymerizable composition described in Japanese Patent Application Publication No. 7-231444. As the addition-polymerizable compound, a cationic polymerization type photocurable resin is known. Recently, a photocationic polymerization type photocurable resin sensitized to a long wavelength region longer than visible light is also disclosed in, for example, -43633, JP-A-8-324137, and the like. The radical polymerizable compound includes ordinary photopolymerizable compounds and thermopolymerizable compounds. The radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and may be any compound as long as it has at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. , Oligomers, polymers and the like having a chemical form. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties. Examples of compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, urethanes, amides. And radically polymerizable compounds such as unsaturated monomers, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. A sensitizer, a polymerization accelerator, a chain transfer agent, a polymerization inhibitor and the like can be added as necessary.

The photocurable resin layer is preferably a layer thickness is 1.0 to 20 g / ^{m 2,} particularly preferably in the range of 3.0~15g / ^{m 2,} in the range of 5.0~20g / ^{m 2} Is more preferable. When the layer thickness of the photocurable resin layer is less than 3.0 g / m ² , the scratch strength of the ID card 10 is lowered, which causes a problem.

  As a method of curing the photocurable resin layer, any method such as a method of curing at the time of manufacture may be adopted. As the light for curing, any light that generates an active electromagnetic wave with respect to the polymerization initiator can be used. Examples of the light source include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a mercury lamp, an electrodeless light source, and an LED.

(C.4) Intermediate layer The transfer foil as the surface protective layer 6 may have an adhesive layer adjacent to the photocurable resin layer, but in order to further improve interlayer adhesion, 1 It is more preferable to construct a layer composed of more than one layer.

  The intermediate layer is preferably composed of a thermoplastic resin. Examples of the thermoplastic resin include vinyl chloride resin, polyester resin, acrylic resin, polyvinyl acetal resin, polyvinyl alcohol, polycarbonate, cellulose resin, styrene resin, urethane resin, urethane acrylate resin, and amide resin. , Urea resins, epoxy resins, phenoxy resins, polycaprolactone resins, polyacrylonitrile resins, thermoplastic elastomers such as styrene (styrene block copolymer (SBC)), olefin (TP), urethane (TPU), polyester System (TPEE), polyamide system (TPAE), 1,2-polybutadiene system, vinyl chloride system (TPVC), fluorine system, ionomer resin, chlorinated polyethylene, silicone system and the like. 6 Chemical Products "(The Chemical Daily Co., Ltd.) SEBS resins described in the like can be used as SEPS resin and their modified products. These resins can be used alone or in combination of two or more.

  As a specific compound, a thermoplastic resin composed of a block polymer of polystyrene and polyolefin, polyvinyl butyral, and the like are preferable.

The intermediate layer may contain at least one selected from a light absorber, an antioxidant, and a light stabilizer in order to increase the light resistance of the normal image 3 and the anti-counterfeit image 4.
As the light absorber, it is sufficient that it functions for light absorption of a dye image and heat transfer is possible. For example, JP-A Nos. 59-158287, 63-74686, 63-145089, and 59-196292. , No. 62-229594, No. 63-122596, No. 61-283595, JP-A-1-204788, etc., and those that improve image durability in photographs and other image recording materials Known compounds can be used.

  Antioxidants described in JP-A-59-182785, JP-A-60-130735, JP-A-1-127387, etc., and improvement in image durability in photographs and other image recording materials. Known compounds can be listed as examples.

  As light stabilizers, JP-A-59-158287, 63-74666, 63-145089, 59-196292, 62-229594, 63-122596, 61-283595 are disclosed. And compounds described in JP-A-1-204788, and known compounds for improving image durability in photographs and other image recording materials.

The intermediate layer containing the light absorber, the antioxidant, and the light stabilizer preferably has a film thickness of 0.05 to 15.0 g / m ² and preferably 0.05 to 10 g / m ^2. Is more preferable, and it is still more preferable that it is 0.1-10.0 g / m < ² >.

(C.5) Adhesive layer As the adhesive layer, ethylene vinyl acetate resin, ethyne ethyl acrylate resin, ethylene acrylic acid resin, ionomer resin, polybutadiene resin, acrylic resin, polystyrene resin, polyester resin, olefin resin, urethane resin, tackifying Agents (for example, phenol resin, rosin resin, terpene resin, petroleum resin, etc.) and the like, and copolymers or mixtures thereof may be used.

  Specifically, as a urethane-modified ethylene ethyl acrylate copolymer, Hitech S-6254, S-6254B, S-3129 and the like manufactured by Toho Chemical Industry Co., Ltd. are commercially available, and as a polyacrylic acid ester copolymer, Japan. Jurimer AT-210, AT-510, AT-613 manufactured by Junyaku Co., Ltd., plus size L-201, SR-102, SR-103, J-4, etc. manufactured by Kyoyo Chemical Industry Co., Ltd. are commercially available. Yes. The weight ratio of the urethane-modified ethylene ethyl acrylate copolymer and the polyacrylic acid ester copolymer is preferably 9: 1 to 2: 8, and the thickness of the adhesive layer is preferably 0.1 to 1.0 μm.

FIG. 7 is a diagram showing a schematic configuration of an information recording medium manufacturing apparatus 200.
As shown in FIG. 7, the information recording medium manufacturing apparatus 200 according to the present invention is an apparatus for manufacturing the ID card 10, and replaces the surface protection mechanism 30 in the information recording medium manufacturing apparatus 100 (see FIG. 2). A pair of transport rollers 61 and 62 and a surface protection mechanism 70 are provided, and the rest of the configuration is the same as that of the information recording medium manufacturing apparatus 100.

  The conveyance rollers 61 and 62 rotate in opposite directions, and convey the base 2 from below the light irradiation mechanism 30 to below the surface protection mechanism 70.

  The surface protection mechanism 70 is provided on the downstream side of the transport rollers 61 and 62 in the transport direction A of the base 2. The surface protection mechanism 70 includes an original winding roller 72 around which the transfer foil 71 constituting the surface protection layer 6 is wound, a winding roller 73 that winds up the transfer foil 71, and a thermal transfer that transfers the transfer foil 71 to the base 2. And a pressure roller 75 disposed opposite to the heat transfer heat roll 74.

  Next, the “information recording medium manufacturing method” according to the present invention will be described.

  In the method for manufacturing the information recording medium, the order of the surface protection steps and the contents thereof are different from those in the method for manufacturing the information recording medium according to the first embodiment, and the other steps are the same.

  That is, the surface protection process is a subsequent process of the light irradiation process. In the surface protection step, the substrate 2 that has passed under the light irradiation mechanism 40 is transported from the transport rollers 61 and 62 to the carry-out rollers 51 and 52 via the surface protection mechanism 70. In this state, the substrate 2 passes between the heat transfer heat roll 74 and the pressing roller 75. At that time, the take-up roller 73 feeds the transfer foil 71 from the original winding roller 72, and the heat transfer heat roll 74 is transferred. While applying heat to the foil 71, the transfer foil 71 is transferred to the base 2 to form the surface protective layer 6.

  The present invention is not limited to the second embodiment, and various improvements and design changes may be made without departing from the spirit of the present invention.

  As one improvement / design change item, as shown in FIG. 8, a second recording head 19 for discharging anti-counterfeit ink may be additionally provided in the image recording unit 13. In this case, the second recording head 18 and the second recording head 19 may eject anti-counterfeit inks having different compositions, or eject anti-counterfeit inks having the same composition. You may do it.

As another improvement / design change item, the transfer foil 71 may be transferred to the substrate 2 by using means capable of applying pressure while heating, such as a heat roller or a hot stamp machine. Specifically, when using a hot stamping machine, it is heated to a surface temperature of 450 to 300 ° C. and heated at a pressure of 50 to 500 kg / cm ² for 0.5 to 10 seconds using a heat roller having a diameter of 5 cm and a rubber hardness of 85. It is better to perform the transfer.

  As other improvements / design changes, there are no particular restrictions on the transfer method to the substrate 2, the transfer foil peeling method from the ID card 10, and the number of transfers, such as JP-A-2001-063294, JP-A-2001-1672, and 2001-1674. Can be used.

(1) Preparation of image recording ink (1.1) Preparation of image recording ink 1 (1.1.1) Preparation of yellow ink The following substances were blended in the following ratio to obtain a yellow pigment dispersion.
CIPigment Yellow-180 ... 15 parts by weight Dispersant (Avecia Solsperse 24000) ... 2 parts by weight Toagosei Aron Oxetane OXT-221 ... 83 parts by weight

After obtaining the yellow pigment dispersion, the yellow pigment dispersion and the following substances are blended at the following ratio, the blend is filtered through a 0.8 μm membrane filter, and dehydrated under reduced pressure while being heated to 50 ° C., A “yellow ink” was obtained.
Yellow pigment dispersion: 17 parts by mass Aron Oxetane OXT-221 manufactured by Toa Gosei 70 parts by mass Daicel UCB Celoxide 2021P: 30 parts by mass Photoacid generator (UVI-6990 manufactured by Dow Chemical): 5 parts by mass

(1.1.2) Preparation of magenta ink The following substances were blended in the following ratios to obtain a magenta pigment dispersion.
CIPigment Red-146 ... 15 parts by weight Dispersant (Avecia Solsperse 24000) ... 2 parts by weight Toa Gosei Aron Oxetane OXT-221 ... 83 parts by weight

Once the magenta pigment dispersion is obtained, the magenta pigment dispersion and the following substances are blended in the following ratios, the blend is filtered through a 0.8 μm membrane filter, and dehydrated under reduced pressure while heating to 50 ° C., "Magenta ink" was obtained.
Magenta pigment dispersion: 17 parts by mass Aron Oxetane OXT-221 manufactured by Toagosei Co., Ltd .: 70 parts by mass Daicel UCB Celoxide 2021P: 30 parts by mass Photoacid generator (UVI-6990 manufactured by Dow Chemical): 5 parts by mass

(1.1.3) Preparation of cyan ink The following substances were blended in the following ratio to obtain a cyan pigment dispersion.
CIPigment Blue15: 4 ... 20 parts by weight Dispersant (Avecia Solsperse 24000) ... 3 parts by weight Toa Gosei Aron Oxetane OXT-221 ... 77 parts by weight

Once the cyan pigment dispersion is obtained, the cyan pigment dispersion and the following substances are blended at the following ratio, the blend is filtered through a 0.8 μm membrane filter, and dehydrated under reduced pressure while heating to 50 ° C., “Cyan ink” was obtained.
Cyan pigment dispersion: 12 parts by mass Aron Oxetane OXT-221 manufactured by Toagosei Co., Ltd .: 70 parts by mass Celcelide 2021P manufactured by Daicel UCB: 30 parts by mass Photoacid generator (UVI-6990 manufactured by Dow Chemical): 5 parts by mass

(1.1.4) Preparation of black ink The following substances were blended in the following ratio to obtain a black pigment dispersion.
CIPigment Black7 ... 20 parts by weight Dispersant (Avecia Solsperse 24000) ... 3 parts by weight Aron Oxetane OXT-221 made by Toa Gosei 77 parts by weight

After obtaining the black pigment dispersion, the black pigment dispersion and the following substances are blended in the following ratio, the blend is filtered through a 0.8 μm membrane filter, and dehydrated under reduced pressure while being heated to 50 ° C., A “black ink” was obtained.
Black pigment dispersion 15 parts by weight Aron Oxetane OXT-221 manufactured by Toa Gosei 70 parts by weight Daicel UCB Celoxide 2021P 30 parts by weight Photoacid generator (UVI-6990 manufactured by Dow Chemical) 5 parts by weight

(1.2) Production of Image Recording Ink 2 (1.2.1) Production of Yellow Ink “Yellow ink” was obtained by blending the following substances in the following ratio.
Dirent Yellow 50 (CI.29025) ... 6 parts by weight Diethylene glycol ... 47 parts by weight Water ... 47 parts by weight

(1.2.2) Preparation of Magenta Ink “Magenta ink” was obtained by blending the following substances in the following ratio.
M: Xylene Red B (CI.45100) ... 6 parts by weight Diethylene glycol ... 47 parts by weight Water ... 47 parts by weight

(1.2.3) Preparation of Cyan Ink “Cyan ink” was obtained by blending the following substances in the following ratio.
C: Light green SF yellowish ... 6 parts by weight Diethylene glycol ... 47 parts by weight Water ... 47 parts by weight

(1.2.4) Preparation of black ink The following substances were blended in the following ratios to obtain “black ink”.
CIPigment Black7 ... 6 parts by weight Diethylene glycol ... 47 parts by weight Water ... 47 parts by weight

(2) Preparation of anti-counterfeiting inks 1 to 8 The photocurable compounds and anti-counterfeiting materials described in Tables 1 and 2 below were mixed at the ratios in the same table, and the mixture was mixed with zirconia beads. Dispersion was carried out with a time sand grinder, and then further dispersion was carried out for 10 minutes with an ultrasonic disperser to obtain eight types of anti-counterfeiting material dispersions.

  Next, for each anti-counterfeiting material dispersion, the photocuring accelerators shown in Tables 1 and 2 below were mixed and stirred at the ratios in the same table, and then each anti-counterfeiting material dispersion was 1 μm. And dehydrated under reduced pressure while heating to 50 ° C. to obtain 8 types of “counterfeit prevention inks 1 to 8”.

(3) Preparation of surface protection layer (precursor) (3.1) Preparation of surface protection ink (3.1.1) Preparation of surface protection ink 1 The following substances were blended in the following ratios, and blended: The product was filtered through a 0.8 μm membrane filter and dehydrated under reduced pressure while being heated to 50 ° C. to obtain “Surface Protection Ink 1”. The surface protecting ink 1 had a transmittance of 97%.
Aron Oxetane OXT-221 made by Toa Gosei 70 parts by mass Daicel UCB Celoxide 2021P ... 30 parts by weight Photoacid generator (UVI-6990 made by Dow Chemical) 5 parts by weight

(3.1.2) Preparation of Surface Protection Ink 2 The following substances were blended in the following ratio, the blend was filtered through a 0.8 μm membrane filter, dehydrated under reduced pressure while being heated to 50 ° C. A surface protecting ink 2 "was obtained. The surface protecting ink 2 had a transmittance of 87%.
Lauryl acrylate: 25 parts by weight Stearyl acrylate: 10 parts by weight Tetraethylene glycol diacrylate: 30 parts by weight Ethylene oxide-modified trimethylolpropane triacrylate (TMP-3EO-A manufactured by Kyoeisha Chemical Co., Ltd.): 29.5 parts by weight Initiator 1 (Ciba Irgacure 907) 5 parts by weight Initiator 2 (diethylthioxanthone) 0.5 parts by weight Dilent Yellow 50 (CI.29025) 0.2 parts by weight

(3.1.3) Preparation of Surface Protection Ink 3 The following substances were blended in the following ratio, the blend was filtered through a 0.8 μm membrane filter, dehydrated under reduced pressure while being heated to 50 ° C., and “ A surface protecting ink 3 "was obtained. The surface protecting ink 3 had a transmittance of 99%.
Polyvinyl alcohol (GL-03 manufactured by Kuraray) 2 parts by weight Diethylene glycol 49 parts by weight Water 49 parts by weight

(3.2) Preparation of transfer foil for surface protection (3.2.1) Preparation of transfer foil 1 for surface protection For one side of polyethylene terephthalate (S-25 manufactured by Diafoil Hoechst Co.) as a support, The following coating solutions were applied by wire bar coating and dried to form “Surface Protective Transfer Foil 1”.

Release layer coating solution (film thickness 0.2μm)
Polyvinyl alcohol (GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) 10 parts by weight Water 90 parts by weight
In the step of forming the release layer, coating was performed under a drying condition of 90 ° C./30 sec.

Photocurable resin layer coating solution (film thickness 7.0 μm)
A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd./EA-1020 manufactured by Shin-Nakamura Chemical Co., Ltd. 35 parts by weight / 11.75 parts by weight Reaction initiator Irgacure 184 manufactured by Ciba-Geigy Japan Inc. Part Dainippon Ink Surfactant F-179 ... 0.25 parts by weight Toluene ... 500 parts by weight The photo-curing resin after application is dried at 90 ° C / 30 sec and then photocured with a mercury lamp (300 mJ / cm ² ). Went.

Intermediate layer coating solution (thickness: 3.0 μm)
Polyvinyl butyral resin (Sekisui Chemical Co., Ltd., S-REC BX-1) 3.5 parts by weight Asahi Kasei Tuftex M-1913 5 parts by weight Curing agent (polyisocyanate, Nippon Polyurethane Coronate HX) 1.5 parts by weight Methyl ethyl ketone: 90 parts by weight After application, the curing agent was cured at 50 ° C. for 24 hours.

Adhesive layer coating solution (film thickness 1.5μm)
Urethane-modified ethylene ethyl acrylate copolymer (Hitech S6254B, manufactured by Toho Chemical Industry Co., Ltd.) 8 parts by weight Polyacrylate copolymer (Jurimer AT510, manufactured by Nippon Pure Chemical Co., Ltd.) 2 parts by weight Water: 45 parts by weight Ethanol: 45 parts by weight After coating, drying was performed at 70 ° C./30 sec.
The transmittance was 95%.

(3.2.2) Preparation of transfer foil 2 for surface protection The following coating solutions were applied to one side of polyethylene terephthalate (S-25 manufactured by Diafoil Hoechst Co., Ltd.) as a support by wire bar coating. And dried to form "Surface Protective Transfer Foil 2".

Resin layer coating solution (film thickness 0.5μm)
Acrylic resin (Dianal BR-87 manufactured by Mitsubishi Rayon Co., Ltd.) 5 parts by weight Polyvinylacetoacetal (SP value 9.4, KS-1 manufactured by Sekisui Chemical Co., Ltd.) 5 parts by weight Dilent Yellow 50 (CI.29025) ... 0.2 parts by weight Methyl ethyl ketone ... 40 parts by weight Toluene ... 50 parts by weight

Intermediate layer coating solution (film thickness 0.3μm)
Polyvinyl butyral resin (Sleek Chemical Co., Ltd. S-Rec BX-1): 5 parts by weight
Asahi Kasei Tuftex M-1913 3.5 parts by weight Curing agent (Polyisocyanate, Nippon Polyurethane Coronate HX) 1.5 parts by weight Methyl ethyl ketone 20 parts by weight Toluene 70 parts by weight This was carried out at 24 ° C. for 24 hours.

Adhesive layer coating solution (film thickness 0.1 μm)
Urethane-modified ethylene ethyl acrylate copolymer (Hitech S6254B, manufactured by Toho Chemical Industry Co., Ltd.) 8 parts by weight Polyacrylate copolymer (Jurimer AT510, manufactured by Nippon Pure Chemical Co., Ltd.) 2 parts by weight Water: 45 parts by weight Ethanol: 45 parts by weight The transmittance was 88%.

(4) Preparation of Samples 1-11, 21-28 Anti-counterfeit Inks 1-8, Image Recording Inks 1, 2 and Surface Protection Layer Precursors (Surface Protection Inks 1-3 and Surface Protection Transfer Foil 1 and 2) were appropriately combined as shown in Table 3 below to produce “Samples 1-11, 21-28 (ID card)”. In preparation thereof, the anti-counterfeit inks 1 to 8, the image recording inks 1 and 2, and the surface protective layer precursor (surface protective inks 1 to 3 and surface protective transfer foils 1 and 2) are combined. The information recording medium manufacturing apparatuses 100 and 200 shown in FIGS. 2, 4, 7 and 8 were used as appropriate.

When using the information recording medium manufacturing apparatuses 100 and 200, the recording heads 14 to 17, the second recording heads 18 and 19, and the surface protection mechanism 30 include a minimum droplet size of 7 pl, a super drop method (one droplet). Applying a piezo-type inkjet nozzle (nozzle diameter 23 μm) that can produce 7 pl and 14 pl multi-size drops at 2 drops / drop), the drive frequency is 10 kHz while controlling the temperature of the ink and the head to 50 ° C. A solid normal image and an anti-counterfeit image were recorded. As the light source 41, a 120 W / cm metal halide lamp (MAL400NL 3kW power source manufactured by Nippon Battery Co., Ltd.) was applied, and the light source 41 was installed so that the instantaneous illuminance was 24 W / cm ² . In using the surface protection mechanism 70, transfer was performed by applying heat at a pressure of 150 kg / cm ² for 1.2 seconds using a heat transfer heat roll heated to a surface temperature of 200 ° C.

(5) Evaluation of samples 1-11, 21-28 (5.1) Forgery / forgery 10 persons (card material designers are asked if each sample 1-11, 21-28 can be easily counterfeited) The samples were evaluated forgery / alteration for each of the samples 1-11, 21-28. The forgery / alteration was quantified according to the following formula and the calculation results are shown in Table 3 below.
Forgery and alteration (%) = (Number of people who answered that forgery is easy) / (Number of respondents)

(5.2) Water resistance Each sample 1-11, 21-28 was put into a tap water-containing cup and kept immersed at 23 ° C. for 3 days, and the water resistance was evaluated in an image deterioration state. The evaluation results are shown in Table 3 below.
In Table 3, the criteria for “◯”, “Δ”, and “×” are as follows.
○… There is no change compared to before immersion △… There is a slight difference, but the function has not deteriorated ×… There is a difference, the function of the solid image and information is lost

(5.3) Chemical resistance Each sample 1-11, 21-28 was put into a toluene solution-containing cup and kept immersed at 23 ° C. for 1 hour, and the chemical resistance was evaluated in an image deterioration state. The evaluation results are shown in Table 3 below.
In Table 3, the criteria for “◯”, “Δ”, and “×” are as follows.
○… There is no change compared to before immersion △… There is a slight difference, but the function has not deteriorated ×… There is a difference, the function of the solid image and information is lost

(5.4) Scratch strength (wear resistance)
Using a wear resistance tester (HEIDON-18), sliding the surface of each of the samples 1-11, 21-28 with a 0.1 mmφ sapphire needle while changing the load within the range of 0-300 g. The load when the image starts to scratch was measured for each of Samples 1-11, 21-27. The measurement results are shown in Table 3 below.
In addition, in the said measurement result, it has shown that it is so favorable that a load is large.

(6) Summary As shown in Table 3, when comparing the samples 1 to 11 and the comparative samples 21 to 28, the samples 1 to 11 are counterfeit, water resistance, chemical resistance, Excellent in all aspects of scratch strength. From the above, it can be seen that recording an anti-counterfeit image with a special anti-counterfeit ink is useful for preventing forgery and improving durability of the information recording medium.

1 is a perspective view showing a schematic configuration of an ID card 1. FIG. 1 is a side view showing a schematic configuration of an information recording medium manufacturing apparatus 100. FIG. It is drawing for demonstrating the one part process of the manufacturing method of an information recording medium. It is a side view which shows the modification of the manufacturing apparatus 100 of an information recording medium. It is drawing for demonstrating the modification of the manufacturing method of an information recording medium. 1 is a diagram illustrating a schematic configuration of an ID card 10. 1 is a side view showing a schematic configuration of an information recording medium manufacturing apparatus 200. FIG. It is a side view which shows the modification of the manufacturing apparatus 200 of an information recording medium.

Explanation of symbols

1,10 ID card (information recording medium)
DESCRIPTION OF SYMBOLS 2 Substrate 3 Normal image 4 Anti-counterfeit image 5, 6 Surface protective layer 100, 200 Information recording medium manufacturing apparatus 12 Platen 13 Image recording unit 14-17 Recording head 18, 19 Second recording head (anti-counterfeit recording head )
DESCRIPTION OF SYMBOLS 20 Stacking part 21 Supply roller 30 Surface protection mechanism 40 Light irradiation mechanism 41 Light source 42 Reflector 51,52 Unloading roller 53 Stacker 61,62 Conveyance roller 70 Surface protection mechanism 71 Transfer foil 72 Original winding roller 73 Winding roller 74 Heat transfer heat roll 75 Pressure roller

Claims (12)

A method of manufacturing an information recording medium for manufacturing an information recording medium for preventing forgery,
A recording step of recording an anti-counterfeit image on an information recording medium by an ink jet method using a photocurable anti-counterfeit ink;
A light irradiation step of irradiating the anti-counterfeit ink with light after the recording step;
An information recording medium manufacturing method comprising: In the manufacturing method of the information recording medium of Claim 1,
A method for manufacturing an information recording medium, comprising: a surface protection step for forming a surface protective layer for protecting the surface of the information recording medium after the recording step and before the light irradiation step. In the manufacturing method of the information recording medium of Claim 1,
A method for producing an information recording medium comprising a surface protection step of forming a surface protective layer for protecting the surface of the information recording medium before the recording step. In the manufacturing method of the information recording medium of Claim 2 or 3,
In the surface protection step, the surface protection layer is formed by an ink jet method using a surface protection ink composed of a photocurable resin and having a transmittance of 90% or more. In the manufacturing method of the information recording medium of Claim 1,
A method of manufacturing an information recording medium, comprising a surface protection step of forming a surface protective layer for protecting the surface of the information recording medium after the light irradiation step. In the manufacturing method of the information recording medium of Claim 5,
In the surface protection step, a transfer foil including a photocurable resin layer is transferred to the surface of the information recording medium to form the surface protective layer. In the manufacturing method of the information recording medium as described in any one of Claims 1-6,
A method for producing an information recording medium, wherein the anti-counterfeit ink contains a photocurable compound, a photocuring accelerator, and a forgery-preventing material. In the manufacturing method of the information recording medium of Claim 7,
A method for producing an information recording medium, wherein the anti-counterfeiting material is an infrared absorber, a scale pigment, a phosphor, metal fine particles, a high refractive index material or a low refractive index material. In the manufacturing method of the information recording medium as described in any one of Claims 1-8,
The method for producing an information recording medium, wherein the forgery-preventing image is a unique image that differs for each information recording medium. In the manufacturing method of the information recording medium as described in any one of Claims 1-9,
A method of manufacturing an information recording medium, wherein the information recording medium is an ID card.   An information recording medium manufactured by the method for manufacturing an information recording medium according to claim 1. In the information recording medium manufacturing apparatus used for the information recording medium manufacturing method according to any one of claims 1 to 10,
An anti-counterfeit recording head for recording an anti-counterfeit image by ejecting a photocurable anti-counterfeit ink onto an information recording medium by an ink jet method
A light irradiation mechanism for irradiating the anti-counterfeit ink with light;
A surface protection mechanism for forming a surface protective layer for protecting the surface of the information recording medium;
An apparatus for manufacturing an information recording medium, comprising:

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