JP6339382B2 - Security film - Google Patents

Description

  The present invention relates to a security film. More specifically, the present invention relates to a security film useful for e-ID cards and e-passports.

  Conventionally, cash cards, credit cards and other ID cards, driver's licenses, health insurance cards, passports and the like are easily forged and require forgery prevention (which can be determined to be authentic). As a method for determining authenticity, there is a method of including fluorescent particles. Specifically, a method for preventing forgery by printing on paper using the ink containing the fluorescent particles, or a method for dyeing the ink containing the fluorescent particles into a thread and using it as a thread for preventing forgery. There is a method for preventing forgery. An authentication card in which fluorescent particles are mixed is known (see, for example, Patent Document 1). Moreover, several techniques are known about forgery prevention (for example, refer patent documents 2-10).

International Publication No. 2007/72795 JP 2011-238044 A JP 2011-131527 A JP 2008-063701 A JP 2006-001094 A JP 2005-338656 A JP 2004-122690 A Japanese Patent Laid-Open No. 11-138974 JP 11-058929 A JP-A-10-006636

  As an element (security element) for carrying a security function of an ID card or the like (that is, a function that is difficult to counterfeit and that can be determined as authentic), the above-mentioned “inorganic phosphor capable of emitting visible light by irradiation with UV light ( Particles) or organic phosphors (particles) ”are already known (Patent Document 1, etc.), but it is difficult to ensure security functions such as ID cards with these“ already known phosphors ”. . That is, since the forger can easily obtain the “already known phosphor”, it is easy to make a forged ID card or the like.

  Moreover, the thing of patent documents 2-10 is completely different from the security film with sufficient light emission intensity and transparency.

  Thus, for an ID card or the like, development of a new security film having a high security function (that is, it is difficult to forge and can reliably determine authenticity) is eagerly desired. That is, the development of a security film having high security function and good transparency because it contains particles that emit light well when irradiated with light has been desired.

  The present invention has been made to solve the above-described problems of the prior art. That is, the present invention provides a security film having high security function and good transparency because it contains particles that emit light well when irradiated with light.

  That is, the security film of the present invention is different from “inorganic phosphors (particles) and organic phosphors (particles) capable of emitting visible light when irradiated with UV light” and “infrared when irradiated with UV light or visible light”. This is a film in which “photoluminescent particles exhibiting light emission” are uniformly dispersed in a transparent thermoplastic resin such as polycarbonate resin. The security film of the present invention can detect authenticity by detecting “infrared light” generated by irradiation of “UV light or visible light”, and has high security such as an ID card. It is useful as a film constituting what is required to have a function. The particles (photoluminescent particles) contained in the security film of the present invention are novel as security elements for ID cards and electronic passports.

  According to the present invention, the following security film is provided.

[1] A photoluminescent film in which photoluminescent particles exhibiting infrared emission by UV light or visible light irradiation are dispersed in a transparent thermoplastic resin, and the photoluminescent particles are irradiated with UV light or visible light. Infrared light emitter particles that emit infrared light, and the light emitter particles include a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following: Particles comprising at least one selected from the group consisting of compounds represented by formula (3), wherein the photoluminescent particles are dispersed in the transparent thermoplastic resin at 0.01 to 1.0% by mass. The compound represented by the following general formula (1) is a light emitter that emits infrared light when excited by irradiation with UV light, and the compound represented by the following general formula (2) is visible light. Is a light emitter that emits infrared light when excited by irradiation with the following general formula ( The compound represented by 3) is a security film that is a light emitter that emits infrared light when excited by irradiation with UV light or visible light.
General formula (1): Ba _1-X SnA _X O ₃ (0 <X <0.4, A is Li or Na)
General formula (2): CaMoO ₄ : M (M is one or more lanthanum group metal ions selected from the group consisting of Nd ³⁺ , Yb ³⁺ , and Er ³⁺ )
General formula (3): Y ₂ SiV ₂ O ₁₀ : Nd ³⁺ , Er ³⁺

[2] The security film according to [1], wherein the photoluminescent particles have a glass transition temperature of 80 ° C. or higher of the transparent thermoplastic resin.

[3] The transparent thermoplastic resin further includes a stabilizer and a lubricant, and the stabilizer is at least one selected from the group consisting of phenol-based, phosphorus-based, and sulfur-based stabilizers. The security film according to [1] or [2], wherein the lubricant is at least one selected from the group consisting of ester-based, olefin-based, and amide-based lubricants.

[4] The surface of the photoluminescent particles is treated with an organic substance, and the organic substance includes an organosilicon compound, a metal complex compound, a fatty acid compound, an alkoxy group, a maleic anhydride group, an epoxy group, an acetamide group, Any one of the above [1] to [3], which is at least one organic substance selected from the group consisting of functional group-containing organic polymers, oligomers, and vinylpyrrolidone containing at least one functional group of oxazoline groups. The security film described.

[5] The transparent thermoplastic resin is an amorphous copolyester resin, an acrylic resin, a transparent acrylonitrile-butadiene-styrene resin, a polycarbonate resin, a polypropylene resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, or an amorphous copolyester. The security film according to any one of [1] to [4], which is at least one selected from the group consisting of a polymer alloy resin of a resin and a polycarbonate resin.

[6] The security film according to any one of [1] to [5], which is a film for forming a hinge sheet of an electronic passport.

  In the security film of the present invention, photoluminescent particles that are predetermined compounds are dispersed. Therefore, since the security film of the present invention contains particles that emit light well when irradiated with light, the security film has a high security function and good transparency.

It is a schematic diagram which shows the cross section of one Embodiment of the security film of this invention. It is a schematic diagram which shows the cross section of the electronic passport using one Embodiment of the security film of this invention. It is a top view which shows typically the surface part of the electronic passport using one Embodiment of the security film of this invention.

  Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments are also within the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should be.

(1) Security film:
An embodiment of the security film of the present invention is a security film 10 shown in FIG. The security film 10 of the present embodiment is a photoluminescent film in which photoluminescent particles 11 that emit infrared light when irradiated with UV light or visible light are dispersed in a transparent thermoplastic resin 12. The photoluminescent particles 11 are infrared photoluminescent particles that emit infrared light when irradiated with UV light or visible light. The photoluminescent particles 11 are represented by the following general formula (1) and the following general formula (2). And at least one kind of particles selected from the group consisting of compounds represented by the following general formula (3). The compound represented by the following general formula (1) is a light emitting body (UV light excitation infrared light emitting body) that is excited by being irradiated with UV light and emits infrared light. The compound represented by the following general formula (2) is a light emitting body (visible light excitation infrared light emitting body) that is excited by irradiation with visible light and emits infrared light. The compound represented by the following general formula (3) is a light emitter (UV light visible light excited infrared light emitter particle) that emits infrared light when excited by irradiation with UV light or visible light. In general formula (3), Nd ³⁺ and Er ³⁺ are activators. In the security film 10, photoluminescent particles 11 are dispersed in the transparent thermoplastic resin 12 at a ratio of 0.01 to 1.0 mass%. The said content rate is a ratio of the part which does not contain the organic substance on the surface (part only of a photoluminescent substance particle), when the surface of the photoluminescent substance particle is processed with the organic substance.
General formula (1): Ba _1-X SnA _X O ₃ (0 <X <0.4, A is Li or Na)
General formula (2): CaMoO ₄ : M (M is one or more lanthanum group metal ions selected from the group consisting of Nd ³⁺ , Yb ³⁺ , and Er ³⁺ )
General formula (3): Y ₂ SiV ₂ O ₁₀ : Nd ³⁺ , Er ³⁺

  FIG. 1 is a schematic view showing a cross section of one embodiment of the security film of the present invention.

  In the security film 10, it is preferable that the photoluminescent particles 11 are dispersed in the transparent thermoplastic resin 12 at a ratio of 0.05 to 0.5 mass%. When the content ratio of the photoluminescent particles 11 is less than the lower limit value, detection with a detector is difficult. When the content ratio of the photoluminescent particles 11 exceeds the upper limit value, the transparency of the security film 10 is lowered, and when there is an image in the lower layer of the security film 10, the image becomes unclear.

  Such a security film 10 is a new film having a high security function (that is, it is difficult to be counterfeited and authenticity can be reliably determined). Specifically, since the security film 10 is a transparent film, it is determined at first glance that this film contains the light emitter particles 11 that are the elements for authenticity determination (security elements). hard. That is, even if forgery is attempted, since the security film 10 is a transparent film, it is difficult to specify the location of the photoluminescent particles 11. In particular, when used for a plastic card or the like, it is more difficult to specify the location of the photoluminescent particles 11. Specifically, since the security film 10 is disposed on the upper layer of the “core sheet layer subjected to offset printing, inkjet printing, silk screen printing, etc.”, the light emission by visual observation is performed depending on the image of the core sheet layer. The location of the body particles 11 can be made more difficult (prevented from being easily specified). It is also difficult to specify the physical properties (excitation wavelength and emission wavelength) of the photoluminescent particles 11 that are security elements. That is, the security film 10 cannot observe the light emission of the photoluminescent particles 11 unless a special condition is employed and the infrared light is emitted by irradiating UV light or visible light.

  Since the photoluminescent particles 11 are dispersed throughout the security film 10, infrared light emission derived from the photoluminescent particles 11 can be observed in any part.

  Further, in a plastic card such as an e-ID card, when a printing layer (a layer on which an image or the like is printed) is disposed below the security film 10, the security film 10 is transparent, so that the image on the printing layer is clear. Can be confirmed.

  From the above, the security film 10 is not particularly limited in use, but is a film useful as a security film for plastic cards such as e-ID cards or electronic passports, for example.

  In this specification, a “security film” is a film that constitutes a film (such as a card or a passport) that requires anti-counterfeiting (authentication determination) because it is easily forged, such as a passport. That is, the security film is provided in the passport or the like as a means for determining the authenticity of the passport or the like. Furthermore, it is used in a wide variety of other applications requiring high security, such as entry / exit cards, civil servant cards, and high precision equipment management cards.

  Here, conventionally, a plurality of techniques as disclosed in Patent Documents 2 to 10 are known as techniques for preventing forgery.

  Patent Document 2 discloses an anti-counterfeit IC label in which an adhesive layer is provided on one side of a base material made of a thermoplastic resin and an information printing layer is provided on the opposite side. This anti-counterfeit IC label is a special near-infrared light emitter of the present invention, which contains a general fluorescent dye of a naphthalimide compound, a perylene compound and a mixture of these two in a base material or an adhesive layer. Different from (photoluminescent particles). In other words, this anti-counterfeit IC label is greatly different from the security film of the present invention which is excellent in transparency because the photoluminescent particles are melt-mixed in a transparent thermoplastic resin and uniformly dispersed.

  Patent Document 3 discloses an anti-counterfeit label obtained by scrubbing a fluorescent dichroic dye having a polarization function into a paper medium. However, the anti-counterfeit label is greatly different from the security film of the present invention in terms of light emitting function and high transparency.

  Patent Document 4 discloses an anti-counterfeit paper in which a transparent hollow fiber unit containing a polymer hydrogel material is mixed in paper. However, the anti-counterfeit paper is based on a completely different technology from the security film of the present invention, and is a completely different product.

  Patent Document 5 discloses an image forming method, and in this method, a transfer sheet comprising a release layer / a relief forming layer / a metal thin film layer / a receiving layer / a transfer target is disclosed. The transfer sheet is characterized in that a fluorescent dye (fluorescent dye F1) is formed on a transfer target. However, the fluorescent dye F1 is characterized in that it emits light that is shifted (up-conversion) to a wavelength longer than the absorption wavelength after absorbing these wavelengths at an excitation wavelength of 500 to 2000 nm. Therefore, the transfer sheet in Patent Document 5 is different in purpose, technology, and product from the security film of the present invention characterized by high transparency.

  Patent Document 6 discloses a transfer sheet (hologram transfer sheet) as in Patent Document 5. Specifically, a hologram transfer sheet comprising an adhesive layer / metal thin film layer / relief forming layer / release layer / base material / heat-resistant slip layer is disclosed, and this hologram transfer sheet comprises a release layer and / or an adhesive layer. It is characterized by containing a fluorescent dye. The fluorescent dye is the same as that of Patent Document 5. Therefore, similarly to Patent Document 5, the hologram transfer sheet described in Patent Document 6 is different in purpose, technology, and product from the security film of the present invention characterized by high transparency.

  Patent Document 7 discloses a method for producing a fluorescent light-emitting printed matter. Specifically, it is disclosed that, in a full color image formed on a substrate by sublimation thermal transfer printing, a fluorescent dye that absorbs ultraviolet light and emits ultraviolet light is contained in the printing ink. However, the fluorescent light-emitting printed matter manufacturing method described in Patent Document 7 is different in purpose, technology, and product from the security film of the present invention characterized by high transparency.

  Patent Document 8 discloses an anti-counterfeit ink. Specifically, an ink containing a fluorescent dye or fluorescent pigment having a specific structure that absorbs visible light (excitation wavelength) and has a wavelength shift of 50 nm or more is disclosed. The fluorescent dye or fluorescent pigment has a structure different from that of the near-infrared light emitter in the present invention (note that the near-infrared light emitter is an inorganic substance and is generally in the category of a fluorescent pigment, but has a different structure. ). Therefore, the anti-counterfeit ink described in Patent Document 8 is different in purpose, technology, and product from the security film of the present invention characterized by high transparency.

  Patent Document 9 discloses an anti-copying recording method characterized in that an arbitrary substrate is colored with an azo fluorescent dye. However, the copy prevention recording method described in Patent Document 9 is different in purpose, technology and product from the security film of the present invention characterized by high transparency.

  The technique described in Patent Document 10 is similar to the technique described in Patent Document 8, and Patent Document 10 discloses an anti-counterfeit ink in which an organic fluorescent dye having a specific structure is contained in the ink. However, the anti-counterfeit ink described in Patent Document 10 is different in purpose, technology, and product from the security film of the present invention characterized by high transparency.

  As described above, these Patent Documents 2 to 10 disclose a paper medium, an opaque medium having a laminated structure, or ink, which is completely different from the security film of the present invention. Furthermore, the fluorescent substance used is a well-known fluorescent dye. In Patent Documents 2 to 10, this fluorescent dye is mixed and mixed in a paper medium or ink. For this reason, the techniques described in Patent Documents 2 to 10 are used for plastic IC cards, electronic passports, and the like that require a high security function, and cannot be used for security films having high transparency. Further, as described above, the techniques described in Patent Documents 2 to 10 and the security film of the present invention are completely different in purpose of use and function.

“Dispersed photoluminescent particles in a transparent thermoplastic resin” means that when a plurality of areas of an arbitrary size of a security film are arbitrarily selected, these areas are uniformly (that is, light Means that the formation of aggregates of phosphor particles is suppressed). More specifically, it means a state in which the number of aggregates of photoluminescent particles is 5 / cm ² or less and is present in the transparent thermoplastic resin in the observation with a microscope.

(1-1) Photoluminescent particles:
As described above, the photoluminescent particles are selected from the group consisting of the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3). And at least one kind of particles. The photoluminescent particles are particles that emit infrared light when irradiated with UV light or visible light. The photoluminescent particles are special particles and are not commercially available, and are novel as security elements for ID cards and electronic passports. Therefore, this particle itself functions as a security element.

  Of the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3), the compound represented by the general formula (1) or the general formula The compound represented by (3) is preferable, and the compound represented by the general formula (1) is more preferable.

  In particular, among the compounds represented by the general formula (1), those in which X satisfies 0.01 to 0.1 are preferable.

  The surface of the photoluminescent particles is preferably treated with an organic substance. Examples of the organic substance include an organosilicon compound containing a alkoxy group, a silanol group, and a hydrogen group, a metal complex compound, a fatty acid ester, and a fatty acid amide. Examples thereof include fatty acid compounds, alkoxy groups, maleic anhydride groups, epoxy groups, acetamide groups, functional group-containing organic polymers containing oxazoline groups, oligomers, and polyvinylpyrrolidone (PVP).

  By treating the surface with the above compound in this way, aggregation of the particles can be suppressed when the photoluminescent particles are melt-mixed in the thermoplastic resin, and high transparency is maintained. Further, since the photoluminescent particles are uniformly dispersed in the film, the detection can be performed with a uniform sensitivity regardless of the part of the film. As the detector, there is a small detector that detects a predetermined wavelength by irradiating a predetermined wavelength. For example, in the case of the photoluminescent particles A represented by the general formula (1), the detector has a function of emitting near infrared light when irradiated with ultraviolet light. A function of receiving infrared light is required.

  Among these, at least one selected from the group consisting of organic silicon compounds, fatty acid compounds such as fatty acid esters and fatty acid amides, functional group-containing organic polymers containing alkoxy groups, maleic anhydride groups and epoxy groups, or oligomers It is preferable to treat the surface of the photoluminescent particles with a seed organic material. By treating the surface of the photoluminescent particles with these compounds, the particle surface can be hydrophobized and the compatibility with the thermoplastic resin can be improved. As a result, the particle dispersibility of the photoluminescent particles in a thermoplastic resin (particularly, a hydrophobic thermoplastic resin) can be improved.

  Examples of the organosilicon compound include silicone and silazane, and an organoalkoxysilane having an alkoxy group and an organic group, an organoalkoxysilane oligomer, and a polysiloxane having a hydrogen group are preferable. Among these, organoalkoxysilane is preferable from the viewpoint of reactivity with the surface of the photoluminescent particles and ease of handling.

  Examples of the metal complex compound include chelate compounds such as Al and Zr, and cyclic oligomers. Among these, chelate compounds such as Al and Zr are preferable because of reactivity and ease of handling.

  Examples of fatty acid compounds such as fatty acid esters and fatty acid amides include Riquemar S-100A, Riquester EW440A (manufactured by Riken Vitamin Co., Ltd.), Rico Wax E, OP, Ricorub WE4, Ricole FA1 (manufactured by Clariant), and the like.

  Examples of the organic polymer and oligomer containing an alkoxy group include an alkoxysilyl group-containing acrylic resin. Specifically, Zemlac (manufactured by Kaneka), ARUFON US-6000 series (manufactured by Toa Gosei), Saimak (Toa Gosei) Etc.).

  Examples of the organic polymer oligomer containing a maleic anhydride group include styrene maleic anhydride polymer SMA resin (manufactured by Kawa Crude Chemical Co., Ltd.), ethylene-ethyl acrylate-maleic anhydride copolymer Modiper A8400 (manufactured by NOF Corporation), α- Examples include olefin-maleic anhydride copolymer, Diacarna (manufactured by Mitsubishi Chemical Corporation), and the like.

  As an organic polymer oligomer containing an epoxy group, an epoxy group-containing acrylic polymer ARUFON UG-4000 series (manufactured by Toa Gosei Co., Ltd.), an ethylene-glycidyl methacrylate copolymer, Bond Fast 2C, E, CG5001 (manufactured by Sumitomo Chemical Co., Ltd.), etc. , Ethylene-glycidyl methacrylate-methacrylate copolymer, Bond Fast 7L, 7M (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the organic polymer oligomer containing an acetamide group include poly-N-vinylacetamide (manufactured by Showa Denko KK).

  Examples of the organic polymer oligomer containing an oxazoline group include Epocros RPS (manufactured by Nippon Shokubai Co., Ltd.).

  Examples of polyvinyl pyrrolidone include polyvinyl pyrrolidone K-30 and K-85 (manufactured by Nippon Shokubai Co., Ltd.).

  The photoluminescent particles preferably have an average particle diameter of 0.3 to 5.0 μm, and more preferably 0.5 to 2.0 μm. Since the photoluminescent particles are produced by a high temperature firing method, it is difficult to produce fine particles of less than 0.3 μm. On the other hand, if it exceeds 5.0 μm, the transparency of the resulting film is undesirably lowered. In the present specification, the “average particle diameter” is a value obtained by measuring the diameter of 80 particles with a transmission electron microscope and obtaining an average value.

(1-2) Transparent thermoplastic resin:
A transparent thermoplastic resin is a transparent thermoplastic resin. Here, “transparent” means that when the thermoplastic resin is formed into a film having a thickness of 100 μm, the total light transmittance of the film is 80% or more.

  Transparent thermoplastic resins include amorphous copolyester resin, acrylic resin, transparent acrylonitrile-butadiene-styrene resin, polycarbonate resin, polypropylene resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and amorphous copolyester resin and polycarbonate resin. And at least one selected from the group consisting of polymer alloy resins. When a security film including such a transparent resin is used for a plastic card such as an IC card or an electronic passport, an offset printed sheet layer can be disposed under the security film. Thus, since the security film is transparent, characters and images color-printed on the printing layer can be viewed well.

  Among these transparent thermoplastic resins, a polycarbonate resin, a polymer alloy resin of an amorphous copolyester resin and a polycarbonate resin is preferable, and a polycarbonate resin is more preferable. Since the security film is required to have a stable and stable high security function, the transparent thermoplastic resin as the base is required to have strength, toughness, heat resistance, and moisture resistance. These resins can meet the demand. In addition, it is considered that the security film of the present invention is often used in the form of a card by heating and laminating a plurality of sheets, rather than being used alone. In such a mode of use, a sheet of the same type of material as the security film of the present invention is placed on the upper layer, the lower layer, or both (upper and lower layers) of the security film of the present invention, and each sheet layer is heated and fused by heat lamination. It is necessary to put on. Therefore, these transparent thermoplastic resins satisfy these requirements. Therefore, the resin is suitable for the above-described use.

  The transparent thermoplastic resin preferably has a glass transition temperature of 80 ° C. or higher, more preferably 80 to 160 ° C., and particularly preferably 90 to 150 ° C. When the glass transition temperature of the transparent thermoplastic resin is in the above range, deformation due to heat (for example, heat due to direct sunlight) is unlikely to occur under the actual usage environment of a card such as an IC card or an electronic passport. Can be used. Furthermore, a data page of a plastic card such as an IC card or an electronic passport (e-passport) is manufactured by laminating and heating a plurality of sheets (laminated sheets), and the heating temperature is set to 200 ° C. or less. It becomes possible. That is, each sheet can be fused by heating the laminated sheet at a temperature of 200 ° C. or lower. For this reason, there is an advantage that a general-purpose device such as a vacuum compression molding machine can be used as the device used in the heating process. When the glass transition temperature is lower than 80 ° C., a card such as an IC card or an electronic passport may be deformed by heat under a temperature in an actual use environment.

(1-3) Other components:
The security film of the present invention preferably contains a stabilizer, a lubricant and the like in addition to the photoluminescent particles and the transparent thermoplastic resin.

  The stabilizer is preferably a phenol-based, phosphorus-based or sulfur-based heat stabilizer. The lubricant is preferably an ester, olefin or amide lubricant.

  Examples of phenol-based heat stabilizers include Sumilizer GM, GS, GP, GA-80, MDP-S, WX-R, WX-RC (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB AO-20, AO-30, A0- 40, AO-50, AO-60, AO-330 (made by ADEKA) etc. are mentioned.

  Examples of phosphorus heat stabilizers include ADK STAB PEP-8, PEP-8W, PEP36, HP-10, 2112, 1500, 3010 (manufactured by ADEKA), GSY-101 (manufactured by Sakai Chemical Co., Ltd.), and the like.

  Examples of the sulfur-based heat stabilizer include Sumilizer TPL-R, TPM, TPS, TP-D (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB A0412S (manufactured by ADEKA), and the like.

  These heat stabilizers are used alone or in combination. When used in combination, phenol and phosphorus heat stabilizers or phenol and sulfur heat stabilizers may be used in combination. preferable.

  By including these thermal stabilizers, the effect of suppressing thermal oxidative degradation of the transparent thermoplastic resin can be obtained in the step of producing pellets by melt kneading extrusion molding of the photoluminescent particles and the transparent thermoplastic resin. Furthermore, the effect of suppressing the thermal oxidative deterioration of the transparent thermoplastic resin can be obtained also in the process of producing a security film by melt kneading extrusion using the pellets. The above-mentioned “process for producing pellets” refers to a process for producing transparent thermoplastic resin compound pellets for security films, that is, “security film compound production process” to be described later.

  Examples of the ester-based lubricant include Riquestar EW440A, Riquemar S-100A, Riquemar SL800, SL900, SL900A (manufactured by Riken Vitamin Co., Ltd.), Rico Wax OP, E, Ricorub WE4 (manufactured by Clariant Japan).

  Olefin-based lubricants include high-wax high-density type, polypropylene decomposition type, oxidation type, acid-modified type, special monomer-modified type (Mitsui Chemicals Co., Ltd.), Ricolb H12, Rico Wax PE520, PED191 (Clariant Japan Co., Ltd.) Etc.

  Examples of the amide-based lubricant include Kao wax EB-G, EB-P, EB-FE (manufactured by Kao Corporation), and Recolb FA1 (manufactured by Clariant Japan).

  These lubricants are used singly or in combination, but ester-based lubricants alone or a combination of ester-based lubricants and olefin-based lubricants are preferred.

  By containing these lubricants, in the process of producing pellets by melt-kneading extrusion molding of photoluminescent particles and transparent thermoplastic resin, the friction between the molding machine wall and the screw wall and the molten resin is reduced. Can do. Furthermore, it has the effect of suppressing thermal oxidative deterioration due to long-term residence of the molten resin and suppressing molecular cutting of the molten resin. Furthermore, in the process of producing a security film by melt kneading extrusion using the above pellets, the friction between the molding machine wall and the squeeze wall and the molten resin can be reduced, and the heat due to the long stay of the molten resin can be reduced. It has the effect of suppressing oxidative degradation and suppressing molecular cutting of the molten resin. The above-mentioned “process for producing pellets” refers to a process for producing transparent thermoplastic resin compound pellets for security films, that is, “security film compound production process” to be described later.

  Therefore, it is particularly preferable to use a stabilizer and a lubricant in combination.

  The blending ratio of the stabilizer is preferably 0.01 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and the blending ratio of the lubricant is 0.01 to 2.0%. It is preferable that it is mass%, More preferably, it is 0.1-0.6 mass%.

  Moreover, the security film of this invention can mix | blend a conventionally well-known additive etc. suitably as needed.

  The security film of the present invention has a thickness of 30 to 500 μm, preferably 50 to 200 μm. In particular, when used for a transparent oversheet such as an IC card (a card including an ID card), the thickness is preferably 50 to 125 μm. When the thickness of the security film is within the above range, it can be controlled within the thickness of a card that is generally used.

  In addition, when used for an electronic passport or an IC card, the electronic passport or the IC card generally has a laminated structure, and its thickness is limited. Therefore, if the thickness of the transparent oversheet (transparent oversheet, transparent laser marking oversheet) in the entire thickness of the electronic passport, IC card, etc. exceeds 500 μm, the entire thickness of the electronic passport, IC card, etc. becomes too thick. . If the thickness of the security film is less than the lower limit, the degree of infrared light emission is small, and it may be difficult to detect light emission. That is, it becomes impossible to obtain a highly sensitive security film. The “transparent laser marking oversheet” is a transparent oversheet that allows laser marking.

  The security film of the present invention preferably has a total light transmittance of 80% or more, and preferably 85% or more. When the total light transmittance of the security film is within the above range, the security film can be said to be a transparent film. Therefore, the security film of the present invention can be suitably used as a transparent layer constituting the outermost layer in a data page of a card such as an IC card or an electronic passport, for example. In this case, when a printing layer (a layer on which an image or the like is printed) is arranged on the lower layer of the security film, the image on the printing layer can be clearly confirmed. The “total light transmittance” is a value when the security film is measured using a transmittance tester (for example, a haze meter NDH-4000 manufactured by Nippon Denshoku Industries Co., Ltd.).

(1-4) Application of security film:
The security film of the present invention can be used for an electronic passport or a plastic card, and is particularly preferably used for a card that handles government-related personal information such as a national ID card, a driver's license, and a health insurance card. It is essential that such a “card that handles government-related personal information” is not easily counterfeited, and the security film of the present invention meets the purpose as a film used for such a card.

  When the security film of the present invention is used for an electronic passport (that is, when the security film of the present invention is used as a film constituting an electronic passport), the security film of the present invention is used for constituting a hinge sheet of an electronic passport. It is preferable to use it as a film. As described above, when used as a film for constituting the hinge sheet, the location of the security film as the security element is not easily found, and the security function is further enhanced.

  2 and 3 show the electronic passport 100. The electronic passport 100 includes a cover 50 having a cover 50 and a cover sheet 60 having a protect sheet 51 attached to a central portion of the inner surface of the cover 50, a data page 20 on which personal information is recorded, a visa sheet 30, have. In the electronic passport 100, the data page 20 has a hinge sheet 21 protruding outward, and the data page 20 is bound to the cover portion by binding the hinge sheet 21 and the cover portion 60 with the sewing thread 40. 60 is fixed. In the electronic passport 100, the visa sheet 30 is also bound together with the data page 20. The hinge sheet 21 is a laminated body in which a plurality of films are laminated, and includes the security film 10. FIG. 2 is a schematic view showing a cross section of an electronic passport using one embodiment of the security film of the present invention. FIG. 3 is a plan view schematically showing a surface portion of an electronic passport using one embodiment of the security film of the present invention.

(2) Security film manufacturing method:
The security film of the present invention can be produced, for example, as follows.

(2-1) Photoluminescent particle production process:
First, photoluminescent particles are prepared by the following method (photoluminescent particle preparation step). Specifically, a specific inorganic compound (oxide, hydroxide, etc.) is uniformly mixed and pulverized, then heated and fired at a predetermined temperature in one stage or multiple stages, and then pulverized to have a predetermined composition. Photoluminescent particles are prepared.

  In addition, it is preferable to further perform the process (surface treatment process) which processes the surface of the obtained particle | grains.

  The surface treatment process includes dry treatment, wet treatment, and integral blend. In the dry treatment, the photoluminescent particles and the surface treatment agent are introduced into a high-speed stirrer such as a disk mill to simultaneously pulverize the particles and perform the surface treatment. In the wet treatment, particles are usually pulverized with a high-speed stirrer such as a disk mill, and then the pulverized particles, water or solvent is put into a sealed stirrer that can be heated and stirred, and then at a predetermined temperature and stirring speed. Then, the surface treatment agent (surface treatment agent aqueous solution or solution) is charged all together or dropped at a predetermined dropping rate, and then stirring is continued for a predetermined time. Thereafter, water or solvent is removed by a method such as removal under reduced pressure to obtain surface-treated photoluminescent particles.

  Furthermore, there is also a surface treatment method called “integral blend” in which transparent thermoplastic resin, photoluminescent particles, surface treatment agent, stabilizer, and lubricant are uniformly mixed and dispersed in the following compound production process.

  These surface treatments are appropriately selected according to the function, use, etc. of the security film.

(2-2) Compound manufacturing process for security film:
Next, a compound for a security film is manufactured using the transparent thermoplastic resin powder, the obtained photoluminescent particles, a stabilizer, and a lubricant. Specifically, the raw materials are put into a closed mixer and stirred uniformly, and then melt mixed at a predetermined temperature using a twin screw extruder with a strand die. And a compound pellet is manufactured from a strand die by melt extrusion molding.

(2-3) Film manufacturing process:
Next, using the obtained compound pellets, a transparent film is produced by melt extrusion molding at a predetermined temperature using a single-screw or twin-screw extruder with a T die.

  Moreover, in a film manufacturing process, a conventionally well-known additive etc. can be mix | blended as needed other than the said component.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to these Examples and a comparative example.

(Production Example 1) Production of UV light-excited infrared luminescent particles A:
The following first raw materials were uniformly mixed, then filled in an alumina crucible in the atmosphere, heated to 1450 ° C. in an electric furnace over 3 hours, and held for 10 hours. Then, it cooled to room temperature. In this way, an inorganic composite metal oxide was obtained. The first raw material was compounded with BaCO ₃ at 1.9537 g (0.0099 mol), SnO ₂ at 1.5071 g (0.01 mol), and Na ₂ CO ₃ .10H ₂ O at 0.0286 g (0.0001 mol). It was a thing.

  The obtained inorganic composite metal oxide was pulverized by a disc mill (vibrating disc mill RS200 manufactured by Lecce) to obtain photoluminescent particles having an average particle diameter of 1 μm.

  Excitation wavelength spectrum and emission wavelength spectrum of the photoluminescent particles were measured with a spectrofluorometer (Hitachi spectrofluorometer F-7000). As a result, this photoluminescent material had an excitation peak wavelength of 380 nm and an emission peak wavelength of 930 nm.

Production Example 2 Production of Visible Light Excited Infrared Emitter Particle B:
After the following second raw material was uniformly mixed in the closed reactor, the water was volatilized by heating at 100 ° C. Thereafter, the temperature was gradually raised to 200 ° C. to cause a decomposition reaction of citric acid, which is an organic acid, to obtain a mixture. This mixture was put into an electric furnace and heat-treated at 900 ° C. for 2 hours. Then, it cooled to room temperature. In this way, an inorganic composite metal oxide was obtained. The second raw materials are (NH ₄ ) 6 Mo ₇ O ₂ 4.4H ₂ O 3.530 g (0.02 mol), Nd (NO ₃ ) ₃ O · 5H ₂ O 0.068 g (0.0002 mol), Ca (NO ₃ ) 2.4.2 g (0.02 mol) of 2.4H ₂ O, 4.620 g (0.022 mol) of citric acid, and 15 ml of water were blended.

  The inorganic composite metal oxide thus obtained was pulverized by a disc mill (vibrating disc mill RS200 manufactured by Lecce) to obtain photoluminescent particles having an average particle diameter of 1 μm.

  Excitation wavelength spectrum and emission wavelength spectrum of the photoluminescent particles were measured with a spectrofluorometer (Hitachi spectrofluorometer F-7000). As a result, this photoluminescent material had an excitation peak wavelength of 585 nm and an emission peak wavelength of 1065 nm.

(Production Example 3) Preparation of UV light visible light excitation infrared luminescent particles C:
After the following third raw material was uniformly mixed with a ball mill, an inorganic composite metal oxide (fired product) was obtained by the following three-stage firing. The obtained fired product was pulverized by a disc mill (vibrating disc mill RS200 manufactured by Lecce) to obtain photoluminescent particles having an average particle diameter of 1 μm. The third raw material is 49.68 g (0.22 mol) of Y ₂ O ₃ , 12.02 g (0.20 mol) of SiO ₂ , 37.85 g (0.21 mol) of V ₂ O ₅ , and Nd ₂ O ₃ 0.336 g (0.001 mol) and Er ₂ O ₃ were blended at 0.114 g (0.0003 mol).
[First Stage] The mixture was filled in an alumina crucible, heated in an electric furnace at 650 ° C. for 4 hours in the atmosphere, then cooled to room temperature and coarsely pulverized to obtain particles having an average particle diameter of 10 μm.
[Second Stage] Next, the fired product obtained in the first stage was heated in an electric furnace at 1100 ° C. for 4 hours in the atmosphere, then cooled to room temperature and coarsely pulverized to obtain particles having an average particle diameter of 3 μm. It was.
[Third Stage] Next, the fired product obtained in the second stage was heated in an electric furnace at 600 ° C. for 2 hours in the atmosphere, and then cooled to room temperature.

  Excitation wavelength spectrum and emission wavelength spectrum of the photoluminescent particles were measured with a spectrofluorometer (Hitachi spectrofluorometer F-7000). As a result, this photoluminescent material had an excitation peak wavelength of 320 nm and an emission peak wavelength of 1050 nm.

(Production Example 4) Production of UV light-excited infrared luminescent particles A surface treatment product D:
10 g of the UV light-excited infrared luminescent particles A obtained in Production Example 1 and 200 g of toluene were put into an autoclave with a dropping device. Thereafter, with stirring while heating at 60 ° C., 1 / 100N-hydrochloric acid water (water: γ-MPTS (γ-methacryloxytrimethoxysilane) (molar ratio = 1: 3), 0.6 g of γ-MPTS, Were added dropwise over 30 minutes, and then the temperature was raised to 80 ° C. and stirring was continued for 3 hours, followed by cooling to room temperature.

  Thereafter, toluene and methanol, which is a hydrolysis-reactive product of γ-MPTS, were removed with an evaporator at 40 ° C. under reduced pressure. Thereafter, it was dried in a vacuum dryer at 60 ° C. for 1 day to obtain UV light-excited infrared phosphor particles A surface-treated product D.

(Production Example 5) Production of UV light-excited infrared luminescent particles A surface-treated product E:
1 g of fatty acid monoglyceride (Riquemar S-100, manufactured by Riken Vitamin Co., Ltd.) and 10 g of toluene were put into a sealed container with a stirrer to dissolve the fatty acid monoglyceride to obtain a dissolved product. Thereafter, the UV light-excited infrared light emitter particles A1 g obtained in Production Example 1 and the above-mentioned dissolved material were mixed, and stirring was continued at room temperature for 60 minutes to prepare a toluene dispersion of UV light-excited infrared light emitter particles A. . Then, it was dried in a vacuum dryer at 60 ° C. for one day and night, and a surface-treated product E of “UV photoexcited infrared luminescent particles A” treated with a special fatty acid ester was obtained.

(Production Example 6) Production of UV light-excited infrared luminescent particles A surface-treated product F:
Using a planetary ball mill (manufactured by Frichche Japan), 10 g of UV light-excited infrared phosphor particles A and α-olefin-maleic anhydride copolymer Diacarna 30 (manufactured by Mitsubishi Chemical Corporation) in 20 g of zirconia beads Was introduced. Thereafter, stirring was continued at 500 rpm for 3 hours to obtain a surface-treated product F of UV photoexcited infrared light emitting particles A.

Example 1
0.1% by mass of UV light-excited infrared phosphor particles A obtained in Production Example 1, 0.1% by mass of a phenol-based heat stabilizer (Sumilyzer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), phosphorus-based heat stability A composition was obtained by adding 0.1% by mass of an agent (Adeka Stab PEP-8, ADEKA) and 0.2% by mass of an ester-based lubricant (Licowax E, manufactured by Clariant Japan). Then, using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.), the above composition was stirred and mixed at 260 ° C. and a rotation speed of 50 rpm for 5 minutes to obtain a uniform polycarbonate resin composition S-1.

  This polycarbonate resin composition S-1 was heated and pressurized under vacuum at 280 ° C. and 2 MPa in a vacuum press machine (manufactured by Kitagawa Seiki Co., Ltd.), then cooled to room temperature and a transparent film P- having a thickness of 100 μm. 1 was obtained.

  Then, when this transparent film P-1 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the UV-excited infrared light emitting particles A were not dispersed and uniformly dispersed in a monodispersed state. I confirmed that The average particle diameter of the UV light-excited infrared luminescent particles A in this film was 1.8 μm.

  When the total light transmittance of the transparent film P-1 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 86% and the transparency was good. It was confirmed.

  About this transparent film P-1, when an excitation wavelength spectrum and an emission wavelength spectrum were measured using a spectrofluorimeter (Hitachi spectrofluorometer F-7000), an excitation peak wavelength was 380 nm and an emission peak wavelength was 930 nm. It was confirmed.

Since the detection sensitivity at these peak wavelengths was 3.0 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  This transparent film P-1 was confirmed to be useful as a security film. The results are shown in Table 1.

(Example 2)
A transparent film P-2 was obtained in the same manner as in Example 1 except that the UV-light-excited infrared light emitter particles A of Example 1 were changed to the visible light-excited infrared light emitter particles B obtained in Production Example 2.

  When this transparent film P-2 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the UV-excited infrared phosphor particles B were not dispersed but uniformly dispersed in a monodispersed state. I confirmed.

  When the total light transmittance of the transparent film P-2 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 84% and the transparency was good. It was confirmed.

  About this transparent film P-2, when the excitation wavelength spectrum and the emission wavelength spectrum were measured using a spectrofluorimeter (Hitachi spectrofluorometer F-7000), it was found that the excitation peak wavelength was 585 nm and the emission peak wavelength was 1065 nm. confirmed.

Since the detection sensitivity at these peak wavelengths was 2.8 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  This transparent film P-2 was confirmed to be useful as a security film. The results are shown in Table 1.

(Example 3)
A transparent film P-3 was obtained in the same manner as in Example 1 except that the UV light-excited infrared light emitter particle A of Example 1 was changed to the UV light visible light-excited infrared light emitter particle C obtained in Production Example 3. It was.

  When this transparent film P-3 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the UV light-excited infrared luminescent particles C were not dispersed but uniformly dispersed in a monodispersed state. I confirmed.

  When the total light transmittance of the transparent film P-3 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 85%, and the transparency was good. It was confirmed.

  About this transparent film P-3, when the excitation wavelength spectrum and the emission wavelength spectrum were measured using a spectrofluorimeter (Hitachi spectrofluorometer F-7000), it was found that the excitation peak wavelength was 320 nm and the emission peak wavelength was 1050 nm. confirmed.

Since the detection sensitivity at these peak wavelengths was 2.9 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  This transparent film P-3 was confirmed to be useful as a security film. The results are shown in Table 1.

Example 4
Except for changing the UV-light-excited infrared luminescent particles A of Example 1 to 0.11% by mass (0.1% by mass as particles A), the surface-treated product D of the UV-photo-excited infrared luminescent particles A obtained in Production Example 4. Was the same as in Example 1 to obtain a transparent film P-4.

  When this transparent film P-4 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the photoexcited infrared luminescent particles A surface treatment product D did not aggregate and was uniformly dispersed. It was confirmed that they were dispersed.

  When the total light transmittance of the transparent film P-4 was measured using a haze meter (Haze Meter NDH7000, manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 89% and the transparency was good. It was confirmed.

  About this transparent film P-4, when the excitation wavelength spectrum and the emission wavelength spectrum were measured using a spectrofluorimeter (Hitachi spectrofluorometer F-7000), it was found that the excitation peak wavelength was 380 nm and the emission peak wavelength was 930 nm. confirmed.

Since the detection sensitivity at these peak wavelengths was 3.9 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  This transparent film P-4 was confirmed to be useful as a security film. The results are shown in Table 1.

(Example 5)
The UV light-excited infrared luminescent particles A in Example 1 were changed to 0.2% by mass (0.1% by mass as the particles A) of the surface-treated product UV-excited infrared luminescent particles A obtained in Production Example 5. A transparent film P-5 was obtained in the same manner as Example 1 except for the above.

  When this transparent film P-5 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the photoexcited infrared luminescent particles A surface-treated product E did not aggregate and was uniformly dispersed. It was confirmed that they were dispersed.

  When the total light transmittance of the transparent film P-5 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 88%, and the transparency was good. It was confirmed.

  About this transparent film P-5, when an excitation wavelength spectrum and an emission wavelength spectrum were measured using a spectrofluorimeter (Hitachi spectrofluorometer F-7000), it was found that the excitation peak wavelength was 380 nm and the emission peak wavelength was 930 nm. confirmed.

Since the detection sensitivity at these peak wavelengths was 3.8 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  This transparent film P-5 was confirmed to be useful as a security film. The results are shown in Table 1.

(Example 6)
Except for changing the UV light-excited infrared light emitter particles A of Example 1 to 0.12% by weight (0.1% by weight as particles A) of the UV light-excited infrared light emitter particles A surface-treated product obtained in Production Example 6. Produced a transparent film P-6 in the same manner as in Example 1.

  When this transparent film P-6 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the photoexcited infrared luminescent particles A surface treatment product F did not aggregate and was uniform in a monodispersed state. It was confirmed that they were dispersed.

  When the total light transmittance of the transparent film P-6 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 89%, and the transparency was good. It was confirmed.

  About this transparent film P-6, when the excitation wavelength spectrum and the emission wavelength spectrum were measured using a spectrofluorimeter (Hitachi spectrofluorometer F-7000), it was found that the excitation peak wavelength was 380 nm and the emission peak wavelength was 930 nm. confirmed.

Since the detection sensitivity at these peak wavelengths was 3.8 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  This transparent film P-6 was confirmed to be useful as a security film. The results are shown in Table 1.

(Example 7)
100 parts by mass of acrylic resin (Acrypet VRL40, manufactured by Mitsubishi Rayon Co., Ltd.), UV photoexcited infrared luminescent particles A obtained in Production Example 1 surface treatment product D0.11% by mass (0.1% by mass as particles A), special Lab Plast Mill (Toyo Seiki Co., Ltd.) 0.1 parts by mass of fatty acid ester (Riquestar EW-440A, manufactured by Riken Vitamin Co., Ltd.) and 0.1 part by mass of glycerol mono fatty acid ester (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.) Was used for stirring for 5 minutes at 240 ° C. and a rotational speed of 100 rpm to obtain a uniform acrylic resin composition.

  This acrylic resin composition was heated and pressure-compressed under vacuum at 260 ° C. and 2 MPa with a vacuum press (manufactured by Kitagawa Seiki Co., Ltd.). Then, it cooled to room temperature and obtained the transparent film P-7 with a thickness of 100 micrometers.

  When this transparent film P-7 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the UV light-excited infrared luminescent particles A were not uniformly aggregated and uniformly dispersed in a monodispersed state. I confirmed.

  When the total light transmittance of this transparent film P-7 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 90%, and the transparency was good. It was confirmed.

  About this transparent film P-7, when the excitation wavelength spectrum and the emission wavelength spectrum were measured using a spectrofluorometer (Hitachi spectrofluorometer F-7000), it was found that the excitation peak wavelength was 380 nm and the emission peak wavelength was 930 nm. confirmed.

Since the detection sensitivity at these peak wavelengths was 3.9 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  This transparent film P-7 was confirmed to be useful as a security film. The results are shown in Table 1.

(Example 8)
Except that the UV light-excited infrared luminescent particles A of Example 1 were treated with the UV light-excited infrared luminescent particles A obtained in Production Example 4 and the surface treatment product D was 0.011% by mass (0.01% by mass as particles A), A transparent film P-8 was obtained in the same manner as Example 1.

  When this transparent film P-8 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Co., Ltd.), the UV-excited infrared light emitting particles A did not aggregate and were uniformly dispersed in a monodispersed state. I confirmed.

  When the total light transmittance of the transparent film P-8 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 90% and the transparency was good. It was confirmed.

  About this transparent film P-8, when the excitation wavelength spectrum and the emission wavelength spectrum were measured using a spectrofluorometer (Hitachi spectrofluorometer F-7000), it was found that the excitation peak wavelength was 380 nm and the emission peak wavelength was 930 nm. confirmed.

Since the detection sensitivity at these peak wavelengths is 2.1 × 10 ⁴ counts, it was confirmed that the detection sensitivity required for the security film was obtained.

  This transparent film P-8 was confirmed to be useful as a security film. The results are shown in Table 1.

Example 9
A transparent film P-9 was obtained in the same manner as in Example 1 except that the UV light-excited infrared luminescent particle A surface-treated product D was 1.1% by mass (1.0% by mass as the particle A). .

  When this transparent film P-9 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the UV-excited infrared light emitting particles A were not dispersed and uniformly dispersed in a monodispersed state. I confirmed.

  When the total light transmittance of the transparent film P-9 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 82%, and the transparency was good. It was confirmed.

  About this transparent film P-9, when the excitation wavelength spectrum and the emission wavelength spectrum were measured using a spectrofluorimeter (Hitachi spectrofluorometer F-7000), it was found that the excitation peak wavelength was 380 nm and the emission peak wavelength was 930 nm. confirmed.

Since the detection sensitivity at these peak wavelengths is 12 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  This transparent film P-9 was confirmed to be useful as a security film. The results are shown in Table 1.

(Comparative Example 1)
A film P-10 was obtained in the same manner as in Example 1 except that the mixing amount of the UV light-excited infrared luminescent particles A in Example 1 was 0.001% by mass.

  When this film P-10 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), the UV light-excited infrared luminescent particles A did not aggregate and were uniformly dispersed in a monodispersed state. It was confirmed.

  When the total light transmittance of the film P-10 was measured using a haze meter (Haze Meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was 90%, and it was confirmed that the transparency was good. did.

  For the film P-10, the excitation wavelength spectrum and the emission wavelength spectrum were measured using a spectrofluorometer (Hitachi spectrofluorometer F-7000). As a result, a weak peak was observed near the excitation peak wavelength of 380 nm, and a weak peak was observed near the emission peak wavelength of 930 nm.

Since the detection sensitivity at these peak wavelengths is 0.2 × 10 ⁴ counts, it can be said that the detection sensitivity is insufficient as a security film, but this transparent film P-10 is poor in practicality as a security film. The results are shown in Table 2.

(Comparative Example 2)
A film P-11 was obtained in the same manner as in Example 1 except that the amount of the UV-light-excited infrared luminescent particles A in Example 1 used was 1.2% by mass. This film P-11 was a slightly cloudy film.

  When this film P-11 was observed with a magnifying microscope (Universal Zoom Microscope MULTIZOOM AZ100, manufactured by Nikon Instruments Company), partial aggregation of the UV light-excited infrared luminescent particles A was observed.

  About the film P-11, the excitation wavelength spectrum and the emission wavelength spectrum were measured using the spectrofluorimeter (Hitachi spectrofluorometer F-7000). As a result, the excitation peak wavelength was 380 nm and the emission peak wavelength was 930 nm.

Since the detection sensitivity at these peak wavelengths is 7.5 × 10 ⁴ counts, it was confirmed that the detection sensitivity was sufficient as a security film.

  However, although this film P-11 has sufficient detection sensitivity, its transparency is deteriorated, and there is a problem that an image of a printed layer disposed under the security film becomes unclear. Therefore, it is poor in practicality as a security film in applications requiring transparency. The results are shown in Table 2.

  As above-mentioned, since the transparent film (security film) of Examples 1-9 emitted light favorably when irradiated with light, it was confirmed that the security function was high and the transparency was good.

  The security film of the present invention can be used as a film constituting a card such as an ID card or an electronic passport.

10: Security film, 11: Photoluminescent particles, 12: Transparent thermoplastic resin, 20: Data page, 21: Hinge sheet, Yarn binding margin, 30: Visa sheet, 40: Sewing thread, 50: Cover, 51: Protect sheet , 60: cover part, 100: electronic passport.

Claims (6)

A photoluminescent film in which photoluminescent particles exhibiting infrared emission by UV light or visible light irradiation are dispersed in a transparent thermoplastic resin,
The photoluminescent particles are infrared photoluminescent particles that emit infrared light by irradiation with UV light or visible light,
The photoluminescent particles are selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3). Particles composed of at least one kind of
The photoluminescent particles are dispersed in the transparent thermoplastic resin at 0.01 to 1.0 mass%,
The compound represented by the following general formula (1) is a light emitter that emits infrared light when excited by being irradiated with UV light.
The compound represented by the following general formula (2) is a light emitter that emits infrared light when excited by irradiation with visible light,
The compound represented by the following general formula (3) is a security film which is a light emitter that emits infrared light when excited by irradiation with UV light or visible light.
General formula (1): Ba _1-X SnA _X O ₃ (0 <X <0.4, A is Li or Na)
General formula (2): CaMoO ₄ : M (M is one or more lanthanum group metal ions selected from the group consisting of Nd ³⁺ , Yb ³⁺ , and Er ³⁺ )
General formula (3): Y ₂ SiV ₂ O ₁₀ : Nd ³⁺ , Er ³⁺   The security film according to claim 1, wherein the photoluminescent particles have a glass transition temperature of 80 ° C. or higher of the transparent thermoplastic resin. The transparent thermoplastic resin further includes a stabilizer and a lubricant,
The stabilizer is at least one selected from the group consisting of phenol-based, phosphorus-based, and sulfur-based stabilizers, and the lubricant is selected from the group consisting of ester-based, olefin-based, and amide-based lubricants. The security film according to claim 1, wherein the security film is at least one kind. The photoluminescent particles have their surfaces treated with organic matter,
Functional group-containing organic polymer or oligomer in which the organic substance contains at least one functional group of an organosilicon compound, a metal complex compound, a fatty acid compound, an alkoxy group, a maleic anhydride group, an epoxy group, an acetamide group, and an oxazoline group And at least one organic substance selected from the group consisting of vinyl pyrrolidone and the security film according to any one of claims 1 to 3.   The transparent thermoplastic resin includes an amorphous copolyester resin, an acrylic resin, a transparent acrylonitrile-butadiene-styrene resin, a polycarbonate resin, a polypropylene resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, and an amorphous copolyester resin and a polycarbonate. It is at least 1 type selected from the group which consists of polymer alloy resin with resin, The security film as described in any one of Claims 1-4.   The security film according to any one of claims 1 to 5, which is a film for constituting a hinge sheet of an electronic passport.

Images