KR101762740B1 - Security film - Google Patents
Security film Download PDFInfo
- Publication number
- KR101762740B1 KR101762740B1 KR1020167007085A KR20167007085A KR101762740B1 KR 101762740 B1 KR101762740 B1 KR 101762740B1 KR 1020167007085 A KR1020167007085 A KR 1020167007085A KR 20167007085 A KR20167007085 A KR 20167007085A KR 101762740 B1 KR101762740 B1 KR 101762740B1
- Authority
- KR
- South Korea
- Prior art keywords
- light
- film
- resin
- photoluminescent
- particles
- Prior art date
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- 239000002245 particle Substances 0.000 claims abstract description 156
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- -1 metal complex compounds Chemical class 0.000 claims description 29
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- 229930195729 fatty acid Natural products 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
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- 239000004925 Acrylic resin Substances 0.000 claims description 8
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- 150000002148 esters Chemical class 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
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- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
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- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
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- 229930003231 vitamin Natural products 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
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- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
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- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
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- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/24—Passports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
- B42D25/378—Special inks
- B42D25/382—Special inks absorbing or reflecting infrared light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
- B42D25/378—Special inks
- B42D25/387—Special inks absorbing or reflecting ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C08K3/0033—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
Abstract
The photoluminescent film 11 is a photoluminescent film in which 0.01 to 1.0 wt% of photoluminescent particles 11 exhibiting infrared light emission by UV light or visible light irradiation are dispersed in the transparent thermoplastic resin 12. The photoluminescent particles 11 are irradiated with ultraviolet light or visible light A compound represented by the general formula: Ba 1-X SnA X O 3 (0 <X <0.4, A is Li or Na), a compound represented by the general formula: CaMoO 4 : M (M is Nd 3+, Yb 3+, and Er is a 3+ groups alone or in combination of two or more is kanjok metal ion is selected from the consisting of a), and the general formula: Y 2 SiV 2 O 10: Nd 3 +, Er 3 It was irradiated to the film 10. the security light particles consisting of at least one member selected from the group consisting of compounds represented by the + because they contain particles which preferably emit light with high security, and, It provides good security reputation film.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a security film, and more particularly, to a security film useful as a plastic card or a security card for a digital passport.
Conventionally, a cash card, a credit card, a driver's license, a health insurance card, a passport and the like are easy to be falsified and require forgery prevention (judgment of authenticity). And, there is a method of including fluorescence particles as a method of judging authenticity. Specifically,. There is a method of performing forgery prevention in which ink containing the fluorescent particles is printed on paper and a method of preventing forgery by using an ink containing the fluorescent particles as a yarn for preventing forgery by staining the yarn. Further, an authentication card incorporating fluorescent particles is known (see, for example, Patent Document 1). In addition, various techniques are known for anti-counterfeiting (see, for example, Patent Documents 2 to 10).
(Security element) for taking charge of a security function (that is, a function that is difficult to be falsified and able to determine authenticity) of an ID card or the like. The inorganic phosphor (particle) or organic Phosphors (particles) 'are already known (Patent Document 1, etc.). However, it is difficult to secure the security function of the ID card or the like by the 'already known phosphor'. That is, since the counterfeiter can easily obtain the 'already known fluorescent substance', it is easy to manufacture the counterfeit ID card or the like.
What is described in Patent Documents 2 to 10 is completely different from a security film having sufficient luminescence intensity and transparency.
Therefore, in ID cards and the like, it is required to develop a new security film that has a high security function (that is, it is difficult to counterfeit and can surely determine authenticity).
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 a light emitting material that emits visible light, which is different from inorganic fluorescent material (particle) and organic fluorescent material (particle) capable of visible light emission by UV light irradiation, Is uniformly dispersed in a transparent thermoplastic resin such as a polycarbonate resin. The security film of the present invention detects 'infrared rays' generated by irradiation of 'UV light or visible light' to enable authenticity determination, and constitutes what requires a high security function such as an ID card It is beneficial as a film.
According to the present invention, the following security film is provided.
[One]
A photoluminescent film in which photoluminescent particles exhibiting infrared light emission through UV light or visible light irradiation are dispersed in a transparent thermoplastic resin. The photoluminescent particles are infrared light-emitting phosphor particles which emit infrared rays through irradiation with UV light or visible light, Wherein the photoluminescent particles are at least one 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) And the photoluminescent particles are dispersed in the transparent thermoplastic resin in an amount of 0.01 to 1.0% by weight, and the compound represented by the following general formula (1) is irradiated with UV light to excite, The compound represented by the following general formula (2) is a light emitting substance which is excited by visible light to emit infrared rays and is represented by the following general formula (3) Wherein the compound represented by the formula (1) is an illuminant that is excited by UV light or visible light to emit infrared light.
Formula (1): Ba 1-X SnA X O 3 (0 <X <0.4, A is Li or Na)
(2): CaMoO 4 : M (M is one or two or more kinds of Lankan group metal ions selected from the group consisting of Nd 3+ , Yb 3+ , and Er 3+ )
(3): Y 2 SiV 2 O 10 : Nd 3+ , Er 3+
[2]
The security film according to the above [1], wherein the transparent thermoplastic resin has a glass transition temperature of 80 캜 or more.
[3]
Wherein the transparent thermoplastic resin further contains 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. The lubricant is at least one selected from the group consisting of esters, olefins, and amides. Or [2].
[4]
4. The compound according to any one of claims 1 to 3,
Wherein the surface of the photoluminescent particles is treated with an organic substance and the organic substance is at least one functional group selected from the group consisting of organic silicon compounds, metal complex compounds, fatty acid compounds, alkoxy groups, maleic anhydride groups, epoxy groups, acetamide groups, The security film according to any one of [1] to [3] above, which is at least one organic substance selected from the group consisting of organic polymer containing functional group, oligomer, and vinylpyrrolidone.
[5]
Wherein the transparent thermoplastic resin is at least one selected from the group consisting of 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 naphthalene resin and an amorphous copolyester resin , And a polymer-alloy resin of a polycarbonate resin. The security film according to any one of the above [1] to [4]
[6]
The security film according to any one of [1] to [5], which is a film constituting the hinge sheet of the ePassport.
In the security film of the present invention, photoluminescent particles, which 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 a good transparency.
1 is a schematic view showing a cross section of one embodiment of the security film of the present invention.
2 is a schematic view showing a cross section of a passport according to an embodiment of the security film of the present invention.
3 is a plan view schematically showing a surface portion of a passport according to an embodiment of the security film of the present invention.
Hereinafter, embodiments for carrying out the present invention will be described, but the present invention is not limited to the following embodiments. That is, it should be understood that appropriate changes, improvements, and the like are applied to the following embodiments based on knowledge of those skilled in the art within the scope of the present invention.
(1) Security film:
As one embodiment of the security film of the present invention, there is the
Formula (1): Ba 1-X SnA X O 3 (0 <X <0.4, A is Li or Na)
(2): CaMoO 4 : M (M is one or two or more kinds of Lankan group metal ions selected from the group consisting of Nd 3+ , Yb 3+ , and Er 3+ )
(3): Y 2 SiV 2 O 10 : Nd 3+ , Er 3+
1 is a schematic view showing a cross section of one embodiment of the security film of the present invention.
It is preferable that the
This
In the
Further, in the case of a plastic card such as an e-ID card, in the case where a print layer (layer on which an image or the like is printed) is disposed under the
From the above, the
In the present specification, the "security film" is a film constituting a thing (card, passport, etc.) which requires forgery prevention (authenticity judgment) because it is likely to be falsified, such as a passport. That is, the security film is a means for determining authenticity of a passport or the like and is provided in a passport or the like. In addition, the security film is used in various applications requiring high security, such as access cards, public official cards, and high-precision apparatus management cards.
Conventionally, various techniques such as Patent Documents 2 to 10 are known as anti-counterfeiting technologies.
Patent Document 2 discloses an anti-fake IC label in which an adhesive layer is provided on one side of a substrate made of a thermoplastic resin and an information printing layer is provided on the opposite side of the substrate. This anti-fake IC label is obtained by incorporating a general fluorescent dye such as a naphthamide compound, a perylene compound, or a mixture of the two in a substrate or an adhesive layer, and is different from the special near-infrared light emitter (photoluminescent particle) of the present invention. That is, the anti-fake IC label is significantly different from the security film of the present invention, which is excellent in transparency, by melting and mixing the photoluminescent particles with a transparent thermoplastic resin and uniformly dispersing them.
Patent Document 3 discloses an anti-falsification label that can be obtained by fusing a fluorescent dichroic dye having a polarizing function on a paper medium. However, this anti-falsification label is significantly different from the security film of the present invention in terms of light-emitting function and high transparency.
Patent Document 4 discloses an anti-falsification paper in which a hollow hollow fiber unit containing a polymer hydrogel material is incorporated into paper. However, this anti-falsification article is based on a technique completely different from that of the security film of the present invention, and is a completely different product.
Patent Document 5 discloses an image forming method. In this method, a transfer sheet comprising a release layer / relief forming layer / metal thin film layer / receptive layer / transfer body is disclosed. This transfer sheet is characterized in that a fluorescent dye (fluorescent dye F1) is formed on the transfer object. However, the fluorescent dye F1 is characterized in that it emits light at an excitation wavelength of 500 to 2000 nm and then up-converts it to a wavelength longer than the absorption wavelength. Therefore, the transfer sheet in Patent Document 5 differs in purpose, technology, and product from the security film of the present invention, which is characterized by high transparency.
Patent Document 6 discloses a transfer sheet (hologram transfer sheet) similar to Patent Document 5. Specifically, there is disclosed a hologram transfer sheet comprising an adhesive layer / metal thin film layer, a relief forming layer, a release layer / substrate / a heat resistant bone layer, and the hologram transfer sheet is characterized in that a fluorescent dye is contained in the release layer and / . The fluorescent dye is the same as in Patent Document 5. Therefore, like the Patent Document 5, the hologram sheet described in Patent Document 6 differs from the security film of the present invention, which is characterized by high transparency, in purpose, technology, and product.
Patent Document 7 discloses a method of producing a fluorescent light-emitting print. Specifically, it has been disclosed that, in a 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 manufacturing method of the fluorescent light-sensitive printed matter described in Patent Document 7 differs from the purpose, technology, and product of the security film of the present invention, which is characterized by high transparency.
Patent Document 8 discloses an anti-falsification ink. Specifically, an ink containing a fluorescent dye or a fluorescent pigment having a specific structure having a wavelength shift of 50 nm or more by absorbing visible light (excitation wavelength) is disclosed. This fluorescent colorant or fluorescent pigment differs from the near-infrared light emitting body of the present invention in a quadratic form (the near-infrared light emitting body is an inorganic substance and generally a fluorescent pigment, but has a different structure). Therefore, the anti-falsification ink described in Patent Document 8 differs from the security film of the present invention, which is characterized by high transparency, in purpose, technology, and product.
Patent Document 9 discloses a copy-protection recording method characterized by coloring an arbitrary substrate with an azo-based fluorescent dye. However, the copy protection recording method disclosed in Patent Document 9 differs from the security film of the present invention, which is characterized by high transparency, in purpose, technology, and product.
The technology described in
As described above, these Patent Documents 2 to 10 disclose a paper medium, an opaque medium having a laminated structure, or an ink, which is quite different from the security film of the present invention. Further, the phosphors used are well-known fluorescent dyes, and in Patent Documents 2 to 10, these fluorescent dyes are mixed with a paper medium and ink. Therefore, the Donny technologies described in Patent Documents 2 to 10 are used for plastic IC cards and electronic passports that require an advanced security function, and can not be used for security films having high transparency. Further, as described above, the technology described in Patent Documents 2 to 10 and the security film of the present invention have completely different purposes and functions.
"Dispersing the photoluminescent particles in the transparent thermoplastic resin" means that, when arbitrarily selecting various regions of an arbitrary size of the security film, uniformity among these arbitrary regions (that is, formation of aggregates of the photoluminescent particles is suppressed ) Is included. More specifically, it means a state in which the number of agglomerates of the photoluminescent particles is present in the transparent thermoplastic resin at not more than 5 / cm 2 in the observation by a microscope.
(1-1) Photoluminescent particles:
As described above, the photoluminescent particles are composed of at least one kind selected from the group consisting of a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3) Particle. This photoluminescent particle is a particle showing infrared light emission by UV light or visible light irradiation. The above-mentioned photoluminescent particles are special particles and are not commercial products, but new ones as security elements of ID cards and e-passports. Therefore, this particle itself functions as a security element.
Among the compounds represented by the general formula (1), the compounds represented by the general formulas (2) and (3), the compounds represented by the general formula (1) or the compounds represented by the general formula (3) Compound is preferable, and the compound represented by the general formula (1) is more preferable.
Particularly, among the compounds represented by the general formula (1), X preferably satisfies 0.01 to 0.1.
The surface of the photoluminescent particles is preferably treated with an organic material. Examples of the organic material include organic silicon compounds containing an alkoxy group, a silanol group and a hydrogen group, fatty acid compounds such as metal complex compounds, fatty acid esters and fatty acid amides, Containing functional group containing an oxazoline group, an oligomer, polyvinyl pyrrolidone (PVP), and the like can be given.
By treating the surface with the above compound, aggregation of 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 detector can be detected with a uniform sensitivity regardless of the film portion. 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 particle A represented by the general formula (1), since the function of emitting near-infrared rays upon irradiation with ultraviolet rays, the detector has a function of irradiating ultraviolet rays to receive near- Is required.
Among them, at least one organic material selected from the group consisting of organic acid compounds, fatty acid esters, fatty acid-based compounds such as fatty acid amides, alkoxy groups, maleic anhydride groups, functional group containing functional groups containing epoxy groups, It is preferable to treat the surface of the phosphor particles. The surface of the photoluminescent particles can be treated with such a compound to make hydrophobic the surface of the particles, and the compatibility with the thermoplastic resin can be improved. As a result, the particle dispersibility of the photoluminescent particles in the thermoplastic resin (particularly, the hydrophobic thermoplastic resin) can be improved.
Examples of the organosilicon compound include silicon and silazane. Organic alkoxysilanes having an alkoxy group and an organic group, an organic alkoxysilane oligomer, and a polysiloxane having a hydrogen group are preferred. Of these, organic alkoxysilanes are preferred because of their 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 them, chelate compounds such as Al and Zr are preferable in terms of reactivity and ease of handling.
Examples of fatty acid compounds such as fatty acid esters and fatty acid amides include Rikemaru S-100A, Rikesta EW440A (Riken Vitamin Co., Ltd.), Ricoh wax E, OP, Ricoribu WE4 and Ricorobu FA1 (Clariant) .
Examples of the organic polymer and oligomer containing an alkoxy group include an alkoxysilyl group-containing acrylic resin. Specific examples of the organic polymer include alkoxysilyl group-containing acrylic resins such as Zemurak (Kaneka), ARUFON US-6000 series And the like.
Examples of the organic polymer oligomer containing a maleic anhydride group include styrene maleic anhydride polymer SMA resin (Kawahara Yuka Co., Ltd.), ethylene-ethyl acrylate-maleic anhydride copolymer Modif A 8400 (similar), -olefin-maleic anhydride copolymer Dicarna (Mitsubishi Chemical Corporation), and the like.
Examples of the organic polymer oligomer containing an epoxy group include an epoxy group-containing acrylic polymer, ARUFON UG-4000 series (East Asian synthetic resin), ethylene-glycidyl methacrylate copolymer, Bond Fast 2C, E, CG5001 (Sumitomo Company) Glycidyl methacrylate copolymer, Bond Fast 7L, 7M (Sumitomo Chemical Co., Ltd.), and the like.
Examples of the organic polymer oligomer containing an acetamide group include poly-N-vinylacetamide (Showa Denko) and the like.
Examples of the organic polymeric oligomer containing an oxazoline group include Epocross RPS (Japan Catalysts).
Examples of the polyvinyl pyrrolidone include polyvinyl pyrrolidone K-30 and K-85 (manufactured by Nippon Kogyo Co., Ltd.).
The photoluminescent particles preferably have an average particle diameter of 0.3 to 5.0 m, more preferably 0.5 to 2.0 m. Since the photoluminescent particles are produced by the high temperature softening method, it is difficult to produce fine particles of less than 0.3 탆. On the other hand, if it exceeds 5.0 m, the transparency of the obtained film is lowered, which is not preferable. In the present specification, the "average particle diameter" is a value obtained by measuring the diameter of 80 particles by a transmission electron microscope and obtaining an average value.
(1-2) Transparent thermoplastic resin:
The transparent thermoplastic resin may be at least one selected from the group consisting of 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, At least one selected from the group consisting of a resin and a polymer-alloy resin of a polycarbonate resin is preferable. When such a security film containing a transparent resin is used in a plastic card such as an IC card and an electronic passport, an offset printed sheet layer can be disposed under the security film. By the transparency of the security film like DI, it is possible to visually check color-printed characters and images on the print layer.
Among these transparent thermoplastic resins, a polycarbonate resin and a polymer-alloy resin with amorphous copolyester resin are preferable, and a polycarbonate resin is more preferable. Since a security film requires a stable persistence of a high security function, a transparent thermoplastic resin as a base (base) thereof is required to have strength, toughness, heat resistance, and moisture resistance. These resins meet the demand. Further, it is considered that the security film of the present invention is often used in the form of a card, in which a plurality of sheets are laminated by heat rather than being used singly. In such a use form, it is necessary to arrange the sheets of the same kind as the security film of the present invention in the upper layer, lower layer, or both (upper and lower layers) of the security film of the present invention and heat laminate them, have. Therefore, such a transparent thermoplastic resin satisfies such a demand. Therefore, the resin is suitable for the above-mentioned use.
The transparent thermoplastic resin preferably has a glass transition temperature of 80 占 폚 or higher, more preferably 80 占 폚 to 160 占 폚, and particularly preferably 90 占 폚 to 150 占 폚. When the glass transition temperature of the transparent thermoplastic resin falls within the above range, deformation due to heat (heat due to direct sunlight or the like for example) hardly occurs in the actual use environment of a card such as an IC card and an electronic passport, . A data page of a plastic card non-electronic passport (e-passport) such as an IC card is manufactured by stacking and heating a plurality of sheets (laminated sheets), but it is possible to set the heating temperature to 200 DEG C or less. That is, the laminated sheet can be heated at a temperature of 200 DEG C or less to fuse each sheet. In view of this, there is an advantage that a general-purpose device such as a vacuum compression molding machine can be used as an apparatus used in a heating process. If the glass transition temperature is lower than 80 캜, thermal deformation or the like may occur in a card such as an IC card and an electronic passport under a temperature in an actual use environment.
(1-3) Other ingredients:
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-based, olefin-based, or amide-based lubricant.
Examples of the phenolic thermal stabilizers include Aderusta AO-20, AO-30, AO-30, etc., such as Sumilizer GM, GS, GP, GA-80, MDP-S, WX-R, WX- 40, AO-50, AO-60, AO-330 (ADEKA).
Examples of heat stabilizers for the phosphorus include GSK-101 (SAKAI CHEMICAL CO., LTD.) Such as adecaster PEP-8, PEP-8W, PEP36, HP-10, 2112, 1500 and 3010 (ADEKA).
Examples of the sulfur-based thermal stabilizers include Sumiraiza TPL-R, TPM, TPS, TP-D (Sumitomo Chemical Industries), Adekasta A0412S (ADEKA) and the like.
These heat stabilizers may be used alone or in combination. When used in combination, it is preferable to use a combination of a phenol-based heat stabilizer and a phosphorus-based heat stabilizer, or a combination of a phenol-based heat stabilizer and a sulfur-based heat stabilizer.
An effect of suppressing thermooxidation deterioration of the transparent thermoplastic resin can be obtained in the step of producing the pellets by melt kneading extrusion molding of the photoluminescent particles and the transparent thermoplastic resin including such heat stabilizers. Further, even in the step of producing a security film by melt-kneading extrusion molding using the pellets, an effect of suppressing thermal deterioration of the transparent thermoplastic resin is obtained. The "process for producing pellets" is a process for producing a transparent thermoplastic resin compound pellet for a security film, that is, a " process for producing a compound for a security film "
Examples of ester-based lubricants include Rikesta EW440A, Rikemaru S-100A, Rikemaru SL800, SL900, SL900A (Riken Vitamin Co., Ltd.), Ricoh wax OP, E and Rikorubu WE4 (Clariant Japan) .
Examples of the olefinic lubricant include Ricohbu H12, Ricoh wax PE520, PED191 (Clariant Japan), etc., such as high wax high density type, polypropylene decomposition type, oxidation type, acid denaturation type and special monomer denaturation type (Mitsui Chemicals) .
Examples of the amide-based lubricant include kao wax EB-G, EB-P, EB-FE (Kao Company), and Recorubu FA1 (Clariant Japan).
Such a lubricant may be used alone or in combination, but it is preferable to use an ester-based lubricant alone or an ester-based lubricant and an olefin-based lubricant.
The friction between the molding machine wall and the screw wall and the molten resin can be reduced in the step of producing the pellets by melt kneading extrusion molding of the photoluminescent particles and the transparent thermoplastic resin containing such a lubricant. In addition, there is an effect of suppressing deterioration of thermal oxidation due to long-term retention of the molten resin and suppressing molecular cutting of the molten resin. Further, even in the step of producing the security film by the melt-kneading extrusion molding using the pellets, the friction between the molding machine wall and the screw wall and the molten resin can be reduced and the deterioration of thermal oxidation deterioration due to the long- And molecular cutoff of the molten resin. The "process for producing pellets" is a process for producing a transparent thermoplastic resin compound pellet for a security film, that is, a " process for producing a compound for a security film "
In this respect, 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 wt%, more preferably 0.1 to 1.0 wt%, and the lubricant is added in an amount of 0.01 to 2 wt% , More preferably 0.1 to 0.6 wt%.
In the security film of the present invention, conventionally known additives and the like may be appropriately compounded as necessary.
The security film of the present invention preferably has a thickness of 30 to 500 m and a thickness of 50 to 200 m. Particularly, when it is used in a transparent over sheet such as an IC card (a card including an ID card), it is preferably 50 to 125 m. Since the thickness of the security film is in the above-mentioned range, it can be controlled within the thickness of a generally used card.
In addition, in the case of being used for an e-passport and an IC card, the e-passport and the card are generally of a laminated structure, and their thickness is limited. Therefore, if the thickness of the transparent over sheet (transparent over sheet or transparent laser marking over sheet) of the total thickness such as the passport is over 500 mu m, the entire thickness of the passport and the IC card becomes too thick. If the thickness of the security film is less than the lower limit value, there is a fear that the degree of infrared light emission is small and it becomes difficult to detect light emission. That is, a security film with high sensitivity can not be obtained. The "transparent laser marking over sheet" is a transparent over sheet capable of laser marking.
The security film of the present invention preferably has a total light transmittance of 80% or more, more preferably 85% or more. If the total light transmittance of the security film is within the above range, the security film may be said to be a transparent film. Therefore, the security film of the present invention can be preferably used as a transparent layer constituting the outermost layer in a card such as an IC card and a data page of an e-passport. In this case, although the print layer (the layer on which the image or the like is printed) is disposed under the security film, the image of the print layer can be clearly identified. The "total light transmittance" is a value obtained when a security film is measured using a transmittance tester (for example, haze meter NDH-4000 manufactured by Nippon Color Industries Co., Ltd.).
(1-4) Use of security film:
The security film of the present invention can be used as an e-passport or a plastic card, and is particularly preferably used as a card for handling personal information of a government ID card, a driver's license, and a health insurance card. Such a "card handling personal information of the government" is required to be difficult to easily falsify, and the security film of the present invention is a film used for such a card and is consistent with the purpose thereof.
When the security film of the present invention is used in a passport (i.e., when the security film of the present invention is used as a film constituting the ePassport), the security film of the present invention is a film constituting a hinge sheet of a passport Is preferably used. As described above, when the film is used as a film for constituting the hinge sheet, the material (location) of the security film, which is a security element, is hard to be easily identified and has a higher security function.
FIGS. 2 and 3 show the
(2) Method of producing security film:
The security film of the present invention can be produced, for example, as follows.
(2-1) Fabrication process of photoluminescent particles:
First, photoluminescent particles are produced by the following method (photoluminescent particle production process). Specifically, specific inorganic compounds (oxides, hydroxides, etc.) are uniformly mixed and ground, heated and fired at a predetermined temperature in a single stage or in multiple stages, and then pulverized to prepare predetermined composition photoluminescent particles.
Further, it is preferable to further carry out a step (surface treatment step) of treating the surface of the obtained particles.
Surface treatment processes include dry treatment, wet treatment, and integral blend. In the dry treatment, pulverization and surface treatment of particles are carried out simultaneously by injecting the photoluminescent particles and the surface treatment agent into a high-speed stirrer such as a disc mill. The wet treatment is usually carried out by pulverizing the particles in a high-speed stirrer such as a disk mill and then introducing the pulverized particles, water or solvent into a heatable and stirrable closed type stirrer, The surface treatment agent aqueous solution or solution) is dropped all at a predetermined rate or dropwise, and then the stirring is continued for a predetermined time. Thereafter, water or a solvent is removed by a method such as depressurization to obtain surface-treated photoluminescent particles.
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 manufacturing process.
Such surface treatment is appropriately selected according to the functions, applications, and the like of the security film.
(2-2) Compound for security film Manufacturing process:
Next, the transparent thermoplastic resin, the obtained photoluminescent particles, the stabilizer, and the lubricant are used to produce a compound for a security film. More specifically, the raw materials are put into a closed mixer, homogeneously stirred, and melt-mixed at a predetermined temperature using a twin-screw extruder with a strand die. Then, compound pellets are produced by melt extrusion molding in a strand die.
(2-3) Film manufacturing process:
Next, the obtained compound pellets are melt-extruded at a predetermined temperature using a single-screw or twin-screw extruder equipped with a T-die to produce a transparent film.
In addition, in the film production process, conventionally known additives and the like may be added, if necessary, in addition to the above components.
[Example]
Hereinafter, the present invention will be described concretely with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.
(Production Example 1) Production of UV light excitation (excitation) infrared luminescent particle A:
After the first raw materials were uniformly mixed, the mixture was charged in an alumina crucible in the air, and the temperature was elevated to 1450 DEG C for 3 hours in an electric furnace, and the mixture was maintained for 10 hours. Thereafter, it was cooled to room temperature. 1.9537 g (0.0099 mol) of BaCO 3 , 1.5071 g (0.01 mol) of SnO 2 and 0.0286 g (0.0001 mol) of Na 2 CO 3 .10H 2 O were compounded as the first raw material.
The obtained inorganic composite metal oxide was pulverized with a desk mill (vibration disc mill RS200, Leche) to obtain photoluminescent particles having an average particle diameter of 1 mu m.
The photoluminescent particles were measured for the excitation wavelength spectrum and the emission wavelength spectrum by a spectrofluorophotometer (Hitachi Spectrofluorophotometer F-7000). As a result, the photoluminescent particles had an excited peak wavelength of 380 nm and a luminescent peak wavelength of 930 nm.
(Production Example 2) Production of visible light-excited infrared luminescent particle B:
The second raw material described below was uniformly mixed in the closed reactor and then heated at 100 캜 to volatilize the water. Thereafter, the temperature was gradually raised to 200 DEG C to proceed the decomposition reaction of citric acid, which is an organic acid, to obtain a mixture. The mixture was placed in an electric furnace and subjected to a high-temperature heat treatment at 900 占 폚 for 2 hours. Thereafter, it was cooled at room temperature. Thus, an inorganic composite metal oxide was obtained. The second raw material, (NH 4) 6Mo7O 2 4 · 4H 2 O is 3.530g (0.02mol), Nd (NO 3) 3 O · 5H 2 O is 0.068g (0.0002mol), Ca (NO 3 ) 4.722 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 (vibration disk mill RS200, Leche) to obtain photoluminescent particles having an average particle diameter of 1 mu m.
The photoluminescent particles were measured for the excitation wavelength spectrum and the emission wavelength spectrum by a spectrofluorophotometer (Hitachi Spectrofluorophotometer F-7000). As a result, the photoluminescent particles had an excitation peak wavelength of 585 nm and an emission peak wavelength of 1065 nm.
(Production Example 3) Production of UV light visible light-excited infrared light-emitting particle C:
After the third raw materials described below were uniformly mixed in a ball mill, inorganic composite metal oxides (calcined product) were obtained by the following three-step calcination. The obtained fired product was pulverized with a disc mill (vibration disc mill RS200, Leche) to obtain photoluminescent particles having an average particle diameter of 1 mu m. The third raw material contained 49.68g (0.22mol) of Y 2 O 3 , 12.02g (0.20mol) of SiO 2 , 37.85g (0.21mol) of V 2 O 5 , Nd 2 O 3 , 0.336 g (0.001 mol) of Er 2 O 3 , and 0.114 g (0.0003 mol) of Er 2 O 3 . <First Step>
The mixture was charged in an alumina crucible and heated in an electric furnace at 650 DEG C for 4 hours in an atmosphere. The mixture was cooled at room temperature and pulverized to obtain particles having an average particle diameter of 10 mu m. <Second Step>
Next, the fired product obtained in the first step was heated in an electric furnace at 1100 DEG C for 4 hours in an atmosphere, and then cooled to room temperature to obtain particles having an average particle diameter of 3 mu m. <Step 3>
Next, the fired product obtained in the second step was heated in an electric furnace at 600 DEG C for 2 hours in an atmosphere, and then cooled to room temperature.
The photoluminescent particles were measured for the excitation wavelength spectrum and the emission wavelength spectrum by a spectrofluorophotometer (Hitachi Spectrofluorophotometer F-7000). As a result, the photoluminescent particles had an excited peak wavelength of 320 nm and a luminescent peak wavelength of 1050 nm.
(Production Example 4) Preparation of UV light-excited infrared luminescent particle A surface-treated product D:
10 g of the UV photoexcitation infrared ray emitter particle A obtained in Production Example 1 and 200 g of toluene were placed in an autoclave equipped with a dropping apparatus. Subsequently, while heating to 60 占 폚 and stirring, 1/100 N hydrochloric acid water (water:? -MPTS (? -Methacryloxytrimethoxysilane), molar ratio 1: 3) and 0.6 g of? Minute. Thereafter, the temperature was raised to 80 占 폚, stirring was continued for 3 hours, and then the mixture was cooled to room temperature.
Thereafter, toluene and methanol as a hydrolysis product of γ-MPTS were removed by evaporator at 40 ° C. under reduced pressure. Thereafter, it was dried in a vacuum drier at 60 ° C overnight to obtain a surface treatment product D of a UV light excitation infrared luminescent particle A.
(Production Example 5) Preparation of UV-excited infrared luminescent particle A surface-treated article E:
1 g of fatty acid monoglyceride (Rikemaru S-100, Riken Vitamin Co., Ltd.) and 10 g of toluene were placed in a sealed container equipped with a stirrer to dissolve the fatty acid monoglyceride to obtain a dissolved product. Thereafter, 1 g of the UV photo-excited infrared luminescent particles A obtained in Production Example 1 was mixed with the above-mentioned lysate, and stirring was continued at room temperature for 60 minutes to prepare a toluene dispersion of the UV light-excited infrared luminescent particles A. Thereafter, it was dried in a vacuum dryer at 60 ° C overnight to obtain a surface-treated product E of "UV photoexcitation infrared ray luminescent particle A" treated with a special fatty acid ester.
(Production Example 6) Preparation of UV light excitation infrared luminescent particle A surface-treated product F:
10 g of the UV photo-excited infrared ray emitter particle A, 2.0 g of? -Olefin-maleic anhydride copolymer diacarna 30 (Mitsubishi Co., Ltd.), and 2.0 g of zirconia bead were mixed in a zirconia bezel using a planetary ball mill Were added. Thereafter, stirring at 500 rpm for 3 hours was continued to obtain a surface-treated product F of the UV photo-excited phosphor particle A.
(Example 1)
0.1% by weight of the UV photo-excited infrared ray emitter particle A obtained in Production Example 1, 0.1% by weight of a phenolic heat stabilizer (Sumilizer GA-80, Sumitomo Chemical Industries, Ltd.) (PEP-8, ADEKA), and 0.2 wt% of an ester-based lubricant (Ricoh Wax E, Clariant) were added to obtain a composition. Thereafter, the above composition was stirred and mixed at 260 DEG C and at a rotation speed of 50 rpm for 5 minutes using a laboratory sintering mill (Dong Yang Chemical Co., Ltd.) to obtain a uniform polycarbonate resin composition S-1.
This polycarbonate resin composition S-1 was heated and pressed under vacuum at 280 캜 and 2 MPa in a vacuum press (Kitagawa Jing-ichi), and then cooled to room temperature to obtain a transparent film P-1 having a thickness of 100 탆.
Thereafter, the transparent film P-1 was observed with an enlargement microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.). As a result, it was confirmed that the UV light-excited infrared light emitting material particles A were uniformly dispersed in a monodisperse state without aggregation Respectively. The average particle diameter of the UV light-excited infrared luminescent particles A in this film was 1.8 μm.
The total light transmittance of this transparent film P-1 was measured using a haze meter (haze meter NDH7000, manufactured by Nippon Shokuhin Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 86% and the transparency was good.
For the transparent film P-1, the excitation wavelength spectrum and the emission wavelength spectrum were measured by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm .
Since the detection sensitivity of the peak wavelength was 3.0 x 10 4 counts, it was confirmed that the security film had sufficient detection sensitivity.
It was confirmed that this transparent film P-1 is useful as a security film. The results are shown in Table 1.
[Table 1]
(Note 1) Amount of photoluminescent particles: Indicates the actual mixture amount of photoluminescent particles excluding the surface treatment agent.
(Example 2)
Transparent film P-2 was obtained in the same manner as in Example 1, except that the UV light-excited infrared light-emitting material particle A of Example 1 was changed to the visible light-excited infrared light emitting material particle B obtained in Production Example 2. [
This transparent film P-2 was observed with an enlarging microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the UV light-excited infrared light-emitting body particles B were homogeneously dispersed in a monodisperse state without aggregation.
The total light transmittance of this transparent film P-2 was measured using a haze meter (haze meter NDH7000 manufactured by Nippon Shokuhin Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 84% and the transparency was good.
The excitation wavelength spectrum and the emission wavelength spectrum of this transparent film P-2 were measured by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 585 nm and the luminescence peak wavelength was 1065 nm .
Since the detection sensitivity of the peak wavelength is 2.8 x 10 4 counts, it can be confirmed that the security film has sufficient detection sensitivity.
It was confirmed that this transparent film P-2 is useful as a security film. The results are shown in Table 1.
(Example 3)
Transparent film P-3 was obtained in the same manner as in Example 1, except that the UV light-excited infrared light-emitting body particle A of Example 1 was changed to the visible light-excited infrared light-emitting body particle B obtained in Production Example 3.
This transparent film P-3 was observed with an enlarging microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the UV light-excited infrared light emitting material particles C were uniformly dispersed in a monodispersed state without aggregation.
The total light transmittance of this transparent film P-3 was measured using a haze meter (haze meter NDH7000, manufactured by Nippon Shokuhin Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 85% and the transparency was good.
The excitation wavelength spectrum and the emission wavelength spectrum of this transparent film P-3 were measured by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 320 nm and the luminescence peak wavelength was 1050 nm .
Since the detection sensitivity of the peak wavelength was 2.9 x 10 4 counts, it was confirmed that the security film had sufficient detection sensitivity.
It was confirmed that this transparent film P-3 is useful as a security film. The results are shown in Table 1.
(Example 4)
Except that the UV photo-excited infrared luminescent particle A of Example 1 was changed to 0.11 wt% of the surface-treated product D of visible light-excited infrared luminescent particle A obtained in Production Example 4 (0.1 wt% by the particle A) 1, a transparent film P-4 was obtained.
The transparent film P-4 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the surface-treated product D of the photoexcited infrared luminescent particle A was uniformly dispersed in a monodisperse state without aggregation Respectively.
The total light transmittance of this transparent film P-4 was measured using a haze meter (haze meter NDH7000, manufactured by Nippon Shokuhin Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 89% and the transparency was good.
The excitation wavelength spectrum and the emission wavelength spectrum of this transparent film P-4 were measured by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm .
Since the detection sensitivity of the peak wavelength was 3.9 x 10 4 counts, it was confirmed that the security film had sufficient detection sensitivity.
It was confirmed that this transparent film P-4 is useful as a security film. The results are shown in Table 1.
(Example 5)
Except that the UV photoexcitation infrared luminescent particle A of Example 1 was changed to 0.2 wt% of the surface-treated product D of visible light-excited infrared luminescent particle A obtained in Production Example 5 (0.1 wt% by the particle A) 1, a transparent film P-5 was obtained.
The transparent film P-5 was observed with an enlarging microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the surface-treated product E of the photoexcited infrared luminescent particles A was uniformly dispersed in a monodisperse state without aggregation Respectively.
The total light transmittance of this transparent film P-5 was measured using a haze meter (haze meter NDH7000, manufactured by Nippon Shokuhin Kogyo Co., Ltd.). As a result, it was confirmed that the total light transmittance was 88% and the transparency was good.
As a result of measuring the excitation wavelength spectrum and the light emission wavelength spectrum of this transparent film P-5 by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), it was confirmed that the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm .
Since the detection sensitivity of this peak wavelength is 3.8 x 10 4 counts, it can be confirmed that the security film has sufficient detection sensitivity.
It was confirmed that this transparent film P-5 is useful as a security film. The results are shown in Table 1.
(Example 6)
Except that the UV photoexcitation infrared luminescent particle A of Example 1 was changed to 0.12 wt% of the surface-treated product D of the visible light-excited infrared luminescent particle A obtained in Production Example 6 (0.1 wt% in terms of the particle A) 1, a transparent film P-6 was obtained.
This transparent film P-6 was observed with an enlarging microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the surface-treated product F of the photoexcited infrared luminescent particle A was uniformly dispersed in a monodisperse state without aggregation Respectively.
The total light transmittance of this transparent film P-6 was measured by using a haze meter (haze meter NDH7000, manufactured by Nippon Shokin Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 89% and the transparency was good.
With respect to this transparent film P-6, the excitation wavelength spectrum and the emission wavelength spectrum were measured by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm .
Since the detection sensitivity of this peak wavelength is 3.8 x 10 4 counts, it can be confirmed that the security film has sufficient detection sensitivity.
It was confirmed that this transparent film P-6 is useful as a security film. The results are shown in Table 1.
(Example 7)
100 parts by weight of an acrylic resin (Acryphet VRL40, manufactured by Mitsubishi Rayon Co., Ltd.), 0.11% by weight (0.1% by weight as a particle A) of the surface treatment D of the UV photoexcitation infrared luminescent particles A obtained in Preparation Example 1, 0.1 part by weight of ester (Rikesta EW-440A, Riken Vitamin) and 0.1 part by weight of glycerin mono fatty acid ester (Rikesta S-100A, Riken Vitamin Co., Ltd.) , 240 DEG C, and 100 rpm for 5 minutes to obtain a uniform acrylic resin composition.
This acrylic resin composition was pressed and pressed under vacuum at 260 DEG C and 2 MPa in a vacuum press (Kitagawa Co., Ltd.). Thereafter, the film was cooled to room temperature to obtain a transparent film P-7 having a thickness of 100 m.
This transparent film P-7 was observed with an enlarging microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the UV light-excited infrared light-emitting body particles A were uniformly dispersed in a monodispersed state without aggregation.
The total light transmittance of this transparent film P-7 was measured using a haze meter (haze meter NDH7000, manufactured by Nihon Furun Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 90% and the transparency was good.
With respect to this transparent film P-7, the excitation wavelength spectrum and the emission wavelength spectrum were measured by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm .
Since the detection sensitivity of the peak wavelength was 3.9 x 10 4 counts, it was confirmed that the security film had sufficient detection sensitivity.
It was confirmed that this transparent film P-7 is useful as a security film. The results are shown in Table 1.
(Example 8)
Except that the UV photoexcited infrared luminescent particle A of Example 1 was changed to 0.011 wt% of the surface-treated product D of the visible light-excited infrared luminescent particle A obtained in Production Example 6 (0.1 wt% in terms of the particle A) 1, a transparent film P-8 was obtained.
This transparent film P-8 was observed with an enlarging microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the UV light-excited infrared light-emitting body particles A were uniformly dispersed in a monodisperse state without aggregation.
The total light transmittance of this transparent film P-8 was measured using a haze meter (haze meter NDH7000, manufactured by Nippon Shokuhin Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 90% and the transparency was good.
The excitation and emission wavelength spectra of this transparent film P-8 were measured by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm .
Since the detection sensitivity of the peak wavelength is 2.1 x 10 4 counts, it can be confirmed that the security film has sufficient detection sensitivity.
It was confirmed that this transparent film P-8 is 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-photo-excited infrared luminescent particle A surface-treated product D of Example 8 was changed to 1.1 weight% (1.0 weight% of the particles A).
This transparent film P-9 was observed with an enlarging microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the UV light-excited infrared light-emitting body particles A were homogeneously dispersed in a monodisperse state without aggregation.
The total light transmittance of this transparent film P-9 was measured using a haze meter (haze meter NDH7000, manufactured by Nippon Shokuhin Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 82% and the transparency was good.
For the transparent film P-9, the excitation wavelength spectrum and the emission wavelength spectrum were measured by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm .
Since the detection sensitivity of the peak wavelength was 12 x 10 4 counts, it was confirmed that the security film had sufficient detection sensitivity.
It was confirmed that this transparent film P-9 is 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 photo-excitation infrared luminescent particles A of Example 1 was changed to 0.001% by weight.
The transparent film P-10 was observed with an enlarging microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and it was confirmed that the UV light-excited infrared light-emitting body particles A were uniformly dispersed in a monodisperse state without aggregation.
The total light transmittance of this transparent film P-10 was measured using a haze meter (haze meter NDH7000, manufactured by Nihon Furun Kogyo Co., Ltd.), and it was confirmed that the total light transmittance was 90% and the transparency was good.
The excitation wavelength spectrum and the emission wavelength spectrum of this transparent film P-10 were measured by a spectrofluorophotometer (Hitachi Spectrofluorophotometer F-7000), and it was confirmed that the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm .
Since the detection sensitivity of such a peak wavelength is 0.2 x 10 4 counts, it can be said that the detection sensitivity is insufficient as a security film, and this transparent film P-10 is not practical as a security film. The results are shown in Table 2.
[Table 2]
(Note 1) Amount of photoluminescent particles: Indicates the actual mixture amount of photoluminescent particles excluding the surface treatment agent.
(Comparative Example 2)
A film P-11 was obtained in the same manner as in Example 1 except that the mixing amount of the UV photo-excited infrared luminescent particles A in Example 1 was changed to 1.2 wt%.
This transparent film P-11 was observed with a magnifying microscope (universal zoom microscope MULTIZOOM AZ100, Nikon Instruments Co.), and partial aggregation of the UV light excitation infrared light emitting particle A was observed.
P-11 was measured for the excitation wavelength spectrum and the emission wavelength spectrum by a spectrofluorophotometer (Hitachi spectrofluorophotometer F-7000). As a result, the excitation peak wavelength was 380 nm and the luminescence peak wavelength was 930 nm.
Since the detection sensitivity of such a peak wavelength is 7.5 x 10 4 counts, it can be confirmed that the security film has sufficient detection sensitivity.
However, this film P-11 has a sufficient detection sensitivity, but is inferior in transparency, and there is a problem that the image of the print layer disposed on the lower layer of the present security film becomes unclear. Therefore, it is not practical as a security film for applications requiring transparency. The results are shown in Table 2.
As described above, it was confirmed that the transparent films (security films) of Examples 1 to 9 have a high security function of emitting light well when irradiated with light, and are excellent in transparency.
The security film of the present invention can be used as a film constituting a card such as an ID card and an electronic passport.
10: Security film,
11: Photoluminescent particles
12: Transparent thermoplastic resin
20: Data page
21: Hinge sheet, thread binding
30: Visa sheet
40: sewing thread
50: Cover
51: Protector sheet
60:
100: The ePassport.
Claims (6)
The photoluminescent particle is an infrared photoluminescent particle that emits infrared rays through irradiation with UV light or visible light,
Wherein the photoluminescent particles are at least one 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) ≪ / RTI >
The above-mentioned photoluminescent particles are dispersed in the transparent thermoplastic resin in an amount of 0.01 to 1.0% by weight,
The compound represented by the following general formula (1) is a light emitting substance which is excited by UV light to emit infrared light,
The compound represented by the following general formula (2) is a phosphor that emits visible light and excites it and emits infrared rays,
The compound represented by the following general formula (3) is a light-emitting substance which is excited by UV light or visible light to emit infrared light,
Wherein the surface of the photoluminescent particles is treated with an organic substance and the organic substance is at least one functional group selected from the group consisting of organic silicon compounds, metal complex compounds, fatty acid compounds, alkoxy groups, maleic anhydride groups, epoxy groups, acetamide groups, and oxazoline groups At least one kind of organic substance selected from the group consisting of organic polymer containing functional group, oligomer, and vinyl pyrrolidone,
Security film with total light transmittance of 85% or more.
Formula (1): Ba 1-X SnA X O 3 (0 <X <0.4, A is Li or Na)
(2): CaMoO 4 : M (M is one or two or more kinds of Lankan group metal ions selected from the group consisting of Nd 3+ , Yb 3+ , and Er 3+ )
(3): Y 2 SiV 2 O 10 : Nd 3+ , Er 3+
Wherein the transparent thermoplastic resin has a glass transition temperature of 80 캜 or higher.
Wherein the transparent thermoplastic resin further contains a stabilizer and a lubricant,
Wherein the stabilizer is at least one selected from the group consisting of phenolic, phosphorus, and sulfur-based stabilizers, and the lubricant is at least one selected from the group consisting of ester, olefin, and amide lubricants.
Wherein the transparent thermoplastic resin is at least one selected from the group consisting of 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 naphthalene resin and an amorphous copolyester resin And a polymer-alloy resin of a polycarbonate resin.
A security film comprising the hinge sheet of the ePassport.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2014043309A JP6339382B2 (en) | 2014-03-05 | 2014-03-05 | Security film |
| JPJP-P-2014-043309 | 2014-03-05 | ||
| PCT/JP2015/055981 WO2015133412A1 (en) | 2014-03-05 | 2015-02-27 | Security film |
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| KR101762740B1 true KR101762740B1 (en) | 2017-07-28 |
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| JP6360641B1 (en) * | 2017-03-06 | 2018-07-18 | 日本碍子株式会社 | Security ink pigment, security ink, printed matter and method for producing security ink pigment |
| JP6286108B1 (en) | 2017-03-06 | 2018-02-28 | 日本碍子株式会社 | Security ink pigment, security ink, printed matter and method for producing security ink pigment |
| ES2814623T3 (en) | 2017-03-20 | 2021-03-29 | Sicpa Holding Sa | Photoluminescent iron doped barium stannate material, security ink composition and security feature of the ink |
| JP2020075487A (en) * | 2018-09-28 | 2020-05-21 | 三菱瓦斯化学株式会社 | Multilayer body, authenticity discrimination method, authenticity discrimination system, and program |
| JP7457313B2 (en) * | 2018-10-22 | 2024-03-28 | 三菱瓦斯化学株式会社 | Thermoplastic resin flat plate-shaped molded body, multi-layer body, authenticity determination method, authenticity determination system, and program |
| KR102027444B1 (en) * | 2019-01-25 | 2019-10-02 | 나노씨엠에스(주) | Near infrared luminescent material excited by near infrared ray and method of manufacturing the same |
| JP6871464B1 (en) | 2020-08-18 | 2021-05-12 | 三菱瓦斯化学株式会社 | Resin composition, resin sheet, multilayer body, and card |
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| JP2012242408A (en) * | 2011-05-16 | 2012-12-10 | Dainippon Printing Co Ltd | Hologram sheet |
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| JP3491101B2 (en) * | 1993-10-05 | 2004-01-26 | 日立マクセル株式会社 | Ink composition and printed matter using this ink composition |
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| JPH11138974A (en) | 1997-11-10 | 1999-05-25 | Nippon Soda Co Ltd | Ink for preventing forgery and toner for electrophotography |
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| BRPI0609824B1 (en) * | 2005-03-17 | 2022-09-27 | Dow Global Technologies Inc | POLYMERIC MIXTURE AND GASKET COMPOSITION |
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| JP2003103707A (en) * | 2001-09-28 | 2003-04-09 | Yupo Corp | Forgery preventing film |
| JP2012242408A (en) * | 2011-05-16 | 2012-12-10 | Dainippon Printing Co Ltd | Hologram sheet |
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| KR20160045789A (en) | 2016-04-27 |
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