KR101957927B1 - Upconversion anti-counterfeiting film, preparation method thereof and anti-counterfeiting article comprising the same - Google Patents

Abstract

The present invention relates to an anti-counterfeiting film having an upconversion light emitting property, a manufacturing method thereof and an anti-counterfeiting object comprising the same. The anti-counterfeiting film comprises: an anti-counterfeiting layer at which a predetermined light emitting pattern comprising a photosensitizer and a first electron acceptor is formed; and a first hydrophilic oxygen blocking layer arranged at one side of the anti-counterfeiting layer.

Description

TECHNICAL FIELD [0001] The present invention relates to an up-conversion anti-falsification film, a manufacturing method thereof, and an anti-falsification article including the anti-

The present invention relates to an anti-falsification film to which an upconversion (upconversion, hereinafter referred to as "UC") technique of photon energy is applied, a manufacturing method thereof, and an anti-falsification article including the anti-falsification film.

Anti-counterfeiting technology is one of the fields that many companies and government agencies pay particular attention to for the high level of security of oil products or money. Examples of the anti-counterfeiting technology include the production of a fine pattern which is hard to be visually recognized, the printing of a pattern having a light emission characteristic, and the production of a hologram.

The printing of the pattern having the light emission characteristic is widely applied to money, credit cards, and the like because it is easy and quick to identify whether or not falsification has occurred. Specifically, the pattern having the luminescent characteristics is formed by a process of printing on a product by mixing an illuminant (chromophore) which absorbs light in the ultraviolet region and emitting light in the visible light region, The process is easy and various characters and shapes can be easily implemented. However, it has a disadvantage in that it can be easily falsified by replacing it with a substance having an emission spectrum similar to that of the above-mentioned light emitting body. Therefore, in recent years, there have been studies to apply anti-counterfeiting technology to UC materials, which have unique luminescent properties. Here, UC refers to a photochemical process in which two or more photons having a low energy are fused and converted into photons having one high energy.

Conventional anti-counterfeiting technologies use light emitting materials to absorb light in the ultraviolet region to emit light in the visible light region, while UC material absorbs photons (e.g., near-infrared light) having a wavelength larger than the visible light region, Emits light in the region. This phenomenon, also called anti-stokes emission, is an artificial phenomenon realized only by a combination of special oil and inorganic materials.

The UC material can be classified into two types, one of which is an inorganic material obtained by doping a rare earth metal, which is a host material, with a metal or another rare earth metal. Such an inorganic material is printed on a substrate by an ink-jet method to form a pattern having a light-emitting property.

However, in order to emit a UC material based on an inorganic material, near infrared rays having a very strong output (several to several tens W / cm 2 or more) must be irradiated, which lowers accessibility, is opaque, and has low flexibility. Further, in the case of a pattern formed by an ink-jet method, there is a problem that it is difficult to form a fine structure pattern because the pattern size is relatively large or the interval between patterns is wide.

The other one of the UC materials is an organic material obtained by introducing a photosensitizer and an electron acceptor into a polymer. Such an organic material has high quantum efficiency and exhibits light emission characteristics in a near-infrared light having a relatively low output (several to several tens of mW / cm 2), and is excellent in transparency and flexibility. However, the organic material is not suitable for forming a pattern by a conventional ink-jet method, and has a problem that the luminescent characteristics are significantly lowered when oxygen is exposed.

Korean Patent Publication No. 2006-0016297

An object of the present invention is to provide an anti-fake film having a fine pattern structure including up-conversion luminescent characteristics and excellent in physical properties such as anti-falsification, flexibility, transparency and oxygen barrier property, and a method for producing the same.

The present invention also provides an anti-counterfeit article comprising the anti-counterfeit film.

According to an aspect of the present invention, there is provided an anti-falsification device comprising: an anti-falsification layer having a predetermined light emission pattern including a light-sensitive material and a first electron acceptor; And a first hydrophilic oxygen barrier layer disposed on one side of the anti-fake layer.

Wherein the anti-fake layer is provided in the matrix polymer comprising at least one member selected from the group consisting of polyurethane, polyisobutylene, polyethylene, polypropylene, polyester, polystyrene, cellulose acetate, polydimethylsiloxane and polycarbonate, And may contain the first electron acceptor.

The anti-fake layer may be such that the emission pattern is distinguishable by triplet-triplet annihilation based UpConversion between triplet-triplet annihilation between the photosensitizer and the first electron acceptor.

The photosensitizer may be at least one selected from the group consisting of a porphyrin compound having a metal atom, a phthalocyanine compound having a metal atom bonded thereto, and a thermally activated delayed fluorescence compound.

The first electron acceptor may be a compound that receives electrons from the photosensitizer and emits photons that are upconverted by triplet-triplet extinction.

The first hydrophilic oxygen barrier layer may include a polyvinyl alcohol-based polymer compound.

The anti-fake film of the present invention may further include a hydrophobic oxygen barrier layer disposed on the side of the first hydrophilic oxygen barrier layer opposite to the anti-fake layer.

The hydrophobic oxygen barrier layer may include a photocurable acrylate-based polymer compound.

The anti-fake film of the present invention may further comprise a second hydrophilic oxygen barrier layer disposed on the other side of the anti-fake layer.

The second hydrophilic oxygen barrier layer may include a polyvinyl alcohol-based polymer compound.

The anti-fake film of the present invention may further comprise a support layer disposed as an outermost layer on the other side of the anti-fake layer.

The anti-fake film of the present invention may further include an anti-fake auxiliary layer disposed between the anti-fake layer and the support layer and including a second electron acceptor.

According to another aspect of the present invention, there is provided a method of manufacturing an anti-fake film comprising the steps of: applying a solution for anti-fake layer containing a photo-sensitizer and a first electron acceptor on a support layer to form an anti-fake layer; And applying a first hydrophilic oxygen barrier layer solution containing the hydrophilic polymer on the anti-fake layer to form a first hydrophilic oxygen barrier layer.

In addition, the method for producing an anti-fake film of the present invention may further comprise forming a hydrophobic oxygen barrier layer by applying a hydrophobic oxygen barrier layer solution containing a hydrophobic polymer on the first hydrophilic oxygen barrier layer.

In the method for manufacturing an anti-fake film of the present invention, the step of forming the anti-fake anti-fouling layer may include the steps of forming a second hydrophilic oxygen barrier layer by applying a second hydrophilic oxygen barrier layer solution containing the hydrophilic polymer on the support layer ; And applying a solution for the anti-fake layer on the second hydrophilic oxygen barrier layer to form an anti-fake layer.

Further, in the method for manufacturing an anti-fake film of the present invention, the step of forming the second hydrophilic oxygen barrier layer may include forming a second anti-fake auxiliary layer on the support layer by applying a solution for the anti-fake auxiliary layer containing the second electron acceptor ; And applying the second hydrophilic oxygen barrier layer solution onto the anti-fake auxiliary layer to form a second hydrophilic oxygen barrier layer.

On the other hand, the present invention provides an anti-counterfeit article comprising the anti-counterfeit film.

The anti-fake film of the present invention is characterized in that a hydrophilic oxygen barrier layer and / or a hydrophobic oxygen barrier layer, which blocks the penetration of oxygen, are disposed on one side and / or the other side of the anti-fake layer and have excellent oxygen barrier properties and exhibit high flexibility and transparency . Further, the anti-fake film of the present invention can exhibit anti-falsification by the anti-fake layer having the light emission characteristic and the minute light emission pattern by up-conversion.

Therefore, when the anti-falsification film of the present invention is applied to an anti-falsification article, it is possible to provide an anti-falsification article having a higher level of security.

1 is a cross-sectional view illustrating an anti-falsification film according to an embodiment of the present invention.
FIG. 2 is a reference diagram for explaining a mechanism of up-conversion occurring in the anti-falsification film according to an embodiment of the present invention.
3 is a cross-sectional view illustrating an anti-falsification film according to another embodiment of the present invention.
FIG. 4 is a reference view for explaining the manufacturing process of the anti-falsification film according to an embodiment of the present invention.
5 to 9 are reference views for explaining Experimental Examples 1 to 3 of the present invention.

Hereinafter, the present invention will be described in detail.

1. Anti-counterfeit film and its manufacturing method

The anti-falsification film according to an embodiment of the present invention includes a anti-falsification layer and a first hydrophilic oxygen barrier layer, which will be described with reference to FIG.

The anti-falsification layer 10 included in the anti-falsification film according to an embodiment of the present invention is formed at least partially or entirely of a predetermined light emission pattern including the photosensitive agent and the first electron acceptor. The anti-fake layer 10 serves to prevent forgery or discriminate whether or not the object is falsified. Specifically, in the anti-falsification layer 10, up-conversion (UC) occurs in which two or more photons having low energy are converted into photons having one high energy, the light emission pattern is emitted in a predetermined form, 10), it is possible to prevent forgery or identify whether or not the image is forged.

The up-conversion in the anti-fake layer 10 can be performed by energy transfer and energy fusion by diffusion of the photo-sensitizer and the first electron acceptor included in the anti-fake layer 10. When specifically referring to FIG. 2 and the following equations ((1) to (6)), first, a light-sensitive first (Sens) absorbs a photon of incident and excited by ¹ Sens * state, hanggan cross (Intersystem crossing, ISC ) To generate ³ Sens * (1). In the presence of oxygen, ³ Sens * reacts rapidly with the ground triphasic oxygen to produce singlet oxygen ( ¹ O ₂ ) (2) and in the absence of a triplet quencher such as oxygen, ³ Sens * translocates to the basal state and produces phosphorescence (3). On the other hand, when a first electron acceptor (Acc) with an appropriate energy level is present with a photosensitizer (Sens), ¹ Acc ⁰ is excited via triplet-triplet energy transfer (TTET) ^It receives electrons from ³ Sens * and is excited to ³ Acc * (4) and forms ¹ Acc * via another ³ Acc * and Triplet-triplet annihilation (TTA) (5). Finally, ¹ Acc * transitions to the base state and undergoes an up-conversion fluorescence process (6). In the anti-falsification layer 10, conversion of low-energy photons, that is, up-conversion occurs.

In order to efficiently perform up-conversion in the anti-falsification layer 10, energy transfer between the photosensitizer and the first electron acceptor must be efficiently performed. This is because the photo-sensitizer, the first electron acceptor, May be implemented by appropriate combination of media.

In order to efficiently transfer energy between the photosensitive agent and the first electron acceptor, the photosensitizer and the first electron acceptor may include one or more triplet energy levels of the photosensitizer between the singlet and triplet energy levels of the first electron acceptor (I.e., the energy level of the photosensitizer is sandwiched by the energy level of the first electron acceptor). In order to increase the efficiency of up-conversion, it is preferable that the lifetime of the first electron acceptor ³ Acc * is long (several tens to several hundreds of μs or more), and the intersection cross ratio is also high.

Considering these points, the photo-sensitizer included in the anti-fake layer 10 can be excited by absorbing photons in the visible region or infrared region, and is preferably a compound having a high inter-edge cross-ratio value Do. Specifically, the photo-sensitizer is at least one selected from the group consisting of a porphyrin compound having a metal atom bonded to the center thereof, a phthalocyanine compound having a metal atom bonded to the center thereof, and a thermally activated delayed fluorescence compound desirable. At this time, the metal atom may be Cu, Pd, Pt, Au, or Ir. More specifically, as the photosensitizer, a compound represented by the following formula may be used.

Also, the first electron acceptor included in the anti-fake layer 10 receives electrons from the photosensitizer through triplet-triplet energy transfer (TTET) and is excited into a triplet state, It is preferred that the electron acceptor in the free state is a compound that forms an excited electron acceptor through triple-triple elimination (TTA). Such a first electron acceptor may be, but is not limited to, an aromatic ring compound having a high fluorescence quantum yield. Specifically, as the first electron acceptor, compounds represented by the following formula can be used.

The anti-falsification layer 10 may be formed of a material having a high refractive index in a matrix polymer containing at least one selected from the group consisting of polyurethane, polyisobutylene, polyethylene, polypropylene, polyester, polystyrene, cellulose acetate, polydimethylsiloxane and polycarbonate. And a structure in which the sensitizer and the first electron acceptor are contained (supported). Since the matrix polymer has elasticity and can increase the diffusion property of the photosensitive agent and the first electron acceptor and is flexible and high in transparency, the anti-fake film of the present invention including the anti-fake layer 10 Conversion efficiency is high, and excellent transparency and flexibility can be exhibited.

The wavelength range of the light source irradiated for up-conversion in the anti-fake layer 10 is not particularly limited, but may be 400 to 900 nm.

The shape of the light emission pattern may be a linear shape, a mesh shape, a circular shape, a dot shape, a geometric shape such as a honeycomb shape or a polygonal shape, a letter, a number, or a QR code.

The width of the light emission pattern formed on the anti-fake layer 10 (corresponding to the width of the repeated pattern) is not particularly limited, but may be a fine size in the range of 5 to 20 μm, And when the light emission pattern is formed on at least a part thereof, it may be formed as a whole size area of 300 μm to 2 cm. That is, the anti-falsification layer 10 has a light emission pattern of a fine structure. Since the up-conversion light emission characteristic is combined with the anti-falsification layer 10 in addition to the minute light emission pattern, Can be provided with a higher anti-fake film.

Though the thickness of the anti-fake layer 10 is not particularly limited, it is preferably less than 100 mu m (specifically, 10 to 50 mu m) in consideration of the thinning of the anti-fake film, the fine luminescence pattern and the upconversion efficiency.

The first hydrophilic oxygen barrier layer 20 included in the anti-fake film according to an embodiment of the present invention is disposed on one side of the anti-fake layer 10 to prevent oxygen from penetrating into the anti-fake layer 10 .

If the anti-falsification layer 10 is exposed to the air, the external oxygen may rapidly penetrate the anti-falsification layer 10 and the up-conversion efficiency may be lowered. According to the present invention, The penetration of oxygen into the film 10 can be blocked, thereby improving the up-conversion efficiency and the optical stability of the anti-falsification film. In addition, when the anti-falsification layer 10 is in contact with an organic solvent, the photosensitive polymer and the first electron acceptor contained therein are diffused and eluted to the outside, or the matrix polymer constituting the anti-falsification layer 10 causes a swelling phenomenon The hydrophilic nature of the first hydrophilic oxygen barrier layer 20 may prevent the photo-sensitizer, the first electron acceptor and the matrix polymer of the anti-fake layer 10 from reacting with the organic solvent, Elution of the sensitizer and the first electron acceptor and swelling of the matrix polymer can be prevented.

The material constituting the first hydrophilic oxygen barrier layer 20 is not particularly limited as long as it is a material having excellent hydrophilicity and oxygen barrier property (oxygen permeation preventive property), but it is preferable to use polyvinyl alcohol (polyvinyl alcohol) having excellent transparency and flexibility, alcohol, PVA) based polymer compound. Specifically, the first hydrophilic oxygen barrier layer 20 may be formed of polyvinyl alcohol having a weight average molecular weight of 30,000 to 200,000.

The first hydrophilic oxygen barrier layer 20 may contain (be supported) inorganic particles (such as clay) in order to further improve the oxygen barrier property. Specifically, the first hydrophilic oxygen barrier layer 20 may be made of polyvinyl alcohol containing inorganic particles.

Although the thickness of the first hydrophilic oxygen barrier layer 20 is not particularly limited, it is preferably 1 to 10 占 퐉 in consideration of thinning of the anti-fake film and oxygen barrier properties.

Meanwhile, the anti-falsification film according to an embodiment of the present invention may further include a second hydrophilic oxygen barrier layer 30 disposed on the other side of the anti-falsification layer 10 in order to improve oxygen barrier property, up-conversion efficiency, . The second hydrophilic oxygen barrier layer 30 may have the same role and material as the first hydrophilic oxygen barrier layer 20. Here, the second hydrophilic oxygen barrier layer 30 may also improve the oxygen barrier property of the support layer 50 when the anti-fake film further includes a support layer 50 described later.

The anti-falsification film according to an embodiment of the present invention may be applied to the anti-falsification layer 10 of the first hydrophilic oxygen barrier layer 20 on the opposite side (i.e., the first hydrophilic oxygen barrier layer 20 (The upper side of the hydrophobic oxygen barrier layer 40). The hydrophobic oxygen barrier layer 40 not only enhances the oxygen barrier property of the anti-falsification layer 10 but also protects the first hydrophilic oxygen barrier layer 20, When it comes in contact with moisture, it enhances the physical stability of the first hydrophilic oxygen barrier layer 20.

The first hydrophilic oxygen barrier layer 20 can be dissolved when it is in contact with water due to its hydrophilic (or water-soluble) property. Thus, the application field of the anti-falsification film may be limited. The present invention relates to a water- The hydrophobic oxygen barrier layer 40 having the property of preventing forgery can prevent the forgery preventing film from being dissolved even when it comes into contact with water, thereby widening the application field of the anti-falsification film.

The material constituting the hydrophobic oxygen barrier layer 40 is not particularly limited as long as it is a material having excellent hydrophobicity and oxygen barrier property. However, the hydrophobic oxygen barrier material is excellent in transparency and flexibility as well as transparency and flexibility. / Polymer) compound. Specifically, the photocurable acrylate-based polymer may be at least one selected from the group consisting of urethane acrylate polymer, ester acrylate polymer, and epoxy acrylate polymer.

Although the thickness of the hydrophobic oxygen barrier layer 40 is not particularly limited, it is preferably 20 to 40 占 퐉 in consideration of thinning of the anti-fake film and oxygen barrier properties.

The anti-falsification film according to an embodiment of the present invention may further include a support layer 50 disposed as an outermost layer on the other side of the anti-falsification layer 10 to have a certain level of mechanical strength. 1 showing the anti-fake film according to an embodiment of the present invention, the second hydrophilic oxygen barrier layer 30 is disposed between the support layer 50 and the anti-fake layer 10, The film may have a structure in which the support layer 50 and the anti-falsification layer 10 are directly coupled without the second hydrophilic oxygen barrier layer 30.

The material forming the support layer 50 is not particularly limited, but may be glass, silicon wafer, paper, or a polymer material (e.g., plastic). Specifically, the support layer 50 is preferably made of polyethylene or polyethylene terephthalate (PET) in consideration of flexibility, transparency, economical efficiency, and the like of the anti-falsification film.

The thickness of the support layer 50 is not particularly limited, but it is preferably 100 to 500 占 퐉 in consideration of thinning and strength of the anti-fake film.

Meanwhile, the anti-falsification film according to another embodiment of the present invention may be provided between the anti-falsification layer 10 and the support layer 50 (in the case where the second hydrophilic oxygen barrier layer 30 is present) The second hydrophilic oxygen barrier layer 30 and the support layer 50) and includes a second electron acceptor, as shown in FIG. 3, As follows.

The second electron acceptor included in the anti-fake auxiliary layer 60 may be the same or different from the first electron acceptor included in the anti-fake layer 10. Specifically, the second electron acceptor may be, but is not limited to, an aromatic ring compound having a high fluorescence quantum yield. More specifically, as the second electron acceptor, compounds represented by the following formula may be used.

The anti-fake auxiliary layer (60) may be formed in a matrix polymer comprising at least one member selected from the group consisting of polyurethane, polyisobutylene, polyethylene, polypropylene, polyester, polystyrene, cellulose acetate, polydimethylsiloxane and polycarbonate And the second electron acceptor may be contained.

Though the thickness of the anti-fake auxiliary layer 60 is not particularly limited, it is preferably 10 to 20 占 퐉 in consideration of thinning of the anti-fake film and prevention of forgery.

The anti-falsification film according to the present invention can exhibit excellent anti-falsity by combining the fine light emission pattern and the up-conversion characteristic. Also, it can exhibit improved up-conversion efficiency and high light stability due to excellent oxygen barrier property, and each layer is made of a high-transparency and flexible polymer material, which can also exhibit excellent transparency and flexibility. Therefore, the anti-falsification film of the present invention can be efficiently applied to applications requiring high security.

The anti-falsification film according to an embodiment of the present invention can be manufactured through a process of forming layers by imprinting and spin coating, and a manufacturing method thereof will be described in detail with reference to FIG. 4 .

A second hydrophilic oxygen barrier layer solution (for example, a polyvinyl alcohol aqueous solution) containing a hydrophilic polymer is applied on the prepared support layer 50 and spin coating is performed. Thereafter, the second hydrophilic oxygen barrier layer 30 is formed by drying at room temperature for 10 to 30 minutes.

Next, a solution for the anti-fake layer (curable soft polymer composition) containing the photosensitive agent and the first electron acceptor is coated on the formed second hydrophilic oxygen barrier layer 30, pressed with a replication mold having a predetermined pattern, The anti-falsification layer 10 having a predetermined light emission pattern is formed.

The light-sensitive agent and the first electron acceptor may be dissolved in an organic solvent to be mixed with a solution for the anti-fake layer (curable soft polymer composition) in a solution state. As the organic solvent in which the photosensitive agent and the first electron acceptor are dissolved, conventionally known organic solvents (for example, tetrahydrofuran, toluene, chloroform) may be used. The photosensitizer may be dissolved in an organic solvent at a concentration of 1.0 to 5.0 mM and the first electron acceptor may be dissolved at a concentration of 10 to 500 mM.

When the polyurethane is selected as the matrix polymer of the anti-falsification layer 10, the curable soft polymer material may be a polyurethane (polyurethane) May be a mixture of a polyol component (a subject) and an isocyanate component (a curing agent) capable of forming a curing agent. Since the polyurethane is not completely dissolved in the organic solvent due to a high level of cross-linking after the curing has proceeded, swelling phenomenon may occur. Therefore, in the cured polyurethane, the photosensitive agent and the first electron acceptor Is mixed with an organic solvent in which a photo-sensitizer and a first electron acceptor are dissolved, and then coated, imprinted, and cured by mixing the photo-sensitizer and the organic solvent in which the first electron acceptor is dissolved, into the curable flexible polymer material in which the polyol component and the isocyanate component are mixed, It is preferable to form the anti-fake layer 10. At this time, the curing may be performed at a temperature of 40 to 60 ° C for 1 to 3 hours.

On the other hand, the replica mold used for forming the predetermined luminescent pattern in the anti-fake layer 10 may be one produced through photo-lithography or soft-lithography. Specifically, a fine pattern having a predetermined shape is designed with an AutoCAD program, a master mold is manufactured through photo-lithography, and then the prepared master mold is subjected to soft-lithography a replication mold (stamp mold) of a polydimethylsiloxane material can be produced through a process of replication through a lithography process.

Since such a replica mold is produced through soft-lithography, it can have a pattern of a finer and precise structure, and since the present invention uses this replica mold to form the anti-fake layer 10, The anti-falsification layer 10 having a light emission pattern can be realized.

After the anti-fake layer 10 is formed, a first hydrophilic oxygen barrier layer solution (for example, a polyvinyl alcohol aqueous solution) containing a hydrophilic polymer is coated on the anti-fake layer 10 and spin coating is performed. Thereafter, the first hydrophilic oxygen barrier layer 20 is formed by drying at room temperature for 10 to 30 minutes.

Next, a hydrophobic oxygen barrier layer solution (for example, a photocurable urethane acrylate composition) containing a hydrophobic polymer (photocurable resin) and a photoinitiator is loaded on the formed first hydrophilic oxygen barrier layer 20 and covered with a glass plate The photocuring proceeds to form a hydrophobic oxygen barrier layer 40. At this time, the photocuring may be performed by irradiating ultraviolet rays for 20 to 40 minutes.

The hydrophobic oxygen barrier layer 40 may be formed directly on the anti-fake layer 10 to have similar oxygen barrier properties, transparency and flexibility as the first hydrophilic oxygen barrier layer 20, It is preferable that the first hydrophilic oxygen barrier layer 20 is formed to protect the light-sensitive agent and the first electron acceptor. That is, the hydrophobic oxygen barrier layer 40 is formed by the decomposition and polymerization reaction of the photoinitiator contained in the hydrophobic oxygen barrier layer solution (photocurable resin composition). At this time, the hydrophobic oxygen barrier layer 40 ), The photo-sensitizer and the first electron acceptor contained in the anti-fake layer 10 can be destroyed (decomposed) by the photoinitiator. Therefore, it is preferable that the hydrophobic oxygen barrier layer 40 is formed on the first hydrophilic oxygen barrier layer 20.

Meanwhile, the anti-falsification film, which further includes the anti-falsification film 60 according to another embodiment of the present invention, is subjected to the same process as the above-described process, And the auxiliary layer 60 may be further formed. Specifically, before forming the second hydrophilic oxygen barrier layer 30, a solution for the anti-falsification auxiliary layer (curable soft polymer composition) containing the second electron acceptor is applied on the support layer 50 and imprinted The anti-falsification auxiliary layer 60 can be formed through a post-curing process. At this time, the second electron acceptor may be dissolved in an organic solvent and mixed with a solution (curable soft polymer composition) for an anti-fake auxiliary layer in a solution state. The curing may be carried out at a temperature of 40 to 60 DEG C for 1 to 3 hours.

2. Anti-counterfeit goods

The present invention provides an anti-falsification article comprising the aforementioned anti-fake film. The anti-counterfeit article may be an identification card, a passport, money, or a credit card. At this time, the above-mentioned anti-falsification film can be applied to the anti-falsification article by a method such as attachment to the material of the anti-falsification article or film formation directly on the material of the anti-falsification article.

The anti-falsification article of the present invention can exhibit more excellent anti-falsification (security) by including the above-mentioned anti-falsification film.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  One]

One) Photo-sensitizer  Stock solution and first electron acceptor storage solution preparation

PdTPBP (palladium tetraphenyltetrabenzoporphyrin), a photo - sensitizer, was dissolved in tetrahydrofuran to prepare a photo - sensitizer storage solution having a concentration of 1.9 mM.

The first electron acceptor, perylene, was dissolved in tetrahydrofuran to prepare a first electron acceptor storage solution having a concentration of 23.7 mM.

2) Master Master mold and Polydimethylsiloxane  a copy Mold ( PDMS  (see Fig. 5)

The line-and-space pattern of fine structure was designed using AutoCAD program, and based on this, we made a photomask through corporate request.

A 6 inch silicon wafer was prepared as a substrate for the photolithography process. A negative photoresist SU-82015 (MicroChem, USA) was spin-coated on the prepared silicon wafer at 500 rpm for 5 seconds and then spin-coated again at 4000 rpm for 30 seconds.

Next, a soft bake was performed for 180 seconds on a 95 hot plate (MSH-10, WiseStir, Korea) for curing the negative photosensitive agent.

A photomask was then placed on the silicon wafer using a mask aligner (MA / BA6, SUSS MicroTec, Germany) and irradiated with ultraviolet light (UV) for 4.5 seconds to enter an energy of about 130 mJ / .

Next, a post exposure bake was performed on a 95 hot plate for 240 seconds, and then exposed to a solution of SU-8 Developer (MicroChem, USA) for 3 minutes to form a fine-structure pre-blank pattern .

Then, the silicon wafer on which the line-space pattern was formed was first washed with DI water for 10 seconds, then secondly washed with isopropyl alcohol for 10 seconds, and dried under a nitrogen atmosphere.

Next, a hard bake was performed on a 95 hot plate for 240 minutes to prepare a master mold.

Then, the prepared master mold was placed in a glass container, and 3 drops of a self-assembled monolayer forming solution (L-SAM, Minuta Tech. Co. Ltd, Korea) was dropped around the master mold. The glass container was then placed in a desiccator and placed in a vacuum for 30 minutes at 1 × 10 ^-3 torr to form a self-assembled monolayer (SAM) on the surface of the master mold.

Next, a master mold with a self-assembled monolayer formed thereon was placed on a clean OHP (Over Head Projector) film, and a frame made of acrylic was placed. Then, a polydimethylsiloxane solution (Sylgard 184, Dow Corning Coporation, USA) was sufficiently poured and cured at room temperature for more than 48 hours to prepare a polydimethylsiloxane replica mold.

3) Anti-counterfeit layer  Polyurethane solution for forming

2 g of a liquid rubber (poly-74-30 from polytek) mixed with a polyol (A) component and a polyisocyanate (B) component in a mass ratio of 1: 1 was collected in a vial, and 2 ml of chloroform Was added and sealed. Then, the mixture was stirred at 70 rpm at 800 rpm using a magnetic stirrer. After the start of stirring, 2 ml of chloroform was added every 40 minutes, 60 minutes, 80 minutes, and 120 minutes. 5 g of the solution obtained after completion of the stirring was collected and placed in a separate glass vial, and the photo-sensitizer storage solution and the first electron acceptor storage solution prepared above were added and mixed with a micropipette to prepare a polyurethane solution Respectively.

4) Support layer / second hydrophilic The oxygen- / Anti-counterfeit layer  Construction of anti-counterfeit film

Polyethylene terephthalate having a thickness of 100 탆 was used as a support layer, and a polyvinyl alcohol aqueous solution was applied on the polyethylene terephthalate, followed by spin coating at 3000 rpm for 60 seconds. Thereafter, it was dried at room temperature for 20 minutes to form a second hydrophilic oxygen barrier layer (thickness: 1 mu m). The polyvinyl alcohol aqueous solution was prepared by adding 14 g of polyvinyl alcohol (Mowiol 4-88) manufactured by Aldrich Co. to 50 ml of distilled water and stirring and dissolving at 90 ° C at 1000 rpm using a magnetic stirrer .

Next, 150 占 퐇 of the polyurethane solution prepared above was coated on the second hydrophilic oxygen barrier layer made of polyvinyl alcohol, and the polydimethylsiloxane replica mold prepared above was placed on the application surface, The reaction was stopped at room temperature for at least 12 hours to evaporate the solvent. Thereafter, a curing process was performed to form a polyurethane anti-fake layer including a light-sensitive material and a first electron acceptor and having a light emission pattern in a line-space form.

Then, the film was stored in a dark room at room temperature for one day to prepare an anti-fake film.

[ Example  2]

A master mold and a polydimethylsiloxane replica mold are produced in a honeycomb pattern instead of the line-vacancy pattern, and then the resulting polydimethylsiloxane replica mold is pressure-stamped to form an anti-forbidden layer in which a honeycomb luminescence pattern is formed A counterfeit preventing film having a support layer / a second hydrophilic oxygen barrier layer / anti-fake layer structure was produced through the same procedure as in Example 1.

[ Example  3]

A master mold and a polydimethylsiloxane replica mold were produced in the form of a mesh instead of the line-vacancy pattern, and then pressure-stamped with the prepared polydimethylsiloxane replica mold to form a mesh- A forgery preventing film having a support layer / a second hydrophilic oxygen barrier layer / anti-fake layer structure was produced through the same procedure as in Example 1, except that the anti-fake layer formed was formed.

[ Example  4]

Instead of the line-space pattern PNU UPCONVERSION LAB. The procedure of Example 1 was repeated except that a master mold and a polydimethylsiloxane replica mold were produced in the form of a logo, and then the resulting polydimethylsiloxane replica mold was pressure-stamped to form an anti- A counterfeit preventing film having a support layer / a second hydrophilic oxygen barrier layer / anti-fake layer structure was prepared.

[ Experimental Example  One]

Anti-falsification films were identified with a scanning electron microscope to confirm respective patterns formed on the anti-falsification films prepared in Examples 1 to 4, and the results are shown in Fig.

Referring to FIG. 6, it can be confirmed that the anti-falsification films prepared in Examples 1 to 4 have clearly defined fine light emission patterns having a size of about 10 μm.

[ Example  5]

The first hydrophilic oxygen barrier layer and the hydrophobic oxygen barrier layer were formed in addition to the anti-falsification film prepared in Example 1 to form the support layer / second hydrophilic oxygen barrier layer / anti-fake layer / first hydrophilic oxygen barrier layer / hydrophobic oxygen barrier layer To prepare an anti-falsification film. At this time, the first hydrophilic oxygen barrier layer and the hydrophobic oxygen barrier layer were formed by the following process.

1) First hydrophilic The oxygen-  formation

A polyvinyl alcohol aqueous solution was coated on the anti-fake layer of the anti-falsification film prepared in Example 1, and then spin-coated at 3000 rpm for 60 seconds. Thereafter, the membrane was dried at room temperature for 20 minutes to form a first hydrophilic oxygen barrier layer (thickness: 1 mu m). At this time, the spin coating was repeated several times or more to a level at which the line-blank pattern could be completely covered. The same polyvinyl alcohol aqueous solution as that used for forming the second hydrophilic oxygen barrier layer in Example 1 was used.

2) Hydrophobicity The oxygen-  formation

The urethane acrylate composition (Minuta Tech, MINS-ERM) was slowly loaded onto the first hydrophilic oxygen barrier layer after the edge of the first hydrophilic oxygen barrier layer was fixed with a tape (serving as a spacer at the time of loading). Next, the urethane acrylate composition coated with a transparent glass plate was covered while taking care not to generate bubbles, and the specimen was exposed to an ultraviolet lamp for 30 minutes to perform photo-curing. Thereafter, the transparent glass plate was removed to form a hydrophobic oxygen barrier layer (thickness: 20 mu m) made of urethane acrylate.

[ Example  6]

An anti-falsification film was produced in the same manner as in Example 5, except that the anti-falsification film prepared in Example 2 was used instead of the anti-falsification film prepared in Example 1.

[ Example  7]

An anti-falsification film was produced in the same manner as in Example 5, except that the anti-falsification film prepared in Example 3 was used instead of the anti-falsification film prepared in Example 1.

[ Example  8]

An anti-falsification film was produced in the same manner as in Example 5 except that the anti-falsification film prepared in Example 4 was used instead of the anti-falsification film prepared in Example 1.

[ Comparative Example  One]

An anti-fake film was formed on the polyethylene terephthalate film having a thickness of 100 탆 as a support layer by using the polyurethane solution prepared in Example 1 to prepare an anti-fake film having a support layer / anti-fake layer structure. At this time, the anti-fake layer was formed in the same manner as in Example 1.

[ Experimental Example  2]

In order to evaluate the UC emission characteristics of the anti-fake films prepared in Examples 5 to 8 and Comparative Example 1, each of the anti-falsification films was irradiated with a red visible ray laser having a wavelength of 635 nm, (short-pass filter, cut-off: 500 nm). The result was observed with a fluorescence microscope. The results are shown in FIG.

Referring to FIG. 7, it can be seen that the anti-falsification films produced in Examples 5 to 8 exhibit a blue UC emission phenomenon depending on the pattern of the emission pattern formed on the anti-fake layer. This supports the possibility of implementing a new type of non-traditional luminescent anti-falsification technology by combining a fine pattern formation technique and a non-traditional luminescence phenomenon, that is, UC emission by triplet-triplet extinction. (Anti-counterfeiting technology), which is based on the principle of unique UC emission, is a counterfeiting prevention technology using conventional UV-to-VIS, Technology.

On the other hand It can be confirmed that the anti-fake film prepared in Comparative Example 1 does not have a hydrophilic oxygen barrier layer and no UC emission phenomenon appears at all. These results support that the presence or absence of the hydrophilic oxygen barrier layer is essential to realize the UC emission phenomenon.

[ Example  9]

Forming an anti-fake auxiliary layer in which an emission pattern of a pre-blank type is formed by a polyurethane solution mixed only with perylene which is a second electron acceptor between the support layer and the second hydrophilic oxygen barrier layer; Anti-fake auxiliary layer / second hydrophilic oxygen barrier layer / anti-fake anti-fake layer / first hydrophilic oxygen barrier layer / anti-fake anti-fouling layer / Layer / hydrophobic oxygen barrier layer (see Fig. 8).

[ Experimental Example  3]

In order to evaluate the anti-falsification (security) of the anti-falsification film manufactured in Example 9, the anti-fake film was irradiated with a laser beam having a wavelength of 365 nm and a laser beam having a wavelength of 635 nm, short pass filter) to confirm the luminescence characteristics by fluorescence microscope. In addition, after the extracted patterns were extracted based on a predetermined luminance, verification was attempted using a QR scanner of a portable terminal, and the results thereof are shown in Fig.

Referring to FIG. 9, when the anti-falsification film manufactured in Example 9 is irradiated with ultraviolet rays, the anti-falsification auxiliary layer and the anti-falsification layer contain perylene, which is an electron acceptor in common, It can be confirmed that the light emission pattern formed on the layer is not distinguished. Accordingly, it can be confirmed that the QR code formed on the anti-fake layer is difficult to recognize through the portable terminal.

On the other hand, when the anti-fake film produced in Example 9 is irradiated with a laser beam having a wavelength of 635 nm, UC emission does not occur in the anti-fake auxiliary layer, but blue light of QR code type appears selectively in the anti- . Accordingly, the QR code formed on the anti-falsification layer can be recognized through the portable terminal and information contained in the QR code can be confirmed. This is because the anti-falsification film of the present invention is superior to the conventional anti-falsification technology This is a result of supporting the fact that we have sex (security).

10: Anti-counterfeit layer
20: First hydrophilic oxygen barrier layer
30: second hydrophilic oxygen barrier layer
40: hydrophobic oxygen barrier layer
50: Support layer
60: Anti-counterfeiting auxiliary layer

Claims (18)

An anti-falsification layer in which a soft lithographic light emission pattern including a photo-sensitizer and a first electron acceptor is formed in the matrix polymer; And
A first hydrophilic oxygen barrier layer disposed on one side of the anti-fake layer and including a hydrophilic polymer,
Wherein the matrix polymer comprises at least one member selected from the group consisting of polyurethane, polyisobutylene, polyethylene, polypropylene, polyester, polystyrene, cellulose acetate, polydimethylsiloxane and polycarbonate,
Wherein the hydrophilic polymer comprises a polyvinyl alcohol-based polymer compound. delete The method according to claim 1,
Wherein the anti-fake layer is emitted by the triplet-triplet annihilation based UpConversion between the photosensitizer and the first electron acceptor such that the light emission pattern is distinguishable. The method according to claim 1,
Wherein the photosensitive agent is at least one selected from the group consisting of a porphyrin compound bonded with a metal atom, a phthalocyanine compound bonded with a metal atom, and a thermally activated delayed fluorescence compound. The method according to claim 1,
Wherein the first electron acceptor is a compound that receives electrons from the photosensitizer and emits photons that are upconverted by triplet-triplet extinction. delete The method according to claim 1,
Further comprising a hydrophobic oxygen barrier layer disposed on an opposite side of the first hydrophilic oxygen barrier layer to the anti-fake layer. The method of claim 7,
Wherein the hydrophobic oxygen barrier layer comprises a photocurable acrylate-based polymer compound. The method according to claim 1,
And a second hydrophilic oxygen barrier layer disposed on the other side of the anti-fake layer. The method of claim 9,
Wherein the second hydrophilic oxygen barrier layer comprises a polyvinyl alcohol-based polymer compound. The method according to claim 1,
Further comprising a support layer disposed as an outermost layer on the other side of the anti-fake layer. The method of claim 11,
And an anti-fake auxiliary layer disposed between the anti-fake layer and the support layer, the anti-fake auxiliary layer including a second electron acceptor. Applying a solution for an anti-fake layer including a matrix polymer, a photo-sensitizer, and a first electron acceptor on a support layer to form an anti-fake layer having a soft-lithography luminescent pattern formed thereon; And
And forming a first hydrophilic oxygen barrier layer by applying a first hydrophilic oxygen barrier layer solution containing a hydrophilic polymer on the anti-fake layer,
Wherein the anti-fake layer contains the photo-sensitizer and the first electron acceptor in the matrix polymer,
Wherein the matrix polymer comprises at least one member selected from the group consisting of polyurethane, polyisobutylene, polyethylene, polypropylene, polyester, polystyrene, cellulose acetate, polydimethylsiloxane and polycarbonate,
Wherein the hydrophilic polymer comprises a polyvinyl alcohol-based polymer compound. 14. The method of claim 13,
And forming a hydrophobic oxygen barrier layer by applying a hydrophobic oxygen barrier layer solution containing a hydrophobic polymer on the first hydrophilic oxygen barrier layer. 14. The method of claim 13,
The step of forming the anti-
Forming a second hydrophilic oxygen barrier layer by applying a second hydrophilic oxygen barrier layer solution containing a hydrophilic polymer on the support layer; And
And applying a solution for the anti-fake layer on the second hydrophilic oxygen barrier layer to form an anti-fake layer. 16. The method of claim 15,
Wherein forming the second hydrophilic oxygen barrier layer comprises:
Applying a solution for an anti-fake auxiliary layer containing a second electron acceptor on the support layer to form an anti-fake auxiliary layer; And
And applying a solution for the second hydrophilic oxygen barrier layer on the anti-fake auxiliary layer to form a second hydrophilic oxygen barrier layer. An anti-fake article comprising the anti-fake film according to any one of claims 1, 3 to 5 and 7 to 12. 18. The method of claim 17,
An identification card, a passport, a currency, and a credit card.

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