JP5961919B2 - Method for manufacturing hologram label - Google Patents

Description

The present invention relates to a method for manufacturing a hologram label, and more specifically, a label that can be recognized only as a transparent brittle label (normally such as a “sealing” character or the like) in which the hologram reproduction image does not appear in normal illumination light illumination. In many cases, the printing layer is applied to a part of the label constituting layer.) For those who improperly change labels, forge or tamper (hereinafter also referred to as unauthorized persons). The present invention relates to a method for manufacturing a hologram label that has an appearance that makes it possible to easily carry out these fraudulent acts, but has a high fraud prevention function.
When a normal brittle label is attached to an envelope and then peeled off, the label itself is destroyed, or only the transparent base material that is part of the label is peeled off preferentially, the transparent base side, Characters such as “open” appear on the remaining part of the label to notify that an illegal opening has been performed.
For such a brittle label, an unauthorized person peels off the label or transparent base material from the sealed portion of the envelope, and then illegally opens the envelope and illegally browses or replaces the enclosed item. After that, a new label is pasted on the remaining portion of the envelope so that the remaining portion of the envelope, such as “open”, is filled, and further, the peeled transparent substrate Misapplying and applying a new adhesive to cover the letters “open” attached on the transparent substrate, as if it appeared to be a uniform adhesive layer and stick it on another envelope, etc. It is assumed that cheating is done.

However, in the hologram label according to the manufacturing method of the present invention, the hologram reproduction image emerges by illumination with a predetermined illumination light. Therefore, the above fraud is performed on the hologram label according to the manufacturing method of the present invention. If a new label that has been illegally attached is illuminated with the specified illumination light, a hologram reconstructed image with “missing” in the letter shape such as “open” appears. Will be.
Of course, even if the peeled off transparent base material is abused, a hologram reproduction image appears from a character-like portion such as “open” attached to the transparent base material (in the form of “image” of the character “open”) From a window with an opening, it is possible to look into a stereoscopic image behind it.
That is, the present invention relates to a method for manufacturing a hologram label that makes it difficult to illegally open or replace a hologram label , and to make forgery or tampering.
In the present invention, the “pattern” “pattern” can be any visible “display pattern” such as characters, figures, symbols, etc. “Character display pattern” such as “open” or “illegal” is adopted in the sense of showing.
“Applying a pattern-like surface activation process” means performing a surface activation process on the image area of these “display patterns”. For example, the “display pattern” is a single letter “open”. If this is the case, each line constituting the character (this is a stroke and is a linear region set on the surface of a predetermined layer) (the inside of the stroke, that is, the stroke). This means that the surface activation treatment is uniformly performed in the line portion.
In addition, when the transparent substrate has a surface that has already been sufficiently activated, the surface of the transparent substrate includes a surface deactivation treatment, and as a result, on the transparent substrate surface, Parts with different degrees of “activation” (this appears as a state where the peel strength between “another layer” formed on the transparent substrate is partially different, that is, different between the regions). Means that it is provided.
In the present specification, “parts” indicating blending are based on mass unless otherwise specified. The “hologram” includes a hologram and a hologram having a light diffractive function such as a diffraction grating.

(Main application) The main application of the hologram label according to the production method of the present invention is a hologram label used in the field of anti-counterfeiting, specifically,
(1) various product fields manufacturers recommendations net positive Hinto, the genuine authentication has the significance, for example, electronic equipment, electrical equipment, computer-related products, and their components, computer-related software, genuine fixtures such ( Printer consumables such as paper and toner) Pharmaceuticals, quasi-drugs, chemicals, etc.
(2) Fields where consumers are strongly required that the product itself is a genuine product, or affixing a label to improve designability, indicate that the product is expensive, and increase the added value of the product Fields, such as books, documents, lectures, plays, movies, photographs, paintings, sculptures, prints, drawings, models, etc., or edits thereof, or those recorded on a recording medium (video cassette, compact disc, digital video disk, etc.) work such as, the predetermined setting, including stuck over ROM board (computer equipment that prevents changes, game machine, the .ROM and board intended for use in a game machine or the like.), Watches, clothing, bags, jewelry such as jewelry, sports equipment, cosmetics, and their luxury brand products,
(3) Identification method (ID card) field, such as passport, driver's license, insurance card, membership card, identification card, resident registration card, hospital card, library card, etc.
(4) Fields that are required to be genuine in order to maintain economic order, such as gift certificates, gift certificates, etc., or prepaid cards, credit cards, cash cards, etc.
(5) Further, the field of packaging these items and sealing the packaging, for example, the field of simply storing or putting them in an envelope as mail or small parcels, or delivering and delivering them in a package, Fields that sell products in packages, fields that are simply packaged, fields that are used as seals for seals, fields that are affixed to prove their authenticity in their instructions and efficacy documents, etc.
Relates like, in particular, the hologram label peeled clever, or lowered the value of itself, the holographic label should distribution Omonbakasu to be reused, or is suitable for the field under consideration.

(Prior Art) In recent years, development of a hologram capable of reproducing a three-dimensional image using light interference has progressed, and this hologram requires advanced manufacturing technology and can be formed into various forms such as labels, seals, and foils. Therefore, it is applied and applied to a part of various things including the above-mentioned field as a forgery prevention means by applying this. This hologram has been widely used since it can be seen at a glance whether it is genuine or not and is difficult to manufacture as described above.
These are peeled off after being affixed to the article, and are peeled off by the support and the hologram layer, or the release layer provided between them and the support or the hologram layer so as not to be misused. In some cases, the entire hologram is destroyed when it is intentionally peeled off. In particular, as in the hologram brittle seal disclosed in Japanese Utility Model Publication No. 5-48210, a support and a hologram forming layer are laminated via a patterned release layer, and a reflective metal thin film layer and an adhesive are formed on the hologram formation. Laminate the layers one after another and cut them into the required size and shape before use, and apply pressure to the counterfeits such as certificates and identification cards, adherends that do not want to be altered, or seals such as seals. There are some that stick while heating.
When the hologram label once attached to the adherend in this way is peeled off, the hologram is destroyed at the boundary section between the release layer portion and the non-release layer portion, and the hologram is formed on the support and the adherend. Since the label remains separated and cannot be peeled off as it is, the hologram label cannot be replaced with another article. The authenticity of the kimono can be guaranteed.

Therefore, in order to rewrite the description items and the seal photograph etc. of the place where the label is pasted, it is necessary to remove the remaining part of the label, and it is difficult to forge or alter it. Further, since the hologram remains only in a pattern on the support, it is impossible to replace the label, and the opening of the sealed portion can be easily recognized by the hologram remaining in the pattern on the adherend.
Therefore, the hologram label of the present invention can be applied not only to an adherend that is not to be counterfeited, but also as a seal of a package, and the hologram label can also be used as a decorative item due to its beauty.
However, the former holographic brittle seal of the former type is abused because it can be reused as a result of completely peeling off the entire hologram seal without breaking the hologram layer and reflective thin film layer depending on how it is peeled off. There is a possibility that. Therefore, as a method for destroying the hologram layer and the reflective thin film layer itself, there is a method disclosed in Japanese Utility Model Publication No. 5-48210. However, in this method, when the hologram brittle seal is attached, Since the pattern-like release layer is provided, the presence of the pattern can be easily visually determined, which not only affects the appearance of the reproduced image of the hologram, but also reveals the existence of anti-counterfeiting measures. Have a problem.
In order to solve this problem, JP-A-8-152842 proposes a method of providing a brittle release layer between the reflective thin film layer and the adhesive layer. If the strength of the layer is large, the difference in adhesion strength with the base material, or the presence of brittle peelability, the hologram forming layer itself could not be broken or partially broken, and its purpose could not be fully achieved. .

Japanese Utility Model Publication No. 5-48210 JP-A-8-152842

Although the hologram according to the manufacturing method of the present invention is a hologram label, the hologram reproduction image cannot be visually recognized under normal illumination but is visually recognized as a “normal label”. When sticking to the adherend, it can be stuck without any problem, and if you try to remove the hologram label from the adherend illegally, only the label base material will be peeled off, For example, the characters “open” and “sealed” appear as “dent characters” on the “remaining ones (hologram forming layer, fluorescent layer, and adhesive layer)” on the adherend side. It turns out that this label is a so-called “brittle label”.
Furthermore, the "remaining ones", when illuminated by a predetermined illumination light, Ru hologram label der hologram reproduced image that contains "letter shaped chipping of opening etc." floats.
That is, the present invention has been made in view of the above-described conventional problems, and the object of the present invention is to reliably detect the replacement of a seal due to an illegal peeling action, The object is to provide a method for manufacturing a hidden hologram brittle seal, that is, it is difficult to find the existence or existence of a partially brittle fracture layer.

The present invention has solved the above problems by means described in the following embodiments.
The first aspect of the manufacturing method of a hologram label according to the present invention, at least, on one surface of a transparent substrate, a hologram forming layer, the adhesive layer is provided, et al are in this order, the adhesive layer side of the front Symbol hologram forming layer is formed with a hologram relief, the fluorescent layer only on the concave portion of the hologram relief is provided, and the fluorescent contained in the phosphor layer material is a manufacturing method of a hologram label is nanophosphors, before Symbol transparent and facilities the surface activation treatment to a Nozomu Tokoro pattern on the surface of the hologram forming layer side of the substrate, greater than the peel strength of the peel strength region other than the region of the surface activation treatment is performed region Kusuru it shall be the features a.

A second aspect of the manufacturing method of a hologram label according to the present invention is a method of manufacturing a holographic label of the first embodiment, the surface activation treatment of the surface of the hologram forming layer side of the transparent substrate is subjected region in a region other than it it said to form a resin having a low interfacial tension than the interfacial tension of the surface activation treatment is performed region.

Therefore, the peel strength between the transparent substrate and the hologram forming layer is suppressed to a low level, and one surface of the transparent substrate is subjected to a surface activation treatment in a desired pattern, so that the transparent substrate and the hologram forming layer Peel strength (180 ° peel test specified in JIS Z0237) with partially improved adhesion (meaning only the surface activated region) and 0.5 kg / 25 mm width to 3.0 kg / 25 mm width In other regions, the adhesiveness with the hologram forming layer is kept smaller than the strength, or surface inactivation processing is performed to further reduce the small strength.
The “pattern” has a size and shape that can be visually recognized, such as characters, figures, symbols, etc., as long as the “pattern” becomes “visible” when the “pattern” is “visualized”. Either of them can be used, and typically, only the stroke area of the characters “open” and “sealed” is surface-activated in order to display the “open” character display in the sense of showing evidence that the label has been peeled off. In addition to the surface activation treatment, the region other than the image area is subjected to surface inactivation treatment.
Carbon dioxide laser irradiation, far infrared carbon dioxide laser irradiation, and 172 nm vacuum ultraviolet (VUV, excimer light) irradiation are used for this surface activation treatment, that is, treatment that greatly increases wettability and treatment that creates functional groups on the surface. , Oxygen-sensitized excimer light irradiation, (open) plasma treatment, corona treatment, electron beam irradiation treatment, etc., with a larger energy (for example, 7.2 eV or more) than the chemical bond energy on the outermost surface of the transparent substrate. Physical treatment such as breaking the chemical bond on the outermost surface or absorbing ozone by atmospheric oxygen to generate ozone or directly excited oxygen and generating functional groups by this contact, such as 172 nm vacuum ultraviolet rays Etc., “surface activation treatment (meaning that surface tension increases)” is applied only to the outermost surface of the transparent substrate, or by chemicals such as oxidants Surface treatment, a chemical treatment such as primer treatment, silane coupling treatment, an argon beam etching, etching solution, more can be used physical 租面 formation processes such as sandblasting or the like.

Then, as the surface inactivation treatment, it is necessary to accurately inactivate the surface of the transparent substrate or only a predetermined portion of the surface activation treatment surface, and the surface directly A method of performing "inactivation treatment", for example, using a transparent base material made of a thermosetting resin or a resin to which a curing agent is added, a part of the outermost surface is completely cured by infrared heating or the like, and unreacted The method of bleeding the release formation to the outermost surface by eliminating the component or partially heating or partially curing the resin containing the release component, or first, the above-mentioned “surface activity on the entire outermost surface of the transparent substrate After that, only a part of the outermost surface (region) of the activated transparent substrate is partially dissolved or reacted with an activated functional group on the outermost surface. Solvents that eliminate functional group activity such as keto (Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc., and further aqueous solutions thereof), aromatics (benzene, toluene, xylene, etc.), esters, ethers ( Tetrahydrofuran etc.), etc., or these transparent base materials that are difficult to adhere to in the first place, such as resins having a low interfacial tension, such as silicone resins, paraffin resins, fluorine resins, their fluorinated hydrocarbon groups, organic silicon Surface of the resin containing a group in a pattern with high accuracy by using a letterpress printing method or an inkjet method, avoiding contact with the surface activation treatment surface, and partially forming the desired pattern as described above. Inactivate it.
At this time, optical properties of the transparent substrate surface (characteristics including those attached to the transparent substrate, optical transparency, refractive index distribution, interface shape reflecting light, etc.) are not changed. Desirably, the solvent is volatilized, and the resin is only for the purpose of surface modification, and the thickness after drying is preferably about 1/2 to 1/10 of the wavelength of light. . Of course, it is also suitable to use these in combination.
Then, when the transparent substrate is lifted from the adherend so as to peel off the hologram label, the transparent substrate and the hologram are formed in the portion not subjected to the surface activation treatment or the portion subjected to the surface inactivation treatment. Peeling easily occurs between the layers, and the surface-activated part remains on the transparent substrate side, and the surface-inactivated part and surface-activated part are applied. Strong shearing force (force to break the hologram forming layer; hologram forming layer at the boundary between the non-exposed portion or the boundary between the surface-inactivated portion and the surface-inactivated portion. The force applied at the time of breaking becomes the breaking strength.).

On this hologram forming layer, a fluorescent layer is provided so as to be in contact with the hologram relief, and with a uniform thickness following the unevenness forming the hologram relief, but this fluorescent layer is very thin. Since it is a layer and contains a large amount of phosphor, the breaking strength of the phosphor layer is very small, and it breaks easily when the hologram forming layer breaks.
The pressure-sensitive adhesive layer provided on the fluorescent layer also has a breaking strength smaller than that of the hologram-forming layer, and breaks along with the hologram-forming layer. It means that it is divided.)
That is, when surface activation processing is applied to the letter “open”, only the hologram forming layer, the fluorescent layer, and the adhesive layer corresponding to the area of the “open” letter are attached to the transparent substrate. (Hereinafter also referred to as the transparent substrate side remainder.) In the portion corresponding to the region other than the characters “opened”, those layers do not adhere to the transparent substrate, the transparent substrate is peeled off, and the adherend side Is a state in which the hologram forming layer, the fluorescent layer, and the adhesive layer are lacking in the “opened” character shape (character-shaped depressions are formed or character-shaped holes are opened. It is also called the body-side remainder.)
Further, when comparing the size (area) of the region of the surface activation treatment portion with the size (area) of the other region (including the region of the surface deactivation treatment portion), this is also the case. However, in many cases, the size of the other region is relatively larger than the size of the region of the surface activation treatment part, which promotes peeling at the interface between the transparent substrate and the hologram forming layer. It also has the effect of

And when the ultraviolet-ray etc. of a predetermined wavelength are irradiated to the to-be-adhered body side remainder on this to-be-adhered body, fluorescent substance will light-emit, and the hologram reproduction image by the light emission wavelength will appear. In this case, the hologram reproduction image is observed as being blocked by the characters “open”.
In the first place, the hologram reproduction image has very high redundancy due to the principle of reproduction, so this “blocking” (the width of the surface activation treatment region, that is, the line width of the letter “open”), the hologram relief and the fluorescent layer are This means that light that contributes to hologram reproduction is not radiated from this area, and the hologram reproduction image is displayed as if it was covered with a letter-like “shield” of “open” from the hologram reproduction image. In order to make it clearly visible, the hologram relief interference fringe period of 0.5 μm to 2 μm is multiplied by 200 to 5000 times. More preferably, it is 500 times to 2000 times.
If the “blocking” is less than 200 times, the hologram reproduction image is strongly reproduced due to the redundancy of the hologram, and the “blocking” is weakened to make it difficult to visually recognize its existence. When this “blocking” exceeds 5000 times , The area of the surface activated part of the area is increased (meaning that the individual line width is increased, and as a result, the overall area is also increased), the transparent substrate itself is difficult to peel off, There arises a problem such that the entire hologram label can be peeled off without any breakage.
The clearness of “blocking” (letters, etc.) when the transparent substrate is peeled is best 500 to 2000 times.
On the other hand, the surface that has not been subjected to the surface activation treatment or the surface deactivation treatment surface has a peel strength of 0.01 kg / 25 mm width to 0.1 kg / 25 mm width and is intended to peel off the hologram label. Then, no matter how it is devised, the transparent base material must be peeled off smoothly from the hologram forming layer, and when the transparent base material is peeled off, the outermost surface of the hologram forming surface is almost mirror-like (such as peeling marks From that portion, it is possible to clearly see the reproduced hologram image underneath.

The surface deactivation treatment using the printing method described above can form a very clear pattern and can greatly increase the difference in adhesion strength between the surface deactivation treatment surface and the surface activation treatment surface. Since it can do, the boundary line which fractures can be made clearer.
Of course, the pattern processing using these surface activation processing and surface deactivation processing is optically transparent, and when the hologram label is observed, the pattern boundary cannot be visually recognized, such as a laser. Maintains its transparency (continuity) even when illuminated with
Among these surface activation treatments, the optical treatment such as laser irradiation or the physical treatment such as plasma treatment does not generate irregularities on the treated surface of the transparent substrate and maintains a mirror surface, and the surface activation treatment. It is particularly desirable and excellent in optical transparency since it is possible to increase the positional accuracy of the surface and the effect of surface deactivation treatment by the surface deactivation treatment is great.
Furthermore, instead of uniformly activating the surface within the “pattern” described above, the “pattern” is “configured by a set of fine patterns”, that is, the “pattern”
More “fine patterns”, for example, a collection of “fine patterns” such as halftone dots, checkered patterns, random patterns, etc., and surface activation treatment only for those “fine patterns”, The boundary line (that is, the opportunity to break) is increased, the “breaking” can be generated more efficiently, and the breaking property of the hologram forming layer when the transparent substrate is peeled off, and In addition, the breakability of the fluorescent layer can be improved.
For example, in the case of a halftone dot shape, surface activation treatment is performed in the halftone dot, and the region between the halftone dots is not subjected to surface activation treatment or is subjected to surface deactivation treatment,
In the case of a checkered pattern, it is uniformly divided by a grid, and only one part of the grid that is skipped is surface-activated, and the other grid is not surface-activated or surface-inactivated. By performing the treatment, the strength at break of the interface between the transparent substrate and the hologram forming layer is imparted with the strength of a fine dot pattern or a fine checkered pattern, thereby improving the “breaking” property.

Therefore, the individual size of the “fine pattern” (if it is a checkered pattern, it means the size of one square) is set to 50 μm to 1 mm.
If the individual size of the “fine pattern” is larger than 1 mm, the effect of improving the “breaking” property is lowered, and if it is less than 50 μm, the individual areas of the surface activation treatment become too small, and the above-mentioned A sufficient surface activation treatment by the method cannot be performed.
The surface activation process can be performed over the entire hologram forming layer. However, since the purpose of the surface activation process is “determination of fraud,” a predetermined partial range of the hologram label ( It is also preferable that the treatment is limited to the range of 1/10 to 1/25 in order to further conceal that such a process exists in a state where the hologram label is attached to the adherend. .
Furthermore, considering the purpose of blocking the redundancy of the hologram, it is desirable to provide the “pattern” uniformly. However, another characteristic at the time of reproducing the hologram image is “a fine light diffractive characteristic having a width of 50 μm to 300 μm. When the hologram is cut into bands, the light diffractive band and the hologram band form a pair of stripes, and the interference effect of the light diffracted from each band has the effect of inhibiting the reproduction of the hologram image. '' In order to “block” hologram reproduction using the phenomenon, it is desirable that the “fine pattern” has a width of 50 μm to 300 μm and the length is the same. In the case of the present invention, the portion corresponding to the fine light diffractive band is a light scattering band.
For example, the size of the halftone dot diameter, the length of one side of a checkered square, and the width of each region of the random pattern are set as this size.
When the transparent substrate is peeled off, the region contributing to hologram reproduction and the region not contributing to hologram reproduction are alternately formed with the above-described sizes, so that one hologram reproduction region and one adjacent hologram non-reproduction region However, the above-mentioned fine “stripes” are formed, and the presence of these strips repeatedly obstructs the reproduction of the hologram image and is recognized as a simple rainbow-colored region. Therefore, in this case, for example, a rainbow colored “open” character is observed.

The transparent base material used in the present invention is preferably one having a thickness that can be reduced and having a mechanical strength and a solvent resistance and a heat resistance that can withstand processing when manufacturing a hologram label. Since it depends on the purpose of use, it is not limited, but a film or sheet plastic having a thickness of 5 to 250 μm is used.
As a transparent resin material that forms a hologram forming layer formed on a transparent substrate, various thermoplastic resins, thermosetting resins, or ionizing radiation curable resins can be used, and a gravure coating method A transparent resin layer having a thickness of 5 μm to 50 μm is formed using various coating methods such as an offset printing method and a screen printing method.
In order to form a hologram forming layer using the above transparent resin material, it can be directly formed by developing the photosensitive resin material by performing interference exposure of the hologram. It is preferable to perform molding by using the replica or a plating mold thereof as a replica mold and pressing the mold surface against the layer of the resin material.
When thermosetting resin or ionizing radiation curable resin is used, curing is performed by heating or ionizing radiation irradiation while keeping the uncured resin in close contact with the mold surface, and then cured by peeling after curing. The fine irregularities of the relief hologram can be formed on one side of the layer made of a transparent resin material. A diffraction grating forming layer having a diffraction grating formed in a pattern by a similar method can also be used as the optical diffraction structure.
A relief hologram is a recording of interference fringes caused by interference of light between an object beam and a reference beam in an uneven relief shape. For example, a laser reproduction hologram such as a Fresnel hologram, a white light reproduction hologram such as a rainbow hologram, There are color holograms utilizing these principles, computer generated holograms (CGH), holographic diffraction gratings, and the like. Further, like a machine readable hologram, the reproduction light may be converted into data by a light receiving unit and transmitted as predetermined information, or authenticity determination may be performed.
In order to precisely create fine irregularities, not only optical methods, but also electron beam lithography equipment can be used to create precisely designed relief structures that produce more precise and complex reproduction light. Good. The relief shape is designed to have a pitch, depth, or specific periodic shape of the unevenness according to the wavelength (range) of the light or light source for reproducing or reproducing the hologram, the direction and the intensity of reproduction or reproduction. The pitch (period) of the unevenness depends on the reproduction or reproduction angle, but is usually 0.1 μm to several μm, and the depth of the unevenness is a factor that greatly affects the reproduction or reproduction intensity, but is usually 0.1 μm. ˜1 μm.

The hologram relief shows a phase difference as a phase hologram in a “relief shape (means an uneven shape)”, and is provided in contact with a “relief shape” having this phase difference (one of the fluorescent layers). The surface is provided along the “relief shape”), or the fluorescent layer is provided with a uniform thickness following the “relief shape”, so that the fluorescence emitted from the fluorescent layer includes the phase difference. It will be issued with or with.
The fluorescent layer has transparency or “white” (meaning that it is visually recognized as “white” due to the light scattering property of the phosphor surface), so that the fluorescent layer emits light. Under illumination light other than light, it is visually recognized as a simple transparent label or a white label.
Therefore, in the use of the various hologram labels described above, printed layers such as characters and designs suitable for the use are placed above and below each layer constituting the hologram label, in particular, between the transparent substrate and the transparent resin layer. It is preferable to provide it.
Here, the principle that the hologram reproduction image appears by the fluorescent layer will be described below.
In the case of the hologram label of the present invention, the fluorescence emitted from the fluorescent layer corresponds to the secondary wave of Huygens generated when reproducing the relief hologram, and the fluorescence corresponding to the secondary wave is arranged on the hologram relief surface. The phase difference of the hologram relief including the diffraction grating group corresponding to the hologram image, which is the fluorescence emission of the body (or also referred to as a fluorescent substance; contained in the fluorescent layer). To emit light to the viewer side.
This emitted light causes an interference phenomenon in the space on the hologram relief surface, and as a result, a predetermined hologram reproduction image appears in a predetermined direction.
A phosphor is a substance that absorbs energy such as ultraviolet rays, electron beams, and X-rays and emits it as visible light. For example, a material obtained by adding a trace amount of metal ions responsible for light emission such as Eu and Ce to a base ceramic crystal. Etc. In this case, metal ions that contribute to light emission are excited by absorbing energy applied from the outside (energy such as ultraviolet rays, electron beams, X-rays, of course, visible rays, infrared rays, etc.), and then the ground state. Lights when returning to. The lattice of the host crystal functions to chemically stabilize the ions by surrounding the metal ions, and to control the emission color and intensity by adjusting the crystal field and coordination environment.

The present invention uses a phosphor material that emits light in the visible light region by Stokes shift among these fluorescent emissions. Of course, a material that emits light in the visible light region due to infrared excitation can also be used.
The present invention reproduces a hologram at a wavelength different from the wavelength of the illumination light source of the hologram, for example, it can be illuminated with ultraviolet light and a green hologram can be visually recognized. In the absence of the normally used green illumination light source, only the hologram shines, appears to float in the air, and is excellent in design.
Of course, because the wavelength range of the light source capable of reproducing the hologram is very narrow, only those who know the specific wavelength range can reproduce the hologram, which is useful for authenticity determination. . Further, only those who can know the Stokes shift value can predict the color tone of the hologram reproduction image, and only the hologram that can pass through the bandpass filter by looking through the bandpass filter adjusted to the reproduction wavelength is authentic. It can also be determined.
Further, the angle (diffraction angle) passing through the bandpass filter also depends on the amount of Stokes shift, and only those who can know the value can make the determination at the predetermined angle.
Furthermore, by including a plurality of phosphors, this reproduced image appears in different colors at a plurality of angles, which is superior both in terms of design and authenticity.

As shown in the Jablonsky diagram shown in FIG. 1, the principle of fluorescence emission is first determined by light absorption from the ground state (S0: singlet state) of the phosphor (including fluorescent dye, fluorescent pigment, fluorescent dye, etc.). The luminescent material excited in any one of the vibration states (S1), second (S2), third excited state (S3),... Or a triplet state (T1, T2) by intersystem crossing. The phosphor in the lowest vibration state of S1 returns to the ground state due to a non-radiation process or emits fluorescence. The molecule in the triplet state returns to the ground state by a non-radiative process or phosphorescence.
Since the transition between singlets occurs instantaneously, the half-life of fluorescence is as short as 10 ⁻⁴ sec or less. The time required for the transition is said to be excited at 10 ⁻¹⁵ sec and then to emit fluorescence at 10 ⁻⁹ to 10 ⁻⁷ sec.
On the other hand, the transition from triplet to singlet is forbidden due to the prohibition of spin change, and spontaneous emission is less likely to occur. Therefore, the half-life of phosphorescence is large, and there are some in seconds.
Whether or not light is emitted when returning to the ground state, whether the intensity of light is strong or weak, and whether the fluorescence lifetime is long or short largely depends on the molecular structure of the phosphor material and the environment in which the molecule is placed.
The wavelength distribution of the emitted light of the phosphor material is called a fluorescence spectrum, and the fluorescence spectrum is created by plotting the fluorescence intensity relative to the fluorescence wavelength. (In actual fluorescence spectrum measurement, excitation light with a constant wavelength and intensity is used as the light source, and when dealing with phosphors, the emission spectrum is called the fluorescence spectrum.) The wavelength (energy) shown in the fluorescence spectrum ) Is equal to the energy difference from the lowest vibration energy level in the primary excited state to the preferential vibration energy level in the ground state.
If the amplitude of the fluorescence is similar to the amplitude structure of the excited state and the ground state, the wavelength of the light energy absorbed by the fluorescent dye and the wavelength emitted as fluorescence are theoretically related to the amplitude of the excitation on the longest wavelength side. Will be the same. However, in practice, the fluorescence spectrum of most fluorescent dyes shifts to the longer wavelength (low energy) side. The difference between the peak wavelengths of the excitation spectrum and the fluorescence spectrum is called the Stokes shift, and this wavelength difference is caused by the energy released in the excited state before the emission of fluorescence being converted into thermal energy.

The Stokes shift is very important in the sensitivity of fluorescence, and when detecting fluorescence, the background can be lowered because it is not affected by excitation light.
When the wavelength and intensity of incident light are constant (for example, when controlled laser light is used as a light source), the emitted fluorescence is directly proportional to the amount of fluorescent material. Therefore, in order to make the fluorescence intensity constant, it is necessary to make the amount of the phosphor in the fluorescent layer formed on the hologram relief surface constant. Of course, when the concentration of the phosphor is high, saturation occurs and the linearity is lost, resulting in a constant intensity, or the distance between the phosphors is very close, and only the vicinity of the surface is excited and the emitted fluorescence is absorbed. Therefore, in order to sufficiently obtain the coherence of fluorescent light, which is the object of the present invention, it exists uniformly only in the vicinity of the hologram relief surface, rather than a large amount of phosphors dispersed in the thickness direction of the fluorescent layer. In order to produce a higher interference phenomenon, it is desirable that the particle size is 1 to 10 times, more preferably 1 to 3 times the particle size of the phosphor. When the phosphor is a dye and is dissolved in the resin forming the fluorescent layer, it is necessary to keep the resin layer thin. When dyeing with a fluorescent dye, the above-mentioned object can be achieved by dyeing only the relief surface of the transparent resin layer itself forming the hologram relief.
Also, depending on the phosphor, the emitted fluorescence intensity (brightness) varies, and the fluorescence intensity directly affects the sensitivity, so the fluorescence intensity of the phosphor is a very important factor. The fluorescence intensity depends on the following two characteristics of the phosphor:
・ Light absorption efficiency (absorption coefficient)
-Conversion efficiency between excitation light and fluorescence (quantum yield)
Since the fluorescence intensity is proportional to the extinction coefficient (ε) and quantum yield (φ) of the phosphor, it is expressed by the following equation.
・ Fluorescence intensity (luminance) 吸 光 Absorption coefficient (ε) × quantum yield (φ)

Here, the extinction coefficient of the phosphor means the amount of light having a specific wavelength absorbed by the phosphor, and the molar extinction coefficient is defined as the optical density of a 1M (1 mol) fluorescent dye solution per 1 cm of the optical path. Useful phosphors have a molar extinction coefficient of 10,000 or more. The conversion efficiency (quantum yield) between excitation light and fluorescence can be obtained from the following equation.
Φ = number of emitted photons / number of absorbed photons Here, the quantum yield (φ) ranges from “0” (non-fluorescent substance) to “1” (efficiency 100%). Examples showing the quantum yield of the phosphor include fluorescein (φ = 0.9) and Cy5 (φ = 0.3). The peak wavelength of the absorption spectrum is used for the usual quantum yield (φ) measurement.
Fluorescein (ε = 70,000, φ = 0.9) and Cy5 (ε = 200,000, φ = 0.3) have extremely high luminance, and these phosphors have quantum yields and extinction coefficients. Although very different, the fluorescence intensity is equivalent.
Therefore, when evaluating the phosphor, it is necessary to consider both the extinction coefficient and the quantum yield. Fluorescence intensity is also affected by the intensity of incident light. Theoretically, when the amount of incident light is increased, the number of excited phosphors increases, and the amount of emitted light (the number of photons or the ground state falls to the ground state) Number) increases and is observed as an increase in fluorescence intensity. However, in reality, if the incident light intensity is increased too much, all the phosphors are always excited, causing fluorescence destruction, resulting in attenuation or disappearance of the fluorescence intensity and loss of correlation with the fluorescence intensity. Therefore, it is necessary to appropriately determine the amount of incident light.
In addition, the quantum yield, excitation spectrum, and fluorescence spectrum of the phosphor are determined based on environmental conditions, that is, environmental temperature, ion concentration, pH, excitation light intensity, covalent bond with resin, non-covalent interaction (intercalation The optical filter (low-pass filter, high-pass filter, band-pass filter, etc.) that makes it easy to recognize the excitation light wavelength and fluorescent light in consideration of these environmental conditions. May need to be set as needed.

Another environmental effect is photobleaching with light. Since the phosphor in the excited state is chemically activated as compared with the ground state, it is more likely to be destroyed and, for example, the “excited fluorescent dye molecule” proceeds with a chemical reaction, but is less frequent. May have a low fluorescence structure. The progress of this chemical reaction depends on the sensitivity of individual phosphors to photobleaching and the chemical environment, the intensity of excitation light, the irradiation time of excitation light, the number of repetitions of optical scans for observation and authentication, etc. Settings according to the purpose are required.
When the wavelength and intensity of incident light are made constant, such as when a controllable laser beam is used as the light source, the emitted fluorescence (number of photons) is directly proportional to the amount of phosphor. If the phosphor is at a very high concentration, the signal response is non-linear.
The number of photons emitted from a certain amount of phosphor can be amplified by repeating the excitation / emission cycle. When the excitation light intensity and the phosphor concentration are constant, the total amount of emitted light is proportional to the irradiation time (period in which excitation light is irradiated to a fluorescent dye or the like). If the irradiation time is longer than the time of the excitation / emission cycle, the phosphor repeats the excitation / emission cycle many times. The fluorescence intensity (number of emitted photons) can be measured by any light receiving element.
When measuring low-intensity light, a photomultiplier tube (PMT) having an amplification mechanism is effective. When light having sufficient energy enters the PMT, electrons are emitted from the cathode, and the electrons are amplified as a current. The currents of these light receiving elements are proportional to the intensity of incident light, and the fluorescence intensity is usually displayed in arbitrary units (eg, rfu: relative-fluorescence units).

The phosphor is generally manufactured by a solid phase reaction method in which a phosphor material is fired. In this solid-phase reaction method, since the raw material mixture is baked at a high temperature, the obtained baked cake often has the phosphor particles hard and aggregated. Therefore, normally, when manufacturing the phosphor, for example, a pulverization process using a ball mill, a mortar, etc., is performed. Substantially monodispersed phosphor-precursor particles are suspended in a flowing gas and baked to produce substantially monodispersed fluorescent particles that are not aggregated. According to this method, fluorescent particles having a size of less than 1 μm can be produced.
In addition, for example, when manufacturing a ZnGa ₂ O ₄ : Mn phosphor, the phosphor raw material before firing is prepared by a wet precipitation method, which enables firing at a low temperature and suppresses aggregation of phosphor particles. can do.
Further, for example, regarding a method for producing a phosphor having an alkaline earth aluminate-based or alkaline earth silicate-based host crystal, strontium nitrate is used as a phosphor raw material containing Sr, and a raw material mixture or suspension There is a method of forming droplets so as to have a desired particle diameter and firing the droplets. As a result, a phosphor having extremely brittle properties can be obtained and can be easily pulverized to a minute size.

As the phosphor material, a compound containing an element constituting the phosphor to be manufactured (hereinafter also referred to as “phosphor constituent element”) can be used. Examples thereof include oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, carboxylates, halides, nitrides and the like containing phosphor constituent elements. When selecting the phosphor raw material, it is preferable to select in consideration of the reactivity to the obtained phosphor. Furthermore, corresponding to each phosphor constituting element constituting the phosphor, one kind of phosphor raw material may be used, or two or more kinds may be used in combination in any combination and ratio.
Further, the impurities contained in each phosphor raw material of the phosphor are not particularly limited as long as the phosphor characteristics are not adversely affected.
The weight median diameter of each phosphor material is usually 0.01 μm or more and 0.5 μm or less. For this reason, depending on the type of the phosphor material, pulverization may be performed in advance by a dry pulverizer such as a jet mill. As a result, each phosphor raw material can be uniformly dispersed in the raw material mixture, and the solid phase reactivity of the raw material mixture can be increased by increasing the surface area of the phosphor raw material, thereby suppressing the generation of impurity phases. It becomes.

For example, specific examples of phosphor materials containing Ba include BaO, Ba (OH) ₂ .8H ₂ O, BaCO ₃ , Ba (NO ₃ ) ₂ , BaSO ₄ , Ba (C ₂ O ₄ ) · ₂ H _2. O, Ba (OCOCH ₃ ) ₂ , BaCl _{2 and the} like.
Specific examples of phosphor raw materials containing Ca include CaO, Ca (OH) ₂ , CaCO ₃ , Ca (NO ₃ ) ₂ .4H ₂ O, CaSO ₄ .2H ₂ O, Ca (C ₂ O ₄ ) · H. ₂ O, Ca (OCOCH ₃ ) ₂ .H ₂ O, anhydrous CaCl ₂ (however, it may be a hydrate).
Specific examples of the phosphor raw material containing Sr include SrO, Sr (OH) ₂ .8H ₂ O, SrCO ₃ , Sr (NO ₃ ) ₂ , SrSO ₄ , Sr (C ₂ O ₄ ) · H ₂ O, Sr. (OCOCH ₃ ) ₂ · 0.5H ₂ O, SrCl _{2 and the} like.
Specific examples of the phosphor material containing Zn include ZnO, Zn (C ₂ O ₄ ) · 2H ₂ O, ZnSO ₄ · 7H ₂ O, and the like.
Specific examples of the phosphor raw material containing Mg include MgCO ₃ , MgO, MgSO ₄ , Mg (C ₂ O ₄ ) · 2H ₂ O, and the like.
Specific examples of the phosphor raw material containing Si include SiO ₂ , H ₄ SiO ₄ , Si (OCOCH ₃ ) _{4 and the} like.
Specific examples of the phosphor material containing Eu include Eu ₂ O ₃ , Eu ₂ (SO ₄ ) ₃ , Eu ₂ (C ₂ O ₄ ) ₃ , EuCl ₂ , EuCl ₃ , Eu (NO ₃ ) ₃ .6H _2. O etc. are mentioned.
Specific examples of each phosphor raw material containing Sm, Tm, and Yb include compounds in which Eu is replaced with Sm, Tm, and Yb, respectively, in the compounds listed as specific examples of the Eu source.

Specific examples of the phosphor raw material containing Mn include MnO, MnO ₂ , Mn ₂ O ₃ , MnF ₂ , MnCl ₂ , MnBr ₂ , Mn (NO ₃ ) ₂ .6H ₂ O, MnCO ₃ , MnCr ₂ O _{4 and the} like. Is mentioned.
Specific examples of the phosphor material containing Cr include Cr ₂ O ₃ , CrF ₃ (may be a hydrate), CrCl ₃ , CrBr ₃ .6H ₂ O, Cr (NO ₃ ) ₂ .9H ₂ O. , (NH ₄ ) ₂ CrO _{4 and the} like.
Specific examples of the phosphor raw material containing Tb include Tb ₄ O ₇ , TbCl ₃ (including hydrate), TbF ₃ , Tb (NO ₃ ) ₃ .nH ₂ O, Tb ₂ (SiO ₄ ) ₃ , Examples thereof include Tb ₂ (C ₂ O ₄ ) ₃ · 10H ₂ O. Further, other phosphor materials (for example, Eu source) and Tb source may be co-precipitated before use.
Examples of phosphor materials containing _{Pr, Pr 2 O 3, PrCl} 3, PrF 3, Pr (NO 3) 3 · 6 H 2 O, Pr 2 (SiO 4) 3, Pr 2 (C 2 O 4 ) ₃ · 10H ₂ O and the like.
Specific examples of the phosphor raw material containing Ce include CeO ₂ , CeCl ₃ , Ce ₂ (CO ₃ ) ₃ .5H ₂ O, CeF ₃ , Ce (NO ₃ ) ₃ .6H ₂ O, and the like.
Specific examples of the phosphor material containing Lu include Lu ₂ O ₃ , LuCl ₃ , LuF ₃ (may be a hydrate), Lu (NO ₃ ) ₃ (may be a hydrate), etc. Is mentioned.
Specific examples of phosphor raw materials containing La include La ₂ O ₃ , LaCl ₃ · ₇ H ₂ O, La ₂ (CO ₃ ) ₃ · H ₂ O, LaF ₃ , La (NO ₃ ) ₃ · 6H ₂ O. , La ₂ (SO ₄ ) _{3 and the} like.
Specific examples of the phosphor material containing Gd include Gd ₂ O ₃ , GdCl ₃ .6H ₂ O, Gd (NO ₃ ) ₃ .5H ₂ O, Gd ₂ (SO ₄ ) ₃ / 8H ₂ O, GdF _{3 and the} like. Is mentioned.

Specific examples of the phosphor material containing Ge include GeO ₂ , Ge (OH) ₄ , Ge (OCOCH ₃ ) ₄ , GeCl _{4 and the} like.
Specific examples of the phosphor material containing Ga include Ga ₂ O ₃ , Ga (OH) ₃ , Ga (NO ₃ ) ₃ .nH ₂ O, Ga ₂ (SO ₄ ) ₃ , and GaCl ₃ .
Specific examples of the phosphor material containing Al include Al ₂ O ₃ such as α-Al ₂ O ₃ and γ-Al ₂ O ₃ , Al (OH) ₃ , AlOOH, Al (NO ₃ ) ₃ · 9H ₂ O, Examples include Al ₂ (SO ₄ ) ₃ and AlCl ₃ .
Specific examples of the phosphor raw material containing P include P ₂ O ₅ , Ba ₃ (PO ₄ ) ₂ , Sr ₃ (PO ₄ ) ₂ , (NH ₄ ) ₃ PO _{4 and the} like.
Specific examples of the phosphor raw material containing B include B ₂ O ₃ and H ₃ BO ₃ .
In addition, you may use the raw material illustrated above, after coprecipitating as needed.
Further, phosphor raw materials corresponding to N element, O element, halogen element, etc. are usually manufactured as phosphors as anion components of the phosphor raw materials of the respective phosphor constituting elements or as components contained in the firing atmosphere. Sometimes supplied.

After preparing a raw material mixture by mixing phosphor raw materials, the raw material mixture is fired at a predetermined temperature and atmosphere. At this time, it is preferable to perform the mixing sufficiently.
Although it does not specifically limit as said mixing method, Specifically, the method quoted as the following (A) and (B) can be used. As for these various conditions, for example, it is possible to select conditions such as mixing and using two kinds of balls having different particle diameters in a ball mill.
(A) Dry pulverizer such as hammer mill, roll mill, ball mill, jet mill, etc., or pulverization using mortar and pestle, and mixer such as ribbon blender, V-type blender, Henschel mixer, or mortar and pestle And a dry mixing method in which the above phosphor raw materials are pulverized and mixed.
(B) Add a solvent or dispersion medium such as an alcohol solvent such as methanol or ethanol or water to the phosphor raw material, and mix using, for example, a pulverizer, a mortar and pestle, or an evaporating dish and a stirring bar, A wet mixing method in which a solution or slurry is made and then dried by spray drying, heat drying, or natural drying.
The mixing of the phosphor raw material can be either wet or dry depending on the physical properties of the phosphor raw material.
In addition, when using a material that easily oxidizes and absorbs moisture, such as halide and nitride, for example, an inert gas such as argon gas or nitrogen gas is filled and mixed in a glove box in which moisture is controlled.

In addition, the phosphor material may be sieved for the purpose of, for example, uniforming the particle size during mixing and pulverization. In this case, various types of commercially available sieves can be used, but it is preferable to use a resin mesh such as a nylon mesh rather than a metal mesh in terms of preventing impurities from being mixed.
In the firing step, a fired product is obtained by firing the obtained raw material mixture. The obtained fired product usually has the composition of the intended phosphor, but the particles are sintered into a fired cake.

Furthermore, when the number of heat-resistant containers in the baking furnace is large in baking, for example, the rate of heat transfer to each heat-resistant container can be made uniform, for example, by slowing the temperature increase rate. It is preferable for firing without any problems.
The firing conditions such as the firing temperature, pressure, and atmosphere in the firing step are preferably set appropriately for each phosphor to be manufactured.
Furthermore, in order to further improve the weather resistance such as moisture resistance or to improve the dispersibility of the phosphor in the phosphor-containing part of the light emitting device, the surface of the phosphor is coated with a different substance as necessary. You may perform surface treatments, such as.
Examples of substances that can be present on the surface of the phosphor (hereinafter also referred to as “surface treatment substances”) include organic compounds, inorganic compounds, glass materials, and the like. Examples of the organic compound include acrylic resins, heat-meltable polymers such as polycarbonate, polyamide, and polyethylene, latex, polyorganosiloxane, and the like.
Examples of inorganic compounds include magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, tin oxide, germanium oxide, tantalum oxide, niobium oxide, vanadium oxide, boron oxide, antimony oxide, zinc oxide, yttrium oxide, oxide Examples thereof include metal oxides such as lanthanum and bismuth oxide, metal nitrides such as silicon nitride and aluminum nitride, orthophosphates such as calcium phosphate, barium phosphate, and strontium phosphate, and polyphosphates. And at least one selected from the group consisting of lithium phosphate, sodium phosphate, and potassium phosphate, and at least one selected from the group consisting of barium nitrate, calcium nitrate, strontium nitrate, barium hydrochloride, calcium hydrochloride, and strontium hydrochloride. Can also be used in combination. Among them, it is preferable to use a combination of sodium phosphate and calcium nitrate. Further, when barium, calcium, or strontium is present on the phosphor surface, the surface treatment can be performed using only a phosphate such as sodium phosphate.

Examples of the glass material include borosilicate, phosphosilicate, and alkali silicate. Any one of these surface treatment substances may be used alone, or two or more thereof may be used in any combination and ratio.
The phosphor subjected to the surface treatment has these surface treatment substances. Examples of the presence of the surface treatment substance include the following.
(I) A mode in which the surface treatment substance constitutes a continuous film and covers the surface of the phosphor.
(Ii) An embodiment in which the surface of the phosphor is coated by the surface treatment substance becoming a large number of fine particles and adhering to the surface of the phosphor.
The adhesion amount or the coating amount of the surface treatment substance on the surface of the phosphor is 0.1% by weight or more, 30% by weight or less, preferably 15% by weight or less based on the weight of the phosphor. desirable. If the amount of the surface treatment substance relative to the phosphor is too large, the light emission characteristics of the phosphor may be impaired. If the amount is too small, the surface coating will be incomplete, and the moisture resistance and dispersibility will not be improved. There is.
The surface treatment method is not particularly limited. For example, a metal oxide (described below)
And a coating treatment method using silicon oxide).
The phosphor is mixed in an alcohol such as ethanol and stirred, and further an alkaline aqueous solution such as ammonia water is mixed and stirred. Next, a hydrolyzable alkyl silicate such as tetraethylorthosilicate is mixed and stirred. After the resulting solution is allowed to stand for 30 minutes, the supernatant containing silicon oxide particles that have not adhered to the phosphor surface is removed. Next, alcohol mixing, stirring, standing, and removal of the supernatant are repeated several times, and then a vacuum treatment is performed at 150 ° C. for 2 hours to obtain a surface-treated phosphor.
In addition to the surface treatment method of the phosphor, for example, a method of attaching spherical silicon oxide fine powder to the phosphor, a method of attaching a silicon compound film to the phosphor, and coating the surface of the phosphor fine particles with polymer fine particles Methods, a method of coating the phosphor with an organic material, an inorganic material, a glass material, etc., a method of coating the surface of the phosphor by a chemical vapor reaction method, a method of attaching metal compound particles, and the like can be used.
As examples of the crystal structure of the phosphor, orthosilicate crystal structures such as (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Garnet-based crystal structure such as Ce, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Epatite-based crystal structure such as Eu, M ₃ Si ₆ O ₁₂ N ₂ : Eu (where M is an alkali A nitride-based crystal structure such as an earth metal element). Among these, an orthosilicate crystal structure or a garnet crystal structure is preferable.

(Green phosphor)
The emission peak wavelength of the green phosphor is usually 500 nm or more, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 542 nm or less, and more preferably 535 nm or less. If this emission peak wavelength λp is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and there is a possibility that the characteristics as green light will deteriorate.
In addition, the half-value width of the emission peak of the green phosphor is usually 10 nm or more and usually 130 nm or less, and is preferably adjusted as appropriate according to the application. If the full width at half maximum FWHM is too narrow, the emission intensity may decrease, and if it is too wide, the color purity may decrease.
The green phosphor has an external quantum efficiency of usually 60% or more, preferably 70% or more, and a median diameter D50 is usually about 1 μm.
As a specific example of the green phosphor, a europium activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fractured surface and emits light in the green region. Examples include earth silicon oxynitride phosphors.

Other green phosphors include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _{2. Si 2 O 8: Eu, (} Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Ce, Tb activated silicate phosphor such as Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu activated borate phosphate phosphor such as Eu, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halo silicate phosphor such as Eu, Zn ₂ SiO _4: Mn-activated silicate phosphors such as _{Mn, CeMgAl 11 O 19: Tb} , ₃ Al ₅ O _12: Tb-activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga 5 SiO 14: Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm activated thiogallate phosphors such as Eu, Tb, Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, Eu activated oxynitride phosphor such as Eu activated β sialon _{, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu such as Eu Activated aluminate phosphors, (La, Gd, Y) 2 O 2 S: Tb Tsukekatsusan sulfide phosphor such as Tb, LaPO _4: Ce, Ce and Tb such, Tb-activated phosphate phosphor, Sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphors such as K, Ce, Tb, Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn Eu, Mn activated halosilicate phosphors such as (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu activated thioaluminate phosphors and thiogallate phosphors such as Eu, (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn activated halosilicate phosphor such as Eu, Mn, M ₃ S i ₆ O ₉ N ₄ : Eu, M ₃ Si ₆ O ₁₂ N ₂ : Eu (where M represents an alkaline earth metal element). It is also possible to use Eu-activated oxynitride phosphors such as

In addition, as the green phosphor, it is also possible to use a pyridine-phthalimide condensed derivative, a benzoxazinone-based, a quinazolinone-based, a coumarin-based, a quinophthalone-based, a naltalimide-based fluorescent pigment, or an organic phosphor such as a terbium complex. is there.
Any one of the green phosphors exemplified above may be used, or two or more may be used in any combination and ratio.
(Orange to red phosphor)
The emission peak wavelength of the orange to red phosphor is usually in the wavelength range of 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. Is preferred.
Examples of such orange to red phosphors include europium represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu that is composed of fractured particles having a red fracture surface and emits light in the red region. The activated alkaline earth silicon nitride phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Eu And europium activated rare earth oxychalcogenide phosphors represented by the formula:
In addition, the half-value width of the emission peak of the red phosphor is usually in the range of 1 nm to 50 nm.
The red phosphor has an external quantum efficiency of usually 60% or more, preferably 70% or more, and a median diameter D50 is usually about 1 μm.

And a phosphor containing oxynitride and / or oxysulfide containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W and Mo, A phosphor containing an oxynitride having an alpha sialon structure in which some or all of the elements are substituted with Ga elements can also be used. These are phosphors containing oxynitride and / or oxysulfide.
In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphors of (Ba, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphors such as Eu and Mn, Eu-activated tungstate phosphors such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, LiY _{9 (SiO 4) 6 O 2:} Eu, (Sr, Ba, Ca) 3 SiO 5: Eu, Sr 2 BaSiO 5: Eu -activated silicate phosphors such as Eu, _{Y, Gd) 3 Al 5 O} 12: Ce, (Tb, Gd) 3 Al 5 O 12: Ce -activated aluminate phosphor such as Ce, (Mg, Ca, Sr , Ba) 2 Si 5 (N, Eu-activated oxides such as O) ₈ : Eu, (Mg, Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Eu , Nitride or oxynitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn activated halophosphate phosphor such as Eu, Mn, Ba ₃ MgSi ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn activated silicate phosphor such as Eu, Mn, 3.5MgO · 0.5MgF ₂ · GeO _2: Mn activated germanate salt phosphors such as Mn, Eu Tsukekatsusan nitride phosphor such as Eu-activated α-sialon, (Gd, Y, Lu, _{a) 2 O 3: Eu,} Eu Bi, etc., Bi-activated oxide phosphor, (Gd, Y, Lu, La) 2 O 2 S: Eu, Eu Bi, etc., Bi Tsukekatsusan sulfide phosphor (Gd, Y, Lu, La) VO ₄ : Eu, Bi activated vanadate phosphors such as Eu and Bi, SrY ₂ S ₄ : Eu and Ce activated sulfide phosphors such as Eu and Ce, CaLa ₂ S ₄ : Ce-activated sulfide phosphor such as Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Eu, such as Mn, Mn activated phosphate phosphor, (Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) x Si y Nz: Eu, Ce (where x, y, z represent an integer of 1 or more. Eu, Ce-activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH): Eu, Mn-activated halophosphoric acid such as Eu, Mn Salt activated phosphor, Ce-activated silicate fluorescence such as ((Y, Lu, Gd, Tb) ₁ -x-yScxCey) ₂ (Ca, Mg) ₁ -r (Mg, Zn) ²⁺ rSiz-qGeqO ₁₂ + δ It is also possible to use a body or the like.

Examples of red phosphors include β-diketonates, β-diketones, aromatic carboxylic acids, red organic phosphors composed of rare earth element ion complexes having an anion such as Bronsted acid as a ligand, and perylene pigments (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.
Among these, as red phosphors, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr , Ba) AlSi (N, O) ₃ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu, It is preferable to contain (La, Y) ₂ O ₂ S: Eu or Eu complex, more preferably (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si. (N, O) ₂ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce, (Sr, Ba) ₃ SiO _{5: Eu, (Ca, Sr} ) S: Eu or _{(La, Y) 2 O 2} S: Eu or Eu (dibenzoylmethane) ₃ · 1, Preferably comprises a β- diketone Eu complex or carboxylic acid type Eu complex such as 10-phenanthroline complex, (Ca, Sr, Ba) 2 Si 5 (N, O) 8: Eu, (Sr, Ca) AlSi ( N, O): Eu or (La, Y) ₂ O ₂ S: Eu is particularly preferred.
Of the above examples, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.
In addition, orange or red fluorescent substance may use only 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

(Blue phosphor)
The emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, more preferably 460 nm or less. Preferably it is.
In addition, the half-value width of the emission peak of the blue phosphor is usually in the range of 20 nm to 80 nm.
The blue phosphor has an external quantum efficiency of usually 60% or more, preferably 70% or more, and a median diameter D50 is usually about 1 μm.
Such a blue phosphor is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape, and europium represented by (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu that emits light in a blue region. The activated barium magnesium aluminate-based phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the blue region (Mg, Ca, Sr, Ba) ₅ (PO ₄ ) ₃ (Cl , F): a europium activated calcium halophosphate phosphor represented by Eu, and a growth crystal having a substantially cubic shape as a regular crystal growth shape, and emits light in a blue region (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: europium-activated alkaline earth aluminate phosphor represented by Eu, which is constituted by fractured particles having a fractured surface, blue-green Emission at a region (Sr, Ca, Ba) Al 2 O 4: Eu or _{(Sr, Ca, Ba) 4} Al 14 O 25: europium-activated alkaline earth represented by Eu aluminate-based phosphor, and the like .

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Tb, Sm, BaAl ₈ O ₁₃ : Eu attached Active aluminate phosphor, Ce-activated thiogallate phosphor such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, Eu, Mn such as (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn Active aluminate phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu, Mn, Eu-activated halophosphate phosphors such as Sb, BaAl ₂ Si _{2 8: Eu, (Sr, Ba} ) 3 MgSi 2 O 8: Eu -activated silicate phosphors such as _{Eu, Sr 2 P 2 O 7} : Eu -activated phosphate phosphor such as Eu, ZnS: Ag, ZnS : Sulfide phosphors such as Ag and Al, Y ₂ SiO ₅ : Ce activated silicate phosphors such as Ce, Tungsten phosphors such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn _{, (Sr, Ca) 10 (} PO 4) 6 · nB 2 O 3: Eu, 2 SrO · 0.84P 2 O 5 · 0.16B 2 O 3: Eu, Mn -activated borate phosphate phosphors such as Eu _{body, Sr 2 Si 3 O 8 ·} 2 SrCl 2: Eu activated halo silicate phosphor such as _{Eu, SrSi 9 Al 19 ON 31} : Eu, Eu Tsukekatsusan nitride phosphor such EuSi ₉ Al ₁₉ ON _{31 , La 1 -xCexAl (Si 6 -zAlz} ) (N 10 -zOz) ( wherein, x, and y are each 0 ≦ x ≦ 1, Is a number satisfying ≦ z ≦ 6.), La 1 -x-yCexCayAl (Si 6 -zAlz) (N 10 -zOz) ( wherein, x, y, and z, respectively, 0 ≦ x ≦ 1, It is also possible to use Ce-activated oxynitride phosphors such as 0 ≦ y ≦ 1 and 0 ≦ z ≦ 6.

In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyralizone-based, triazole-based compound fluorescent dyes, thulium complexes and other organic phosphors can be used. .
Among the above examples, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu or (Ba, Ca, Mg, Sr) ₂ SiO \ f ₁₄ : Eu is preferably included, and (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu or (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu is more preferable, and BaMgAl ₁₀ O ₁₇ : Eu, Sr ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu or Ba ₃ MgSi ₂ O ₈ : Eu is more preferable. Of these, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu or (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu is particularly preferred for illumination and display applications.
In addition, only 1 type may be used for blue fluorescent substance and it may use 2 or more types together by arbitrary combinations and a ratio.
(Yellow phosphor)
The emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. .
Further, the half-value width of the emission peak of the yellow phosphor is usually in the range of 60 nm to 200 nm.
The yellow phosphor has an external quantum efficiency of usually 60% or more, preferably 70% or more, and a median diameter D50 is usually about 1 μm.
Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.

In particular, RE3M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M consists of Al, Ga, and Sc. Or Ma ₃ Mb ₂ Mc ₃ O ₁₂ : Ce (where Ma is a divalent metal element, Mb is a trivalent metal element, and Mc is a tetravalent metal). A garnet-based phosphor having a garnet structure represented by AE ₂ MdO ₄ : Eu (where AE is at least one selected from the group consisting of Ba, Sr, Ca, Mg, and Zn) And Md represents Si and / or Ge.) Orthosilicate phosphors represented by the above, etc., and oxynitrides obtained by substituting part of oxygen of constituent elements of phosphors of these systems with nitrogen -Based phosphor, AEAlSi (N , O) ₃ : Ce (wherein AE represents at least one element selected from the group consisting of Ba, Sr, Ca, Mg and Zn), etc., nitride-based phosphors having a CaAlSiN ₃ structure, etc. And phosphors activated with Ce.
Other examples of yellow phosphors include sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu. Body, Ca x (Si, Al) ₁₂ (O, N) ₁₆ : a phosphor activated by Eu such as an oxynitride phosphor having a sialon structure such as Eu, (M ₁ -a-bEuaMnb) ₂ (BO ₃ ) _1- p (PO ₄ ) pX (wherein M represents one or more elements selected from the group consisting of Ca, Sr, and Ba, and X is selected from the group consisting of F, Cl, and Br) A, b, and p each represent a number that satisfies 0.001 ≦ a ≦ 0.3, 0 ≦ b ≦ 0.3, and 0 ≦ p ≦ 0.2. It is also possible to use a Eu-activated or Eu-Mn co-activated halogenated borate phosphor.
Examples of yellow phosphors include brilliant sulfoflavine FF (Color Index Number 56205), basic yellow HG (Color Index Number 46040), eosine (Color Index Number 45G80), 45G Etc. can also be used.

Furthermore, a bis (triazinylamino) stilbene disulfonic acid derivative, a bisstyryl biphenyl derivative (ultraviolet excitation 400 to 450 nm fluorescence), or the like can also be used.
In particular, the nano fluorescent material: Si nano fluorescent material, ZnS nanophosphors, YAG: Ce nanophosphors, LaPO _4: Ln nanophosphors, dye-doped silica nanoparticles phosphors, semiconductor nanoparticles, CdSe-ZnS quantum dots or the like, the Since the particle diameter is much smaller than the relief period of the hologram relief, it can be formed uniformly on the relief surface, and the formation thickness is easy to control. When the semiconductor thin film is formed by ultra-fine processing, the semiconductor thin film can be formed with high precision and an ultra-thin film, and the coherence can be improved by controlling the waveform and intensity of the emitted light.
In the fluorescent semiconductor quantum dot, the central core (core) is made of, for example, cadmium selenide (CdSe), and the outer side thereof is covered with a zinc sulfide (ZnS) coating layer (shell). Yes. By changing the diameter of the metal compound, the emitted fluorescence wavelength changes. Since the biopolymer arranged around the quantum dot has a reactive group peculiar to the biopolymer, the phosphor can be specifically arranged using the reactive group.
As the ultraviolet light-emitting phosphor, the peak of the fluorescence spectrum that is emitted when excited by ultraviolet light and returns to a lower energy level is in a wavelength region such as blue, green, and red. Examples of such ultraviolet light-emitting phosphors include Ca ₂ B ₅ O ₉ Cl: Eu ²⁺ , CaWO ₄ , ZnO: Zn, Zn ₂ SiO ₄ : Mn, Y ₂ O ₂ S: Eu, ZnS: Ag. YVO ₄ : Eu, Y ₂ O ₃ : Eu, Gd ₂ O ₂ S: Tb, La ₂ O ₂ S: Tb, Y ₃ Al ₅ O ₁₂ : Ce, etc. Several of these are mixed and used at an appropriate ratio.
These have peaks in the fluorescence spectrum outside the blue, red, and green wavelength regions. Further, the weight ratio of the ultraviolet fluorescent substance in the ink is not limited as long as the fluorescence can be detected by the light receiving element of the reading head.
On the other hand, some infrared light emitting phosphors have the property of receiving visible light having a wavelength λ2 upon receiving excitation light having a wavelength λ1, and having the properties of λ1 = λ2 and λ1> λ2. Examples of such infrared light emitting phosphors include YF ₃ : Yb, Er, ZnS: CuCO, and the like.

Specific examples include Lumogen FV Violet 570 (Naphthalimide: 374 nm → 413 nm), Lumogen F Yellow 083 (perylene: excitation wavelength 476 nm → emission wavelength 490 nm: the same applies hereinafter), Lumogen F orange (perylene: 525 nm → 539 nm). ), Lumogen F Red 305 (perylene: 578 nm → 613 nm), etc.
Fluorescent pigments manufactured by Deigro: Gropril T / GT series, ACT series, Z / ZQ series, GPL series, LHY series, Fluorescent dyes: DIVELIGHT D-818 Roanoke yellow, D-784 ALPARTA yellow, D-208 APACHI yellow D-288 Cherokee Red, D-688 Colorado Red, D-298 Columbia Blue, etc.
Fluorescent pigments manufactured by Sinloi: Sinroicolor FZ-2000 series (FZ-2001RED, etc.), FZ-2800 series (FZ-2808 Blue, etc.), SX-100 series (SX-104 Orange, etc.), SX-1000 series (SX-1004 Orange) SX-1005 Lemon Yellow, SX-1007 Pink, SX-1037 Magenta: average particle size 1.0 μm or less, SW-10 series (SW-11 Red Orange, SW-12NG Green, SW-13 Red Orange, SW-14 NO Orange, SW-15N Lemon Yellow , SW-16N Orange Yellow, SW-07Cerise, SW-17Pink, SW-27Rose, SW-37Rubine, SW-47Viole , SW-28Blue: average particle size 1.0 μm or less), SP series, SF-3000 series (ultrafine particle type), SF-5000 series (ultrafine particle type), SF-8000 series (ultrafine particle type), Lumilite Nano RY202 ( Particle size 30 nm, 365-370 nm → 619 nm), etc.

Manufactured by Moritechx Co., Ltd .: fluorescent particles (green: 468 nm → 508 nm) G25 (particle size 0.03 μm), G40 (particle size 0.04 μm), G50 (particle size 0.05 μm), G75 (particle size 0.07 μm), G85 (particle size 0.09 μm), G100 (particle size 0.10 μm), G140 (particle size 0.14 μm), G200 (particle size 0.20 μm), G250 (particle size 0.25 μm), G300 (particle size 0) .30 μm), G400 (particle size 0.40 μm), G450 (particle size 0.45 μm), G500 (particle size 0.50 μm),
Fluorescent particles (green: 360 nm → 530 nm) 34-1 (average particle size 3.0 μm),
Fluorescent particles (blue: 365 nm → 447 nm) B50 (particle size 0.05 μm), B100 (particle size 0.10 μm), B150 (particle size 0.14 μm), B200 (particle size 0.20 μm), B300 (particle size 0) .30 μm), B400 (particle size 0.40 μm), B500 (particle size 0.50 μm),
Fluorescent particles (red: 542 nm → 612 nm) B50 (particle size 0.05 μm), B60 (particle size 0.05 μm), B100 (particle size 0.10 μm), B160 (particle size 0.16 μm), B200 (particle size 0) .20 μm), B300 (particle size 0.30 μm), B400 (particle size 0.40 μm), B500 (particle size 0.50 μm), etc.

UV excitation fluorescent pigments UVP-1 (emission wavelength 421 nm), UVB-1 (emission wavelength 453 nm), UVG-2 (emission wavelength 517 nm), UVR-2 (emission wavelength 626 nm), visible light excitation fluorescent pigment LMS-570 (450-520 nm → 570 nm), LMS-560 (450-467 nm → 560 nm), LMS-550 (450-465 nm → 550 nm), LMS-540 (450-465 nm → 540 nm), etc.
Qdot525 nanocrystal (350-488 nm → 525 nm), Qdot565 nanocrystal (350-488 nm → 565 nm), Qdot585 nanocrystal (350-488 nm → 585 nm), Qdot605 nanocrystal (350-488 nm → 605 nm), Qdot625 nano Crystal (350-488 nm → 625 nm), Qdot655 nanocrystal (350-488 nm → 655 nm), Qdot705 nanocrystal (350-488 nm → 705 nm), Qdot800 nanocrystal (350-488 nm → 800 nm), etc.
Evidot manufactured by Evident Technologies, Inc .: CdSe / ZnS core shell Evidot (average particle size 7.2 to 9.6 nm, emission wavelength 490 nm to 620 nm), etc.
Quantum dots manufactured by Nippon Quantum Design Co., Ltd .: carboxyl group type, amino group type: diameters of 3.0 nm to 8.3 nm and emission wavelengths of 530 nm to 620 nm can be suitably used.

Next, the principle of holography will be described.
If the object is illuminated with coherent light and the light diffracted from the object illuminates the recording medium (photoresist, etc.), the object wave diffracts from the object and reaches the recording surface.
F (x, y) = A (x, y) EXP [φ (x, y)]
It is expressed. here,
A (x, y) is the amplitude distribution of the object wave,
φ (x, y) is a phase distribution.
At this time, the intensity distribution of the light wave reaching the recording medium is recorded on the recording medium. Its intensity distribution is
I (x, y) = | F (x, y) | ² = A ² (x, y) (1)
Thus, the phase distribution is not recorded.
Here, when an object wave and a coherent light wave (referred to as a reference wave) are superimposed, the intensity distribution of the recorded light wave is
I (x, y) = | F (x, y) + R (x, y) | ²
= | F (x, y) | ² + | R (x, y) | ²
+ F (x, y) R ^* (x, y) + F ^* (x, y) R (x, y) (2)
It becomes. (* Represents a complex conjugate term.)

However, if the reference light is a plane wave incident on the recording surface at an angle θ,
R (x, y) = r (x, y) EXP (2πiαx) (3)
Write,
α = SIN (θ) / λ (4)
It is. In the first and second terms of (2), the phase information is missing for both the intensity of the object wave and the intensity of the reference wave. The third term and the fourth term are interference terms. F (x, y) R * (x, y) =
A (x, y) r (x, y) EXP [i [φ (x, y) -2παx]] (5)
F * (x, y) R (x, y) =
A (x, y) r (x, y) EXP [-i [[phi] (x, y) -2 [pi] [alpha] x]] (6)
The phase term φ (x, y) of the object remains. (5) and (6) are complex conjugates of each other, and the third term in (4.2) includes the complex amplitude distribution of the object. Substituting (5) and (6) into (2),
I (x, y) = | F (x, y) | ² + | R (x, y) | ²
+ 2A (x, y) r (x, y) COS [2παx−φ (x, y)] (7)
It becomes. It can be seen that the object wave and the reference wave interfere to form an interference fringe.

In this way, holography is a method in which a reference wave is superimposed on an object wave and interference recording is performed, and the phase information of the object is recorded without being lost. A recording of (7) is called a “hologram”. The intensity transmission or amplitude reflectance of the hologram is the recorded intensity distribution I (x, y)
Proportional,
T (x, y) = τI (x, y) (8)
Let's call it. When the reference wave used when recording on this hologram is at a predetermined angle, the wavefront transmitted or reflected by the hologram is
T (x, y) R (x, y) = τ (| F (x, y) | ² + | R (x, y) | ² )
+ ΤF (x, y) | R (x, y) | ²
+ ΤF ^* (x, y) R ² (x, y) (9)
Can be expressed. This second term is τF (x, y) | R (x, y) | ² =
τA (x, y) r ² (x, y) EXP [iφ (x, y)]] (10)
The third term is
τF * (x, y) R ² (x, y) =
τA (x, y) r ² (x, y) EXP [−iφ (x, y) + 2πiα] (11)
Call it.

Therefore, the first term of (9) is a light beam penetrating the hologram in the same direction as the illumination light or a specularly reflected light beam, and the second term is a light wave having an amplitude proportional to the object light from (10). From (11), it can be seen that the third term is a light wave having a phase distribution conjugate with the object wave and propagating in the direction of 2θ.
In this way, the complex amplitude distribution can be recorded and reproduced using the holographic technique.
In the case of the present invention, the amplitude transmittance or reflectance of the hologram is proportional to the recorded intensity distribution and is expressed by the equation (8), but the reference wave used when recording on this hologram. Is not a predetermined angle, but a light-emitting wave having a spatial distribution similar to the amplitude transmittance or amplitude reflectance of (8) is emitted from this hologram.
Therefore, the emission wave is emitted while maintaining the phase term already recorded in the hologram, regardless of the conventional principle of hologram reproduction in which the phase term recorded in the hologram is given to the reference light. Therefore, theoretically, it has a three-dimensional continuous curved light emitting surface having a spatial function including the phase difference of an object, and light is emitted from the one curved surface.
To simplify the conventional hologram reproduction principle for the transmission type, when parallel light as reference light is applied to the hologram, the parallel light is shielded in the shielding part, and the parallel light is transmitted only from the transmission part. Diffraction occurs at the boundary between the transmission part and the shielding part, receives the phase term of the object, and the entire component transmitted through the hologram is superimposed, which becomes the hologram reproduction light and reaches the observer's eyes.
In the case of the present invention, there is no parallel light as the reference light described above, and the emitted light retains the phase term of the object when emitting light on the light emitting surface provided in contact with the hologram relief. Hologram reproduction is performed by an interference phenomenon between radiated lights.

The interference effect between synchrotron radiation that does not have temporal and spatial coherence does not cause sufficient interference like laser light, but hologram reproduction is performed at the same level as when a hologram is illuminated with low coherent light. . Since the reproduction is based on the principle as described above, the reference light at the time of hologram photographing is preferably parallel light (because complicated reference light cannot be reproduced), or “hologram represented by a diffraction grating” (diffraction The grating is preferably both object light and reference light.) The diffraction grating formed by electron beam drawing, such as a computer generated hologram, is precise and suitable.
Further, for the above reason, in order to make the hologram reproduction image clearer, it is necessary to give the radiation light a characteristic similar to temporal or spatial coherence, for example, the light emitting surface of the light emitter. It is desirable to reduce the thickness of the light emission and to narrow the emission wavelength width. Further, the excitation light source is also preferably a small shape, and a spot shape or the like is particularly suitable.
In addition, it is desirable that the wavelength difference between the excitation light for exciting the illuminant and the emission wavelength is large, and it is also effective to amplify only the emission light by filtering the excitation light during observation.
As an excitation light source, energy such as ultraviolet rays, visible rays, electron beams, X-rays and the like, and depending on the case, a light source capable of emitting infrared energy can be used to emit fluorescence, etc. In order to use it for hologram authentication, it is necessary to use a light source corresponding to the phosphor, and an ultraviolet light source, a visible light source having a predetermined intensity, wavelength, and size of an illumination spot, an infrared light source is used in some cases. .
From the fluorescent layer provided so as to be in contact with the hologram relief surface by illumination by these light sources, and more specifically, from the phosphor contained in the fluorescent layer, fluorescence of a wavelength different from the wavelength of the illumination light source, etc. To express. Since the fluorescence emission and the like have the same spatial phase as the hologram relief and have a wavelength (fluorescence wavelength) different from that of the illumination light source, the direction of specularly reflected light (0th order diffracted light) by the hologram relief, illumination The hologram image is reproduced in a direction different from the diffraction direction by the light wavelength (excitation light wavelength), that is, in the diffraction direction by the fluorescence wavelength.

However, when the thickness of the fluorescent layer is distributed on the hologram surface irrespective of the hologram relief, the fluorescence emission intensity distribution resulting from the thickness distribution may be reproduced in some cases. Unnecessary interference with light can occur, which can be a cause of blurring of the hologram reproduction image.
In order to eliminate this factor, the fluorescent layer is formed with a uniform thickness following the irregularities forming the hologram relief so that light emission of the same intensity can be generated from any position on the hologram relief surface. The reproduced image can be sharpened.
When ultraviolet light or infrared light other than visible light is used as the illumination light (excitation light) of the hologram label of the present invention, the light is not visible to the observer, and the hologram reproduction image is seen from the place where there is no illumination light. However, even if the illumination light is temporally and spatially coherent, as a result, this hologram reconstructed image emits light through a process of excitation and fluorescence. Therefore, the temporal and spatial coherence between the emitted lights is small, although the phase of the spatial hologram at the time of emission is included, the hologram reproduction image is a normal laser reproduction relief hologram. It is weaker than the reproduced image and is unclear.
Of course, if only observing the beam-shaped diffracted light, it is easy to check its color tone and diffraction direction, and it can be used as it is to determine the authenticity, but this weak and unclear hologram reproduction. In order to allow the observer to recognize the image and accurately determine its presence, the luminous performance of the phosphor is improved, and the diffraction angle is increased to increase the wavelength-diffraction angle dependency. It is necessary to increase the difference in the fluorescent light diffraction angle and further reduce the thickness of the fluorescent layer to suppress variation in the thickness direction of the fluorescent layer and make it uniform. (Since the light emitting surface contains phase information, its spatial shape is accurately reproduced.)

Furthermore, in order to express temporal coherence, excitation is performed with a pulse laser of 10 ⁻¹⁵ sec or less as a light source, and illumination is performed with a time interval between pulses of 10 ⁻⁷ sec or more that is a fluorescence emission time. It is also suitable. Thus, one fluorescent light emitting surface generated by one excitation pulse does not cause a disturbance phenomenon with the fluorescent light emitting surface generated by the next excitation pulse, and one fluorescent light emitting surface expressed by one pulse. Due to the holographic interference phenomenon caused by the above, a clear hologram reproduction image can be observed. Of course, even if a strobe light source that is simply turned on and off in seconds is used, the viewer seems to emit light continuously. When confirming with the above, the above-described effects can be sufficiently obtained.
The phosphor layer is made of phosphor ink mixed with resin or dispersed in a solvent (or water) on the hologram relief by gravure method, offset method, silk screen method, nozzle coating method or ink jet method. Can be formed.
At this time, by adjusting the content ratio of the phosphor in the fluorescent ink, the formed fluorescent layer can be formed with a uniform thickness following the unevenness forming the hologram relief.
The unevenness of the hologram relief is, for example, a gentle curve having an unevenness of a depth of 0.01 μm with a period of 1 μm level and can be regarded as a substantially flat surface. 1 to 10 pascals / second), exhibiting the leveling effect due to the weight of the ink itself, and by setting the solid content in the ink to 20% or less, further 10% or less, for example, for a thickness of 1 μm The variation can be suppressed to 1/10 or less, and further to 1/20 or less.

Here, although the fluorescent layer is on the order of 1 μm, in order to improve the clarity of the hologram reproduction image, it is preferable to make the fluorescent layer thin. For this purpose, the size of the phosphor is about 1.0 μm or less. Hereinafter, for example, 0.1 μm to 0.5 μm, more preferably 0.5 μm to 0.1 μm, and more preferably 3 to 10 nm, which is uniformly present in the hologram relief plane and in the thickness direction of the fluorescent layer Is preferably in a state of being arranged within 1 to 10 particles or 1 to 3 particles in units of one phosphor particle.
In particular, the nozzle coating method and the ink jet method can be formed only with a solvent and a phosphor without using a resin, and can be formed very thin as a phosphor layer (for one to three phosphors, etc.). Therefore, it is preferable. A resin may be formed thereon to fix the phosphors.
The hologram relief has an irregular shape with a period of about 1 μm, a depth of 0.01 μm, and a maximum of 0.5 μm. By providing a fluorescent layer only in this recess, the hologram relief is synchronized with the period of the hologram relief. The presence or absence of a fluorescent layer, that is, the presence or absence of fluorescent emission can also be provided.
The concave portion of the hologram relief is a concave portion when the fluorescent layer is formed on the hologram relief, and becomes the convex portion side when observed from the normal observation method, that is, from the hologram forming layer side. In order to form the light emission intensity distribution using the presence or absence of the fluorescent layer, it may be formed partially on either the concave or convex portion, and the entire concave portion may be filled with the fluorescent layer or the lowest portion of the concave portion. You may form in only a part of. However, since it is necessary to synchronize the phase distribution and the distribution to be formed, when forming a part thereof, it is necessary to always form the same phosphor at the same position.
As a method for selectively forming the fluorescent layer in the concave portion, a phosphor having a very small particle size (particle size is 10 nm, etc., not including a resin) dispersed in a solvent or the like is used. Alternatively, the fluorescent ink layer may be formed and the phosphor particles may move from the convex portion to the concave portion under its own weight while the solvent is volatilized.

Also, a regular diffraction grating is provided, and the phosphor layer uniformly provided thereon is tuned to the regular diffraction grating using photolithography, and is exposed, developed, and etched, so that the unevenness and the phosphor layer are synchronized. It can also be provided. According to this method, it is possible to control the thickness and size of the fluorescent layers scattered in the respective recesses, so that the entire relief surface can be formed so as to be “uniformly”.
What is formed by the above method includes the phase information of the hologram relief described in the hologram principle described above, and further includes amplitude information synchronized with the phase information. Is.
Therefore, the hologram light information of both the phase hologram and the amplitude hologram can be included in the emitted light, and a clearer hologram can be obtained. Also, since the fluorescent layer is formed discontinuously, individual parts of the fluorescent layer are very mobile when the hologram label is illegally peeled off, and the fluorescent layer is very easy to break. The authenticity can be improved.
In order to increase the clarity of the hologram reproduction image based on the above-mentioned hologram principle, it is desirable that the thickness of the fluorescent layer is thin. However, the thinner the thickness, the lower the fluorescence emission intensity during hologram reproduction. The layer thickness must be 0.003 μm or more and 1.0 μm or less, and more preferably 0.01 μm or more and 0.5 μm or less.
If it is less than 0.003 μm (one phosphor of the smallest particle size), the fluorescence emission intensity is too weak, and even if amplified using a photomultiplier tube, it is difficult to distinguish it from noise such as stray light. The emission intensity is sufficient for the purpose of the present invention, but the position of the curved surface carrying the phase information of the hologram relief is caused by the emission of a plurality of phosphors in the thickness direction. A plurality of holograms are present in the thickness direction, and as a result, the hologram reproduction image becomes unclear.
On the other hand, the fluorescence emission intensity is ensured as 0.01 μm or more (for three phosphors having the smallest particle diameter), and the position of the curved surface carrying the phase information is clarified as 0.5 μm or less, so that a hologram reproduction image is obtained. It shall be clear.
Since such a fluorescent layer is very easily broken when the hologram label is illegally peeled off, it is possible to further improve authenticity determination.

An adhesive layer can be provided on the fluorescent layer to form the hologram label of the present invention.
As the transparent resin that can be used for the adhesive layer, polymethyl methacrylate, polybutyl acrylate, polyvinylidene, methyl cellulose, fluororesin, melamine resin, or a mixture thereof can be appropriately used, and a plasticizer as necessary. , And other additives can be used (meaning an adhesive).
These pressure-sensitive adhesives are appropriately dissolved in a solvent or water and coated on the hologram relief of the relief hologram using a coating method such as gravure printing, silk printing, or a solvent-free hot melt method. The thickness after drying may be 5 μm to 50 μm.
If the thickness is less than 5 μm, the adhesive strength to the adherend to which the hologram label is attached (adhesion strength or peel strength) is insufficient, and if it exceeds 50 μm, the hologram label is suitable for handling. It will be lacking.
The transparent resin used for the above-mentioned pressure-sensitive adhesive layer is appropriately selected from those having strong adhesiveness with the fluorescent layer.
The adhesive layer is made of a material having light scattering properties, for example, transparent inorganic pigment fine particles having a high refractive index (titanium dioxide pigment: refractive index 2.70, iron oxide pearl pigment: refractive index 3.0, etc.). It is possible to mix a relatively large amount (because the light passing through the adhesive layer does not contribute to “image formation of the hologram reproduction image on the side to be observed”). The light traveling in the direction opposite to the observation side can be diffusely reflected and attenuated, and the viscosity of the adhesive layer can be suppressed to prevent the hologram label from blocking.
180-degree peel strength between the adhesive layer and the fluorescent layer (peel strength is measured according to JIS Z-0237, with a peel rate of 500 mm / min) is 100 g / 25 mm to 3 kg / 25 mm, particularly 300 g / 25 mm or more. Is desirable. When the hologram label is less than 100 mm / 25 mm, when an attempt is made to remove the hologram label illegally after the hologram label is attached to the adherend, peeling at the interface between the fluorescent layer and the adhesive layer is likely to occur. It becomes difficult to break.

In terms of preventing fraud, it is desirable that the peel strength between the adhesive layer and the fluorescent layer is high, but an adhesive exceeding 3 kg / 25 mm is inferior in label processing suitability and label sticking suitability.
After applying a hologram label that can only be seen as a mere “label” on the appearance to an appropriate position on a desired adherend, an unauthorized person tries to remove the “label” illegally. Easily peels off, the transparent substrate side remainder remains on the transparent substrate side, the adherend side residue remains on the adherend side, characters such as "open" appear, and this "label" is "brittle label" It turns out that it was.
At this stage, the fraudster thinks that if the remaining part on the adherend side is removed with a solvent or the like, the surface of the adherend is deteriorated with the solvent, etc., and the original `` label '' is left while leaving the remaining part on the adherend side. It will try to restore the sticking state.
That is, as a fake “label”, a normal brittle label that does not have a hologram forming layer is prepared separately, and the adhesive layer of the fake “label” is used to fill in the recess or hole in the remaining part of the adherend. Then, the fake “label” is stuck on the remaining part of the adherend.
The fraudster is convinced that the fraudulent act could be concealed by returning the adherend to the original place, assuming that the original "label" sticking state could be restored by this act. When the “true owner” of the body applies predetermined illumination light such as ultraviolet rays of a predetermined wavelength from this false “label” shape, the fluorescent layer remaining on the adherend side is emitted, Since the hologram reproduction image by the emission wavelength is expressed, and the hologram reproduction image appears in a state of being “shielded” in a letter shape such as “open”, it is easy that some “injustice” has been performed, And it can judge reliably.
Of course, even if a new fake “label” is created using a transparent substrate peeled off by an unauthorized person, if the “label” is placed under the same illumination light, this time, “open”, etc. A hologram reproduction image appears only in the character portion of, indicating the presence of an “injustice” act.
Furthermore, trying to restore the original state using a fake “label” using the transparent base material that the unauthorized person has peeled off, accidentally, the position of the depression on the adherend side remaining part and the transparent base side remaining part Even if the positions of the holograms match, the position of the hologram relief is spatially deviated, so that the image formation position of the hologram reproduction image is also deviated, indicating the presence of “illegal”.
In addition, even if an unauthorized person attempts to use the transparent base material that has been peeled off, and directly bond the position of the depression on the adherend side remaining part and the position on the transparent base material side residual part, It is very difficult to obtain the original clear hologram reproduction image due to deterioration of the hologram relief due to the rupture of the hologram forming layer or the fluorescent layer, or air mixing at the time of bonding, and of course, the hologram forming layer Since even the existence of itself cannot be known, it is impossible to confirm whether or not the “compensation” was successful.

According to the present invention , when the hologram label according to the production method of the present invention is peeled off after being attached to a desired adherend, peeling is preferentially performed at the interface between the transparent substrate of the hologram label and the hologram forming layer. After being generated and peeled off, the fluorescent layer corresponding to the region where the desired pattern has been surface activated is easily broken.

It is a Jablonsky figure. It is sectional drawing of the hologram label A which shows one Example of this invention. 1 is a process for stripping an embodiment of the present invention. FIG. 4 is a process for determining after peeling according to an embodiment of the present invention. FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
(Transparent substrate) The transparent substrate 1 used in the hologram label of the present invention can be reduced in thickness, and is suitable for mechanical strength and processing and processing in producing the hologram label A. Those having solvent resistance and heat resistance are preferred. Since it depends on the purpose of use, it is not limited, but a film-like or sheet-like plastic is preferable. (See Figure 2.)
For example, various plastic films such as polyethylene terephthalate (PET), polycarbonate, polyvinyl alcohol, polysulfone, polyethylene, polypropylene, polystyrene, polyarylate, triacetyl cellulose (TAC), diacetyl cellulose, and polyethylene / vinyl alcohol can be exemplified. .
One surface of the transparent substrate 1 is subjected to a surface activation treatment in a pattern to provide a surface activated portion 2, and a portion other than the surface activated portion 2 is subjected to a surface inactivation treatment. do it,
The difference in adhesion between the transparent substrate 1 and the hologram forming layer 3 between the surface activated portion 2 and the other portion, that is, the difference in peel strength is increased. (See Figure 2.)
The thickness of the transparent substrate 1 is usually 5 to 250 μm, but is preferably 25 to 100 μm for proper handling as a “label”.
Further, a transparent resin may be coated on one surface of the transparent substrate 1, and the above-described effects may be obtained by performing the above-described treatment on the transparent resin. (Not shown)
In addition to the above resin group, the resin used for the hologram forming layer 2 described below can be used for this transparent resin.

Furthermore, for the purpose of expanding the difference in peel strength between the surface-activated part 2 and the other or surface-inactivated part, it is between the transparent substrate 1 and the hologram forming layer 3, that is, A transparent resin which is formed as a protective layer on the hologram forming layer 3 and has a peelability from the transparent substrate 1 may be provided. (Not shown)
Also in this case, as the transparent resin, in addition to the resin group described above, a resin used for the hologram forming layer 3 described below can be appropriately used.
Of course, in consideration of environmental impact, a transparent biodegradable plastic film or sheet can also be used. As a chemical synthesis system, a lactone resin: ε-caprolactone, 4-methylcaprolactone, 3,5,5 -Trimethylcaprolactone, 3,3,5-trimethylcaprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, a homopolymer of enanthlactone or a copolymer of two or more of these monomers, a mixture thereof, polycaprolactone Or polybutylene succinate resin: polybutylene succinate adipate, a mixture of polybutylene succinate and polycaprolactone, a mixture of polybutylene succinate and polybutylene succinate adipate, and polybutylene succinate adipate A mixture of polylactic acid, or a polylactic acid, a mixture of polylactic acid and D-lactic acid, or a polyester resin synthesized from a low molecular weight aliphatic dicarboxylic acid and a low molecular weight aliphatic diol, such as succinic acid and butanediol, ethylene Polymerization by adding aliphatic isocyanate to a mixture of modified polyvinyl alcohol, aliphatic polyester resin and starch, low molecular weight aliphatic polyester, such as combinations with glycols, oxalic acid and neopentyl glycol, butanediol, ethylene glycol, etc. What was made to be suitable is suitable.
In addition, natural products such as animal natural materials such as gelatin, plant natural materials such as cellulose, etc .: starch fatty acid ester, starch chitonan, cellulose, etc., as microbial production systems such as polyhydroxybutyrate and polyesters: carbon source P based on 3-hydroxypropionic acid, 4-hydroxybutyric acid, γ-butyrolactone (3HB-CO-4HB), propionic acid as carbon source, P based on valeric acid (3HB-CO-3HV), etc. Is preferred.

(Surface activation treatment)
Surface activation treatment for one surface of the transparent substrate 1 includes carbon dioxide laser irradiation, far infrared carbon dioxide laser irradiation, 172 nm vacuum ultraviolet (VUV, excimer light) irradiation, oxygen sensitized excimer light irradiation, plasma treatment, and open. The chemistry of the outermost surface of the transparent substrate 1 by photon energy (7.2 eV), discharge energy, electron beam energy, etc. larger than the chemical bond energy of the outermost surface of the transparent substrate 1 such as plasma treatment, corona treatment, electron beam irradiation treatment, etc. Physical treatment such as breaking bonds, or absorbing ozone by atmospheric oxygen to generate ozone or directly excited oxygen, such as 172 nm vacuum ultraviolet light, and generating functional groups by this contact;
Oxidation treatment of transparent substrate by applying oxidizing agents such as permanganate and peroxide, primer coating treatment, vinyl / epoxy / methacryloxy / amino / mercapto / acryloxy / isocyanate / styryl / alkoxy oligomer type silane cup Physical treatment such as chemical treatment such as treatment using a ring agent, argon beam etching treatment that is vacuum treatment, etching solution treatment that partially dissolves the transparent base material, and sandblasting that mechanically scrapes the surface of the transparent base material A rough surface forming process or the like can be used. (The process is not shown.) (See FIG. 2.)
By the surface activation treatment of the transparent substrate 1, a high peel strength can be obtained even for a resin having low adhesion to the transparent substrate 1, that is, a resin having a low peel strength.

The surface tension or surface energy of the transparent substrate 1 is increased using the above surface activation treatment. Since the peel strength is determined by the resin used for the hologram forming layer 3 and the method of forming the resin, the interfacial tension value cannot be uniquely specified, but 60 to 80 mN / m is suitable as a guide. (In polyethylene terephthalate resin, 36 mN / m increases to 60 mN / m, and the peel strength from the melamine resin as the hologram forming layer increases from 0.4 kg / 25 mm width to 2.1 kg / 25 mm width.)

Therefore, one surface of the transparent substrate 1 is surface activated to improve the adhesion between the transparent substrate 1 and the hologram forming layer 3 formed thereon in the surface-activated portion 2, and 0.5 kg / 25 mm width to 3.0 kg / 25 mm width strength (by 180 ° peel test specified in JIS Z0237), leaving the surface activated part 2 as a desired pattern that can be visually recognized, and others Surface inactivation treatment is performed for the region.
This "pattern" can be any visible display such as characters, figures, symbols, etc., but typically, it displays a character display such as "open" in the sense that it shows evidence that the label has been peeled off. Therefore, assuming a design in which two characters “open” and “sealed” are repeatedly expanded vertically and horizontally, the outermost surface portion on the transparent substrate 1 corresponding to the inside of the line of those characters is surfaced. The activation treatment is performed to obtain the surface activated portion 2.
Among the surface activation treatments, the optical treatment such as laser irradiation or the physical treatment such as plasma treatment does not generate irregularities on the treated surface of the transparent substrate 1 and maintains the specularity. Since the surface activation effect by the activation treatment is large, it is particularly desirable and excellent in optical transparency.
Further, instead of performing the surface activation treatment uniformly in the above-mentioned “pattern”, the “pattern” is further refined into a “fine pattern”, for example, a fine pattern such as a halftone dot pattern, a checkered pattern, or a random pattern. Surface activation treatment is performed only on a certain region (for example, by performing surface activation treatment in a dot pattern, portions other than halftone dots in the “pattern” remain as portions not subjected to surface activation treatment). The action of the force to break the hologram forming layer 3 and the fluorescent layer 4 when the transparent substrate 1 is peeled (the direction of action of the force, its magnitude, etc.) is further complicated and the “breaking” property is improved. Can be made.

After the entire surface is activated on one surface of the transparent substrate 1, the shape obtained by reversing the above-mentioned “pattern” from light to dark (“pattern” as “positive pattern” means “negative pattern” obtained by reversing it) In order to form a “surface-inactivated part”, or to form a “surface-inactivated part” having a desired shape directly on the transparent substrate 1. ,
Solvents such as ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, which dissolves only the outermost surface of the transparent substrate 1 or reacts with activated functional groups to eliminate the activity of the functional groups. Cyclohexanone, diacetone alcohol, isophorone, diisobutyl ketone, etc.), alcohols (methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, etc., and further aqueous solutions thereof), aromatics ( Benzene, toluene, xylene, Solvesso No. 100, Solvesso No. 150, Cactus P-180, etc.), cyclic hydrocarbons (cyclohexane, etc.), esters (ethyl acetate, butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate) The , Cellulose acetate, ethyl-3-ethoxypropionate, etc.), ethers (tetrahydrofuran, methyl cellosolve, ethyl cellosolve, butyl cellosolve, t-butyl cellosolve, etc.) etc. Pattern formation avoiding contact with the activated surface, reacting with only the activated outermost surface of the transparent substrate 1 (obtained from the transparent substrate 1 in the thickness direction), and surface only that portion Inactivate. (Not shown)
At this time, since the solvent does not volatilize instantaneously and needs to remain on the surface of the transparent substrate for a predetermined time, the boiling point is adjusted to 60 degrees or more and 200 degrees or less, preferably 100 degrees or more and 160 degrees.
This method is particularly suitable in the sense that it hardly affects the surface roughness of the transparent substrate 1 and only changes its properties.

Alternatively, it is difficult to adhere to the transparent substrate 1 in the first place, and a resin having a low interfacial tension, such as a silicone resin, a paraffin resin, a fluorine resin, a resin containing these fluorinated hydrocarbon groups or organic silicon groups, or a nonvolatile Oil (drying oil such as linseed oil, poppy oil, walnut oil, non-drying oil such as olive oil and peanut oil, semi-drying oil such as sesame oil and rapeseed oil) etc. By partially forming the desired pattern, the surface is inactivated in a pattern with high accuracy. (Not shown)
At this time, it is desirable not to give an optical change on the transparent substrate 1 after the partial formation, the solvent etc. is volatilized, and the resin etc. is only for the purpose of surface modification and is formed after drying. It is desirable that the thickness be about 1/50 to 1/10 of the wavelength of light. Of course, it is also suitable to use these in combination.
By this surface deactivation treatment, the surface deactivation treatment portion can have a peel strength between the transparent substrate 1 and the hologram forming layer 3 of 0.01 kg / 25 mm width to 0.1 kg / 25 mm width, When trying to peel off the hologram label, a gap is always generated between the transparent base material 1 and the hologram forming layer 3, and only the transparent base material 1 is peeled off at that portion.
Then, when the transparent substrate 1 is completely peeled off, the outermost surface of the hologram forming layer 3 corresponding to the surface-inactivated portion becomes almost a mirror surface, and the hologram reproduction image underneath is clearly visible from that portion. It can be visually recognized.
Furthermore, the transparent substrate 1 was peeled off by subjecting the above-mentioned “pattern” to surface activation treatment only for a finer area such as a halftone dot, a checkered pattern, or a random pattern. It is possible to further complicate the working condition of the force and improve the “breaking” property of each layer.
The minimum size of each “fine pattern” can be 50 μm using a high-precision printing method and can be provided with an interval of about 10 μm. It can also be expanded to the line width constituting the “pattern”. It is clear that it is difficult to use a direct surface activation treatment method using a mask that is a conventional method in order to construct a “pattern” with such a set of “fine pattern” sizes. .
Preferably, one halftone dot with a size of 50 μm to 300 μm (halftone dot ratio is preferably 30% to 70%) or checkered pattern (square, rectangular, other shapes) is inactive to skip one. In addition, in order to avoid the occurrence of diffraction phenomenon that does not require regular processing, the size of the halftone dots and their squares and rectangles are randomly changed between 50 μm and 300 μm Is used. (Not shown)

(Hologram forming layer)
As the transparent resin material for constituting the hologram forming layer 3 of the present invention, various thermoplastic resins, thermosetting resins, or ionizing radiation curable resins can be used. Thermoplastic resins include acrylic ester resins, acrylamide resins, nitrocellulose resins, or polystyrene resins. Thermosetting resins include unsaturated polyester resins, acrylic urethane resins, epoxy-modified acrylic resins, and epoxy-modified unsaturated resins. A polyester resin, an alkyd resin, a phenol resin, etc. are mentioned. (See Figure 2.)
These thermoplastic resins and thermosetting resins can be used alone or in combination of two or more. One or more of these resins may be cross-linked using various isocyanate resins, or various curing catalysts, for example, metal soap such as cobalt naphthenate or zinc naphthenate may be blended. Or peroxide such as benzoyl peroxide and methyl ethyl ketone peroxide for initiating polymerization with heat or ultraviolet light, benzophenone, acetophenone, anthraquinone, naphthoquinone, azobisisobutyronitrile, or diphenyl sulfide good.
Examples of the ionizing radiation curable resin include epoxy acrylate, urethane acrylate, acrylic-modified polyester, etc., for the purpose of introducing a crosslinked structure into such an ionizing radiation curable resin or adjusting the viscosity, A monofunctional monomer, a polyfunctional monomer, or an oligomer may be blended and used.
In order to form the hologram forming layer 3 using the above resin material, it can be directly formed by developing the photosensitive resin material by performing interference exposure of the hologram. It is preferable to perform molding by using a replica or a plating mold thereof as a replica mold and pressing the mold surface against the layer of the resin material.

When thermosetting resin or ionizing radiation curable resin is used, curing is performed by heating or ionizing radiation irradiation while keeping the uncured resin in close contact with the mold surface, and then cured by peeling after curing. The fine irregularities of the relief hologram can be formed on one side of the layer made of a transparent resin material. A diffraction grating forming layer having a diffraction grating formed in a pattern by a similar method can also be used as the optical diffraction structure.
A hologram is a recording of interference fringes due to the interference of light between object light and reference light in an uneven relief shape. For example, laser reproduction holograms such as Fresnel holograms, white light reproduction holograms such as rainbow holograms, There are color holograms utilizing the above principle, computer generated holograms (CGH), holographic diffraction gratings and the like. Further, like a machine readable hologram, the reproduction light may be converted into data by a light receiving unit and transmitted as predetermined information, or authenticity determination may be performed.
In order to precisely create fine irregularities, not only optical methods, but also electron beam lithography equipment can be used to create precisely designed relief structures that produce more precise and complex reproduction light. Good. The relief shape is designed to have a pitch, depth, or specific periodic shape of the unevenness according to the wavelength (range) of the light or light source for reproducing or reproducing the hologram, the direction and the intensity of reproduction or reproduction. The pitch (period) of the unevenness depends on the reproduction or reproduction angle, but is usually 0.1 μm to several μm, and the depth of the unevenness is a factor that greatly affects the reproduction or reproduction intensity, but is usually 0.1 μm. ˜1 μm.
As in the case of a single diffraction grating, when the unevenness of exactly the same shape is repeated, as the adjacent unevenness is the same shape, the degree of interference of reflected light increases and the intensity increases, and the maximum value is reached. Converge. Diffraction in the diffraction direction is also minimized. When a single point of an image converges to a focal point, such as a stereoscopic image, the convergence accuracy to the focal point is improved, and a reproduced or reproduced image becomes clear.

Further, in the case of a transparent metal compound thin film , that is, when a so-called “transparent metal compound thin film” is provided for the hologram relief, the upper and lower surfaces of the thin film have the same relief shape, and The more uniform the distance between the surfaces (ie, the film thickness), the greater the reproduction or reproduction strength. In addition, if there are irregularities having a period and shape different from the irregularities of the hologram image on the relief surface, this becomes noise during reproduction or reproduction of the hologram or diffraction grating, which causes the image to become unclear.
The relief shape is shaped (also referred to as replication) by using an original plate on which diffraction gratings and interference fringes are recorded in a concavo-convex shape as a press die (referred to as a stamper) on the hologram forming layer 3 or described below. The concavo-convex pattern of the original plate can be duplicated by superimposing the original plate on the fluorescent layer 4 and heat-pressing both of them with an appropriate means such as a heating roll. The hologram pattern to be formed (a hologram relief that expresses one hologram reproduction image is referred to as one hologram pattern) may be single or plural. Further, the shape of the region for forming the hologram relief may be a single region or a plurality of regions.
In order to accurately reproduce the above-mentioned extremely fine shape and to minimize distortion and deformation such as heat shrinkage after replication, the original plate is made of metal and replicated at low temperature and high pressure.
For the original plate, a metal having high hardness such as Ni is used. After a Cr or Ni thin film is formed on the surface of a glass master or the like formed by optical photography or electron beam drawing by vacuum deposition or sputtering, Ni or the like is electrodeposited (electroplating, electroless plating, Furthermore, after forming 50-1000 micrometers by composite plating etc., it can make by peeling a metal.
In order to use it for high-pressure rotation type replication, it is necessary to increase the thickness accuracy of this Ni layer, and it is usually ± 10 μm, preferably ± 1 μm. For this reason, you may use the back surface grinding | polishing or the planarization method.
Since the replication method is a high pressure, a rotary method is used instead of a flat plate method, and the linear pressure is 0.1 ton / m to 10 ton / m, preferably 5 ton / m or more. If the diameter of the duplication cylinder is small, the reproducibility of the relief is lowered. Therefore, it is preferable that the duplication cylinder diameter is large. Usually, an arc having a diameter of 0.1 m to 2.0 m, preferably 1.0 m or more is used. To do.
The hologram forming layer 3 on the transparent substrate 1 is pressed along this duplication cylinder, and duplication is carried out from the back side with a metal cylinder at the above pressure. In order to minimize distortion and deformation such as heat shrinkage after replication, a method of heating only a part of the hologram forming layer 3 side rather than heating the entire transparent substrate 1 is desirable. Usually it is heated to 60 ° C to 110 ° C. Furthermore, the precision can be further improved by keeping the metal cylinder on the back surface at room temperature or cooling it.

(Fluorescent layer)
In the present invention, the fluorescent layer 4 is formed on the hologram relief surface of the hologram forming layer 3. (See Figure 2.)
This fluorescent layer 4 is produced by using a resin-dispersed fluorescent ink in which the phosphor is uniformly dispersed in a transparent resin or a solvent-dispersed fluorescent ink in which the phosphor is dispersed in water or a solvent. Using various forming methods such as a method, a coating method, and an ink jet method, the hologram forming layer 3 has a uniform thickness so as to be in contact with and follow the hologram relief, and further to the recess. It can be partially formed.
In addition, after forming the fluorescent layer 4 on the hologram forming layer 3, it is aligned with the diffraction grating pattern by photolithography using a photoresist, exposed to light, developed, and unnecessary portions are removed to remove the photoresist pattern. It is possible to remove the fluorescent layer by etching in synchronization with the recess and leave the fluorescent layer 4 only in the recess.
On the contrary, a photoresist layer is formed on the hologram forming layer 3, aligned with the diffraction grating pattern, exposed, developed, and unnecessary portions removed to leave the photoresist on the convex portions and expose the concave portions. After forming the fluorescent layer, the photoresist on the convex portion is removed, and at the same time, the fluorescent layer 4 directly above the portion is partially removed, so that the fluorescent layer 4 can be left only in the concave portion.
The resin-dispersed fluorescent ink includes the above-described phosphor, a transparent resin, for example, an acrylic ester resin, an acrylamide resin, a nitrocellulose resin, or a polystyrene resin as a thermoplastic resin, and a thermosetting resin. Ball mills and kneaders using glass beads or steel beads to reduce secondary aggregation in unsaturated polyester resins, acrylic urethane resins, epoxy-modified acrylic resins, epoxy-modified unsaturated polyester resins, alkyd resins, or phenol resins Thoroughly kneading with a roll mill, etc., adjusting the viscosity with a solvent, etc., and using a gravure method, offset method, silk screen method, curtain coating method, nozzle coating method, and even an ink jet method as appropriate, a uniform thickness Can be formed.

In order to set the thickness of the fluorescent layer 4 to 0.003 μm or more and 1.0 μm or less, and further 0.01 μm or more and 0.5 μm or less, the solid content of the resin-dispersed ink is 1 to 10%, When the coating film using water as a solvent is, for example, 10 μm, the thickness after evaporation of the solvent (thickness of the fluorescent layer) is set to 1/10 to 1/100, and 1 μm. ˜0.1 μm.
Since the solvent-dispersed fluorescent ink does not include a resin component and includes only a phosphor and a solvent, the thickness of the fluorescent layer 4 can be made thinner than that of the resin-dispersed type.
As a solvent, water, an alcohol solvent, a cellsolve solvent, or a paraffin solvent is used to disperse and hold a phosphor having a small particle size, and is provided on the hologram forming layer 3 by stirring, curtain coating, nozzle coating, or the like. be able to.
In this case, by adjusting the evaporation rate of the solvent, the phosphor can be moved to the recess by its own weight while the solvent is volatilized.
Furthermore, several μm of a slow volatile solvent having solubility is applied to the resin forming the hologram relief surface (a ketone solvent such as cyclohexanone for acrylic, vinyl chloride, vinyl acetate resin, polyester resin, etc.). It is also possible to dilute this solvent with a non-soluble solvent and use it to make the remaining components 0.1 μm or less.) Dissolve only the outermost surface of the hologram relief surface, There is also a method for forming the fluorescent layer 4 that imparts adhesiveness to the surface and sprays the phosphor as powder on the surface so that only the phosphor particles in contact with the adhesive surface remain on the hologram relief surface. Is preferred.
According to this method, the fluorescent layer 4 becomes almost one particle film, is uniformly formed on the hologram relief surface, and the fluorescence emission surface when the excitation light is applied from the hologram forming layer 3 side is the same as the hologram relief surface. .
In any case, since the unevenness of the hologram relief is very small, the fluorescent layer 4 has a uniform thickness and the phosphors in it have a uniform density or evenly on the hologram relief surface (partial In the case of formation, in order to form a uniform portion), it is preferable that the phosphor has a smaller particle diameter, and a nanophosphor is particularly suitable.

(Adhesive layer)
The pressure-sensitive adhesive layer 5 may be any conventionally known solvent-based or water-based pressure-sensitive adhesive, such as vinyl acetate resin, acrylic resin, vinyl acetate-acrylic copolymer, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl acetate copolymer. Examples thereof include polymers, polyurethane resins, and rubber resins such as natural rubber and chloroprene rubber. Natural latex such as natural rubber latex, natural rubber latex obtained by graft polymerization of natural rubber with styrene, especially methacrylic acid methyl, in particular, to make natural material composition You may use what was produced from the raw material.
The coating amount of the adhesive layer 5 is generally about 8 to 30 g / m ² (solid content), and is applied and dried by a conventionally known method, that is, a gravure coat, roll coat, comma coat or the like. Thus, the adhesive layer 5 is formed. (See Figure 2.)
Further, the adhesive strength of the adhesive layer 5 is the peel strength between the fluorescent layer 4 and the adhesive layer 5, and is preferably in the range of about 0.1 to 1 kg in the 180 ° peel method according to JIS Z0237. Of course, even higher peel strengths are suitable for the purposes of the present invention.
The type and the coating amount of the pressure-sensitive adhesive as described above are such that when the pressure-sensitive adhesive layer 5 is formed on the transparent substrate 1, the hologram forming layer 3 and the fluorescent layer 4, the peel strength is within the above range. It is preferable to select and use.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this. In addition, except a solvent, each composition of each layer is a mass part of solid content conversion.
(Example 1) A 38 μm polyethylene terephthalate resin film was used as the transparent substrate 1, and one side of the film was irradiated with excimer light having a wavelength of 172 nm using an excimer UV03 reformer manufactured by Excimer Co., Ltd. 10mm size “open” and “sealed” characters are arranged in a row and row continuously in the image area of the characters (the line width of the image area is 1000 μm). The surface activation treatment was performed by irradiating and forming “surface activated treatment portion 2” in a “pattern” shape. (See Figure 2.)
On top of that, after the hologram forming layer 3 made of melamine resin was formed (peeling strength between the transparent substrate 1 and the hologram forming layer 3: activated surface 1.2 kg / 25 mm width, other portions 300 g / 25 mm This corresponds to a width.) A Ni original plate provided with a hologram having a high designability photographed using a laser optical system is prepared, and the relief surface of the Ni original plate is aligned with the hologram forming layer 3 described above. A hologram relief is formed on the hologram forming layer 3 by a forming apparatus (original cylinder diameter 1.0 m, original surface temperature 100 ° C., pressurized cylinder diameter 0.3 m, water-cooled, pressure 2 ton / m, replication speed 10 m / min). did.
On this hologram forming layer 3, a resin dispersed fluorescent ink having the following composition was coated by a gravure coating method and dried to form a fluorescent layer 4 having a thickness of 2.0 μm so as to be in contact with the hologram relief. (In FIG. 2, the surface of the fluorescent layer 4 in contact with the hologram forming layer 3 has the same shape as that of the hologram relief, as shown in FIG. (The hologram relief shape as shown in Fig. 2 forms a slightly different curved surface. This difference greatly depends on the formation thickness of the fluorescent layer 4 and the formation method.)
・ <Fluorescent ink composition>
UV-excited fluorescent pigment UVR-2 manufactured by Tail Navi Co., Ltd. 5 parts by mass Acrylic resin 10 parts by mass Methyl ethyl ketone 40 parts by mass Ethyl acetate 45 parts by mass On the fluorescent layer 4, a pressure-sensitive adhesive composition for the adhesive layer 5 having the following composition is a gravure coating method. Was applied and dried to form the adhesive layer 5 with a thickness of 20 μm, and the hologram label A of Example 1 was produced. (See Figure 2.)

・ <Adhesive composition for adhesive layer 5>
Vinyl acetate-acrylic copolymer 30 parts by mass Isophorone diisocyanate 1 part by mass Toluene 20 parts by mass Ethyl acetate 30 parts by mass Methyl isobutyl ketone 19 parts by mass This hologram label A is used for sealing an envelope, and is attached to the sealed part. Then, when observed under room illumination light, a hologram reproduction image is not observed (not shown), and the hologram label A is peeled off from the envelope. As a result, the transparent base material 1 was easily peeled off, and the transparent base material-side remaining portion was continuously attached to the vertical and horizontal shapes in the form of “open” and “sealed” on the transparent base material 1 side. (The peeled transparent substrate 6. See FIG. 3. In FIG. 3, the characters “open” and “sealed” are schematically drawn one by one.)
In addition, on the envelope side, the adherend-side remaining portion in which concave portions that are continuous in the vertical and horizontal directions in the form of “open” and “sealed” remained. (The adherend side remaining part 7 remaining on the adherend is shown. See FIG. 3. In FIG. 3, the characters “open” and “seal” are drawn one by one.)
When the peeled transparent substrate 9 was illuminated using a 365 nm wavelength light source 8 (UV-LED module LC-L2 manufactured by Hamamatsu Photonics), this ultraviolet light was not visible, and “open” and “sealed” A red hologram reproduction image could be visually recognized in the image line part (position of the remaining part on the transparent base material side). (See Figure 4.)
Similarly, the remaining part 11 on the adherend side on the envelope was illuminated 10 using a 365 nm wavelength light source 10 (UV-LED module LC-L2 manufactured by Hamamatsu Photonics). In addition, a red hologram reproduction image was visible. (See Figure 4.)
After that, another common transparent adhesive label of the same size as this "label" is facilitated and pasted so as to cover the remaining part of the adherend, and the same as if presenting the same appearance as the original state The “label” was pressure-bonded using a roller.
When illuminated with 365 nm wavelength illumination light using the above-mentioned light source from above the crimped “label”, a red hologram reproduction image containing “open” and “sealed” letter-like chips appears (see FIG. Not shown.), I was able to clearly determine that the fraud was done.
From this, it was considered that the hologram label A has a high anti-opening effect.

(Example 2) A 38 μm polyethylene terephthalate resin film was used as the transparent substrate 1, and one surface of the film was subjected to a surface activation treatment by a corona treatment system using a polydyne low frequency corona treatment system manufactured by Navitas. The surface deactivation treatment solvent composition is negative, positive and reverse in a 10 mm x 10 mm vertical and horizontal pattern, with a thickness of 1 μm. A hologram label A of Example 2 was obtained in the same manner as in Example 1 except that it was formed in the same manner as in Example 1. (Refer to FIG. 2. As a result, the portion not subjected to the surface deactivation treatment becomes the portion 2 subjected to the surface deactivation treatment.)
<Surface deactivation treatment solvent composition>
Methyl ethyl ketone (boiling point 80 ° C.) 40 parts Toluene (boiling point 100 ° C.) 30 parts Methyl isobutyl ketone (boiling point 115 ° C.) 29 parts Linseed oil 1 part When evaluated in the same manner as in Example 1, the transparent substrate 1 was removed from the hologram forming layer 3. The same effect as in Example 1 was obtained except that it was peeled off very easily.
(Example 3) On a hologram forming layer 3 formed in the same manner as in Example 1, a resin dispersed fluorescent ink having the following composition was coated by a gravure coating method at a coating thickness of 20 μm, dried quickly after application, and fluorescent. A hologram sheet A of Example 3 was produced in the same manner as in Example 1 except that the layer 4 was formed with a thickness of 0.6 μm. (See Figure 2.)
The fluorescent layer 4 at this time followed the hologram relief of the hologram forming layer 3 and had a uniform thickness.
・ <Fluorescent ink composition>
Lumilite nano RY202 (particle size 30 nm) 1 part by weight Polyvinyl alcohol resin 2 parts by weight Ethyl alcohol 27 parts by weight Isopropyl alcohol 20 parts by weight Ethyl acetate 50 parts by weight When this hologram sheet A was observed in the same manner as in Example 1, a brighter red color was observed. The hologram reproduction image can be confirmed, and only the red reproduction image appears to be floating in the space, and the same effect as in Example 1 is obtained except that the fraud determination can be performed more accurately. Obtained.

(Example 4) On the hologram forming layer 3 formed in the same manner as in Example 1, resin-dispersed fluorescent ink having the following composition was coated by a gravure coating method and dried, so that the fluorescent layer 4 had a thickness of 0.1 μm. A hologram sheet A of Example 4 was produced in the same manner as Example 1 except that it was formed. (See Figure 2.)
・ <Fluorescent ink composition>
Lumilite nano RY202 (particle size 30 nm) 5 parts by mass Polyvinyl alcohol resin 10 parts by mass Isopropyl alcohol 40 parts by mass Water 45 parts by mass When this hologram sheet A was observed in the same manner as in Example 1, a remarkably clear red hologram reproduction image was confirmed. Thus, the same effect as in Example 1 was obtained except that only the red reproduced image appeared to float in the space, and fraud determination could be performed more accurately.
(Example 5) After forming the hologram forming layer 2, after forming a 3 μm coating film (before drying) with a gravure coating method with a solvent having the following composition and volatilizing only the quick-drying component,
・ <Solvent composition>
Cyclohexanone 1 part by weight Methyl ethyl ketone 40 parts by weight Cyclohexane 59 parts by weight Sprinkle the phosphor as powder (hologram-forming surface 2 faced down and then sprayed). A hologram sheet A of the present invention was produced in the same manner as in Example 1 except that it was dried and the remaining solvent was volatilized.
The fluorescent layer 4 at this time followed the hologram relief of the hologram forming layer 3 and had a uniform thickness.
When observed in the same manner as in Example 1, the same effect as in Example 1 was obtained except that a hologram reproduction image with clearer and stronger fluorescence intensity could be confirmed.
(Example 6) The basic shape as a “fine pattern” is “a rectangle of 50 μm × 100 μm”, and this basic shape is developed in a “checkered pattern” shape within the image line portions of “open” and “sealed”, A hologram label A of Example 6 was obtained in the same manner as in Example 1 except that the surface activation treatment was applied to one skip to form the “open” and “sealed” “pattern” described above. .
When evaluated in the same manner as in Example 1, the same effect as in Example 1 was obtained, and the characters “open” and “sealed” after peeling of the transparent substrate 1 were clearly visible. The same effect as in Example 1 was obtained.

(Comparative example)
(Comparative Example 1) A transparent “label” of Comparative Example 1 was obtained in the same manner as in Example 1 without performing surface activation treatment or surface deactivation treatment, and without providing a hologram forming layer.
When this “label” was evaluated in the same manner as in Example 1, the transparent substrate 1 was not easily peeled off, peeled off from the adhesive layer 5, and irradiated with ultraviolet rays. Only stayed.
Therefore, it was thought that if this “label” was carefully removed, it could be illegally removed, and misuse such as reattachment could be possible.

A hologram label 1 transparent substrate 2 part of one surface of the transparent substrate surface-treated in a pattern
(At the interface between the transparent substrate and the hologram forming layer, the portion other than this portion is referred to as a portion that has not been subjected to surface activation treatment or a portion that has been subjected to surface inactivation treatment.)
3 Hologram forming layer 4 Fluorescent layer 5 Adhesive layer 6 Transparent substrate peeled off when the hologram label A was peeled off (the remaining portion on the transparent substrate is attached)
7 When the hologram label A is peeled off, the adherend-side remaining portion remaining on the adherend (the state where the transparent substrate-side remainder is removed)
8 Predetermined illumination light (example of ultraviolet rays)
9 The transparent base material that was peeled off when the prescribed illumination light was applied (the remainder of the transparent base material is attached)

10 Predetermined illumination light (example of ultraviolet rays)
11 The remaining part on the adherend side when the predetermined illumination light is irradiated (the state where the remaining part on the transparent base material side is removed).

Claims (2)

At least on one surface of a transparent substrate, a hologram forming layer, the adhesive layer is provided, et al are in this order, are formed hologram relief on the adhesive layer side of the front Symbol hologram forming layer, the concave portion of said hologram relief A fluorescent layer is provided only, and the phosphor contained in the phosphor layer is a method for producing a hologram label, which is a nanophosphor,
Before SL and facilities the surface activation treatment to a Nozomu Tokoro pattern on the surface of the hologram forming layer side of the transparent substrate, than the peel strength of the peel strength region other than the region of the surface activation treatment is performed region method for producing a hologram label, wherein the size Kusuru. In a region other than the surface activation treatment is performed region of the surface of the hologram forming layer side of said transparent substrate, forming a resin having a low interfacial tension than the interfacial tension of the surface activation treatment is performed region The method for producing a hologram label according to claim 1, wherein:

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