JP2013076802A - Hologram label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hologram label, namely a brittle hologram label having hidden hologram, which enables firm discovery of re-sealing resulting from an illegitimate peeling action and makes it difficult to find existence of a second hologram or existence of a layer susceptible to be partially broken.SOLUTION: A surface activation treatment 2 is applied, in a pattern, to one surface of a transparent base material 1 constituting a hologram label A, a photochromic thin film layer 4 having a second hologram relief shape is provided in a region including a position corresponding to a surface activation treatment region.

Description

  The present invention relates to a hologram label, and more specifically, a normal hologram can be visually recognized in normal illumination light, and a label that can only be recognized as a holographic brittle label (a normal printing layer such as a letter of “sealing”). In many cases, it is applied to a part of the label component layer.) For those who illegally replace labels, forge or falsify (hereinafter also referred to as fraudsters) The present invention relates to a hologram label having a high anti-fraud function while exhibiting an appearance that makes it seem that the act can be easily implemented.

  When a normal hologram brittle label is attached to an envelope or the like and then peeled off, the label itself is destroyed, or only the transparent base material, which is a part of the label, is peeled off preferentially. In the remaining part of the label, characters such as “open” appear to inform the user that the illegal opening has been performed.

  For such a hologram brittle label, an unauthorized person peels off the label or transparent substrate from the sealed portion of the envelope, then opens the envelope illegally, and illegally browses or replaces the enclosed item. After that, a new label is pasted on the remaining part of the envelope so that the remaining part of the envelope, such as “open”, is filled, or the peeled transparent substrate is removed. Abuse the material and apply a new adhesive to cover the letters “open” attached on the transparent substrate, as if it were a uniform adhesive layer, and stick it on another envelope. It is assumed that illegal activities will be conducted.

  Further, it is assumed that a person with a higher level of technology forges a hologram brittle label using a similar hologram design.

  However, in the hologram label of the present invention, another hidden hologram reproduction image (hereinafter referred to as “second”) emerges steadily due to the color developed by irradiating predetermined excitation light. When the fraud as described above is performed on the hologram label of the present invention, the second excitation light is irradiated on the new label that has been illegally pasted, so that the second The hologram reproduction image does not appear at all, or the second hologram reproduction image in which the “chip” is generated appears constantly.

  Of course, when 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 “line” shape of the characters “open”) It is theoretically possible to look into a stereoscopic image in the back from a window with an opening.) Although it can theoretically be done, due to the rupture of the hologram forming layer and the adhesive layer when peeling the label, The photochromic thin film layer included therein is greatly deformed, and a normal second hologram reproduction image can no longer be obtained.

  In addition, when the photochromic thin film layer is provided so as to include not only the character part such as “open” attached to the transparent substrate but also the character part, the photochromic thin film is removed by this peeling action. The layer is divided, and the second hologram reproduction image in which “chip” and “deformation” are generated from the portion adhering to the transparent substrate side and the portion remaining on the adherend, respectively. It appears regularly and it is possible to easily determine that an illegal act has been performed. Furthermore, even if the act of returning the material once peeled off is performed again, large deformation remains in each photochromic thin film layer as described above, and the position of the photochromic thin film layer (top and bottom, left and right, and deep) It is very difficult to accurately restore the direction), so that it is possible to easily find out that fraud has been performed.

  That is, the present invention relates to a hologram label that makes it difficult to illegally open or replace the hologram label, and to forge or tamper.

  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.

    Here, the “reflective” of the “reflective thin film layer” means that all light in the visible light region, that is, light having a wavelength of 400 nm to 800 nm is reflected, and does not transmit light in the visible light region. Means that.

  However, it is physically impossible to provide a “layer” that reflects 100% of all light within the wavelength range, and “total reflection” here means, for example, an aluminum metal thin film layer, This means a “layer” that reflects light within that wavelength range with a reflectance of 90% to 100% (the value varies depending on the wavelength of the light to be measured), and thus the transmittance of this layer within that wavelength range. Means a “layer” of less than 10%.

  By providing such a “layer”, the hologram label of the present invention observes the hologram reproduction image only in the “reflection type”.

  The “transparent reflectivity” of the “transparent reflective thin film layer” means that the light in the visible light region, that is, the light having a wavelength of 400 nm to 800 nm is partially reflected and partially transmitted. It means a thin film layer that transmits at least 10% of light in the wavelength region.

  By providing such a “thin film layer”, the hologram label of the present invention can observe both types of hologram reproduction images of “reflection type” and “transmission type”.

  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 of the present invention is a hologram label used in the field of anti-counterfeiting, specifically,
(1) Various product fields, such as genuine products manufactured by manufacturers, where certification of genuine products is significant, such as electronic equipment, electrical equipment, computer-related products, and their components, computer-related software, genuine equipment (paper Consumables such as printers and toner etc.) Pharmaceuticals, quasi-drugs or chemicals,
(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 Works such as discs), ROM boards that have been set and prevented from being changed (used for computer equipment, game machines, game machines, etc., including stickers across ROM and boards), watches, Clothing, bags, jewelry such as jewelry, sports equipment, cosmetics, and their luxury brand products, etc.
(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.
In particular, it is suitable for a field in which the hologram label is skillfully removed to reduce the value of the hologram label or to be reused.
(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, and the hologram label is covered by the difficulty of counterfeiting or altering the hologram itself. 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. The strength of the layer is large, the difference in adhesive strength with the base material, and the presence of brittle releasability, the hologram forming layer itself does not break or is partially broken, and it is difficult to achieve its purpose sufficiently In addition to the problem, in the first place, when it is illegally peeled off, it has the disadvantage that it informs the unauthorized person that the hologram forming layer is a label that breaks, giving it an opportunity to hide something illegally.

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

  Although the present invention is a hologram label, in addition to the first hologram reproduction image that can be viewed under normal illumination light, the second hologram that cannot be viewed under normal illumination and appears only upon irradiation with predetermined irradiation light A hologram label having a reconstructed image, which can be attached without any problem when the label is attached to the adherend, and if the label is illegally removed from the adherend, Only the material is peeled off, and for example, the characters “open” and “sealed” appear as “dent-like characters” on what is left on the adherend side as the peeled traces. It turns out to be a so-called “hologram brittle label”.

  Furthermore, when the “remaining one” is irradiated with a predetermined irradiation light, a hologram label is provided in which a second hologram reproduction image including “letters such as opening” appears.

  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 label replacement due to an illegal peeling action. In other words, it is difficult to detect the presence of a hologram and a layer that partially brittlely breaks, that is, to provide a hologram brittle label having a hidden hologram.

To solve the above problem,
The first aspect of the hologram label of the present invention is:
Hologram label having a pattern-like surface activation treatment region on one surface of a transparent substrate, and a hologram forming layer having a first hologram relief thereon, a reflective thin film layer, and an adhesive layer A photochromic thin film layer having a second hologram relief shape is provided in a region including at least a position corresponding to the patterned surface activation treatment region in the hologram forming layer. To do.

According to the hologram label of the first aspect,
Hologram label having a pattern-like surface activation treatment region on one surface of a transparent substrate, and a hologram forming layer having a first hologram relief thereon, a reflective thin film layer, and an adhesive layer A photochromic thin film layer having a second hologram relief shape is provided in a region including at least a position corresponding to the patterned surface activation treatment region in the hologram forming layer. It is possible to provide a hologram label that can be easily determined that an illegal act has been performed while appearing like a normal hologram brittle label.

The second aspect of the hologram label of the present invention is:
A hologram having a patterned surface activation treatment region on one surface of a transparent substrate, and a hologram forming layer having a first hologram relief thereon, a transparent reflective thin film layer, and an adhesive layer. A photochromic thin film layer having a second hologram relief shape is provided in a region of the label including at least a position corresponding to the patterned surface activation treatment region in the adhesive layer. It is what.

According to the hologram label of the second aspect,
A hologram having a patterned surface activation treatment region on one surface of a transparent substrate, and a hologram forming layer having a first hologram relief thereon, a transparent reflective thin film layer, and an adhesive layer. A photochromic thin film layer having a second hologram relief shape is provided in a region of the label including at least a position corresponding to the patterned surface activation treatment region in the adhesive layer. A hologram label that can be easily determined that an illegal act has been performed while appearing as a normal transparent hologram brittle label can be provided.

The third aspect of the hologram label of the present invention is:
The photochromic thin film layer has a thickness of 0.01 μm or more and 0.5 μm or less.

According to the hologram label of the third aspect,
A thickness of the photochromic thin film layer is 0.01 μm or more and 0.5 μm or less, and the hologram label according to the first or second aspect can be provided, and the first or second aspect. In addition to the features described above, it is possible to provide a hologram label capable of causing a clearer hologram reproduction image to appear.

The fourth aspect of the hologram label of the present invention is:
The surface activation treatment is a light treatment or a physical treatment.

According to the hologram label of the fourth aspect,
The surface activation treatment may be a light treatment or a physical treatment, and the hologram label according to any one of the first to third aspects may be provided. Features of the aspect In addition, it is possible to provide a hologram label that is more easily brittle fractured and is less likely to find the presence of a brittle fractured layer.

The fifth aspect of the hologram label of the present invention is:
The pattern is constituted by a set of fine patterns.

According to the hologram label of the fifth aspect,
It is possible to provide the hologram label according to any one of the first to fourth aspects, wherein the pattern is constituted by a set of fine patterns. In addition to the features, it is possible to provide a hologram label that is more easily brittlely broken and that is more difficult to find the presence of a brittle fracture layer.

  That is, in the hologram label of the present invention, a patterned surface activation treatment region is formed on one surface of the transparent substrate to form a patterned surface activation treatment region, and the first hologram relief is formed thereon. A hologram label provided with a hologram forming layer, a reflective thin film layer or a transparent reflective thin film layer, and an adhesive layer, the position corresponding to the pattern-shaped surface activation treatment region in the hologram forming layer The photochromic thin film layer having the second hologram relief shape is provided over the region including the region corresponding to the pattern-like surface activation processing region in the adhesive layer, and the use of the hologram label described above In, it sticks to a part of desired adherends, sealing parts, such as an envelope.

This hologram label is peeled off from its adherend or sealed part without leaving any pasted traces, and the hologram label is also peeled off in its complete original state, and can be replaced with another adherend prepared improperly. After opening the envelope or box and replacing the contents, it is as if the contents of the adherend, envelope or box are genuine, or the original hologram label is peeled off. In order to prevent fraud, such as reducing its value,
Although it is desirable that the hologram label base material and the hologram forming layer itself are ruptured, the rupture strength of the hologram label base material and the hologram formation layer is very large, and the adhesive strength as a label or the like (180 defined in JIS Z0237). In the peel test, 0.1 to 1.0 kg / 25 mm width), it is difficult to break these layers 100%.

  Therefore, the peel strength between the transparent base material and the hologram forming layer is suppressed to a low level, and one surface of the transparent base material is subjected to a surface activation treatment in a desired pattern, thereby forming a pattern-like surface activation treatment region. The adhesion between the transparent substrate and the hologram forming layer is partially improved (meaning only the surface activated region), and the width is 0.5 kg / 25 mm width or more and 3.0 kg / 25 mm width or less. Peel strength (by 180 ° peel test specified in JIS Z0237). For other areas, the adhesion to the hologram forming layer is kept lower than that strength, or the small strength is further reduced. Therefore, surface inactivation treatment is performed.

  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 to peel off the hologram label, the part that has not been subjected to the surface activation treatment or the part that has been subjected to the surface inactivation treatment (both are the surface activation treatment region) In this case, the peeling occurs easily between the transparent base material and the hologram forming layer, and the surface activated portion (meaning the surface activated region) is a transparent group. The hologram forming layer remains attached to the material side, and the boundary between the surface-inactivated portion and the surface-inactivated portion, or the surface-inactivated portion and the surface-inactivated treatment A strong shearing force (a force to break the hologram forming layer. The force applied when the hologram forming layer breaks becomes the breaking strength) at the boundary with the portion. The Kukoto.

  Then, in the “hologram forming layer having the first hologram relief (hereinafter also simply referred to as a hologram forming layer)” or “adhesive layer” and at least the pattern-shaped surface activation treatment region Is provided in a region including the position corresponding to (2), “a photochromic thin film layer having a second hologram relief shape (hereinafter, also simply referred to as a photochromic thin film layer)”.

  That is, the “hologram forming layer” or the “transparent resin” constituting the “adhesion layer” is formed with a thickness of, for example, 1/2, and the second hologram relief is formed on the surface, and then the first A photochromic thin film layer is provided in a uniform thickness so as to contact the “predetermined part” of the hologram relief 2 and to follow the irregularities forming the “predetermined part” of the second hologram relief. While covering the photochromic thin film layer, the entire second hologram relief is formed of the “transparent resin” with the remaining half thickness, and includes the photochromic thin film layer having the second hologram relief shape. A “hologram forming layer” or “adhesive layer” is provided.

  Then, a “first hologram relief” is newly provided on the “surface” of the “hologram forming layer”, and a reflective thin film layer or a transparent reflective layer is provided on the “first hologram relief” surface. A thin film layer is formed so as to follow the first hologram relief.

  As a result, the normal illumination light is reflected from the reflective thin film layer and the transparent reflective thin film layer, and the first hologram reproduction image by the first hologram relief can be visually recognized.

  The above-mentioned “predetermined portion” is an area on the second hologram relief surface in “an area including a position corresponding to at least a pattern-shaped surface activation treatment area”, on a transparent substrate. When the surface activation treatment area of the pattern is, for example, a character area of “open” or “sealing”, the “hologram forming layer having the first hologram relief” immediately below the character area, Alternatively, the “second hologram relief” means a “region” including at least “a character region of“ open ”or“ sealed ”on the second hologram relief surface” provided in the “adhesive layer”. If it includes “open” and “sealed” character areas ”on the surface, it can be“ arbitrary size and arbitrary shape ”.

  However, it is desirable that the existence of this photochromic thin film layer is not recognized at all by an unauthorized person, and “a character region of“ open ”or“ sealed ”on the second hologram relief surface” is “approximately the same size, and It is preferable to use the same shape (meaning one that is one size larger) "or a rectangular or elliptical shape that encloses the individual characters in one size larger. Here, “one size larger” means about 1.1 to 2.0 times the line width of each character, or 1.1 to 2 times the vertical size of each character. It means about 0 times.

  As a result, when an unauthorized person peels off the hologram label of the present invention, a hologram having a “broken first hologram relief” is formed on the transparent substrate side in the form of “character area of“ open ”or“ sealed ”. ”Formation layer and adhesive layer” are adhered, and the label area (“remaining hologram formation layer and adhesive layer”) having “dents” or “holes” in the character area remains on the adherend. However, as a result, the photochromic thin film layer is divided and present on the transparent substrate side and the adherend, respectively, and it is based on “light of a predetermined wavelength such as ultraviolet rays” that an unauthorized person cannot know. Illumination makes it possible to easily confirm the state of division.

  Such anti-counterfeiting is not only because the photochromic thin film layer is of a color developing type, that is, colorless and transparent, or from white that expresses a predetermined color tone, but also from a color changing type, that is, a color tone that exhibits a certain color tone. Even if the color changes to a color different from the color tone, the color tone is sufficiently exhibited. Hereinafter, the “coloring type” will be mainly described, but the “color changing type” can also be used in the same manner.

  In the case of the discoloration type, since the photochromic thin film layer has a color tone under the general illumination light of a fluorescent lamp even before excitation light irradiation, a hologram reproduction image of that color tone can be visually recognized. By irradiation, the photochromic thin film layer is discolored to exhibit a different color tone, and a hologram reproduction image having the new color tone appears.

  That is, the presence of this new tone hologram contributes to anti-counterfeiting.

  In addition, in this way, a “photochromic thin film layer” is provided only on a portion of the second hologram relief provided on the surface of the “hologram forming layer” or the “transparent resin” constituting the “adhesion layer”. In the region other than the region where the “photochromic thin film layer” is provided by covering the “photochromic thin film layer” and overlaying the “transparent resin” on the entire second hologram relief, Since the unevenness of the second hologram relief is filled with “material having the same refractive index”, the filled portion behaves optically as if such unevenness was not originally present. That is, it has optical continuity, is “completely transparent”, does not cause any diffraction or refraction, and behaves as a uniform layer.

  And the photochromic thin film layer provided in this way is a very thin layer, and its breaking strength is very small, and it can be easily changed along with the breaking of the hologram forming layer and the adhesive layer as well as the deformation of those layers. Break.

  In other words, when surface activation treatment is applied to the letter “open”, including a portion of the hologram forming layer corresponding to the area of the letter “open” and a photochromic thin film layer in which the adhesive layer is divided, Adhering to the 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, On the adherend side, the hologram forming layer and the adhesive layer include the remaining divided photochromic thin film layer, and the state of lacking the character of “open” (character-like depression occurs, or In the state where the character-like hole is opened, hereinafter, it is also referred to as the adherend side remaining part).

  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

  Then, when UV light having a predetermined wavelength is applied to the remaining part of the adherend on the adherend, the “photochromic molecule” existing in the photochromic thin film layer is colored, and the second hologram reproduction by the colored wavelength is performed. An image appears. In this case, the second hologram reproduction image is observed as being blocked by the characters “open”.

  In the first place, the hologram reproduction image has very high redundancy from the principle of its reproduction, so this “blocking” (the width of the surface activation treatment region, that is, the line width of the character “open”) is the second hologram relief shape. This means that the light contributing to the reproduction of the second hologram reproduction image is not radiated from this region because the photochromic thin film layer having been removed is removed, and it is as if "open" from above the second hologram reproduction image. In order to make it possible to clearly see the path of the light that forms the second hologram reproduction image). The magnitude of “blocking” is 200 to 5000 times, more preferably 500 to 2000 times the period of the interference fringes of the second hologram relief, 0.5 μm to 2 μm.

  If the “blocking” is less than 200 times, the second hologram reproduction image is strongly reproduced due to the redundancy of the hologram, and the “blocking” is weakened so that it is difficult to visually recognize its existence. Exceeds the surface area, the area of the surface-activated portion becomes large (individual line width increases, resulting in an overall area increase), and the transparent substrate itself is difficult to peel off. Or 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 transparent resin surface becomes almost mirror-like (peeling marks etc. From that portion, it is assumed that the first and second hologram reproduction images underneath can be clearly seen.

  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 photochromic thin film 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 area contributing to hologram reproduction and the area not contributing to hologram reproduction are alternately formed with the above-described size, so that one hologram reproduction area and one hologram reproduction area adjacent thereto are not reproduced. 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-like or sheet-like 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 hologram forming 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 provide a hologram relief in the hologram forming layer using the above-described transparent resin material, the formation of the hologram forming layer is divided into two steps. First, the transparent layer having a thickness of 1/10 to 9/10 is formed. At this stage, a second hologram relief is formed on the outermost surface, and after the photochromic thin film layer is formed, the entire layer including the transparent layer including the photochromic thin film layer is covered. As described above, the remaining layers of the transparent resin are stacked to form the hologram forming layer having the above thickness.

  Of course, using this method, a plurality of hologram reliefs are provided in one interface in the hologram forming layer, or a plurality of photochromic thin film layers are provided by changing their photochromic molecules or by changing their thicknesses. Furthermore, a plurality of photochromic thin film layers may be similarly provided at different locations in the thickness direction of the hologram forming layer. The more formation positions and types of the photochromic thin film layers, the more difficult it is for an unauthorized person to find all the configurations, and the fraud prevention effect can be enhanced.

  In order to form the second hologram relief, it is possible to form the second hologram relief directly by carrying out interference exposure of the hologram on the photosensitive resin material and developing it. Alternatively, it is preferable to perform molding by using a plating mold or the like as a replication 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 relief of the second 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. (With respect to the second relief hologram, the one provided on the outermost surface of the hologram forming layer, that is, the one provided on the interface between the hologram forming layer and the reflective thin film layer or the transparent reflective thin film layer is the first relief hologram. And)
The “relief hologram” itself is a recording of interference fringes due to the interference of light between the object light and the reference light in an uneven relief shape. For example, a laser reproduction hologram such as a Fresnel hologram and a white color such as a rainbow hologram There are optical reproduction holograms, 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.

  In addition, the “hologram relief” itself shows a phase difference as a phase hologram in a “relief shape (means an uneven shape)”, but is provided so as to be in contact with a “relief shape” having this phase difference ( One side of the photochromic thin film layer is provided along the “relief shape”), or the photochromic thin film layer is provided with a uniform thickness following the “relief shape”, thereby generating the photochromic thin film layer Light is emitted including or having the phase difference.

  That is, the photochromic thin film layer itself has a second hologram relief shape.

  Since the photochromic thin film layer is transparent or “white” (meaning that it is visually recognized as “white” by the light scattering property of the photochromic molecule surface), the photochromic thin film layer emits light. Under illumination light other than the illumination light to be generated, it is visually recognized as a simple transparent label or a white label.

  Therefore, in the applications of the various hologram labels described above, printed layers such as characters and designs suitable for the application are placed above and below each layer constituting the hologram label, in particular, between the transparent substrate and the hologram forming layer. It is preferable to provide it.

  Here, the principle that a hologram reproduction image appears by the photochromic thin film layer will be described below.

  In the case of the unsealing prevention label of the present invention, the “light” that the photochromic thin film layer exhibits by “coloring” or “discoloration” is generated when the relief hologram is reproduced (the source of hologram reproduction). The color corresponding to this secondary wave is the color tone (hereinafter referred to as “color development” or “color change” for the convenience of the photochromic thin film disposed on the hologram relief surface. "Light emitted" or "discolored color" is generally expressed as "colored light" or "emitted light" by summarizing "light" from general lighting such as fluorescent lamps for convenience. This “colored light” plays the role, and includes the phase difference of the hologram relief including the diffraction grating group corresponding to the hologram image. It is intended to.

  This “colored 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.

  The manner in which the photochromic thin film changes its color tone will be described below using a photochromic molecular potential curve (see FIG. 1).

The photochromic molecule A obtains energy by irradiation with light having a certain wavelength λ and becomes a molecule A * in an excited state. (STEP1)
At this time, the excited photochromic molecule A * undergoes an intramolecular reaction, for example, cis-trans isomerization reaction, ring-closing / ring-opening reaction, oxidation / reduction reaction, tautomerization by hydrogen transfer, etc. Changes the molecular geometry and electronic structure.

  By this change, the photochromic molecule A * changes to a photochromic molecule B that absorbs light λ ′ having a wavelength different from that of the photochromic molecule A.

  Then, the photochromic molecule B 1 absorbs light having the absorption wavelength λ ′ (STEP 2) or absorbs thermal energy (STEP 3), and returns to the photochromic molecule A again.

  Then, STEP 1 to STEP 3 can be repeated.

At this time, the ease of heat return from the photochromic molecule B 1 to the photochromic molecule A is based on the ground state potential energy ΔE (FIG. 1: STEP 3
).

If it is difficult for heat to return, that is, if ΔE is extremely large, if it is stored in a dark place, the colored body will be maintained as it is. (Such photochromic molecules are called P-type in the sense that they depend only on light.)
On the other hand, ΔE is relatively small when the light is lost and the color is quickly removed or the original color tone is restored. (Such photochromic molecules are called T-type in the sense that they are thermally dependent.)
That is, the photochromic thin film is composed of photochromic molecules A in some cases, and is composed of photochromic molecules B in some cases.

  Each of the photochromic molecules A or B has a characteristic light absorption curve. The photochromic molecule A has a large absorption (curved) portion at the wavelength λ and the photochromic molecule B has a large absorption (curved) portion at the wavelength λ ′.

  As an example, when the wavelength λ of the photochromic molecule A is in the ultraviolet region, the photochromic molecule A is colorless and transparent, and only after it has changed to the photochromic molecule B through the excited state A *, is in the visible light region. A specific color tone is exhibited by absorption of light centered on the wavelength (which may be the wavelength λ ′).

  This "color tone" situation is that the photochromic molecule B has a predetermined light absorption curve in the visible light region, and when the photochromic molecule B is irradiated with white light, a predetermined wavelength including a specific wavelength is included. The light in the wavelength region that absorbs the light in the region and is not absorbed is emitted as divergent light from the holographic film layer made of the photochromic molecule B.

  In the unsealing prevention label according to this example, the divergent light emitted from the photochromic molecule B plays a role of the Huygens secondary wave described above.

  Therefore, when the photochromic thin film layer is composed of photochromic molecules A, this photochromic thin film layer is colorless and transparent, and it cannot be recognized that there is a hologram at that position, and what is behind the photochromic thin film layer is visible. However, by applying illumination light of wavelength λ to the photochromic thin film layer, the photochromic thin film layer diverges light in the above-mentioned wavelength region, and due to interference of the divergent light, a hologram based on the “color tone” of the divergent light is in the air. It will appear to float.

  When the photochromic thin film layer is the above-described P-type, the hologram reproduction image by the “color tone” of the diverging light is maintained in the “color tone” for a while and is gradually decolored, and the photochromic thin film layer is In the case of the above-described T type, the “color tone” disappears relatively quickly and becomes colorless and transparent again.

  Further, when both of the photochromic molecules A and B exhibit a color tone in the visible region, a discoloration phenomenon that changes the color tone of the hologram reproduction image appears.

  Such an effect of the unsealing prevention label of the present invention may be regarded as a design and may be employed for appreciation.

  Also, among T-types, it is designed so that the speed of decolorization is very fast, and it is designed so that it is erased at the same time as the illumination of wavelength λ is removed. Label attachment) Keep the unsealing label (or unsealing label attachment) from the holder, quickly irradiate the light of wavelength λ for a short time, and at the moment, visually recognize the hologram reproduction image by the above colored light. Confirm that it is authentic, and then promptly return the anti-opening label (or attached anti-opening label) to the holder without making the holder's notice of authenticity. Can also be made possible.

  In this case, it is necessary to design the decoloring speed as a half-life of the color development intensity (color density) and to have a half-life of 0.1 to several seconds. In this way, when the light with the wavelength λ is irradiated, the above-described change occurs quickly, and a “color tone” hologram reproduction image of the photochromic molecule B appears. When the irradiation with the light with the wavelength λ is stopped, Thus, an unsealing prevention label excellent in authenticity determination can be provided.

  Of course, it is also preferable to use a determination system that confirms color development after irradiating light of wavelength λ and quickly irradiates light of wavelength λ ′.

  Next, the principle of holography will be described.

If an object is illuminated with coherent light and light diffracted from the object illuminates a recording medium (photoresist, etc.), the object wave is diffracted 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. . For example, “light generated artificially” such as “fluorescent lamps” used in ordinary homes and general offices without using special light sources such as laser light. Also, it is possible to reproduce the hologram sufficiently. However, even if it is “artificially generated light”, is the size of the light source “point light source” or “linear”? Alternatively, depending on whether it is “planar”, whether the emission wavelength is “monochromatic light”, and whether the half-value width of the emission curve is narrow, etc. "Clarity" will be greatly affected.

  Since the reproduction is based on the principle as described above, it is preferable that the reference light at the time of photographing the original hologram is parallel light (because complicated reference light cannot be reproduced), or “hologram represented by a diffraction grating” (The diffraction grating is preferably parallel light for both the object light and the 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 impart characteristics similar to temporal or spatial coherence to the emitted light that is “coloring light”. It is desirable to make the color-developing layer thin or 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 that excites the color-developing layer and the color development wavelength after the change is larger, and it is also effective to amplify only the emitted light by filtering the excitation light during observation. .

  As the excitation light source, energy such as ultraviolet rays, visible rays, electron beams, X-rays, and the like can be used for color development using a light source capable of emitting infrared energy. In order to use it for sex determination, it is necessary to use a light source corresponding to the photochromic molecule, and an ultraviolet light source, a visible light source, and in some cases an infrared light source having a predetermined intensity, wavelength, and illumination spot size are used.

  From the photochromic thin film layer provided so as to be in contact with the second hologram relief surface by illumination with these light sources, and more specifically, from the photochromic molecules contained in the photochromic thin film layer, the wavelength of the illumination light source is different. Wavelength fluorescence and the like are expressed. Since the colored light or the like has the same spatial phase as that of the second hologram relief and has a wavelength (coloring wavelength) different from that of the irradiation light source, the specularly reflected light (0 next time) by the second hologram relief. The second hologram image is reproduced in a direction different from the diffraction direction by the (folding light) direction and the diffraction direction by the irradiation light wavelength (excitation light wavelength), that is, by the diffraction direction by the coloring light wavelength.

  However, when the thickness of the photochromic thin film layer is distributed on the hologram surface irrespective of the second hologram relief, the color light intensity distribution resulting from the thickness distribution is, in some cases, Unnecessary interference may occur with the light for reproducing the hologram, which may cause the second hologram reproduction image to become unclear.

  In order to eliminate this factor, the photochromic thin film layer is formed with a uniform thickness following the concavity and convexity forming the second hologram relief, and the same intensity can be obtained from any position on the second hologram relief surface. Light emission can be generated, and the second hologram reproduction image can be sharpened.

  When ultraviolet light or infrared light other than visible light is used as the irradiation light (excitation light) of the hologram label of the present invention, the light is not visible to an observer, and it is as if special illumination light for hologram reproduction is used. The second hologram reproduction image is observed as if the hologram reproduction image is raised from the place where it is not present. As a result, even if the irradiation light has temporal and spatial coherence, Since light is emitted through a process of excitation and color development, the temporal and spatial coherence between the emitted lights is small even though the phase of the spatial hologram at the time of emission is included. This hologram reproduction image is weaker than the reproduction image of a normal laser reproduction relief hologram and is unclear.

Of course, if only the beam-shaped diffracted light is observed, it is easy to check the color tone and the diffraction direction, and the authenticity can be determined as it is. In order to enable the observer to recognize and accurately determine the presence of the hologram reproduction image, the light emission performance of the photochromic molecule is improved, and the wavelength-diffraction angle dependency is increased by increasing the diffraction angle, and the irradiation light It is necessary to increase the difference between the diffraction angle and the colored light diffraction angle, and to further reduce the variation in the thickness direction of the photochromic thin film layer and make it uniform by making the photochromic thin film layer thinner. (Since the light emitting surface contains phase information, its spatial shape is accurately reproduced.)
Furthermore, in order to express temporal coherence, it is also preferable to illuminate with a pulse laser having a light emission time of 10 ⁻¹⁵ sec or less as an illumination light source. As a result, the light emitting surface of one colored light generated by one illumination pulse does not cause a disturbance phenomenon with the colored light surface generated by the next lighting pulse, and one colored light surface expressed by one pulse. Due to the holographic interference phenomenon caused by the above, a clear second 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 photochromic thin film layer is a second hologram formed by gravure method, offset method, silk screen method, nozzle coating method, ink jet method, etc., in which photochromic molecules are mixed in resin or dispersed in a solvent (or water). It can be formed on the relief.

  At this time, the formed photochromic thin film layer can be formed with a uniform thickness following the unevenness forming the second hologram relief by adjusting the content ratio of the photochromic molecules in the ink.

  The unevenness of the second 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. By adjusting to (0.1 to 10 Pascal / second) and exhibiting the leveling effect due to the weight of the ink, and by setting the solid content in the ink to 20% or less, further 10% or less, for example, thickness With respect to 1 μm, the variation can be suppressed to 1/10 or less, and further to 1/20 or less.

  Here, the photochromic thin film layer is set to the order of 1 μm. However, in order to improve the clarity of the second hologram reproduction image, it is also preferable to discretely provide the photochromic thin film layer. For this purpose, the photochromic thin film is formed. The unit (size) of the region may be about 1.0 μm or less, for example, 0.01 μm to 0.5 μm, more preferably 0.01 to 0.05 μm, and the regions may be uniformly scattered in the hologram relief surface. Is preferred. In the photochromic thin film layer thickness direction, 1 to 10 molecules or 1 to 10 particles are preferably arranged in units of photochromic molecules or fine particles adsorbed with photochromic molecules.

  Above all, the nozzle coating method, ink jet method, and physical vapor deposition methods such as chemical vapor deposition can form a thin film only with a solvent and photochromic molecules and particles without using a resin, and are very thin as a photochromic thin film layer. It is preferable because it can be formed (photochromic molecules, particles 1 to 10 molecules, etc.). An appropriate transparent resin layer may be formed as a protective layer in order to fix the photochromic thin film thereon.

  By the way, the photochromic material can be used as a hologram recording material or an optical memory recording material itself, and such applications are already known. However, these are used for holographic recording (interference fringe recording) directly on the photochromic material. Recording), and recording fine brightness and darkness on the photochromic material.

  This recording is read out using a technique that does not change the photochromic molecules in the recorded area (such as irradiation with light having a wavelength that does not change).

  On the other hand, the unsealing prevention label of the present invention illuminates all the uniformly formed photochromic thin film layers in a similar manner (uniformly), and generates a uniform color. The photochromic thin film layer does not require a complicated process such as exposing the photochromic thin film layer, and the hologram information is carried in the uneven shape that the photochromic thin film layer itself has as its shape, so that the photochromic thin film layer is uniform. The hologram information can be “acquired” (meaning “acquirement of“ hologram reproduction information ”) by simply forming the hologram information.

  The second hologram relief has a concavo-convex shape with a period of about 1 μm, a depth of 0.01 μm, and a maximum of 0.5 μm. By providing a photochromic thin film layer only in this concave part, the period of the hologram relief is increased. It is also possible to provide the presence or absence of a photochromic thin film layer, that is, presence or absence of colored light, in a synchronized manner.

    The concave portion of the second hologram relief is a concave portion when the photochromic thin film layer is formed on the second hologram relief. When the observation is performed from the normal observation method, that is, from the hologram forming layer side, the concave portion is formed. It becomes the club side. In order to form the light emission intensity distribution using the presence or absence of the photochromic thin film layer, it is only necessary to partially form the unevenness, and the entire recess may be filled with the photochromic thin film layer, or You may form only in a part of bottom part.

However, since the phase distribution and the distribution to be formed need to be synchronized, in the case of forming a part, it must always be formed with the same photochromic molecular weight at the same position. (Because this “amount” is proportional to the emission intensity.)
As a method for selectively forming the photochromic thin film layer in the concave portion, fine particles (particle diameter of 0.01 μm, etc., containing a photochromic molecule having a very small particle diameter dispersed in a solvent or the like, or adsorbed on the surface thereof are used. Ink may be used to form an ink layer on the hologram relief, and the fine particles may move from the convex portion to the concave portion under its own weight while the solvent volatilizes.

  In addition, the photochromic thin film layer uniformly provided on the regular diffraction grating is provided by photolithographic exposure, development and etching in synchronism with the regular diffraction grating. Can be provided synchronously. According to this method, it is possible to control the thickness and size of the photochromic thin film layers scattered in the respective recesses, and the so-called “uniformly” can be formed on the entire relief surface.

  What is formed by the above method is that the phase information of the second hologram relief is included in the colored light (radiated light) described in the principle of the above hologram, and the amplitude information synchronized with the phase information is included. It is also included.

  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. In addition, since the photochromic thin film layer is formed discontinuously, individual portions of the photochromic thin film layer are very easy to move when the hologram label is illegally peeled off, and the photochromic thin film layer is very easy to break. Therefore, the authenticity determination property can be improved.

  From the above-mentioned hologram principle, the photochromic thin film layer is desirably thin in order to increase the clarity of the second hologram reproduction image. However, the thinner the photochromic thin film layer is, the more colored light during the second hologram reproduction is. Since the strength becomes weak, the thickness of the photochromic thin film layer needs to be 0.01 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 0.01 μm, the emission intensity is too weak, and even if it is amplified using a photomultiplier tube, it is difficult to distinguish it from noise such as stray light. If it exceeds 1.0 μm, the emission intensity is the object of the present invention. Can obtain sufficient intensity, but due to the light emission of multiple photochromic molecules in the thickness direction, there are multiple curved surface positions in the thickness direction that carry the phase information of the second hologram relief. As a result, the second hologram reproduction image becomes unclear.

On the other hand, the intensity of the colored light is secured at 0.01 μm or more, and the position of the curved surface carrying the phase information is clarified by setting it to 0.5 μm or less, and the second hologram reproduction image is made clear.
Since such a photochromic thin film layer is very easy to break when the hologram label is illegally peeled off, the authenticity determination property can be further improved.

  Next, fine irregularities of the first hologram relief are formed on the outermost surface of the hologram forming layer including the “photochromic thin film layer having the second hologram relief shape” provided in this manner. .

  As the method for forming the first hologram relief, the same method as that for forming the second hologram relief can be used.

  At this time, an unnecessary change is not made to the “shape” of the photochromic thin film layer having the second hologram relief shape already formed in the layer by heating and pressurizing at the time of forming the first hologram relief. Therefore, a method of heating only the outermost surface of the hologram forming layer is suitable. As for the pressurization condition, the hologram forming layer itself functions as a single "single-phase object", and even if a large pressure is applied to the hologram forming layer in the vertical direction, the "force" that changes its "shape" Can hardly apply, so a relatively large pressure can be applied.

  Then, a reflective thin film layer such as a metal thin film layer or a transparent thin film layer such as a metal compound thin film layer is formed on a vacuum thin film such as a vapor deposition method so as to contact and follow the first hologram relief. Using a chemical thin film forming method such as a forming method or a plating method, the film is formed with a thickness of 20 nm to 2000 nm.

  The hologram label of the present invention can be formed by providing an adhesive layer on the reflective thin film layer thus formed or the transparent reflective thin film layer.

  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 coating methods such as gravure printing, silk printing, and further using the solvent-free hot melt method, the above reflective thin film layer, or On the transparent reflective thin film layer, it can be provided with a formation thickness after drying of 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 adhesive layer is appropriately selected from a reflective thin film layer or a resin having strong adhesion to the transparent reflective thin film layer.

  The adhesive layer is also the same as the hologram forming layer, that is, the formation is divided into at least two stages, the second hologram relief is formed on the outermost surface of the first layer, and the photochromic thin film layer is formed on a part thereof. By providing the photochromic thin film layer having the second hologram relief shape, at least the position corresponding to the surface activation treatment of the pattern shape in the adhesive layer can be provided.

  In this case, when the hologram label of the present invention is illegally peeled off, the photochromic thin film layer is divided as described above due to the fracture of the adhesive layer, and the same effect as described for the hologram forming layer is obtained in the adhesive layer. Appear.

  Furthermore, it is also preferable to provide such a photochromic thin film layer on both the hologram forming layer and the adhesive layer in order to enhance the anti-counterfeit effect.

  Since the pressure-sensitive adhesive layer is more easily deformed by pressure than the hologram forming layer, it is relatively easy to provide the concave and convex shapes of the second hologram relief on the outermost surface of the transparent resin used for the pressure-sensitive adhesive layer.

  However, due to its nature, after providing a photochromic thin film layer, when a transparent resin layer is further stacked, a phenomenon that deteriorates the hologram relief shape of the already formed photochromic thin film layer is likely to occur. It is preferable to use a screen printing method, a curtain coating method, or an ink jet method with a low formation pressure (meaning “printing pressure” of the printing method) as a method of stacking layers.

  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 observation side”), thereby causing the photochromic thin film layer to emit light. At this time, 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 being blocked.

  Of course, when a photochromic thin film layer is provided in the adhesive layer, only the transparent resin provided after the photochromic thin film layer is formed is made light scattering.

  180-degree peel strength between the adhesive layer and the reflective thin film layer or the transparent reflective thin film 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. When the hologram label is less than 100 mm / 25 mm, the film is peeled off at the interface between the reflective thin film layer or the transparent reflective thin film layer and the adhesive layer when the hologram label is illegally peeled off after being stuck to the adherend. Is likely to occur, and the hologram forming layer is difficult to break.

  In terms of preventing fraud, it is desirable that the peel strength between the adhesive layer and the reflective thin film layer or the transparent reflective thin film layer is high, but an adhesive exceeding 3 kg / 25 mm is suitable for label processing and labeling. It will be inferior to sticking aptitude.

  Of course, the 180-degree peel strength between the hologram forming layer and the reflective thin film layer or the transparent reflective thin film layer needs to be sufficiently large, and the vacuum thin film forming method is suitable for this purpose.

  After applying a “label” that can only be visually recognized as a “hologram label” to an appropriate position on a desired adherend, an unauthorized person tries to remove this “label” illegally. The material is easily peeled off, the transparent substrate side remainder remains on the transparent substrate side, the adherend side remainder remains on the adherend side, characters such as “open” appear, and this “label” is labeled “hologram” It turns out that it was a "brittle label".

  At this stage, the fraudster thinks that if the remaining part on the adherend side is removed with a solvent, etc., the surface of the adherend will be deteriorated with the solvent, etc. It will try to restore the sticking state.

  That is, as a fake “label”, a hologram brittle label having a similar reflective hologram design and a metal reflective thin film layer such as an aluminum reflective layer is separately prepared, and the fake “label” adhesive layer is used to apply the fake “label”. The fake “label” is pasted on the adherend-side remainder so as to fill in the recess or hole in the adherend-side remainder.

  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 a predetermined irradiation light such as ultraviolet rays of a predetermined wavelength from the false “label”, the aluminum reflective layer blocks the illumination light, and any fluorescent color By not emitting light and, of course, the second hologram reproduction image by color development does not appear, it can be easily and reliably determined that some “injustice” has been performed.

  Of course, even if a new fake “label” is created using a transparent base material that has been peeled off by unauthorized persons, if the “label” is subjected to the same irradiation light treatment, this time, characters such as “open” A hologram reproduction image appears only in the portion, indicating the presence of an “injustice” act.

  Furthermore, 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 the deterioration of the hologram relief due to the rupture of the hologram forming layer or photochromic thin film layer, or the mixing of air at the time of bonding. Even the existence of the layer itself cannot be known, so it is impossible to confirm whether or not the “compensation” was successful.

  Similarly, when the hologram label of the present invention has a transparent reflective thin film layer and a photochromic thin film layer having a second hologram relief shape is provided in the adhesive layer under the transparent thin film layer, Therefore, it is possible to easily determine “restoration”.

According to the present invention, a hologram-forming layer, a reflective thin film layer, and an adhesive having a patterned surface activation treatment region on one surface of a transparent substrate and having a first hologram relief thereon. A hologram label provided with a layer,
A photochromic thin film layer having a second hologram relief shape is provided in a region including a position corresponding to the patterned surface activation treatment region in the hologram forming layer or in the adhesive layer. A hologram label characterized by the above can be provided, and when this hologram label is attached to a desired adherend, if the hologram label that is not originally peeled off is to be removed for an illegal purpose, the hologram label can be provided. Peeling occurs preferentially at the interface between the transparent substrate and the hologram forming layer. After the peeling, a message indicating fraud is displayed, and when a predetermined irradiation light is applied, Provided is a hologram label that makes it easy to determine whether fraud has occurred by raising a hologram reproduction image that includes `` chip-like defects ''. Can.

It is a figure explaining a photochromic molecular potential curve. It is sectional drawing of the hologram label A which shows one Example of this invention. It is sectional drawing of hologram label A 'which shows another 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 FIG. 2 and FIG. 3.)
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 FIG. 2 and FIG. 3.)
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 3 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, 3, 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 a polybutylene succinate resin: polybutylene succinate adipate, a mixture of polybutylene succinate and polycaprolactone, a mixture of polybutylene succinate and polybutylene succinate adipate, polybutylene succinate adipate A polyester resin synthesized from a low molecular weight aliphatic dicarboxylic acid and a low molecular weight aliphatic diol, such as succinic acid and butane Addition of aliphatic isocyanate to a mixture of modified polyvinyl alcohol, aliphatic polyester resin and starch, and low molecular weight aliphatic polyester, such as combinations of diol and ethylene glycol, oxalic acid and neopentyl glycol, butanediol, and ethylene glycol A polymerized product is preferred.

  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 1 by applying oxidizing agents such as permanganate and peroxide, primer coating treatment, vinyl / epoxy / methacryloxy / amino / mercapto / acryloxy / isocyanate / styryl / alkoxy oligomer type silane Chemical treatment such as treatment using a coupling agent, argon beam etching treatment that is vacuum treatment, etching solution treatment that partially dissolves the transparent substrate 1, and sandblasting that mechanically scrapes the surface of the transparent substrate 1 A physical surface forming process such as the above 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.

Using the above surface activation treatment, the interfacial tension or surface energy of the transparent substrate 1 is increased. 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 for breaking the hologram forming layer 3 and the photochromic thin film layer 4 when the transparent base material 1 is peeled (the direction of action of the force, its magnitude, etc.) is further complicated, and its “breaking” property is improved. Can be improved.

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 , Cellosolve 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 non-volatile Oil (dry seed 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 typographic printing, inkjet printing, 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 FIG. 2 and FIG. 3.)
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, but on the transparent substrate 1, The above transparent resin material is directly formed by a predetermined thickness using an injection molding method or an extrusion molding method, or diluted in an appropriate solvent, a gravure coating method, a screen printing method, Using a curtain coating method or the like, it can be formed to a uniform thickness.

  Then, a second relief hologram prepared in advance or a duplicate thereof, or a plating mold thereof is used as a replication mold, and the mold surface is a layer of the resin material (1/10 of the thickness of the hologram forming layer 3). It is better to carry out shaping by pressing against a layer having a thickness of ˜9 / 10.

  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 relief of the second 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.

  The method of shaping (also called replicating) the relief shape is to use 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), and the resin material layer (the thickness of the hologram forming layer 3). By layering the original plate on the photochromic thin film layer 4 to be described below and heating and press-bonding both of them by an appropriate means such as a heating roll. It is possible to reproduce the concavo-convex pattern of the original plate. The second hologram pattern to be formed (the hologram relief that expresses one hologram reproduction image is referred to as one hologram pattern) may be single or plural. Also, the shape of the region forming the second 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 layer of the resin material on the transparent substrate 1 is pressed along this duplication cylinder, and duplication is carried out at the above pressure with a metal cylinder from the back side. In order to minimize distortion and deformation such as heat shrinkage after replication, a method of heating only a part of the outermost surface side of the layer of the resin material rather than heating the entire transparent substrate 1 is desirable. . Usually, it heats to 60 to 110 degreeC. Furthermore, the precision can be further improved by keeping the metal cylinder on the back surface at room temperature or cooling it.

  After the photochromic thin film layer 4 is provided in a predetermined region on the second hologram relief thus provided, the second region is formed on the photochromic thin film layer 4 and in a region other than the photochromic thin film layer 4. A transparent resin material having the same composition is provided so as to be in direct contact with the hologram relief, and a layer of the transparent resin material corresponding to the remaining thickness of the hologram forming layer 3 is provided. (Accordingly, naturally, the refractive indexes of the two layers of the transparent resin material that are stacked are also exactly the same).

(Photochromic thin film layer)
In the present invention, the second hologram relief surface formed on the transparent resin material layer used for the hologram forming layer 3 described above corresponds to a predetermined position, that is, at least the pattern-shaped surface activation treatment described above. The photochromic thin film layer 4 is formed in the region including the position. (See Figure 2.)
As photochromic molecules (photochromic materials) used for the photochromic thin film layer 4, there are an organic compound type and an inorganic compound type.
As an organic compound system,
Azobenzenes (cis-trans isomerism): dimethylaminoazobenzenes, etc.
Spiropyrans (intramolecular ring-opening): spirobenzothiopyran, spiroselenazolinobenzopyran, spirobenzoselenazolinonaphthoxazine, etc. More specifically, 1,3,3-trimethylindolino-6 ′ -Nitrobenzopyrospirane, 1 ', 3'-dihydro-8-methoxy-1', 3 ', 3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2', 2 '-(2H)- Indole], 1,3,3-trimethylindolinobenzopyrospirane, 1,3,3-trimethylindolino-6'-bromobenzopyrrirospirane, 1,3,3-trimethylindolino-8'-methoxy Benzopyrospirane, 1,3,3-trimethylindolino-β-naphthopyrilospirane, etc.
Spirooxazines (intramolecular ring-opening): Spiroquinoxazines, spironaphthoxazines, spirophenanthrooxazines, spirobipyridoxazines, etc., compounds having a heterocyclic structure containing a nitrogen atom in the molecule Etc. (red purple to blue. “Coloring” quickly disappears)
Spiroperimidines: 2,3-dihydro-2-spiro-4 ′-[8′-aminonaphthalen-1 ′ (4′H) -one] perimidine, 2,3-dihydro-2-spiro-7 ′-[8 '-Imino-7,8-dihydronaphthalene-1'-amine] perimidine, etc.
Arylethenes: symmetrical diarylethene, asymmetrical 2,3-diarylmaleic anhydride, asymmetrical diarylperfluorocyclopentene, etc.
1,2-bis (2,4-dimethyl-5-phenyl-3-thienyl) -3,3,4,4,5,5-hexafluoro-1-cyclopentene, 1,2-bis [2-methylbenzo [ b] thiophen-3-yl] -3,3,4,4,5,5-hexafluoro-1-cyclopentene, 2,3-bis (2,4,5-trimethyl-3-thienyl) maleic anhydride 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, cis-1,2-dicyano-1,2-bis (2,4,5-trimethyl-3-thienyl) ethene, etc. More specifically, color development wavelength: 425 nm, 469 nm, 526 nm, 534 nm, 550 nm, 562 nm, 578 nm, 583 nm, 611 nm, 620 nm, 628 nm, 665 nm, 680 nm, 828 nm, etc. Green, yellow, red, etc. coloring.),
Frugides: Diphenyl fulgide, triphenyl fulgide, etc.
Chromenes: 6-morpholino-3,3-bis (3-fluoro-4-methoxyphenyl) -3H-benzo (f) chromene, 6-morpholino-3- (4-methoxyphenyl) -3- (4-tri Fluoromethoxyphenyl) -3H-benzo (f) chromene, 6-piperidino-3-methyl-3- (2-naphthyl) -3H-benzo (f) chromene, 6-piperidino-3-methyl-3-phenyl-3H -Benzo (f) chromene, 6-morpholino-3,3-bis (4-methoxyphenyl) -3H-benzo (f) chromene, 6-hexamethyleneimino-3-methyl-3- (4-methoxyphenyl)- 3H-benzo (f) chromene, 6-morpholino-3- (2-furyl) -3-methyl-3H-benzo (f) chromene, 6-morpholino-3- (2-thienyl) -3 Methyl -3H- benzo (f) chromene, 6- morpholino-3- (2-benzofuryl) -3-methyl -3H- benzo (f) chromene, etc. (colored orange-yellow.),
Cyclophanes: Anthracene-containing cyclophanes such as anthracenophanes, anthracenonaphthalenophanes, anthracenoparacyclophanes, metacyclophanes, etc.
Chalcone (1,3-diphenyl-2-propen-1-one) -flavylium, etc.
Fulgimide compounds: N- cyanomethyl-6,7-dihydro-4-methyl-2-phenyl-spiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^{3 , 7} ] decane), N-cyanomethyl-6,7-dihydro-2- (4′-methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3 3.1.1 ^3,7 ] decane), N-cyano-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane), N-cyano-6,7-dihydro-4-methylruspiro (5,6-benzo [b] furandcarboximide-7,2-tricyclo [3.3 .1.1 ^3,7 Decane), N- cyano-4-cyclopropyl-6,7-dihydro-spiro (5,6-benzo [b] flange carboximidoyl -7,2- tricyclo [3.3.1.1 ^{3, 7]} decane) N-cyano-6,7-dihydro-4-methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane), N- Cyanomethyl-4-cyclopropyl-6,7-dihydrospiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane), N-cyanomethyl -4-cyclopropyl-6,7-dihydro-2- (4'-methoxyphenylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1 ^{3, 7]} decane), N- Anomechiru 4-cyclopropyl-6,7-dihydro-2-phenyl-spiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^{3, 7]} decane) N- (3′-cyanophenyl) -6,7-dihydro-4-methyl-2- (4′-methoxyphenyl) spirobenzothiophenecarboximide-7,2′-tricyclo [3.3.1.1 ^3,7 ] Decane (colored orange to blue),
Thioindigos (cis-trans isomerism), salicylidene anilines (intramolecular hydrogen transfer: crystal type), nitrobenzylpyridines (intramolecular hydrogen transfer: crystal type), tetrachloro-α-ketodihydronaphthalene, bis (Triphenylimidazolyl) s, tetraphenylhydrazines, beanthrones, pyridylside nonones, anthracene derivatives (photodimerization), methylene blue (photoredox), triphenylmethanes (ion dissociation), hexaphenylbiimidazole (radicals) Dissociation), polycyclic aromatic compounds (oxygenation), etc.
Can be used.

In particular, a product obtained by dispersing diarylethenes in a transparent resin and a crystallized product of diarylethenes are excellent in physical properties and weather resistance.
As an inorganic compound system,
Ternary compounds selected from AgBr, AgCl, AgI, CuBr2, CuCl2, CuCl, CuI2, CuI, Ag alone, Cu alone, etc.
Silver nanoparticles-titanium oxide, etc.
Can be used.

  Furthermore, among these photochromic molecules (materials), it is preferable that the emission intensity curve (wavelength as a horizontal axis) as the photochromic molecule B has only one peak in the visible region, A half-width of the peak of 10 to 50 nm is preferable because it gives a clearer hologram reproduction image.

  As a forming method, it is possible to use a general printing method, a coating method, etc., but as a method for forming a more precise thin film, a spin coating method, a casting method, a screen printing method, a blade coating method, a roll coating method. , Water surface development method, LB (Langmuir-Blodget) method and the like, and dry process include vacuum deposition method, sputtering method, chemical vapor deposition method and the like. In particular, chemical vapor deposition is suitable for forming a thin film of an organic compound system uniformly and at the molecular level.

  More specifically, a resin-dispersed ink in which photochromic molecules are uniformly dispersed in a transparent resin or a solvent-dispersed ink in which photochromic molecules are dispersed in water or a solvent are prepared, and using them, a printing method or Further, a predetermined position on the hologram relief surface formed on the layer of the transparent resin material used for the transparent resin layer 3 by using various forming methods such as a coating method and an ink jet method, that is, at least the above-described pattern The photochromic thin film layer 4 can be formed in a region including the position corresponding to the surface activation treatment in a shape so as to be in contact with the hologram relief, to follow, or partially in the recess.

  In addition, it is preferable to form the photochromic thin film layer 4 directly on the hologram relief surface by a chemical vapor deposition method from the hologram relief followability and the uniformity thereof, and the electron beam heating vacuum deposition method. This is preferable because there is no collision of a high-temperature electron beam and argon atoms in sputtering, and it is easy to maintain the molecular structure.

Further, after the photochromic thin film layer 4 is formed on the hologram relief surface, it is aligned with the diffraction grating pattern by a photolithography method using a photoresist, exposed to light, developed, and unnecessary portions are removed to remove the photoresist pattern. The photochromic thin film layer can be removed by etching in synchronization with the concave portion of the pattern, and the photochromic thin film layer can be left only in the concave portion. (Not shown)
Conversely, a photoresist layer is formed on the hologram relief surface, aligned with the diffraction grating pattern, exposed to light, developed, and unnecessary portions removed to leave the photoresist on the convex portions and expose the concave portions. After the thin film layer is formed, the photochromic thin film layer 4 can be left only in the concave portion by removing the photoresist on the convex portion and at the same time partially removing the photochromic thin film layer immediately above it. (Not shown)
Resin-dispersed ink includes the above-described photochromic molecule, a transparent resin, for example, an acrylic ester resin, an acrylamide resin, a nitrocellulose resin, or a polystyrene resin as a thermoplastic resin, and as a thermosetting resin, Ball mills, 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, phenol resins, etc. Thoroughly knead with a roll mill, etc., adjust the viscosity with a solvent, etc., and use a gravure method, offset method, silk screen method, curtain coat method, nozzle coat method, and ink jet method as appropriate to achieve a uniform thickness Forming It can be.

  In order to make the thickness of the photochromic thin film layer 4 0.01 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%, Alternatively, when the coating film using water as a solvent is, for example, 10 μm, the thickness after evaporation of the solvent (the thickness of the photochromic thin film layer) should be 1/10 to 1/100. 1 μm to 0.1 μm.

  Since the solvent-dispersed optical ink does not include a resin component and includes only a photochromic molecule and a solvent, the photochromic thin film layer 4 can be made thinner than the resin-dispersed type.

  As the solvent, water, an alcohol solvent, or a cellsolve or paraffin solvent is used to disperse and hold photochromic molecules having a small particle system, and is used for the transparent resin layer 3 by curtain coating, nozzle coating or the like while stirring. It can be provided on a layer of transparent resin material.

  In this case, by adjusting the evaporation rate of the solvent, it is possible to move the photochromic molecule to the concave portion 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, Method for forming photochromic thin film layer 4 by imparting adhesiveness to the surface and spraying photochromic molecules as powder on the surface so that only photochromic molecular particles in contact with the adhesive surface remain on the hologram relief surface Is also suitable.

  According to this method, the photochromic thin film layer 4 becomes almost one particle film, is uniformly formed on the hologram relief surface, and emits light when excitation light is applied from the transparent resin material layer side used for the transparent resin layer 3. The surface is the same as the hologram relief surface.

  In any case, since the unevenness of the hologram relief is very small, the photochromic thin film layer 4 has a uniform thickness and the photochromic molecules in it have a uniform density, or evenly on the hologram relief surface ( In the case of partial formation, in order to form a uniform portion), it is preferable that the particle size of the photochromic molecule is small, and the nanophotochromic molecule is particularly suitable.

The photochromic thin film layer 4 can also be provided in the adhesive layer 5 by the same method as described above. (See Figure 3.)
In this case, instead of the transparent resin material used for the transparent resin layer 3, a transparent resin material used for the adhesive layer 5 described below, that is, an adhesive is used.

  In addition, the difference in refractive index between the transparent resin material used for the transparent resin layer 3, the photochromic thin film layer 4, and the adhesive layer 5 described below is within 0.1, and further within 0.03. Thus, it is possible to prevent the appearance of an unnecessary hologram reproduction image and improve forgery prevention.

  Excitation light suitable for the photochromic molecule used, for example, ultraviolet light (wavelength 365 nm, wavelength 245 nm, etc.) is applied to the hologram label thus produced at an intensity of 10 μW / cm 2 to 10 mW / cm 2 for 1.0 second. For those that irradiate for ~ 100 seconds or change color tone in the visible region, irradiate LED light or semiconductor laser light close to a predetermined wavelength to develop a specific color tone or change the color tone. The authenticity can be determined by visually recognizing the hologram reproduction image in the color tone.

  At this time, the visibility may be enhanced or a mechanical determination may be performed using a specific filter, a reproduction light amplifying device, or the like.

In addition, the existence of a hologram reproduction image of a specific color tone may not be realized by a person who possesses a hologram label, that is, a person who possesses an authenticity identification object to which a hologram label is transferred or pasted. It is also suitable to devise so that the color tone disappears or returns to the original color tone promptly (within several seconds to several tens of seconds) after authenticity confirmation.
(Reflective thin film layer and transparent reflective thin film layer)
The reflective thin film layer 5 or the transparent reflective thin film layer 5 is provided on the hologram forming layer 3 having the first hologram relief described above. (See FIG. 2 and FIG. 3.)
When the hologram label of the present invention includes the photochromic thin film layer 4 in the hologram forming layer 3, the reflective thin film layer 5 is used, and the photochromic thin film layer 4 is included in the adhesive layer 6. Uses the transparent reflective thin film layer 5.

  As the reflective thin film layer 5, a metallic luster reflective layer such as a metal thin film formed by a vacuum thin film method or the like is used.

  As the transparent reflective thin film layer 5, a transparent reflective layer such as a metal compound thin film layer is provided.

  When the transparent reflective layer is provided, when the photochromic thin film layer 4 in the adhesive layer 6 emits light, the light emission can be visually recognized through the transparent reflective thin film layer 5. That is, the second hologram reproduction image can be determined through the transparent reflective thin film layer 5.

  Further, after the hologram label A ′ is attached, an image on the adherend covered with the hologram label A ′ can be observed through the hologram label A ′.

As the transparent reflective layer, it is a substantially colorless and transparent hue, and its optical refractive index is different from that of the hologram forming layer 3, so that it is possible to visually recognize the glitter such as a hologram even though there is no metallic luster, A transparent hologram can be produced. For example, a thin film having a higher refractive index than that of the hologram forming layer 3, for example, ZnS, TiO ₂ , Al ₂ O ₃ , Sb ₂ S ₃ , SiO, SnO ₂ , ITO, or the like. Preferably, it is a metal oxide or nitride, specifically, Be, Mg, Ca, Cr, Mn, Cu, Ag, Al, Sn, In, Te, Ti, Fe, Co, Zn, Ge, Pb. Cd, Bi, Se, Ga, Rb, Sb, Pb, Ni, Sr, Ba, La, Ce, Au, and other oxides or nitrides, and the like can be exemplified by a mixture of two or more thereof. Also, a general light-reflective metal thin film such as aluminum can be used with transparency when the thickness is 50 nm or less.

  The transparent metal compound is formed by vapor deposition and sputtering on one side of a transparent biodegradable plastic film or sheet 1 in the same manner as a metal thin film so as to have a thickness of about 20 to 2000 nm, preferably 50 to 1000 nm. It may be provided by a vacuum thin film method such as ion plating or CVD (chemical vapor deposition). In particular, the CVD method causes little thermal damage to the hologram forming layer 3. Even if other thin film forming methods are used, if the thin film layer to be formed is made thin, the thermal damage can be reduced.

(Adhesive layer)
An adhesive layer 6 is provided on the reflective thin film layer 5 or the transparent reflective thin film layer 5 described above.

  As the adhesive layer 6, a conventionally known solvent-based or water-based transparent resin material, that is, an adhesive, for example, vinyl acetate resin, acrylic resin, vinyl acetate-acrylic copolymer, vinyl acetate-vinyl chloride. Examples thereof include copolymers, ethylene-vinyl acetate copolymers, 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 6 is generally 10 μm to 50 μm, and is applied and dried by a conventionally known method, that is, a gravure coat, roll coat, comma coat or the like, to form the adhesive layer 6. This is the hologram label A of the present invention. (See Figure 2.)
Further, the adhesive strength of the adhesive layer 6 is the peel strength between the hologram forming layer 4 and the adhesive layer 6, and is desirably in the range of about 0.1 to 1 kg in the 180 ° peeling method in accordance with JIS Z0237. Of course, even higher peel strengths are suitable for the purposes of the present invention.

  The kind and the coating amount of the pressure-sensitive adhesive as described above are formed on the “reflective thin film layer 5 or the transparent reflective thin film layer 5” or “the transparent resin material used for the pressure-sensitive adhesive layer 6”. When the remaining thickness of the adhesive layer 6 is formed on the photochromic thin film layer 4 ”, it is preferably selected and used so that the peel strength is in the above range.

The photochromic thin film layer 4 can also be provided in the adhesive layer 6 by a method similar to the method of providing the photochromic thin film layer 4 in the hologram forming layer 3. (See Figure 3.)
In this case, instead of the transparent resin material used for the hologram forming layer 3, a transparent resin material used for the adhesive layer 6, that is, an adhesive, is used, and similarly, 1/10 of the thickness of the adhesive layer 6. A second relief hologram prepared in advance or a duplicate thereof, or a plating mold thereof is used as a replication mold for a layer having a thickness of ˜9 / 10, and the mold surface is a layer of the transparent resin material (adhesive) Shaping by pressing on the agent layer). (Not shown)
Then, on the second hologram relief, the photochromic thin film layer 4 is provided in the same manner. On the photochromic thin film layer 4 and where the photochromic thin film layer 4 is not present, directly on the second hologram relief, The remaining layer of the adhesive layer 6 is provided by the method described above, and the adhesive layer 6 is formed to obtain the hologram label A ′ of the present invention. (See Figure 3.)
At this time, the photochromic thin film layer 4 that has already been formed and the “underlying layer having a thickness of 1/10 to 9/10 of the thickness of the pressure-sensitive adhesive layer 6” are re-dissolved and unnecessary deformation is performed. In order to avoid this, it is preferable to use a screen printing method, a curtain coating method, or an ink jet method with a low forming pressure.

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 “sealing” characters are designed to be arranged vertically and horizontally, and the inside of the image area of the characters (the line width of the image area is 1000 μm) is masked for each character. In this manner, the surface activation treatment was performed to form “surface activated portion 2” (patterned surface activation treatment region) in a “pattern” shape. (See Figure 2.)
In addition, a melamine resin is used as a transparent resin material used for the hologram forming layer 3, and a “transparent resin used for the hologram forming layer 3 having a thickness of 2.0 μm, which is 1/5 of the thickness of the hologram forming layer 3. After forming “material layer 1” (peeling strength between transparent base material 1 and “layer 1 of transparent resin material used for hologram forming layer 3”: activation treatment surface 1.2 kg / 25 mm width, other than that (Equivalent to a portion of 300 g / 25 mm width.)) An Ni original plate provided with a relief hologram having a second hologram relief with a high design taken using a laser optical system was prepared. Rotating relief hologram forming apparatus (original cylinder diameter 1.0 m, original plate surface temperature 100 ° C.) Pressurized cylinder diameter 0.3m water-cooled, to form a pressure 2 tons / m, the second hologram relief at the replication rate 10 m / min) on "a layer 1 of the transparent resin material used for the hologram forming layer 3". (Not shown)
On this “transparent resin material layer 1 used for hologram forming layer 3”, a resin-dispersed photochromic molecule-containing ink (ink composition for photochromic thin film layer 4) having the following composition is coated with the above-mentioned transparent group. As a region including “position corresponding to“ surface activated portion 2 ”” in “pattern” shape on material 1, “surface activated treatment was performed in“ pattern ”shape on transparent substrate 1. In the shape of the area that is slightly larger, including the portion 2 "", that is, in the shape of a vertical and horizontal 12 mm × 12 mm area, and printed and dried, the photochromic thin film layer 4 has a thickness of 2.0 μm, It formed so that it might touch 2 hologram reliefs.

・ <Ink composition for photochromic thin film layer 4>
1,2-bis [2-methylbenzo [b] thiophen-3-yl]-
3,3,4,4,5,5-hexafluoro-1-cyclopentene Crystalline material B2629 manufactured by Tokyo Chemical Industry Co., Ltd. 0.5 parts by mass Urethane resin 14.5 parts by mass Toluene 25 parts by mass Methyl ethyl ketone 30 parts by mass Ethyl acetate 30 parts by mass On the photochromic thin film layer 4 and on the second hologram relief not provided with the photochromic thin film layer 4, the thickness is 4/5 of the hologram forming layer 3 using the melamine resin described above. “Transparent resin material layer 2 used for hologram forming layer 3” having a thickness of 8.0 μm is formed, and “Transparent resin material layer 1 used for hologram forming layer 3” and “Transparent material used for hologram forming layer 3” are formed. In addition, a layer 2 of resin material ”was combined to form a hologram forming layer 3 having a thickness of 10.0 μm. As a result, the photochromic thin film layer 4 is included in the hologram forming layer 3. (See Figure 2.)
A first hologram relief is formed on the outermost surface of the hologram forming layer 3 in the same manner as described above, and is further followed on and in contact with the first hologram relief on the first hologram relief. An aluminum thin film layer is provided with a thickness of 200 nm as the reflective thin film layer 5 using a vacuum vapor deposition machine manufactured by ULVAC, Inc., and an adhesive composition for the adhesive layer 6 having the following composition is further formed thereon by a gravure coating method. The adhesive layer 6 was formed to a thickness of 20 μm, and the hologram label A of Example 1 was produced. (See Figure 2.)
・ <Adhesive composition for adhesive layer 6>
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. (Pressurized with a roller of 2 kg load.) When observed under room illumination light, the hologram forming layer 3 having the first hologram relief is more specifically provided on the first hologram relief. The first hologram reproduction image could be visually recognized by the reflected light in a certain reflective thin film layer 5. (See FIG. 4. The envelope is not shown.)
Furthermore, when the hologram label A was tried to be peeled off from the envelope, the transparent base material 1 was easily peeled off, and the transparent base material-side remainder was in the form of letters “open” and “sealed” on the transparent base material 1 side. It was continuously attached to the vertical and horizontal. (The peeled transparent base material 7. See FIG. 4. In FIG. 4, 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. (Adherent side remaining portion 8 remaining on the adherend. See FIG. 4. Similarly, in FIG. 4, the letters “open” and “sealed” are drawn one by one. The envelope is not shown. )
When the peeled transparent substrate 10 is irradiated with a light source 9 having a wavelength of 365 nm (UV-LED module LC-L2 manufactured by Hamamatsu Photonics), the ultraviolet rays are not visible to the eyes, and the letters “open” and “sealed” The second hologram reproduction image of red by the colored light of the photochromic thin film layer 5 having the second hologram relief shape can be steadily visually recognized in the image line portion (position of the remaining portion on the transparent substrate side). It was. (See Figure 5.)
Similarly, when the adherend side remaining part 12 on the envelope was irradiated with a 365 nm wavelength light source 11 (UV-LED module LC-L2 manufactured by Hamamatsu Photonics), In addition, the red second hologram reproduction image by the colored light of the photochromic thin film layer 5 having the second hologram relief shape could be steadily viewed. And this 2nd hologram reproduction image contained the character-like chipping of "open" and "sealed". (See Figure 5.)
After that, another hologram brittle label having the same size as this “label” (having an aluminum reflective layer as a thin film layer and reproducing a hologram reproduction image similar to the first hologram reproduction image) is prepared. The “label” was bonded using a similar roller so as to have the same appearance as the original state, so as to cover the remaining part of the adherend side. (Not shown)
When the ultraviolet light having a wavelength of 365 nm is irradiated from above the pressure-bonded “label” using the above-mentioned light source, the aluminum reflecting layer shields the irradiated light, and the “under another hologram brittle label” The photochromic thin film layer 4 in the remaining part 12 on the adherend side does not develop color, and the second hologram reproduction image by colored light does not appear (not shown). I was able to judge.

From the above, it was considered that the hologram label A of the present invention has a high anti-counterfeit 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 degrees) 40 parts Toluene (boiling point 100 degrees) 30 parts Methyl isobutyl ketone (boiling point 115 degrees) 29 parts Linseed oil 1 part When this hologram label A was evaluated in the same manner as in Example 1, transparent substrate 1 The same good results as in Example 1 were obtained except that the film was peeled off from the hologram forming layer 3 very easily.
(Example 3) On a "transparent resin material layer 1 used for hologram forming layer 3" formed in the same manner as in Example 1, a resin-dispersed fluorescent ink having the following composition was applied at a coating thickness of 10 μm by a gravure coating method. The hologram label A of Example 3 was produced in the same manner as in Example 1 except that the coating was applied and dried quickly after application to form the photochromic thin film layer 4 with a thickness of 0.3 μm. (See Figure 2.)
At this time, the photochromic thin film layer 4 followed the first hologram relief of the “transparent resin material layer 1 used for 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 label A was observed in the same manner as in Example 1, it was due to colored light. Example 1 except that a clearer red hologram reproduction image can be confirmed, and only the red reproduction image appears to be floating in the space, and the fraud determination can be performed more accurately. Good results similar to those obtained.
(Example 4) In Example 1, the photochromic thin film layer 4 is not provided in the hologram forming layer 3, and the hologram forming layer 3 having a thickness of 10.0 μm is formed on the transparent substrate 1 subjected to the surface activation treatment. A TiO ₂ thin film layer having a thickness of 100 nm is formed on the first hologram relief provided on the hologram forming layer 3 as a transparent reflective thin film layer 5 using an electron beam heating vapor deposition apparatus manufactured by ULVAC. When the pressure-sensitive adhesive layer 6 is provided, the pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer 6 having the following composition is coated on the transparent reflective thin film layer 5 by a gravure coating method and dried. The layer 1 ”made of a transparent resin material for use is formed with a thickness of 4.0 μm, which is 1/5 the thickness of the adhesive layer 6, and the second surface is formed on the outermost surface in the same manner as in Example 1. A hologram relief is formed (however, The setting conditions of the type relief hologram forming apparatus were an original plate surface temperature of 60 ° C., a pressure of 0.5 ton / m, and a replication speed of 5 m / min.) On this second hologram relief, in the same manner as in Example 1. The photochromic thin film layer 4 is formed, and the adhesive composition for the adhesive layer 6 having the same composition is further formed thereon, and the “adhesion” having a thickness of 16.0 μm, which is 4/5 the thickness of the adhesive layer 6. “Layer 2 made of transparent resin material for layer 6” is formed, and “Layer 1 made of transparent resin material for pressure-sensitive adhesive layer 6” and “Layer 2 made of transparent resin material for pressure-sensitive adhesive layer 6” are combined. A hologram label A ′ of Example 4 was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive layer 6 had a thickness of 0.0 μm. As a result, the photochromic thin film layer 4 is included in the adhesive layer 6. (See Figure 3.)
・ <Adhesive composition for adhesive layer 6>
Vinyl acetate-acrylic copolymer 30 parts by weight Isophorone diisocyanate 1 part by weight Toluene 20 parts by weight Ethyl acetate 30 parts by weight Methyl isobutyl ketone 19 parts by weight This hologram label A ′ is used for sealing an envelope and is attached to the sealed part. (When pressed with a 2 kg load roller) and observed under room illumination light, the hologram forming layer 3 having the first hologram relief is more specifically provided on the first hologram relief. The first hologram reproduction image could be visually recognized by the reflected light in the transparent reflective thin film layer 5. Further, through the hologram label A ′, it was possible to visually recognize the design of the envelope behind the hologram label A ′. (See FIG. 4. The envelope is not shown.)
Further, when the hologram label A ′ was peeled off from the envelope, the transparent base material 1 was easily peeled off, and the transparent base material side remaining on the transparent base material 1 side was the characters “open” and “sealed”. It was continuously attached to the vertical and horizontal sides. (The peeled transparent base material 7. See FIG. 4. In FIG. 4, 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. (Adherent side remaining portion 8 remaining on the adherend. See FIG. 4. Similarly, in FIG. 4, the letters “open” and “sealed” are drawn one by one.)
When the peeled transparent substrate 10 is irradiated with a light source 9 having a wavelength of 365 nm (UV-LED module LC-L2 manufactured by Hamamatsu Photonics), the ultraviolet rays are not visible to the eyes, and the letters “open” and “sealed” The second hologram reproduction image of red by the colored light of the photochromic thin film layer 5 having the second hologram relief shape can be steadily visually recognized in the image line portion (position of the remaining portion on the transparent substrate side). It was. (See Figure 5.)
Similarly, when the adherend side remaining part 12 on the envelope was irradiated with a 365 nm wavelength light source 11 (UV-LED module LC-L2 manufactured by Hamamatsu Photonics), In addition, the red second hologram reproduction image by the colored light of the photochromic thin film layer 5 having the second hologram relief shape could be steadily viewed. And this 2nd hologram reproduction image contained the character-like chipping of "open" and "sealed". (See Figure 5.)
After that, another transparent hologram brittle label having the same size as this “label” (having a ZnS reflective layer as a thin film layer and reproducing a hologram reproduction image similar to the first hologram reproduction image) is prepared. The “label” was adhered using a similar roller so as to have the same appearance as the original state, so as to cover the remaining part of the adherend side. (Not shown)
When irradiation light with a wavelength of 365 nm is irradiated from above the pressure-bonded “label” using the above light source, the irradiation light is transmitted through the ZnS transparent reflection layer, and the inside of the adhesive layer 6 of the hologram label A ′. The photochromic thin film layer 4 in FIG. 1 emitted light, and a red second hologram reproduction image by the second hologram relief appeared. Moreover, the second hologram reproduction image includes “open” and “sealed” in the shape of “missing”, and it was possible to clearly determine that some sort of fraud was performed. (Not shown)
From this, it was considered that the hologram label A ′ of the present invention has a high anti-counterfeit effect.
(Example 5) As a “fine pattern”, the basic shape is “50 μm × 100 μm rectangle”, and this basic shape is developed in a checkered pattern in the open and “sealed” image areas. The surface activation treatment was applied to one skip to form the “pattern” of “open” and “sealed”, and on the “checkered” mesh that is this “fine pattern” A hologram label A of Example 5 was obtained in the same manner as Example 1 except that the photochromic thin film layer 4 composed of a “60 μm × 120 μm rectangular” region was provided as a slightly larger region. (See FIG. 2. “Fine pattern” is not shown.)
When evaluated in the same manner as in Example 1, the same good results as in Example 1 were obtained, and the letters “open” and “sealed” after peeling of the transparent base material 1 were clearly visible. Except for this, the same effect as in Example 1 was obtained.

(Comparative example)
(Comparative Example 1) Surface activation treatment or surface deactivation treatment was not performed, a uniform hologram forming layer was provided on a transparent substrate, and a photochromic thin film layer was not provided in the hologram forming layer A “hologram label (only the first hologram relief is present)” of Comparative Example 1 was obtained in the same manner as in Example 1 except that there was no second hologram relief.

  When this “hologram 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 6, and no light emission occurred even when irradiated with ultraviolet rays. .

  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, A ′ Hologram label 1 Transparent substrate 2 Part of one surface of transparent substrate surface-treated in a pattern
(Pattern surface activation treatment region. At the interface between the transparent substrate and the hologram forming layer, the portion other than this portion is a region other than the pattern surface activation treatment region and is subjected to the surface activation treatment. (It is said that it is a non-exposed part or a part that has been surface-inactivated.)
3 Hologram forming layer 4 Photochromic thin film layer 5 Reflective thin film layer or transparent reflective thin film layer 6 Adhesive layer 7 When the hologram label A was peeled off, the transparent substrate peeled off (the remaining portion on the transparent substrate side is attached).
8 When the hologram label A is peeled off, the adherend-side remaining part remaining on the adherend (the state where the transparent substrate-side remainder is removed)
9 Predetermined irradiation light (ultraviolet light is exemplified)
10 The transparent base material that was peeled off when the prescribed irradiation light was applied (the balance on the transparent base material side is attached).
11 Predetermined illumination light (example of ultraviolet rays)
12 The remaining part on the adherend side when the predetermined irradiation light is irradiated (the state where the remaining part on the transparent base material side is removed).

Claims (5)

Hologram label having a pattern-like surface activation treatment region on one surface of a transparent substrate, and a hologram forming layer having a first hologram relief thereon, a reflective thin film layer, and an adhesive layer Because
A hologram label, wherein a photochromic thin film layer having a second hologram relief shape is provided in a region including at least a position corresponding to the patterned surface activation treatment region in the hologram forming layer.
A hologram having a patterned surface activation treatment region on one surface of a transparent substrate, and a hologram forming layer having a first hologram relief thereon, a transparent reflective thin film layer, and an adhesive layer. A label,
A hologram label, wherein a photochromic thin film layer having a second hologram relief shape is provided in an area including at least a position corresponding to the patterned surface activation treatment area in the adhesive layer.
The hologram label according to claim 1 or 2, wherein the photochromic thin film layer has a thickness of 0.01 µm to 0.5 µm.
The hologram label according to any one of claims 1 to 3, wherein the surface activation treatment is light treatment or physical treatment.
  The hologram label according to any one of claims 1 to 4, wherein the pattern is constituted by a set of fine patterns.

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