JP2016173469A - Hologram sheet and card with hologram - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hologram sheet and a card with hologram having enhanced forgery preventing property, in which authenticity of a hologram can be visually determined.SOLUTION: A sheet type thin film light source layer is disposed on a hologram formation layer in such a manner that only when the sheet type thin film light source layer is subjected to a predetermined light-emission process, a hologram having a predetermined visible light wavelength appears in a space of the sheet. Thereby, a hologram reproduction image, which is normally invisible, is reproduced at a wavelength different from that of an illumination light source in a room or the like, by a process of applying a voltage or the like to emit light at a predetermined wavelength.SELECTED DRAWING: None

Description

  The present invention is a novel hologram sheet, in particular, a sheet substrate, a sheet-like thin film light source layer, a transparent resin layer having a hologram relief, and a hologram having at least four layers comprising a transparent layer provided so as to cover the hologram relief. The present invention relates to a sheet (a three-layer structure that does not include a “sheet base material” as long as it can be handled) and a hologram-equipped card in which the hologram sheet is embedded in a card base material.

  The “sheet substrate” used in the hologram sheet of the present invention is a “sheet substrate” having “transparency” or a “sheet substrate” having “opacity” depending on the use of the hologram sheet of the present invention. Among them, as the “sheet base material having“ opacity ””, for example, the transmittance for illumination light having a wavelength in the visible region is 30% or less, particularly The transmittance of light emitted from the sheet-like thin film light source layer is 30% or less, “resin film sheet (the resin itself is opaque, or the resin material is added with an inorganic pigment such as titanium dioxide) Etc.) ”and“ Inorganic material sheet (excluding transparent inorganic materials such as glass) ”can be adopted, but in the following explanation,“ sheet material having “transparency” ” " It stipulates that "transparent substrate", below, per If you want to use this "transparent substrate", will be described in detail. Needless to say, the following description can be applied to the hologram sheet of the present invention when the “sheet base material having“ opacity ”” is used.

  The hologram sheet of the present invention includes a “sheet-like thin film light source layer” as a light source layer that emits transmitted illumination light that illuminates a “hologram relief” of a relief hologram that exhibits a “phase hologram”. "Luminescence" (emitted under a predetermined condition, having a predetermined wavelength and having a spherical wavefront) enters the "relief hologram" Based on the “hologram relief”, a “relief hologram reproduction image” by “light of a predetermined wavelength” appears, and a self-luminous hologram sheet, and the hologram sheet, such as an ID card (“ID”) Means “Identification”, and an IC card (“IC” means “Integrated circuit”). : "Integrated circuit" means a card with this "IC" embedded in it is called an "IC card. This" IC card also includes an IC tag. " Card ".

Furthermore, the reflection diffraction efficiency (hereinafter referred to as “the normal to the sheet surface (front surface)” of the hologram sheet, with respect to incident light that forms a “predetermined angle” and travels from the transparent layer side toward the hologram relief. Abbreviated as "reflective diffraction efficiency for predetermined incident light at a predetermined angle", and "predetermined reflective diffraction efficiency").
The "predetermined angle" (the above-mentioned "predetermined angle" has a relationship of "vertical angle" with respect to the "normal line to the sheet surface") of the hologram sheet. It is expressed using the “predetermined angle” which is an expression of the above, but considering the “traveling direction” as well, these two “predetermined angles” are different from each other, and the “predetermined angle” described above is used. On the other hand, the “predetermined angle” described later means “an angle different from the angle shown above by 180 degrees.” That is, “the angle is the same and the directions are opposite to each other”. ) "And transmission diffraction efficiency (hereinafter referred to as" transmission diffraction efficiency for predetermined incident light at a predetermined angle "for incident light from the transparent resin layer side toward the hologram relief, Abbreviated as “efficiency”.) Te,
A “hologram relief” having a characteristic that “the predetermined reflection diffraction efficiency” is “smaller” than the “predetermined transmission diffraction efficiency” (all “predetermined angle” ranges, that is, 0 This means that the hologram sheet is always “small” in the range of degrees to 90 degrees. Preferably, the ratio is 1/2 to 1/1000, particularly 1/10 to 1/100.

  The “predetermined angle” is of course also referred to as “reference light” in the sense of illumination light for reproducing the relief hologram (incident light having the same role as “reference light” at the time of recording the relief hologram). In the case of electron beam drawing recording, it means “(theoretical) assumed illumination light (reference light)”) and “the same angle”, but in the hologram sheet of the present invention, Even if an angle other than that angle is set as “predetermined angle”, the above relationship is maintained (meaning that “the magnitude relationship” does not change even if the “angle” is changed).

  Furthermore, as the “set wavelength” (also referred to as “measurement wavelength”) of “illumination light (including assumed illumination light)” incident at such “predetermined angle”, the “sheet-like thin film” described above is used. Naturally, the “wavelength” (“predetermined wavelength”) of “light emission” from the “light source layer” and the “same wavelength” are used, but the “set wavelength of illumination light” (“measurement wavelength”). Other “arbitrary wavelengths in the visible light region” may be adopted, and even in that case, it is more preferable to configure the hologram sheet of the present invention so as to maintain the above-described magnitude relationship. .

The characteristics of such “hologram relief” are described in detail below.
It is determined by “the refractive index of the transparent layer”, “the refractive index of the transparent resin layer”, and “the“ depth ”of the hologram relief (particularly, the ratio to the“ optimum depth ”)”.

Here, on the “side of the transparent layer in contact with the transparent resin layer” or “the side of the transparent resin layer in contact with the transparent layer”, a transparent compound thin film layer having a low refractive index such as MgF ₂ (refractive index: 1.37) , The “refractive index function” at the upper and lower interfaces and “refractive index stabilizing function and optical mirroring function” at the upper and lower interfaces are added. Is also an important factor. (In the following description, in order to avoid complications, such a “transparent compound thin film layer” is not referred to, but it goes without saying that it can be similarly applied.)
And, “the“ optimum depth ”in the“ predetermined reflection diffraction efficiency ”” and “the“ optimum depth ”in the“ predetermined transmission diffraction efficiency ”” have different “depth values”. The “depth” closer to the “optimum depth” in the “predetermined transmission diffraction efficiency” and the “depth” far from the “optimum depth” in the “predetermined reflection diffraction efficiency” (Meaning that “value” is closer to “optimum depth at a predetermined transmission diffraction efficiency” than the midpoint between the two “optimum depths”).

In addition, any of the above-mentioned “diffraction efficiencies” changes depending on the “emission wavelength of the measurement light source” (meaning the above “measurement wavelength”) when measuring the diffraction efficiency (“measurement”). Meaning "wavelength dependence" for "emission wavelength of light source"),
Furthermore, the above-mentioned “optimum depth” also has a “value corresponding to the“ measurement wavelength ”” or a “value” corresponding to “an integer multiple of the measurement wavelength”. Because it has characteristics (meaning there is periodicity),
The wavelength of the light source for measurement for measuring these “diffraction efficiencies” (“measurement wavelength”) is emitted from a predetermined light emitting point in the “sheet-like thin film light source layer” with a predetermined wavelength and a spherical wave front. The emission is set to match the “predetermined wavelength” (meaning “same” or “the difference is 30 nm or less”).

  However, these two “optimal depths” are “theoretically correlated” with each other and cannot be set independently (that is, “maximum optimum depth of one diffraction efficiency”). "Simply" means that "the other diffraction efficiency" does not become "the smallest, the depth".), "The predetermined transmission diffraction efficiency" becomes relatively large and at the same time "the predetermined diffraction efficiency" It is set to “depth” at which “reflection diffraction efficiency” is relatively small.

  Such “depth” is set, for example, under various conditions (for example, recording a “hologram relief” on a photoresist or an electron beam resist by an optical recording method or an electron beam drawing recording method) Possible by adjusting the resist formation conditions, exposure intensity, etc.) and various conditions (development processing solution type, concentration, processing temperature, processing time, other processing environment, etc.) during development processing. It becomes.

  Specifically, one or more “conditions” are “added / subtracted or made excessive” with respect to the “conditions” for obtaining the “optimum depth” (for example, “development time”). Can be adjusted to be shorter or longer than a predetermined time).

  Of course, in the case of “development time” given as an example, strictly speaking, the “development depth- (relief) depth” correlation curve is drawn and the target “(relief) depth” is not read until the correlation curve is read. Can be obtained.

  That is, the “development time− (relief) depth” correlation shows a linear correlation or an exponential correlation from the start of development to a certain time t, and the “depth” changes rapidly. When the time t is exceeded, the change rate of the “depth” decreases rapidly (the time t is the “saturation time” or “standard processing time” in the so-called “development processing time”). Draw a characteristic correlation curve.

  Accordingly, after setting (fixing) other conditions to predetermined values, a “development time- (relief) depth” correlation curve is drawn in advance, and based on the “correlation curve”, a desired “ “Hologram relief depth” (meaning the desired “hologram relief depth” that can provide the desired “predetermined reflection diffraction efficiency” and “predetermined transmission diffraction efficiency”). The “development time” is read and set.

  Here, the “predetermined reflection diffraction efficiency” and the “predetermined transmission diffraction efficiency” of the “hologram relief” in the “hologram sheet” of the present invention will be described in detail below.

  First, assuming a “simple two-layer laminate” of “transmission layer (refractive index n1) / simple plane shape interface / transparent resin layer (refractive index n2)”, The measurement light (1) that is parallel to the vertical “normal” and incident from the “transparent layer” side is “incident light (1)” (“predetermined angle” = parallel to the normal = 0 °). Similarly, the measurement light (2) parallel to the “normal line” and incident from the “transparent resin layer” side is referred to as “incident light (2)” (this “measurement light (2)” is parallel to the normal line. Even so, the incident angle should be expressed as “180 degrees.” However, since “measurement light (1)” and “measurement light (2)” are both “parallel to the normal”, In addition, it may be expressed that “any measurement light is incident at a predetermined angle”).

  Of course, the measurement light (α1) incident at “predetermined angle = α degree” with respect to the “normal” or the measurement light incident on the “transparent resin layer” side in parallel to the measurement piece (α1) The light (α2) can be set similarly.

For this “simple two-layer laminate”, “interface reflectance R ₀ ” by “simple planar interface” of “incident light (1)” is R ₀ = (n2−n1) from the Fresnel formula. ² / (n1 + n2) ² . (For reference, the “interface transmittance is (2 × n2) ² / (n1 + n2) ² ” by “incident light (1)” at this time)
Further, the “interface transmittance T ₀ ” of the “incident light (2)” with respect to the “simple two-layer laminate” is also T ₀ = (2 × n1) ² / (n1 + n2) ²

  Next, “two-layer laminate” of “transmission layer (refractive index n1) / interface is“ hologram relief ”shape / transparent resin layer (refractive index n2)”, which is a partial configuration of the “hologram sheet” of the present invention. Is assumed.

Then, for this “two-layer laminate”, “incident light (1)” and “incident light (2)” are defined again, as in the above-mentioned “simple two-layer laminate”. , “Substantial interface reflection diffraction efficiency =“ predetermined reflection diffraction efficiency R _DIF ”” by “incident light (1)” and “substantially incident light (2)” with respect to this “two-layer laminate” Interface transmission diffraction efficiency = “predetermined transmission diffraction efficiency T _DIF ”.

The “hologram relief” is determined by the “shape” of “reflection diffraction efficiency R100 _DIF ” (assuming that the interface reflectance is 100%) and “transmission diffraction efficiency T100 _DIF ” (assuming that the interface transmittance is 100%. ). (At this time, “hologram relief surface” is regarded as “substantially flat” or “continuous connection of minute planes”, and the interface reflectance at the “substantially flat surface” or “small plane” is 100 % Or assuming that the interface transmittance is 100%.)
Here, if “the depth of the hologram relief” is “D _H1 ”, this R100 _DIF is a function having “n1 × D _H1 ” as its variable (element).

That is, since R100 _DIF is determined only by the value of “n1 × D _H1 ”, R100 _DIF = F {n1 × D _H1 } is expressed.

If the “hologram relief depth” is “D _H2 ”, the T100 _DIF is a function having “(n2−n1) × D _H2 ” as its variable (element).

That is, since the T100 _DIF is determined only by the value of “(n2−n1) × D _H2 ”, it is expressed as T100 _DIF = G {(n2−n1) × D _H2 }.

In this case, naturally, the “optimum values” of “D _H1 ” and “D _H2 ” are different, and the relationship of “optimum value of D _H1 ” << “optimum value of D _H2 ” is established.

However, since the depth _DH of the “hologram relief” of the “hologram sheet” of the present invention takes “one value” according to the setting of the various conditions described above, when it is set to “the optimum value of _DH2 ,” The value is “distant” from the “optimum value of D _H1 ”. If the value is set to “optimum value of D _H1 ”, the value is “far from the optimum value of D _H2 ”.

Therefore, in the "hologram sheet" of the present invention, the depth D _H of the "hologram relief", "D optimum value of the _H2" and from the middle of the "optimum value of D _H1", somewhat "optimum value of D _H2" It will be set to a value close to. (D _H = D _H1 + <D _H2 −D _H1 > × β: 1/2 <β <1)
In any case, if these “(variable) values” are used, “substantially” “incident light (1)” for this “two-layer laminate” based on “hologram relief” of “two-layer laminate”. Interfacial reflection diffraction efficiency = “predetermined reflection diffraction efficiency R _DIF ” is represented by “product” of “interface reflectance R ₀ ” and “reflection diffraction efficiency R 100 _DIF ”, and “R _DIF = R ₀ × R100”. _DIF "
Similarly, “substantial interface transmission folding efficiency =“ predetermined transmission diffraction efficiency T _DIF ”” by “incident light (2)” with respect to this “two-layer laminate” is expressed by “interface transmittance T ₀ ” and “transmission”. It is represented by “product” with “diffraction efficiency T100 _DIF ”, and becomes “T _DIF = T ₀ × T100 _DIF ”.

And by setting the depth _DH of the “refractive index of the transparent layer”, “refractive index of the transparent resin layer”, and “hologram relief” of the “hologram sheet” of the present invention to each desired “value”, The “hologram sheet” of the present invention realizes ““ predetermined reflection diffraction efficiency R _DIF ”<“ predetermined transmission diffraction efficiency T _DIF ”” (the refractive index of “transparent substrate” corresponds to this magnitude relationship) Because the impact is small, it is omitted from the explanation.

  In the above description, for the sake of simplification, the description has been made assuming that “the“ predetermined angle ”= 0 degrees (or 180 degrees)”, but this “predetermined angle = α degrees” (0 degrees <α <90 degrees). ) Is the same.

  When the “hologram sheet” is embedded in the “card substrate”, the surface in contact with the “card substrate” of the “hologram sheet” is the other surface of the “transparent substrate” of the “hologram sheet” Or the outermost surface of the “transparent layer” of the “hologram sheet” (in the latter case, the “card substrate” has transparency and the “card substrate” Through the transmission phase hologram).

  Furthermore, when embedding the “hologram sheet” in the “card substrate”, if possible, the “transparent substrate” is peeled off (except), However, in the following description, the representative structure is as follows: “The surface of the“ hologram sheet ”that is in contact with the“ card substrate ”is the other surface of the“ transparent substrate ”. "Case".

  The “sheet-like thin film light source layer” in the present invention refers to any of the following “light source layers (1) to (3)” or a combination thereof.

(1) “Light emission phenomenon due to photoexcitation” by “irradiation of light” to the “sheet-like thin film light source layer” (fluorescence emission, phosphorescence emission by “light irradiation” such as ultraviolet irradiation, visible light irradiation, or infrared irradiation) Or “luminescent phenomenon” that stores phosphorescence.Hereinafter, these “light emission” are also collectively referred to as “fluorescence emission” or “photoluminescence.” This “photoluminescence” is a so-called “semiconductor”. When irradiating the light with energy higher than the forbidden band of the semiconductor, the semiconductor absorbs the light and forms more electron-hole pairs than the thermal equilibrium state. Needless to say, the “recombination process” when they return to the equilibrium state includes a phenomenon in which “light of a predetermined wavelength” is emitted from the “semiconductor”. ,
“Light emission having a spherical wavefront (hereinafter also simply referred to as“ spherical wave ”) starting from the“ light emission center ”in the“ light source layer ”(this is the“ predetermined light emission point ”). ) "Is emitted with a wavelength (predetermined wavelength) peculiar to each emission center," sheet-like (meaning a state having a relatively large area) ", and" thin film (several μm) ""Sheet-like thin-film fluorescent layer", which is a "light source layer" of "very thin and uniform thickness" that is less than or less than 10 nm. .

  In particular, the “multiple reflection phenomenon” described in detail below, that is, the upper and lower “surfaces” of the “sheet-like thin film fluorescent layer” form an “optical mirror surface” and have the same wavelength as the light wavelength. “Directivity”, which is also described in detail below, by “the“ multiple reflection phenomenon ”that occurs between the upper and lower surfaces of“ excitation light ”and“ emitted light ”” by facing each other in parallel at a distance. " "Sheet-like thin film fluorescent layer" that emits "waves of light with a light"

(2) “Luminous phenomenon caused by recombination of“ electrons / holes ”by applying a predetermined DC voltage or AC voltage to a“ sheet-like thin film light source layer ”” (electroluminescence; hereinafter referred to as “EL Is also abbreviated.)
The “light emission center” (in the light source layer) (the recombination point of “electrons” and “holes”), that is, the position of “holes”, but this position is the “light emission center”. “Emission with spherical wavefront (spherical wave)” starting from “origin” (predetermined emission point)) has a specific wavelength (predetermined wavelength) at each emission center. "Sheet (means a state having a relatively large area)" and "thin film (several μm or less and several tens of nanometers or more," very thin, And “a uniform thickness”.) ”Light source layer”, “sheet-like thin film LED (Light Emitting Diode) layer”, “sheet-like thin film inorganic EL layer”, “sheet-like thin film” "Organic EL layer" (The two are collectively called "sheet-like thin film EL layer". "Sheet-like thin-film disk laser (laser emitting light perpendicular to the thin-film surface) layer" and "Sheet-like thin-film surface-emitting laser (SEL: Surface Emitting Laser) layer". (Here, the “disk laser layer” and the “surface emitting laser layer” have “emitted light” between two opposing “reflection layers (at least one of which is a half mirror)”. Due to the “stimulated emission” phenomenon caused by repeated passage, the layer already having a remarkably high directivity is inserted between the semiconductor p-type layer and the semiconductor n-type layer. The “phosphor layer” in (1) has a similar state, that is, “the layers are sandwiched between two reflective interfaces, even though the above-mentioned“ laser layer ”cannot be repeatedly passed. "State" appears, and "excitation light" or "emitted light itself" repeatedly passes through the "layer containing fluorescent light emitter" and "fluorescent layer" at "speed of light" The so-called “stimulated emission” phenomenon The `` spherical wave '' is deformed and directed to a predetermined direction `` wave of light with directivity '' or `` light emission with an elliptical wavefront '' (both spherical waves, When a set of plane waves with small areas that are slightly different in direction, the plane wave with a small area that goes in a predetermined direction has the greatest intensity, and the intensity of the plane wave that has a small area in a direction different from that direction is It is smaller depending on the angle deviation from the direction.

In the following, a representative example of “waves of light with directivity” will be mainly described. The content can be easily applied to “elliptical wave” and “plane wave”. )
(3) Based on “light emission phenomenon caused by deformation stress” (so-called “stress light emission: a kind of mechanical light emission, elastic deformation light emission”) by “external force load” on “sheet-like thin film light source layer”.
The “light emission center” in the “light source layer” (recombination point of “electrons” and “holes”, usually the position of “holes”. This recombination point is the “light emission center”. ”, Which is a“ predetermined light emission point ”).“ Light emission having a spherical wavefront (spherical wave) ”starting from (origin) is a wavelength specific to each light emission center (predetermined wavelength). "Sheet (means a relatively large area)" and "thin film (several tens of μm or less and several hundreds of nanometers or more" “Sheet-like thin film stress light emitting layer”, which is a “light source layer” of “.

  In particular, the above-mentioned “multiple reflection phenomenon”, that is, the upper and lower “surfaces” of the “sheet-like thin film stress-emitting layer” form an “optical mirror surface” and have a distance similar to the wavelength of light. By facing each other in parallel, “waves of directional light”, which are also described in detail below, by “the“ multiple reflection phenomenon ”that occurs between the upper and lower surfaces of“ emitted light ”” ” "Sheet-like thin film stress light emitting layer".

  As described above, in the “fluorescence layer”, the “fluorescence emitter” molecule itself, and the elements (atoms) added (doping, etc.) to constitute the “fluorescence emitter” are the above-mentioned “ In the “thin film LED layer”, “thin film inorganic EL layer”, “disk laser layer”, and “surface emitting laser layer”, the “emission center” is a “junction surface between a p-type semiconductor and an n-type semiconductor” (so-called “pn”). "Junction surface") "point" (position) where "electron" and "hole" caused "recombination", or "double heterostructure with light emitting layer in between" or "organic In the thin-film EL layer (for example, “comprised of“ negative electrode / electron transport layer / light emitting layer / hole transport layer / plus electrode ””), “element (atom)” in the “light emitting layer” In `` recombination point '' and `` stress emission layer '', In the structure "," electronic, "" a hole (also referred to as a lattice defect.) "Is" caused recombination "" point "(position), the above-mentioned" emission center ".

Then, the light emitted from the “sheet-like thin film light source layer” (radiated light. In its “wavelength-intensity curve”, it has the “center wavelength λ ₀ ” having the highest intensity, On the short wavelength side, it has a gradually decreasing intensity (that is, light having a wavelength width of several tens to several hundreds of nm) is a “light emitting point” in the “sheet-like thin film light source layer”. (One point: illuminant, luminescent molecule, and luminescent position in the luminescent molecule.) ”Is spreading and spreading as a“ wave of directional light ”(with a bias in a given direction). In the minute region in that direction, the phase also moves relatively uniformly.) The “hologram relief surface” composed of the “interface” of the “transparent resin layer” and “transparent layer” is ”Passes through the phase difference of the hologram relief and causes a holographic interference phenomenon to occur, and a relief hologram reproduction image (transmission hologram reproduction image. Hereinafter, simply“ relief hologram reproduction image ”, or , Also abbreviated as “hologram reproduction image”).

  The relief hologram reproduction image at this time corresponds to each of the above-mentioned “one point”, and “one relief hologram reproduction image” is reproduced respectively. Further, for each “wavelength width”, , Because the imaging direction is “spread (meaning that it has an angle“ width ”)” in a predetermined angular direction, because the “relief hologram reproduction image group” is reproduced (having a “wavelength width” , Synonymous with the presence of a plurality of "single wavelength" lights in succession, meaning that "individual imaging directions" exist for each single wavelength.) The emitted "light". In the case of a simple “spherical wave”, it becomes an “light image” in which the reproduction directions overlap each other innumerably.

  In addition, in such a “state where a large number of hologram reproduction images are overlapped with a slight“ shift ””, the observer cannot visually recognize “a clear hologram reproduction image of“ one ”.

  Here, the meaning expressed as “one” means, for example, that “a large number of lines” continuously overlap with a “deviation” of about several hundred μm. "It can only be identified as a line", so it defines and expresses the meaning of "Visible as" one "when viewed by an observer" or "Not visible as" one "when viewed by an observer" .

  Furthermore, since the wavelength of the light emitted from the “sheet-like thin film light source layer” and the wavelength of the light constituting the hologram reproduction image to be formed are “strictly the same”, for example, in the “green background color” In addition, it is not easy to visually interpret the “picture” as if it was a “green picture”.

  The above is the case where the “sheet-like thin film light source layer” of the present invention is not used, that is, the above-mentioned “any one of the light source layers of (1) to (3) or a combination thereof”. If not used as a `` light source layer '', it is not `` waves of light with directivity '' as described above, but `` light '' traveling in all directions with uneven phase and uneven intensity. Illuminates the “hologram relief” with “a collection of random spherical waves” (scattered light) in terms of phase, intensity, and direction by a “light source (layer) that emits light with a simple planar spread”. In other words, in the `` bright background color '', it is necessary to observe the `` reproduced hologram reproduction image '' consisting of the exact same `` color '' in a so-called `` buried state ''. Wide emission wavelength range of “illumination light” Is also to the "blurring of the hologram reproduction image" due to the fact that is exerted, no longer, with the emergence of a "hologram reproduced image", it can not be secured and the reliability of that "determining the authenticity".

  Therefore, by using the “sheet-like thin film light source layer” of the present invention, the illumination light of “hologram relief” consisting of “a collection of random spherical waves” is changed to “a wave of light with directivity”. By illuminating the “hologram relief” with such a “directional wave of light”, it becomes an “image of light” whose reproduction directions overlap, and such “ It is assumed that the observer can visually recognize “a clear hologram reproduction image of“ one ”” as a state where a large number of hologram reproduction images are overlapped without “shift”.

  As a result, even if the wavelength of the light emitted from the “sheet-like thin film light source layer” and the wavelength of the light constituting the hologram reproduction image to be formed are “strictly the same”, that is, “green background color” Even if a “green picture” is drawn, it is easy to visually interpret the “picture” and to ensure the reliability of such “authenticity determination”. is there.

In addition, the “multiple reflection phenomenon”, that is, the “repetitive reflection phenomenon between the upper and lower surfaces”, causes a “stimulated emission phenomenon (a phenomenon that occurs in laser oscillation operation. ) ”,“ Amplification of light ”is caused, and“ directivity (meaning that it has a part of directivity like laser light) ”of“ light emitted ”is expressed, and In order to sufficiently achieve the effect, the “repetitive reflection” is more fully generated in a precisely aligned form while maintaining the reflection intensity.
“Upper surface and / or lower surface” of the “sheet-like thin film light source layer” is referred to as “half mirror surface (surface having a reflectance of 30 to 70% with respect to light of a predetermined wavelength)” The additional “reflecting surface (reflectance is 50% or more)” or the additional “reflecting layer (same as on the left)” is referred to as the back surface of the “sheet-like thin film light source layer” (behind the lower surface). Meaning.) Is also suitable.

  This “stimulated emission phenomenon” means that in “laser oscillation”, the emitted light has to reciprocate precisely in the “long active layer of several millimeters” (the phase and direction are aligned due to its high accuracy. .)) When used as a light source for an optical system system, the construction accuracy (geometrical or optical accuracy) of the entire optical system must be very high. The “reciprocating distance” in the “sheet-like thin film light source layer” is set to “very short distance”, which is only 10 nm to several tens of μm, which is 1/100 to 1/100000, Since the determination is also “visual determination”, the configuration accuracy as high as “(laser light source for optical system)” is not required.

  However, the upper and lower surfaces of the “sheet-like thin film light source layer” and the interface between the other layers, etc., are improved in order to enhance the above-mentioned functions by “optical mirror surface” (the “surface” has a substantially smooth surface. Furthermore, the average surface roughness Ra is preferably 0.01 μm to 0.1 μm.)

  In particular, in the hologram sheet of the present invention, “the thickness of the“ sheet-like thin film light source layer ”is 0.01 μm to 2.0 μm”, so that the “reciprocation distance” is further shortened, and such “ It is preferable to further increase the “stimulated emission phenomenon”.

  This means that “the two“ interfaces ”are“ a very short distance (interval) ”, and while maintaining a“ uniform distance ”, in a so-called“ parallel ”state, they are arranged side by side.” A scientific paper that theoretically analyzed the so-called “transparent hologram”, which is a structure provided on the relief surface (published by the Japan Printing Association, “Theoretical analysis of transparent holograms” published by the Japan Printing Society, Vol. 25 2 (1988) pp. 75-88), “2.1.3 MODEL 3.2 Interface Type Phase Grating. This is considered to be the simplest model of a multi-interface hologram. The distance H between the relief surfaces is preferably equal to or less than the relief pitch (2π / b), and in order to make multiple reflection more effective, H << 2π / b (13) There is a need to( 77-78) ", and by reducing the distance between the two interfaces, that is, the thickness of the sheet-like thin film light source layer, from the (hologram) relief pitch of about 1-2 μm, It can be said that the “multiple reflection” phenomenon is effectively generated between the two surfaces to promote the “stimulated emission phenomenon” described above.

  And in the present invention, “the hologram sheet is embedded in the card substrate, and the exposed surface of the hologram sheet is flush with the surface of the card substrate, or is in a position recessed from the surface of the card substrate. "" Hologram sheet itself "of the present invention, that is," all layers "constituting the hologram sheet of the present invention are" embedded in a card substrate ", and are intended to be counterfeited or altered. Even if you try to peel off the whole hologram sheet or a part of its layer, you can not put nails in its cross section, and eventually there is no other way to scrape those layers, and once you scrape, In the recess, it is very difficult to restore the layers, and it shows a card with a hologram that makes it impossible to alter or forge them. “The“ all layers ”constituting the hologram sheet of the present invention are“ embedded in the card substrate ”finally means that“ the outermost surface of the hologram sheet of the present invention, that is, the “most layer of the transparent layer” “Surface (exposed surface)” means that “the surface of the card substrate is flush with the surface of the card substrate, or is recessed from the surface of the card substrate”.

  Further, in the present invention, “the card substrate is a battery-embedded IC card substrate in which an IC driving battery is incorporated, and the IC driving battery is a light emitting power source that emits light from the hologram sheet. Also, the “card with hologram” (hereinafter also referred to as “IC card with hologram of the present invention” or simply “IC card with hologram”) means at least a so-called “secure microcomputer for IC card (abbreviated). (This card is called a “contact IC card”) or “non-contact IC chip (Type B or FeliCa <Felica: Sony Corporation). ) (Registered trademark) type element) ”(the card that contains this IC chip is called“ non-contact IC card ”) In the following description, the “IC tag” incorporating this IC chip is also included in this “non-contact IC card” for convenience, and these “secure microcomputer” and “non-contact type” As a power source for driving the “IC chip” (that is, a battery for driving the IC) and as a power source for causing the hologram sheet to emit light, a primary battery or a secondary battery is placed in the card substrate. It means "built-in".

Here, as a matter of course, the “sheet-like thin film light source layer” used in the “hologram sheet” of the present invention is driven by such a built-in battery and uses a “light source layer” of a type that emits light. Assumed. However, it is not excluded to provide another type of “light source layer”. (The same applies hereinafter.)
When these “batteries” further include “a“ control unit ”for controlling a secure microcomputer or a non-contact type IC chip” and “a“ display unit ”such as a liquid crystal display”, the “control unit” Needless to say, it is used as a power source for driving “]” and “display unit” ”.

  Furthermore, in addition to these “built-in” “batteries”, the card base material also includes “(auxiliary) power source comprised of a solar cell and a capacitor for storing electric energy generated by the solar cell”. Is also included in the meaning of “incorporating an IC driving battery”.

  As a result, a person who uses the IC card with hologram of the present invention simply removes the IC card with hologram from the outside (meaning that it is exposed to the sun's light) and is generated by irradiating the solar cell with light. The stored electrical energy is stored in a capacitor, and can be used as a stable (auxiliary) power source.

  Further, an ON / OFF switch for making the hologram sheet of the present invention emit light or extinguish can be incorporated.

  In the present specification, “part” indicating the formulation is based on mass. The “hologram” includes a hologram and a hologram having a light diffractive function such as a diffraction grating.

(Main applications)
The main use of the hologram sheet of the present invention or a card with a hologram is in the art / craft field and the commercial field where the hologram itself is used for decoration. Sheets or cards with holograms, specifically those that can damage card holders or card companies, etc. when used forged as credit cards, driver's licenses, employee ID cards, members Identification cards such as ID cards, admission tickets for entrance examinations, passports, banknotes, gift certificates, point cards, stock certificates, securities, lottery tickets, horse pass tickets, passbooks, pass tickets, air tickets, various events There are admission tickets, play tickets, prepaid cards for transportation and public telephones.

  Each of these is an information recording body that holds information having economic or social value, and it is desirable to have a function that can identify the authenticity of the recording body for the purpose of preventing damage caused by forgery. .

  In addition to these information recording media, expensive products such as luxury watches, luxury leather products, precious metal products, jewelry, etc., often referred to as luxury brand products, or storage of such expensive products. Boxes and cases can also be forged. In addition, mass-produced products of famous brands, such as audio products, electrical appliances, etc., or tags that are hung on them are also subject to forgery.

  Furthermore, a storage body in which music software, video software, computer software, game software, or the like, which is a copyrighted work, or cases thereof can also be forged. In addition, it is desirable that products such as printer toner, paper, and the like in which supplies to be replaced are limited to genuine materials have a function of identifying their authenticity for the purpose of preventing damage caused by forgery.

(Background technology)
Conventionally, for the purpose of preventing counterfeiting of information recording bodies and various articles described above (collectively referred to as authenticity identification objects), it is said that they have manufacturing difficulties due to the precision of their structures. Often, holograms are applied as authenticity distinguishable. However, since the hologram manufacturing method itself is known and can be precisely processed by that method, when the hologram is merely for visual judgment, there is no difference between a genuine hologram and a forged hologram. It is difficult to distinguish.

  These authentic identification objects, in particular, articles that have been subjected to hologram images in a label form or transfer form, are not only used for authentic identification of visual confirmation of hologram images, but also by using a new authenticity identification method. There is a need to identify the authenticity of.

(Prior art)
In order to meet these requirements, there has been proposed a hologram sheet having a light selective reflection layer that is laminated on a hologram and reflects only one of the left-handed polarized light and the right-handed polarized light among the incident light. (For example, refer to Patent Document 1.)
As this light selective reflection layer, cholesteric liquid crystal is used, and the anti-counterfeiting property is enhanced by a method of confirming using a polarizing plate or the like.

  However, as described in Patent Document 1, since the reflectance of the reflective thin film layer on the hologram forming layer is high, the light that is transmitted without being reflected by the cholesteric liquid crystal layer (complementary light of selective reflected light) Reflecting on the reflective thin film layer and returning to the cholesteric liquid crystal layer again (hereinafter referred to as return light), this return light becomes a noise component when observing the cholesteric liquid crystal and is added to and mixed with the selectively reflected light. However, the color tone was not the original color of the liquid crystal, and it was even difficult to see and identify.

  In addition, the cholesteric liquid crystal material itself is expensive, and in order to bring out the liquid crystal performance, it is indispensable to form an alignment film in contact with the liquid crystal layer. Furthermore, due to the light scattering property of the cholesteric liquid crystal, the hologram There have been problems such as blurring and distortion of the image when light for reproducing the image passes through the liquid crystal layer.

  For this reason, it has been devised to suppress the light scattering property of the cholesteric liquid crystal layer or to make the cholesteric liquid crystal layer itself thin. However, in order to suppress the light scattering property of the cholesteric liquid crystal layer, the refractive index difference is reduced or the cholesteric liquid crystal layer is reduced. When the liquid crystal layer is made thin, the function as the light selective reflection layer described above is deteriorated, and it has a drawback that it is difficult to obtain optimum conditions for ensuring the clarity and anti-counterfeit performance of the hologram image. .

JP 2007-90538 A

  Accordingly, the present invention has been made to solve such problems. The purpose is to provide a sheet-like thin film light source layer, a transparent resin layer having a hologram relief corresponding to the hologram image, and a transparent layer in this order so as to cover the hologram relief on one surface of the sheet substrate, When a sheet-like thin film light source layer emits light at a predetermined wavelength, a hologram sheet capable of visually recognizing a hologram that emits light at the predetermined wavelength and a card with a hologram in which the hologram sheet is embedded in a card substrate are provided.

  Then, the light itself emitted from the sheet-like thin film light source layer becomes “directional light”, passes through the “hologram relief”, and a hologram sheet on which a reproduced relief hologram reproduction image to be reproduced becomes clearer. It is to provide a novel decorative property and an anti-counterfeit property applying this.

  In particular, an IC card substrate with a built-in battery is used as a card substrate, and the IC driving battery also serves as a power source for light emission of the hologram sheet, thereby further improving its design and anti-counterfeiting properties. Card with hologram.

To solve the above problem,
The first aspect of the hologram sheet of the present invention is:
On one surface of the sheet substrate, a sheet-like thin film light source layer, a transparent resin layer having a hologram relief corresponding to the hologram image, and a transparent layer provided so as to cover the hologram relief are provided in this order. A hologram sheet, the magnitude of the reflection diffraction efficiency with respect to the incident light from the transparent layer side toward the hologram relief at a predetermined angle with respect to the normal to the surface of the hologram sheet The transmission diffraction efficiency is smaller than the incident light from the transparent resin layer side toward the hologram relief.

According to the hologram sheet of the first aspect,
On one surface of the sheet substrate, a sheet-like thin film light source layer, a transparent resin layer having a hologram relief corresponding to the hologram image, and a transparent layer provided so as to cover the hologram relief are provided in this order. A hologram sheet, the magnitude of the reflection diffraction efficiency with respect to the incident light from the transparent layer side toward the hologram relief at a predetermined angle with respect to the normal to the surface of the hologram sheet The hologram sheet is characterized in that it is smaller than the size of the transmission diffraction efficiency with respect to the incident light directed to the hologram relief from the transparent resin layer side, and its designability and forgery prevention It is possible to provide a hologram sheet having excellent properties.

The second aspect of the hologram sheet of the present invention is:
In the reflection diffraction efficiency of the hologram sheet of the first aspect, the reflection diffraction efficiency with respect to the incident light whose predetermined angle is 0 degree is 0.01 to 1.0%. To do.

According to the hologram sheet of the second aspect,
In the reflection diffraction efficiency of the hologram sheet of the first aspect, the reflection diffraction efficiency with respect to the incident light whose predetermined angle is 0 degree is 0.01 to 1.0%. The hologram sheet can be provided, and a hologram sheet that can reproduce a clearer hologram reproduction image can be provided.

The third aspect of the hologram sheet of the present invention is:
In the hologram sheet according to any one of the first aspect and the second aspect,
The sheet-like thin film light source layer has a thickness of 0.01 μm to 2.0 μm.

According to the hologram sheet of the third aspect,
In the hologram sheet according to any one of the first aspect and the second aspect,
The sheet-like thin film light source layer has a thickness of 0.01 μm to 2.0 μm, and can provide a hologram sheet that can reproduce a clear hologram reproduction image. Can be provided.

The card with hologram of the fourth aspect of the present invention is
The hologram sheet according to any one of the first to third aspects is embedded in the card substrate, and the exposed surface of the hologram sheet is flush with the surface of the card substrate, or the surface of the card substrate. It is characterized by being in a recessed position.

According to the card with a hologram of the fourth aspect,
The hologram sheet according to any one of the first to third aspects is embedded in the card substrate, and the exposed surface of the hologram sheet is flush with the surface of the card substrate, or the surface of the card substrate. Therefore, it is possible to provide a card with a hologram that is in a recessed position, and to provide a card with a hologram that is excellent in design and forgery prevention.

The card with hologram of the fifth aspect of the present invention is
In the card with hologram according to the fourth aspect, the card base is a battery built-in type IC card base containing an IC driving battery, and the IC driving battery is used for light emission of the hologram sheet. It also serves as a power source.

According to the card with a hologram of the fifth aspect,
In the card with hologram of the fourth aspect, the card base is a battery-integrated IC card base containing an IC driving battery, and the IC driving battery is for light emission of the hologram sheet. It is possible to provide a hologram-equipped card that also serves as a power source, and to provide a hologram-equipped card that is remarkably excellent in design and forgery prevention.

  The hologram sheet of the present invention is provided with a sheet-like thin film light source layer on one surface of a “sheet substrate” (hereinafter referred to as a “transparent substrate”). A planar shape (meaning that the upper and lower surfaces of the “layer” form “two parallel planes”) ”, and a hologram image is reproduced on the“ planar shape ”sheet-like thin film light source layer Interference fringes and diffraction grating groups are formed as a hologram relief on a surface of the transparent resin layer as a substantially flat surface (this is a “transparent resin layer having a hologram relief corresponding to a hologram image”), and this hologram relief. A “transparent layer” is provided on the top of the hologram relief so as to fill the hologram relief.

  The “transparent layer” fills the hologram relief of the transparent resin layer, and the surface of the “transparent layer” opposite to the surface that is in contact with the transparent resin layer has a “planar shape of one plane”. (The "layer" that combines the "transparent resin layer" and the "transparent layer" means "planar shape".)

And, the relationship between the “transparent resin layer”, the “hologram relief” provided thereon, and the “transparent layer” provided so as to fill the hologram relief are as follows:
“The angle of reflection diffraction efficiency with respect to the incident light traveling from the transparent layer side to the hologram relief at a predetermined angle with respect to the normal to the surface of the hologram sheet is transparent at the predetermined angle. In order to satisfy the relationship of “smaller than the size of transmission diffraction efficiency” with respect to the incident light traveling from the resin layer side toward the hologram relief, respectively, “the refractive index of the transparent resin layer”, “the depth of the hologram relief”, and The “refractive index of the transparent layer” is set as described above.

  Further, the sheet-like thin film light source layer may be provided so as to correspond to the entire surface of the hologram relief forming region, or may be provided so as to correspond only to a part of the hologram relief forming region. Here, the sheet-like thin film light source layer is provided so as to correspond to only a part of the hologram relief forming region, for example, in a “desired pattern shape” expressing characters and figures, or from 30 μm to 300 μm. This means that it is provided in a “checkered pattern (in the case of an electroluminescence type, all grids of the checkered pattern are considered to be conductive)”.

  Therefore, when the sheet-like thin film light source layer emits light, only the partially provided region emits light, and only a part of the hologram relief forming region corresponding to the emitted region emits the emitted light. Thus, a relief hologram reproduction image based on only a part of the hologram relief forming area is reproduced.

  Furthermore, “hologram relief (in the above checkerboard pattern, corresponding to each checkered portion of the checkered pattern) corresponding to the sheet-like thin film light source layer provided in the desired pattern shape”. Corresponding to the hologram image H1) ”and a position other than the desired pattern-like region (in the above-mentioned checkerboard pattern, the portion corresponding to the“ adjacent ”blank portion of each checkered portion. ) Is provided with a “hologram relief (corresponding to the hologram image H2)” different from the “hologram relief corresponding to the hologram image H1”, and the relief hologram reproduction when the sheet-like thin film light source layer is not caused to emit light is provided. New relativity when light is emitted to the image (a state where both “hologram image H1” and “hologram image H2” are reproduced). Off to ensure that the hologram reconstructed image floats even (state only "hologram image H1" has increased brightness.), Make it possible to enhance the design property and anti-counterfeiting properties, are preferred.

  The hologram relief shows a phase difference as a phase hologram in a “relief shape”, and a “transparent layer” is provided so as to cover this “relief shape having a phase difference”.

  This “providing so as to cover” means “providing the“ relief shape ”so as to“ fill ””, and therefore the thickness of this “transparent layer” is at least the depth of the unevenness of the hologram relief. It has a sufficient thickness to fill the gap.

  And, by providing a “difference” between the refractive index of the “transparent resin layer” and the refractive index of the “transparent layer”, it becomes an “interface” between the “transparent resin layer” and the “transparent layer”. Ensure the “existence” of the “hologram relief surface”. The greater the difference in refractive index, the more clear the reproduced relief hologram reproduced image based on this “hologram relief”. However, for the purpose of preventing counterfeiting, this “hologram relief surface” ”Must be concealed, and it is desirable to make the difference in refractive index as small as possible.

In particular, in the hologram sheet of the present invention, it is possible to receive illumination by light emission of the sheet-like thin film light source layer from its very close back surface. Unlike the “hologram relief”, the “illumination intensity” attenuates in inverse proportion to the square of the distance, and the “illumination intensity” is extremely weak on the “hologram relief” surface. Since the “hologram relief” can be directly illuminated with almost no attenuation of the illumination intensity, it is sufficient that the difference in refractive index is 0.01 to 0.05 (relief hologram reproduction at the time of illumination). Meaning that the sharpness of the image is sufficient.) If the difference in refractive index is 0.01 to 0.1, particularly 0.01 to 0.05, illumination by sunlight or indoors firefly Alone is illuminated by lights, the can hardly visible relief hologram reproduced image based on the hologram relief is suitable will the presence of the hologram possible concealment. (In general, a hologram reproduction image observed as part of the reflected light from the hologram sheet in the observation from the illumination light irradiation side such as the indoor fluorescent lamp is a so-called “reflection hologram reproduction image”. In the observation from the side opposite to the illuminating side, the hologram reproduction image observed as a part of the transmitted light of the hologram sheet becomes a so-called “transmission type hologram reproduction image”. The `` transmission hologram '' in the `` hologram sheet '' of the present invention is light that appears on the observation side after the illumination light passes through the hologram relief from behind the hologram relief, and in such a relationship between illumination and observation, That is, the present invention relates to a “transmission hologram” reproduced by such illumination light and a “transmission hologram reproduction image”.
Further, the “transparent layer” is formed by “flattening” (meaning “optical mirror surface”) one surface of the “transparent layer” so that the surface becomes a general “ “Specular reflection” of illumination light such as “fluorescent lamp” which is “indoor illumination light” (meaning illumination light not intended for the reproduction of relief holograms) and concealing the “relief hologram” behind it (When such “specular reflection light” is observed in the “specular reflection angle direction”, “dazzling light” is observed as if the illumination light is directly viewed. If there are a plurality of such mirror reflection lights, there will be a lot of such specular reflection light).

  Alternatively, in order to further enhance the concealment effect, the outermost surface of the “transparent layer” is not “flattened” but “roughened (average surface roughness Ra, 0.1 to 3.0 μm)”. It is also suitable. The relief hologram reproduction image appears due to the “interference phenomenon” in the “front space area (actually in the transparent layer)” of the “surface” provided with this “rough surface” (relief). "Interference" for forming a hologram reproduction image has already been "completed".) Such a "rough surface", that is, the "scattering phenomenon due to the rough surface" is a relief hologram reproduction image. Does not significantly affect the clarity of the image.

  In addition to the above, the “hologram sheet” of the present invention has a “reflection diffraction efficiency magnitude” of the “hologram relief” for illumination light incident on the “hologram sheet” with a predetermined incident angle. ”Is set to“ smaller ”than the“ transmission diffraction efficiency ”of the“ hologram relief ”, and the“ reflection diffraction efficiency ”of the“ hologram relief ”is set under a predetermined condition. , “0.01 to 1.0%”, which is suppressed to a remarkably small value, promotes the above-described effects.

  In addition, the “hologram card” of the present invention has the “hologram sheet” of the present invention embedded in the “card substrate”, and the exposed surface of the “hologram sheet” faces the surface of the “card substrate”. One or a position recessed from the surface of the “card substrate”.

Examples include: “transparent substrate” having a thickness of 12 μm, “sheet-like thin film light source layer” having a thickness of 5 μm, “transparent resin layer having a hologram relief” having a thickness of 10 μm, and “transparent layer having a thickness of 3 μm. The hologram sheet (laminate) with a total thickness of 30 μm ”(the“ transparent substrate ”side is placed in contact with the surface of the card substrate.“ Transparent resin layer ”and“ transparent layer ” "Interface" is a hologram relief.) Comprising: "Strip" (meaning "small piece" of total thickness 30μm, width 10mm, length 30mm. Width 10mm x length 30mm x height 30μm Is placed at the center of the surface of a “card substrate” made of a soft vinyl chloride sheet having a credit card size and a thickness of 760 μm, and this “card substrate” is placed at room temperature → 150 Degree → normal temperature heating While applying a pressure of 1.0 MPa (megapascals, N / square millimeter) in a flat plate pressure state sandwiched between “a surface mirror-finished stainless steel plate” by an icle (30 minutes to 90 minutes per cycle), The entire thickness of the strip is embedded in the 760 μm soft vinyl chloride sheet. (At this time, for the “sheet-like thin film light source layer”, an anode terminal for applying a voltage to each of the “anode” and the “cathode” (referred to as a lead portion; the same shall apply hereinafter) and a cathode terminal. <Lead portion, the same applies hereinafter> is arranged so as to be exposed on the surface of the card substrate and embedded, so that the "anode" and "cathode" of the "sheet-like thin film light source layer" and the outside In order to connect the anode terminal and the cathode terminal from the electrode or the internal electrode, the “anode” and the “cathode” are respectively provided with lead portions and may be appropriately processed so that they are joined. However, the details thereof are omitted, and an adhesive layer having a thickness of 1 μm may be provided on the back surface of the hologram sheet, that is, the exposed surface of the “transparent substrate”. Only `` transparent substrate '' The "hologram sheet" released may be embedded in the "card substrate" may this time, be added a suitable adhesive layer.)
Here, the surface of the card base after the “embedding” is measured using a stylus type surface roughness meter, and the boundary area of the embedded portion is measured, and the step at the boundary is 1.0 μm or less. It is in a state of “same”.

  In addition, a 6-layer laminate in which the above-described strip is further laminated with 10 μm-thick polyethylene terephthalate having one surface peelable, and embedded in the card substrate in the same manner as above, and then the polyethylene terephthalate Is peeled off, and the outermost surface of the strip can be made “dented” by a depth of 10 μm from the surface of the card substrate.

  That is, using the above-mentioned stylus type surface roughness meter, the step of the recessed portion is measured, and the state where the step is 10 μm is the state “10 μm recessed from the card substrate surface”.

  This “dent” is desirably 1.0 μm to 30 μm in a “card substrate” in the form of a credit card. If the dent is less than 1.0 μm, the effect of the indentation is lost, and if it exceeds 30 μm, the catching of the step will hinder the handling of the hologram-equipped card.

  This dent is 1/10 or less, preferably 1/20 or less of the card substrate thickness. In addition, when the size of the strip is smaller than the size of the dent, a “gap” is generated between the dent and the strip. This “gap width” is set to “toe” or “toe” in consideration of the forgery prevention property. The size of the “metal spatula” is difficult to insert, that is, a width of 5.0 mm or less, preferably 1.0 mm or less.

  Further, in order to embed the strip in the card substrate, a recess having a depth of 33 μm, a width of 11 mm, and a length of 31 mm is provided on the surface of the card substrate in advance. Sometimes a “dent” may be provided, or the card base surface may be cut by cutting or the like to provide a recess.) In addition, the above-described strip may be fixed in the recess. It is preferable from the viewpoint of stability. In this case, since there is no need for high-temperature heating or high-pressure press as described above, the “transparent substrate”, “sheet-like thin film light source layer”, and “transparent resin layer having a hologram relief” in the above-described strip. In addition, deformation or distortion of the “transparent layer” or “hologram relief surface” hardly occurs, and there is no problem such as breakage (meaning disconnection) of the lead portion as the anode terminal or cathode terminal. There is an advantage that it can be surely provided.

  However, from the viewpoint of preventing forgery and alteration, a method of embedding in a “card substrate” by heating and pressurization is desirable.

  Also, the shape of the card substrate can be any shape, that is, a sheet shape, a film shape, a plate shape, a cube shape, a rectangular parallelepiped shape, a card shape, a tag shape (including a label shape), a postcard shape, a slip shape, an envelope shape. A disc shape, an ellipsoid shape, a sphere shape, a rod shape, a combination thereof, a combination thereof, a shape obtained by processing such as deformation, cutting, drilling, adhesion, or the like can be employed.

  The thickness is not particularly limited as long as it can be handled, but is usually 3.0 μm to 3.0 mm. Of course, if it is an envelope shape or a box shape, the dimension of the three-dimensional shape is suitable for each application, and it is not necessary to be within this range.

  As typical examples of these card base materials, card base materials and shapes used as so-called “prepaid cards”, card base materials and shapes used as “plastic cards”, particularly, JIS standards and ISO standards. There is something that is stipulated. In other words, because of its “embedding suitability” and “general versatility” (including processing versatility), the “card base material and shape used as a“ plastic card ”defined in JIS and ISO standards” is the most. desirable.

  These are already widely distributed and popular all over the world, so there is no resistance to handling and holding them, and peripheral devices when carrying or using them, Since related goods and the like are already popular, application to these items is also smooth and suitable.

  The IC card with hologram of the present invention uses a “battery-integrated IC card base material incorporating an IC driving battery”, and in that case, the IC driving battery is the hologram of the present invention. It also serves as a power source for emitting light from the sheet.

  That is, as the “card substrate”, a “contact IC card” incorporating at least a “secure microcomputer” or a “non-contact IC card” incorporating at least a “non-contact IC chip” is used.

  As these “card base materials”, those conforming to ISO / IEC 7816 and JIS X 6300 can be used for contact IC cards, and ISO / IEC 14443 for non-contact IC cards. (Depending on the communication distance, it is classified into “contact type”, “proximity type”, “neighboring type”, or “remote type”, and the proximity type is further changed to “Type A” or “Type B”. And those conforming to JIS X 6321-6323 can be used. These “card base materials” are suitable for the same reason as described above.

  The hologram-equipped IC card according to the present invention uses these “card base materials” and further drives the “secure microcomputer” and the “non-contact IC chip”. It also contains an “IC drive battery” consisting of a secondary battery, and the “IC drive battery” is a “hologram sheet” embedded in the IC card substrate (a “sheet-like type that requires a power source”). In the case of using the “thin film light emitting layer”), it also serves as a power source for light emission.

  Further, the IC card with hologram of the present invention can further include “a“ control unit ”for controlling a secure microcomputer or a non-contact type IC chip” and “a“ display unit ”such as a liquid crystal display”. The “battery” is used as a power source for driving the “control unit” and “display unit”.

  Further, the IC card with hologram of the present invention is constituted by “a solar cell and a capacitor for storing electric energy generated by the solar cell (auxiliary) in addition to these“ built-in ”“ battery ”. "Power supply" can also be included in the "card substrate".

  In addition, an “ON / OFF switching switch” can also be incorporated. In this case, the “switch” can cause the hologram sheet of the present invention to emit light or be extinguished.

  In the following description, “sheet-like thin film EL (electroluminescence) layer” will be described as an example of “sheet-like thin film light source layer used in“ hologram sheet ”of the present invention”.

  The following explanation is another example of “sheet-like thin film light source layer”, “sheet-like thin film fluorescent layer”, “sheet-like thin film LED layer”, “sheet-like thin film disk laser layer”, “sheet-like thin film surface emitting” Needless to say, the same applies to the “laser layer” and the “sheet-like thin film stress light emitting layer” (of course, the principle and structure of “light emission” are different).

  In the first place, “electroluminescence” is a phenomenon in which a fluorescent material or the like emits light by the energy of an electric field, and it is possible to obtain a surface light source, which is roughly classified into organic electroluminescence and inorganic electroluminescence.

  Organic electroluminescence is a light emission phenomenon using an organic substance having a property of emitting light when an electric current is passed, and has a structure in which an organic substance is sandwiched between layers serving as a base.

  By passing a current between the layers, molecules of the organic substance are excited to emit light.

  A typical layer structure is / anode (transparent conductive layer) / hole transport layer / organic material layer / electron transport layer / cathode (conductive reflective layer), and light emitted from the anode side is emitted.

  In other words, an organic electroluminescence device formed of a thin film has an electron that has reached the organic material layer from the cathode (cathode layer) through the electron transport layer and a hole that has reached the organic material layer from the anode through the hole transport layer. Light is emitted by excitons (excitons) generated by recombination.

  That is, when an organic substance molecule or the like is excited by the energy generated at the time of recombination and returns from the excited state to the ground state again, fluorescence (including phosphorescence) emission or the like occurs.

  As shown in the Jablonski diagram shown in FIG. 1, the principle of fluorescence emission is first absorbed by energy absorption from the ground state (S0: singlet state) of the organic substance (including a complex system of a plurality of substances). The molecules of the organic substance excited in one of the vibration states of one (S1), the second (S2), the third excited state (S3),... Or the triplet state (T1, T2) by intersystem crossing.

  The phosphor in the lowest vibration state of S1 returns to the ground state by a non-radiation process or emits fluorescence, and the molecule in the triplet state returns to the ground state by phosphorescence or by phosphorescence.

  Energy that cannot be used well for light even when excited is non-radiatively deactivated (thermally deactivated).

Since the transition between singlets occurs instantaneously, the half-life of fluorescence is as short as 10 ⁻⁴ sec or less. The time required for the transition is said to be excited at 10 ⁻¹⁵ sec and then to emit fluorescence at 10 ⁻⁹ to 10 ⁻⁷ sec.

  On the other hand, the transition from triplet to singlet is a forbidden transition due to the prohibition of spin change, and spontaneous emission is less likely to occur. Therefore, the half-life of phosphorescence is large, and there are some in seconds. Of course, the phosphorescent type has maintained light emission for a longer time.

  Whether or not light is emitted when returning to the ground state, whether the light intensity is strong or weak, and whether the fluorescence lifetime is long or short depends greatly on the molecular structure of the organic substance molecule and the environment in which the molecule is placed. To do.

  The wavelength distribution of emitted light such as molecules of an organic substance is called an emission spectrum, and the emission spectrum is created by plotting the emission intensity relative to the emission wavelength. The wavelength (energy) shown in the emission spectrum is equal to the energy difference from the lowest vibration energy level in the primary excited state to the preferential vibration energy level in the ground state.

  Inorganic electroluminescence is a physical phenomenon that emits light when an electric field is applied to a substance, and its mechanism is that electrons that exist in advance in a solid when a voltage is applied to a phosphor (light emitting layer) of an inorganic compound that is a solid. Alternatively, the electrons injected from the electrode are accelerated by a high electric field, collide with the light emission center and excite it, and the generated electrons and holes recombine to emit light. The organic EL that emits light by recombination of electrons and holes injected by current from the outside is different in terms of excitation.

  That is, an inorganic electroluminescent element formed of a thin film has a double insulation structure, and light emission occurs when an electric field is applied to this structure.

  The configuration of the light emitting layer is divided into “dispersion type” and “thin film type”. In the dispersion type, an insulating layer in which a ferroelectric powder is dispersed in an organic binder and a phosphor powder are dispersed in the organic binder. The light emitting layer is laminated and sandwiched between the transparent electrode and the back electrode. The typical structure is / transparent electrode / insulating layer / light emitting layer / back electrode / or / transparent electrode / insulating layer / Light emitting layer / insulating layer / back electrode /.

  The thin film type is a structure in which a light emitting layer made of a thin film phosphor and an insulating layer are laminated on a substrate with a thin film electrode, and an electrode is attached. The layer is formed using a thin film forming method such as sputtering or vacuum evaporation. To do. Its typical configuration is the same as that of the distributed type.

  In either case, emitted light is emitted from the transparent electrode side.

  The present invention applies a conventional hologram reproduction method, that is, illuminating light from an illumination light source arranged at a distance of several tens of centimeters to several meters above the hologram (the larger the separation distance, the larger the distance). The illumination light approaches the so-called “parallel light that is ideal illumination light.”) Unlike the one that reproduces the hologram of the wavelength of the illumination light by the interference phenomenon of the reflected light on the hologram relief surface. By applying a voltage, the electroluminescence element or the like emits light, and the emitted light becomes a “directional wave of light”, and the “transparent resin layer” and the “transparent layer” “ As a result of illuminating and passing through the “hologram relief surface” which is an “interface”, an interference phenomenon occurs, and a hologram at the wavelength of the emitted light is reproduced. Therefore, the diffraction angle also depends on the wavelength of the emitted light.

  For example, in a transparent space where almost nothing can be seen (such as a laser reproduction hologram that requires single wavelength light for its reproduction cannot be viewed with a white light source such as a fluorescent lamp. Also suitable for white light reproduction. Even in the case of a rainbow hologram, when the “interface reflection intensity” of the hologram relief surface is small, it is difficult to visually recognize.In the present invention, it is needless to say that this “interface reflection intensity” is set small. ) For the first time by applying a voltage or the like, for example, a hologram of “green (when the emitted wavelength corresponds to“ green ”)” can be visually recognized, so that the observer's eyes will be able to reproduce normal holograms. The entire hologram sheet emits light weakly at the same time as the “green illumination light source” used in the Come, the hologram reproduced image, it appears to be floating in the air, not only surprising resistance, but also excellent design.

  Since the present invention reproduces (images) a hologram reproduction image based on such a principle, it is recorded on the “transparent resin layer having a hologram relief corresponding to the hologram image” in the hologram sheet of the present invention. The hologram image to be made is “a hologram image reproduced (imaged) by transmission reference light”, that is, “a hologram relief corresponding to the hologram image reproduces a transmission hologram reproduction image” ( Specifically, the depth of the hologram relief is set close to the “optimum depth of the transmission type.” This “optimum depth” is the “refractive index of the transparent resin layer” and “refractive index of the transparent layer. ”And“ predetermined wavelength ”, specifically, it is much deeper than“ optimum depth of reflection type ”, and from“ optimum depth of reflection type ” The "depth" as well outside. This also, the reflection type hologram reproduction image by the hologram relief is designed to hardly appeared.).

  That is, even if the “hologram relief surface present in the hologram sheet of the present invention, that is, the“ interface ”between the“ transparent resin layer ”and the“ transparent layer ”receives illumination light from natural light or a fluorescent lamp, The “reflected light (reflected light including the phase of the hologram relief generated by the illumination light)” generated at the “interface” does not appear as a clear hologram reproduction image.

  This is a clear hologram reproduction image <transmission type hologram reproduction image> when it receives "light transmitting through this hologram relief (meaning that the illumination light is observed through the hologram sheet)" as illumination light of this hologram relief However, even if “light reflected from this hologram relief (observed from the illumination light side and reflected by the hologram sheet, the“ reflected light ”is observed”) is received as illumination light. This means that no hologram reproduction image <reflection hologram reproduction image> appears.

  Further, in which part a power supply terminal (an anode terminal and a cathode terminal that can reproduce a hologram. A plurality of power supply terminals can be provided, or a dummy terminal can be provided to improve forgery prevention). It can be made difficult to discriminate and can be used for authenticity determination by providing only those who can know the structure to be able to reproduce the hologram. Or, only those who know the wavelength of the emitted light can predict the color tone of the hologram reproduction image, and can look through the separately prepared “bandpass filter” adjusted to the reproduction wavelength and pass through the “bandpass filter”. Only the hologram (meaning that the hologram reproduction image has a wavelength that can pass through this filter) can be determined to be authentic.

  In addition, the angle (diffractive angle; meaning the direction toward this filter) that passes through this “bandpass filter” also depends on the emission wavelength, and only those who can know the “value” can obtain the predetermined value. Judgment can be made by angle.

  Furthermore, by including a plurality of electroluminescent elements formed of a thin film (meaning including a plurality of elements having different emission wavelengths), this reproduced image appears in different colors at a plurality of angles. Further, it can be made more excellent in terms of authenticity determination.

  Of course, the electroluminescence device has a light emission spectrum that varies greatly depending on the voltage applied (meaning that it has an applied voltage dependency), and also has an emission characteristic unique to each device. Even if a counterfeiter who does not know the voltage (voltage strength, frequency, etc.) tries to produce a hologram sheet that is exactly the same as the genuine product, it can be said that it is physically impossible.

  Specifically, the structure of the organic electroluminescence element has a single layer structure in which an organic thin film serving as a light emitting layer is sandwiched between a cathode and an anode, or a structure having a hole transport layer between the anode and the light emitting layer. , Having an electron transport layer between the cathode and the light-emitting layer, having a light-emitting layer portion having a three-layer structure of an electron transport layer, a light-emitting layer, and a hole transport layer, and having a multilayered structure as necessary A thing etc. can be used.

  The layers sandwiched between these anodes and cathodes are all composed of an organic thin film (solid), and the thickness of each layer is 10 to 100 nm.

  If the thickness is less than 10 nm, the function of each layer cannot be sufficiently exerted, and if the thickness is 100 nm, it is sufficient to achieve the function of each layer. The following.

  The light-emitting layer is a two-component system of a main material (host material) and an impurity material (dopant material: added for improving functions such as emission intensity improvement). 30% addition is uniformly dispersed in the main material.

  If it is less than 0.1%, the luminescent property is insufficient, and if it exceeds 30%, the impurity property (existence as a singular point) is weakened and the luminescent property starts to decrease.

  For the anode, a transparent conductive thin film called ITO thin film (indium / tin oxide thin film), tin-doped tin oxide, antimony-doped tin oxide, zinc-doped tin oxide, fluorine-doped oxidation, which is both transparent and conductive Examples thereof include metal oxides such as tin and zinc oxide, multilayer structures in which a thin film of silver is sandwiched between high refractive index layers, and conjugated polymers such as polyaniline and polypyrrole.

  As a forming method, a thin film forming method, that is, a sputtering method, a vacuum evaporation method, or the like is used to form a film with a thickness of 50 to 500 nm. From the above consideration, the surface resistance value of the transparent conductive thin film is set to 0.001Ω / □ to 0.1Ω / □.

  Although a printing method or the like can be used as a forming method, the film thickness of this layer needs to be thin and uniform with high accuracy so as not to cause unnecessary unevenness in the relief hologram reproduced image. (Furthermore, in order to make the surface an “optical mirror surface”), the above-described thin film forming method is desirable.

  Considering the above, the film thickness is 50 nm to 500 nm.

On the cathode, a metal thin film such as aluminum, gold, silver, platinum, copper, iron, silver / magnesium alloy, graphite, or the like is formed with a thickness of 50 to 500 nm.
If the thickness is less than 50 nm, the conductivity is insufficient, and if it exceeds 500 nm, unnecessary unevenness tends to occur on the surface (interface).

  Furthermore, the transparent substrate is deteriorated by the heating load during the formation of the thin film, and as a result, unnecessary unevenness is easily generated in the relief hologram reproduction image.

  Since the metal thin film has high reflectivity, it has the effect of improving the efficiency of electroluminescence emission. Needless to say, the metal thin film may be provided with a dot-like hole to add transparency, or a transparent conductive thin film may be formed in the same manner as the anode instead of the metal thin film.

  For the organic thin film which is a light emitting layer, a low molecular weight type and a high molecular weight type can be used.

For low molecular weight systems, TPAC (1,1-bis [4- [N, N-di (p-tolyl) amino] phenyl] cyclohexane), TPD (N, N′-diphenyl-N) are used as hole transport materials. N′-di (m-tolyl) benzidine), CuPc (phthalocyanine copper), α-NPD (4,4′-bis [phenyl (1-naphthyl) amino] -1,1 ′ biphenyl, etc.
As an electron transport material, BND (2,5-bis (1-naphthyl) -1,3,4-oxadiazole), PBD (2- (tertiary-butylphenyl) -5- (4-biphenyl) -1 , 3,4-oxadiazole), Butyl-PBD (2-biphenyl-5- (para-tert-butylphenyl) -1,3,4-oxadiazole), TAZ (1-phenyl-2-biphenyl- 5-para-tert-butylphenyl-1,3,4-triazole), Alq ₃ (tris (8-hydroxyquinolinato) aluminum), Beq ₂ (bis (8-hydroxy-quinolino) beryllium), Zn (BOZ) 2 (zinc-bis-benzoxazole), Zn (BTZ) 2 (zinc-bis-benzothiazole), Eu (DBM) 3 (Phen) (tris (1,3-di Nenyl-1,3-propanediono) (monophenanthroline) europium (III), etc. As a light emitting layer material, ZnPBO (bis [2- (2-benzoxazolyl) phenolato] zinc), etc. As a doping dye material, Coumarin 6 (3- (2-Benzothiazolyl) -7- (diethylamino) coumarin, QN- (N, N′-dimethylquinacridone), Nile red, beryllenlabrene, TBP (1,1,4,4-tetraphenyl-1,3-butadiene) quinacridone Etc., 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran, 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) ) -1,2,4-triazole, 4,4′-bis (9-carbazolyl) biphenyl, etc. Can be used.

  These low molecular weight materials can be provided by a thin film forming method such as a vacuum deposition method or a CVD method (chemical vapor deposition method).

In the polymer system, as the light emitting layer material, PPV (polyparaphenylene vinylene) system, PAT (polythiophene) system, PF (polyfluorene) system, PPP system (polyparaphenylene), etc.
PEDOT (poly-3,4-ethylenedioxythiophene) + PSS (polystyrene sulfonic acid: dopant) copolymer, PEDOT + PVS (polyvinyl sulfonic acid) copolymer, polyaniline + PSS copolymer, polypyrrole as hole layer materials + PSS copolymer or the like can be used.

  These polymer materials can be provided by various coating methods and printing methods. The applied DC voltage is 1 to 10V.

  The structure of the inorganic electroluminescence element is a basic structure in which a transparent electrode, an insulating layer, a light emitting layer, and a back electrode are laminated, and light emission comes out of a phosphor film that is a light emitting layer. In the case of a thin film type, a phosphor is a mixture of a dielectric base material with a small amount of an additive impurity that becomes a luminescent center, and when it receives energy, it moves to the outer shell orbit of the luminescent center substance or higher order. When excited (excited) electrons of the emission center substance return to the original order (transition), light emission occurs.

  A structure in which a phosphor film as a light emitting layer is sandwiched between dielectrics as insulating layers and electrodes are arranged at both ends thereof can be considered as a circuit in which three capacitors are connected in series. When applied, polarization occurs in the dielectric and the phosphor, the applied voltage is increased, and when the electric field applied to the phosphor film becomes 100 MV / m or more, the energy of collision of electrons etc. whose emission center is accelerated by the electric field. To become excited.

As the light-emitting layer, ZnS or SrS or other group II sulfide is used as the base material, Mn or rare earth is added to the light emission center, and BaAL ₂ S ₄ (barium / aluminum composite sulfide) is used as the base material. A material in which Eu is added to the material is used.

  The light emitting layer is selected from the group consisting of at least one element selected from the group consisting of Group 2 elements and Group 16 elements of the Periodic Table and / or Group 13 elements and Group 15 elements of the Periodic Table. A semiconductor containing at least one kind of element can be preferably used.

The carrier density is preferably 10 ¹⁷ / cm ³ or less.

  Specific examples of the material forming the light emitting layer include CdS, CdSe, CdTe, ZnSe, ZnTe, CaS, MgS, GaP, GaAs, GaN, InP, InAs, and mixed crystals thereof. CaS or the like can be preferably used.

_{Furthermore, BaAl 2 S 4, CaGa 2} S 4, Ga 2 O 3, Zn 2 SiO 4, Zn 2 GaO 4, ZnGa 2 O 4, ZnGeO 3, ZnGeO 4, ZnAl 2 O 4, CaGa 2 O 4, CaGeO 3 , Ca ₂ Ge ₂ O ₇ , CaO, Ga ₂ O ₃ , GeO ₂ , SrAl ₂ O ₄ , SrGa ₂ O ₄ , SrP ₂ O ₇ , MgGa ₂ O ₄ , Mg ₂ GeO ₄ , MgGeO ₃ , BaAl ₂ O ₄ , Ga ₂ Ge ₂ O ₇ , BeGa ₂ O ₄ , Y ₂ SiO ₅ , Y ₂ GeO ₅ , Y ₂ Ge ₂ O ₇ , Y ₄ GeO ₈ , Y ₂ O ₃ , Y ₂ O ₂ S, SnO ₂ and the like It is possible to use a mixed crystal of

  The carrier density and the like can be obtained by a generally used Hall effect measurement method or the like.

As the dielectric film that is an insulating layer, a metal oxide or a nitride is used. Perovskite-based oxides such as BaTiO ₃ have a high dielectric constant and are preferable.

  As elements that can be included in the oxide, Group 2, Group 9, Group 9, Group 12 (former 2B (former IIb group)), Group 13 (former 3B (former III)) of the periodic table, Group 14 (former group 4B (former group IV)), group 15 and group 16 elements are preferred, and at least one element selected from the group consisting of group 12, group 13 and group 14 elements is used. More preferably. Specifically, Ga, In, Sn, Zn, Al, Sc, Y, La, Si, Ge, Mg, Ca, Sr, Rh, Ir and the like can be mentioned, and more preferably Ga, In, Sn, Zn, Si, Ge, etc. In addition to these elements, the transparent semiconductor can preferably contain chalcogenides such as S, Se, and Te, Cu, Ag, and the like.

  The layer thickness of the insulating layer and the light emitting layer is 0.1 μm to 2 μm. Of course, by making the thickness more than 2 μm and about 10 μm, the light emission performance can be further improved, but in order not to cause unnecessary unevenness of the surface (interface) and unnecessary unevenness in the relief hologram reproduction image. Is 2 μm.

  The transparent electrode and the back electrode are preferably made of ITO or a metal thin film, as in the case of the organic electroluminescence element.

  The phosphor films of different emission colors can be arranged in parallel to make a multicolor, but a color conversion material (coumarin system: coumarin 6, rhodamine system: rhodamine) is formed on a single color phosphor film with high luminance. 6G, a mixture of fluorescent dyes such as rhodamine B, and a mixture of two or more kinds of fluorescent dyes having a benzo-α-bilon skeleton absorb light with a wavelength of 350 nm to 600 nm and emit light in the visible region with a wavelength of 600 nm or more. It is also preferable to make multiple colors by superimposing light having a light emission.

  As the applied voltage, an AC power source of 100 V · 50 to 1000 Hz or the like can be used.

  Next, the principle of holography will be described.

If the object is illuminated with coherent light and the light diffracted from the object illuminates the recording medium (photoresist, etc.), the object wave diffracts from the object and reaches the recording surface.
F (x, y) = A (x, y) EXP [φ (x, y)]
It is expressed. here,
A (x, y) is the amplitude distribution of the object wave,
φ (x, y) is a phase distribution.

At this time, the intensity distribution of the light wave reaching the recording medium is recorded on the recording medium. Its intensity distribution is
I (x, y) = | F (x, y) | ² = A ² (x, y) (1)
Thus, the phase distribution is not recorded.

Here, when an object wave and a coherent light wave (referred to as a reference wave) are superimposed, the intensity distribution of the recorded light wave is
I (x, y) = | F (x, y) + R (x, y) | ²
= | F (x, y) | ² + | R (x, y) | ²
+ F (x, y) R ^* (x, y) + F ^* (x, y) R (x, y) (2)
It becomes. (* Represents a complex conjugate term.)
However, if the reference light is a plane wave incident on the recording surface at an angle θ,
R (x, y) = r (x, y) EXP (2πiαx) (3)
Write,
α = SIN (θ) / λ (4)
It is. In the first and second terms of (2), the phase information is missing for both the intensity of the object wave and the intensity of the reference wave. The third term and the fourth term are interference terms. F (x, y) R * (x, y) =
A (x, y) r (x, y) EXP [i [φ (x, y) -2παx]] (5)
F * (x, y) R (x, y) =
A (x, y) r (x, y) EXP [-i [[phi] (x, y) -2 [pi] [alpha] x]] (6)
The phase term φ (x, y) of the object remains.

  (5) and (6) are complex conjugates of each other, and the third term in (4.2) includes the complex amplitude distribution of the object.

Substituting (5) and (6) into (2),
I (x, y) = | F (x, y) | ² + | R (x, y) | ²
+ 2A (x, y) r (x, y) COS [2παx−φ (x, y)] (7)
It becomes. It can be seen that the object wave and the reference wave interfere to form an interference fringe.

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

  Therefore, the first term of (9) is a light beam penetrating the hologram in the same direction as the illumination light or a specularly reflected light beam, and the second term is a light wave having an amplitude proportional to the object light from (10). From (11), it can be seen that the third term is a light wave having a phase distribution conjugate with the object wave and propagating in the direction of 2θ.

  In this way, the complex amplitude distribution can be recorded and reproduced using the holographic technique.

  In the case of the present invention, the amplitude transmittance or reflectance of the hologram is proportional to the recorded intensity distribution and is expressed by the equation (8), but the reference wave used when recording on this hologram. The “light” from the “sheet-like thin film light source layer” plays the “role” of the “reference wave” (not the same as the reference wave, "Position" means the same.)

  Then, the “light” multiplied by T (x, y) in (8) becomes a hologram reproduction image. That is, R (x, y) in (9) is replaced with this “light”, and (10) and (11) appear accordingly.

  Therefore, regardless of the conventional principle of hologram reproduction in which the phase term recorded in the hologram is given to the “reference light”, the phase term already recorded in the hologram is given to the “light”.

  The conventional hologram reproduction principle will be described in a simplified manner with respect to the transmission type. When the parallel light as the reference light is applied to the hologram, the parallel light is shielded at the shielding portion, and the parallel light is transmitted only from the transmission portion. 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 “sheet-like thin film light source layer” provided in the very vicinity (several μm to several tens of μm) of the hologram relief is, to say, “ The light emitted from the “planar light-emitting surface” illuminates and passes through the hologram relief that forms the “interface” between the “transparent resin layer” and “transparent layer” in the very vicinity of the light, so that the transmitted light is transmitted through The hologram is reproduced by the phenomenon of interference between the passing lights while maintaining the phase term.

  The interference effect between radiated light (or passing light) that does not have complete temporal and spatial coherence does not cause sufficient interference like laser light, but at least low-coherent light from a distance apart The hologram reproduction is performed at the same level as when the hologram is illuminated by the above.

  Since the reproduction is based on the principle as described above, the reference light at the time of hologram photographing is preferably parallel light (because complicated reference light cannot be reproduced), or “hologram represented by a diffraction grating” (diffraction The grating is preferably 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 (CGH) is precise and suitable.

  Furthermore, for the above reason, in order to make the hologram reproduction image clearer, it is preferable to add (add) characteristics regarding temporal or spatial coherence to the emitted light. The thickness of the light emitting part (distance in the radial direction) is made thin, the “variation” in the thickness direction of the light emitting point is made small, the light emitting layer and other layers are uniform (the layer thickness is uniform, the uniform) It is desirable to reduce the “dispersion” of the emission spectrum and the “width” of the emission spectrum by eliminating dispersion in the layer such as dispersion and uniform composition.

  In addition, “main wavelength (wavelength of reference light)” of light used when optically recording a hologram, and “main wavelength (assumed as illumination light) of diffracted light assumed when forming a diffraction grating, etc. And the emission wavelength from the electroluminescence element are the same or substantially the same (the difference is several nm to 10 nm), whereby a clearer hologram reproduction image can be obtained.

  Of course, in order to improve the anti-counterfeiting property, it is also preferable that the wavelength of light emission is different from the wavelength at the time of hologram recording. In that case, it is necessary to theoretically predict and confirm beforehand the deformation of the hologram reproduction image and the change in the diffraction angle due to the different reproduction wavelengths.

  Furthermore, partial variations in the electroluminescent element formation region, that is, variations in emission wavelength and emission intensity depending on the formation location deteriorate the quality of the hologram reproduction image, so the uniformity of the light emitting layer is important.

  At least the partial variation of the peak value of the emission wavelength (difference between a certain 1 mm diameter spot region and the adjacent spot region of 1 mm diameter) and the half value width variation are within 30 nm, and the emission intensity variation is 10 % Is preferable. When the peak value of the emission wavelength and the variation of the half-value width exceed 30 nm, the reproduction position of the hologram reproduction image varies, and the hologram reproduction image is blurred and unclear. Further, if the variation in emission intensity exceeds 10%, variation in light interference also occurs, resulting in unclear reproduction.

  In addition, when the electroluminescent element is provided as a large number of fine spots (for example, halftone dots) discretely (such as only the light emitting layer is halftone dots, the entire element may be provided discretely. In this case, only a single layer or a plurality of layers may be provided in a discrete manner.) Although the amount of light emission is reduced and the overall brightness is reduced, the light emitted from the areas adjacent to the individual spots is reduced. Therefore, the sharpness of the hologram reproduction image is increased, which is preferable.

  However, when the size of the spot and the thickness of the light emitting layer, etc. are discretely formed on the hologram surface regardless of the hologram relief, the size distribution and the thickness distribution result. In some cases, the fluorescence emission intensity distribution may cause unnecessary interference with the light for reproducing the hologram, or may disturb the desired interference and blur the hologram reproduction image.

  In order to eliminate this factor, even when the light emitting layer is formed continuously or discretely, the light emitting layer is formed with a uniform thickness and a uniform distribution. It is necessary to make the hologram reproduction image clear from any region of the EL layer so as to emit light of the same intensity.

  In the hologram sheet of the present invention, the hologram reproduction image cannot be recognized very much under indoor illumination light or natural light illumination, and only when a voltage is applied (only when the “sheet-like thin film light source layer” emits light), suddenly. A hologram reproduction image appears, and the hologram reproduction image is observed as if it is floating in a place where there is no illumination light.

  However, since the metal layer of the cathode has high reflectivity (meaning that it is considered “as an example” only), the reflected light like a mirror can be visually recognized by the reflection of this layer. Become. Therefore, making the cathode itself a transparent layer, making it impossible to recognize the presence of holograms under indoor illumination light or natural light illumination also contributes to the improvement of anti-counterfeiting and the design in the sense of unexpectedness. To do.

  Although the hologram reproduction image of the hologram sheet of the present invention includes the phase of a spatial hologram, the temporal and spatial coherency between the emitted lights is small. The intensity of light is weaker (meaning that the image is weaker) than the reconstructed image of the relief hologram reconstructed with “light”, and it is more unclear (same as on the left).

  Of course, if only observing the so-called “beam-shaped” diffracted light (receiving light with an appropriate light-receiving element, etc.), it is easy to check the color tone and the diffraction direction, and it is still possible to determine the authenticity as it is. However, in order to enable the observer to recognize the weak and unclear hologram reproduction image and accurately determine its presence, the luminous performance of the illuminant is improved and the diffraction angle is increased to increase the wavelength. -Strengthen the diffraction angle dependency, increase the difference between the angle of the 0th-order diffracted light and the diffraction angle of light emission, and further reduce the thickness of the light-emitting layer to suppress variations in the thickness direction of the light-emitting layer and make it uniform. Is also suitable.

Furthermore, in order to express temporal coherence more strongly, it is also preferable that the voltage is applied in a pulsed manner and the time interval between the pulses is set at 10 ⁻⁷ sec or more, which is the emission time of fluorescence or the like. It is. As a result, one fluorescent light emitting surface generated by one applied pulse does not cause a disturbance phenomenon with the fluorescent light emitting surface generated by the next applied pulse, and one fluorescent light emitting surface expressed by one pulse. Due to the holographic interference phenomenon caused by the above, a clear hologram reproduction image can be observed. Of course, even if a voltage application method (level that can be manually applied) that is simply turned on and off in units of seconds is used, the observer seems to emit light continuously. Even if it is a simple means, when it confirms visually, the above-mentioned effect can fully be acquired.

  In the hologram sheet of the present invention, by increasing the distance from the surface of the “sheet-like thin film light emitting layer” to the hologram relief surface of the hologram forming layer as much as possible, from one light emitting point in the “sheet thin film light emitting layer” The emitted “wave of light with directivity” can illuminate a relatively large area of the hologram relief (meaning that the same wavefront illuminates many irregularities), which makes it clearer A hologram reproduction image can be obtained.

  From the above, it is preferable that the thickness of the sheet-like thin film EL layer, that is, the thickness of the entire element is thin, and is the same with respect to the unevenness depth and pitch size of the hologram relief. The level is desirably 0.01 μm to 2.0 μm.

  If the thickness is 0.01 μm, that is, less than 10 nm, the performance as an element is insufficient, and if it exceeds 2.0 μm, it becomes difficult to obtain a clear hologram reproduction image.

  The “transparent resin layer (hologram forming layer) having a hologram relief corresponding to the hologram image” and the “transparent layer” used in the hologram sheet of the present invention can be made of a transparent resin material, and various thermoplastic resins can be used. A thermosetting resin or an ionizing radiation curable resin can be used.

  However, although the refractive index difference between the two layers is set to satisfy the above-mentioned conditions, for example, 0.01 to 0.5, particularly 0.01 to 0.1, further 0.01 (In addition, “refractive index of the transparent resin layer”> “refractive index of the transparent layer” is also suitable to make the refracted light more widespread as “incident angle <refractive angle”. And a “transparent layer” covering the hologram relief of the “hologram forming layer”, a gravure coating method, a roll coating method, a curtain coating method, a stainless screen printing method, an intaglio printing method, an ink jet method, and a transfer method. When it is formed, etc., unnecessary deformation, scratches and unevenness are not generated on the hologram relief surface of the “hologram forming layer”, that is, the “interface” between the “hologram forming layer” and the “transparent layer”. Sea urchin to consider.

  For this reason, in the “transparent layer” ink composition used to form the “transparent layer”, the resin material used is hardly compatible with the resin used in the “hologram forming layer” and is used. It is assumed that the solvent system used is difficult to dissolve the resin used for the “hologram forming layer”.

  And when the refractive index difference between the two layers is set to a slight difference such as 0.01 to 0.1, particularly 0.01 to 0.05, the "difference" is stabilized, and In order to make it uniform throughout the sheet, the resin material used for both layers has high refractive index stability, that is, high thermal stability (the refractive index of the resin changes due to expansion and contraction). Therefore, select materials that are difficult to denature with solvents and moisture.

  The thickness of the “transparent layer” is substantially the same, that is, 1 μm to 50 μm, particularly 1 μm to 10 μm, for the same purpose as the hologram forming layer.

According to the hologram sheet of the present invention,
On one surface of the transparent substrate, a sheet-like thin film light source layer, a transparent resin layer having a hologram relief corresponding to the hologram image, and a transparent layer are provided in this order so as to cover the hologram relief. When the layer emits light at a predetermined wavelength, it is possible to provide a hologram sheet in which a hologram that emits light at the predetermined wavelength can be visually recognized, and a hologram-equipped card in which the hologram sheet is embedded in a card substrate.

  Then, the light itself emitted from the sheet-like thin film light source layer becomes “directional light”, passes through the “hologram relief”, and a hologram sheet on which a reproduced relief hologram reproduction image to be reproduced becomes clearer. It is possible to provide a novel decorative property and an anti-counterfeit property to which this is applied.

  In particular, an IC card substrate with a built-in battery is used as a card substrate, and the IC driving battery also serves as a power source for light emission of the hologram sheet, thereby further improving its design and anti-counterfeiting properties. A card with a hologram can be provided.

Is a Jablonsky diagram. These are sectional drawings of hologram sheet A showing one example of the present invention.

(The “sheet-like thin film EL layer 3 (represented by one layer)”, which is a representative example of the “sheet-like thin film light source layer”, is provided in a “flat plate shape” on the “transparent substrate 1”. Is an example.)
Is a process for determining an embodiment of the present invention.

(A diagram showing an observation state. Illumination light 4 is visible light such as room illumination light. “Hologram reproduction image 5” by illumination of illumination light 4 is not visible. A predetermined “voltage is applied from a predetermined electrode”. If it is in state 6, “green transmission hologram reproduction image 7 (reproduction image by light emission)” appears.)
FIG. 2 is a diagram of a card C1 with a hologram in which the hologram sheet A of the present invention is embedded in a card substrate C0 and the exposed surface of the hologram sheet A is flush with the surface of the card substrate C0. Here, the hologram sheet A (the “hologram sheet A” itself is not displayed but the layers constituting the “hologram sheet A” are individually displayed) is placed on the card base C0 at a predetermined position. The surface of the substrate C0 and the outermost surface of the hologram sheet A (exposed surface of the “transparent layer L1”) are embedded so as to be “equal”. These are figures of the card | curd with a hologram C2 which embedded the hologram sheet A of this invention in card | curd base material IC0 (battery built-in type | mold IC card base material). Here, the card substrate IC0 is a contact IC card, and its configuration is illustrated in detail. The hologram sheet A is embedded in the card substrate IC0 and at the same time, emits light from the built-in battery IC2 for driving the secure microcomputer IC1 (IC driving battery, which also serves as a “hologram sheet light source”). (The lead wire is displayed), and the exposed surface of the hologram sheet A is “same” with the surface of the card substrate IC 0 (this “same” state) Is not shown.)

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  In the following description, the “sheet-like thin film EL layer 3 (also referred to as“ electroluminescence layer ”)” will be mainly described as the “sheet-like thin film light source layer”, but the same applies to other “light source layers” as well. It can be done.

(Transparent substrate) The transparent substrate 1 used in the present invention can be reduced in thickness, and can withstand mechanical strength and solvent resistance and heat resistance that can withstand processing when manufacturing the hologram sheet A. Those having the following are preferred. Since it depends on the purpose of use, it is not limited, but a film-like or sheet-like plastic is preferable. (See Figure 2.)
For example, various plastic films such as polyethylene terephthalate (PET), polycarbonate, polyvinyl alcohol, polysulfone, polyethylene, polypropylene, polystyrene, polyarylate, triacetyl cellulose (TAC), diacetyl cellulose, and polyethylene / vinyl alcohol can be exemplified. .

  Among them, those having resistance to excitation light such as ultraviolet rays, for example, those containing ultraviolet absorbers may be used. Those containing an ultraviolet absorber also have the effect of preventing unscheduled hologram reproduction, although faint due to ultraviolet rays contained in natural light or the like.

  The thickness of the transparent substrate 1 is usually 5 to 100 μm, but when considering the “optical specularity” of the surface (meaning “transparent substrate 1” having “optical specularity”). As a result, in order to improve the visibility of the hologram reproduction image, it is desirable that the thickness be 5 to 50 μm, particularly 5 to 25 μm.

(Transparent resin layer having hologram relief: also referred to as hologram forming layer)
On the transparent base material 1 of the hologram sheet A of the present invention, a sheet-like thin film EL layer 3 provided in a thin film and a flat plate shape is provided, and “transparent resin layer 2 having hologram relief (hologram forming layer 2)” is provided thereon. Is provided. (See Figure 2.)
As the transparent resin material for constituting the hologram forming layer 2, various thermoplastic resins, thermosetting resins, or ionizing radiation curable resins can be used.

  As the thermoplastic resin, acrylic ester resin, that is, polymethyl methacrylate (refractive index n = 1.49), polymethyl acrylate (n = 1.47), polybenzyl methacrylate (n = 1.57), polybutyl acrylate (N = 1.44), polyisobutyl acrylate (n = 1.48), etc. Cellulosic resins, ie, cellulose nitrate (n = 1.54), methylcellulose (n = 1.50), cellulose acetate propio Nates (n = 1.47), vinyl resins, ie, polyvinyl acetate (n = 1.47), polyvinyl chloride / vinyl acetate (n = 1.54), acrylamide resins (n = 1.50) ), Polystyrene resin (n = 1.60) or the like, and as the thermosetting resin, unsaturated polyester resin (n = 1. 4), acrylic urethane resin (n = 1.60), epoxy-modified acrylic resin (n = 1.55), melamine resin (n = 1.56), epoxy-modified unsaturated polyester resin (n = 1.64), Alkyd resin (n = 1.54), phenol resin (n = 1.60), silicon resin (n = 1.41-1.60), or fluorinated resin (n = 1.35-1.38) Etc.

  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 2 using the above resin material, it can be directly formed by developing the photosensitive resin material by performing interference exposure of the hologram. Using replicas or their plating molds as replication molds, the mold surface on the transparent substrate 1, using various forming methods such as coating method, gravure printing method, curtain coating method, inkjet method, It is preferable to perform molding by pressing the above resin against the hologram forming layer 2 formed to a thickness of 1 μm to 50 μm, particularly 1 μm to 10 μm. (See Figure 2.)
The hologram forming layer 2 is required to have high transparency with respect to the emission wavelength (predetermined wavelength) by the electroluminescence element.

  When thermosetting resin or ionizing radiation curable resin is used, curing is performed by heating or ionizing radiation irradiation while keeping the uncured resin in close contact with the mold surface, and then cured by peeling after curing. The fine irregularities of the relief hologram can be formed on one side of the layer made of a transparent resin material. A diffraction grating forming layer having a diffraction grating formed in a pattern by a similar method can also be used as the optical diffraction structure.

  A hologram is a recording of interference fringes due to interference of light between object light and reference light in an uneven relief shape. For example, a laser reproduction hologram such as a Fresnel hologram, a white light reproduction hologram such as a rainbow hologram, There are color holograms, computer generated holograms (CGH), holographic diffraction gratings, holographic stereograms, and the like that utilize the above principle. 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 any case, it is necessary to record as a “transmission hologram”.

  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.

  In addition, a color hologram image is formed by a diffraction grating pixel consisting of diffraction grating lines (a minimum unit of a single diffraction grating area consisting of the same diffraction grating line. A set of light emitted from these pixels as diffracted light is one color hologram image. It is also possible to form the image by using an image processing method in which element decomposition is performed and a predetermined pixel size, grid line pitch, and grid line angle are assigned to each element and reproduced.

  The pitch (period) of the unevenness depends on the reproduction or reproduction angle, but is usually 0.01 μm to several μm, and the depth of the unevenness is a factor that greatly affects the reproduction or reproduction intensity, but is usually 0.01 μm. ˜several 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.

  A method of shaping (also referred to as replicating) the hologram relief shape is a method of coating on the sheet-like thin film EL layer 3 using an original plate on which diffraction gratings and interference fringes are recorded in an uneven shape as a press die (referred to as a stamper). The concavo-convex pattern of the original plate can be replicated by superimposing the original plate on the hologram forming layer 2 formed by an appropriate printing method, etc., and heat-pressing them with an appropriate means such as a heating roll. The hologram pattern to be formed may be single or plural.

  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 layer is formed on the surface of a glass master or the like formed by optical imaging or electron beam drawing or the like by vacuum deposition or sputtering, Ni or the like is electrodeposited (electroplating, electroless plating) Further, it can be made by peeling the metal after forming 50 to 1000 μm by composite plating or the like.

  The duplication method uses a flat plate type or a rotary type, the linear pressure is 0.1 ton / m to 10 ton / m, and the duplication temperature is usually 60 ° C. to 200 ° C.

  The hologram forming layer 2 is preferably an ionizing radiation curable type (particularly, an ultraviolet curable type) in order to suppress damage to the sheet-like thin film EL layer 3 when the relief shape is formed, and after the relief is formed. Further, it is more preferable to perform additional heat treatment or additional ionizing radiation treatment for improving the degree of curing.

  Moreover, in order to ensure electrical insulation when a voltage is applied, it is desirable that the material has no electrical conductivity and high insulation, and has a dielectric breakdown strength (ASTM-149) of 15 MV / m or more, and further 20 MV. / M or more is desirable. The dielectric breakdown strength can be made higher by mixing a filler such as glass powder, but for the purpose of the present invention, since optical transparency is required, the dielectric breakdown strength is Even if it is high, it is 50 MV / m or less.

  When the dielectric breakdown strength is less than 15 MV / m, the voltage applied to the electroluminescence element is not stable, and light emission becomes uneven, so that the hologram reproduction image is deteriorated. In addition, there remains a fear of electric shock due to leakage of electricity.

  In view of this, it is preferable to use a thermosetting resin or an ionizing radiation curable resin, and as the thermoplastic resin, an acrylate resin, an acrylamide resin, a polycarbonate resin, or a polystyrene resin, Examples of the thermosetting resin include melamine resin, urea resin, aniline resin, unsaturated polyester resin, and the like.

However, in the case where the hologram forming layer itself serves as an anode in the electroluminescence element, it is also preferable to use a resin having conductivity and apply a hologram forming relief to the resin layer. . In this case, the layer configuration is simplified, and various loads when forming the transparent conductive thin film can be avoided.
(Transparent layer)
On the transparent base material 1 of the hologram sheet A of the present invention, a sheet-like thin film EL layer 3 provided in a thin film and in a flat plate shape is provided. Further, the transparent layer L1 is formed so as to cover the hologram relief of the hologram forming layer 2 (so as to fill the “relief”). (See Figure 2.)
As a material used for the transparent layer L1, various thermoplastic resins, thermosetting resins, or ionizing radiation curable resins having transparency can be used.

  As the thermoplastic resin, acrylic ester resin, that is, polymethyl methacrylate (refractive index n = 1.49), polymethyl acrylate (n = 1.47), polybenzyl methacrylate (n = 1.57), polybutyl acrylate (N = 1.44), polyisobutyl acrylate (n = 1.48), etc. Cellulosic resins, ie, cellulose nitrate (n = 1.54), methylcellulose (n = 1.50), cellulose acetate propio Nates (n = 1.47), vinyl resins, ie, polyvinyl acetate (n = 1.47), polyvinyl chloride / vinyl acetate (n = 1.54), acrylamide resins (n = 1.50) ), Polystyrene resin (n = 1.60) or the like, and as the thermosetting resin, unsaturated polyester resin (n = 1. 4), acrylic urethane resin (n = 1.60), epoxy-modified acrylic resin (n = 1.55), melamine resin (n = 1.56), epoxy-modified unsaturated polyester resin (n = 1.64), Alkyd resin (n = 1.54), phenol resin (n = 1.60), silicon resin (n = 1.41-1.60), or fluorinated resin (n = 1.35-1.38) Etc.

  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.

  However, the refractive index difference between the refractive index of the hologram forming layer 2 and the refractive index of the transparent layer L1 shall satisfy the above-mentioned conditions, for example, 0.01 to 0.5, in particular 0.01 to It selects so that it may be set to 0.1 and also 0.01-0.05.

At this time, either the refractive index of the hologram forming layer 2 or the refractive index of the transparent layer L1 may be larger. (The reflectance at the “interface” between the two layers is determined by the Fresnel formula and depends solely on the “refractive index difference.” However, in order to increase the transmitted light efficiency, “Refractive index” <“refractive index of the transparent layer L1” and “refractive index of the hologram forming layer 2”> “refractive index of the transparent layer L1” in order to spread the transmitted refracted light.)
The resin used for the transparent layer L1 is selected to have a low compatibility with the resin constituting the hologram forming layer 2, and the solvent system used for the ink composition for the transparent layer L1 dissolves the hologram forming layer 2. It will be difficult.

  As a method of forming the transparent layer L1 on the hologram forming layer 2, the same method as that of the hologram forming layer 2 can be used, but the outermost surface after the formation of the transparent layer L1 can be made more “flat”. The method is more preferred. Of course, in order to make this outermost surface more “flat”, a stainless steel plate having a mirror-finished surface is used, and the outermost surface is subjected to a heat press treatment or the like, so-called “mirror processing” is performed. It is also preferable to use an “optical mirror surface” (when a stainless steel plate whose surface is finished in the above-mentioned “rough surface” shape is used, the outermost surface can be made the above “rough surface”).

As described above, the thickness of the transparent layer L1 is 1 μm to 50 μm, particularly 1 μm to 10 μm.
(“Sheet-like thin film EL layer” as a representative example of “Sheet-like thin film light source layer” and other “Sheet-like thin film light source layers”)
The sheet-like thin film EL layer 3 is formed by sequentially providing constituent layers on the transparent substrate 1. (See FIG. 2. In FIG. 2, the detailed configuration of the sheet-like thin film EL layer 3 is not shown.)
As this sheet-like thin film EL layer 3, when using either an organic electroluminescence element or an inorganic electroluminescence element, it is first formed from an anode or a cathode which is an “electrode”. Below, the example formed from an anode is demonstrated. It can be easily guessed that the cathode is provided in the same manner as this method.

  Examples of the anode material include transparent conductive materials such as ITO thin film (indium / tin oxide thin film), indium oxide, tin-doped tin oxide, antimony-doped tin oxide, zinc-doped tin oxide, fluorine-doped tin oxide, and zinc oxide. , Conductive polymers such as polyaniline, polypyrrole, polyacetylene, polyalkylthiophene derivatives, polysilane derivatives, and the like can be used.

  Methods for forming the anode include sputtering, vacuum deposition, chemical vapor deposition (CVD), spin coating, sol-gel using a casting method, spray pyrolysis, ion plating, and the like. For example, a method of applying and forming a coating solution having the composition described above can be employed.

In particular, it is preferable to employ an electron beam heating vacuum deposition method or a high-frequency magnetron sputtering method. Specifically, the film is formed under the conditions of a degree of vacuum of 1 × 10 ⁻⁷ to 1 × 10 ⁻³ Pa, a film formation rate of 0.1 to 50 nm / second, and a substrate temperature of −10 to 100 ° C.

  A typical anode is an ITO thin film, which is a transparent conductive thin film, and is formed on the transparent substrate 1 by, for example, about 300 nm by an electron beam heating vacuum deposition method.

  The conductivity of the transparent conductive thin film is controlled by its surface resistance value, and the heating rate of indium and tin and the amount of oxygen gas introduced are controlled so as to be 0.1Ω / □ or less.

  The transparent substrate 1 is sufficiently cooled and processed at a high speed so that the flatness of the surface of the transparent substrate 1 is not changed by heating due to the formation of this thin film or impact such as collision of metal particles. Therefore, the film thickness is reduced.

  Thoroughly control the film thickness of the transparent conductive thin film, and the variation in film thickness is kept within a few percent (several% of 300 nm → 10 nm level), and the surface of the transparent conductive thin film (adhered to the transparent substrate 1) The surface opposite to the surface is made to have substantially the same shape as the surface of the transparent substrate 1.

  In order to further reduce damage to the transparent substrate 1, a CVD method (chemical vapor deposition method) or the like can also be used. In the case of the CVD method, there is almost no damage to the transparent substrate 1, but additional processing such as heat treatment after forming the thin film is required, and the surface property of the thin film becomes somewhat rough.

  Next, as for the layer to be formed, in the case of an inorganic electroluminescence element, as the simplest configuration, an insulating layer is provided on this transparent conductive thin film.

Specifically, the material used for the insulating layer is an amorphous oxide such as Y ₂ O ₃ , Al ₂ O ₃ , Ta ₂ O ₅ , SiO ₂ , Si ₃ O ₄ , BaTiO ₃ , PbTiO _3, etc. Ferroelectric, SiNx, SiOF, SiOC, Pb (Zr, Ti) O ₃ , (Pb, La) (Zr, Ti) O ₃ , Bi ₄ Ti ₃ O 1 ₂ , and perovskite ferroelectric, tungsten Examples thereof include a bronze ferroelectric and a bismuth layer structure ferroelectric.

  Furthermore, organic ferroelectrics using π-electron acid-base two-component organic substances, such as dihydroxy having a hydroxyl group with strong acidity (H + (proton) donating ability) such as chloranic acid and bromanilic acid. -P-benzoquinones, or chloranilic acid as an acid, phenazine (Phz) in which a nitrogen atom of a proton accepting group is incorporated into a benzene ring as a base to form a 1: 1 molecular compound, and the like It is also possible to use these aggregated molecules in which hydrogen bonds are formed between them to form a one-dimensional network.

  The formation method includes sputtering, vacuum deposition, chemical vapor deposition (CVD), spin coating, sol-gel method using cast method, spray pyrolysis method, ion plating method, and the like. A method of applying and forming a coating liquid having a composition can be employed.

As a dielectric film which is an insulating layer, a BaTiO ₃ thin film is typically formed with a thickness of, for example, 500 nm by using a sputtering (using Ar gas) method. In this case, since the metal oxide thin film is already formed on the transparent substrate 1, the heat resistance of the surface of the transparent substrate 1 is relatively high, and the thin film can be formed relatively easily. it can.

  This layer is desirably thicker (˜2 μm) in order to ensure insulation, but in consideration of damage to the surface of the transparent substrate 1, it has a uniform thickness and smooth surface properties. Therefore, it is preferable to set the thickness to 100 nm to 500 nm.

  Here, when the insulating layer is formed all the way on the transparent conductive thin film, the anode terminal cannot be provided. Therefore, a part of the transparent conductive thin film is balanced with the size of the hologram provided thereafter by the masking method. For example, in the case of a hologram having a size of 50 mm × 40 mm, masking of 2 mm × 4 mm is performed to form an insulating layer.

  Furthermore, the light emitting layer for inorganic electroluminescent elements is provided on it.

The light emitting layer is formed using a light emitting phosphor having a desired light emitting color. For example, ZnS, Mn / CdSSe, etc. as red light emitting phosphors, ZnS: TbOF, ZnS: Tb as green light emitting phosphors, for example. Examples of the blue light emitting phosphor include SrS: Ce, (SrS: Ce / ZnS) n, CaGa ₂ S ₄ : Ce, and Sr ₂ Ga ₂ S ₅ : Ce. Moreover, SrS: Ce / ZnS: Mn etc. are mentioned as a white light emission fluorescent substance, These fluorescent substances can be selected suitably and can be used.

  As the light-emitting layer, typically, a base material using ZnS and Mn added to the light emission center is formed with a thickness of, for example, 1 μm by using a sputtering (using Ar gas) method.

  This light emitting layer also employs a film forming method capable of ensuring the uniformity of the thickness of each layer and the smoothness of the interface.

  The same masking process is performed on the above-described position also when the light emitting layer is formed.

  The cathode provided thereon is formed of a metal thin film such as aluminum, gold, silver, platinum, copper, iron, silver / magnesium alloy, graphite or the like with a thickness of 50 to 500 nm. Typically, it may be an aluminum thin film, and can be formed stably by a vacuum deposition method, for example, with a thickness of 300 nm.

  The same masking process is performed at the above-described position also when forming the cathode.

  As described above, the sheet-like thin film EL layer 3 made of an inorganic electroluminescence element can be provided on the transparent substrate 1 while maintaining the flatness of the transparent substrate 1. And when this sheet-like thin film EL layer 3 is observed from the cathode side, the transparent conductive thin film layer which is an anode appears to be exposed on a part of the aluminum metal surface.

When an AC voltage of 100 V to 100 Hz is applied between the anode and the cathode (“voltage applied state 6”, hereinafter, also simply referred to as “application 6” of voltage), an electroluminescence layer (sheet The thin film EL layer 3) emits light from the anode side, and passes through the hologram forming layer 2 provided on the electroluminescence layer (sheet-like thin film EL layer 3) to transmit a “color” transmission hologram. A reproduced image, for example, “green transmission hologram reproduced image 7” can be visually recognized. (See Figure 3.)
Next, an organic electroluminescence device will be described. An electroluminescence device in which an organic thin film serving as a light emitting layer is formed on the transparent conductive thin film layer and sandwiched between cathodes is the simplest organic electroluminescence device. Element 3 is formed.

  The light-emitting layer is a two-component system of a main material (host material) and an impurity material (dopant material), and the impurity material that emits light is uniformly dispersed in the main material with addition of 0.1 to 1%.

Since the electron mobility of the organic thin film is not intended for high-speed response, it can be used even if it is relatively small, and is preferably set to a value of 1 × 10 ⁻⁶ cm ² / V · s or more.

  When a low molecular weight system is used for the organic thin film that is the light emitting layer, ZnPBO (bis [2- (2-benzoxazolyl) phenolato] zinc) is used as the light emitting layer material, and Coumarin 6 (3- (2) is used as the doping dye material. -Benzothiazolyl) -7- (diethylamino) coumarin is used to form a 50 nm thick film by CVD.

  When a polymer system is used for the organic thin film as the light emitting layer, the PPV (polyparaphenylene vinylene) system is used as the light emitting layer material, and the PEDOT (poly-3,4-ethylenedioxythiophene) is used as the hole layer material. The + PSS (polystyrene sulfonic acid: dopant) copolymer has a solid content of 0.5% and a thickness after drying of 100 nm by a coating method.

  In addition, it is also preferable to use an organic thin film in combination with a fluorescent whitening agent such as benzothiazole, benzimidazole or benzoxazole, a metal complex having a styrylbenzene compound or an 8-quinolinol derivative as a ligand. In addition, a distyrylarylene skeleton such as 4,4′-bis (2,2-diphenylvinyl) biphenyl is used as a host, and a strong fluorescent dye from blue to red, for example, a coumarin or a fluorescent dye similar to the host is doped. It is also suitable to use those used together.

As a formation method, methods such as a vacuum deposition method, a spin coating method, a casting method, an LB (Langmuir-Blodget) method, and a sputtering method can be employed. For example, when forming by a vacuum evaporation method, the conditions of a degree of vacuum of 1 × 10 −7 to 1 × 10 ⁻³ Pa, a film formation rate of 0.1 to 50 nm / second, and a substrate temperature of −10 to 100 ° C. may be adopted. preferable.

  An organic thin film can also be formed by dissolving an appropriate resin functioning as a binder and a material for an organic thin film in a predetermined solvent to form a solution and then reducing the film by a spin coating method or the like. be able to. In addition, the organic thin film is a film formed by selecting a formation method and formation conditions as appropriate and deposited from a gas phase material compound, or a film formed by solidification from a solution state or liquid phase material compound. It is preferable to use a molecular deposited film.

  On top of these, metals, alloys, their oxides, electrically conductive compounds or mixtures thereof are used as the cathode layer. Specifically, magnesium, aluminum, indium, lithium, sodium, cesium, silver, tin, and the like can be used alone or in combination of two or more.

  Typically, as the cathode layer, an aluminum thin film layer is provided in the same manner as described above to obtain a sheet-like thin film EL layer 3 made of an organic electroluminescence element.

  Also in an organic electroluminescent element, the method of exposing an anode terminal is taken like an inorganic electroluminescent element.

When a DC voltage of 10V is applied 6 between the anode and the cathode (the voltage is applied 6), light emission occurs in the electroluminescence layer (sheet-like thin film EL layer 3). The light is emitted from the anode side, and “color” corresponding to light emission of a predetermined wavelength is transmitted through the hologram forming layer 2 provided on the electroluminescence layer (sheet-like thin film EL layer 3) and the transparent layer L1 provided thereon. ", For example," green transmission hologram reproduction image 7 "can be visually recognized. (See Figure 3.)
Further, as the “sheet-like thin film light source layer” (not shown) other than the “sheet-like thin film EL layer 3”, the following can be adopted.

  First, in the “sheet-like thin film fluorescent layer”, a resin-dispersed fluorescent ink in which the phosphor is uniformly dispersed in a transparent resin and a solvent-dispersed fluorescent ink in which the phosphor is dispersed in water or a solvent are prepared. Using these, various formation methods such as a printing method, a coating method, and an ink jet method are used to form a uniform thickness on the entire surface or partially on the transparent substrate 1. can do.

The resin-dispersed fluorescent ink includes the above-described phosphor, a transparent resin, for example, an acrylic ester resin, an acrylamide resin, a nitrocellulose resin, or a polystyrene resin as a thermoplastic resin, and a thermosetting resin. Ball mills and kneaders using glass beads or steel beads to reduce secondary aggregation in unsaturated polyester resins, acrylic urethane resins, epoxy-modified acrylic resins, epoxy-modified unsaturated polyester resins, alkyd resins, or phenol resins Sufficiently kneading with a roll mill, etc.
Viscosity is adjusted with a solvent, etc., and a gravure method, offset method, silk screen method, curtain coating method, nozzle coating method, and ink jet method are used as appropriate to form a uniform thickness of 0.01 μm to 10.0 μm. can do.

  In particular, in order to make the thickness of the sheet-like thin film fluorescent layer 0.003 μm or more and 1.0 μm or less, and further 0.01 μm or more and 0.5 μm or less, the solid content of the resin dispersed ink is 1 to 10%. When the coating film using a solvent or water as a solvent is, for example, 10 μm, the thickness after evaporation of the solvent (the thickness of the fluorescent layer) becomes 1/10 to 1/100. Thus, the thickness is set to 1.0 μm to 0.1 μm.

Since the solvent-dispersed fluorescent ink does not include a resin component and includes only a phosphor and a solvent, the thickness of the sheet-like thin film fluorescent layer can be made thinner than that of the resin-dispersed type.

As a solvent, water, an alcohol solvent, or a cell solve solvent or a paraffin solvent is used to disperse and hold a phosphor having a small particle system, and is stirred on the transparent substrate 1 by curtain coating, nozzle coating, or the like. Can be provided.

  In addition, a slow volatile solvent is applied to several μm (a ketone solvent for acrylic resin, vinyl chloride, vinyl acetate resin, polyester resin, etc., such as cyclohexanone, etc. This solvent is diluted with an insoluble solvent and used. It is also possible to make the remaining component 0.1 μm or less.) Only the outermost surface of the transparent substrate 1 is dissolved to give adhesiveness to the outermost surface, and the phosphor is powdered thereon. A method of forming a sheet-like thin film phosphor layer is also preferred in which only the phosphor particles that are in contact with the sticky surface remain on the surface of the transparent substrate 1 while spraying the body as it is.

  According to this method, the sheet-like thin film fluorescent layer is substantially one particle film, is formed uniformly on the surface of the transparent substrate 1, and the fluorescent light emitting surface when excited light is applied from the transparent substrate 1 side is the transparent substrate. 1 is the same as the flat surface.

  In any case, the “sheet-like thin film phosphor layer” is formed with a uniform thickness and a uniform density of phosphors therein (in the case of partial formation, the formed portions are uniform). In order to do so, the particle size of the phosphor is preferably small, and the nanophosphor is particularly suitable.

  By using a nanophosphor, the “excitation light” that excites the “sheet-like thin film phosphor layer” tends to cause multiple reflection in the layer, and the “sheet-like thin film phosphor layer” “Light of a predetermined wavelength” also causes a multiple reflection phenomenon and further a stimulated emission phenomenon in the layer, thereby increasing the emission intensity and directivity.

In particular, in order to amplify the “stimulated emission phenomenon”, the interface above the “sheet-like thin film phosphor layer”, that is, “the interface between“ sheet-like thin film phosphor layer ”and“ hologram forming layer 2 ””, “air The ratio of “transmittance / reflectance” to “light of a predetermined wavelength” at the interface between the transparent layer L1 and the transparent layer L1 is 90/10 to 40/60. Preferably, 80/20 to 60/40. (This ratio may be one performance of the above-mentioned “interface” or the whole performance of the above-mentioned “interface”.)
Then, the interface on the “sheet-like thin film fluorescent layer”, that is, “the light of a predetermined wavelength” of the “transparent substrate 1 and the sheet-like thin film phosphor layer” or “the interface between the transparent substrate 1 and the air”. The ratio of “transmittance / reflectance” is preferably 0/100 to 50/50. Therefore, you may provide "metal reflective layers", such as aluminum and silver, in appropriate thickness in the upper surface of the transparent base material 1, or a lower surface.

  Of course, the distance between the “upper and lower interfaces” having this reflectivity is the same length as the “length” of the given wavelength, or “shorter” than that, as described in the academic paper mentioned above. Thus, it goes without saying that the multiple reflection phenomenon and the stimulated emission phenomenon that occur between the “upper and lower interfaces” can be amplified.

  The above “multiple reflection phenomenon” and “stimulated emission phenomenon” also occur in other “sheet-like thin film light source layers” used in the “hologram sheet A” of the present invention, and each of the appropriate “interfaces”. The above-described “transmittance / reflectance” is set, but detailed description thereof is omitted.

  A phosphor is a substance that absorbs energy such as ultraviolet rays, electron beams, and X-rays and emits it as visible light. For example, a material obtained by adding a trace amount of metal ions responsible for light emission such as Eu and Ce to a base ceramic crystal. Etc. In this case, metal ions that contribute to light emission are excited by absorbing energy applied from the outside (energy such as ultraviolet rays, electron beams, X-rays, of course, visible rays, infrared rays, etc.), and then the ground state. Lights when returning to. The lattice of the host crystal functions to chemically stabilize the ions by surrounding the metal ions, and to control the emission color and intensity by adjusting the crystal field and coordination environment.

The present invention uses a phosphor material that emits light in the visible light region by Stokes shift among these fluorescent emissions. Needless to say, a phosphor that emits light in the visible light region by infrared excitation can be used. Generally, a phosphor is manufactured by a solid-phase reaction method in which a phosphor material is fired. In this solid phase reaction method, since the raw material mixture is fired at a high temperature, the obtained fired cake is often a product in which phosphor particles are hard and aggregated. Therefore, normally, when manufacturing the phosphor, for example, a pulverization process using a ball mill, a mortar, etc., is performed. Substantially monodispersed phosphor-precursor particles are suspended in a flowing gas and baked to produce substantially monodispersed fluorescent particles that are not aggregated. According to this method, fluorescent particles having a size of less than 1 μm can be produced.

In addition, for example, when manufacturing a ZnGa ₂ O ₄ : Mn phosphor, the phosphor raw material before firing is prepared by a wet precipitation method, which enables firing at a low temperature and suppresses aggregation of phosphor particles. can do.

  Furthermore, for example, the present invention relates to a method for producing a phosphor having an alkaline earth aluminate-based or alkaline earth silicate-based host crystal. There is a method of forming droplets so as to have a desired particle diameter and firing the droplets. As a result, a phosphor having extremely brittle properties can be obtained and can be easily pulverized to a minute size.

  As the phosphor material, a compound containing an element constituting the phosphor to be manufactured (hereinafter also referred to as “phosphor constituent element”) can be used. Examples thereof include oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, carboxylates, halides, nitrides and the like containing phosphor constituent elements. When selecting the phosphor raw material, it is preferable to select in consideration of the reactivity to the obtained phosphor. Furthermore, corresponding to each phosphor constituting element constituting the phosphor, one kind of phosphor raw material may be used, or two or more kinds may be used in combination in any combination and ratio.

  Further, the impurities contained in each phosphor raw material of the phosphor are not particularly limited as long as the phosphor characteristics are not adversely affected.

  The weight median diameter of each phosphor material is usually 0.01 μm or more and 0.5 μm or less. For this reason, depending on the type of the phosphor material, pulverization may be performed in advance by a dry pulverizer such as a jet mill. As a result, each phosphor raw material can be uniformly dispersed in the raw material mixture, and the solid phase reactivity of the raw material mixture can be increased by increasing the surface area of the phosphor raw material, thereby suppressing the generation of impurity phases. It becomes.

For example, specific examples of phosphor raw materials containing Ba include BaO, Ba (OH) ₂ .8H ₂ O,
BaCO ₂ , Ba (NO ₃ ) ₂ , BaSO ₄ , Ba (C ₂ O ₄ ) · 2H ₂ O, Ba (OCOCH 3) ₂ , BaCl _{2 and the} like can be mentioned.

  In addition, phosphor materials including Ca, Sr, Zn, Mg, Si, Eu, Sm, Tm, Yb, Mn, Cr, Tb, Pr, Ce, Lu, La, Gd, Ge, Ga, P, and B Can be mentioned.

  After preparing a raw material mixture by mixing phosphor raw materials, the raw material mixture is fired at a predetermined temperature and atmosphere. At this time, it is preferable to perform the mixing sufficiently.

  Although it does not specifically limit as said mixing method, Specifically, the method quoted as the following (A) and (B) can be used. As for these various conditions, for example, it is possible to select conditions such as mixing and using two kinds of balls having different particle diameters in a ball mill.

  (A) Dry pulverizer such as hammer mill, roll mill, ball mill, jet mill, etc., or pulverization using mortar and pestle, and mixer such as ribbon blender, V-type blender, Henschel mixer, or mortar and pestle And a dry mixing method in which the above phosphor raw materials are pulverized and mixed.

  (B) Add a solvent or dispersion medium such as an alcohol solvent such as methanol or ethanol or water to the phosphor raw material, and mix using, for example, a pulverizer, a mortar and pestle, or an evaporating dish and a stirring bar, A wet mixing method in which a solution or slurry is made and then dried by spray drying, heat drying, or natural drying.

  The mixing of the phosphor raw material can be either wet or dry depending on the physical properties of the phosphor raw material.

  In addition, when using a material that easily oxidizes and absorbs moisture, such as halide and nitride, for example, an inert gas such as argon gas or nitrogen gas is filled and mixed in a glove box in which moisture is controlled.

  In addition, the phosphor material may be sieved for the purpose of, for example, uniforming the particle size during mixing and pulverization. In this case, various types of commercially available sieves can be used, but it is preferable to use a resin mesh such as a nylon mesh rather than a metal mesh in terms of preventing impurities from being mixed.

  In particular, nanophosphors, namely Si nanophosphors, ZnS nanophosphors, YAG: Ce nanophosphors, LaPO4: Ln nanophosphors, dye-doped silica nanophosphors, semiconductor nanoparticles, CdSe-ZnS quantum dots, etc. Since its particle size is extremely small, it can be formed uniformly on a flat surface, and the formation thickness is easy to control. When the semiconductor thin film is formed by ultrafine processing, the semiconductor thin film can be formed with high precision and with a very thin film, and the coherence can be improved by controlling the waveform and intensity of the emitted “light”.

  In the fluorescent semiconductor quantum dot, the central core (core) is made of, for example, cadmium selenide (CdSe), and the outer side thereof is covered with a zinc sulfide (ZnS) coating layer (shell). Yes. By changing the diameter of the metal compound, the emitted fluorescence wavelength changes. Since the biopolymer arranged around the quantum dot has a reactive group peculiar to the biopolymer, the phosphor can be specifically arranged using the reactive group.

As the ultraviolet light-emitting phosphor, the peak of the fluorescence spectrum that is emitted when excited by ultraviolet light and returns to a lower energy level is in a wavelength region such as blue, green, and red. Examples of such ultraviolet light-emitting phosphors include Ca ₂ B ₅ O ₉ Cl: Eu ²⁺ , CaWO ₄ , ZnO: Zn, Zn ₂ SiO ₄ : Mn, Y ₂ O ₂ S: Eu, ZnS: Ag. YVO ₄ : Eu, Y ₂ O ₃ : Eu, Gd ₂ O ₂ S: Tb, La ₂ O ₂ S: Tb, Y ₃ Al ₅ O 1 ₂ : Ce, etc. Several of these are mixed and used at an appropriate ratio.

  These have peaks in the fluorescence spectrum outside the blue, red, and green wavelength regions. Further, the weight ratio of the ultraviolet fluorescent substance in the ink is not limited as long as the fluorescence can be detected by the light receiving element of the reading head.

On the other hand, some infrared light emitting phosphors have the property of receiving visible light having a wavelength λ2 upon receiving excitation light having a wavelength λ1, and having the properties of λ1 = λ2 and λ1> λ2. Examples of such infrared light emitting phosphors include YF ₃ : Yb, Er, ZnS: CuCO, and the like.

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

Manufactured by Moritex Corporation: fluorescent particles (green: 468 nm → 508 nm) G25 (particle size 0.03 μm), G40 (particle size 0.04 μm), G50 (particle size 0.05 μm), G75 (particle size 0.07 μm), G85 (Particle size 0.09 μm), G100 (particle size 0.10 μm), G140 (particle size 0.14 μm), G200 (particle size 0.20 μm), G250 (particle size 0.25 μm), G300 (particle size 0. 30 μm), G400 (particle size 0.40 μm), G450 (particle size 0.45 μm), G500 (particle size 0.50 μm), fluorescent particles (green: 360 nm → 530 nm) 34-1 (average particle size 3.0 μm) , Fluorescent particles (blue: 365 nm → 447 nm) B50 (particle diameter 0.05 μm), B100 (particle diameter 0.10 μm), B150 (particle diameter 0.14 μm), B200 (particle diameter 0.20 μm), 300 (particle size 0.30 μm), B400 (particle size 0.40 μm), B500 (particle size 0.50 μm), fluorescent particles (red: 542 nm → 612 nm) B50 (particle size 0.05 μm), B60 (particle size 0) 0.05 μm), B100 (particle size 0.10 μm), B160 (particle size 0.16 μm), B200 (particle size 0.20 μm), B300 (particle size 0.30 μm), B400 (particle size 0.40 μm), B500 (Particle size 0.50 μm), etc.
UV excitation fluorescent pigments UVP-1 (emission wavelength 421 nm), UVB-1 (emission wavelength 453 nm), UVG-2 (emission wavelength 517 nm), UVR-2 (emission wavelength 626 nm), visible light excitation fluorescent pigment LMS-570 (450-520 nm → 570 nm), LMS-560 (450-467 nm → 560 nm), LMS-550 (450-465 nm → 550 nm), LMS-540 (450-465 nm → 540 nm), etc. 350-488 nm → 525 nm), Qdot565 nanocrystal (350-488 nm → 565 nm), Qdot585 nanocrystal (350-488 nm → 585 nm), Qdot605 nanocrystal (350-488 nm → 605 nm), Qd ot625 nanocrystal (350-488 nm → 625 nm), Qdot655 nanocrystal (350-488 nm → 655 nm), Qdot705 nanocrystal (350-488 nm → 705 nm), Qdot800 nanocrystal (350-488 nm → 800 nm), etc., manufactured by Evident Technologies Evidot: CdSe / ZnS core shell Evidot (average particle size 7.2 to 9.6 nm, emission wavelength 490 nm to 620 nm), etc. An emission wavelength of 530 nm to 620 nm and the like with a diameter of 8.3 nm can be suitably used.

  Further, the “sheet-like thin film stress light emitting layer” is composed of the “stress light emitting material layer” described below.

  The “stress luminescent material layer” may be a so-called “ceramic plate or a ceramic thin film layer (hereinafter, collectively referred to as“ ceramic plate etc. ”) composed of“ stress luminescent material itself ”. . In that case, 100% of the “stress luminescent material layer composition” is “stress luminescent material”.

  Then, “a notched portion and / or a recessed portion having a predetermined shape is provided on the surface of the stress-stimulated luminescent material layer as a predetermined portion, which will be described in detail below. May be.

  Alternatively, the “stress luminescent material layer” may be “stressed luminescent material composed of fine particles dispersed in a predetermined transparent resin”.

  That is, the “stress luminescent material which is a ceramic material” is changed to “fine particles having a predetermined shape” using “grinding means and classification means”, or “for molding or firing”. "Stress luminescent material" is put into "Mold" and molded (fired) to make "fine particles with a predetermined shape", "fine particles with composition of stress luminescent material" are used with "dispersing means" The “fine-particle composition” is “dispersed” in “predetermined transparent resin”, and 100% of the “fine particle composition” is composed of “stress luminescent material”.

  And the “shape” of the “fine particles” made of the “stress luminescent material” has a large number of “uneven shapes” on the surface, and in particular, the “part of the bottom of the dent” of the “uneven shape” The “predetermined part” is set, and the “stress concentration coefficient α” of the “predetermined part” is 2 or more.

And, the “light having a wavelength peculiar to“ the structure constituting the stress-stimulated luminescent material ”” is “light of a predetermined wavelength”, and usually in the wavelength range of “visible light”, that is, the wavelength of light, In the range of 400 nm to 800 nm, light of one wavelength is emitted corresponding to one type of “stress light emitting material”. Therefore, based on the emitted “light of a predetermined wavelength”, the observer can visually recognize the transmission relief hologram reproduced image. However, the intensity of the “light of a predetermined wavelength” is at least 1. in order to make it “visible” by means of “light emission luminance” (an index of “light intensity”). A size of 0 mcd / cm ² (milli candela / square centimeter) is required.

The above-mentioned “stress luminescent material” is likely to cause “twinned pseudoelastic deformation” when “stress” is applied to the material accompanied by “physical deformation” in the vicinity of so-called “thermoelastic martensitic transformation”. When “stress” is applied to the material accompanied by “physical deformation” such as “Eu-added SrAl ₂ O ₄ (also referred to as“ SAOE ”)” A material that emits light of a predetermined wavelength and whose emission intensity increases in accordance with the applied "stress" is fired and sintered into a predetermined shape (flat plate shape). It is.

Here, the meaning of “physical deformation” means, of course, that it is not “chemical composition change”, but “only part of the crystal structure inside the material changes its lattice structure. It shows that it is “deformation” that leads to “change in the outer shape of the entire material”. (In this way, “deformation accompanied by“ deformation of the outer shape that can be recognized in appearance ”” is called “physical deformation.” That is, deformation of the lattice structure occurs only in the microscopic region. (It means not a state but a state in which the deformation of the lattice structure propagates in the material and occurs over a large area that can be visually recognized.)
Therefore, in order to promote the “light emission” of the “stress light emitting material” used for the “stress light emitting material layer”, the “outline of the whole material” can be “changed” (the “movable range” as the movable region). To be expressed).

  Next, the above-described “stress concentration coefficient α” will be described.

  In the first place, “stress concentration” means that when an external force is applied to the material due to the “discontinuity” of the “shape” of a material, a “stress” corresponding to the external force is generated inside the material. In the vicinity of the “discontinuous portion”, “large stress” is generated as compared with “stress” generated in other regions.

  And as a factor of this “stress concentration”, there are “steps (abrupt changes in cross section)”, “dents”, “unevenness”, “through holes”, “notches”, Furthermore, there are “abrupt changes in material composition” in the material (sintered boundary surface and bonded surface by welding, etc.).

  This “stress concentration” is expressed numerically as “stress concentration coefficient α”, where α = σmax / σ0 (where σ0 is the “average value of“ stress ”” generated in the entire material. Σmax is expressed as “maximum value of“ stress ”” generated at the stress concentration point.

  As a simple example, a cylindrical material (a rod-shaped material whose upper and lower surfaces are the same circle) is sandwiched between its upper and lower surfaces (the area of each surface is S square millimeters). When an external force F (N: Newton) is applied in the vertical direction at a position where the cross-sectional area becomes 1/2 of the upper surface (lower surface) at the intermediate position of the cylindrical shape (the cross-sectional area of this portion is S / 2 ) Is [(proportional constant k) × F / S] (N / mm 2), and σmax is [(proportional constant k) × 2 F / S] (N / Mm2), and the stress concentration coefficient α = σmax / σ0 = 2.0.

  This example is an example of stress generation that does not involve the “physical deformation” as described above, but was used dare to simplify the explanation.

In order to set the “stress concentration coefficient α” of the “stress luminescent material” used for the “stress luminescent material layer” to 2 or more, a part of the “stress luminescent material” having a “layered” outer shape is used. It can be obtained by providing “dents” or “notches” having a depth of 1/10 to 1/5 of the thickness of the “stress luminescent material layer”.
The shape of the “dent” is changed to “shallow shape of bottom. For example, [(opening width / depth) ratio] is 1/20 to 1/10” or “deep shape of bottom. , [(Opening width / depth) ratio] is 1/5 to 1/1, “stress concentration” occurs around the “bottom” of this “dent”, and the “stress concentration coefficient α "Is 2 or more.

  Similarly, the value of “stress concentration coefficient α” can be adjusted by providing “steps”, “unevenness”, and “abrupt changes in material composition”.

  The “stress luminescent material” used for the “stress luminescent material layer” has a light emission intensity that increases in proportion to the magnitude of the generated “stress”. The larger the value, the higher the emission intensity, and the visibility can be improved.

  The “stress concentration coefficient α” is preferably as large as possible, and is set to 2 or more. Furthermore, by setting it to 10 or more, and more preferably 100 or more, it is possible to make the emission intensity of the portion “high luminance” and make it easier to visually recognize.

However, the greater the “stress concentration factor α”, the more “discontinuity” of the “shape” of the “stress luminescent material” becomes so-called “rapid”, and the “stress luminescent material” “lights”. If the “deformation” is repeated, it is easily “destructed” and no longer emits “light”. (This means that “stable light emission at least 100 times or more” is necessary to ensure the reliability of authenticity determination, but the reliability cannot be ensured.)
The “stress luminescent material layer” can also be formed by dispersing fine particles having the composition of “stress luminescent material” in a predetermined transparent resin.

  That is, “stress luminescent material (including“ stress luminescent material composite ”composed of a plurality of stress luminescent materials)” has a maximum diameter of 0.1 μm to 50 μm, preferably 5.0 μm to 20 μm. Prepared as “fine particles” or “fine particles” having an average particle diameter D50 of 0.05 μm to 20 μm, preferably 0.5 μm to 10 μm, and this is prepared as a thermoplastic resin and / or thermosetting. From the resins, the “resin” having the following “transmittance” is selected to be “transparent resin”, and the secondary aggregation of the “fine particles” is suppressed in the “transparent resin”. It means “dispersed” while “dispersed” “fine particles” of “stress luminescent material” “transparent resin”, that is, “mixed” “stress luminescent material layer”.

  In particular, “fine particles” of “stress luminescent material” are obtained by physically pulverizing “stress luminescent material flat plate” and “stress luminescent material lump” into “fine particles”. In the pulverization, for example, using an impact pulverizer, the “fine particles” are controlled to have a relatively irregular shape, and the collision between the pulverized fine particles is suppressed, In the “classifier”, “fine particles” having a desired shape and a desired particle diameter are produced.

  Furthermore, “a composition for“ stress luminescent material ”before firing” (hydroxide containing a predetermined ratio of each element to be a desired “stress luminescent material” by a predetermined “baking” procedure. , Hydrates, oxides, complex oxides, nitrates, hydrochlorides, carbonates, acetates, sulfates, and other raw materials and their mixtures, also called “precursors.” Also, the luminescent center element is doped. It can also be added separately by means, etc. These mixtures, and also powder mixtures or powder mixtures are directly “baked”), and are decomposed by “baking” such as cellulose resins and ethyl cellulose resins. Resin for easy manufacturing ”(so-called“ ceramics ”manufacturing resin. The component of the resin becomes carbon dioxide gas or water when burned, and it is almost completely burned down. Relatively few In other words, the individual “stressed luminescent materials before firing” are dispersed in the form of “individually dispersed as individual particles” (separated from each other by this resin). It is possible to sinter and “stress luminescent material” as “individually dispersed as individual particles” by being subjected to predetermined firing, and sintering. It is possible to make each individual shape more complicated, and therefore, it is possible to easily realize a “shape” having a large stress concentration coefficient α, which is preferable.

  Furthermore, a spray pyrolysis method, a sol-gel method, a flux feeder method, and the like can also be used.

  Of course, in order to obtain a “shape” having a large stress concentration coefficient α, a “mold” (made of metal or ceramics) having the desired “shape” as its internal shape is used. In addition, the above-mentioned “stressed light emitting material composition before firing” is filled (or filled simultaneously with molding with the mold), and after firing, the manufacturing method of taking out from the mold is also adopted. Can do.

  The more irregular the “shape” of the “fine particles”, and the more rough the surface of the “fine particles”, the wider the “site” where the “stress concentration coefficient α ≧ 2” is. And α has a very large shape (α ≧ 500).

  Here, the “transparent resin” is a “resin having a high visible light transmittance”. Specifically, the transmittance of sodium atoms at the D-line (590 nm) is 50% or more, preferably 80%. % Or more.

  Such a “stress luminescent material” has a “potential luminescent structure” in the “material” itself, that is, the “material composition” or “material structure”, and applies a relatively small stress. It is a new “light emitting material” developed by Mr. Xu et al. Of the National Institute of Advanced Industrial Science and Technology, which has a new “light emission” mechanism that can cause the “material” to emit light. Is a “material exhibiting stress luminescence” with a relatively small “elastic deformation region”.

  In the first place, “stress luminescence” uses “mechanical force” as an excitation source of “luminescence”, and the “mechanical force (mechanical energy) applied from the outside” It is defined as “a phenomenon that does”.

  The conventional "stress luminescence" phenomenon can be divided into "destructive luminescence" and "deformed luminescence". Among these, "destructive luminescence" is the "light" generated by breaking or crushing the material. It is a phenomenon that has been observed when cracking "calcite". On the other hand, “deformation light emission” is not accompanied by such “destruction”, and it appears in a so-called “stress-strain curve” that appears when an external force load is gradually applied to a material. ”Is shown as a“ straight line ”(meaning that“ stress ”is proportional to“ strain ”). The light emission in the“ elastic deformation region ”and this“ straight line ”are interrupted at the“ yield point of the material ” This means that the proportional relationship ends.) Light emission in the “plastic deformation region”, which is entering the stage of “structural destruction”, is little by little inside the material. The “destructive luminescence” phenomenon has been observed in a large number of material systems, and about half of the inorganic substances are said to have the property of “destructive luminescence”.

In contrast, “deformed luminescence” has been reported to be weak emission in the “plastic deformation region” although there have been several reports of radiation-induced alkali halides and certain polymers. doing.
In contrast, the “stress luminescent material” developed by Mr. Xu et al. Of the National Institute of Advanced Industrial Science and Technology is different from this “deformed luminescence” and “stress luminescence” in the “elastic deformation region”. It is a material which shows.

All of these are materials (ceramics) in which an element serving as a luminescent center is added to an inorganic crystal skeleton with a highly controlled structure. By selecting the type of inorganic material and luminescent center, ultraviolet to visible to Materials that emit light at various wavelengths in the infrared have been obtained.
Typical examples of emission centers include strontium aluminate added with europium (SrAl ₂ O ₄ : Eu: green emission), zinc sulfide added with manganese as the emission center (ZnS: Mn, yellow-orange emission), and the like. is there.

  The “stress luminescent material” used for the “sheet-like thin film light source layer” of the “hologram sheet A” of the present invention is located in the “three-dimensional structure” including the “composition” and further in this “structure”. “Transition width” of the electronic state by “elements at lattice positions with high electron density” or “elements at lattice positions with low electron density (including those with“ lattice defects: no element ””) And emits "light" with energy equivalent to this "transition width".

  That is, based on an internal stress (“mechanical energy”) generated by an external force, it is based on the formula of “energy E = Planck constant × light frequency” & “light wavelength = light speed / light frequency”. Although light of a predetermined wavelength is emitted, no matter how the magnitude of the internal stress is increased, and no matter how large the rate of applying the internal stress is (ie, how much the strain rate is increased). ), “Predetermined wavelength” itself does not change and is “constant” (meaning “unique” for the material).

The light emission mechanism of this new "stress luminescent material" is a representative "stress luminescent material" by Mr. Yamada (National Institute of Advanced Industrial Science and Technology) and Mr. Matsuo, Nippon Steel Corporation. Since a certain SrAl ₂ O ₄ : Eu system has been announced in detail, only the outline will be described below. ("National Institute of Advanced Industrial Science and Technology, Production Measurement Technology Research Center, Head of Stress Luminescence Technology Team, Xuo Xu (Editorial Representative), Naohiro Ueno, Tadashi Terasaki, Hiroshi Yamada (Editorial Committee), etc. and Novel Structural Health Diagnosis ", published by NTS, Inc., August 2012").
The former host crystal is a stuffed-tridymite structure, and has become a honeycomb structure AlO4 tetrahedra are shaped in "corner-sharing", the large pores therein, the Sr ²⁺ ions It has a structure that is arranged.

Then, in the host crystal, as a luminescent center, and Eu ²⁺ ions are added, and are replaced by two types of sites of Sr ²⁺ ions described above, the Eu ²⁺ ion "4f- It is assumed that light emission occurs due to radiation transition associated with “5d electron orbit transition” (the difference in electron orbit energy at this time is the above energy E).

In the latter, a thermoelastic martensitic transformation from the β phase to the α phase of SrAl ₂ O ₄ occurs at the time of forming the sintered body, a “twin interface” is formed in the crystal, and the electron density near the interface has a gradient. When “stress” is applied to the “stress luminescent material” that is generated and excited from Eu by ultraviolet irradiation or the like and trapped in a hole or the like, “twinned pseudoelastic deformation” occurs. As the “twin crystal interface” moves along with this, the electron density distribution changes, the trapped carriers are released, and light emission occurs due to recombination with the Eu ²⁺ emission center.
When this stress is unloaded, the “twin interface” returns to its original position. At that time, carriers are excited from Eu ²⁺ , trapped in vacancies, etc., and return to the original state. The phenomenon is going to be repeated.

  From these light emission mechanisms, it is inferred that “stress luminescent material” does not require “excitation” by mechanical energy and is a phenomenon different from “triboluminescence”.

  In any case, the “deformation” of the matrix structure itself, and therefore the “physical deformation (specifically, macroscopic scale, bending or twisting its“ shape ”as“ stress luminescent material ”. ) ”Is essential, and in order to enable such“ deformation ”of“ stress luminescent material ”, the“ ease of movement ”of“ stress luminescent material ”and actually The “hologram sheet A” having a “moving area (meaning“ movable space ”) is also required.

This “light with a wavelength unique to the“ structure ”constituting the stress-stimulated luminescent material” is the above-mentioned “light with a predetermined wavelength”, and is usually in the wavelength range of “visible light”, that is, the wavelength of the light. Thus, light having one wavelength is emitted corresponding to one kind of “stress light emitting material” in the range of 400 nm to 800 nm. However, in order to set the intensity of the “light of a predetermined wavelength” to a level at which an appearing relief hologram reproduced image appears, the “light emission luminance” is set to a size of at least 1.0 mcd / cm ² .

In particular, in order to make the image clearer, the reliability of the determination in the case where 10 mcd / cm ² or more is further recognized as “high luminance” and the “relief hologram reproduction image” is used for the authenticity determination. In order to make it higher, it is preferable to have “emission luminance” of 100 mcd / cm ² or more.

Of course, one “stress luminescent material” may include “multiple structures (crystal structures, different luminescent central elements, etc.)” or “stress luminescent material layer” may include multiple types of “stress luminescent materials”. "Material" may be included to emit light having a plurality of wavelength regions, and further, "stress emission" may be performed in a wavelength region other than visible light (stress of ultraviolet light or infrared light). A material that emits light is used.) “Phosphor layer (a layer containing an appropriate fluorescent material)” that is appropriately included in the “hologram sheet A” of the present invention with the emitted light. The “phosphor pattern layer (phosphor layer formed in a pattern)” may be “excited” to emit light in the visible light region, and as a result, visible light may be visually recognized. (Not shown)
In addition, the “stress luminescent material” may be subjected to a “predetermined surface treatment” for improving the “water resistance” of the stress luminescent material.

  That is, “predetermined surface treatment” for the purpose of “improving water resistance” by “silylation treatment” on the individual surfaces of “stress luminescent material” or on the surface of “stress luminescent material layer” ”To prevent the crystal structure of the“ stress luminescent material ”from collapsing due to“ moisture ”and the loss of luminescence. Furthermore, it is also preferable to perform “predetermined surface treatment” for forming a “coating” of a thermoplastic resin or a thermosetting resin so as to cover the “silylation-treated surface”.

As described above, the “stress luminescent material” is accompanied by “physical deformation” in the vicinity of the “thermoelastic martensitic transformation”. “Eu-added SrAl ₂ O ₄ (SAOE)” or the like, which is a material that is likely to occur. A material that emits light and whose emission intensity increases in accordance with the applied “stress” is fired and sintered to have a predetermined shape (layered shape).

Here, "loading the material with 'stress' with 'physical deformation'" means
When the “predetermined external force load on the hologram sheet A” is transferred to the “external force load on the“ stress luminescent material ”,“ stress strain ”is generated in the“ stress luminescent material ”. This means that the “stress luminescent material” itself causes “physical“ deformation ”=“ stress strain ”.

In other words, when an external force load is applied to the “stress luminescent material”, the “stress-strain diagram” has its “elasticity region (a region that changes linearly in the stress-strain diagram). Then, it tries to return to the original state.) (This behavior is so-called “elastic deformation”.)
“Stress luminescence” of the “stress luminescent material” uses the phenomenon that occurs in this “elastic deformation” region, and the luminescence phenomenon can occur stably from several hundred to tens of thousands of times. This is suitable for the purpose of judging the authenticity by visually recognizing the “light emission”, that is, for the purpose of repeatedly performing the “light emission” and the “determination”.

  In this way, “loading the material with“ stress ”along with“ physical deformation ”” can cause a “physical deformation” that is large enough to be visually observed on the outer shape of the material, Promotes deformation and movement of the crystal structure itself (lattice shape, etc.) and crystal walls (crystals and crystal walls) within the material, and increases “luminescence” based on the “deformation and movement”. be able to.

  The “stress luminescent material” used for this “stress luminescent material layer” has a basic structure in which alkali metal ions or alkaline earth metal ions are inserted in the space of the matrix structure formed by a plurality of molecules of a polyhedral structure. And a tetrahedral structure of a stress luminescent material, an AlO-like structure, and a SiO-like structure, part of which is substituted by at least one kind of metal ions of rare earth metal ions or transition metal ions A stress-stimulated luminescent material in which a luminescence center is inserted into a basic structure having a three-dimensional structure formed by a plurality of molecules and an asymmetrical flexible frame structure, piezoelectric effect, lattice by forming strain energy Stress luminescent materials that emit light by mechanisms such as heat generation due to defects and deformation, stress luminescent materials mixed with a mixture of multiple crystal structures, and more The light emission brightness of these stress light emitting materials is increased several hundred times or more, high light emission stress light emitting materials, ultraviolet light (infrared light) light emitting stress light emitting materials that emit light outside the visible light region, or ultrafine particles. A stress luminescent material that is dispersed in a transparent resin to form a “transparent material” can be used.

  Further, by using a “stress luminescent material” having a large “stress concentration coefficient α”, the “size” of “stress” applied to the “stress luminescent material” is, for example, JIS X 6305 (2010: ISO / IEC 10373). -1) “Test method of identification card—Part 1: General characteristics”, “Apply 0.7 N load (F) for 1 minute to the entire area within 3 mm on the right side of the card”. “Large stress load (estimated to be about 10 MPa)”, but “size” that can be lightly bent by the “hand” of the observer can obtain sufficient light emission. The stress load can be set to 5 kPa to 1 MPa, preferably 5 kPa to 100 kPa.

  However, the greater the “stress concentration factor α”, the more “discontinuity” of the “shape” of the “stress luminescent material” becomes so-called “rapid”, and the “stress luminescent material” “lights”. When the “deformation” is repeated, it is easily “destructed” and no longer emits “luminescence”. Therefore, it is inappropriate that the “stress concentration coefficient α” exceeds 1000.

  The calculation of the “stress concentration factor α” is easy for a simple shape such as the “cylindrical shape” described above, but for a “stress luminescent material” having a more complicated shape, and “stress luminescent material” The “stress concentration” at the “predetermined part” and the “stress concentration coefficient α of the“ predetermined part where the “stress concentration factor α is 2 or more” in the “stress luminescent material” ”. In order to obtain the value of “”, it is necessary to apply “structural analysis software (stress distribution analysis software)” using the “finite element method”.

As such a “stress luminescent material”, the following can be used.
(1) An alkali metal ion and / or an alkaline earth metal ion has a basic structure inserted in a space of a base crystal formed by a plurality of molecules of a polyhedral structure, and is inserted into the space. At least one of the alkali metal ions and / or alkaline earth metal ions is selected from the group consisting of rare earth metal ions, transition metal ions, group III metal ions, and group IV metal ions A stress-stimulated luminescent material that is replaced by a metal ion of a species.
This stress-stimulated luminescent material is the basic structure of the base crystal,
Triclinic structure belonging to the P-1 space group, in particular, anorthite-like structure, and structure similar to the anorthite structure as long as alkali metal ions and alkaline earth metal ions can be inserted into the three-dimensional structure space Including (similar compositions),
A tetragonal structure belonging to the P-42m space group, in particular, an akermanite-like structure, and an akermanite within a range in which alkali metal ions and alkaline earth metal ions can be inserted into the space of the host crystal. Including structures similar to structures (similar compositions),
The trigonal structure belonging to the R-3 space group, in particular, the feldspar structure having the aluminosilicate composition, and the tetrahedral structure SiO molecule and AlO molecule are the smallest units, and these molecules are all A three-dimensional structure in which a plurality of vertices are connected together and an alkali metal or a space (gap) formed in the three-dimensional structure. With an alkaline earth metal inserted,
Feldsparoid structures such as leucite KAlSiO, nepheline NaAlSiO, and compositions similar in crystal structure to these compositions, etc.
And this basic structure uses what is shown by any one of the following general formula (1)-general formula (6).

  That is, MxN1-xAl2Si2O8 ... (1) / XxY1-xAlSi3O8 ... (2) / (XxM1-x) (SixAl1-x) AlSi2O8 ... (3) / XxMyCa1-x-yAl2-xSi2 + xO8 ... (4) / MxN2-xMgSi2O7 (5) / MxN3-x (PO4) 2 (6) (wherein M and N are divalent metal ions, and at least one Is Ca, Sr, Ba, Mg or Mn, X and Y are monovalent metal ions, at least one of which is Li, Na or K, and 0 ≦ x, y ≦ 0. 8).

Among them, the host crystal of the stress-stimulated luminescent material (1) exhibiting ultraviolet light emission has a general formula M1-x-yNxQyAl2Si2O8 (7) (wherein M and N in the formula are Ca, Sr in the anorthite structure, respectively) , Mg, or Ba, and in the feldspar structure, Li, Na, or K, Q is a rare earth metal ion, a transition metal ion, a group III metal ion, or a group IV metal ion, and 0 ≦ X ≦ 0.8 and 0.001 ≦ y ≦ 0.1.)
Further, in the host crystal of the stress luminescent material, Ca is selected as the alkaline earth metal ion, and a part of the Ca site is substituted with Ce as the rare earth metal ion, that is, the general formula (8), Ca1-yQyAl2Si2O8 (8) (wherein Q is Eu or another luminescent center ion, and y is a number satisfying 0.001 ≦ y ≦ 0.1). As for 8), what can be expressed as Ca1-mCemAl2Si2O8 (wherein m is a number satisfying 0.001 ≦ m ≦ 0.1) can be used.

And as the luminescent center of this stress luminescent material,
As rare earth metal ions, europium (Eu), dipsirosium (Dy), lanthanum (La), gadolinium (Gd), cerium (Ce), samarium (Sm), yttrium (Y), neodymium (Nd), terbium (Tb) Ions of praseodymium (Pr), erbium (Er), thulium (Tm), ytterbium (Yb), scandium (Sc), promethium (Pm), holmium (Ho), lutetium (Lu), etc.
Further, as transition metal ions, chromium (Cr), manganese (Mn), iron (Fe), antimony (Sb), titanium (Ti), zirconium (Zr), vanadium (V), cobalt (Co), nickel ( Illustrative are ions such as Ni), copper (Cu), zinc (Zn), niobium (Nb), molybdenum (Mo), tantalum (Ta), tungsten (W) and the like. Further, ions of aluminum (Al), gallium (Ga), indium (In), thallium (Tl), or the like can be used as group III metal ions.
In addition, group IV metal ions include germanium (Ge), tin (Sn), lead (Pb), and the like, and further rare earth metal ions, transition metal ions, group III metal ions, and IV Selected from the group of metal ions, and the content of the rare earth metal ion and transition metal ion, in other words, the content of the luminescent center is 0.1 mol% or more and 20 mol% Those within the following range, preferably those within the range of 0.2 mol% or more and 10 mol% or less, and particularly preferably those within the range of 0.5 mol% or more and 5 mol% or less can be used.
Here, the content is 0. If it is less than 1 mol%, efficient light emission cannot be obtained, and if it exceeds 20 mol%, the base crystal is disturbed, resulting in a decrease in light emission efficiency.
(2) Alkali is introduced into the space of the base crystal formed by a plurality of molecules having at least an AlO-like structure and a tetrahedral structure of an SiO-like structure sharing a vertex atom of the tetrahedral structure. It has a basic structure in which at least one of a metal ion and an alkaline earth metal ion is inserted, and the base crystal further has an asymmetric framework structure, and an alkali metal inserted into the space A stress-stimulated luminescent material in which at least a part of at least one of ions and alkaline earth metal ions is substituted with at least one metal ion of rare earth metal ions and transition metal ions, in particular at least AlO-like Structure and three-dimensional structure (three-dimensional frame structure) formed by multiple molecules with tetrahedral structure of SiO-like structure and asymmetry By having a structure in which a light emission center is inserted into a basic structure having a flexible frame structure, the “hologram sheet A” of the present invention containing this stress light emitting material emits light only by being lightly deformed by hand. What you can do.
The stress-stimulated luminescent material has a flexible three-dimensional frame structure and an asymmetric flexible framework structure at the same time, so that in addition to the three-dimensional frame structure, “spontaneous strain” or “elastic anisotropy” Such a host crystal is easily distorted and easily converts the strain energy into a change in the electronic structure of the luminescent center at the center of the frame. ing.

  In addition, in order to further facilitate distortion of the base crystal, a part of the alkali metal or alkaline earth metal inserted into the space of the base crystal may be another ion (for example, a rare earth metal ion or a transition). (Metal ion) may be substituted.

  The ion to be substituted at this time is not particularly limited as long as the crystal structure of the base crystal (asymmetrical flexible three-dimensional frame structure) can be maintained. Examples of the ion to be substituted include, for example, an alkali metal ion inserted in a space formed in the parent crystal and a rare earth metal ion or a transition metal ion having an ion radius different from that of the alkaline earth metal ion. Is preferred. As a result, the base crystal can be easily distorted, and a stress-stimulated luminescent material that exhibits stronger light emission can be provided. Note that the rare earth metal ion or transition metal ion here is for making the base crystal easily distorted, and may not function as the emission center described later.

  This host crystal has a feldspar structure having an aluminosilicate composition, particularly an anorthite-like structure. Such a basic structure is more preferably, for example, an aluminosilicate represented by any one of the general formulas (1) to (4) described above.

  As the light emission center, by using Eu as the rare earth metal ion of the light emission center, it is possible to obtain a light emitter that preferably emits blue light. Further, the emission center is not limited to one type, and a plurality of types of mixtures may be used. For example, a mixture of Eu and Dy can be used.

  More specifically, stress-stimulated luminescent materials exhibiting particularly strong blue light emission are the following M1-x-yNxQyAl2Si2O8 (9) and X1-xy-xYyQxAl2-xSi2 + xO8 (10) (wherein And M and N are each a divalent metal ion, at least one is Ca, Sr, Mg or Mn, X and Y are monovalent metal ions, and at least one is Li, Na or K, and Q is a rare earth metal ion or transition metal ion, and is a number satisfying 0 ≦ X ≦ 0.8 and 0.001 ≦ y ≦ 0.1. It is preferable.

However, in the case of an alkaline earth metal as in the formula (9), Al and Si remain 2 respectively and do not change according to the formula X. On the other hand, in the case of an alkali metal as in the formula (10), in order to balance the charge, the number of monovalent alkali metals increased by X, the number of tetravalent Si increased to (2 + X), and 3 Al is reduced (2-X).
Further, in the stress luminescent material, a stress luminescent material in which Ca is selected as the alkaline earth metal and a part of the Ca site is substituted with at least one kind of luminescent center is more preferable. That is, Ca1-yQyAl2Si2O8 (11) (wherein Q is Eu and at least one of other emission centers, and y is a number satisfying 0.001 ≦ y ≦ 0.1). And

  In addition, Formula (11) can also be expressed as Ca1-m-nEumAl2Si2O8 when the emission center is only Eu. (However, m and n in the formula are numbers satisfying 0.001 ≦ m ≦ 0.1.) In this case, m is in the range of more than 0 and 0.1 or less, and the emission center is EU. And other emission center ions, the content (m) of the mixture as the emission center may be in the range of greater than 0 to 0.2.

Such a stress-stimulated luminescent material can exhibit blue light emission particularly strongly. In the formula (11), it is preferable that the emission center (Q) includes at least Eu. Furthermore, in the formula (11), it is preferable that at least Eu is contained as the rare earth metal ion of the emission center. For example, it is more preferable that the emission center is only Eu or a mixture of Eu and Dy. Thus, if Eu is contained as the emission center, a stress-stimulated luminescent material that exhibits blue light emission can be obtained.
(3) A stress-stimulated luminescent material that satisfies the conditions for emitting light by strain energy, that is, a stress-stimulated luminescent material that emits light by a mechanism such as piezoelectric effect, lattice defects, and heat generation due to deformation by forming strain energy.

By using this stress-stimulated luminescent material, the “hologram sheet A” of the present invention containing this stress-stimulated luminescent material can be made to emit light simply by lightly deforming it by hand.
Light emission due to this piezoelectric effect is caused by the addition of strain-forming force, resulting in strain energy in the “material”, and electricity is generated by the piezoelectric effect associated with the strain energy, thereby causing “electroluminescence”. .

  For this reason, the crystal structure does not have a center of symmetry, and has a structure in which spontaneous polarization occurs. As an example of such a “material” that emits light strongly due to the piezoelectric effect, an α-SrAl 2 O 4 phase crystal material can be suitably used.

  In the case of light emission due to a lattice defect, when a lattice defect exists in a material, electrons and holes (holes) trapped in the lattice defect can be recombined by strain energy, and this causes “light emission”. Is.

  In order to realize a light emission mechanism derived from lattice defects in a stress luminescent material, at least one, preferably two or more types of metal ions are added to the center of the defect center in the base material contained in the stress luminescent material. What is necessary is just to add as an ion.

In such a stress-stimulated luminescent material, as described later, various “metal elements” are added so that metal ions are substituted for Sr sites and Al sites in the α-SrAl 2 O 4 phase crystal material.
Light emission due to heat generation occurs when the material is deformed due to the formation of strain, and heat is generated along with this deformation, and thermoluminescence (thermoluminescence) is generated along with heat generation (temperature increase), resulting in “light emission”. Here again, α-SrAl 2 O 4 can be mentioned as the base material.
(4) A stress-stimulated luminescent material containing a “mixed phase” formed by mixing (mixing) a plurality of crystal structures. In other words, by using a “mixed phase” in which a plurality of crystal structures are mixed, a light-emitting material capable of visually observing high-efficiency (high-intensity) red stress emission, which could not be realized with a single crystal structure. .

  The mixed phase has at least two kinds of crystal structures from the crystal structure of zinc oxide having a wurtzite structure and cubic or zinc sulfide having a wurtzite structure and cubic manganese oxide. A composite crystal is preferable. With this configuration, it is possible to obtain a red light emitter that cannot be realized by using one of zinc oxide, zinc sulfide, and manganese oxide, or two of them.

  That is, a red light emitting material can be realized by using a mixed phase represented by the general formula (xZnO + yZnS + zMnO).

Some of the metal ions constituting the mixed crystal may be substituted with other metal ions. In this case, it is preferable that another metal ion different from the metal ion constituting the mixed crystal is Te ion. Thereby, the intensity of red light emission of the stress-stimulated luminescent material can be greatly improved. ("High brightness red stress luminescent material")
The Te ions are preferably in the range of 0.1 mol or more and 5 mol or less with respect to 100 mol of metal ions constituting the mixed crystal.

  Further, this stress-stimulated luminescent material is composed of tetragonal barium titanate, orthorhombic calcium titanate, rhombohedral magnesium titanate, and cubic strontium titanate. Therefore, at least two kinds or more may be included. In this case, a part of the metal ions constituting the mixed crystal may be replaced with other metal ions.

  The stress-stimulated luminescent materials include general formulas (Ca1-xA'x) yBa1-yTiO3, (Mg1-xA'x) yBa1-yTiO3, and (Sr1-xA'x) yBa1-yTiO3 (where 0. 0001 ≦ x ≦ 0.05, 0.005 ≦ y ≦ 0.995, and A ′ is a rare earth element selected from the group consisting of Dy, La, Gd, Ce, Sm, Y, Nd, Tb, Pr, and Er. ).

  With this configuration, it is possible to obtain a light emitting material having both a light emitting property of emitting light by applying a stress or an electric field and a piezoelectric property.

As the rare earth element shown as A ′, praseodymium (Pr) is most preferably used. Further, from a ferroelectric tetragonal Ba1-xCaxTiO3: Pr solid solution (0 <x <0.23) and a paraelectric orthorhombic BayCa1-yTiO3: Pr solid solution (0.9 <y <1). It may be “mixed phase”.
The Ca ratio is preferably in the range of 40% to 80%, or in the range of 1% to 35%. The Ca ratio is more preferably in the range of 55% to 65%, or in the range of 25% to 35%.
The stress-stimulated luminescent material emits light by applying a mechanical external force such as stress, shear force, impact force, pressure, etc., and the luminescence intensity generally increases as the applied external force increases.

Furthermore, as a “stress luminescent material” that can be used for the “hologram sheet A” of the present invention,
(5) As a base crystal, an oxide or composite oxide of at least one metal belonging to groups 2A, 3A, 4A, and 3B of the periodic table, particularly MgO, SrO, CaO, ZrO ₂ , CeO ₂ , metal oxides selected from HfO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , Cr ₂ O ₃ , and Ti ₂ O ₃ , or composite oxides thereof, among others, spinel structure, fluorite One having a structure, a yttria structure, a corundum structure, or a β-alumina structure, particularly selected from ZrO ₂ , CeO ₂ , HfO ₂ , Y ₂ O ₃ , Cr ₂ O ₃ , and Ti ₂ O ₃ And having a crystal structure selected from a fluorite structure, a yttria structure, and a corundum structure,
The emission center has an unstable 3d, 4d, 5d, or 4f electron shell, and can generate a radiative transition in the electron shell, and a transition metal ion, particularly a first ionization At least one metal ion selected from rare earth metal ions and transition metal ions having an energy of 8 eV or less, in particular, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, in particular, a rare earth metal ion selected from Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy, Or Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, especially A transition metal ion selected from V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ta, and W.
(6) the host crystals, oxides of FeS ₂ structure, sulfides, carbides, and, one or more of nitrides, in particular, Sr ₃ Al ₂ O ₆ of FeS ₂ structure or,, Ca ₃ Al ₂ O ₆ In which the emission center is the same as in (5) above.
(7) The base crystal is selected from among spinel-structured MgAl ₂ O ₄ and CaAl ₂ O ₄ , corundum-structured Al ₂ O ₃ , and β-alumina-structured SrMgAl ₁₀ O ₁₇ , One type of metal oxide or composite oxide is used, and its emission center is the same as in (5) above.
(8) A base material mainly comprising a composite of at least one metal oxide selected from Y, Ba, and Mg and an oxide of Si as a base crystal, and in particular, , Y ₂ SiO ₅ , BaSi ₂ O ₅ , and Ba ₃ MgSi ₂ O ₈ , which uses at least one complex oxide, the emission center of which is the above (5) The same thing.
In particular, a rare earth element that emits light when electrons excited by mechanical energy return to the ground state, or a light emission center composed of one or more transition metals is added.
(9) The base crystal is composed of CaYAl ₃ O ₇ , Ca ₂ Al ₂ SiO ₇ , Ca ₂ (Mg, Fe) Si ₂ O ₇ , Ca ₂ B ₂ SiO ₇ , CaNaAlSi ₂ O ₇ , Ca ₂ MgSi having a melilite structure. ₂ O ₇ , (Ca, Na) ₂ (Al, Mg) (Si, Al) ₂ O ₇ , and Ca ₂ (Mg, Al) (Al, Si) From one or more kinds of oxides of SiO ₇ And a light emitting center similar to the above (5).
(10) A compound represented by MN ₂ O ₄ (M and N are selected from the group of Mg, Sr, Ba, Zn, and the group of Ga and Al, respectively) oxide consists of more metal elements), and, those using those ₂ 0% 0.001 mol% of the emission center element against represented metallic element in M, particularly, MgGa ₂ O ₄ , ZnGa ₂ O ₄ , ZnAl ₂ O ₄ , SnZn ₂ O ₄ , BaAl ₂ O ₄ , MgAl ₂ O ₄ , and further, the base material is composed of a compound having a spinel structure An oxide containing a pseudo-spinel or inverse spinel structure, the emission center of which is the same as in (5) above.
(11) It is composed of a compound represented by MN2O ₄ (M and N are at least one metal element selected from the group of Mg, Sr, Ba, Zn and the group of Ga, Al, respectively). Oxide having a base defect and 0.0001 to 20 mol% of lattice defects with respect to M or N.
(12) In the base crystal, (A) General formula xM1O.yAl ₂ O ₃ .zSiO ₂ (M1 in the formula is Ca, Ba, or Sr, a part of which is Na, K, and Mg. least may be replaced by one in the, x, y, and, z is aluminosilicate represented by a is) number of 1 or more, (B) the general formula xM2O · yAl ₂ O ₃ (in the formula M2 is Ca or Ba, part of which may be replaced with at least one of Mg and La. X and y are the same as described above.) (C) General formula xM3O · ySiO2 (wherein M3 is Ca or Sr, a part of which is selected from Na, Mg, Zn, Be, Mn, Zr, Ce, and Nb) It may be replaced by at least one selected. And, y is the same.), Or, silicate represented by _{Ba 2 MgSiO 7, (D)} M4 of the general formula xM4O · yM5O ₁₁ (in the formula, Ca, Ba or, Sr, M5 is, Ta , And Nb, and x and y have the same meaning as described above) or niobate, (E) General formula xM5O · yGa ₂ O ₃ ( M5 in the formula is Ca, Ba, or Sr, a part of which may be replaced by La. X and y are the same as described above.) At least one oxide selected from ZrO ₂ , in particular, a general formula xSrO ₂ y Al ₂ O ₃ .z S i O ₂ (a part of Sr in the formula is Na, K, and , May be replaced with at least one of M g .X, y, and, z is a number of 1 or more.), Some of the general formula xSrO · ySiO ₂ (Sr in the formula, N a, M g, Z n, B e, M n, Z and may be replaced by at least one selected from r 1, C e, and N b, and x 1 and y are the same as above), or a general formula xSrO · yM4 O ₁₁ (wherein M is at least one of Ta and Nb, and x and y are the same as described above.), And a base material made of a strontium complex oxide having a composition represented by: xSrO · yAl ₂ O _{As 3} · zSiO ₂ , (Sr, K ₂ , N a ₂ ) Al ₄ Si ₁₄ O ₃₆ , (Sr, Na) (Mg, Fe, Al, Ti) (Si, Al) ₂ O ₆ , (Sr, Na ) ₂ (Al, Mg, Fe) (Si, Al) ₂ O ₇ , Sr ₂ (M g, Al) (Al, Si) SiO ₇ , Sr ₂ Al ₂ SiO ₇ , SrNa ₂ Al ₄ Si ₄ O _{16 and the} like, and the elements in parentheses can be replaced with each other.

Further, as xSrO · ySiO ₂ , Sr (Zn, Mn, Fe, Mg) Si ₂ O ₆ , Sr ₂ (Mg, Fe) Si ₂ O ₇ , Sr ₂ B ₂ SiO ₇ , Sr ₂ BeSi ₂ O ₇ , Sr ₂ MgSi ₂ O ₇ , Sr ₂ Na ₄ CeFeNb ₂ Si ₈ O ₂₈ , Sr ₃ Si ₂ O ₇ , SrFeSi ₂ O ₆ , SrMgSi ₂ O _6, etc., or xSrO · yM ₄ O ₁₁ as Sr (Ta, Nb ) ₄ O ₁₁
Those having particularly high emission intensity are Sr (Ta, Nb) ₄ O ₁₁ , Sr (Zn, Mn, Fe, Mg) Si ₂ O ₆ , Sr ₂ (Mg, Al) (Al, Si) SiO ₇ , Sr _2. Al ₂ SiO ₇ , Sr ₂ MgSi ₂ O ₇ , Sr ₂ Na ₄ CeFeNb ₂ S ₈ O ₂₈ , and SrMgSi ₂ O _6, and SrGa ₁₂ O ₁₉ and SrLaGa ₃ O ₇ .
These oxides are represented by point groups (in the simplified expression index) 1, -1, 2, 2 / m, 6 / m, m3m, (-4) 2m, 622 in terms of crystal structure. In which the emission center has an unstable 3d, 4d, 5d, or 4f electron shell and can cause a radiative transition in the electron shell. Rare earth metal ions and transition metal ions, in particular, at least one metal ion selected from among rare earth metal ions and transition metal ions whose first ionization energy is 8 eV or less, in particular, Sc, Y La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, in particular, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Selected from Tb and Dy Earth metal ions, or Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W , Re, Os, Ir, Pt, Au, in particular, a transition metal ion selected from V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ta, and W.

Furthermore, strontium represented by the composition formula, SrMgAl ₆ O 11, SrLaAl ₃ O ₇ , or SrYAl ₃ O ₇ , and an aluminum-containing composite metal oxide as a base material, with europium as the emission center.
(13) to the luminescent center, at least, comprise a europium (Eu), composition formula _{(1) (Eu 1 -xA'x)} yB '1 -yAl 2 O 4 or a composition formula (2) (Eu ₁ -xa 'x) B' ₁ -yMgAl ₁₀ O ₁₇ {wherein A 'is a rare earth metal, B' is an alkaline earth metal of any one of strontium (Sr), barium (Ba), or calcium (Ca) In which 0 ≦ x ≦ 0.99 and 0.001 ≦ y ≦ 0.550}.
(14) In the base crystal, the general formula xBaO.yAl ₂ O ₃ .zSiO ₂ (Ba in the formula may be partially replaced by at least one of Na, K, and Mg, x, y, and z are numbers of 1 or more), xBaO · yAl ₂ O ₃ (in the formula, a part of Ba may be replaced by Mg, and x and y are the same as above) ), Or xBaO · ySiO ₂ (in which Ba is partially substituted with at least one of Mg, Fe, Mn, Zn, and Be, and x and y are As in the above, at least one oxide selected from barium composite oxides having a composition represented by: xBaO · yAl ₂ O ₃ · zSiO ₂ , For _{example, Ba 2 (Mg, Al)} (Al _{Si) SiO 7, Ba 2 Al} 2 SiO 7, BaAl 2 Si 2 O 8, BaNaAlSi 2 O 7,
As what is represented by xBaO · yAl ₂ O ₃ , for example, BaAl ₈ O 1 ₃ , BaMgAl ₆ O 11,
As xBaO · ySiO ₂ , for example, Ba (Zn, Mn, Fe, Mg) Si ₂ O ₆ , Ba ₂ (Mg, Fe) Si ₂ O ₇ , Ba ₂ BeSi ₂ O ₇ , Ba ₂ MgSi ₂ O ₇ , Ba ₂ MgSiO ₇ , etc.
Particularly large emission _{intensity, Ba 2 Al 2 SiO 7,} Ba 2 MgSi 2 O 7, BaAl 2 Si 2 O 8, BaAl 8 O1 3 a is one.

These oxides are represented by point groups (in terms of simplified expressions) 1, -1, 2, 2 / m, 6 / m, m3m, (-4) 2m, 622 in terms of crystal structure. A rare earth metal ion that has an unstable 3d, 4d, 5d, or 4f electron shell and can cause a radiative transition in the electron shell; And transition metal ions, in particular, rare earth metal ions having a first ionization energy of 8 eV or less, and at least one metal ion selected from transition metal ions, in particular, Sc, Y, La, Ce, Pr , Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, especially Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy Selected rare earth metal ions, and Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir , Pt, Au, in particular, transition metal ions selected from V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ta, and W.
(14) (Ca1-pPrp) qBa1-qTiO luminescent material composed of _{3 (0.0001 ≦ p ≦ 0.05,0.005 ≦} q ≦ 0.995), further, barium titanate tetragonal structure crystal phase And a phosphorescent material in which a portion of metal ions constituting the mixed phase is replaced with Pr ions, particularly a plurality of different sizes. The crystal phase of barium titanate has a large particle size, the crystal phase of calcium titanate is composed of a small particle size, and the crystal phase of a small particle size is a crystal phase of a large particle size. uniformly dispersed and luminescent material between the particles, also ferroelectric tetragonal Ba1-xCaxTiO _3: Pr solid solution (0 <x <0.25) and, in the paraelectric orthorhombic crystallization Ba1 yCayTiO _3: Pr solid solution luminescent material is a mixed phase consisting of (0.9 <y <1) and, and, [(1-x) BaTiO 3 -xCaTiO 3]: Pr (x is, 0.01 ≦ x ≦ 0 .9), in particular, a light-emitting material (x is 0.4 ≦ x ≦ 0.8) or (x is 0.01 ≦ x ≦ 0.35) can be used.

Alternatively, a light-emitting material in which the above light-emitting material is a light-emitting material that exhibits red light emission and a light-emitting material in which the light emission intensity is proportional to the magnitude of a mechanical external force applied to the light-emitting material can be used. .
(15) Alkali is introduced into the space of the matrix structure formed by a plurality of molecules having at least an AlO 4 -like structure and a tetrahedral structure of SiO 4 -like structure by sharing atoms at the apexes of the tetrahedral structure. A basic structure in which at least one of a metal ion and an alkaline earth metal ion is inserted, and the base structure further has an asymmetric framework structure, and an alkali metal ion and an alkali inserted in the space At least one of the earth metal ions is substituted with at least one kind of metal ions of rare earth metal ions and transition metal ions, and the basic structure is MxN1-xAl2Si2O8 (wherein M and N Is a divalent metal ion, at least one of which is Ca, Sr, Ba, Mg, or Mn, and 0 x ≦ 0.8.) Ca0.985Eu0.01Dy0.005Al2Si2O8, Ca0.995Dy0.005Al2Si2O8, Ca0.97Eu0.01Nd0.02Al2Si2O8, Ca0.93Eu0.02Dy0.05Al2Si2O8, Sr0.97Eu0.01Dy0.02Al2Si2O8 Ba0.97Eu0.01Dy0.02Al2Si2O8, Ca0.8Sr0.17Eu0.01Ho0.02Al2Si2O8, Sr0.17Ba0.80Eu0.01Ho0.02Al2Si2O8, Sr0.17Ba0.80Eu0.01Dy0.02Al2Si2O8, Mg0.2Sr0.77Eu0.01Dy0.02Al , Ba0.2Sr0.77Eu0.01Dy0.02 Stress luminescent material having a composition represented by L2Si2O8.
(16) A square phase structure oxide represented by the general formula CaM1Al ₃ O ₇ (M1 represents Y, La, or Gd) and Eu ^2+, and formed from the raw material of the oxide A stress-stimulated luminescent material that further includes an impurity phase, and in particular, a stress-stimulated luminescent material that further includes an oxide crystal having a lattice defect structure in which an atom represented by M1 is missing.

Then, Eu ²⁺ is contained in an amount of 0.01 mol to 20 mol with respect to 100 mol of the oxide, and further, the substance forming the impurity phase is 0.1 mol to 80 mol with respect to 100 mol of the oxide. A stress luminescent material. In particular, the stress luminescent material whose oxide is CaYAl ₃ O ₇ and whose impurity phase contains at least one of Y ₂ O ₃ , Y ₃ Al ₅ O1 ₂ , or Y4Al ₂ O ₉ .
(17) The host crystal includes at least one compound selected from the group consisting of metal oxides, metal nitrides, and metal sulfides. In particular, the metal oxides include aluminate and aluminosilicate. Using at least one compound selected from the group consisting of acids, the emission center of which further includes at least one element of transition metals (excluding rare earth metals), Si, and Sn; At least a part is contained in the matrix material in a non-solid solution state. Further, the element is in the form of particles and is present on the surface of the matrix material (matrix crystal), and the content of the element is 0.1 to 90 mol%, in particular 10 to 90 mol%, or 0.1 to 10 mol%, and the elements are Zr, Ti, V, Cr, Mn, Fe, Co, Ni Cu, Zn, Hf, At least one metal selected from the group consisting of Nb, Mo, Ta, and W.
(18) (ZnO) 0.6 (MnS) 0.4-x (MnTe) x (0.001 ≦ x ≦ 0.05), in particular, a crystalline phase of a wurtzite type zinc oxide, cubic crystal, Or a mixed phase comprising at least two kinds of crystal phases selected from a wurtzite-type zinc sulfide crystal phase and a cubic manganese oxide crystal phase, and constituting the mixed phase A stress-stimulated luminescent material in which a part of metal ions is replaced by Te ions. Furthermore, it has a plurality of crystal phases having different sizes, the crystal phase of manganese oxide has a large particle size, and the crystal phase of zinc sulfide and the crystal phase of zinc oxide are configured with a small particle size. The crystal phase of the small particle size is uniformly dispersed among the particles of the crystal phase of the large particle size, and in particular, it exhibits red light emission and has a mechanical external force with a load of light emission intensity. Proportional, stress-luminescent material.
(19) A stress-stimulated luminescent material containing monoclinic LiSrPO4: Eu2 ⁺ . In particular, in a phosphor further containing hexagonal LiSrPO4: Eu ²⁺ , a phosphor composed of monoclinic LiSrPO4: Eu ²⁺ , or a space formed in a host structure composed of orthorhombic LiBaPO4, ions europium (Eu) as an emission center is inserted LiBaPO4: a Eu ^2+, the content of the emission center is 2.0 to 3.5 mol% LiBaPO4: Eu ²⁺ a light emitting material.

Further, as a “stress luminescent material” (hereinafter, also referred to as “high-brightness stress luminescent material”) that enables light emission with high luminance, it is preferable to use the following.
(20) An alkaline earth metal deficient type composed of an alkaline earth metal oxide and an aluminum oxide and lacking the composition ratio of alkaline earth metal ions therein, and having the formula MxAl ₂ O ₃ + _{x, MxQAl 10 O 16 + x} , Mx1Qx 2 Al 2 O 3 + x1 + x2 _{or,, Mx1Qx2LAl 10 O 16 + x1} + x2 [M in the formula, Q, and, L is respectively Mg, Ca, Sr, Alternatively, Ba is the main component, and the compound represented by x is 0.8 ≦ x ≦ 0.99, x1, and x2 is a number satisfying 0.8 ≦ (x1 + x2) ≦ 0.99]. A substance comprising at least one kind of aluminate having a non-stoichiometric composition and having a lattice defect that emits light when a carrier excited by mechanical energy returns to the ground state, or a rare earth metal in the host substance Ions and A high-intensity stress luminescent material comprising a substance containing at least one metal ion selected from transition metal ions as a central ion of a luminescent center. In particular, a substance composed of an aluminate having lattice defects has an alkaline earth metal ion content of 1 to 20 mol% less from the stoichiometric composition ratio, and the rare earth metal ion and transition metal are contained in this substance. A high-luminance stress luminescent material containing 0.01 to 10 mol% of at least one metal ion selected from ions as a central ion of a luminescent center.
(21) General formula xM1Al. (1-x) M2A2 (wherein M1 and M2 are selected from Zn, Mn, Cd, Cu, Eu, Fe, Co, Ni, Mg, and Ca) At least one atom, and A1 and A2 are at least one atom selected from chalcogens, which are different from M1A1 and M2A2, and x is greater than 0 and less than 1 A high-intensity stress luminescent material in which the composite semiconductor crystal has a coexistence structure of a wurtzite structure and a zincblende structure.
Furthermore, M1 is Mn or Eu, A1 and A2 are the same chalcogen, or M2 is composed of Zn and Cd or Zn and Cu. Among them, general formula xMA. (1-x) MnA (wherein M is Zn or Zn partially substituted by Cu, A is chalcogen, x is a number greater than 0 and less than 1) And a high intensity stress luminescent material comprising a composite semiconductor crystal having a crystal grain size of 20 nm or less. In particular, a high-luminance stress luminescent material in which A is S or Te.
(22) A stress-stimulated luminescent material containing a first aluminate having a monoclinic crystal structure, wherein the matrix material of the first aluminate is α-SrAl ₂ O ₄ , More than one kind of metal ion is added to the base material as a central ion at the defect center, and the added central ion replaces at least the Sr site of α-SrAl2O4, and the central ion is more ion than Sr. A high-intensity stress luminescent material in which both a small diameter and a large diameter are added, and a metal ion whose ionic diameter is smaller than Sr is Eu, in particular, a second aluminate whose crystal structure is not a single crystal In addition, a lattice defect is formed in the crystal structure having spontaneous polarization of the base material by addition of the central ion, and further, the tunnel structure is included in the crystal structure. As a high-intensity stress luminescent material in which elements arranged therein are arranged by ion bonding, and metal ions having an ion diameter smaller than that of Sr, Mg, Na, Zn, Cu, Eu, Tm, Ho, Dy, Sn, At least one selected from the group consisting of Mn, Nd, Pr, and Ca is used, and a high-intensity stress luminescent material in which Ba and / or K is used as a metal ion having an ionic diameter larger than that of Sr, and α The metal ions substituting the Sr sites of -SrAl ₂ O ₄ are added in an amount of 0.1 to 40 mol% based on Sr, and the total amount of metal ions is less than the stoichiometry. The central ion is replacing the Al site of α-SrAl ₂ O ₄ , the metal ion added as the central ion is smaller in ion diameter than Al, and Si and B are The metal ion added as a central ion has a larger ion diameter than Al, and Ga and In are used. The Al ion of α-SrAl ₂ O ₄ is added as a central ion. The substituting metal ions are added at 0.1 to 20 mol% based on Al, and at least two or more metal ions having different valences are added as metal ions to be added as central ions. A high-intensity stress luminescent material characterized by emitting light in proportion to the strain energy density of the material.

Moreover, the following can also be used as a “stress light emitting material” that enables light emission in the ultraviolet region (light wavelength: 200 nm to 400 nm).
(23) A structure represented by MN (PO3) 4 (wherein M is a monovalent metal ion and N is a trivalent metal ion) is a base structure, and one of the above M or N A stress-stimulated luminescent material in which part is substituted by at least one of a rare earth ion or a group III metal ion.

In particular, a stress-stimulated luminescent material that is Na1-xQxLa (PO) 4 (wherein Q is Ce ion or Tl ion and 0.01 ≦ x ≦ 0.2).
(24) It has a basic structure in which alkaline earth metal ions are inserted in a space of a matrix structure formed by a plurality of molecules of a polyhedral structure, and a part of the alkaline earth metal ions inserted in the space , A stress-stimulated luminescent material substituted with Ce ions, the basic structure of which has a spontaneous strain, and the polyhedral structure molecule comprises at least one of tetrahedral structure AlO4 and SiO4 and de, its basic structure, indicated by general formula _{MxN1-xAl 2 Si 2 O 8} ( in the formula, M and N is a divalent metal ion, at least one is a Ca or Sr _Yes , 0 ≦ x.) The stress- _stimulated luminescent materials are Ca _2.2 Sr _2.77 Ce _2.225 Dy _2.22 Al ₂ Si ₂ O ₈ , Ca _2.2 Sr _2.79 Ce _2.225 Tb _2.225 Al ₂ Si ₂ O ₈ , Ca _2.995 Ce _2.225 Al ₂ Si ₂ O ₈ Ca _2.97 Ce _2.23 Al ₂ Si ₂ O ₈ , Ca _2.2 Sr _2.77 Ce _2.23 Al ₂ Si ₂ O ₈ , or Ca _2.8 Sr _{2. 17} Ce _2.23 Al ₂ Si ₂ O ₈ A stress-stimulated luminescent material.
(25) A structure represented by a general formula MN (PO ₃ ) ₄ (wherein M is a Na ion and N is a La ion) is a base structure, and a part of M is a rare earth The rare earth ion that is substituted by at least one of ions or group III metal ions and that is substituted for a part of M is a rare earth ion selected from the group consisting of Eu, Dy, Ce, and Tb. The group III metal ion substituted for a part of M is a Tl ion.

  For the “stress luminescent material”, a material corresponding to the above-described composition is prepared, that is, for each matrix crystal material, an oxide or the like containing an element serving as a corresponding luminescent center is determined in terms of its metal atom. (Generally, a predetermined value in the range of 0.1 to 100 mol with respect to 100 mol of the base crystal material), and in an inert atmosphere such as nitrogen gas, 900 to After gradually raising the temperature to a temperature in the range of 1100 ° C., it can be obtained by firing at a temperature in the range of 1200 to 1500 ° C. in a reducing atmosphere such as hydrogen-containing argon gas.

  Here, in order to make the “stress luminescent material” into a predetermined shape, a “molding die having a desired shape in advance (a material made of a ceramic material with relatively little deformation at the above-described high temperature is selected). The above-mentioned material is put into “,” a predetermined firing, and then removed from the “mold”.

  However, in order to make the surface of the “stress luminescent material” smooth and “flat surface”, a metal material with a high melting temperature (the metal material has higher surface smoothness than the ceramic material, After “baking”, the surface thereof may be the surface of the “stress luminescent material” and further the surface of the “stress luminescent material layer”).

  In addition, at a high temperature described above, a flat “with sufficient heat resistance” using a resin material such as a cellulose-based resin material or an acetylcellulose-based resin material that is completely burned down and hardly adheres to the fired product. On the “ceramics plate”, a resin coating film is formed with an appropriate thickness, and at that time, on the surface of the resin coating film, a recess corresponding to a desired shape (shape called “stress luminescent material”) The material prepared as described above is put into the concave portion, and the material prepared as described above is baked in the same manner as above to burn off the resin coating, and at the same time, on the "ceramics plate" It is also preferable to adopt a method of leaving a “stress luminescent material” having a shape and further a “stress luminescent material layer”. Such a “stress luminescent material layer” is a single layer of “stress luminescent material layer” without being provided on the “transparent substrate 1”, and is a “sheet-like thin film light source layer (without the transparent substrate 1)”. It can also function as.

  In addition, for the “stress luminescent material”, a material corresponding to the above-described composition is prepared, that is, each element serving as a matrix crystal material, and an element serving as a luminescence center corresponding to the matrix crystal material. Oxides, nitrates, hydrochlorides, and the like containing the above are mixed at a predetermined ratio in terms of metal atoms (the luminescent center material is determined in a predetermined range of 0.1 to 100 mol with respect to 100 mol of the base crystal material. ), “Composite for“ stress luminescent material ”before firing”, and “cavity” having a “shape having a portion where the stress concentration coefficient α is 2 or more” prepared in advance is provided. Filled into the “cavity” of the “firing mold” and gradually in a vacuum state or in an inert gas atmosphere such as nitrogen gas, argon gas, carbon dioxide, etc., to a temperature in the range of 900 to 1100 ° C. After raising the temperature (this The so-called “temperature rise curve” is set corresponding to each “stress luminescent material” composition.) In a “reducing atmosphere” such as hydrogen-containing argon gas, the temperature rises from 1200 to 1500 ° C. The temperature is raised to a temperature within the range, and then “baking (reduction baking with limited oxygen supply)” and / or sintering (also called tightening after “baking”), and then naturally cooling and / or predetermined. (The so-called “cooling curve” at this time is set corresponding to each “stress luminescent material” composition or “stress luminescent material”, respectively.) By the way, from the “firing mold”, the “firing target object (“ stress light emitting material ”having a desired“ shape ”)” is taken out (this is the “firing” procedure), and further, Of the obtained "stress luminescent material" A “flat plate or lump” can be obtained by “micronizing” with a predetermined pulverizing means or the like.

  The shape of the “cavity” is “the shape having a portion where the stress concentration coefficient α is 2 or more” itself, or “shape change (mainly shrinkage)” due to “firing” or “sintering”. It is the shape that was provided assuming.

  More specifically, “predetermined oxide or the like”, which becomes the “stress luminescent material” included in the “stress luminescent material layer” by the above “predetermined firing” in the “cavity”. As a “stressed luminescent material composition” before being fired, which is diluted with a solvent (including an aqueous solvent) and has fluidity, it is poured at a predetermined pressure. In the “firing environment”, the temperature is raised to the “firing temperature” to release the solvent component (water component), the organic material component, and the softening of the low melting point component. Through the structural change, it becomes a “stress luminescent material” included in the “stress luminescent material layer”.

  The “predetermined oxides” includes the “matrix or simple substance of the main element” that appears in the crystal matrix, emission center, and other additives of the target “stress luminescent material”, hydration Products, anhydrous compounds, oxides, composite oxides, nitrates, hydrochlorides, carbonates, acetates, sulfates, and the like, and “the main element is chelated and bonded with an organic material (such as an organometallic compound). ”, Fine powders and powders already used as“ stress luminescent materials ”, various caking aids (olefin resins, especially propylene copolymers, and styrene elastomers) Binder, methacrylic acid ester-based baking binder, cellulose resin, in particular, a caking additive for baking in which sodium silicate, polyvinyl alcohol, polyethylene glycol, etc. are added to methylcellulose) Furthermore, low melting ceramics (softening point, 200 to 700 degrees ceramics. Also called glass frits.) Which was added like, and plus and firing the molding aid propylene is used.

  Moreover, an electric furnace (muffle furnace) or a gas furnace can be used for the above-mentioned “firing” and “consolidation”. Because of the structure and principle of this electric furnace, atmospheric furnaces such as resistance heating furnaces, induction heating furnaces, arc heating furnaces, etc. that use metal heating elements, silicon carbide, molybdenum, lanthanum chromite, carbon graphite as heating elements (Oxidizing atmosphere furnace), gas atmosphere furnace, vacuum gas replacement furnace, low vacuum furnace, high vacuum furnace, and the like, and further, a box furnace, a tubular furnace, a continuous furnace, a rotary kiln that fires while rotating an object, and the like.

  Here, in order to make the “stress luminescent material” into a predetermined shape, a “molding die (ceramics with relatively little deformation at the above-mentioned high temperature) having a desired shape in advance using the various means described above. The material is selected from the “molding die” after the above-mentioned material is put into the selected material and fired to a predetermined degree.

  However, in order to sharpen the shape of the “stress luminescent material” and make the surface smooth, the metal material having a high melting temperature (the metal material has higher surface smoothness than the ceramic material, After “baking”, the surface thereof may be the surface of the “stress luminescent material”).

  In addition, at the high temperatures described above, the resin material such as cellulose-based resin material and acetylcellulose-based resin material, which is completely burned down and has less adhesion of soot to the fired product, has sufficient heat resistance. A resin coating film is formed on a flat “ceramics plate” with an appropriate thickness, and at that time, the surface of the resin coating film corresponds to a desired shape (“stress luminescent material”). A concave portion (which becomes a fine concave portion) is provided, and the material prepared as described above is put into the concave portion and fired in the same manner as above to burn off the resin coating, and at the same time on the “ceramics plate” It is also preferable to adopt a method of leaving a “stress luminescent material” having a desired shape.

  In addition, the “stress luminescent material” included in the “stress luminescent material layer”, “fine particles” is originally fired the composition for “stress luminescent material” under predetermined conditions, and has a thickness of 10 μm to 3 μm. 0.0 mm “flat plate (meaning sheet-like plate)” or three-dimensional shape for pulverization, for example, tablet length, pellet shape, columnar shape, rectangular parallelepiped shape, cube shape, etc. with a maximum length of 0.5 mm to 100 mm The “stress luminescent material” such as “bulky” is pulverized into fine particles by using a predetermined pulverizing means, and the fine particles are selected by using a predetermined classifying means to obtain “fine particles”. Alternatively, the “fine particles at the stage of micronization” are dispersed in the “transparent resin” selected from the resins used for the “predetermined transparent resin” described below to form pellets again. , Crush and classify If the particles are made into “fine particles” or “fine particles” and the collision between the fine particles is suppressed during the treatment, the shape of the “fine particles” itself forms a complicated shape. Furthermore, the surface of the “fine particles” can also maintain a very random uneven shape.

  Here, the “transparent resin” selected from the resins used for the “predetermined transparent resin” refers to a “resin” having the same transparency as the “predetermined transparent resin”. It is preferable that the “transparent resin” has a larger volume elastic modulus than that of the fine particles, and that the “deformation” loaded on the resin is directly transmitted to the “fine particles”. The composition ratio of the “transparent resin” and the “stress luminescent material” is 10/1 to 1/10.

A ball mill, a rod mill, an autogenous grinding mill, a SAG (semi-autogenous grinding) mill, a high-pressure grinding roll, a vertical axis impactor (VSI) mill, or the like is used as a grinding machine as a grinding means.
Further, once the “stress luminescent material” is changed to “fine particle”, and further to “ultrafine particle (average particle diameter is 0.01 to 1.0 μm, particularly 0.01 to 0.1 μm” “Particles” are called “ultrafine particles. Larger particles are called“ fine particles. ”) Using“ granulating ”means such as a granulator, The “secondary aggregate” may be “fine particles”.

  “Stress luminescent material” (“stress luminescent material” 100% composition, “stress luminescent material complex” composed of a plurality of stress luminescent materials, Including those composed of a stress-stimulated luminescent material and a transparent resin ”) are sorted using a classifying means, or further granulated using a granulating means and then sorted using a classifying means. The maximum diameter is “microparticles” of 0.1 μm to 50 μm, preferably 5.0 μm to 20 μm, or the average particle diameter D50 is 0.05 μm to 20 μm, preferably 0.5 μm to 10 μm. Let it be “fine particles”.

  The “fine particles” made of the “stress luminescent material” are dispersed in the “transparent resin” and formed on the transparent substrate 1 as a “stress luminescent material layer”. As the “transparent resin”, various thermoplastic resins, thermosetting resins, or ionizing radiation curable resins are used.

  As the thermoplastic resin, acrylic ester resin, that is, polymethyl methacrylate (refractive index n = 1.49), polymethyl acrylate (n = 1.47), polybenzyl methacrylate (n = 1.57), poly Cellulose resins such as butyl acrylate (n = 1.44), polyisobutyl acrylate (n = 1.48), that is, cellulose nitrate (n = 1.54), methyl cellulose (n = 1.50), cellulose acetate Propionate (n = 1.47) and other vinyl resins, that is, polyvinyl acetate (n = 1.47), polyvinyl chloride / vinyl acetate (n = 1.54), acrylamide resin (n = 1) .50), polystyrene resin (n = 1.60) or the like, and as the thermosetting resin, unsaturated polyester resin (n 1.64), acrylic urethane resin (n = 1.60), epoxy-modified acrylic resin (n = 1.55), melamine resin (n = 1.56), epoxy-modified unsaturated polyester resin (n = 1.64) ), Alkyd resin (n = 1.54), phenol resin (n = 1.60), silicon resin (n = 1.41-1.60), or fluorinated resin (n = 1.35-1. 38) etc. are used.

  These thermoplastic resins and thermosetting resins may be used alone or in combination of two or more, and may be crosslinked using various isocyanate resins, or various curing catalysts such as cobalt naphthenate, Or a metal soap such as zinc naphthenate or a peroxide such as benzoyl peroxide or methyl ethyl ketone peroxide to initiate polymerization with heat or ultraviolet light, benzophenone, acetophenone, anthraquinone, naphthoquinone, azobisisobutyrate Ronitrile or diphenyl sulfide may be blended.

  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 addition, a mixture of the above thermoplastic resin or thermosetting resin with a silicon resin or a fluorine-containing resin, or a silicone oil, or a thermoplastic resin or a thermosetting resin and a silicon resin or a fluorine-containing resin. Or a thermoplastic resin or a material in which a siloxane bond [—Si (R1) (R2) —O—] or a fluorine atom [—F] is introduced into the molecule of a thermosetting resin is used. Can do.
Furthermore, it is also possible to use the above thermoplastic resin or thermosetting resin in which silicon powder fine particles or fluorine powder fine particles are dispersed.

  Fluorinated resins include perfluorinated fluorocarbon resins, tetrafluorinated resins, partially fluorinated resins, trifluorinated resins, polyvinylidene fluoride, polyvinyl fluoride, and fluorinated resin copolymers. Tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer and the like can be used.

  Furthermore, the “refractive index difference” between the refractive index of “transparent resin” and the refractive index of “fine particles” (the refractive index n of “fine particles” is 1.7 to 2.5) is 0.3. Hereinafter, it is further set to 0.1 or less.

  By doing so, the reflectance at the “interface” between the “transparent resin” and “fine particles” is reduced, the “multiple reflection phenomenon” can be increased, and the “light” emitted from the “fine particles” can be increased. Efficiently communicate to the observer.

  In particular, the “refractive index difference” between the refractive index of “transparent resin” and the refractive index of “transparent resin” contained in “fine particles” is 0.1 or less, and further 0.03 or less. .

  As a result, the interface reflectance at the interface of those “resins” can be made almost “0”, and “light” emitted from “fine particles” can be transmitted to the observer more efficiently. .

  The content ratio between the “transparent resin” and the “fine particles” is 5/95 to 100/5, particularly 5/30 to 100/30.

  If this mixing ratio is less than 5/95, the toughness of the “stress luminescent material layer” will be reduced, and in applications for the purpose of preventing counterfeiting, it will be unreliable and will exceed 100/5. , The emission intensity is insufficient.

  Further, the ratio of the solvent with respect to the “mixture of“ transparent resin ”and“ fine particles ”” has individual suitability ranges depending on various methods such as the coating described above, but is generally 100/5 to 1/20.

  Then, in order to “disperse” the “fine particles” in the “transparent resin”, the “transparent resin” can be mixed with solvents such as cyclic hydrocarbons (cyclohexane etc.), alcohols (methanol, ethanol, isopropyl alcohol). , N-propyl alcohol, isobutyl alcohol, n-butyl alcohol, etc., and further aqueous solutions thereof), ethers (tetrahydrofuran, methyl cellosolve, ethyl cellosolve, butyl cellosolve, t-butyl cellosolve, etc.), ethylene glycol Glycol derivatives such as monobutyl ether, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, isophorone, diisobutyl ketone, etc.), aromatics (benzene, toluene, xylene, Solvesso No. 100) In a solution dissolved in Solvesso No. 150, Cactus P-180, etc.), esters (ethyl acetate, butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, ethyl-3-ethoxypropionate, etc.) Or, when “water-soluble resin (water-based resin)” is used for the “transparent resin”, “water” and / or “lower alcohol” such as methanol, ethanol, propanol, butyl alcohol, glycol `` Particulates '' are mixed in a solution dissolved in a sorbent, cellosolve, etc., and `` fine particles '' are added to `` transparent resin '' using a stirrer such as a resolver or mixer, or a kneader such as a kneader or roll mill. After containing uniformly, the mixed solution is gravure coating method, curtain coating method Using blade coating method, roll coating method, spin coating method, offset printing method, letterpress printing method, screen printing method, intaglio printing method, ink jet printing method, casting method, die coating method, etc. It is provided on a “substrate” with a predetermined thickness, and dried under a predetermined condition (natural drying, contact heat drying at 40 to 80 degrees, hot air drying at 40 to 200 degrees, vacuum drying, etc. In addition, drying using a curing reaction by electron beam irradiation may be used alone or in combination, and peeled from the “appropriate substrate” to obtain a “stress luminescent material having a predetermined thickness. Get a layer.

  Furthermore, a “diode” is formed by joining a P-type semiconductor made of an intermetallic compound semiconductor such as gallium phosphide (GaP) or gallium arsenide phosphorus (GaAsP) and an N-type semiconductor to the “sheet-like thin film LED layer”. When the "+ electrode" and the "-electrode" are arranged in each, and a current is passed in the forward direction, a light emitting a predetermined wavelength is emitted from the "junction surface of the P-type semiconductor and the N-type semiconductor". Use.

  Specifically, the structure is “p-electrode layer, p-gallium nitride layer, etc., light emitting layer (GaInN etc.), n-gallium nitride layer, etc., n-electrode layer”, etc. A material having a predetermined thickness of 0.01 to 10.0 μm, particularly 0.01 to 0.5 μm, is used on the substrate 1.

  The “sheet-like thin film disk laser layer” is a kind of infrared LD (laser diode) excitation solid-state laser. On the transparent substrate 1, “totally reflective metal thin film layer (also serves as a cooling layer)”. "Thin-disk thin-film disk laser layer" consisting of "/ thin-film disk-shaped solid laser medium layer (laser crystal) / anti-reflective thin-film layer" and its front side, that is, "transparent resin layer 2" From the side, the one that irradiates excitation LD light and oscillates “light of a predetermined wavelength” is used.

  The thickness is usually about 100 μm, and the “laser structure” is used, but the “hologram sheet A” of the present invention has “high coherence and very high” up to the so-called “laser oscillation”. Since “light emission” as an output is not required, a thickness of 1.0 to 30 μm is used.

Further, the “sheet-like thin film surface emitting laser layer” is a kind of semiconductor laser called VISEL (Vertical Cavity Surface Emitting Laser), and includes “InGaAs / GaAs surface emitting laser structure” and “ "P-side multilayer thin film mirror & p-side electrode / n-InP / p-GaInAsP (active layer) / n-InP / n-side multilayer thin film mirror & n-side electrode structure" can be used. The sheet A has a thickness of 1.0 to 30 μm because it does not require “light emission” having high coherence and very high output until the so-called “laser oscillation”. Is used.
(Card base material)
As the card substrate C0 used for the card C1 with hologram of the present invention, or as a material that can be used for the card substrate IC0, at least the hologram sheet A of the present invention is used as the card substrate C0 or IC0 (card Regarding the base material IC0, it is further required that an electronic component such as a secure microcomputer, which will be described in detail below, can be built in.) Any material that can be embedded in the substrate IC0, that is, a plastic material, Metal materials, ceramic materials, biomaterials, composite materials thereof, and those having a multilayer structure or a more complicated combination thereof can be used. In addition, an appropriate display by means such as printing according to the use of the hologram-equipped card C1 of the present invention may be provided on the front surface or the back surface. (See FIG. 4. FIG. 4 illustrates the case where the surface of the card substrate C0 and the outermost surface of the hologram sheet A are “same surface.” In other cases, this is not shown.)
The shape can be any shape, that is, sheet, film, plate, cube, rectangular parallelepiped, card shape (magnetic card, IC card, non-contact IC card, post card, greeting card, business card, point card, license. Card, game card, etc.), postcard shape, leaf shape, form shape, slip shape, S-mail shape, label shape, seal shape, securities shape, passbook shape, passport shape, postal shape, delivery shape, Envelope shape, bag shape, box shape, case shape, disk shape, disk shape, ellipsoid shape, sphere shape, curved surface shape, rod shape, and combinations thereof, and processing such as deformation, cutting, drilling, adhesion, etc. What you gave can be used. Furthermore, any industrial product or any product such as an electronic terminal or a portable terminal can be used as the card substrate C0 or IC0.

  The thickness is not particularly limited as long as it can be handled, but is usually 30 μm to 3.0 mm. Of course, if it is an envelope shape or a box shape, the dimension of the three-dimensional shape is suitable for each application, and it is not necessary to be within this range.

Further, as representative examples of these card base materials C0 and IC0, materials and shapes used as so-called “plastic cards”, materials and shapes used as “prepaid cards”, particularly ISO standards (ISO / IEC7810 series, ISO / IEC7816 series, ISO / IEC14443 series, ISO / IEC15457 series, etc.) and JIS standards ("prepaid card JIS X 6310 series"), JIS X 6301, JIS X 6300 series, JIS X 6320 series, JIS X 6330 series, etc.). (Not shown)
Among them, the “embedding appropriate” (hologram sheet A can be stably embedded in the card substrate C0 or IC0, and the outermost surface of the hologram sheet A and the surface of the card substrate C0 or IC0 And “general versatility” (including processing versatility. “Processing versatility” means “protective layer / magnetic layer / adhesive layer”). It means that a manufacturing line and manufacturing conditions have been established that embed a magnetic stripe consisting of "Plastic card" and "card base material and shape used as" IC card "" are desirable.

  These are already widely distributed and popular all over the world, so there is no resistance to handling and holding them, and peripheral devices when carrying and using them (Meaning gate terminals for entrance / exit, station gate terminals, credit card terminals, IC card terminals, and other card-using devices) and related goods (card holders for carrying cards, ornaments for cards, etc.) Etc.) are already in widespread use, and the application to these is also smooth and suitable.

  In particular, an opaque film-like or sheet-like plastic is preferable in terms of its processing suitability and cost, and it is possible to reduce the thickness, and it also has mechanical strength, solvent resistance and heat resistance. It is done. For example, polyethylene terephthalate (PET), polycarbonate, polyvinyl alcohol, polysulfone, polyethylene, polypropylene, polystyrene, polyarylate, triacetyl cellulose (TAC), diacetyl cellulose, polyethylene / vinyl alcohol, polyvinyl chloride, polyvinylidene chloride And various plastic film materials. When these plastics are transparent, an opaque material such as titanium dioxide or calcium carbonate is added for the purpose of opacification. Moreover, a film-like or sheet-like plastic can be exemplified.

  Furthermore, a plastic film in which fluorine resin powder, silicon resin powder, or the like is mixed with these materials is preferable because it has extremely high scratch resistance.

Hereinafter, the hologram sheet A and the card substrate C0 will be described as representative examples. (When the card base IC0 is used, the description is almost the same as the following description.)
The hologram sheet A is placed in the card substrate C0 at a heating temperature of 60 ° C. to 200 ° C., preferably 80 ° C. to 150 ° C., and a press pressure of 10 ⁴ Pa to ^{10 10} Pa (N / square meter), preferably Under the condition of 10 ⁶ Pa to 10 ⁸ Pa, those that can be embedded “in a plane” are used.

  The thickness of the card substrate C0 made of such a film-like or sheet-like plastic material is usually 30 μm to 1.0 mm, but it is 200 to 840 μm because of proper processing and handling as a “various purpose card”. Is desirable.

If the thickness is less than 30 μm, the processing accuracy when the hologram sheet A is provided or embedded on the card base C0 is inferior in processing suitability. If the thickness exceeds 1.0 mm, sheet processing is performed. And is difficult to handle in the winding process. (See FIGS. 5 and 6.)
Specifically, a soft vinyl chloride sheet or a hard vinyl chloride sheet having a thickness of 50 μm to 1000 μm, or a combination thereof (meaning a laminate) is preferable.

  Using a 100 μm soft vinyl chloride sheet as the card substrate C0, a hologram sheet A (laminate) having a total thickness of 32 μm (a strip shape having a width of 10 mm. The thickness of the card substrate C0 is about 1/3 of the thickness of the card substrate C0. With a heating of 150 ° C. and a pressure of 106 Pa between stainless steel plates with a surface mirror finish of 1 mm thickness, and heating and cooling cycle of “normal temperature → heating → 150 ° C. → cooling → normal temperature” (When one cycle is 30 minutes to 90 minutes), all the laminates are embedded in the card substrate C0, and the outermost surface of the hologram sheet A and the surface of the card substrate C0 are flush with each other. It was.

  Under the same conditions, a laminated body of 5 μm to 50 μm can be “same” with respect to a thickness of 100 μm of the card substrate C 0, but for a laminated body having a thickness exceeding 50 μm. The step at the boundary exceeds 1.0 μm, and it is necessary to set the conditions at higher temperature and higher pressure in order to be “level”.

  However, setting the above conditions to more severe conditions causes large deformation and alteration of the card base C0, and is unsuitable for use as the card C1 with a hologram of the present invention. The embedding depth with respect to the thickness is “1/20 to 1/2 of the thickness of the card substrate C0”.

  Further, as described above, the “level” state means a state in which the step at the boundary is 1.0 μm or less, but “a small piece to be embedded (meaning the above-described stripe or the like)”. Depending on the size, when the entire “small piece” is uniformly embedded (the thickness of the card substrate C0 including the “small piece” is the same at the place where the “small piece” is present or at other places) If there is a bias in the embedding amount of the “small piece” (the embedding amount of the central portion of the “small piece” is smaller than the end portion of the “small piece” (the portion close to the boundary)), the card base This includes the case where the material of the material C0 flows so as to cover the cross section of the “small piece”, and as a result, indicates that the “small piece” is embedded in the same plane.

  Furthermore, in order to change from the “flat” state to the “recessed state”, a “heat-resistant peelable film (10 μm) is added instead of the above-mentioned total thickness of 32 μm, and other layers are added. As a result, the “laminate” having the same total thickness was embedded in the card substrate C0 under the same conditions, and the peelable film was peeled off. However, the surface of the card substrate C0 can be recessed by 10 μm.

  That is, the thickness of the “peelable film” in the laminate can be recessed from the surface of the card substrate C0.

  This “dent” is 1/10 or less, preferably 1/20 or less, with respect to the thickness of the card substrate C0.

In addition, since such a “peelable film” serves as a substitute for the protective layer of the hologram sheet A, it is left in the manufacturing process or in the distribution process, and an authorized purchaser of the card C1 with a hologram can obtain the card C1 with a hologram. By removing the film immediately before using the film, it is possible to prevent the outermost surface (exposed surface) of the hologram sheet A from becoming dirty or scratched. Furthermore, once the “peelable film” is peeled off, it is no longer easy to return it to the original state. Therefore, when an unauthorized person tries to restore the original state by applying an adhesive or the like, the “peelable film” In addition to impairing the peelability of the card, the “step” exceeds 1.0 μm and has a function of suggesting that fraud has been performed, so the card C1 with a hologram added with a “peelable film” is provided. It is also suitable. (The indented state and the state with a “peelable film” added are not shown.)
Here, the hologram card C2 of the present invention will be described.

The card with hologram C2 of the present invention is a so-called “IC card with hologram”, and as the card substrate IC0, a “battery-integrated IC card substrate incorporating an IC driving battery” is used. The basic configuration is a “contact IC card (with a secure microcomputer IC1)”, an IC drive battery IC2 (thin 3V film battery, etc.), an ON / OFF switch IC3 (display switch, etc.) ), Display panel controller IC4 (driver for liquid crystal display, etc.), display panel IC5 (film liquid crystal, etc.), auxiliary battery IC6 (3V output solar cell film, etc.), etc. . (See FIG. 5. The card C2 with hologram in FIG. 5 shows an example in which all of these electronic components are mounted on the card substrate IC0 or as the card substrate IC0.)
Further, the hologram-equipped card C2 of the present invention has a “non-contact IC card (with a built-in non-contact IC chip)” as its basic configuration, and “an interface IC (having radio wave → digital conversion function). .) ”Driving battery (this is also a kind of IC driving battery, such as a thin 3V film battery), and further has an ON / OFF switch IC3 (display switching switch, etc.), A display panel control unit IC4 (a liquid crystal display driver or the like), a display panel IC5 (film liquid crystal or the like), an auxiliary battery IC6 (3V output solar cell film or the like), or the like can be used. . (Not shown)
These IC drive batteries IC2 also serve as a light emission power source for the hologram sheet A.

As a “power source” (IC driving battery IC2) for driving the secure microcomputer IC1 and “non-contact IC chip”, and as a “power source” for causing the hologram sheet A of the present invention to emit light, The primary battery or the secondary battery is “built in” in the card substrate IC0.
These “batteries” include “a“ control unit ”(display panel control unit IC 4 etc.) that controls the secure microcomputer IC1 or non-contact IC chip” and “a“ display unit ”such as a liquid crystal display (display panel IC5). Etc. ”is used as a power source for driving those“ control unit ”and“ display unit ”.

  Further, in addition to these “built-in” “batteries”, “cards and auxiliary cards (auxiliary battery IC 6 etc.) composed of a solar cell and a capacitor for storing electric energy generated by the solar cell” Inclusion in the base material IC0 is also included in the meaning of “incorporating an IC driving battery”.

  As a result, a person using the IC card C2 with hologram of the present invention simply takes the IC card C2 with hologram “outside” (by holding it outdoors with natural light, or indoors under the illumination of an indoor fluorescent lamp). The electrical energy generated by irradiating the solar cell with light is stored in a capacitor, which can be used as a stable auxiliary power source.

  In addition, when an ON / OFF switch (not shown) for causing the hologram sheet A of the present invention to emit light or to extinguish it is also provided, the convenience is greatly improved, and authenticity determination is improved. It can be significantly easier.

Example 1
As the transparent substrate 1, an aluminum thin film having a thickness of 500 nm was formed on the surface of a 12 μm PET film as a cathode by a vacuum deposition method.

  On top of that, a light-emitting layer having ZnS as the base material and Mn added to the light emission center was formed with a thickness of 1 μm by sputtering (using Ar gas). Zinc sulfide (ZnS) added with 0.5 mol% of manganese sulfide (MnS) was used as the target, and high-purity argon gas was used as the target gas. At this time, in order to leave the cathode terminal, a masking process was performed in a 3 mm × 3 mm region below the right end.

  On this light emitting layer, as a dielectric film which is an insulating layer, BaTiO 3 was masked at the same position and formed with a thickness of 1 μm by sputtering (using Ar gas).

  Further, an ITO thin film was masked at the same position on the insulating layer, and formed with a thickness of 300 nm by electron beam heating vacuum deposition. The surface resistance value of the ITO thin film was 0.1Ω / □.

As described above, the sheet-like thin film EL layer 3 made of an inorganic electroluminescence element having a four-layer structure of a cathode layer, a light emitting layer, an insulating layer, and an ITO thin film on the transparent substrate 1 (light emission wavelength = predetermined wavelength: λ ₀ = 550 nm). (See FIG. 2. However, in FIG. 2, this sheet-like thin film EL layer 3 is indicated as “one layer”.)
On the sheet-like thin film EL layer 3, a 3 mm × 3 mm region below the right end is exposed (becomes a cathode terminal, not shown), and a part of the ITO thin film is exposed (left end). An area of 3 mm × 3 mm was secured below, which would serve as the anode terminal (not shown), and an acrylamide resin composition (refractive index n1 = 1.50) was applied to provide a hologram image position detection pattern. Of the transmission type relief hologram (the hologram relief corresponding to the hologram image reproduces the transmission type hologram reproduction image. 30 mm × 40 mm size: character image of “light emission”: see FIG. 3) Then, a relief hologram was formed by heat-curing while being in contact, and a hologram forming layer 2 having a thickness of 30.0 μm was obtained. (See FIG. 2. The cathode terminal and anode terminal area are not shown.)
The dielectric breakdown strengths of the PET film and acrylamide resin were 50 MV / m and 20 MV / m, respectively.

At this time, the depth _DH of the “hologram relief” of the transmission relief hologram is changed to “the“ optimum depth ”D _H1 of“ reflection diffraction efficiency ”in the“ transmission relief hologram ”” and its “transmission relief”. It was set closer to the “optimum depth” of the “transmission diffraction efficiency” than the “depth” in the middle of the “optimum depth” D _H2 of the “transmission diffraction efficiency” in the “hologram”. More specifically, “D _H = D _H1 + <D _H2 −D _H1 > × 0.8”. (Not shown)
For this purpose, after developing the above “hologram” on a predetermined photoresist using a predetermined optical system, the development time t ₀ of the photoresist is defined as a development time t _H1 for D _H1 and D _{Expressed by} the development time t _H2 for _H2 , “t ₀ = t _H1 + <t _H2 −t _H1 > × 0.8”. (Not shown)
Similarly to the formation of the hologram forming layer 2 as the transparent layer L1 so that a part of the ITO thin film is exposed on the hologram forming layer 2 and covers the hologram relief in the hologram relief forming region. In addition, a polymethyl acrylate (refractive index n2 = 1.47) is applied so that a part of the ITO thin film is exposed, a transparent layer L1 having a thickness of 5.0 μm is provided, and the hologram according to the first embodiment of the present invention is applied. Sheet A was obtained. (See Figure 2.)
Further, incident light traveling from the transparent layer L1 side toward the hologram relief at a predetermined angle (0 degrees, 30 degrees, 60 degrees) with respect to the normal to the surface of the hologram sheet A according to the first embodiment of the present invention. It is confirmed that the reflection diffraction efficiency is smaller than the transmission diffraction efficiency with respect to the incident light from the transparent resin layer 2 side toward the hologram relief at each angle. (Thus, it was estimated that the same was true even if the predetermined angle was 0 to 90 degrees).

  When the hologram sheet A of Example 1 is observed under the indoor illumination light 4, only a “mirror surface” is observed from the transparent base material 1 side, and also from the transparent layer L1 side. The hologram reproduction image of the characters “light emission” (meaning “hologram reproduction image 5” by illumination of the illumination light 4) was not clearly visible.

Then, an alternating voltage of 100 Hz was applied at 100 V between the cathode terminal portion and the anode terminal portion of the hologram sheet A to obtain “state in which voltage was applied 6”. Luminescence "occurred. Also in this case, only a “mirror surface” was observed from the transparent base material 1 side, but when observed from the transparent layer L1 side, in addition to “light emission” over the entire hologram sheet A, a predetermined value was obtained. A green “light emission” character as light emitted in the direction was visually recognized as “green transmission hologram reproduction image 7”. (See Figure 3.)
When the voltage application to the hologram sheet A was stopped, the state before application was restored.

From the above, it was found that this hologram sheet A is a genuine product.
(Example 2)
A hologram sheet A of Example 2 of the present invention was produced in the same manner as in Example 1 except that the ITO thin film was changed to a layer having a thickness of 300 nm by an electron beam heating vacuum deposition method as the cathode. (See Figure 2.)
When evaluated in the same manner as in Example 1, the hologram sheet A was observed as a “transparent sheet” in the observation before voltage application, and a slightly unclear hologram reproduction image (“hologram by illumination of illumination light 4” from both sides thereof was observed. It was possible to see the existence of the reconstructed image 5 ”), but a clear hologram reconstructed image could not be visually recognized.

However, when “predetermined voltage 6 is applied” by applying a predetermined voltage, a clear “green transmission hologram reproduction image 7 (character of“ light emission ”)” floats in the space, and the design is also improved. It was excellent. Then, it was confirmed that when the voltage application was stopped, the original state was restored. (See Figure 3.)
In addition, when the voltage application was a repetitive pattern of ON / OFF in units of 1 second, the “green transmission hologram reproduction image 7” could be visually recognized more clearly. (Not shown)
(Example 3)
The cathode on the transparent substrate 1 is formed with a thickness of 100 nm, the light emitting layer thereon is formed with a thickness of 500 nm, the insulating layer thereon is formed with a thickness of 300 nm, and further thereon A hologram sheet A of Example 3 of the present invention was obtained in the same manner as Example 1 except that the ITO thin film was formed with a thickness of 100 nm. (See Figure 2.)
When evaluated in the same manner as in Example 1, the clarity of the “green transmission hologram reproduction image 7” at the time of light emission is improved, the characters can be judged more clearly, and the authenticity can be judged more reliably. It was. (See Figure 3.)
Example 4
On the transparent substrate 1, an ITO thin film was formed as an anode with a thickness of 100 nm by an electron beam heating vacuum deposition method.

  On top of that, TPAC (1,1-bis [4- [N, N-di (p-tolyl) amino] phenyl] cyclohexane) as a hole transporting material with a thickness of 60 nm and ZnPBO ( Bis [2- (2-benzoxazolyl) phenolato] zinc) and 3% Coumarin 6 (3- (2-benzothiazolyl) -7- (diethylamino) coumarin) as doping dye material, at a thickness of 100 nm, and electrons As a transport material, BND (2,5-bis (1-naphthyl) -1,3,4-oxadiazole) was subjected to the same masking treatment as in Example 1 by a vacuum deposition method at a thickness of 50 nm, Formed.

  Further, an ITO thin film was masked at the same position on the ITO thin film, and formed with a thickness of 100 nm by an electron beam heating vacuum deposition method.

  A melamine resin composition is applied on the sheet-like thin film EL layer 3 to reproduce a relief hologram (30 mm × 40 mm size: “Luminescent” character image: see FIG. 3) with a hologram image position detection pattern. A relief hologram was formed by heating and curing the mold surface in contact with the mold surface to obtain a hologram forming layer 2 having a thickness of 3 μm.

By the above, Example except having formed the sheet-like thin film EL layer 3 which consists of an organic electroluminescent element which consists of an anode layer, a positive hole transport layer, a light emitting layer, an electron carrying layer, and a cathode layer on the transparent base material 1 was carried out. In the same manner as in Example 1, a hologram sheet A of Example 4 of the present invention was produced. (See Figure 2.)
When this hologram sheet A was observed under the illumination light 4 in the room, the hologram reproduction image 5 by the illumination light 4 could not be clearly seen from the transparent base material 1 side and the transparent layer L1 side.

When a DC voltage of 6 V is applied between the anode terminal portion and the cathode terminal portion of the hologram sheet A to make “a state where a voltage is applied 6”, light emission occurs, and the clear space is further sharpened. “Green transmission hologram reproduction image 7” could be visually recognized. (See Figure 3.)
When the voltage application to the hologram sheet A was stopped, the state before application was restored.

From the above, it was possible to easily and reliably determine that this hologram sheet A is a genuine product.
(Example 5)
On the transparent substrate 1, as a sheet-like thin film EL layer 3, using a target for anode (cerium molar ratio 0.05) obtained by sintering a powder of indium oxide and cerium oxide, the degree of vacuum is 3 × 10. ^In a state where the pressure is reduced to ^-1 Pa, a gas in which oxygen gas is mixed with argon gas is sealed, and in this atmosphere, a transparent electrode film having a thickness of 100 nm is formed by high-frequency sputtering at an ultimate vacuum of 5 × 10 ^-4 Pa. NPD (N, N′-di (naphthalen-1-yl) -N, N′-diphenylbenzidine having a vacuum degree of 7 × 10 ⁻⁴ Pa and a thickness of 50 nm as a hole transport layer is formed thereon. ) A thin film is formed by a vacuum deposition method at a deposition rate of 6 nm / min, and further, Alq ₃ (tris (8-hydroxyquinolinato) having a thickness of 50 nm as an organic light emitting material layer / electron transport layer is formed thereon. ) Al A thin film of (minium) is formed by a vacuum vapor deposition method at a vapor deposition rate of 6 nm / min, and a 200 nm magnesium-silver thin film (composition ratio 10/1) is formed on the surface as a cathode by a co-vapor deposition method. Thus, an organic electroluminescence element composed of four layers was produced, and a sheet-like thin film EL layer 3 was obtained. A hologram sheet A of Example 5 of the present invention was obtained in the same manner as Example 4 except that the anode terminal was prepared by masking treatment when forming each thin film. (See Figure 2.)
When a DC voltage of 6 V is applied between the anode terminal portion and the cathode terminal portion of the hologram sheet A to make “a state where a voltage is applied”, light emission occurs, and the sheet-like light emission is used as a background. Among them, a relatively bright and clear “green transmission hologram reproduction image 7” having a luminance of 10 cd / m ² could be visually recognized. (See Figure 3.)
When the voltage application to the hologram sheet A was stopped, the state before application was restored.

From the above, it was possible to easily and reliably determine that this hologram sheet A is a genuine product.
(Example 6)
In Example 1, the refractive index n1 of the transparent resin layer 2 was set to 1.50, and the refractive index n2 of the transparent layer L1 was adjusted to 1.49. The hologram sheet A of Example 6 was obtained. (See Figure 2.)
At this time, in the hologram sheet A of Example 6, the magnitude of the reflection diffraction efficiency with respect to the incident light was 0.1% with the predetermined angle being 0 degree.

The “hologram sheet A” of Example 6 was evaluated in the same manner as in Example 1. As a result of observation from the transparent layer L1 side under the illumination light 4 in the room, a hologram reproduction image of the characters “light emission” ( A good result similar to that of Example 1 was obtained except that “hologram reproduction image 5” by illumination of illumination light 4 was not visible at all (see FIG. 3).
(Example 7)
“Light” of “predetermined wavelength: λ ₀ = 550 nm” is “60% transmitted” between “transparent resin layer 2” and “sheet-like thin film EL layer 3” of “hologram sheet A” in Example 1. In addition, “holographic sheet A” of Example 7 was obtained by adding “dielectric multilayer vapor-deposited film (forms“ half mirror structure ”; heat absorption was ignored)” reflecting “40%”. Except for this, a “hologram sheet A” of Example 7 of the present invention was obtained in the same manner as Example 1 (not shown).

The “hologram sheet A” of Example 7 was evaluated in the same manner as in Example 1. As a result, “Green transmission hologram reproduction image 7” was observed more clearly (see FIG. 3). Good results similar to Example 1 were obtained.
(Example 8)
As a card substrate C0 for the card with hologram C1 of the present invention, a hard vinyl chloride sheet having a thickness of 560 μm is sandwiched between two soft vinyl chloride sheets having a thickness of 100 μm, and a three-layer laminated vinyl chloride sheet having a total thickness of 760 μm ( Credit card size).

Predetermined design printing was performed on the hard vinyl chloride sheet by offset printing, and then a three-layer laminate was formed under predetermined lamination conditions. (Refer to FIG. 4. The state of lamination of the card base C0 is not shown. FIG. 4 is a diagram in which the hologram sheet A of the present invention is already embedded.)
In the central portion of the surface of the card substrate C0, the hologram sheet A of Example 1 (however, the anode terminal and the cathode terminal are arranged so as to be exposed to the transparent substrate 1 side of the hologram sheet A by shifting their positions). , 10 mm wide × 30 mm long strip-shaped) is arranged so that the surface of the card substrate C0 and the cathode layer of the sheet-like thin film EL layer 3 of the hologram sheet A are in contact with each other. It is sandwiched between mirror-finished stainless steel plates and heated, pressurized, and cooled at 120 ° C., 106 Pa, and 60 minutes, so that the outermost surface of the transparent substrate 1 of the hologram sheet A and the surface of the card substrate C0 are “ As a result, a hologram-equipped card C1 of Example 8 of the present invention was obtained. (See Figure 4.)
When the card with hologram C1 of Example 8 was observed under a normal indoor fluorescent lamp (illumination light 4), only the "embedded strip" could be observed on the card C1 with hologram. The existence of “hologram reproduction image 5 by illumination of illumination light 4” reproduced from the strip could not be clearly recognized. (See FIG. 3 for the appearance of the “strip” embedded on the card C1 with hologram. The “strip” in the eighth embodiment is “rectangular”, but in FIG. 3, it is an elliptical example. ing.)
Next, a voltage was applied to the anode terminal and the cathode terminal of the hologram sheet A embedded in the hologram-equipped card C1 of Example 8 in the same manner as in Example 1 to obtain a “voltage applied state 6”. The same “green transmission hologram reproduction image 7” as in Example 1 could be visually recognized.

Further, only the hologram sheet A was peeled off from the card C1 with hologram, but the cross section of the hologram sheet A could not be captured, and it seemed impossible to forge or alter the card C1 with hologram. (Not shown)
About the other than that, the same favorable result as Example 1 was obtained.
Example 9
As a card substrate IC0 for the card C2 with hologram of the present invention, a hard vinyl chloride sheet having a thickness of 600 μm is sandwiched between two soft vinyl chloride sheets having a thickness of 100 μm, and a three-layer laminated vinyl chloride sheet having a total thickness of 800 μm ( The “contact type IC card (secure microcomputer) having the structure of FIG. 5, which is a credit card size) IC card substrate and is a“ battery-integrated IC card substrate IC0 having a built-in IC driving battery IC2 ”. IC1 is mounted.) ".

As shown in FIG. 5, the card base IC0 has a “contact IC card” as its basic configuration, a thin 3V film battery (IC driving battery IC2), a display switching switch (ON / OFF switch IC3), A driver for liquid crystal display (display panel control unit IC4), a film liquid crystal (display panel IC5), and a 3V output solar cell film (auxiliary battery IC6) are mounted or built in. (FIG. 5 has already been embedded with the hologram sheet A of the present invention.)
The hologram sheet A of Example 1 (however, a strip of width 10 mm × length 30 mm) is cut into a central portion (a position not overlapping with each electronic component) of the surface of the card substrate IC0, and further, an anode terminal and a cathode Connect the lead terminal to the terminal and connect it to the built-in thin 3V film battery (IC driving battery IC2) anode and cathode terminal.) It is sandwiched between mirror-finished stainless steel plates and heated, pressurized, and cooled at 120 ° C., 106 Pa and 60 minutes, and the outermost surface of the transparent substrate 1 and the surface of the card substrate IC0 of the hologram sheet A are “ As a result, a hologram card C2 of Example 9 of the present invention was obtained. (See Figure 5.)
When the card with hologram C2 of Example 9 was observed under a normal indoor fluorescent lamp (illumination light 4), only the “embedded strip” could be observed on the card C2 with hologram, The existence of a hologram reproduction image reproduced from the strip (meaning “hologram reproduction image 5” by illumination of illumination light 4) could not be clearly recognized.

Next, the voltage from the thin 3V film battery (IC driving battery IC2) is supplied to the anode terminal and the cathode terminal of the hologram sheet A embedded in the hologram-equipped card C2 of Example 9, and the “apply voltage” is applied. In this case, it is an operation by “switch” (not shown in FIG. 5) <same as display switch: ON / OFF switch IC3>. It is desirable that its presence be concealed.) The same “green transmission hologram reproduction image 7” as in Example 1 could be visually recognized. (See FIG. 4 for the observation state of the “strip” embedded on the card C2 with hologram. Here, the “strip” in Example 9 is “rectangular”, but in FIG. It has become.)
Also, from this card with hologram C2, only the hologram sheet A is peeled off and taken out, but the section of the hologram sheet A cannot be captured, and such an action causes the disconnection of the lead terminal described above. The same good results as in Example 1 were obtained except that it was assumed that forgery or alteration of the card C2 with holograms was very difficult. (Not shown)
(Comparative Example 1)
In Example 1, the depth D _H of the "hologram relief", its ",""optimal depth of" reflection diffraction efficiency "of the relief hologram", "D _H1" and the possible, and the cathode layer 2.0 .mu.m, emission Sheet-like thin film EL composed of an inorganic electroluminescent element having a four-layer structure (all layers have thicknesses of 2.0 μm or more) of a layer of 5.0 μm, an insulating layer of 5.0 μm, and an ITO thin film of 3.0 μm. A hologram sheet of Comparative Example 1 was formed in the same manner as in Example 1 except that it was a layer, and was used as a comparative example.

  At this time, with respect to the normal to the surface of the hologram sheet of Comparative Example 1, a predetermined angle (0 degrees, 30 degrees, 60 degrees) is formed, and the incident light directed to the hologram relief from the transparent layer L1 side is The magnitudes of the reflection diffraction efficiencies were higher than the transmission diffraction efficiencies for incident light from the transparent resin layer 2 side toward the hologram relief at the respective angles.

  When observed in the same manner as in Example 1, the hologram reproduction image 5 by illumination of the illumination light 4 can be clearly seen visually with a normal indoor fluorescent lamp (illumination light 4), and after voltage application ( In the state 6) where the voltage is applied, the entire sheet is colored green, and only a slightly blurred “light image” appears in the “green” background. The character-like green transmission hologram reproduction image 7 was not clearly determined.

  From this, it was determined that the hologram sheet of Comparative Example 1 was not authentic.

A hologram sheet 1 transparent substrate 2 transparent resin layer having hologram relief (hologram forming layer)
3 Sheet-like thin film EL layer L1 Transparent layer 4 Illumination light 5 Hologram reproduction image by illumination light 4 6 Voltage applied state 7 Green transmission hologram reproduction image C0, IC0 Card substrate C1, C2 Hologram card IC1 Secure microcomputer IC2 IC drive battery IC3 ON / OFF switch IC4 Display panel controller IC5 Display panel IC6 Auxiliary battery

Claims (5)

On one surface of the sheet substrate, a sheet-like thin film light source layer, a transparent resin layer having a hologram relief corresponding to the hologram image, and a transparent layer provided so as to cover the hologram relief are provided in this order. A hologram sheet,
A predetermined angle is formed with respect to the normal to the surface of the transparent layer,
The magnitude of the reflection diffraction efficiency for incident light from the transparent layer side toward the hologram relief is
Forming the predetermined angle,
A hologram sheet, wherein the hologram sheet has a transmission diffraction efficiency smaller than that of incident light directed from the transparent resin layer side toward the hologram relief.
In the reflection diffraction efficiency in the hologram sheet according to claim 1,
The hologram sheet according to claim 1, wherein the reflection diffraction efficiency with respect to the incident light having the predetermined angle of 0 degrees is 0.01 to 1.0%.
3. The hologram sheet according to claim 1, wherein the sheet-like thin film light source layer has a thickness of 0.01 μm to 2.0 μm.
The hologram sheet according to any one of claims 1 to 3 is embedded in a card substrate, and an exposed surface of the hologram sheet is flush with the surface of the card substrate or recessed from the surface of the card substrate. A card with a hologram, characterized by being in an open position.
  5. The card with a hologram according to claim 4, wherein the card base is a battery built-in type IC card base containing an IC driving battery, and the IC driving battery emits light from the hologram sheet. A card with hologram, which also serves as a power source.

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