JP6540207B2 - Anti-counterfeit paper - Google Patents

Description

  The present invention relates to anti-counterfeit paper, and in particular, it comprises paper threads, paper threads and "threads" in the form of strips and is composed of stress light emitting material layers, and the "threads" When it is contained in a state of being in contact with the paper pulp fiber and a predetermined external force is applied to the anti-counterfeit sheet, the anti-counterfeit sheet is pulled, bent, bent or twisted by the external force. Being bent, this causes the paper pulp fibers to be deformed while at the same time containing the "threads" contained in contact with the paper pulp fibers being deformed and at the same time constituting the "threads" The stress light emitting material layer is deformed to generate a predetermined deformation stress at a predetermined portion of the stress light emitting material layer, and light of a predetermined wavelength is determined depending on the magnitude of the deformation stress. Emitting intensity of (emits light) it becomes, to a forgery preventing paper.

  In the present invention, "paper pulp fiber" means "pulp fiber (hereinafter also referred to as" pulp "), which is plant fiber separated for use in" papermaking ", and" animal fiber "or , “Chemical fiber” or “man-made fiber” etc. are not included.

  However, in addition to the "paper and pulp fibers", the inclusion of such "animal fibers", "chemical fibers", "man-made fibers" and the like as appropriate is not excluded.

  In the present invention, the "strip-like form" of the "thread" used is at least a two-layer structure of the "predetermined substrate" and the "stress light emitting material layer" provided on one surface of the "predetermined substrate". Refers to the “form” of a “thread”, the cross-section of the “thread” being rectangular (long × horizontal), the direction perpendicular to the cross-section of the “thread” being “longitudinal”, ie “long And the ratio of "long" to "horizontal" is 1: 2 to 1: 1000, and the ratio of "horizontal" to "length" is 1: 2 to 1: 500. Means "form"

Here, the "stress light emitting material layer" may cover the "entire surface" of one surface of the "predetermined base material" or may cover a part thereof. (Thus, "the cross section of the thread" may be "shape" other than "rectangle", but in the above description, it is represented by "rectangle" for convenience.)
In addition to the "paper pulp fibers", the "anti-counterfeit paper" of the present invention is a "stress light-emitting material" which is composed of "stress luminescent materials" consisting of so-called "ceramics" on "predetermined base materials" A “paper” including at least a two-layered “thread” provided with a layer ”(the structure of“ thread ”, the composition and structure of“ stress light emitting material ”, etc. will be described in detail below) In addition, the "thread" is included in the papermaking stage of the anti-counterfeit paper (meaning "in the papermaking process") by "making in", the "paper pulp fiber" and its "thread" ( That is, the “stress light emitting material layer” in the “thread” exists in contact with the inside of the “paper”, and the “paper” is subjected to a predetermined external load, for example, “finger force”. Use a hand to force the "paper" in a jig that has a curved or appropriate curved surface. When you give them to, firstly, results in a "modified" its "paper pulp fibers" in the "paper" is by the external force load.

  And, when the "paper" is "curved", the "deformation" of the "paper pulp fiber" is the "thread" which is in "contact (partially coupled)" with the "paper pulp fiber" That is, it causes “deformation” of “stress light emitting material layer”, and in particular, “tensile stress” with physical movement in “contact point” of “paper pulp fiber” and “stress light emitting material layer”. , "Shear stress" and "displacement stress" (hereinafter sometimes collectively referred to as "stress") are generated.

  Of course, the pressure on the "stress light emitting material layer" directly due to the "curve" of the "paper" and the "curve" of the "paper pulp fiber" also generates the "stress" generated in the "stress light emitting material" To encourage.

  The "stress light emitting material layer" or the "stress light emitting material" constituting the "stress light emitting material layer" is a so-called "ceramic", among which "oxides, nitrides, carbides or sulfides of metal or silicon". Products, and at the point of contact between “paper pulp fiber” and “stress light emitting material”, “paper pulp fiber” as well as “hydrogen bond” by “hydroxyl group of cellulose” at the contact point between “paper pulp fiber” "Hydrogen bond" between "cellulose hydroxyl group" and "oxide, nitride, carbide or sulfide oxygen atom, nitrogen atom, carbon atom or sulfur atom" at the contact point "doing.

  In the "stress light emitting material" described above, the location of the "contact" with the "paper pulp fiber" is the "predetermined portion of the stress light emitting material", and also the "tensile stress" and "shear" described above. “Stress” or “slip stress” is “a deformation stress corresponding to the deformation of paper pulp fiber”, and “a stress luminescent material” used for “a stress luminescent material layer” of the present invention Strength in proportion to “size” and “strength in accordance with the direction in which stress acts” on “structure (including composition, crystal structure, etc. constituting stress light emitting material)” described in detail below. This means “the strength according to the deformation stress.)) It emits light of a wavelength unique to the“ structure ”.

  Of course, the "stress light emitting material" and the point where they are in direct contact (the points where they cross each other) generate such "stress" as described above, and further, "a stress light emitting material If there are notches or depressions, or even projections, in itself, the “curved” of the “stress light emitting material” itself generates “stress” also in those locations, and the “stress light emitting material It will function as one of "predetermined parts".

  In the forgery prevention paper of the present invention, in the paper making process (to be described in detail below), the "thread" being "made into" is "on the one side of the" predetermined base material ". The "stress light emitting material layer" is provided in the "stress light emitting material layer" of the "stress light emitting material layer", and the "composition" of the "stress light emitting material layer" is "stress light emitting". Composed of materials.

  That is, the "stress light emitting material layer" is a so-called "ceramic plate or a thin film layer of ceramic (hereinafter collectively referred to as" ceramic plate etc. ") composed of the" stress light emitting material itself ". The “composition of the stress light emitting material layer” means that 100% of the “composition of the stress light emitting material layer” is a “stress light emitting material”.

  The phrase "having a notch and / or a recess having a predetermined shape as a predetermined portion on the surface of the stress light emitting material layer" means the "predetermined base material" of such a "ceramic plate etc." The non-contacting "surface", that is, the "surface" opposite to the predetermined substrate and / or the "surface" forming the end (cross section) of the ceramic plate or the like will be described in detail below. It means that “a notched portion and / or a recess having a predetermined shape where the stress concentration coefficient α is 2 or more” (these are “predetermined portions”) are provided.

  Alternatively, the “stress light emitting material layer” of the “thread” is “the fine particles composed of the stress light emitting material are dispersed in a predetermined transparent resin”, and “the stress light emitting material is a ceramic material. "Pulverization means and classification means" to make "particles having a predetermined shape" or "stress-light emitting material" in a "mold" for "molding or firing" The "fine particles having the stress light emitting material" as "fine particles having a predetermined shape" by putting and molding (firing) into "predetermined transparent resin" using the "dispersion means" The "dispersion" is formed on the "predetermined substrate", and 100% of the "fine particle composition" is composed of the "stress light emitting material".

  The "shape" of the "fine particles" made of the "stress light emitting material" has a large number of "concave shapes" on the surface, and in particular, the "portion at the bottom of the recess" is the "concave shape". It becomes a "predetermined portion", and the "stress concentration coefficient α" of the "predetermined portion" is 2 or more.

  In particular, by using a "resin system" having many "hydroxy groups" such as a cellulose resin as the "predetermined transparent resin", a "contact point (bonding point)" between the "fine particles" and the "paper pulp fiber" Not only that, as a "stress light emitting material layer", "contact points (bonding points)" with "paper pulp fibers" can be increased.

Of course, in the "stress light emitting material layer" of the present invention, "the shape of the fine particles" means "the average shape of many fine particles" and can be determined by a so-called optical fine particle shape measuring device etc. I assume. (Meaning "average value" of "shape" measured by the "measuring device".)
However, it is most desirable that all the "fine particles" have a shape having "a site with a stress concentration coefficient α 2 2", in which case the visibility of "light emission" can be sufficiently secured. It goes without saying that the object of the present invention can be achieved as long as at least all of the "fine particles" (ie, "fine particle shape") sampled and measured using the aforementioned "apparatus" satisfy this condition. Yes.

  And, "the light of the wavelength specific to" the structure that constitutes the stress light emitting material "is" the light of the predetermined wavelength ", and usually, in the wavelength range of" visible light ", that is, the wavelength of light, The light of one wavelength emits in the range of 400 nm to 800 nm, corresponding to one kind of “stress light emitting material”. Therefore, the observer can visually recognize the emitted "light of predetermined wavelength".

However, the intensity of the “light of a predetermined wavelength” is at least 1.0 mcd / s as “emission luminance” (one index of “intensity of light”) in order to be “visible visually”. A size of cm ² (Millicandela / square centimeter) is required.

  Further, in the present invention, "the rigidity of the thread is 1/10 to 50/10 of the rigidity of the anti-counterfeit paper" is, for example, an index of "stiffness" applied to "relatively thin paper". , Compare the "value" of "Clark stiffness (Clark stiffness): JIS P 8143" with the "value" of "thread alone" and the "value" of "non-thread containing forgery prevention paper", and This means that the ratio is "thread alone" / "anti-counterfeit paper not including thread" = 1/10 to 50/10 ".

  That is, in the forgery prevention paper of the present invention, the "stiffness" of the "portion" of the "portion where the" thread "is inserted" and the "portion where the" thread "is not inserted" If evaluated locally, the "stiffness" of the "part where the" thread "is inserted" corresponds to the "stiffness" of the "part where the" thread "is not inserted". It means that it is in the range of “double to 6.0 times”.

  Here, it is needless to say that the "rigidity" of the "anti-counterfeit prevention sheet without threads" can be substituted by the "anti-counterfeit protection sheet" itself.

  Moreover, it is also possible to employ | adopt another index, for example, JIS-P8125 (Taber method) etc. as a parameter | index of above-described "rigidity."

  It is difficult to set "stiffness of thread" to "less than 1/10 of the rigidity of anti-counterfeit paper" because of its layer constitution and material characteristics ("base material" and "stress light emitting material constituting" thread ") Young's modulus of “layer” is “0.1 to 500 GPa”, particularly “10 to 200 GPa”, and is often considerably larger than “several GPa” which is the Young's modulus of “paper made of paper pulp fibers”. In addition, Young's modulus can be converted to "bulk modulus" by "conversion equation". "Stiffness of thread" is "more than 50/10 of rigidity of anti-counterfeit paper" Then, not only does the handling aptitude of the "anti-counterfeit paper" deteriorate, but also the processing when the "thread" is pulled out, that is, the "thread" is a "ribbon" of several hundred meters to a thousand meters in length. Problems occur in the process of rolling up etc. It is assumed that "roll-up processing" of "anti-counterfeit paper" is not performed when "sheet processing" is performed on "anti-counterfeit paper") and "anti-counterfeit paper" As a result, various processing aptitudes such as perforation processing and slitter processing, and printing aptitude for various printers are also deteriorated.

    Furthermore, in the anti-counterfeit paper of the present invention, “the stress light emitting material is subjected to a predetermined surface treatment to improve the water resistance of the stress light emitting material” means “stress light emission described in detail below. The “prescribed surface treatment” is applied to the material, and this treatment improves the “water resistance” of the “stress light emitting material” itself, and further, the “water resistance” as the “stress light emitting material layer”. It means that.

  Here, "water resistance" refers, for example, to "test time (time to soak in water)" in "test" conducted according to "water immersion test" in JIS K 6404-9: 1999. It shall evaluate by setting it as the time to which the luminescence intensity of a stress luminescent material halves, and "the improvement of water resistance" means "half time" of "the thing which performed predetermined surface treatment" in the evaluation. This means that the “half-life” is 2.0 times or more as compared with the “half-life” of “the one that has not been subjected to the predetermined surface treatment”.

  That is, after “testing time (time to soak in water)” corresponding to “half time” of “thing that has not been subjected to predetermined surface treatment” has been applied to “one that has been subjected to predetermined surface treatment”. The luminescence intensity is 1/2 or more of the "luminescence intensity before test" and "equivalent" (meaning that the decrease in the luminescence intensity is suppressed).

Further, in the present invention, "the thread is machined to the forgery prevention paper in the papermaking process for the forgery prevention paper",
Suspension of "paper and pulp fibers" as the "paper making process 1: wiring & squeezing water" process among the "process for producing" anti-counterfeit paper "described in detail below, that is," the paper making process " There is a step of spreading (also called slurry) on a so-called “mesh (plastic wire etc.)” and drying, but in this series of steps,
A suspension of “paper pulp fiber” is supplied in two parts, and after the first supply (spreading on a wire and removing moisture), “ribbons (long From the strip form, it is called "ribbon". "To" strip form thread "along the" flow direction (winding direction of "paper" as winding up) "of the papermaking process. (Almost parallel), feed on top of the suspension and feed on it a second suspension (covering both the first suspension and the ribbon) Proceed to the next step "paper making step 2: drying & pressing treatment".

  Of course, the suspension may be supplied in several times, and after the first supply of the suspension, the "thread" position may be "recessed" by the "recessing process" to "Threads" may be provided to align the

  Furthermore, it is also preferable to provide a depth difference in the "dent" so that a part of the surface of the "thread" is finally exposed to the surface of the "paper".

  In addition, by combining the supply of the suspension and the next step “drying and pressing”, various sequences of suspension supply, drying, pressing, denting, and “thread” supply are assembled. It is also preferable to make the "paper" configuration a more complex configuration.

  It is preferable to make the above-mentioned "dent" deeper than the "thickness" of the "thread", and change the depth in the "flow direction" or to make the width larger than the width of the "thread". A portion of one side or both sides of the “thread” may be “thinned” than the “paper thickness” of the other portion to produce a pseudo “watermark effect”.

  And it is also preferable to make the "front and back" of a "thread" be exposed to the "front and back" of a "paper" by making a "dent" part into a "penetration part."

In the present invention, “stress light emitting material” means “twin pseudoelastic deformation” when “stress” is applied to the material with “physical deformation” in the vicinity of so-called “thermoelastic martensitic transformation”. "Stress" was loaded on the material with "physical deformation" represented by "Eu-doped SrAl ₂ O ₄ (also referred to as" SAOE ") etc. At that time, the material which emits light of a predetermined wavelength and whose emission intensity increases according to the loaded “stress” is fired and sintered to form a predetermined shape (layered). It is a thing.

Here, the meaning expressed as "physical deformation", of course, indicates that it is not "chemical composition change", but furthermore, "only the crystal structure of a part of the inside of the material changes its lattice structure. "Deformation" which leads to "change in the outline of the entire material". (Thus, "deformation accompanied by" deformation that can be recognized in appearance "is referred to as" physical deformation ". That is, deformation of the lattice structure occurs only in microscopic regions. It is not a state, but means that the deformation of the lattice structure propagates in the material and occurs over a visible large area.)
Therefore, in order to promote the "light emission" of the "stress light emitting material" used in the "stress light emitting material layer" of the present invention, the "region" in which the "outside of the whole material" may be "changed" Region is expressed as “region”, and “stress light emitting material” is “paper” or “paper” as in “stress light emitting material” used for “stress light emitting material layer” of the present invention. It is important to be able to move relatively freely with the "paper".

  Next, “stress concentration coefficient α” in the present invention will be described.

  In the first place, “stress concentration” refers to the “discontinuity” of the “shape” of a material, when an external force is applied to the material and “stress” is generated inside the material according to the external force. That is, "large stress" is generated in the vicinity of the "discontinuity" compared to "stress" generated in other regions.

  And, as a factor of this "stress concentration", "steps (rapid change of the cross section)", "concave", "concave", "through hole", "notch", existing in the "material" Furthermore, there are “a sudden change in material composition” (sintered interface, joint surface by welding etc.) in the material.

The “stress concentration factor α” is a value representing the state of “stress concentration” as a numerical value, and α = σmax / σ ₀ (wherein, σ ₀ is the average of “stress” generated in the entire material. And σ max is expressed as “the maximum value of“ stress ”” occurring at the stress concentration point.

As a simple example, the upper surface and the lower surface (the area of each surface is S square mm) are sandwiched between the cylindrical material (the rod-like material in which the upper surface and the lower surface are the same circle). When an external force F (N: Newton) is applied in the vertical direction at a point where the cross-sectional area is half of the upper surface (lower surface) at the middle position of the cylindrical shape (the cross-sectional area of this point is S / 2 ₀₎ is [(proportional constant k) × F / S] (N / mm ² ), and σ max is [(proportional constant k) × 2 F / S]. It becomes (N / mm ² ), and the stress concentration coefficient α = σmax / σ ₀ = 2.0.

  Although this example is an example of stress generation without "physical deformation" as described above, it was used intentionally to simplify the explanation.

  In order to set the "stress concentration coefficient α" of the "stress light emitting material" used in the "stress light emitting material layer" of the present invention to 2 or more, the "stress light emitting material" having an outer shape of "layer" It is obtained by providing a "dent" or "notch" having a depth of 1/10 to 1/5 of the thickness of the "stress light emitting material layer".

  The shape of this "dent" is, for example, a shape with a shallow bottom. For example, [(aperture width / depth) ratio] is 1/20 to 1/10 or a "bottom with a deep shape." If the ratio of [(opening width / depth)] is 1/5 to 1/1, "stress concentration" occurs around the "bottom" of this "dent", and the "stress concentration factor α" "Is 2 or more.

  Similarly, the value of the “stress concentration coefficient α” can be adjusted by providing “steps”, “concave and convex” and “rapid change in material composition”.

  The "stress light emitting material" used in the "stress light emitting material layer" of the present invention has an increase in emission intensity substantially proportional to the size of the generated "stress", so that the "stress concentration factor" As the α ′ is larger, the emission intensity is increased, and the visibility can be improved.

  The “stress concentration factor α” is preferably as large as possible, and is set to 2 or more. Furthermore, by setting the area to 10 or more, more preferably to 100 or more, the light emission intensity of the portion can be made more easily visible as "high luminance".

However, as the “stress concentration coefficient α” is larger, the “discontinuity” of the “shape” of the “stress light emitting material” becomes so-called “rapid” and causes the “stress light emitting material” to emit light. It is inappropriate for repeating "deformation", because it is easily "broken" and no longer "luminesce". (This means that "at least 100 stable light emission" is required to ensure the reliability of authenticity determination, but that reliability can not be ensured.)
Further, in the present invention, the “stress concentration factor α” in the description of “the shape of the stress light emitting material is a shape having a portion where the stress concentration factor α is 2 or more with respect to a predetermined external load”. In this case, the “stress concentration coefficient α” in the “stress light emitting material” itself is used as a numerical value attributable to the “shape” of the “stress light emitting material”.

    Moreover, in the "stress light emitting material layer" of the present invention, "made by dispersing fine particles having a stress light emitting material as a composition in a predetermined transparent resin" means the following.

That is, “a stress-stimulated luminescent material (comprised of a plurality of stress-stimulated luminescent materials, including“ a composite of stress-stimulated luminescent materials ”)” is 0.1 μm to 50 μm, preferably 5.0 μm to 20 μm in maximum diameter Prepared as "fine particles" or as "fine particles" with an average particle diameter D ₅₀ of 0.05 μm to 20 μm, preferably 0.5 μm to 10 μm, which are thermoplastic resin and / or thermosetting Select the "resin" which has the "transmission rate" to be described below from the functional resin and set it as the "transparent resin". In the "transparent resin", secondary aggregation of the "fine particles" is suppressed. Mean that “fine particles” of “stress light emitting material” are “included” in “transparent resin”, that is, “stress light emitting material layer” is mixed “mixed”. .

  In particular, the "fine particles" of the "stress light emitting material" physically crush the "flat plate of the stress light emitting material" and the "mass of the stress light emitting material" to form "fine particles" (this is "fine-ization") ), During the pulverization, for example, using an impact crusher to control the “fine particles” to have a relatively irregular shape, while suppressing the collision between the pulverized particles, A "classifier" produces "particulates" having the desired shape of the desired particle size.

  Furthermore, a hydroxide containing “predetermined composition for“ stress light emitting material ”before firing” (the “stress light emitting material” as a target according to a predetermined “firing” procedure, containing a predetermined ratio of each predetermined element) Raw materials such as hydrates, oxides, complex oxides, nitrates, hydrochlorides, carbonates, acetates, sulfates, etc. and mixtures thereof are also referred to as “precursors”. It can also be added separately by means etc. The mixture, further, the powder mixture or the powder mixture is directly "baked". Easy-to-use resin (so-called resin for producing "ceramics". The component of the resin becomes carbon dioxide gas and water by firing, and it burns out almost completely. Relatively few And the individual “stress light emitting materials before firing” are separated from each other by the “independently dispersed as individual particles” (by this resin). Meaning "state", and by performing predetermined baking, "stress light emitting material" is baked as it is "in the state of being dispersed independently as individual particles" and sintered, also after baking It is possible to make it possible to make the individual shapes of s more complex, and thus to easily realize a large “shape” of the stress concentration coefficient α, which is preferable.

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

  Of course, in order to obtain the desired "shape" in order to obtain a large "shape" of the stress concentration factor α, "the mold (made of metal or ceramic)" having the desired "shape" as its internal shape In addition, a method of filling the above “composition for“ stress light emitting material ”before firing” (or filling at the same time as molding with the molding die) and adopting the method for taking out from the molding die after firing is also adopted. Can.

  The more irregular the “shape” of this “fine particle”, and the rougher the surface of the “fine particle”, the wider the “site” where “stress concentration coefficient α ≧ 2” In addition to having, it will have a form in which α is very large (αα500).

  Here, the "transparent resin" is a "resin having a high visible light transmittance", and specifically, the transmittance of sodium atom at D line (590 nm) is 50% or more, preferably 80%. % Or more.

  However, in the “stress light emitting material layer” and the “predetermined base material” of the present invention, the “stress light emitting material” constituting the “stress light emitting material layer” emits “light” with respect to “light” of a predetermined wavelength. "Transparency" is sufficient, for example, to ensure "transparency" in a wavelength range of. +-. 5% or even at least. +-. 1% with respect to "predetermined wavelength" (in the "wavelength range" It means that the transmissivity is 50% or more, preferably 80% or more.) In the other wavelength range, the transmissivity may be less than 50% or less, “emission” The unexpectedness of the time can be enhanced, which is preferable.

  For example, in “ink color (observed as black)” created by three-color mixing of R (red color), G (green color) and B (blue color), ± 1% wavelength range of “predetermined wavelength” described above Only by adjusting the absorption wavelength distribution (absorption wavelength curve) of each color to ensure a transmittance of 50% or more (the absorption wavelength area of each color is not overlapped without gaps, but the absorption wavelength area of each color is low (Don't let parts overlap, let's leave it daringly.) From the appearance of "film" that is considered as "black", light of a given wavelength by external force load, so to speak, "that's" black " It is possible to realize the phenomenon of "glowing out" from the film.

  Furthermore, a region including the “stress light emitting material” (a “stress light emitting material layer” of the “thread” is partially provided, or a portion having a high density of the “stress light emitting material” in the “stress light emitting material layer” Or “combination areas” of those “areas” and those “composite areas” of them, which are combined patterns of a plurality of “stress light emitting material layers” emitting light of different emission wavelengths. The "predetermined pattern" shape, for example, a character, a figure or symbol of a predetermined size, in particular, a "shape" representing some "message (such as a character of" authentic ") for authenticity determination." It is provided in a predetermined size, and the "predetermined pattern" is made visible by causing the "stress light emitting material" to emit light.

  In the present specification, "parts" indicating a composition is on a mass basis.

(Major applications)
In the first place, the "paper", "paper board" (hereinafter collectively referred to simply as "paper") and the "paper" in which the "anti-counterfeit paper" of the present invention is used are used. The "paper" as the name including "use" includes the following, and the main applications of the "anti-counterfeit paper" of the present invention are also "paper", "paperboard", and "paper". Is used in the same field as that used.

  "Paper", "paperboard" and "paper" are generally printing paper, information paper, packaging paper, sanitary paper, hybrid paper, cardboard base paper, or paperboard for paperboard, depending on the purpose of use. It is roughly divided into others.

As a further subdivision,
High quality paper, medium quality paper, color high quality paper, art paper, coated paper, matte coated paper, mirror coated paper, cast coated paper, cast coated paper, art post, processed paper, advanced printing paper, intermediate printing paper, low grade printing paper, fine coating Paper, light-weight coated paper (The above, printing paper. All commonly used classification names are listed. Therefore, classification names where “target objects” overlap are also described. The same applies to the following.), Kent paper, Printer paper such as new paper, carbonless paper, imitation paper, glass paper, recycled paper, white paperboard, colored paperboard, inkjet paper, POD paper, sublimation heat transfer paper, foam paper, carbonless paper, thermal paper, OCR paper, OMR Paper, magnetic recording paper etc. (above, information paper.), Unbleached kraft paper, semi-bleached kraft paper, coated bleached kraft paper, recyclable moisture-proof paper etc. (above, packaging paper. Etc.), various embossing on the surface added , Paper mixed with other materials, Paper with texture, Pearl-treated paper, Liner, Core base paper etc. (above, corrugated cardboard). With no pigment on the surface, wood (raw material) Uncoated paper, high-quality paper, medium-grade paper with a mixture of chemically treated chemical pulp and mechanical pulp that has been loosened with wood (raw material) For paper made from wood pulp such as coated paper, etc., which has a gloss through between them, and made to a large amount by the machine, コ ウ (Kozo), Mitaka (Mitsumata), 雁 (Gampi), Hemp, 檀Japanese paper made from Mayumi etc.

  More special one is resin impregnated paper.

  Among them, "high-quality paper" is manufactured only with chemical pulp, and includes advanced printing paper (printing paper A, writing paper, drawing paper), thin printing paper, special printing paper (color high-quality paper, etc.) "Chemical pulp" 100% of "printing paper" and "information paper", and "medium-grade paper" in a narrow sense if it only refers to printing paper B and, in a broad sense, middle-grade paper Also, it includes lower grade paper and newsprint, and at least "mechanical pulp" is included in "chemical pulp". For this "medium grade paper", there are semi high quality paper, printing paper B, printing paper C, gravure paper, etc., and for "lower grade paper", printing paper D (over color, upside, upside down, rough up, etc.), It contains printing paper (100% recycled pulp) and the like.

In addition, specific “applications” and “fields” in which “paper”, “board”, and “paper” are used are
Debt, certificate of deposit, certificate of receipt, bill, check, passbook, magnetic slip, transfer card, gift certificate, coupon, voucher, gift certificate, movie ticket, membership certificate, securities such as beer vouchers, securities as evidence securities, etc. In the field, catalogs, flyers, brochures, leaflets, posters, POPs, greeting cards, postcards, stickers, invitations, invitations, reports, proceedings, directories, name cards, business cards, certificates of participation, manuals, manuals, companies History, PR magazine, company newsletter, rate sheet, transfer form, order form, production instruction, delivery note, various slips such as sales slips, call charges statement, payroll statement, various statements such as statement, various items Bills, business forms, forms to be postcards and sealed letters, notebooks, envelopes, letter paper, diaries, diaries, postcards, crimped postcards, stamps, direct mail, secret Mail, wrapping paper, soft packaging, plastic containers, paper containers, commercial fields such as toys, or novels, picture books, encyclopedias, other books, newspapers, magazines, trade papers, maps, phone books, textbooks, reference books, music sheets, etc. There is a publishing field of

  In particular, "paper" used in the field of forgery prevention, which, in particular, may damage the holder or issuing company of securities if the securities or the like is forged and used, driver's license, etc. , ID cards such as employee ID cards, membership cards etc, admission tickets for examinations, passports, etc., banknotes, gift certificates, gift cards, point cards, stock cards, lottery tickets, betting tickets, bank passbooks, tickets, passage tickets, airline tickets, etc. There are admission tickets for special events, game tickets, and cash vouchers for transportation.

  All of these are information recording bodies holding information having economic or social value, and it is desirable that they have a function capable of identifying the authenticity of the recording body itself for the purpose of preventing damage caused by forgery. .

  In addition, even if it is other than these information recording materials, the high-end products, such as high-end watches, high-end leather products, precious metal products, or jewelry, etc. Or, those high-priced goods storage boxes or cases themselves can be forged. Furthermore, even if it is a mass-produced product, it is apt to be forged, for example, a product that is certified by being attached to an audio product, an electric appliance or the like, or a tag that is suspended from them.

  In addition, those that "provide" that they are copyrighted music software, video software, computer software, game software, etc. are recorded, or those cases themselves are also subject to forgery. It can be In addition, it is desirable that a toner for paper, a product such as paper, etc. which is replaced with genuine materials be provided with a function capable of identifying the authenticity of the product for the purpose of preventing damage caused by forgery.

(Background art)
First of all, “light emission” means to emit light, and when it is classified in the “phenomenon” aspect, it burns an object, flows a large amount of current to a conductive material with a large electric resistance, and also performs nuclear fusion Heat the material or material into a high temperature state, cause the atoms or molecules that make up the material or material to vibrate at high speed, and emit light corresponding to that temperature. Also known as body radiation (light from flames, incandescent lamps, stars, etc.) ”,“ luminescent (luminescent) light that emits light when a quantum system (such as electrons) in an excited state transitions to a lower excited or ground state. ), Electromagnetic radiation that occurs when a charged particle is decelerated sharply or bent in an electric field, “breming radiation” of a charged particle beam, the velocity of the charged particle is the speed of light in the material Transfer through the material faster than There are "Cherenkov radiation" etc. which occur when carrying.

  And this "breming radiation" includes synchrotron radiation, and refers to the fact that electrons are stopped by atoms in a narrow sense. The principle of artificially generating X-rays in an X-ray tube is bremsstrahlung, and the collision of high-speed electrons with the target also generates bremsstrahlung in the target. That is, when the beta ray (electron beam) is shielded by lead (target) or the like, the beta ray itself stops at lead, but at the same time, X-ray by bremsstrahlung also occurs.

  In addition, “luminescence” is excited when a substance receives energy by irradiation of electromagnetic waves, application of an electric field, collision of electrons, etc. and the ratio of the distribution number of high energy states to the distribution number of low energy states is a thermal equilibrium state It is a light emission phenomenon due to spontaneous emission that occurs when it is made larger compared to (in contrast to this, the phenomenon that a substance in thermal equilibrium emits light is black body radiation), and the distribution of low energy states In an inverted distribution where the ratio of the number of distributions of high energy states to the number is greater than one, amplification of light by stimulated emission occurs.

  And what stops light emission as soon as the supply of energy from the excitation source is stopped is called "fluorescence", and what has afterglow is called "phosphorescence", but both may be collectively called "fluorescence". Chemically, the emission associated with the deactivation from the excitation singlet (transition to the ground state) is "fluorescence", and the emission associated with the deactivation from the excitation triplet is "phosphorescence". The transition from this excitation triplet to the ground state (ground singlet) is a forbidden transition because the spin multiplicity is different, so that the state of the excitation triplet has a long lifetime, and the excitation triplet is The energy level is often lower than the excitation singlet, so the wavelength of "phosphorescence" tends to be longer than "fluorescence".

  “Luminescence” refers to photoluminescence (PL), which is emission by excitation by light irradiation, and “emission by excitation by electron beam irradiation,” depending on how “electrons are excited from the ground state to the excited state”. Certain cathodoluminescence (CL), electroluminescence (EL) that is emission by voltage excitation, sonoluminescence (SL) that is emission by acoustic energy excitation, thermoluminescence that is emission by thermal excitation Triboluminescence, which is light emission by excitation by mechanical energy such as friction force or impact, Chemiluminescence, which is light emission by excitation by chemical reaction, Solvatoluminescence, which is light emission excited by solvent, by piezoelectric effect It is classified into, for example, piezo luminescence which is light emission upon excitation.

  Further, the chemical reaction includes, for example, bioluminescence which emits light by a chemical reaction such as oxidation of a luminescent substance using an enzyme.

  In the above-mentioned "heat radiation", it is special and unusual for "light emission", such as making the object or material in a high temperature state or vibrating the atoms or molecules constituting the object or material at high speed. In the “luminescence,” excitation by light irradiation, excitation by electron beam irradiation, excitation by voltage, excitation by acoustic energy are also required in “luminescence”, respectively. In order to "excite", such as excitation by mechanical energy, excitation by chemical reaction, excitation by solvent, excitation by piezoelectric effect, etc., some process is required, and this process also has sufficient "emission" It was necessary to put a corresponding excessive load on it.

(Prior art)
With respect to these "light emission" mechanisms, the "material" itself, that is, the "composition of the material" or the "structure of the material" has the "potential light emission structure" and only relatively small stress is loaded. Thus, novel "stress light emitting materials" having a novel "light emitting" mechanism that can cause the "material" to emit light have been discovered.

  This new "stress light emitting material" is a new "light emitting material" developed by Xu et al. Of the National Institute of Advanced Industrial Science and Technology (Independent Administrative Corporation) and has a relatively small "elastic deformation region" of "dynamic energy" And “a material exhibiting stress luminescence”.

  First of all, “stress light emission” uses “mechanical force” as an excitation source for “light emission”, and “the light is emitted from the material by“ mechanical force (dynamic energy) applied from the outside ”. It is defined as "the phenomenon to be done".

  The conventional "stress light emission" phenomenon can be divided into "destructive light emission" and "deformed light emission". Of these, "destructive light emission" means "light" by breaking or crushing the material. It is a phenomenon that is released, and is a phenomenon that has been observed when "calcite" is broken. On the other hand, “deformed light emission” is one that does not involve such “breaking” and appears when so-called “stress-strain curve” appears when an external load is gradually applied to a certain material. "Is shown as" straight line "(meaning that" stress "is proportional to" strain ".) The light emission in the" elastic deformation region "and this" straight line "cease at the" yield point of the material "(the Meaning that the proportional relationship ends.) It is divided into light emission in the “plastic deformation area” which is gradually entering the stage of “structural failure” inside the material.

  The "destructive light emission" phenomenon has been observed in a large number of material systems, and about half of the inorganic substances are said to have "destructive light emission" properties.

  On the other hand, with regard to "deformed luminescence", although there have been several reports of radiation-irradiated alkali halides and certain polymers, this has been found to be weak luminescence in the "plastic deformation region". doing.

  Unlike “stress light emitting materials” developed by Xu et al. Of the National Institute of Advanced Industrial Science and Technology (Independent Administrative Agency), among these “deformed light emission”, “stress light emission in the“ elastically deformed area ” "Is a material showing". "

  All of these are materials (ceramics) in which an element serving as a light emission center is added to an inorganic crystal skeleton whose structure is highly controlled (ultraceramics). By selecting the type of the inorganic material and the light emission center, Materials have been obtained which emit at various wavelengths in the infrared.

As typical ones, strontium aluminate added with europium (SrAl ₂ O ₄ : Eu: green light emission), zinc sulfide added as manganese as a light emission center (ZnS: Mn, yellow orange light emission), etc. are shown as light emission centers is there. (See Patent Document 1)
And, the stress light emitting material of the present invention is a single unit of the structure (the structure is all composed of the "stress light emitting material"), or a laminate in which the structure is simply stacked on another structure etc. It has been disclosed that external stress is directly applied to them to make the structure itself or the laminate simply emit light. (See Patent Document 2)
However, according to many technical disclosures made thereafter including these technical disclosures, this stress-emitting structure is produced by the “prescription”, or this stress-emitting structure alone or a laminate is produced. It has become less difficult to make something that produces the same effect.

  In addition, "paper" for the purpose of forgery prevention, that is, as "paper for preventing forgery", its authenticity is determined by ultraviolet irradiation, "fluorescent ink" printing paper, securities paper in which a hologram thread is embedded, etc. Although many "papers" that can confirm the nature are also disclosed, such "anti-counterfeit paper" needs a "light source for irradiating light" such as an "ultraviolet lamp" to determine its authenticity. For example, in order to confirm the authenticity of a passport, an immigration examiner makes a "judgment" under the table for the examination, etc., or ensures that the authenticity is in a place where illumination light does not reach or "darkness". It has the drawback of being difficult to judge.

  The applicant has disclosed a "hologram thread paper" which is extremely excellent in anti-counterfeit properties including a liquid crystal layer in addition to the hologram layer and the fluorescent layer, but this "paper" is also the same as above. In addition, it is necessary to use an illumination light source or a special polarizing filter to determine authenticity. (See Patent Document 3)

Japanese Patent Application Laid-Open No. 2007-055144 Unexamined-Japanese-Patent No. 2003-253261 JP 2001-21297 A

  Therefore, the present invention has been made to solve such problems. Its purpose is to include "stress light emitting material" in "thread" in a form that can not be recognized at all from the appearance, while letting it be recognized that the appearance is merely using "thread paper". At the same time, the "paper pulp fiber" is deformed by a predetermined external load applied to the "thread paper", and at the same time a "deformation stress" is generated at a predetermined portion of the "stress light emitting material". It is possible to easily determine the authenticity of the “thread paper” without any special illumination light, because light of a predetermined wavelength having an intensity according to the deformation stress is emitted from the part of and becomes visible. To provide "Anti-counterfeit paper".

  Moreover, this "stress light emitting material" is made into a specific shape, the "light emission" is increased, moreover, the "stress light emitting material" is arranged in the "predetermined pattern" shape, and the "light emission" of the "stress light emitting material" The “pattern of light” according to the present invention can be visually recognized, and an “anti-counterfeit paper” is provided that has improved design and anti-counterfeit properties.

In order to solve the above problems,
The first aspect of the forgery prevention paper of the present invention is
The anti-counterfeit paper comprising at least a paper pulp fiber and a thread, wherein the thread is in the form of a strip in which a stress light emitting material layer containing a stress light emitting material is provided on a predetermined substrate. The thread is milled in a process of making the anti-counterfeit sheet, and a predetermined external load on the anti-counterfeit sheet causes the thread to deform in the anti-counterfeit sheet while the thread is deformed. The light emitting material layer is deformed to generate a deformation stress corresponding to the deformation of the thread at a predetermined portion of the stress light emitting material layer, and has a light emission intensity corresponding to the deformation stress from the predetermined portion Light of a predetermined wavelength is emitted, and the light of the predetermined wavelength is visible.

According to the anti-counterfeit sheet of the first aspect,
The anti-counterfeit paper comprising at least a paper pulp fiber and a thread, wherein the thread is in the form of a strip in which a stress light emitting material layer containing a stress light emitting material is provided on a predetermined substrate. The thread is milled in a process of making the anti-counterfeit sheet, and a predetermined external load on the anti-counterfeit sheet causes the thread to deform in the anti-counterfeit sheet while the thread is deformed. The light emitting material layer is deformed to generate a deformation stress corresponding to the deformation of the thread at a predetermined portion of the stress light emitting material layer, and has a light emission intensity corresponding to the deformation stress from the predetermined portion It is possible to provide a forgery prevention sheet characterized in that light of a predetermined wavelength is emitted and light of the predetermined wavelength can be visually recognized, and the design property and the forgery prevention property are excellent. It is possible to provide a granulated preventing paper.

The second aspect of the forgery prevention paper of the present invention is
In the anti-counterfeit sheet according to the first aspect, the rigidity of the thread is 1/10 to 50/10 of the rigidity of the anti-counterfeit sheet.

According to the forgery prevention paper of the second aspect,
In the anti-counterfeit sheet according to the first aspect, it is possible to provide the anti-counterfeit sheet characterized in that the rigidity of the thread is 1/10 to 50/10 of the rigidity of the anti-counterfeit sheet. It is possible to provide a forgery-preventing paper sheet that is excellent in handling suitability, various processing suitability, and printing suitability.

The third aspect of the forgery prevention paper of the present invention is
In the anti-counterfeit paper of the first aspect or the second aspect, the stress light emitting material is subjected to a predetermined surface treatment for improving the water resistance of the stress light emitting material. It is said that.

According to the forgery prevention paper of the third aspect,
In the anti-counterfeit paper of the first aspect or the second aspect, the stress light emitting material is subjected to a predetermined surface treatment for improving the water resistance of the stress light emitting material. It is possible to provide a forgery-preventing paper, and to provide a forgery-preventing paper that is excellent in "papermaking suitability", has improved stability of light emission intensity, and is also excellent in forgery prevention suitability.

The fourth aspect of the forgery prevention paper of the present invention is
In the forgery prevention paper according to any one of the first to third aspects, the composition of the stress light emitting material layer is composed of the stress light emitting material, and the surface of the stress light emitting material layer is the predetermined portion. A notch and / or a recess having a predetermined shape, and the stress concentration coefficient α at the predetermined portion is 2 or more.

According to the anti-counterfeit sheet of the fourth aspect,
In the forgery prevention paper according to any one of the first to third aspects, the composition of the stress light emitting material layer is composed of the stress light emitting material, and the surface of the stress light emitting material layer is the predetermined portion. A forgery-preventing sheet can be provided, characterized in that it has notches and / or recesses of a predetermined shape, and the stress concentration coefficient α at the predetermined part is 2 or more. In addition, it is possible to provide a forgery-preventing sheet which is particularly excellent in its design and anti-counterfeit properties.

The fifth aspect of the forgery prevention paper of the present invention is
In the anti-counterfeit paper according to any one of the first to third aspects,
The stress light emitting material layer is formed by dispersing fine particles containing the stress light emitting material in a predetermined transparent resin, and the shape of the fine particles of the stress light emitting material has a stress concentration coefficient α of 2 or more. It is a shape having a portion where the portion is a predetermined portion of the stress light emitting material layer.

According to the forgery prevention paper of the fifth aspect,
In the anti-counterfeit paper according to any one of the first to third aspects,
The stress light emitting material layer is formed by dispersing fine particles containing the stress light emitting material in a predetermined transparent resin, and the shape of the fine particles of the stress light emitting material has a stress concentration coefficient α of 2 or more. A forgery-preventing sheet characterized in that the site is a predetermined site of the stress light-emitting material layer, the emission intensity is increased, and the designability, and It is possible to provide anti-counterfeit paper which is particularly excellent in anti-counterfeit properties.

A sixth aspect of the forgery prevention paper of the present invention is
In the forgery prevention paper according to any one of the first to fifth aspects, the light of the predetermined wavelength can be visually recognized as displaying a predetermined pattern.

According to the forgery prevention paper of the sixth aspect,
The anti-counterfeit sheet according to any one of the first to fifth aspects, wherein the light of the predetermined wavelength can be viewed as displaying a predetermined pattern. It is possible to provide a forgery-preventing sheet which is excellent in designability and forgery-preventing property.

  The "anti-counterfeit paper" of the present invention is a "paper" process of the "paper", the "thread" consisting of the "predetermined base material and stress light emitting material layer", together with the "paper pulp fiber", "paper" The pulp fiber and the stress light emitting material layer are in contact with each other, the external force load on the paper is transmitted to the paper pulp fiber in the inside, and the paper pulp fiber is pulled mutually In the stage of bending or "deforming", the "deformation" received by the "paper pulp fiber" is "thread" in contact with the "paper pulp fiber", and further, the stress emission of the "thread" Acting as "deformation" pressure on the material layer ", as a result," stress light emitting material constituting the stress light emitting material layer "is subjected to" deformation "pressure, and" deformation stress "inside the" stress light emitting material " Occurs, and the “deformation stress” Having a strength (roughly proportional.), Light of a predetermined wavelength has a structure that emits light.

  1 to 3 show this state as a "schematic diagram".

  In FIG. 1 to FIG. 3, "paper part made of paper pulp fibers (hereinafter simply referred to as" paper ")" is referred to as "Y1" and "thread (layer structure is omitted and displayed as one piece) Is displayed as “SL0”, and the “anti-counterfeit sheet” of the present invention is indicated as “G1”.

  FIG. 2 is a cross-sectional view of the “x-x” cross section of the anti-counterfeit sheet G1 in FIG. 1, and FIG. 3 is a “y-y” cross-sectional view of the anti-counterfeit sheet G1 in FIG.

  The “thread embedded portion G2” and the “thread exposed portion G3” in FIG. 1 reflect the change in the depth direction of the “thread SL0” in FIG. 3, and in FIG. 3 the “thread SL0” The portion appearing on the surface of the “paper Y1” is the “exposed portion G2 of the thread” in FIG. 1, and the portion in which the “thread SL0” is embedded in the “paper Y1” in FIG. It becomes "embedded part G1 of thread" in No.1.

  In the forgery prevention paper G1 of the present invention, the width (the length in the direction orthogonal to the direction in which the thread SL0 is embedded) of the “thread SL0 (same as below SL1 to SL3)” is the same as that of the forgery prevention paper G1. The width (the length of the sheet Y1 in the direction orthogonal to the embedding direction of the thread SL0) is 1/500 to 1/4, and the thickness of the thread SL0 is 1/1 of the thickness of the forgery prevention sheet G1. It is 10 to 1/2.

  If the width is less than 1/500 or the thickness is less than 1/10, the visibility of light emission of the thread SL0 is lowered, and "thread processing" is disturbed. In addition, if this width exceeds 1⁄4 or this thickness exceeds 1⁄4, not only “threading” is difficult but also it deviates from the concept of “thread”.

  Furthermore, as shown in FIGS. 5-8, the specific form of the thread SL0 is “a two-layer structure” of “stress light emitting material layers A0 to A3” and a base material B0, and the “stress light emitting material layer A0 to A3 are subjected to deformation stress due to deformation of the thread SL0 due to external load applied to the forgery prevention paper G1, and stress is applied to the "predetermined portion (stress concentration portion)" of the "stress light emitting material layer A0 to A3". Concentrated, the "predetermined part" emits light at "predetermined wavelength".

Since “thread SL0” in FIG. 5 is a so-called “rectangular solid”, “external force load” is such that “forgery prevention paper G1” is bent or twisted with respect to “forgery prevention paper G1”. By addition, the "paper pulp fibers" included in the "paper Y1" are deformed, and the "cuboid" in contact with the "paper pulp fibers" is deformed according to the "deformation" thereof. And, under the “deformation” of bending or twisting the “rectangle”, the stress concentrates on the part in contact with the “paper-pulp fiber”, and becomes “predetermined part”. , Emits light. (The state under deformation and the light emission state are not shown.)
In addition, depending on the “external force load”, stress concentration is likely to occur at the center line position or the diagonal position of the “cuboid”, which can be a “predetermined portion” and emits light (same as above).

  Further, “threads SL1 to SL3” in FIGS. 6 to 8 are “a thin portion in the“ stress light emitting material layer A1 ”(a predetermined portion S1; see FIG. 6)” and “a stress”. Portion of the apex angle of the notch K1 in the light emitting material layer A2 (predetermined portion S1; see FIG. 7) and “on the surface of the fine particle P1 in the“ stress light emitting material layer A3 ” The deformation stress is concentrated on the bottom portion (the predetermined portion S1; see FIG. 8) of the concave portion having the concavo-convex shape, and light emission with higher emission intensity than other portions is exhibited.

  These “predetermined portions S1” are “stress concentration portions”, and “stress concentration coefficient α” there is 2 or more, 10 or more, particularly 100 or more.

  That is, the "stress" generated in the "predetermined portion S1 (stress concentration portion)" of the "stress light emitting material layers A0 to A3" or the "fine particles P1" is increased.

  Then, the observer visually recognizes the emitted light of the predetermined wavelength.

  The "papermaking process" for "papermaking" that "papermaking" the "anti-counterfeit paper" of the present invention is typically, as shown in FIG. 4, "pulping process", "pulp bleaching process", "pulp selection and dewatering process" "Raw material adjustment step 1: Melting and beating", "Raw material adjusting step 2: Addition of chemicals such as sizing agents", "Paper making step 1: Wiring & water squeezing", "Paper making step 2: Drying & press treatment", and "Processing and finishing process" mainly includes "thread" in "paper making process 1: wiring & squeezing water" during this process.

  Of course, "thread" may be inserted in other processes, and "layer of paper pulp fiber" (also referred to as "wet paper" in this process. One layer before drying is formed. Means "state") and "thread" on top of that "layer" to form a two-layer configuration of "'thread' / 'paper and pulp fiber'" (to overlap the two layers before drying, In the boundary area where two materials are mixed, it may be in a more preferable "contact" state.

  In addition, as "paper pulp fiber" / "thread" / "paper pulp fiber" and "" paper pulp fiber "/" thread "/" paper pulp fiber "/" thread "/" paper pulp fiber " Of course, multiple "threads" may be inserted in parallel.

  At this time, by arranging the “stress light emitting material layer” so as to face the outermost side of the “anti-counterfeit paper”, the “light emission” can be easily visually recognized, and the reliability of the authenticity determination can be enhanced.

  Furthermore, the “stress light emitting material layer” may be disposed to face the inside of the “anti-counterfeit paper”, or the arrangement may be used to “shield the emitted light as a“ predetermined base material ”constituting the“ thread ”. "For example, by using a" visible light opaque material ", light emitted in the" stress light emitting material layer "can be observed only from the back surface of the" anti-counterfeit paper ", or, further, The forgery prevention property can also be significantly enhanced by making it possible to observe only from the end of the "thread" (the end of the forgery prevention paper) which can not be observed from either side of the front or back of the forgery prevention paper ". It is suitable.

  As "paper pulp fibers" used in the present invention, "pulp fibers (" pulp "), which are plant fibers separated for use in" papermaking ", are used.

  Here, in this "paper-pulp fiber", plant-derived fibers such as regenerated cellulose fiber obtained by dissolving cellulose in a solvent and re-fiberizing it, and "corn fiber" made of "starch" of "corn" are used. Also includes synthetic fibers of

  As used in the present invention, "fiber" or "shape" represented as "fibrous" is a morphological property and is "slender", ie, "thickness" (maximum diameter or its diameter) The “length” is extremely large with respect to the “width” or “thickness” of the cross section, and the aspect ratio value (“thickness” versus “length”) is 1:50. The one with about 1: 2000 is used.

  The shape of the "paper pulp fiber" of the present invention is respectively representative of its "softwood pulp fiber (" N material ")" and "hardwood pulp fiber (referred to as LKBP or" L material ")" respectively. , “Thickness” is about 30 to 50 μm, “Length” is 1.0 to 6.0 mm, or “Thickness” is about 10 to 30 μm, and “Length” is 0.5 to 3.0 mm. have.

  The "anti-counterfeit paper" of the present invention is a "paper" including a "thread" composed of a "stress light emitting material layer" and a "predetermined base material" in addition to the "paper pulp fiber". A paper pulp fiber and its “stress light emitting material layer” are in contact with each other near the surface of the “paper”, and the “paper” is curved with a predetermined external load, for example, “finger force”. When the "paper" is pressed against a jig having an appropriate curved surface with the force of a hand, "paper and pulp fibers" in the "paper" produce "deformation" due to the external force load.

  The "deformation" of the "paper pulp fiber" at this time can be expressed as follows.

  That is, the thickness of "paper" is compared with the thickness of a common high quality paper, "100 μm thickness", and this "paper" is a section (length is arbitrary) of 30 mm (30,000 μm) In the "section" of this "" 100 μm thickness × 30,000 μm length (image of the cross section of "paper" ")" is cut into ".)" A “fiber” with a length of several mm (several thousands of μm) and a length of several micrometers (several thousands of μm) is in a state where the “fiber” is stretched, and the “fibers” are It is expressed that it is stretched and in contact at a plurality of points "(this state is expressed as" a state in which a plurality of <fibers> are entangled ", and" paper and pulp fibers " "Hybrid bond" is linked to each other by And Te.) "Is assumed.

  Then, with respect to this “complex”, “predetermined external force load”, for example, when the “complex” is “curved” by pinching both ends of the “complex” with a finger, the “complex” The individual "fibers" trapped in the "will be bent" in "in the direction of their" curvature "depending on their" curvature ".

Moreover, the “bonds (hydrogen bonds)” at the “contacts” between the “paper and pulp fibers” are very weak compared to general chemical bonding of polymers, adhesion between resins, etc., as described above The "predetermined external force load (ie, bending)" easily breaks the bond, and their "paper-pulp fibers" are pulled not only to "do", but also to both ends of the "section" At the same time, it causes "physical horizontal movement". (Meaning that it involves macroscopic movement)
And "paper and pulp fibers" again absorb "moisture" in the air, that is, moisture, and "bond" again at the newly created "another contact point" after mutual bonds are broken. It will be.

  As described above, the very elongated "fibers (paper and pulp fibers)" entrapped in the very thin and spread "composite (paper)" are those when the "composite" is "curved". According to the "curvature", "horizontal movement" occurs simultaneously with "dwelling".

  In particular, in the case of "paper pulp fibers" included in such "paper", this "deformation" is not limited to a simple "curve", that is, "in a jig having an appropriate curved surface" "Deformation" (in other words, soaking the surface of the "paper" against the surface of the jig (meaning sliding on the surface)) while pressing the paper with hand power (so far "curved"). In addition to the deformation stress associated with the “curvature”, the “displacement stress” can also be generated inside the “paper” by providing the “displacement deformation”.

  Then, when such a "slip stress" occurs, the "physical horizontal movement" described above is promoted, and the "paper" remains the "curved" shape, which is again referred to as the original. In order to return to the "flat state", it is necessary again to perform the "deformation process with offset stress" in the "same and reverse direction".

  The "stress light emitting material layer" of the "thread" contained in the "anti-counterfeit paper" of the present invention is a "stress light emitting material layer" made of a "stress light emitting material", and the entire "stress light emitting material layer" A “layer” that has either a “stress light emitting material” or a structure that partially includes a “stress light emitting material” in the “stress light emitting material layer” ".

  And in any case, in the "shape" of such "stress light emitting material", the "site" (this is the "predetermined site") where the "stress concentration coefficient α" is 2 or more. Can contain various “stresses” such as “tensile stress”, “shear stress”, and / or “displacement stress” for the “stress light emitting material layer” The “external force load” on the stress light emitting material layer causes “physical deformation” in the “stress light emitting material layer” (the “layer” is “bent”, “flexure”, and / or “twisting” Etc.) and, along with the “deformation” of the “stress light emitting material layer”, the “stress light emitting material” is also “deformed” And “deformation stress” is generated inside the “stress light emitting material”. The "deformation stress" is concentrated on the "site" of the "stress light emitting material" (the "deformation stress" of the "site" means that it is significantly larger than the deformation stress of the region around it), and the concentration Due to the “deformation stress”, “light of a predetermined wavelength having an emission intensity according to the deformation stress” is “luminesced” from that “site” (“emission” is also generated around the “site”, It becomes significantly smaller than the “emission” generated in the “site”.) The viewer can view the “light of a predetermined wavelength”.

  That is, the "shape" of the "stress light emitting material" constituting the "stress light emitting material layer" or included in the "stress light emitting material layer" is the "stress concentration" in the "predetermined portion" of the "stress light emitting material" It has a "shape" having the "site" where the coefficient α "is 2 or more.

  Further, the “shape” of such “stress light emitting material layer” is, for example, the “stress light emitting material layer” having a “basic shape” of a rectangular solid of 30 mm wide × 100 mm long × 50 μm thick When, as "a predetermined part" mentioned above, "a part which becomes 1/2 or less in width" and / or "a thickness becomes 1/2 or less in a part of the" cuboid which is a basic shape " "Shape" refers to a "shape" that includes at least one or more sites.

That is, the thickness is 1⁄4 at the center of a “basic shape (a part of“ strip ”is cut out for explanation)” of width 30 mm × length 100 mm × thickness 50 μm. If "a predetermined portion S1 (the cross-sectional portion indicated by hatching in Fig. 6)" is provided, it has a shape like "stress light emitting material layer A1" of "thread SL1" of Fig. 6. (See Figure 6)
Assuming that this “stress light emitting material layer A1” is a rectangular solid of width 30 mm × length 100 mm × thickness 50 μm, “cross section” is obtained by cutting the “rectangle” into a plane group parallel to its “end portion (end surface)” Group has a “shape” obtained by deforming the “rectangle” so as to form a continuously changing rectangle between “rectangles of 50 μm × 30 mm horizontal” to “rectangles 12.5 μm × horizontal 30 mm” Furthermore, at the center of the length direction (100 mm), a "predetermined portion S1" (described above) having a thickness of 12.5 μm (having a thickness of 1/4 of a thickness of 50 μm of the "basic shape") It has a "shape" with a "portion" that forms a cross-section of "a rectangle of 50 μm × 30 mm wide" parallel to "the end (end face)", and this "portion" It is "predetermined part S1" which is 2.0 ".

  The “stress light emitting material layer A1” is superimposed on the “predetermined substrate B0” (“the stress light emitting material layer A1” is formed on the “predetermined substrate B0” using various methods described below) Or two layers are pressure-bonded or laminated using an appropriate adhesive, etc. The same applies hereinafter), “thread SL1”.

  Of course, the "predetermined portion" may not be located at the center of the "basic shape" in the lateral direction (100 mm), or may be any position in the lateral direction (100 mm) (1/1 in the lateral direction). 3) or 1⁄4), or, more broadly, in part of the “basic shape”, “the cross-sectional area of the portion is“ the average cross-sectional area (here, When there is a portion having a "cross section" which is 1/2 or less of a rectangular area of 25 μm × 30 mm in width ", the" portion "is a" predetermined portion "of" stress concentration coefficient α 」2" Become.

  Here, the “average cross-sectional area” of a “shape” is the direction in which one predetermined stress acts in the direction in which various stresses are generated when a predetermined external load is applied to the “shape”. Of the “area” (cross-sectional area) of all “cross-sections” whose “shape” is cut off at a plane perpendicular to (in the above example, a plane group parallel to its “end (end face)”) , “Average value” in the entire “shape”.

  And such "a shape such that a cross section having a cross-sectional area of 1/2 or less of the average cross-sectional area exists" is a "shape having a portion where the stress concentration coefficient α is 2 or more", The "site" having the "cross section" is the "predetermined site of the stress light emitting material layer".

  Further, it is needless to say that the “basic shape” exemplified here is not limited to the “basic shape” as described above, but can be applied to “any shape of an object” (any shape is referred to as “original shape” Meaning that can be assumed.).

  Furthermore, as the “shape having a portion where the stress concentration coefficient α is 2 or more”, taking the above “basic shape” as an example, a hemispherical surface (a spherical surface is formed on a part of the surface of the “basic shape” Recesses having a shape such as a three-dimensional curved surface cut out in a plane or an elliptic surface (a three-dimensional curved surface cut in a flat surface with an ellipsoidal surface), a cut having a sharp “cut point” shape, or a corner "Shape" such as "shape" where there are projections, including "shape" whose surface has a predetermined uneven shape, more generally, "a cross section cut in a plane perpendicular to the direction in which stress acts in It can be said that the change of the shape has a stress concentration coefficient .alpha. Of 2 or more at that portion.

  For these “shapes”, the “shapes” are grasped as three-dimensional image data by a so-called “three-dimensional shape analysis device” or the like, and the “three-dimensional image data” of the “shapes” is By applying software (stress distribution analysis software), it can be confirmed that the “shape having a portion where the stress concentration coefficient α is at least 2 or more”.

  Of course, “a shape having a portion where the stress concentration coefficient α is 2 or more” can simulate various “shapes” by the above-mentioned “structural analysis software (stress distribution analysis software)”, for example, as described above "Shape provided with" spherical cavity "" in "Basic shape", "Basic shape" itself as "Ellipsoidal" or "Needle-like", further, "Powder-like", that is, "Fine particles" Not only "a shape with a stress concentration coefficient α of 2 or more," but also "a shape with a stress concentration coefficient α of 10 or more." Or “a shape having a stress concentration coefficient α of 100 or more” can be designed, and based on the design, a “stress light emitting material layer” including an actual “stress light emitting material” and a “stress light emitting material” itself are manufactured can do.

  And it is also possible to repeat this "design" and "preparation", the "number of" predetermined portions "in" the stress light emitting material layer "(the" number of portions existing in a unit volume in the "stress light emitting material layer" And “the concentration of stress (stress concentration coefficient α)” at each portion can be increased, which is preferable.

  Furthermore, the "stress light emitting material shape" in the "stress light emitting material layer" in the "thread" included in the "anti-counterfeit paper" of the present invention is "layer" and its "layer" The surface of the “stress light emitting material” in the above has a shape having “a notch and / or a recess having a predetermined shape” as a predetermined portion.

  The phrase "having a notch and / or recess having a predetermined shape" means at least one or more "notches" on the surface of the "layered", that is, a so-called "flat" "stress light emitting material". Or having at least one or more "recesses", and further having at least one or more "notches and depressions".

  Of course, this "plate-like" includes "the one having a change in longitudinal, lateral, and thickness", and further, "the notched portion and / or the recess having a predetermined shape" is referred to as "the flat-like". It may be provided not only on the "front surface and / or back surface" of the "stress light emitting material" but also on the "end surface" of the "flat" "layer".

  Here, the "notched portion of a predetermined shape" is a recess having a "wedge" shape.

  In the "wedge shape", one side (one rectangle) of one "triangular column" is located on the outermost surface, and the other two sides (two rectangles) and the upper and lower surfaces (two triangles) of the "triangular column" are "Layer" is a form that forms the "four faces" of the indented part inside, and is formed by the faces of the two triangles (cross section) (upper and lower faces) and three parallel sides connecting the three vertices Of which two sides are located at the opening and the other side is located at the bottom of the recess.

That is, for example, for a “basic shape” of width 30 mm × width 100 mm × thickness 50 μm,
“Notched portion K1 of a predetermined shape,” which is a recess having a wedge shape, as a predetermined portion on one surface thereof (in FIG. 7, “base” is “predetermined portion S1” When it is provided, it becomes like "stress light emitting material layer A2" of "thread SL2" of FIG. (See Figure 7.)
Here, FIG. 7 is a “schematic view”, and only six “cutouts” having the same triangular prism shape are displayed in an orderly manner, but actually, “the notched portion” is actually shown in FIG. According to the purpose of the "stress light emitting material layer" included in the "anti-counterfeit paper", the shape (three-dimensional shape), size, and orientation of the bottom ("bottom" means Not only “straight line” but also “curved” may be used, and the shape of the opening (not only “rectangle” but may be another “planar shape”), size, direction (vertical and horizontal of opening) Direction), the number of “notches”, the arrangement of “notches” (not only “orderly array” but also “random array”, and further, “arrangement for displaying a predetermined pattern as described below ) May be changed in various ways. (These are also true for "recesses".)
Then, when an "external force load" is added to the "wedge shape", that is, when the "two sides of the opening" are deformed in a direction to open, "the remaining side (one side of the bottom. This is a predetermined portion. The “stress concentration factor α” in “2)” is equal to or more than 2 equally, and at the same time, the maximum. Furthermore, the smaller the “opening angle” (corresponding to the apex angle of the triangle) at the “one side of the bottom”, the smaller the 10 degrees to 90 degrees, and the “stress concentration factor α” increases. If this "opening angle" is less than 10 degrees, the "stress concentration coefficient α" can be extremely increased, but the "stress light emission" included in the "anti-counterfeit paper" of the present invention including the "baking" step In the production process of the material layer, the production stability is lacking, and it becomes difficult to withstand repeated deformation.

In addition, the “value” of “stress concentration coefficient α” in “one side of the bottom” varies depending on the direction in which “deformation” is applied. That is, depending on the direction in which the “predetermined external force load” is applied, its “value” fluctuates, and for example, when it is deformed in the direction to open the above “triangle of upper and lower surface”, “stress concentration” in “one side of bottom” In the coefficient α, stress is concentrated at the middle point of the “one side of the bottom” (not shown, but in such a deformation, the “middle point” is a predetermined portion).

  In other words, the “wedge shape” recess is a third order determined by the “direction” in the “three-dimensional space” (the ratio of the sizes of the three-dimensional space components) of the “predetermined external force load” loaded on the “wedge shape” The “emission intensity (or the distribution thereof)” and the “position of the light emitting point (or light emitting region)” are changed by “the source vector”.

  This means that the "stress light emitting material" of the "predetermined external load" to be applied to the "stress light emitting material layer" of the "thread" included in the "anti-counterfeit paper" of the present invention provided with the "wedge shape" For a layer, and hence for the "notch" of the "whip-shaped", by "direction in three-dimensional space (the direction of the vector, the" external force "represented by the" three-dimensional vector ")". The “light emitting state (position distribution of light emitting points and intensity distribution of individual light emitting points)” of the “stress light emitting material layer” are different.

Then, the "direction" with respect to the "stress light emitting material layer" of the "external force load" transmitted from the "predetermined external force load" added to the "anti-counterfeit paper" is changed, and the light emitting state of the "stress light emitting material layer" It is also preferable to determine the authenticity by visually recognizing the change.
In addition, the “wedge shape” is a “wedge shape having a rectangular bottom,” that is, “a trapezoidal shape,” a polygonal pyramid such as a quadrangular pyramid, a pentagonal pyramid, a cone or an elliptical pyramid, and Also included are shapes whose shapes are "triangles, polygons such as quadrilaterals, circles, ellipses, and their variants."

Furthermore, in the “stress light emitting material layer” included in the “anti-counterfeit paper” of the present invention, the “predetermined shape concave portion” is a concave having a “concave shape” and is a semi-cylindrical concave shape, a semi-cylindrical shape The bottom of the recess, such as an ellipsoidal concave shape, a hemispherical concave shape, and a combination thereof, can be defined as a “dent” having a “three-dimensional curved surface shape”.
Of course, it is also preferable that the “concave shape” be “arbitrary three-dimensional curved surface” on the premise that the shape is “controllable” (meaning that there is manufacturing reproducibility).

  The depth of the "notch" and the "recess" (hereinafter collectively referred to simply as "recess") is, for example, a "stress light emitting material layer" having a "flat (layered)" outer shape. If it is provided on a part of the surface of the “layer”, “cut” at a depth of 1/10 to 4/5 of the “thickness of the layer” (meaning the “thickness” at the position where they are provided) It is obtained by providing a "chip" and a "recess".

  Moreover, the shape of the "dent" is a so-called "socket" in which the "dent" itself reflects and condenses the light of the light source to the "light" emitted from the "bottom" of the "dent". Play a role of "meaning like a" concave reflecting mirror "to enhance the light collection and directivity of the" light "and improve the visibility of the" light ".

  The shape of this "notch" or "recess", that is, "dent" is "shallow bottom", for example, less than 1/10 of the thickness of "layer", and further If the ratio of [(opening width W / depth D)] is 20/1 or more, even if "stress concentration" occurs around the "bottom" of this "dent", the "stress" The concentration factor α "is less than 2.

  Or, "a deep form of the bottom, for example, one whose depth is more than 4/5 to 5/5 of the thickness of the" layer "is very close to the" bottom "of the" dent ". Although large "stress concentration" occurs, the "bottom" etc. is easily cracked due to repeated deformation operations, and "stable light emission at least 100 times or more" can not be secured, ensuring reliability as a forgery prevention medium Can not.

  “Stress light emitting material layer A1 or A2” (stress light emitting material layer A1 or A2 made of a predetermined stress light emitting material) of “thread SL1 or thread SL2” used for “forgery prevention paper G1” of the present invention In order to produce), first, for firing, a "cavity" (meaning the space inside the "mold") having the above-mentioned "shape having a portion where the stress concentration coefficient .alpha. Is 2 or more" is provided in advance. Prepare a mold, fill the “composition for“ stress light emitting material ”before firing” in the “cavity” of the “mold”, and simultaneously fill the “fill (before firing)” and the “mold”. After heating to a predetermined temperature using a predetermined means and at a predetermined heating rate and holding at a predetermined temperature for a predetermined time, cooling is also performed at a predetermined cooling rate using the predetermined means. From the "type" at the point near the normal temperature, the " Procedure to take out the filler (after firing) (This is the procedure of “firing”. After “pre-baking” in air, which is an oxidizing atmosphere, adding “forming” treatment to this, and then reducing In the atmosphere, a procedure such as "main firing" is also a "firing" procedure, which is preferable.

Here, the firing mold is a “mold” such as ceramic or metal, and the target (before firing) flows into the mold and is filled, and the mold and the like have predetermined conditions. The "fired" is taken out from the "type" to obtain a "fired object (after firing)" having a predetermined composition and having a predetermined "shape". The “stress light emitting material layer A1 or A2” is stacked on the “predetermined base material B0” to be “thread SL1 or thread SL2”. (Refer to FIG. 6 and FIG. 7.)
In addition, the shape of the “cavity” is “the shape having the portion where the stress concentration coefficient α is 2 or more” itself, or, in consideration of the material shrinkage at the time of “firing”, the “hollow” It means that the shape is determined. However, in practice, a predetermined solvent (including an aqueous solvent), such as "predetermined hydroxide or the like to be a" stress light emitting material "by predetermined baking" described below, is included in this "cavity". So-called “spout (for filling the composition in the“ cavity ”) for pouring“ the composition for “stress light emitting material” before firing ”diluted and having flowability with a predetermined pressure Part) (also referred to as “flow port”), and after firing, the part corresponding to the “gate” is cut and planarized (the part is made flat as if the “gate” did not exist. ) Will do. (Other than this, the same applies to “air vent” and “portion connecting individual fired products in multi-sided firing (bond)”.)
Also, in order to obtain such a "mold" in which the "cavity" inside the "mold" is "a shape having a portion where the stress concentration coefficient α is 2 or more", the shape is formed Method of cutting out the "formed object" such as appropriate plastic material provided in step 2 and predetermined shape, create a numerical program from 3D data produced by CAD, and use the program to make a cutting machine tool An NC machine that manufactures a three-dimensional three-dimensional object while controlling coordinate positions, and a method using a so-called ultra-precision machine tool are precise and preferable), wet etching methods (including resist processing), and dry etching Methods obtained from “forms” (meaning scraped) such as plastic materials etc. obtained using methods (including energy beam etching methods), as well as their “molds” and “forms Molding mold, or, as firing a mother die, we perform shaping and sintering, comprising a predetermined material composition, a method of obtaining a "type" of the above.

  Furthermore, using the above-described “baking mold”, the “stress light emitting material” which is molten and itself has fluidity is allowed to flow into the “cavity” of the “baking mold”, and the cavity is “Stress luminescent material layer A1 or A2 consisting of“ stress luminescent material ”having rapid cooling or gradual cooling after filling up without gaps (vacuum suction etc. may be performed) You may get At this time, as the condition for "rapid cooling or gradual cooling", a condition is selected in which the "volume contraction rate" by cooling of the "stress light emitting material layer" becomes smaller.

  Also, from such a "molding die" or using such a "baking die" as a "molding die", the "stress light emitting material layer A1 or A2" can be obtained by the "molding means". You can also get it.

  In particular, when adopting such a "forming means", a mixture of "stress light emitting material fine particles P1" and "transparent resin J2" in the "cavity" of the "forming mold" (furthermore, Containing the organic solvent) is preferred.

  And the "mold" used for such "mold for molding" and "mold for firing" has a high molding load, an open "mold" having an opening, and a relatively low molding load and molding by the closed space. Or, it is classified as a closed type “mold” that performs baking, the former “mold” includes a press mold or a forging mold, etc., and the latter “mold” includes an injection mold, compression molding There are molds, casting molds, glass molds, powder molds ("molds" for forming powders by injection molding) and the like.

  Among these, "casting mold" includes open mold and closed mold, and furthermore, "die-casting mold" in which melt is poured directly into "mold" for casting, or mold for casting melt is molded. There is a "green sand mold" for this. Both are suitable because the changes in the "cavity shape" and the "post-fired shape" after the "mold" are taken are small.

  When this "casting mold" is used for "molding mold" or "baking mold", "fine particles P1 of stress light emitting material" and "transparent resin J2 (suitable solvent is added to adjust the flowability ) Are mixed and molded in a “mold” (the one used as a “molding mold”. The solvent added is evaporated.) Furthermore, after the molding, the molded product is subjected to predetermined conditions. Firing (sintering) (Used as a "firing mold". The transparent resin J2 is burnt away).

  More specifically, 60 to 90% of the particles P1 of the stress light emitting material and 40 to 10% of the transparent resin J2 (100% in total) are used as the molded product. Alternatively, after firing (sintering) the molded product, the transparent resin J2 is made “approximately 0%”, and a sintered product with a relative density of 98% or more of the stress light emitting material is obtained.

Furthermore, since the "stress light emitting material layer A2" has a "shape" having "a notch K1 of a predetermined shape and / or a recess" on the surface of the "layer", the viewer looks only Alternatively, it has a problem that it is possible to easily grasp the existence of the “notched portion K1 and / or concave portion of a predetermined shape”, the shape and the arrangement thereof by measuring with a simple surface roughness meter. In order to prevent such an action and to further enhance its anti-counterfeit property, this "notched portion K1 and / or recess" of a predetermined shape is identical to the "color tone" of the "stress light emitting material" It is also preferable to “fill in” the “filler” having the color tone and conceal the presence of the “notched portion K 1 and / or recess” of a predetermined shape, the shape and the arrangement thereof. (Not shown)
Such a "filler" has the same color tone as that of the "stress light emitting material", that is, the color difference ΔE between the color tone of the "filler" and the color tone of the "stress light emitting material" is 0. It is possible to use so-called "ceramics" having a size of 5 or less, and "the one obtained by dispersing" ceramics "in" appropriate resin "(hereinafter collectively referred to as" ceramics etc. ").

  Here, as this "ceramics", one having a composition substantially the same as the composition of the "stress light emitting material" used for the "stress light emitting material layer A2" and excluding only the luminescence center element, that is, the "stress" When "a material consisting only of a host crystal (a material that does not emit light)" of "light emitting material" is used, such a "a material consisting only of a host crystal (a material that does not emit light)" of "a stress light emitting material" is The color difference ΔE, which is the difference between the “color tone” of the “filler” and the “color tone” of the “stress light emitting material”, has almost the same color tone as the “stress light emitting material” ) And become the most preferable "filler".

In addition, “appropriate resin” is appropriately selected from any resin which is colored or colorless, or transparent or opaque. ("Opacity" or "Opacity" means that the above-mentioned "Transmittance" is 30% or less.)
Of course, when "deterioration stress is applied to the" notched portion K1 and / or recess "of the" predetermined shape ", the" ceramics etc. "as the" filling material "does not disturb the transmission of the" stress ". In addition, the “volume modulus” of the “ceramics” is set to 1/10 to 1/2 of the “volume modulus” of the “stress light emitting material” used.

  In the first place, “ceramics” is a generic term for products obtained by firing inorganic compounds, and regardless of metals or nonmetals, semiconductors such as silicon, or moldings of inorganic compounds such as carbides, nitrides and borides, It is used as a powder. There are a plurality of raw materials, and oxides such as alumina and zirconia, hydroxides such as hydroxyapatite, carbides such as silicon carbide, nitrides such as silicon nitride, and halides such as fluorite And carbonates, and further phosphates.

  In addition, as “filler”, “powder (having the same particle size as“ fine particles P1 ”)” of “ceramics” may be used as “filler” to “resin having transparency (resin similar to“ transparent resin J2 ” "Filler" by using the one mixed with "(the mixture ratio of the resin having transparency to the" powder "is 10/1 to 1/10). While keeping the bulk modulus of “the resin having transparency and the bulk modulus of the“ mixture of the powder ”lower than that of the“ stress light emitting material ”, It is possible to transmit the “light” emitted from the predetermined portion S1 of the “notched portion K1 and / or the recess” (the portion “filled” by the “filler” allows sufficient transmission of the “light” "Transparent resin" in "filling material" This “transparency” increases as the mixing ratio increases.) This makes it possible to achieve both the secrecy of the “notched portion K1 and / or recess of a predetermined shape” and the visibility of “light” at the time of stress emission. It is preferable and can be done.

  The “stress light emitting material layer” of the “thread” of the “threads” included in the “anti-counterfeit paper” of the present invention is, for example, “thread SL3” of FIG. Like "stress light emitting material layer A3," "stress light emitting material layer A3" formed by dispersing "fine particles P1 composed of stress light emitting material" in "predetermined transparent resin J2" In the state where the stress luminescent material is included in the “layered” stress light emitting material layer A3, the “shape of the fine particles P1” corresponds to the “shape of the included stress light emitting material”. Do.

Then, in FIG. 8, in particular, the “portion at the bottom of the recess” of the uneven portion on the surface of “the fine particle P1” is the “predetermined portion S1”. (Refer to FIG. 8. In FIG. 8, one of “predetermined portion S1” is indicated by an arrow.)
Therefore, the “shape of the fine particle P1” is the “shape” having the “predetermined portion S1” in which the “stress concentration coefficient α” in the “predetermined portion S1” of the “stress light emitting material” is 2 or more. In this sense, the “shape” of such “stress light emitting material”, that is, the “shape of stress light emitting material“ included in the stress light emitting material layer ”” It can be said that the shape of the “fine particle P1” is

  Such “fine particles P1” are primarily obtained by firing the “stress light emitting material” composition under a predetermined condition to form “plate-like” or “bulk” as a “stress light emitting material”. What is "particulated" using crushing means or classification means or "fine particles" is "transparent resin" (a "resin" similar to "predetermined transparent resin J2". In particular, "the resin" Assuming that the bulk modulus of the resin is larger than that of the fine particles, the “deformation” loaded on the resin is directly transmitted to the “fine particles”, so that “transparent resin” and “stress light emitting material” are preferable. The compositional ratio of “1” is 10/1 to 1/10 The volume modulus and other indexes, Young's modulus, Poisson's ratio, stiffness, and the first constant of the glitter have a predetermined correlation. In the form of pellets, etc.), and The particles are either classified and "fine-ized", and further, during the treatment, when the collisions between the particles are suppressed and treated (when the particles after crushing collide with one another, the surface of the particles gradually becomes smooth The shape of the “fine particles P1” itself is a complicated shape, and furthermore, the surface of the “fine particles P1” is also very irregular asperity (the period and depth of the unevenness) In the small ones, from the very fine ones of nano size to the large ones in the size of several micrometers and the distribution width, it means that they exist at random. can do.

  Examples of a pulverizer as a pulverizing means include a ball mill, a rod mill, an autogenous pulverizing mill, a SAG (quasi-autogenous pulverizing) mill, a high pressure pulverizing roll, and a vertical axis impactor (VSI) mill.

  Here, it is a typical crusher for obtaining fine particles, and a metal ball is clogged in a cylinder slightly inclined or horizontally rotating, and it collides with the ball and the friction There are dry ball mills and wet ball mills (all have an internal volume of 100 to 10,000 liters, and a rotation speed of 10 to 50 revolutions / minute).

  Moreover, a rod mill uses not a ball | bowl but a rod (metal cylinder) as a grinding | pulverization medium, and it grinds | pulverizes by giving an impact of a rod to a ground material with a rotating drum (body). In particular, the impact mill is a pulverizer that rotates impact teeth at high speed and pulverizes the raw material by impact force, and rotates a rotating disc with a diameter of 100 to 1000 mm at a high speed of 500 to 10000 revolutions / min. The shape itself is likely to be complicated, and the surface of the fine particles is also likely to be rough and uneven.

  In addition, once the "stress light emitting material" is "made into fine particles", and further, it is made "very fine particles (average particle diameter is 0.01 to 1.0 .mu.m, particularly 0.01 to 0.1 .mu.m Is called “ultrafine particles.” Those larger than this are “fine particles”. ”Using“ granulation ”means such as a granulator, etc.,“ the bonding between the “ultrafine particles” is strong. By setting it as a secondary aggregate, it is possible to obtain “fine particles P1” of a “stress light emitting material” which has “an irregular shape” and a “complex shape”.

  Such a granulator is an apparatus that solidifies "powder" and "fine particles" into "granular" and is also called a pelletizer because it can produce "granular" pellets.

  And, in this "granulation" system, a swirling system (rotor system), a kneading system, a stirring system, a rolling system, a fluidized bed system, a forced granulation compression system (roll press system), a self-supporting granulation, There are a twin-screw extrusion type, a wet extrusion type, and a type that combines these, etc., and there is also a type that continuously performs mixing, dispersion, and granulation.

“Pulsitized” “stress light emitting material” (the one composed 100% of “stress light emitting material”, “a composite of stress light emitting materials consisting of a plurality of stress light emitting materials”, And the like) are classified using a classification means, or further granulated using a granulation means, and then classified using a classification means, The maximum diameter is 0.1 μm to ₅₀ μm, preferably 5.0 μm to 20 μm “fine particles P1”, or the average particle diameter D ₅₀ is 0.05 μm to 20 μm, preferably 0.5 μm to 10 μm The “fine particle P1” of

  The “particle size” and the “particle shape” at this time are determined using an apparatus based on various particle size distribution measurement methods, such as a laser diffraction type particle size distribution measurement apparatus.

  In such a particle size distribution measurement method, an X-ray transmission sedimentation method in which the particle concentration in the dispersion medium is directly measured using a finely focused X-ray beam, and the particles pass through the detection region of pores (aperture) An electrical detection zone method that measures the change in electrical resistance between two electrodes that occurs when the particles are uniformly dispersed in a predetermined dispersion medium and pass through the flow cell, and light is emitted from the light source to the flow cell, An image analysis method for capturing a projected image when particles pass through the cell with a high sensitivity CCD camera, digitally converting the particle image, and calculating equivalent circular diameter and shape information of the particles by program processing for analysis (Use dozens of shape parameters and image analysis models such as circular model, fiber model, rectangular model, polygonal model, elliptical model, irregular model, etc.), "Brownian motion" in particle suspension Do Dynamic light scattering method to measure the particle diameter from scattered light by the particles that are moving and irradiating the laser beam to the particles, and the diffraction / scattering phenomenon of light by irradiating the particles with the laser beam The intensity pattern of the diffracted / scattered light depends on the particle size, and different intensity patterns (intensity distribution) are observed depending on the angle of the Laser diffraction scattering method to find the particle size distribution using the Mie scattering theory, When air is flowed in the powder packed bed, the powder particles become smaller and harder to flow, and the particle diameter of the powder and the permeation of fluid The air permeation method etc. which obtain | require the specific surface area of powder from the correlation between property can be used.

  And in "stress light emitting material layer A3," "the shape of fine particles" means "the average shape of many particles P1 contained in" stress light emitting material layer A3 ", and so-called optical fine particle shape measurement It shall be a "shape" that can be determined by the device etc Of course, it is most desirable that all the "fine particles P1" contained in the "stress light emitting material layer A3" have a shape having "a portion with a stress concentration coefficient α 2 2", and the visibility of "emission" is also sufficient. Although it can be secured, it is preferable that at least all of the "particulates P1" (that is, "the shape of the sampled particulates P1") that have been "sampled and measured" using each device based on the various methods described above are all exceptionally The object of the present invention is as long as it satisfies this condition (“the shape of the stress light emitting material is the shape of the fine particle P1 and has a portion S1 where the stress concentration coefficient α is at least 2 or more”). It goes without saying that it is possible to achieve.

  Of course, specifically, for example, 100 areas of 10 mm × 10 mm of the “stress light emitting material layer A3” are cut out of the condition of “sampling measurement”, and the “transparent resin J2” contained is dissolved. After dissolving "transparent resin J2" using a solvent to be used, it is possible to extract the "fine particles P1" contained therein to carry out the above measurement.

Then, this "fine particle P1" is selected from "thermoplastic resin and / or thermosetting resin,""resin" having the above "transmittance", and "predetermined transparent resin J2". In the “transparent resin J2”, the “fine particles P1” are “dispersed” while suppressing further “aggregation” (meaning that “aggregation” is prevented more than necessary. The contact portion produced by such “cohesion” has a “shape” that is very easy to concentrate stress, judging from the appearance, that is, only from the “shape” around it. Because it is easily separated and cut by a small external load, it is not suitable for the purpose of the present invention.) As “transparent resin J2” containing “fine particles P1” of “stress light emitting material” "Stress luminescent material used for" thread SL3 "of the present invention A layer A3 ". (See Figure 8)
In addition, “dispersing” “fine particles P1” in “transparent resin J2” means that “transparent resin J2” is an appropriate solvent (“water” in the case of “water-soluble resin (aqueous resin)”) And / or “lower alcohol”. “Particulates P1” is mixed in a solution dissolved in “lower alcohol”, and a stirrer such as a dissolver or mixer, a kneader such as a kneader or roll mill, a magnetic stirrer system, an aeration system or spray After uniformly containing “fine particles P1” in “transparent resin J2” using a stirring apparatus such as a dry method, the mixed solution is a gravure coating method, a curtain coating method, a blade coating method, a roll coating method Method, spin coating method, offset printing method, letterpress printing method, screen printing method, intaglio printing method, inkjet printing The film is provided on a “predetermined substrate B0” at a predetermined thickness using a formula, casting method, die coating method, etc., and dried under a predetermined condition (natural drying, contact heating drying, hot air drying, vacuum Drying etc. It may also include special drying techniques such as ionizing radiation drying etc.) to obtain "thread SL3" of the present invention. (See Figure 8)
Among the stirring devices described above, particularly magnetic stirrer type, aeration type and spray drying type stirring devices make it possible to minimize unnecessary load of "shear stress" on "particulates P1" as much as possible, which is desirable. .

  As the above-mentioned "transparent resin J2", various thermoplastic resins, thermosetting resins, or ionizing radiation curable resins can be used.

  As the thermoplastic resin, an acrylic ester resin, a cellulose resin, a vinyl resin, an acrylamide resin, or a polystyrene resin, etc. having transparency, and as the thermosetting resin, also having transparency, non-transparent resin Examples thereof include saturated polyester resins, urethane resins, epoxy resins, melamine resins, silicone resins, and fluorinated resins.

  Furthermore, if the refractive index of these resins is set according to the refractive index of the "fine particles P1" of the "stress light emitting material" used, the "emission" from the "fine particles P1" is intensified and the visibility thereof is It can be enhanced.

  For example, assuming that the “refractive index difference” between the refractive index of “transparent resin J2” and the refractive index of “fine particles P1” is 0.3 or less, further 0.1 or less, “transparent resin J2” The reflectance at the “interface” of the “fine particle P1” is reduced, and the “light” generated by the “light emission” of the “fine particle P1” can be efficiently transmitted to the observer.

  In addition, the “refractive index difference” of the refractive index of “transparent resin J2” and the refractive index of “transparent resin” contained in “fine particles P1” is 0.1 or less, furthermore, 0.03 It is also preferable to set the interface reflectance at the interface of those “resins” to approximately “0”, and “the“ stress light emitting material ”contained in the“ fine particles P1 ”(the“ stress light emitting material ”contained therein) is also preferable. It is preferable because the "light" emitting "light" can be further efficiently transmitted to the observer.

  Here, the content ratio of “transparent resin J2” to “fine particles P1” is 5/95 to 100/5, particularly 5/30 to 100/30.

  If this mixture ratio is smaller than 5/95, the toughness of the "stress light emitting material layer A3" is lowered, and in the application for the purpose of forgery prevention, it becomes unreliable and exceeds 100/5. Then, the light emission intensity becomes insufficient.

  Furthermore, the ratio of the solvent to the “mixture of“ transparent resin J2 ”and“ fine particles P1 ”” has an individual suitability range depending on various methods such as the coating described above, but is generally 100/5 to 1/20. .

  Further, in the stress light emitting material layers A1 to A3 of the present invention, the stress light emitting material layers A1 to A3 are stressed by applying a predetermined external load and the stress light emitting material layers A1 to A3 are deformed by the deformation. When the deformation stress is concentrated on the portion S1 of the stress light emitting material contained in the layers A1 to A3 and at the same time visible light of a predetermined wavelength having a luminous intensity corresponding to the deformation stress is emitted from the portion S1 By setting “the part S1” so that the light of the predetermined wavelength “displays a predetermined pattern”, the observer appears by a predetermined external force load that “predetermined pattern” (“light It becomes possible to visually recognize the "pattern" of "." And to determine the authenticity more reliably.

  At this time, the “point of action” (the position of “stress light emitting material layer A1 to A3” on which the external force load acts) to “stress light emitting material layer A1 to A3” of “predetermined external force load”, and The direction from the point of action toward the inside of the stress light emitting material layers A1 to A3, the size of the external force load, and the speed with which the external force load is applied (the light emission intensity of the stress light emitting material) Means that the displayed "predetermined pattern" is "changed" (meaning that a different "pattern" is displayed because "the external load increases in proportion to the speed at which the external load is applied"). By doing this, it is possible to achieve more advanced forgery prevention.

  Here, "it is assumed that the" predetermined pattern "to be displayed is" changed "means" change of the switching pattern "(the point of action, the direction, the size, and the speed of loading). Depending on "," "display" of "predetermined pattern" means "switch to different ones" variously) or "progressively changing pattern" (similar "change", "predetermined pattern" "Display" means "switching gradually to various different things."

  Furthermore, by “changing” these “point of action, direction, magnitude, and loading speed” in time and space, the “light emitting point, It is also preferable to be able to observe "movement itself" of the light emission pattern, "change in display accompanying movement", or "locus of movement" and to be able to determine the authenticity by the confirmation.

  As an example, the "position" where "the stress light emitting material layer A1 to A3" is bent is moved from one end face of the layer to the other end face to emit light, ie, one end face of the layer "Linear (or band-like)" light emitting area "appearing on the" line (or band) "shows" predetermined change "for the" length "and" width "of the line (zone), gradually The observer determines the "state of movement" of the "linear (or strip-like)" light emitting area "as" moving "to the other end face (the end face on the opposite side).

  These "light emitting point", "light emitting region" and "light emitting pattern" appear by their "prescribed external force load" on the "stress light emitting material layers A1 to A3" at that time, each "part S1 thereof" "The light of a predetermined wavelength" itself or a collection of "lights", and the "predetermined pattern" means their "aggregate of" light emitting point "or" light emitting area ", Furthermore, it means "predetermined information" recognized by "a set of" light emission patterns "" (meaning that "predetermined information" is displayed).

  And "the part S1 is set" causes each "predetermined pattern" at each time to appear such that "the light of the predetermined wavelength" "displays" the "predetermined pattern". Therefore, the respective portions S1 to be generated are arranged (arranged) in advance at predetermined positions in correspondence with "the respective" predetermined external load loads on the stress light emitting material layers A1 to A3 "" at respective points in time. This means that each part S1 of a predetermined position (arrangement) emits light with a predetermined intensity in each “predetermined load of external force”, and “an "Display" predetermined "information" according to "pattern", and further "stress light emission" so that a desired site S1 is generated for such individual "predetermined external load". The shape of "material", "stress light emitting material Stress concentration factor α is 2 or more at a given site S1 of is to shape "with the site S1.

  Alternatively, the shape of the "stress light emitting material" may be the shape of the "stress light emitting material layer A1 or A2" so that the desired portion S1 is generated for such individual "predetermined external force load". And on the surface of the stress-stimulated luminescent material, as the portion S1 thereof, a shape having a notch K1 and / or a recess of a predetermined shape, or such individual “predetermined external force load” "The light emitting material" has the shape of the "fine particle P1" so that the stress concentration coefficient α is 2 or more "so that the desired portion S1 is generated. Above, “fine particles P1” having the “stress light emitting material” as a composition is to be “stress light emitting material layer A3” formed by dispersing it in a predetermined transparent resin J2.

  Here, "predetermined information" recognized by the "predetermined pattern" or their "aggregation of" light emitting point "or" light emitting area ", and further" collection of "light emission pattern" " "Represents, for example, characters, figures, or symbols of a predetermined size, and in particular, a message or the like having a predetermined size of" a message (such as a character of "authenticity") "for authenticity determination. As “arranged (for example, a predetermined“ character ”represented by a discrete“ dot ”), and the characters, figures, symbols, and the like as“ information ” Any other "information" that can be recognized at least visually and can be used, and "the information that should be disclosed only to the legitimate right holder who can know the" predetermined information "is also preferable. is there.

  Of course, a mere combination of the "predetermined information" and other "information" (which may be concealed or disclosed) carried by the "stress light emitting material layers A1 to A3", or their " "Information" may be synthesized by various information synthesizing means (including encryption processing) to "form information to be disclosed to the right holder".

  Furthermore, as the "predetermined information" displayed by the "stress light emitting material layers A1 to A3", a personal identification number, a personal identification number, an account number, other individual specific numbers or symbols, a lottery number or symbol, a management number or Symbols or simple serial numbers or symbols that express their effectiveness by registration, the same number such as a common key number which is an encryption key number, and a completely random number , A person who is permitted to know (such as a legitimate purchaser, etc.) which is generated when producing "stress light emitting material layers A1 to A3" and is devised so that no one including the creator knows the contents of the number Of course, the system configuration of “system (a system for managing and supporting various economic activities such as ticketing system and distribution system) using“ stress light emitting material layers A1 to A3 ””. May or may not be included in the issue of "stress light emitting material layers A1 to A3". Numbers or symbols set so that others can not easily view. There is.

  In addition, depending on the application of the "stress light emitting material layer A1 to A3", not only numbers or symbols but characters, figures, marks, etc., individuals, and individuals of "stress light emitting material layers A1 to A3" can be commonly recognized. Anything can be used as long as it is (this object is all the so-called "information").

  And also the recognition method adopts a recognition method other than visual observation, for example, an optical reading method, a magnetic reading method, or any other physical or chemical reading method while having at least information that can be recognized by visual confirmation. It is suitable for enhancing its anti-counterfeit property.

  The "stress light emitting material layer" or the "stress light emitting material" (hereinafter also referred to as "stress light emitting material layer etc.") contained in the "anti-counterfeit paper" of the present invention is a ceramic, in particular, a metal or , With the composition of oxides, nitrides, carbides and sulfides of silicon, and at the contact point of "paper pulp fiber" and "stress light emitting material layer", by "hydroxyl group of cellulose" at the contact point of "paper pulp fiber" "Hydrogen bond", "cellulose hydroxyl group" constituting "paper pulp fiber", "oxide, nitride, carbide or sulfide oxygen atom, nitrogen atom, carbon atom or sulfur atom" The “hydrogen bond” of is used to “bond” at its contact point.

  As a result, the "deformation" of the "paper pulp fiber" when the "composite" is "curved" is the "deformation" of the "stress light emitting material layer etc." which is "combined" with the "paper pulp fiber". In particular, at the contact point of “paper pulp fiber” and “stress light emitting material layer etc.”, “tensile stress”, “shear stress”, “slip stress” are generated with physical movement.

  Of course, the pressure on the "stress light emitting material layer etc." directly due to the "curve" of this "complex" and the "curve" of "paper pulp fiber" is also the "stress light emitting material layer etc." Promote the occurrence of stress.

  And in this "stress light emitting material layer etc.", the location of the contact point of "paper pulp fiber" becomes "predetermined portion such as stress light emitting material layer", and this "tensile stress", "shear stress", "misalignment" “Stress” is “a deformation stress corresponding to the deformation of paper pulp fibers”, and the strength is in proportion to the “size of the stress”, and more specifically, “a structure (such as a stress light emitting material layer) Light with a wavelength specific to that “structure” (meaning that there is a dependence on the direction of application of stress). .

  The “stress light emitting material” used in the “anti-counterfeit paper” of the present invention has a “three-dimensional structure” including its “composition” and, further, a “high electron density lattice position” located in the “structure”. The “transition width” of the electronic state is determined by “element” or “element at a lattice position with low electron density (including those in which“ lattice defects are in a state without elements ”)”, and this “transition width” Emits "light" with energy equivalent to

  That is, it receives an internal stress ("mechanical energy") generated by an external force, and is based on the equation "energy E = Planck constant x frequency of light" & "wavelength of light = speed of light / frequency of light". Although it emits light of a predetermined wavelength, no matter how large the magnitude of this internal stress is, and also how large the rate of giving this internal stress is (that is, how large the strain rate is). ), “Predetermined wavelength” itself does not change, and is “constant” (meaning “specific” to the material).

  Therefore, it is possible to highly reliably carry out the authenticity determination of the "anti-counterfeit paper" of the present invention in which such "stress light-emitting material layer etc." is included as a "thread".

  Furthermore, the strength distribution of the "deformation stress" generated in the "stress light emitting material layer etc.", that is, the "method of deformation" of the "stress light emitting material layer etc." Since the "emission intensity" of the "light of a predetermined wavelength" and the "emission distribution" on the "thread" of the "anti-counterfeit paper" differ depending on the "method of deformation", the authenticity using this property It also enables judgment.

Actually, when the "anti-counterfeit paper" of the present invention is mass-produced by an appropriate paper machine, the "emission distribution" of the individual "anti-counterfeit paper" on the surface of the paper (the thread portion therein) Although the "average luminous intensity" can be controlled, the "emission distribution" on the surface of the individual "anti-counterfeit paper" (in the thread part therein), for example, the 20 mm width of the A4 size The “emission intensity” when the center of the strip-shaped “thread” is made to emit light sequentially from the upper end to the lower end in the “longitudinal direction (thread flow direction)” with a certain “width” A curve (a graph in which the horizontal axis is “the position in the vertical direction on the thread” and the vertical axis is the “emission intensity”) is a curve with relatively strong vertical fluctuation, and by the setting of the “width” The way of the change also changes greatly, Light intensity curve "is becomes a" unique "to the individual" anti-falsification paper. " (The arrangement and contact condition of the individual "threads" with "paper pulp fibers" means that artificial control is impossible.)
Furthermore, in order to make such "emission distribution" significantly different in each "anti-counterfeit paper", the "stress light emitting material layer" in the thread may be partially provided, or the "stress light emitting material layer" May be formed by combining a plurality of stress light emitting materials (division into regions or change in mixing ratio).

  In addition, when the “light of a predetermined wavelength” is visually recognized, the authenticity is observed by, for example, observing through an appropriate optical filter (a wavelength filter or the like which allows only the “light of the predetermined wavelength” to pass). It is also possible to further increase the reliability of the determination.

The light emission mechanism of this new "stress light emitting material" is a representative "stress light emitting material" by Mr. Yamada (National Institute of Advanced Industrial Science and Technology) and Mr. Matsuo from Nippon Steel Corp. Since a certain SrAl ₂ O ₄ : Eu system has been announced in detail, only an outline thereof will be described below. (Senior Research Institute for Industrial Technology Research and Development, Stress Light Technology Research Team Head, Sutra Xu (Editorial Representative), Ueno Naohiro, Terazaki Tadashi, Yamada Koshi (Editor), et al., “Structure Diagnosis Technology by Stress Emission Mechanoluminescence and Novel Structural Health Diagnosis, "NTS Co., Ltd., published in August 2012."
In the former, the host crystal is a stuffed tridymite structure, and the honeycomb structure is formed by “sharing the vertices” of the AlO ₄ tetrahedra, and the large pores in it form Sr ²⁺ ions. Has a structure that is placed. 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 by radiative transition associated with “5d electron orbital transition” (the difference in electron orbital energy at this time is the above-described energy E).

In the latter, thermoelastic martensitic transformation of SrAl ₂ O ₄ from β phase to α phase occurs at the time of forming a sintered body to form a “twin interface” in the crystal, and the electron density near the interface has a gradient When "stress" is applied to a "stress light emitting material" in which carriers excited from Eu by UV irradiation or the like are trapped in pores or the like, "twin pseudoelastic deformation" occurs and the deformation occurs According to the movement of the “twin interface”, the electron density distribution changes, the trapped carriers are released, and it recombines with the Eu ^{2+ of} the luminescence center to cause luminescence.

Then, when this stress is unloaded, the “twin interface” returns to the original position, and at that time, carriers are excited from Eu ²⁺ , trapped in vacancies etc, and returned to the original state. The phenomenon is said to be repeated.

  From these light emission mechanisms, it is inferred that “stress light emitting 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 hence the “physical deformation” (specifically, on a macroscopic scale, bending or twisting as the “stress light emitting material”, its “shape” Meaning “to change”), and in order to make such “deformation” possible for “stress light emitting material”, “the ease of movement” of “stress light emitting material” and In addition, it is necessary to design the configuration of the "anti-counterfeit paper" which has "moving area (meaning" moving space ").

  Then, this "light of a wavelength specific to the" structure "constituting the stress light emitting material" is the above-mentioned "light of a predetermined wavelength", and usually, 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, the observer can visually recognize the emitted "light of predetermined wavelength".

However, in order to make the intensity of the “light of a predetermined wavelength” visually recognizable, the “emission luminance” is set to a size of at least 1.0 mcd / cm ² .

In particular, in the case of visual observation outdoors, 10 mcd / cm ² or more, furthermore, it is recognized as “high luminance”, and the reliability of the judgment in the case of using the “emission” for authenticity judgment is higher. In order to achieve this, the “emission luminance” of 100 mcd / cm ² or more is given.

  Of course, one “stress light emitting material” may include “a plurality of structures (crystal structure, different emission center elements, etc.)” or “threads” “stress light emitting material layer” may have a plurality of types. The “stress light emitting material” may be included to emit light having a plurality of wavelength regions, or “stress light emission” may be performed in a wavelength region other than visible light (ultraviolet light or red A material that emits stress light from outside light is used.) The phosphor layer (a layer containing a suitable fluorescent material) is appropriately included in the “anti-counterfeit paper” of the present invention in advance using the emitted light. Or “fluorescent substance pattern layer (fluorescent substance layer formed in a pattern)” may be “excited” to emit light in a visible light region, and as a result, visible light may be viewed.

  In the first place, "paper" is "made thin and flat while entangling fibers such as plants." According to the Japanese Industrial Standard (JIS), "paper" is manufactured by sticking vegetable fibers and other fibers. It is defined as "thing".

  As a material of "paper in a broad sense", if it is in the form of elongated fibers with a diameter of 100 μm or less, "paper in a broad sense" is made using almost any kind of material such as mineral, metal, animal origin or synthetic resin. In some cases, “non-woven fabrics” etc. are also classified as a type of “paper”.

  However, "paper" used in the present invention is "plant fiber" and "paper and pulp fiber" is used as a raw material, and the "paper" manufacturing method ("paper making" method) is also The "paper pulp fiber" is dispersed in an appropriate "water", and then spread on a "mushroom" or a "net" to use a product made through a dewatering process, a drying process, and the like. However, it does not exclude what was manufactured by the "dry process" which does not use "water."

  In addition, the “predetermined base material B0” constituting “threads SL0 to SL3” used for the “forgery prevention paper G1” of the present invention can be reduced in thickness and mechanical strength, Those having solvent resistance and heat resistance that endure the processing when producing the "thread", and those having good adhesion to the "stress light emitting material layer" are preferable.

That is, it is made of a material such as polyethylene terephthalate (PET), polycarbonate, polyvinyl alcohol, polysulfone, polyethylene, triacetyl cellulose (TAC), etc., has a thickness of 1.0 to 50 μm and has transparency or is opaque Use a plastic film. (Refer to FIGS. 5-8.)
Then, a "stress light emitting material layer" is provided on the "predetermined base material" on the entire surface of one side or a part thereof to form "threads" used for the "anti-counterfeit paper" of the present invention. In order to effectively transmit the "deformation stress" associated with the "thread" to the "stress light emitting material layer", the "thickness of the" stress light emitting material layer "and the" predetermined substrate "in the" thread " The ratio is set to 1/10 to 30/10.

  Since the Young's modulus of the “stress light emitting material layer” is about the same as the Young's modulus of the “predetermined base material”, or several times to several tens of times, the above “thickness ratio” is 30 If it exceeds 10, the rigidity as the "thread" becomes too large, and if the "thickness ratio" is less than 1/10, the visibility due to the light emission of the "thread" decreases. And if it is in said range, the "deformation stress" of a "predetermined base material" will be easily transmitted as a "deformation stress" of a "stress light emitting material layer."

  As a result, also, in order to satisfy various aptitudes such as handling aptitude as "anti-counterfeit paper", the rigidity of the "thread" used for the "anti-counterfeit paper" of the present invention is the "rigidity of the" anti-counterfeit paper " 1/10 to 50/10 of the

  As an evaluation of this "stiffness", for example, "value" of "Clark stiffness (Clark stiffness): JIS P 8143" which is an index of "stiffness" applied to "relatively thin paper", "thread" alone The “value” of (SL0 to SL3) ”and the“ value ”of“ anti-counterfeit paper (paper Y1) not including a thread ”are compared, and the“ ratio ”, that is,“ thread alone ”/“ thread ” The ratio of “Anti-forgery-proof paper not containing” is 1/10 to 50/10.

  Furthermore, another index, for example, JIS-P8125 (Taber method) or the like may be adopted as the index of "stiffness".

Further, since the "stress light emitting material" used for the "anti-counterfeit paper" of the present invention has inferior water resistance properties, the "stress light emitting material" can be used to improve the "water resistance" of the stress light emitting material Apply "predetermined surface treatment". (The condition of the surface treatment is not shown.)
That is, a "predetermined surface treatment" for the purpose of "improvement of water resistance" by "silylation treatment" on individual surfaces of "stress light emitting material" or on the surface of "stress light emitting material layer" To prevent the collapse of the crystal structure of the “stress light emitting material” by “water” and the loss of luminescence (especially because a large amount of “water” treatment is essential in the “paper-making process”).

  Furthermore, a "predetermined surface treatment" for forming a "coating" of a thermoplastic resin or a thermosetting resin is applied to cover the "silylation treated surface".

  In particular, cellulose resins such as methyl cellulose, ethyl cellulose, cellulose nitrate, cellulose acetate propionate and the like which are easily entangled with "paper pulp fibers" are used.

  As a "surface treatment agent" used for the "predetermined surface treatment", at least any acidic group of phosphoric acid group, phosphorous acid group, sulfonic acid group, carboxylic acid group, and silanol group, or ester thereof These "surface treatment agents" can be applied by a method of reacting them with a "stress light emitting material" using a compound containing them.

  That is, the above-mentioned "surface treatment agent" is dissolved in the corresponding organic solvent, the "stress light emitting material" is added to the solution and stirred, or the method of immersing the "thread" in the solution, Furthermore, a "predetermined surface treatment" is performed on the surface of the "stress light emitting material layer" of the "thread" using a spray method, a gravure coating method, an offset printing method, a screen printing method or the like.

  In particular, surface treatment with a silylating agent such as trimethylsilyl chloride or hexamethyldisilazane is preferable.

  Using the above method, the water resistance of the "stress light emitting material" is improved, and the light emission performance in the "water" treatment step in the above-mentioned "paper making step" is prevented from being deteriorated. Water resistance and weather resistance can be improved.

  And as a method of evaluating this "water resistance", for example, "anti-counterfeit paper" with predetermined adjustment in JIS K 6404-9: 1 999, or "ribbed ribbon thread before inserting into anti-counterfeit paper" Using the "hot water" of the specified temperature, "water immersion test" is performed using "" (In the above JIS standard, "4 hours" of "water immersion test" is to be conducted However, in this test, the light emission intensity of the light emission from the “stress light emitting material layer” of “the thread not subjected to the surface treatment” or “the forgery prevention paper using the thread not subjected to the surface treatment” is reduced by half. The “water immersion test” is to be continued until that point, and in that sense the test is conducted according to the above-mentioned JIS standard), “the test time (time to soak in water)”, “the stress emission” The light emission intensity of the material is halved Evaluation is made by setting as “time”, and in the evaluation, “water resistance is improved” means “half time” of “predetermined surface treatment” and “prescribed surface treatment” The “half-life” of “the one that was not” is compared, which means that the “half-life” is 2.0 times or more.

  Of course, as the surface treatment is carried out several times or the thickness of the formed "coating" is increased, "water resistance can be improved", but the complexity of the operation and "water resistance improvement" Considering that the effect is saturated, the target “half time” is 2.0 times or more and 10 times or less.

  As raw materials of "paper pulp fiber" used for "anti-counterfeit paper" in the present invention, "wood" itself, "imported wood chips", "non-wood plants", which are raw materials of so-called "Japanese paper" and "western paper" Furthermore, "waste paper" can be used, and "non-wood pulp" such as "wood pulp", straw pulp, kenaf pulp or "waste paper pulp" obtained by "pulping" them can be used.

  Or, in classification by the method of “pulping,” “mechanical pulp (MP) such as“ groundwood pulp (GP) ”and“ refiner ground pulp (RGP) ”or“ kraft pulp (KP) ” Chemical pulp (CP) can be used.

As described above, the “stress light emitting material” used in the “stress light emitting material layer” of the present invention is “stress” in the material with “physical deformation” in the vicinity of “thermoelastic martensitic transformation”. Is a material that is prone to “twin pseudoelastic deformation”, such as “Eu-added SrAl ₂ O ₄ (SAOE)”, etc. “With physical deformation”, the When light is loaded, light of a predetermined wavelength is emitted, and the light emission intensity increases according to the loaded “stress”. The material is fired and sintered to have a predetermined shape (layered. Use the ones).

Here, "to apply" stress "to the material with" physical deformation "means
The "prescribed external force load on the anti-counterfeit paper" transmitted the "external force load" to the "external force load on the" paper pulp fiber "and further transmitted to the" external force load on the "stress light emitting material" Sometimes, "stress strain" occurs in "stress light emitting material", which means that "stress light emitting material" itself causes "physical" deformation "=" stress strain ".

That is, the "stress light emitting material" used in the "stress light emitting material layer" of the present invention has an "elastic range (linear in stress-strain diagram) in a so-called" stress-strain diagram "when an external load is applied. The region that changes in (1), so that it tries to return to its original state when the external load is removed. (This behavior is what is called "elastic deformation".)
The "stress light emission" of the "stress light emitting material" used in the "stress light emitting material layer" of the present invention utilizes the phenomenon that occurs in this "elastic deformation" region, and the light emission phenomenon is repeated several hundred times. The light emission can be stably generated about several tens of thousands of times, and by visually recognizing this "light emission", it is suitable for the purpose of determining the authenticity, that is, the application of repeatedly performing the "light emission" and "determination".

  Thus, "loading the material with" stress "with" physical deformation "can produce a" physical deformation "that is visibly large with respect to the material contour, Promotes deformation and movement of the crystal structure itself (such as lattice shape) inside the material, and crystal walls (crystals and crystal walls), and increases “luminescence” based on the “deformation or movement” be able to.

  More specifically, although it is described as "an explanation for making it easy to grasp a" conceptual image "about" what kind of change does the crystal structure make ", it can be compared as follows.

  That is, one of the crystal lattices “tetragonal” is caused to “involve“ physical deformation ”, for example,“ phase transformation accompanied by shear deformation in one axial direction of tetragonal ”. Change in appearance as if it were "deformed" into "triclinic", or "displacement deformation" is caused between the crystal layers in a state where a plurality of crystal structures overlap in layers. , “Material” as a whole can be compared to a deformation that produces “macroscopic deformation (measurable or visible level of deformation)”. (It is just an image.)

  Then, when the above "physical deformation" exceeds the so-called "yield point" in the "stress-strain diagram" and reaches the "plasticity area", the "material" is changed according to the external load. The deformation in such a “plastic area” is the same as the “deformation” of the present invention, since it only stretches and continues to “stretch” until the “material” “breaks” and is no longer able to emit light repeatedly. There is not.

  In addition, “increase the internal stress of the material without substantially changing the shape of the material” does not fall under the “deformation” of the present invention.

  For example, “Even if external pressure of several hundred N (newtons) is applied to the outer surface of the material to increase the internal stress of the material,“ stress strain ”does not occur, and“ material shape ”is almost not In the "non-changed state", deformation or deformation to the crystal structure itself (such as lattice shape) inside the material or to the crystal wall (wall between one crystal structure and another crystal structure). Movement is considered not to occur, in other words, simply “the condition where those structures withstand high pressure applied while maintaining the spacing between the atoms that make up the lattice and their arrangement,” Because there is no change in the "electronic state" assumed from the atomic arrangement etc. (therefore, there is no light emission due to electronic transition), unlike the "external force load and its deformation" of the present invention, Does not occur at all.

  In the "stress light emitting material" used in the "stress light emitting material layer" of the present invention, an alkali metal ion or an alkaline earth metal ion is inserted in the space of a matrix structure formed by a plurality of molecules of polyhedron structure. Stress-stimulated luminescent material having a basic structure, a part of which is substituted by at least one metal ion of rare earth metal ions and transition metal ions, AlO-like structure, and SiO-like tetrahedron A stress-stimulated luminescent material, which is a configuration in which a light emission center is inserted into a basic structure having a three-dimensional structure formed by a plurality of molecules having a structure and a flexible flexible frame structure, a piezoelectric effect by forming strain energy. Such as stress light emitting materials that emit light due to mechanisms such as heat generation due to lattice defects and deformation, mixed stress light emitting materials in which a plurality of crystal structures are mixed, etc. Is a high emission luminance stress luminescent material, an ultraviolet light (infrared light) emission stress luminescent material that generates luminescence other than the visible light region, or ultrafine particles, in which the luminescence brightness of these stress luminescent materials is enhanced several hundred times or more It is possible to use a stress light emitting material or the like which is made into a “transparent material” by dispersing it into a transparent resin.

  Further, since the "stress light emitting material layer" of the "thread" of the present invention is "layered" and has a so-called "strip-like shape", it is near the middle of the "length" in the "strip" direction. Alternatively, the same effect can be obtained by providing an "elliptical through hole" having a major axis diameter of 1/10 to 1/3 of the width of the "band".

  In particular, in the case of the "band-like shape", when the "band" is bent to be folded in the longitudinal direction, when folded in the width direction, it is further bent to fold the side of the "band" In addition, depending on the direction of the major axis of the elliptical through hole, the value of the “stress concentration factor α” can be largely different.

  In the case where the "through hole" or a very "sharp gap" is to be provided, a method is used in which "a resin which is burnt away at the time of firing" is packed in the place.

  The "stress light emitting material" used in the "stress light emitting material layer" of the present invention has an increase in emission intensity substantially proportional to the size of the generated "stress", so that the "stress concentration factor" As the α ′ is larger, the emission intensity is increased, and the visibility can be improved.

  The “stress concentration factor α” is preferably as large as possible, and is set to 2 or more. Furthermore, by setting it to 10 or more, more preferably to 100 or more, the light emission intensity can be made “high luminance”, which is preferable.

  In addition, the “size” of the “stress” applied to the “stress light emitting material” can be determined, for example, according to JIS X 6305 (2010: A load (F) of 0.7 N is applied for 1 minute over the entire area within 3 mm on the right side of the card presented in “Testing methods for identification cards-Part 1: General characteristics” of ISO / IEC 10373-1. "Large external force load. (Estimated to be around 10MPa)" and "size" of a degree that is lightly bent with the "hand" of the observer, sufficient luminescence can be obtained. Such external force load can be set to 5 kPa to 1 MPa, preferably 5 kPa to 100 kPa.

  However, as described above, as the “stress concentration coefficient α” is larger, the “discontinuity” of the “shape” of the “stress light emitting material” becomes so-called “abrupt” and the “stress light emitting material” It is inappropriate for the “stress concentration factor α” to be more than 1000, since repeated “deformation” for “light emission” is easily “broken down” and no longer “light emission”.

  The calculation of “stress concentration factor α” is easy in simple shapes such as “cylindrical” described above, but for “stress light emitting materials” having more complicated shapes, and “stress light emitting materials” In the “predetermined part”, “the stress is concentrated” and “the stress concentration factor α” of the “predetermined part where“ the stress concentration factor α is 2 or more ”in the“ stress light emitting material ” In order to obtain the value of 』, it is necessary to find it by applying“ structural analysis software (stress distribution analysis software) ”using the“ finite element method ”.

  Of course, the "stress concentration coefficient α" at the contact point in the state in which the "thread", that is, the "stress light emitting material layer" is embedded on the entangled "paper pulp fiber" is calculated by simulation to the last But you can ask for it.

  By this method, it is possible to estimate which region the “stress concentration coefficient α” becomes high when an external force of what size is applied to the “stress light emitting material layer” from which direction, and further, With respect to the "anti-counterfeit sheet" of the present invention itself, the magnitude and direction of the pulling force of the anti-counterfeit sheet, the magnitude and direction of the bending force, and the size and direction of the twisting force It is possible to estimate the internal stress concentration tendency.

  In this way, the stress concentration tendency of the "anti-counterfeit paper" of the present invention is analyzed, and further, the "stress light emitting material layer" included in the inside, the "shape" and the arrangement of the "stress light emitting material" are analyzed. By doing this, finally, the magnitude of the “stress” of the “stress light-emitting material layer” or the “stress-light-emitting material” at the “site (predetermined site) where the stress is concentrated” is estimated.

  Here, the “stress concentration factor” in the description of “the shape of the stress light emitting material is a shape having a portion where the stress concentration factor α is 2 or more with respect to a predetermined external force load” used in the present invention “α” is, to the last, the “stress concentration coefficient α” in the “stress light emitting material” itself, and a numerical value derived from the “shape” of the “stress light emitting material” is used.

  The chemicals and additives used in the "papermaking" process of "anti-counterfeit paper", ie, the "sizing agent" as a generic term for these additives used in the "anti-counterfeit paper" of the present invention, And “chemicals added to improve the proportion (yield) of“ paper pulp fibers ”and mineral fillers remaining on“ nets (wires) ”, mainly polymers such as aluminum sulfate and polyacrylamide , Starches, and further, carboxymethyl cellulose and inorganic colloidal silica are used, a retention agent, a chemical agent added for improving water loss and improving drying property in the “paper-making process”, which is polyethyleneimine And polyacrylamide, cationized starch, etc., are added to the drainage improvement agent, "paper" to give strength, and used in the internal addition method Such as urea formaldehyde resin, melamine formaldehyde resin, polyamidepolyamine epichlorohydrin, polyvinylamine, etc., a wet paper strength agent to give strength in a wet and moistened state, cationized starch, and cationic or amphoteric polyacrylamide Dry paper strength agents, used to increase the strength of the paper in the normal dry state, such as co-polymers, used in the surface mode, on the surface of the paper, such as modified starch, polyacrylamide, polyvinyl alcohol, etc. by coating or spraying A natural strength agent such as a troir oyster, which has the effect of keeping the paper strength agent, the "paper pulp fiber" of "machine-made Japanese paper" dispersed in water, and preventing the adhesion of the superposed paper. Synthetic thickeners such as polyacrylamide (synthetic spring), rosin soap, alkyl ketene Apply by a gate roll coater or liquid film transfer such as immer, alkenyl succinic anhydride, polyvinyl alcohol, etc. of internal addition type, or oxidized starch, styrene-acrylic copolymer (copolymer), styrene-methacrylic copolymer, etc. This is a surface type, and it is used to reduce the permeability of liquids such as ink to "paper", to prevent offset and bleeding, and to provide a certain degree of water resistance. In order to maintain the opacity and printing performance while keeping up with the degradation, with a surfactant such as a fatty acid ester emulsion, it has the effect of increasing the freeness while giving an effect by partially watering the fiber surface, A bulking agent, which is an agent added for the purpose of reducing the density of paper and increasing its volume, making the paper opaque and preventing strikethrough, white Mineral powder to be blended or coated to have a degree of smoothness, etc., mainly talc, kaolin (white clay), calcium carbonate, titanium oxide, barium sulfate etc., and amorphous silica (white Carbon), urea resin is also used as an organic filler, and as a filler, kaolin, calcium carbonate or organic white pigment is used as a pigment, and a synthetic rubber latex mainly composed of butadiene is used as a binder, paper surface Apply a paint solution containing a white pigment to increase the whiteness, smoothness, printability and water resistance, and add starch, casein, carboxymethyl cellulose etc. There are coating chemicals and the like that are used as modifiers.

  In addition, "area" ("area" on the surface of "stress light emitting material layer" of "thread") containing "stress light emitting material" may be in the form of "predetermined pattern", for example, characters and figures of predetermined size. Or, a symbol, in particular, a "shape" representing some "message (such as characters of" true ")" for authenticity determination, provided in a predetermined size, and "the predetermined pattern" "Light pattern" by emitting "."

  Furthermore, a large number of the above-mentioned "cutouts and / or recesses" are arranged side by side continuously, and "a predetermined pattern is represented (meaning that a predetermined pattern is represented by a series of light spots)". I assume.

  As such "predetermined pattern", depending on the application of the "anti-counterfeit paper", not only numbers or symbols but also letters, figures, marks, others, individuals and suppliers of the "anti-counterfeit paper" are common Any object can be used as long as it can be recognized (this object is all the so-called "information").

  And also as the recognition method, a recognition method other than visual observation, for example, an optical reading method can be employed while having at least information that can be recognized by visual confirmation.

  In particular, it is also preferable to adopt, as the “predetermined pattern”, the type and model number of the “anti-counterfeit paper”, the name of the manufacturer and the date of manufacture thereof, and secure the traceability of the “anti-counterfeit paper”.

  In addition, the "forgery prevention paper" manufactured for use for a limited purpose or purpose has "information" according to the purpose or purpose, for example, logos, seals, etc., and has identification with other companies. Letters, figures, symbols, etc., that is, brand logo display, publisher, author, game machine operating company, high-end brand, security company, cash ticket issuer or issuer, delivery or delivery company, sales company, etc. The name of an organization, etc., and "information" including characters and symbols representing authenticity, and its logo, characters, figures, symbols, etc. are the added value of the paper, reliability such as quality assurance, etc. It is possible to employ something that enhances

  Furthermore, it is a mere serial number or a symbol, and its validity is exhibited by registration, the same number such as a common key number which is an encryption key number, or even a completely random number A person who is permitted to know (such as a legitimate purchaser, etc.) is used to generate a prevention sheet when making it, and a person or other person, including the producer, is devised to know the contents of the number. The designer of the entire system, the issuer of the product to which the "Anti-counterfeit paper" is applied, etc. may be included, etc.), and other persons can not physically see it. The numbers or symbols may be used.

  And, as a method of confirming such a "hidden pattern", it is a "jig" of a predetermined shape, for example, "a size of the bottom is a square-shaped 100-200 mm wide and 100-300 mm wide". The observer presses the "anti-counterfeit paper" of the present invention onto the curved surface of the projecting portion of the "jig" whose radius of curvature of the projecting portion is 50 mm to 300 mm so that the observer emits light The method can be adopted.

  Furthermore, it is preferable that the character size of the "hidden pattern" to be confirmed should be able to be read on the curved surface of the "jig" as 1 to 20 mm long x 1 to 20 mm wide, and more stable Enables authenticity determination.

  As an example, the size of "thread" is a band of 15 mm in width, and the character size of "hidden pattern" on the "thread" is 10 mm long x 15 mm wide (1 / 1.5 aspect ratio) Horizontal), and multiple pieces are arranged at intervals of 30 mm on the curved surface of a jig with a curvature radius of 100 mm and a bottom size of 150mm x 250mm. The observer presses the "anti-counterfeit paper" of the invention with a finger of the hand and further pulls the both ends of the "anti-counterfeit paper" downward or moves it so that it rubs against the jig in that state (paper It is also expressed as a “shimmering” operation), and the lighted “hidden pattern” character is visually recognized and judged.

  According to the "anti-counterfeit paper" of the present invention, the "stress emission" is recognized in a form that can not be recognized from the external appearance at all while the external appearance makes it recognize that a simple "thread sheet" is used. The material is included in the “thread”, and the “paper pulp fiber” is deformed by a predetermined external load applied to the “thread paper”, and at the same time the “deformation stress is applied to a predetermined portion of the“ stress light emitting material ” Is generated, and light of a predetermined wavelength is emitted from the predetermined portion and having an intensity according to the deformation stress, and becomes visible, the authenticity of the “thread paper” is determined without special illumination light. An "anti-counterfeit paper" is provided, which can be easily determined.

  Moreover, this "stress light emitting material" is made into a specific shape, the "light emission" is increased, moreover, the "stress light emitting material" is arranged in the "predetermined pattern" shape, and the "light emission" of the "stress light emitting material" The present invention provides an "anti-counterfeit paper" which makes the "pattern of light" according to

These are figures of the forgery prevention paper G1 which shows one Example of this invention. These are xx sectional drawing of anti-counterfeit paper G1 which shows one Example of this invention. These are yy sectional drawings of the forgery prevention paper G1 which shows one Example of this invention. FIG. 6 is a diagram showing a flow of a “paper making process” for producing the “anti-counterfeit paper G1” according to an embodiment of the present invention.

FIG. 6 is a cross-sectional view of “thread SL 0” used for the forgery prevention paper G 1 showing one embodiment of the present invention. FIG. 6 is a view of “thread SL1” used for the forgery prevention paper G1 showing one embodiment of the present invention. These are figures of "thread SL2" used for the forgery prevention paper G1 which shows one Example of this invention. Is a cross-sectional view of "thread SL3" used for anti-counterfeit paper G1 showing an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
(Paper pulp fiber, sizing agent, paper, and anti-counterfeit paper)
The "paper pulp fiber" used for "paper Y1" of "anti-counterfeit paper G1" of the present invention is a "pulping process", a "pulp bleaching process", and a "selected pulp" in the paper making process of FIG. It can be obtained through the dehydration step and the "raw material preparation step 1: melting and beating" steps. (Refer to FIG. 1 to FIG. 3 and FIG. 4. In FIG. 1 to FIG. 3, "sizing agent" is not displayed.)
“Wood,” “Imported wood chips,” and “Waste paper” are mainly used as raw materials for “paper and pulp fiber”, but from the viewpoint of suppressing deforestation by “paper”, kenaf, sugar cane, bamboo, etc. The "non-wood plants" of are sometimes used.

  The "non-wood plant" is called "linen pulp" and has been the main raw material of paper for a long time, asa, and the main raw material of kanaki, gampi, mitsumata, mayumi, and "Japanese paper" And bamboo, which is a raw material for bamboo paper, which is easy to grow, and rice bran and wheat bran, which are relatively weak in paper because the fibers are thin and short, are the main raw materials of Western paper, cotton; The short fibers (linter) such as ground hair produced in the process of processing can also be ground as a raw material to make "paper", and a linter where "fiber" is made from short fibers such as relatively long rug pulp and cotton ground hair Cotton, which is a raw material of pulp, sugar cane, which is a raw material of bagasse (squeezed) pulp, and Manila asaly, which is a raw material of Abaca (a plant of the Salamander family) which can make relatively thin fibers, flexible and strong "paper". , Close to trees It has the quality, growth is very fast, banana kenaf as a substitute for wood, fiber stem is utilized, a very high strength, used fiber pomace, and the like palm.

  For the purpose of the present invention, as a raw material of "paper pulp fiber", "N material" which is more flexible than "L material" is preferable, and a material to be a raw material of "Japanese paper" is particularly preferable. Further, among the above-mentioned "non-wood plants", "Manila Asa" and "Apricot" having high strength and long fibers and having "pliability" in a similar sense are preferable.

  "Waste paper" dissolves in water and uses mechanical force, gravity, chemicals such as surfactants, etc. Foreign substances (metal, film, adhesive resin, printing ink, copy toner, etc.) other than "paper pulp fiber" ) Is separated, removed and bleached to increase the whiteness according to the application, dewatered and dried to form “paper pulp fiber”, but its recovery route, type of “paper” to be recovered, sorting condition Although the composition and the quality are greatly influenced by the light source, the material of the “Anti-counterfeit paper G1” of the present invention is somewhat unsuitable, but it can be used because of its low price.

  In addition, the metal fiber or resin fiber (polymer fiber, aramid fiber, etc.) is reinforced with strength of the “Anti-counterfeit sheet G1” of the present invention (“the anti-counterfeit sheet G” is torn or deteriorated by repeated deformation) It is preferable to add 5% to 20% to "paper and pulp fibers" for the purpose of preventing the problem and promoting the restoration of the original shape. If the addition amount is less than 5%, the "reinforcement" effect is insufficient, and if it exceeds 20%, the "paper pulp fiber" and the "stress light emitting material" are entangled and the binding is inhibited. It becomes.

  As "wood", conifers ("N material") such as fir and pine, and hardwoods ("L material") such as eucalyptus and poplar are used, and in coniferous trees, tracheids are In hardwoods, wood fiber cells are mainly used. Since fibers of softwood are thicker and longer than fibers of hardwood, the "anti-counterfeit paper G1" produced from softwood is a stronger "paper". However, most of the "information paper" is mainly made of hardwood.

  As "imported wood chips", those from lumber backboards, etc. that are imported from the United States, Australia, New Zealand, Chile, China, etc., those manufactured from thinnings, scraps, etc. Use planted trees produced from eucalyptus and acacia.

  "Plant fiber" which is the raw material of "paper pulp fiber" is mainly composed of "cellulose", and when subdivided, it is divided into "cellulose", "hemicellulose" and "lignin", and "cellulose" has a skeleton Forming, "hemicellulose" promotes connection, and "lignin" is responsible for void filling.

Among these, "cellulose" has the property of being linked by "hydrogen bond" since it has a great number of "OH groups" in its structure. Due to this "hydrogen bond" and with the help of the moisture (H-OH) contained in the "anti-counterfeit paper G1", the "paper and pulp fibers" bond at their intersections I'm doing it. (In FIG. 1, the bonding site of this "paper pulp fiber" is not shown.)
"Pulp and pulp fibers" is a material obtained by pulping to remove lignin and hemicellulose as a matrix from "plant fibers" and separating (disintegrating) pulp fibers (cell wall units) to be refined.

  Since "paper pulp fiber" has many hydroxyl groups on its surface, it forms hydrogen bonds to be self-adhesive when dried, and also bonds with "stress luminescent material layers A0 to A3" of "threads SL0 to SL3". Thus, the "forgery prevention sheet G1" is obtained. After drying, it contributes mainly to the deformation of the "anti-counterfeit paper G1" and its restoration by the swelling ability of the "paper-pulp fibers" and the mutual adaptability.

  The "paper pulp fiber" is further "fibrillated" using various techniques to extract "cellulose nanofibers" and use the "cellulose nanofibers" to make "transparent paper" The technology is also already disclosed.

  By adding 1% to 20% of such “cellulose nanofibers” to “paper pulp fibers”, the transparency of “paper Y1” of “anti-counterfeit paper G1” is increased, and thus “stress emission” It is also preferable to promote the light emission of the “threads SL0 to SL3” of the “forgery prevention paper G1” based on the light emission of the “material”.

  In addition, “pulp” as a raw material of “paper pulp fiber” is classified as mechanical pulp (MP: mechanical pulp) made by a method of crushing wood by physical force according to the manufacturing method, and chemical Chemical reactions (CP: chemical pulp) which can be produced by a method of decomposing crushed wood chips and separating lignin etc. (digestion).

  This "mechanical pulp" includes ground pulp (GP, Ground Pulp), refiner ground pulp (RGP, Refiner GP), thermomechanical pulp (TMP, Thermo-MP), chemithermomechanical pulp (CTMP, Chemi-TMP), etc. If the "mechanical pulp" is mainly used, the "forgery prevention paper G1", that is, the "paper Y1" becomes a "paper" having a relatively large "rigidity".

  Further, "chemical pulp" includes kraft pulp (KP, Kraft Pulp), sulfide pulp (SP, Sulfide Pulp), alkali pulp (AP, Alkaline Pulp) and the like. "Paper pulp fiber" obtained from "chemical pulp" is "smoothly" because it contains cellulose of very high purity, and since "smoothly" "twists", the strength as "anti-counterfeit paper G1" is strong, It is suitable.

  For example, in the case of using "wood" as a raw material, the "pulping process" in the paper making process of FIG. 4 removes bark from the "wood" and grinds it into so-called "chips" to be hydroxylated. It is a process of heating at high temperature in an aqueous solution of sodium or sodium chloride to chemically make "wood" into "pulp" one by one.

  The next "pulp bleaching step" is a step of bleaching this "pulp" with a bleaching agent such as chlorine dioxide to make "white" pulp.

  For example, for mechanical pulp and waste paper pulp, bleach the "pulp" with a bleaching agent such as hydrogen peroxide or hydrosulfite. Further, in the case of chemical pulp, this step includes a step of removing impurities such as lignin remaining in the "pulp".

  And in the "selection and dewatering process of pulp", "unbroken fiber" and "dust" contained in "pulp" are removed using a cleaner etc. and dewatered to form "pulp sheet". It is a process.

  Furthermore, in the "raw material preparation step 1: melting and beating" step, the "pulp sheet" was melted again into "water" using a pulper or the like, and the "pulp" was uniformly mixed with a sufficient amount of water In a state, put a melt of pulp between two metal blades (double disc refiner), put it in a suitable refiner (refiner), cut “pulp” into a suitable size, and at the same time make it fluff (fibril ) Is a process to facilitate the bonding between fibers.

Through these "pulping step", "pulp bleaching step" and "pulp selection and dewatering step", "paper pulp fibers" used for the "anti-counterfeit paper G1" of the present invention is obtained. (See Figure 4)
Among the "sizing agents" used for the "paper Y1" of the "anti-counterfeit paper G1" of the present invention, the "mixing type sizing agent" and the like are the "raw material adjusting step 2: sizing agent" in the papermaking process of FIG. In the “addition of additives”, the “paper pulp fiber” obtained through the “selection and dewatering process of pulp” is added at an appropriate ratio.

As described above, the "contaminated type sizing agent" includes retention agents, drainage improvers, viscosifying agents, internally added sizing agents, bulking agents, etc. Each of them is added in an appropriate ratio according to an application method of the sheet G1. (Not shown)
Another “sizing agent” is “lamination type sizing agent”, ie, a paper strength agent used in the surface mode, a surface mode sizing agent such as oxidized starch, and various coating chemicals (fillers, Pigments, water retention agents, modifiers, etc., etc., in the "paper making process 1: wiring & squeezing water" process, or in the "paper making process 2: drying & pressing process", "material sprinkle system", "spray system" Or “printing method or coating method” or the like, and added at an appropriate ratio and in an appropriate method. (Not shown)
The "paper pulp fiber" of the present invention is "white" in the above-mentioned bleaching step, but this is because the surface is roughened, and the material itself is highly "transparent". Have.

  Therefore, since the factor that affects the "color tone" of the "anti-counterfeit paper G1" of the present invention is the "sizing agent", the "color tone" of the "sizing agent" and the "threads SL0 to SL3" of the present invention By setting the color difference with the "color tone" of the "stress light emitting material layers A0 to A3" to 0.5 or less, the "thread embedded portion G2 of the" threads SL0 to SL3 "of the" forgery prevention paper G1 "of the present invention It is possible to hide the

As a result, the “contrast” of the “thread embedded portion G2” of the “threads SL0 to SL3” and the “contrast” of the “thread exposed portion G3” can be increased, and the design can be enhanced.
(Stress light emitting material, stress light emitting material layer, predetermined base material, and thread)
As "predetermined base material B0" used for "thread SL0 to thread SL3" of "anti-counterfeit paper G1" of the present invention, polyethylene terephthalate (PET), polycarbonate, polyvinyl alcohol, polysulfone, polyethylene, polypropylene, polystyrene, poly Various plastic films such as arylate, triacetyl cellulose (TAC), diacetyl cellulose, polyethylene / vinyl alcohol and the like can be exemplified.

  Furthermore, it is also preferable to use an environmentally friendly, biodegradable plastic film.

Then, depending on the manner of insertion of “threads SL0 to SL3” (whether the predetermined base material B0 is a surface, the stress light emitting material layers A0 to A3 is a surface, or a combination thereof). A plastic film having transparency or a plastic film having opacity is used. (Refer to FIGS. 5-8.)
The thickness is 1.0 to 50 μm, and in particular, the film having a relatively small "stiffness (Clark stiffness)" and a thickness of 1.0 to 12 μm is used. .

  Then, the "stress light emitting material layers A0 to A3" are provided on the "predetermined base material B0" on the entire surface of one side or a part thereof, and they are used for the "forgery prevention paper G1" of the present invention. Although "threads SL0 to SL3" are used, the "thickness ratio" of "stress light emitting material layers A0 to A3" and "predetermined base material B0" in "threads SL0 to SL3" is 1/10 to 30 / 10.

As a method of providing "stress light emitting material layers A0 to A3" on the "predetermined base material B0",
Various coating methods such as a gravure coating method, various printing methods such as an offset printing method, an ink jet method, and the like on the "predetermined substrate B0" using the "stress light emitting material" dispersed in a predetermined solvent , Forming a “stress light emitting material layer A0 to A3” by using a transfer method, a lamination method, etc., injecting “predetermined base material B0” onto “stress light emitting material layer A0 to A3” Method of forming by overlapping using molding method, injection molding method, extrusion coding method, etc., “predetermined base material B0”, and “stress light emitting material layers A0 to A3” are pressure bonded and laminated Alternatively, a method of bonding via an appropriate adhesive may be employed.

Then, the laminates are cut or slit to a desired width to form “thread SL0 to thread SL3” having a desired width and a desired thickness (including a thickness ratio). (These manufacturing processes are not shown.)
In particular, "thread SL3" consisting of a system in which "fine particles P1" are dispersed in "transparent resin J2" on "predetermined base material B0" consisting of a plastic film with relatively small "stiffness (Clark stiffness)" The “thread SL3” provided in an overlapping manner can easily suppress its rigidity to a low level, and is excellent in slit processing suitability, for example, a “thread ribbon” having a width of 1 to 5 mm and a length of 500 m to 1000 m. It is preferable because it can be manufactured stably, and furthermore, the bias of the "stiffness" of the "anti-counterfeit paper G1" after the "paper making" can be suppressed to a low level.

As the “stress light emitting material” used for the “stress light emitting material layers A0 to A3” of the “forgery prevention paper G1” of the present invention, the following can be used. (Refer to FIGS. 5-8.)
(1) An alkali metal ion and / or an alkaline earth metal ion has a basic structure inserted in a space of a host crystal formed by a plurality of molecules of polyhedral structure, and is inserted in the space At least one member selected from the group consisting of a rare earth metal ion, a transition metal ion, a group III metal ion, and a group IV metal ion, wherein at least one of the alkali metal ion and / or the alkaline earth metal ion is selected; Stress-stimulated luminescent material substituted by metal ions of species.

This stress luminescent material is used as a host crystal which is its basic structure,
A triclinic structure belonging to the P-1 space group, in particular, an anorthite-like structure, and a structure similar to the anorthite structure to the extent that alkali metal ions and alkaline earth metal ions can be inserted into the three-dimensional structure space (Including similar compositions),
Okermanite, to the extent that alkali metal ions and alkaline earth metal ions can be inserted into the space of an akermanite (akermanite) -like structure and a host crystal, belonging to the P-42 m space group, in particular. Also encompassing structures similar to structures (similar compositions),
The trigonal structure belonging to the R-3 space group, in particular the feldspar structure with the composition of the aluminosilicate, and the SiO and AlO molecules of the tetrahedral structure are the smallest units, these molecules being all Alkali metal or in a three-dimensional structure, a space formed in the three-dimensional structure (a gap), or a plurality of three-dimensional structures that share and share a vertex. With alkaline earth metals inserted,
Semi-feldspar (feldspathoid) structures, such as eg leucite (leucite) KAlSiO, nepheline (nepheline) NaAlSiO, and compositions whose crystal structure is similar to these compositions, etc.
And this basic structure uses what is shown by any one of following General formula (1)-General formula (6).

_{That, MxN 1 -xAl 2 Si 2 O} 8 ··· (1) / XxY 1 -xAlSi 3 O 8 ··· (2) / (XxM 1 -x) (SixAl 1 -x) AlSi 2 O 8 ·· _{· (3) / XxMyCa 1 -x} -yAl 2 -xSi 2 + xO 8 ··· (4) / MxN 2 -xMgSi 2 O 7 ··· (5) / MxN 3 -x (PO 4) 2 ··· (6) (wherein, M and N are divalent metal ions, at least one of which is Ca, Sr, Ba, Mg or Mn, and X and Y are monovalent metal ions And at least one is Li, Na, or K, and 0 ≦ x, y ≦ 0.8).

Among them, host crystal of the stress luminescent material showing the ultraviolet light (1) has the general formula _{M 1 -x-yNxQyAl 2 Si 2} O 8 ··· (7) ( where each of M and N in the formula, anode The site structure is Ca, Sr, Mg or Ba, and the feldspar structure is Li, Na or K, and Q is a rare earth metal ion, a transition metal ion, a group III metal ion, or a group IV metal ion And a compound satisfying 0 ≦ X ≦ 0.8 and 0.001 ≦ y ≦ 0.1.
Furthermore, in the host crystal of the stress light emitting material, Ca is selected as the alkaline earth metal ion, and a part of the Ca site is replaced with Ce as the rare earth metal ion, that is, a compound represented by the general formula (8), Ca ₁ -yQ yAl ₂ Si ₂ O ₈ (8) (wherein, Q is Eu or another luminescent center ion, and y is a number satisfying 0.001 ≦ y ≦ 0.1) Moreover, the general formula _{(8), Ca 1 -mCemAl 2 Si 2 O} 8 ( where, m is a number satisfying a 0.001 ≦ m ≦ 0.1.) using what may be expressed as be able to.

And as a luminescent center of this stress luminescent material,
As ions of rare earth metals, europium (Eu), dipiscosium (Dy), lanthanum (La), gadolinium (Gd), cerium (Ce), samarium (Sm), yttrium (Y), neodymium (Nd), terbium (Tb) Ions such as praseodymium (Pr), erbium (Er), thulium (Tm), ytterbium (Yb), scandium (Sc), promethium (Pm), holmium (Ho), lutetium (Lu), etc.
Further, as ions of a transition metal, chromium (Cr), manganese (Mn), iron (Fe), antimony (Sb), titanium (Ti), zirconium (Zr), vanadium (V), cobalt (Co), nickel ( Examples of the ions include Ni), copper (Cu), zinc (Zn), niobium (Nb), molybdenum (Mo), tantalum (Ta), tungsten (W) and the like. Furthermore, ions of aluminum (Al), gallium (Ga), indium (In), thallium (Tl) and the like can be used as the group III metal ion.

  In addition, as metal ions of group IV, ions of germanium (Ge), tin (Sn), lead (Pb), etc., ions of these rare earth metals, ions of transition metals, metal ions of group III, and IV Of at least one ion selected from the group metal ions, and the content of the rare earth metal ion and the transition metal ion, that is, the content of the luminescent center in a range of 0.1 mol% to 20 mol% It is possible to use one in the following range, preferably in the range of 0.2 mol% to 10 mol%, particularly preferably in the range of 0.5 mol% to 5 mol%.

Here, the content is 0. If it is less than 1 mol%, efficient light emission can not be obtained, and if it exceeds 20 mol%, the host crystal is disturbed and the light emission efficiency is lowered.
(2) An alkali in the space of a host crystal formed by bonding a plurality of molecules having at least an AlO-like structure and an SiO-like tetrahedral structure by sharing atoms at the apex of the tetrahedral structure An alkali metal having a basic structure in which at least one of a metal ion and an alkaline earth metal ion is inserted, and the host crystal further having an asymmetric framework structure and inserted in the space It is a stress light emitting material in which at least one of ions and alkaline earth metal ions is substituted by rare earth metal ions and at least one metal ion of transition metal ions, in particular, at least AlO-like. Three-dimensional structure (three-dimensional frame structure) formed by a plurality of molecules having a tetrahedral structure of a structure and a SiO-like structure, and asymmetry By having a configuration in which the light emission center is inserted into the basic structure having a flexible frame structure, the "Anti-counterfeit paper G1" of the present invention including this stress light emitting material emits light only by light deformation by hand. What can be done.

  In addition to the three-dimensional frame structure, this stress light-emitting material simultaneously has a flexible three-dimensional frame structure and an asymmetric flexible framework structure, as a “spontaneous strain” or “elastic anisotropy”. In such a host crystal, it is easy to distort the strain energy and efficiently change the electronic structure of the luminescent center at the center of the frame. ing.

  In addition, in order to make the host crystal more likely to be distorted, a part of the alkali metal or alkaline earth metal inserted in the space of the host crystal is another ion (eg, 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 it can maintain the crystal structure (asymmetrical flexible three-dimensional frame structure) of the host crystal. For example, an alkali metal ion inserted in the space formed in the host crystal, and a rare earth metal ion or transition metal ion having an ion radius different from that of the alkaline earth metal ion are included in this replacing ion. It is suitable. Accordingly, the host crystal can be easily distorted, and a stress-stimulated luminescent material can be provided which exhibits stronger light emission. Note that the rare earth metal ions or transition metal ions here are for making the host crystal easy to be distorted, and may not function as a light emission center described later.

  The host crystal is a feldspar (Feld spar) structure having an aluminosilicate composition, in particular, an anorthite-like structure. It is more preferable that such a basic structure is, for example, an aluminosilicate represented by any of the general formulas (1) to (4) described above.

  By using Eu as the rare earth metal ion of the light emission center as the light emission center, it is possible to make a light emitting body preferably emitting blue light. In addition, the luminescent center is not limited to one type, and a mixture of plural types may be used. For example, a mixture of Eu and Dy can also be used.

More specifically, the stress light-emitting material exhibiting particularly strong blue emission, the next _{M 1 -x-yNxQyAl 2 Si 2} O 8 ··· (9), _{and, X 1 -x-yYxQyAl 2 -xSi} 2 + xO 8 (10) (wherein each of M and N is a divalent metal ion, at least one is Ca, Sr, Mg or Mn, and X and Y are monovalent metals At least one ion of Li, Na, or K, and Q is a rare earth metal ion or transition metal ion, and a number satisfying 0 ≦ X ≦ 0.8, 0.001 ≦ y ≦ 0.1 It is preferable that it is the light-emitting body shown by

  However, as in the case of the formula (9), in the case of an alkaline earth metal, Al and Si remain at 2 respectively and do not change with X in the formula. On the other hand, in the case of an alkali metal, as shown in equation (10), the number X of monovalent alkali metals increases to balance the charge, and the number of tetravalent Sis increases (2 + X). The value of Al is reduced (2-X).

Furthermore, in the stress-stimulated luminescent material, a stress-stimulated luminescent material is more preferable in which Ca is selected as the alkaline earth metal and a part of the Ca site is replaced with at least one type of luminescent center. That is, Ca ₁ -yQ yAl ₂ Si ₂ O ₈ (11) (wherein Q is Eu, and at least one of other luminescent centers, y is 0.001 ≦ y ≦ 0.1 It is a number to satisfy.)

Incidentally, formula (11), the light emitting center, in the case of Eu alone, may be expressed as _{Ca 1 -m-nEumAl 2 Si 2} O 8. (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 luminescent center is E _In the case of a mixture of _U and other luminescent center ions, the content (m) of the mixture as a luminescent center may be in the range of more than 0 and 0.2 or less.

Such a stress-stimulated luminescent material can exhibit particularly strong blue emission, and in the formula (11), the luminescent center (Q) preferably contains at least Eu. Furthermore, in the formula (11), it is preferable that at least Eu be contained as the rare earth metal ion of the light emission center, for example, it is more preferable that the light emission center is only Eu or a mixture of Eu and Dy. As described above, if Eu is contained as the light emission center, a stress light emitting material which exhibits blue light emission particularly strongly can be obtained.
(3) A stress-stimulated luminescent material satisfying the condition of light emission by strain energy, that is, a stress-stimulated luminescent material which emits light by a mechanism such as a piezoelectric effect, a lattice defect, and heat generation due to deformation by formation of strain energy.

  By using this stress light emitting material, the "Anti-counterfeit paper G1" of the present invention containing this stress light emitting material can be made to emit light only by lightly deforming it by hand.

  The light emission by this piezoelectric effect is that strain energy is generated to generate strain energy in the “material”, and electricity is generated by the piezoelectric effect accompanying the strain energy, whereby “electroluminescence” is generated. .

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

  The light emission due to lattice defects causes “light emission” because it enables recombination of electrons and holes trapped in lattice defects by strain energy if lattice defects exist in the material. It is a thing.

  In the stress light emitting material, in order to realize a light emitting mechanism derived from lattice defects, at least one, preferably two or more types of metal ions are added to the base material contained in the stress light emitting material, the center of the defect center It may be added as ions.

In such a stress light emitting material, as described later, various “metal elements” are added to the crystal material of the α-SrAl ₂ O ₄ phase so that metal ions substitute for Sr sites and Al sites.

The light emission due to heat generation is such that when a material is deformed due to strain formation, heat is generated along with the deformation, and thermoluminescence (thermoluminescence) is generated along with heat generation (temperature rise) to “light”. Here too, α-SrAl ₂ O ₄ can be mentioned as the base material.
(4) A stress-stimulated luminescent material containing a “mixed phase” in which a plurality of crystal structures are mixed (mixed). That is, by using a “mixed phase” in which a plurality of crystal structures are mixed, a light emitting material capable of visualizing highly efficient (high brightness) red stress light emission which can not be realized with a single crystal structure is realized. .

  The mixed phase has at least two or more kinds of crystal structures among crystal structures of zinc oxide of wurtzite structure, zinc sulfide of cubic crystal or wurtzite structure, and manganese oxide of cubic crystal. It is preferably a complex crystal. With this configuration, it is possible to obtain a red light emitter which can not be realized by zinc oxide, zinc sulfide and manganese oxide alone or in combination of these two.

  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 replaced by other metal ions. In this case, it is preferable that another metal ion other than the metal ion constituting the mixed crystal is a Te ion. This makes it possible to greatly improve the intensity of red light emission of the stress-stimulated luminescent material. (It becomes "High brightness red stress light emitting material".)
It is preferable to make this Te ion be 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.

  Furthermore, among the stress-luminescent materials, the mixed crystal is selected from barium titanate having a tetragonal structure, calcium titanate having an orthorhombic structure, magnesium titanate having a rhombohedral structure, and strontium titanate having a cubic structure. Therefore, at least two or more types may be included, and in this case, a part of metal ions constituting the mixed crystal may be substituted by another metal ion.

Further, the stress light-emitting material has the general formula _{(Ca 1 -xA'x) yBa 1 -yTiO} 3, (Mg 1 -xA'x) yBa 1 -yTiO 3, and, (Sr ₁ -xA'x) yBa ₁ -YTiO ₃ (where, 0.0001 x x 0.05 0.05, 0.005 y y 0.99 0.995, A 'represents Dy, La, Gd, Ce, Sm, Y, Nd, Tb, Pr, Er Or a rare earth element selected from the group consisting of

  With this configuration, a light emitting material having both light emitting property of emitting light by application of stress and an electric field and piezoelectricity can be obtained.

Further, praseodymium (Pr) is most preferably used as the rare earth element shown as A ′. Furthermore, ferroelectric tetragonal Ba ₁ -xCaxTiO ₃ : Pr solid solution (0 <x <0.23) and paraelectric orthorhombic BayCa ₁ -yTiO ₃ : Pr solid solution (0.9 <y < It may be "mixed phase" consisting of 1).

  The ratio of Ca is preferably in the range of 40% to 80%, or in the range of 1% to 35%. Further, the ratio of Ca is more preferably in the range of 55% to 65%, or in the range of 25% to 35%.

  The above-described stress light emitting material emits light by applying mechanical external force such as stress, shear force, impact force, pressure and the like, and the light emission intensity generally becomes higher as the external force applied is larger.

Furthermore, as a "stress light emitting material" that can be used for the "forgery prevention paper G1" of the present invention,
(5) As a host crystal, an oxide or a composite oxide of at least one metal belonging to the periodic table groups 2A, 3A, 4A and 3B, 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 Having a structure, yttria structure, corundum structure, or β-alumina structure, in particular, selected from ZrO ₂ , CeO ₂ , HfO ₂ , Y ₂ O ₃ , Cr ₂ O ₃ and Ti ₂ O ₃ A metal oxide having a crystal structure selected from a fluorite structure, a yttria structure, and a corundum structure,
A rare earth metal ion having an unstable 3d, 4d, 5d or 4f electron shell and capable of causing a radiative transition in this electron shell, and a transition metal ion, in particular, first ionization At least one metal ion selected from among rare earth metal ions having energy of 8 eV or less and transition metal ions, 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, in particular A transition metal ion selected from among 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 luminescence center is the same as in (5) above.
(7) At least the host crystal selected from the group consisting of MgAl ₂ O _{4 of} spinel structure, and CaAl ₂ O ₄ , Al ₂ O _{3 of} corundum structure, and SrMgAl ₁₀ O ₁₇ of β-alumina structure One type of metal oxide or composite oxide is used, and the luminescence center thereof is the same as the above (5).
(8) A host material comprising, as a main component, at least a complex of an oxide of at least one metal selected from Y, Ba, and Mg and an oxide of Si as a host crystal, in particular _{, Y 2 SiO 5, BaSi 2} O 5, and selected from among Ba ₃ MgSi ₂ O _8, be one to use at least one of the composite oxide, the emission center, and the (5) Same thing.

In particular, those to which a luminescent center composed of one or more types of rare earths or transition metals that emits light when electrons excited by mechanical energy return to the ground state are added.
(9) As a host crystal, 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 of a melilite type structure _From one or more of the oxides of ₂ O ₇ , (Ca, Na) ₂ (Al, Mg) (Si, Al) ₂ O ₇ , and Ca ₂ (Mg, Al) (Al, Si) SiO ₇ The host material is used, and the luminescence center thereof is the same as the above (5).
(10) At least one compound represented by MN ₂ O ₄ (M and N each selected from the group of Mg, Sr, Ba and Zn, and Ga and Al, respectively, as the host crystal An oxide composed of any of the above metal elements, and one represented by M, in which the molar percentage of the luminescence center element to the metal element is 0.001 to 20%, particularly MgGa ₂ O ₄ , In an oxide represented by ZnGa ₂ O ₄ , ZnAl ₂ O ₄ , SnZn ₂ O ₄ , BaAl ₂ O ₄ , MgAl ₂ O ₄ and, further, in the case where the base material is composed of a compound having a spinel structure, An oxide containing a pseudo spinel or inverse spinel structure, the luminescence center of which is the same as the above (5).
(11) a compound represented by MN ₂ O ₄ (wherein M and N are at least one or more metal elements respectively selected from the group of Mg, Sr, Ba and Zn, and the group of Ga and Al) An oxide containing as a base material and having 0.0001 to 20 mol% of lattice defects with respect to M or N.
(12) to the host crystal, (A) the general formula _{xM1O · yAl 2 O 3 · zSiO} 2 (M1 in the formula Ca, Ba, or a Sr, a portion of Na, K, and, of Mg Aluminosilicate represented by at least one of x, y, and z is a number of 1 or more, and (B) a general formula xM2O · yAl ₂ O ₃ (wherein M2 is Ca or Ba, and a part thereof may be replaced by at least one of Mg and La. X and y are the same as described above. , (C) General formula xM3O · ySiO ₂ (wherein M 3 is Ca or Sr, and a portion thereof is Na, Mg, Zn, Be, Mn, Zr, Ce, and Nb) It may be replaced by at least one selected from x. And, y is the same.), Or, silicate represented by Ba ₂ MgSiO _7, (D) Formula xM4O · yM5 ₄ O ₁₁ (M4 in the formula, Ca, Ba or, Sr, M5 is , Ta, and at least one of Nb, wherein x and y have the same meanings as above), or a tantalate, or (N) (N) a general formula xM5O · yGa ₂ O ₃ (wherein M 5 is Ca, Ba or Sr, and a part of which may be replaced by La. X and y are as defined above) gallate and, selected from among ZrO _2, at least one oxide of, particularly, some of the general formula _{xSrO · y a l 2 O 3} · z S i O 2 (Sr in formula, N a, K And even if at least one of M g is replaced There .x, y, and, z is a number of 1 or more.), The general formula xSrO · ySiO ₂ (part of Sr in the formula, N a, M g, Z n, B e, M n, It may be substituted by at least one selected from among Z r, C e and N b, x and y are as defined above, or a general formula xSrO · yM 4 O ₁₁ (wherein M is at least one of Ta and Nb, and x and y are as defined above, and a matrix material comprising a strontium complex oxide, and further, xSrO · yAl ₂ as _{O 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 ( Mg, Al) (Al, Si) SiO ₇ , Sr ₂ Al ₂ SiO ₇ , SrNa ₂ Al ₄ Si ₄ O ₁₆ etc. can be mentioned, and the elements in parentheses can be mutually replaced.

Moreover, 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 or the like, or Sr (Ta, Nb) ₄ as xSrO y M ₄ O ₁₁ What is O ₁₁ ,
In particular, those having high luminous 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 or SrGa ₁₂ O ₁₉ or SrLaGa ₃ O ₇

  And these oxides are shown in the crystal structure in point group (in the index of simplification expression) 1, -1, 2, 2 / m, 6 / m, m 3 m, (-4) 2 m, 622 The light emitting center has an unstable 3d, 4d, 5d, or 4f electron shell, and a radiation transition can occur in this electron shell Rare earth metal ions 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 among transition metal ions, 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, Chosen 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, transition metal ions selected from V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ta, and W.

As a "stress light emitting material" that can be used for the "forgery prevention paper G1" of the present invention,
A strontium- or aluminium-containing composite metal oxide represented by the composition formula, SrMgAl ₆ O ₁₁ , SrLaAl ₃ O ₇ , or SrYAl ₃ O ₇ as a base material, and europium as an 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- y MgAl ₁₀ O ₁₇ (wherein, A 'is a rare earth metal, B' is an alkaline earth metal of any of strontium (Sr), barium (Ba) or calcium (Ca) And is a light emitter represented by 0 ≦ x ≦ 0.99 and 0.001 ≦ y ≦ 0.550.
(14) In the host crystal, general formula xBaO. YAl ₂ O _3. ZSiO ₂ (wherein Ba may be partially replaced with at least one of Na, K and Mg, x, y, and z are each a number of 1 or more, xBaO · yAl ₂ O ₃ (wherein Ba may be partially replaced with Mg, and x and y are the same as above) ) Or xBaO · ySiO ₂ (wherein Ba may be replaced with at least one of Mg, Fe, Mn, Zn, and Be, and x and y are At least one oxide selected from barium complex oxides having the composition represented by the above:
Here, as the one 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 ₁₃ , BaMgAl ₆ O ₁₁ ,
Examples of the material represented by xBaO · ySiO ₂ include Ba (Zn, Mn, Fe, Mg) Si ₂ O ₆ , Ba ₂ (Mg, Fe) Si ₂ O ₇ , Ba ₂ BeSi ₂ O ₇ , and Ba ₂ MgSi. ₂ O ₇ , Ba ₂ MgSiO ₇ , etc.
In particular, Ba ₂ Al ₂ SiO ₇ , Ba ₂ MgSi ₂ O ₇ , BaAl ₂ Si ₂ O ₈ , and BaAl ₈ O ₁₃ are the ones with high emission intensity.

And, these oxides are shown by crystallographically in point group (in the index of simplification expression) 1, -1, 2, 2 / m, 6 / m, m 3 m, (-4) 2 m, 622 A rare earth metal ion which has an unstable 3d, 4d, 5d or 4f electron shell and which can cause a radiative transition in this electron shell, using one belonging to the 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 among transition metal ions, 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, Tb and Dy Rare earth metal ions selected from among , 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) A light emitting material consisting of (Ca ₁ -pPrp) q Ba ₁ -qTiO ₃ (0.0001 ≦ p ≦ 0.05, 0.005 ≦ q ≦ 0.995), and further, barium titanate having a tetragonal crystal structure A light emitting material including a mixed phase in which a crystal phase and a crystal phase of calcium titanate having an orthorhombic structure are mixed, and a part of metal ions constituting the mixed phase is substituted by Pr ions, particularly, different sizes It has multiple crystal phases, the crystal phase of barium titanate is large particle size, the crystal phase of calcium titanate is composed of small particle size, and the crystal phase of small particle size is a crystal of large particle size Light-emitting materials uniformly dispersed among the particles of the phase, and also ferroelectric tetragonal Ba ₁ -xCaxTiO ₃ : Pr solid solution (0 <x <0.25) and paraelectric orthorhombic Ba ₁ 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 (x is 0.4 ≦ x ≦ 0.8), or (x is 0.01 ≦ x ≦ 0.35), may be used.

Alternatively, it is possible to use a light emitting material in which the above light emitting material is a light emitting material that emits red light, and in which the light emission intensity is proportional to the magnitude of the mechanical external force applied to the light emitting material. .
(15) In a space of a matrix structure formed by a plurality of molecules having at least an AlO ₄ -like structure and a SiO ₄ -like tetrahedral structure being shared by atoms at the apex of the tetrahedral structure And an alkaline metal ion and / or an alkaline earth metal ion, and the matrix structure further has an asymmetric framework structure, and the alkali metal ion inserted in the space And at least one of the alkaline earth metal ions is replaced by at least one of rare earth metal ions and transition metal ions, and the basic structure thereof is MxN ₁ -xAl ₂ Si ₂ O ₈ (Wherein, M and N are divalent metal ions, at least one of which is Ca, Sr, Ba, Mg, or Mn, 0 a x ≦ 0.8 is.) is indicated _{by, Ca0.985Eu0.01Dy0.005Al 2 Si 2 O 8,} Ca0.995Dy0.005Al 2 Si 2 O 8, Ca0.97Eu0.01Nd0.02Al 2 Si 2 O 8, _{Ca0.93Eu0.02Dy0.05Al 2 Si 2 O 8, Sr0.97Eu0.01Dy0.02Al} 2 Si 2 O 8, Ba0.97Eu0.01Dy0.02Al 2 Si 2 O 8, Ca0.8Sr0.17Eu0.01Ho0.02Al 2 Si _{2 O 8, Sr0.17Ba0.80Eu0.01Ho0.02Al 2 Si 2} O 8, Sr0.17Ba0.80Eu0.01Dy0.02Al 2 Si 2 O 8, or Mg0.2Sr0.77Eu0.01Dy0.02Al ₂ Si ₂ O _8, , Ba0.2Sr0.77Eu0.01Dy0.02A stress luminescent material having a composition represented by l ₂ Si ₂ O _8.
(16) an oxide of tetragonal phase structure represented by the general formula CaM1Al ₃ O ₇ (M1 is, Y, La, or represents Gd.) Comprises a, and Eu ² +, formed from the material of the oxide The stress-stimulated luminescent material further includes a crystal of an oxide having a lattice defect structure in which an atom represented by M1 is deficient.

Then, 0.01 mol to 20 mol of Eu ² + is contained 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 There is a stress luminescent material. In particular, a stress-stimulated luminescent material, wherein the oxide is CaYAl ₃ O ₇ and the impurity phase contains at least one of Y ₂ O ₃ , Y ₃ Al ₅ O ₁₂ or Y ₄ Al ₂ O ₉ .
(17) The host crystal comprises at least one compound selected from the group consisting of metal oxides, metal nitrides, and metal sulfides, and in particular, the metal oxides are aluminates, and aluminosilicates. And at least one compound selected from the group consisting of acids, the luminescent center of which further comprises at least one element of a transition metal (except for rare earth metals), Si and Sn; At least a part is contained in the base material in a non-solid solution state, and further, the element is in the form of particles and is present on the surface of the base material (base 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 element is 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, the crystalline phase of zinc oxide of wurtzite structure, cubic, Alternatively, it comprises a mixed phase consisting of a mixture of a crystal phase of zinc sulfide of wurtzite structure and a crystal phase of at least two or more kinds selected from among crystal phases of cubic manganese oxide, and constituting the mixed phase A stress-stimulated luminescent material in which part of metal ions is replaced by Te ions. Furthermore, it has a plurality of crystal phases of different sizes, and the crystal phase of manganese oxide is a large particle size, and the crystal phase of zinc sulfide and the crystal phase of zinc oxide are composed of small particle sizes. The crystal phase of the small particle size is uniformly dispersed among the particles of the crystal phase of the large particle size, and shows red luminescence among others, and the magnitude of the mechanical external force with which the light emission intensity is loaded. Proportional, stress luminescent material.
(19) A stress-stimulated luminescent material containing monoclinic LiSrPO ₄ : Eu ²⁺ . In particular, it is formed into a light emitting material further containing hexagonal LiSrPO ₄ : Eu ²⁺ , a light emitting material consisting of monoclinic LiSrPO ₄ : Eu ²⁺ , or a base structure consisting of orthorhombic LiBaPO ₄ the space, LiBaPO ions europium (Eu) as an emission center is inserted _4: a Eu ^2+, the content of the emission center is 2.0 to 3.5 mol% LiBaPO _4: Eu ²⁺ Light emitter.

Furthermore, it is preferable to use the following as “stress light emitting material” (hereinafter also referred to as “high brightness stress light emitting material”) that enables high brightness light emission.
(20) An alkaline earth metal deficient type which is composed of an alkaline earth metal oxide and an aluminum oxide and in which the composition ratio of alkaline earth metal ions is deficient, which is represented by the formula MxAl ₂ O ₃ + _{x, MxQAl 10 O 16 + x} , Mx 1 Qx 2 Al 2 O 3 + x 1 + x 2, _{or, Mx 1 Qx 2 LAl 1 0O} 16 + x 1 + x 2 [M in the formula, Q and, L is Mg, Ca, Sr or Ba, respectively, x is 0.8 ≦ x ≦ 0.99, x ₁ and x ₂ is 0.8 ≦ (x ₁ + x ₂ ) ≦ 0.99 And at least one of the aluminates having a non-stoichiometric composition whose main component is a compound represented by the following formula], and emits light when carriers excited by mechanical energy return to the ground state A substance having a lattice defect, or a rare earth metal ion in the matrix substance, and High brightness stress light-emitting material formed of a material containing at least one metal ion as central ion of the luminescent center selected from among transfer metal ions. In particular, the substance composed of aluminate with lattice defects has a stoichiometric compositional ratio less than 1 to 20 mol% of alkaline earth metal ion, and rare earth metal ion and transition metal in this substance. A high brightness stress light emitting material comprising 0.01 to 10% by mole 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, A1 and A2 are at least one atom selected from among calcogens, which are different from M1A1 and M2A2, and x is more than 0 and less than 1 A high-intensity stress-stimulated luminescent material having a coexistence structure of a wurtzite structure and a zinc-blende structure, in particular, the compound semiconductor crystal represented by

Furthermore, a high-intensity stress light-emitting material, wherein M1 is Mn or Eu, A1 and A2 are the same calcogen, or M2 is Zn and Cd, or Zn and Cu, Among them, the general formula xMA · (1-x) MnA (wherein M is Zn or Zn partially substituted by Cu, A is a calcogen, x is a number larger than 0 and smaller than 1) There is a high-brightness, stress-stimulated luminescent material comprising a composite semiconductor crystal having a crystal particle size of 20 nm or less. In particular, a high brightness stress light emitting 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 base material of the first aluminate is α-SrAl ₂ O ₄ , 3 More than one kind of metal ion is added to the base material as a central ion of the defect center, and the added central ion substitutes at least the Sr site of α-SrAl ₂ O ₄ , and the central ion is Sr A high-intensity stress-stimulated luminescent material in which metal ions having both smaller and larger ion diameters and having a smaller ion diameter than Sr are Eu, in particular, the second whose crystal structure is not single crystal A lattice defect is formed in the crystal structure having the spontaneous polarizability of the host material by the addition of the central ion without containing the aluminate, and further, the tunnel structure is formed in the crystal structure. A high-intensity stress-stimulated luminescent material in which an element to be disposed therein is disposed by ion bonding, and further, as metal ions having a smaller ion diameter than Sr, Mg, Na, Zn, Cu, Eu, Tm, Ho, Dy, Sn, A high brightness stress light emitting material in which at least one selected from the group consisting of Mn, Nd, Pr, and Ca is used, and Ba and / or K is used as a metal ion having a larger ion diameter than Sr, and α -The metal ion substituting the Sr site of SrAl ₂ O ₄ is added at 0.1 to 40 mol% based on Sr, and the addition amount of all the metal ions is smaller than the stoichiometry , the central ion has to replace the Al site of the α-SrAl ₂ O _4, metal ions added as the central ion has been made in the ion diameter is smaller than the Al, Si, and B Need is that the metal ions added as the central ion is, there is a large ion diameter than Al, Ga, that In is used, is added as a central ion, the Al site of α-SrAl ₂ O ₄ The substituting metal ion is added in an amount of 0.1 to 20 mol% based on Al, and at least two or more kinds of metal ions having different valences are added as a metal ion added as a central ion, A high brightness stress light emitting 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" which enables light emission of an ultraviolet region (200 nm-400 nm as a wavelength of light).
(23) A structure represented by MN (PO ₃ ) ₄ (wherein, M is a monovalent metal ion and N is a trivalent metal ion) is a host structure, and the above M or N is A stress luminescent material partially substituted by at least one of a rare earth ion and a group III metal ion.

In particular, a stress-stimulated luminescent material in which Na ₁ -xQxLa (PO) ₄ (wherein Q is a Ce ion or a Tl ion, and 0.01 ≦ x ≦ 0.2).
(24) A basic structure in which an alkaline earth metal ion is 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 ion inserted in the space is , A stress-stimulated luminescent material substituted by Ce ions, the basic structure of which has a spontaneous strain, and a polyhedral molecule of which is a tetrahedral structure of at least one of AlO ₄ and SiO _4. And the basic structure is represented by the general formula MxN ₁ -xAl ₂ Si ₂ O ₈ , where M and N are divalent metal ions, and at least one is Ca or a Sr, is 0 ≦ x.), the stress luminescent _{material, Ca0.2Sr0.77Ce0.005Dy0.02Al 2 Si 2 O 8,} Ca0.2Sr0.79Ce0.005Tb0.005Al 2 _{i 2 O 8, Ca0.995Ce0.005Al 2 Si} 2 O 8 Ca0.97Ce0.03Al 2 Si 2 O 8, or _{Ca0.2Sr0.77Ce0.03Al 2 Si 2 O 8,,} Ca0.8Sr0.17Ce0.03Al 2 Si _The stress luminescent material which has a composition shown by ₂ O ₈ .
(25) A structure represented by the general formula MN (PO ₃ ) ₄ (wherein, M is Na ion and N is La ion) is a host structure, and a part of M is a rare earth element. And the rare earth ion substituted by at least one of the group III metal ions and substituted with a part of the M is a rare earth ion selected from the group consisting of Eu, Dy, Ce, and Tb. , A group III metal ion substituted with a part of M thereof is a Tl ion, a stress-stimulated luminescent material.

  The "stress light emitting material" used for the "anti-counterfeit paper G1" of the present invention prepares a material corresponding to the above composition, that is, for each base crystal material, an element serving as a corresponding light emission center Oxides and the like to be contained are mixed at a predetermined ratio in terms of metal atom, (generally, a predetermined value in the range of 0.1 to 100 mol with respect to 100 mol of the host crystal material). By gradually raising the temperature to a temperature in the range of 900 to 1100 ° C. in an inert atmosphere such as nitrogen gas, and then firing at a temperature in the range of 1200 to 1500 ° C. in a reducing atmosphere such as hydrogen-containing argon gas , Can get.

  Here, in order to make the “stress light emitting material” used for the “stress light emitting material layers A0 to A3” of the “forgery prevention paper G1” of the present invention into a predetermined shape, “forming” having a desired shape in advance The above material can be placed in a mold (the above high temperature, which is made of a ceramic material with relatively little deformation), subjected to a predetermined firing, and then taken out from the “mold”. .

  However, in order to smooth the surface of the “stress light emitting material”, metal materials having a high melting temperature (metallic materials have higher surface smoothness than “ceramic materials, and their surface after“ baking ” The surface may be the surface of the “stress light emitting material”, and further, may be the surface of the “stress light emitting material layers A0 to A2”) may be used as the mold.

  In addition, flat resin with sufficient heat resistance using cellulose resin material or acetylcellulose resin material, which completely burns off and adheres less to the baked product at high temperatures mentioned above. A resin coating film is formed on the “ceramic plate” with an appropriate thickness, and at that time, on the surface of the resin coating film, a concave portion (finely shaped) corresponding to a desired shape (a shape to be a “stress light emitting material”) The above prepared material is put in the recess and fired in the same manner as above to burn out the resin coating film and at the same time desired on the “ceramic plate”. It is also preferable to adopt a method of leaving the "stress light emitting material" having a shape, and the "stress light emitting material layers A0 to A2".

  The "stress light emitting material" contained in the "stress light emitting material layers A0 to A3" prepares a material corresponding to the above-described composition, that is, an element to be each base crystal material, and its base crystal material On the other hand, oxides, nitrates, hydrochlorides, etc. containing elements corresponding to the luminescence centers are mixed at a predetermined ratio in terms of metal atoms thereof (the luminescence center material is And a predetermined value in the range of 0.1 to 100 mol), “a composition for“ stress light emitting material ”before firing”, and a shape having a portion where “the stress concentration coefficient α is 2 or more prepared in advance” In the “cavity” of the “baking mold” provided with the “cavity” having the “”, it is filled in a vacuum or in an inert gas atmosphere such as nitrogen gas, argon gas or carbon dioxide. Temperatures in the range of ~ 1100 ° C After gradually raising the temperature (so-called “temperature-rising curve” at this time is set respectively corresponding to the composition for “stress light-emitting material”), “reducing atmosphere such as hydrogen-containing argon gas etc. The temperature is raised to a temperature in the range of 1200 ° C. to 1500 ° C. to “sinter (reduce with limited supply of oxygen)” and / or after sintering (also called tightening after “sintering”). , Naturally cooled, and / or subjected to predetermined forced cooling (so-called “cooling curve” at this time corresponds to each “stress light emitting material” composition or “stress light emitting material” respectively) When it gets close to the room temperature, the "fired object (desired" shape "" stress light emitting material ") is taken out from the" baking mold ", and (this is" baked " It is a procedure.)) In order to obtain the "stressed light-emitting material" obtained, the "plate-like or lump-shaped" can be obtained by "particulated" by a predetermined crushing means or the like.

  The shape of the "cavity" is either "the shape having a portion where the stress concentration coefficient α is 2 or more" itself, or "the shape change (mainly shrinkage) by" sintering "or" sintering ". It is a shape provided on the assumption of

  More specifically, “a predetermined oxide, etc., becomes a“ stress light emitting material ”included in the“ stress light emitting material layers A0 to A3 ”by the above“ predetermined baking ”in the“ cavity ”. As a “composition for stress light-emitting material” before firing, diluted with a predetermined solvent (including an aqueous solvent) to give fluidity, and poured in at a predetermined pressure, and “oxide etc.” In the "predetermined baking environment", the temperature is raised to the "baking temperature" to release the solvent component (water component) or the organic material component, or the low melting point component is softened. Through the composition change and the structural change, the "stress light emitting material" is included in the "stress light emitting material layers A0 to A3".

  And in this "predetermined oxide etc.", hydroxide of "elementary substance or complex of main element" and hydration appearing in crystal base, light emission center and other additives of the target "stress light emitting material" Compounds, anhydrides, oxides, complex oxides, nitrates, hydrochlorides, carbonates, acetates, sulfates, etc., and further, those obtained by "chelating and binding an organic material to the main element (organic metal compounds etc.)" "Fine powder or powder of what is already" stress light emitting material ", and various caking aids (olefin based resins, in particular, propylene based copolymers and styrene based elastomers) are mixed with them. Binders, caking aids for methacrylic acid ester baking, cellulose resins, in particular, those obtained by adding sodium silicate, polyvinyl alcohol, polyethylene glycol, etc. 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 "baking" and "sintering." In this electric furnace, due to its structure and principle, resistance heating furnaces, induction heating furnaces, arc heating furnaces, etc., those using metal heating elements, silicon carbide, molybdenum, lanthanum chromite, carbon graphite, etc. as heating elements, air furnaces (Oxidizing atmosphere furnace), gas atmosphere furnace, vacuum gas displacement furnace, low vacuum furnace, high vacuum furnace, etc. Furthermore, there are a box furnace, a tubular furnace, a continuous furnace, a rotary kiln for firing while rotating an object, and the like.

  Here, in order to make the “stress light emitting material” into a predetermined shape, “the mold having a desired shape in advance using the various means described above (ceramics relatively less deformed at the above-mentioned high temperature) The above-mentioned material is put into the material selected, and after predetermined baking is performed, a method of taking it out from the “molding die” can be used.

  However, in order to sharpen the shape of the “stress light emitting material” and to smooth its surface, a metal material having a high melting temperature (a metal material has higher surface smoothness than a ceramic material, After “baking”, it means that those surfaces become the surface of “stress light emitting material”.) May be used as the mold.

  In addition, it has sufficient heat resistance by using a resin material such as a cellulose resin material or an acetyl cellulose resin material, which completely burns off at the above-described high temperature and causes less adhesion of soot and the like to the fired product. A resin coating film is formed with a suitable thickness on a flat "ceramic plate", and at that time, the surface of the resin coating film corresponds to a desired shape (a shape to be a "stress light emitting material") A concave portion (which becomes a fine concave portion) is provided, and the material prepared as described above is put in the concave portion, and fired in the same manner as described above to burn off the resin coating film and at the same time on the "ceramic plate". It is also preferable to adopt a method of leaving a "stress light emitting material" having a desired shape.

  In addition, “fine particles P1”, which are “stress light emitting materials” included in “stress light emitting material layers A0 to A3”, are primarily obtained by firing the composition for “stress light emitting materials” under predetermined conditions 10 μm to 3.0 mm “plate-like (meaning sheet-like plate)”, or three-dimensional for crushing purpose, for example, tablet-like, pellet-like, columnar-like, with a maximum length of 0.5 mm to 100 mm The “stress light emitting material” in the form of “bulk” such as a rectangular solid or cube is crushed into fine particles using a predetermined crushing means, and the fine particles are sorted using a predetermined classification means etc. The “stress light emitting material” contained in the light emitting material layers A0 to A3, “particulates P1”, or “fine particles in a simply micronized state” are described below ““ predetermined transparent resin J2 Selected from the resins used in What was dispersed in "transparent resin" and made into pellet form etc. is again ground and classified to "particulate" to form "particulate P1", and further, those During processing, when processing is performed by suppressing collisions between fine particles, the shape of those “fine particles P1” themselves forms a complicated shape, and furthermore, the surface of the “fine particles P1” also maintains a very random uneven shape It can be done.

  Here, “transparent resin” selected from the resins used for “predetermined transparent resin J2” means “resin” having the same transparency as “predetermined transparent resin J2”, and in particular Preferably, the bulk modulus of the "transparent resin" is larger than that of the fine particles, and the "deformation" loaded on the resin is considered as it is transmitted to the "fine particles". The composition ratio of the “transparent resin” to the “stress light emitting material” is set to 10/1 to 1/10.

  And, as a crusher as a crusher, a ball mill, a rod mill, an autogenous pulverizing mill, a SAG (quasi-autogenous pulverizing) mill, a high pressure pulverizing roll, a vertical axis impactor (VSI) mill or the like is used.

  In addition, once the "stress light emitting material" is "particulated", and further, "ultra-particulated (average particle diameter is 0.01 to 1.0 .mu.m, in particular 0.01 to 0.1 .mu.m" Fine particles are referred to as “ultrafine particles.” Those larger than this are “fine particles”), and using “granulation” means such as a granulator, etc. What made it as "secondary aggregate" may be made "the microparticles | fine-particles P1."

“Pulsitized” “stress light emitting material” (the one composed 100% of “stress light emitting material”, “a composite of stress light emitting materials consisting of a plurality of stress light emitting materials”, The composition comprising stress light emitting material and transparent resin J2 ′ ′) is sorted out using a classification means, or further granulated using a granulation means, and then sorted using a classification means To a maximum diameter of 0.1 μm to ₅₀ μm, preferably 5.0 μm to 20 μm, or “average particle diameter D ₅₀ , 0.05 μm to 20 μm, preferably 0.5 μm. It is set as "microparticles P1" of -10 micrometers.

The “fine particles P1” made of the “stress light emitting material” are dispersed in the above “transparent resin J2” to form “stress light emitting material layer A3”. (See Figure 8)
For the "transparent resin J2", 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 Butyl acrylate (n = 1.44), polyisobutyl acrylate (n = 1.48), etc. Cellulose-based resin, that is, cellulose nitrate (n = 1.54), methyl cellulose (n = 1.50), cellulose acetate Propionate (n = 1.47), etc., vinyl-based resin, ie, polyvinyl acetate (n = 1.47), polyvinyl chloride / vinyl acetate (n = 1.54), etc., acrylamide resin (n = 1) .50) or polystyrene resin (n = 1.60) or the like, and as a 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), silicone resin (n = 1.41 to 1.60), or fluorinated resin (n = 1.35 to 1.1). 38) etc.

  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, etc. Or a metal soap such as zinc naphthenate or a peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide to initiate polymerization by heat or ultraviolet light, benzophenone, acetophenone, anthraquinone, naphthoquinone, azobisisobuty Ronitrile or diphenyl sulfide may be blended.

  In addition, as the ionizing radiation curable resin, epoxy acrylate, urethane acrylate, acrylic modified polyester and the like can be mentioned, and for the purpose of introducing a crosslinked structure into such ionizing radiation curable resin or adjusting the viscosity, A monofunctional monomer or a polyfunctional monomer, or an oligomer may be blended and used.

In addition, the above-mentioned thermoplastic resin or thermosetting resin, silicone resin or fluorine-containing resin, furthermore, a mixture of silicone oil, or thermoplastic resin, or thermosetting resin and silicon resin or fluorine-containing resin Or those obtained by introducing a siloxane bond [-Si (R ₁ ) (R ₂ ) -O-] or a fluorine atom [-F] into a molecule of a copolymer of thermoplastic resins or a thermosetting resin. It can be used.
Furthermore, those obtained by dispersing silicon powder particles or fluorine powder particles in the above-described thermoplastic resin or thermosetting resin can also be used.

  As a fluorinated resin, a tetrafluorinated resin as a completely fluorinated resin, a trifluorinated resin as a partially fluorinated resin, a polyvinylidene fluoride, a polyvinyl fluoride, and a perfluoroalkoxy fluorine resin as a fluorinated resin copolymer. A tetrafluoroethylene / hexafluoropropylene copolymer, an ethylene / tetrafluoroethylene copolymer, an ethylene / chlorotrifluoroethylene copolymer, and the like can be used.

  Furthermore, the refractive index difference of the “transparent resin J2” and the refractive index of the “fine particle P1” (the refractive index n of the “fine particle P1” is 1.7 to 2.5), It is 0.3 or less, further 0.1 or less.

  By doing this, the reflectance at the “interface” between the “transparent resin J2” and the “fine particle P1” decreases, and the “light” emitted by the “fine particle P1” can be efficiently transmitted to the observer .

  In particular, the "refractive index difference" of the refractive index of the "transparent resin J2" and the refractive index of the "transparent resin" contained in the "fine particles P1" is 0.1 or less, further 0.03 or less. I assume.

  By this, the interface reflectance at the interface of those “resins” can be made almost “0”, and the “light” generated by the “light emission” of the “fine particles P1” can be further efficiently transmitted to the observer it can.

  The content ratio of “transparent resin J2” to “fine particles P1” is 5/95 to 100/5, particularly 5/30 to 100/30.

  If this mixture ratio is smaller than 5/95, the toughness of the "stress light emitting material layer A3" is lowered, and in the application for the purpose of forgery prevention, it becomes unreliable and exceeds 100/5. Then, the light emission intensity becomes insufficient.

  Furthermore, the ratio of the solvent to the “mixture of“ transparent resin J2 ”and“ fine particles P1 ”” has an individual suitability range 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 P1" in the "transparent resin J2", the "transparent resin J2" is added to the solvents such as cyclic hydrocarbons (cyclohexane etc.), alcohols (methanol, ethanol, etc.) Isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol etc. and their aqueous solutions), Ethers (tetrahydrofuran, methyl cellosolve, ethyl cellosolve, butyl cellosolve, t-butyl cellosolve etc.) , Glycol derivatives such as ethylene glycol monobutyl ether, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, isophorone, diisobutyl ketone, etc.), aromatics (benzene, toluene, xylene, Solvesso) 100, 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.), etc. When a “water-soluble resin (water-based resin)” is used in a dissolved solution or for the “transparent resin J2”, “water” and / or “water,” such as methanol, ethanol, propanol, butyl alcohol, etc. “Particulates P1” are mixed in a solution dissolved in lower alcohol, glycols, cell solves, etc., and “transparent resin” using a dissolver, stirrer such as mixer, kneader such as kneader, roll mill, etc. After uniformly containing “fine particles P1” in “J2,” the mixed solution is gravure coated. , Curtain coating method, blade coating method, roll coating method, spin coating method, offset printing method, letterpress printing method, screen printing method, intaglio printing method, inkjet printing method, casting method, die coating method, etc., resin film Etc. on a "suitable base material" such as a predetermined thickness, and drying under predetermined conditions (natural drying, contact heating drying at 40 degrees to 80 degrees, hot air drying at 40 degrees to 200 degrees, vacuum drying Etc. UV irradiation, drying using curing reaction by electron beam irradiation, etc. may be used alone or in combination, and it may be separated from its “appropriate substrate” to have a predetermined thickness. The “stress light emitting material layer A3” is obtained. (See Fig. 8. "The appropriate base material" and the manufacturing method are not shown.)
Here, in order to improve the water resistance of the stress light emitting material, it is also preferable to apply a surface treatment to the “stress light emitting material” or the “stress light emitting material layers A0 to A3”.

  In this surface treatment, an appropriate amount of the surface treatment agent is dissolved in an appropriate organic solvent (organic solvent) at room temperature or by heating, and the solution is subjected to an appropriate amount of the above according to the purpose. The stress-stimulated luminescent material is added, and after stirring for an appropriate period of time using an appropriate stirring device such as a dissolver or a mixer, the resultant is obtained by drying under appropriate conditions.

  At this time, it is needless to say that the conditions are set so as to maintain the "shape" of the stress light emitting material without breaking it.

  Further, in order to further improve the water resistance, it is also preferable to simultaneously mix an appropriate amount of a thermoplastic resin or thermosetting resin for forming a "film" with respect to the stress light emitting material in the above-mentioned solution.

  The thickness of this "coating" is set to be 0.1 μm to 10 μm.

  As the thermoplastic resin, acrylic ester resin, that is, polymethyl methacrylate, polymethyl acrylate, polybenzyl methacrylate, polybutyl acrylate, polyisobutyl acrylate, etc. Cellulose resin, that is, cellulose nitrate, methyl cellulose, ethyl cellulose, cellulose acetate pro As the thermosetting resin, pyonate etc., vinyl resin, ie polyvinyl acetate, polyvinyl chloride / vinyl acetate etc., acrylamide resin, polystyrene resin etc., and unsaturated polyester resin, acrylic urethane resin, epoxy resin A modified acrylic resin, a melamine resin, an epoxy modified unsaturated polyester resin, an alkyd resin, a phenol resin, a silicone resin, or a fluorinated resin may, for example, be mentioned.

As a surface treatment agent, typically, a silylating agent or a silane coupling agent is used. As the silylating agent or silane coupling agent,
Having vinyl group, vinyltrimethoxysilane, vinyltriethoxysilane, etc., epoxy group, 3-glycidoxypropylmethyldimethoxysilane, etc., styryl group, P-styryltrimethoxysilane, etc., acrylic group, 3-acryloxypropyltrimethoxysilane and the like, methacryl group-containing 3-methacryloxypropyltrimethoxysilane and the like, isocyanate group-containing 3-isocyanatopropyltriethoxysilane and the like, and further, trimethylsilylcurolalide, hexamethyldichloride Silazane, BSTFA (N, O-bis-trimethylsilyl-trifluoroacetamide), triethylsilyl chloride, chloromethyltrimethylsilane, trimethylsilylacetylene, hexamethyldisilane, N, N'-bist Or the like can be used methylsilyl urea.

  The organic solvent (organic solvent) used for the surface treatment includes alcohol solvents such as ethyl alcohol, propyl alcohol or butyl alcohol, ketone solvents such as acetone or methyl ethyl ketone, toluene, xylene or benzene Aromatic hydrocarbon solvents, glycol ether solvents such as methyl cellosolve, ethyl cellosolve, propyl cellosolve or butyl cellosolve, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, or tripropylene glycol, Oxyethylene such as polypropylene glycol, oxypropylene addition polymer, ethylene glycol, propylene glycol, or alkylene glycol such as 1,2,6-hexanetriol, Phosphorus, can be preferably used 2-pyrrolidone, more preferably, ethyl alcohol, propyl alcohol, alcohol-based solvents such as butyl alcohol, acetone, a ketone solvent such as methyl ethyl ketone is used.

  At this time, it is more preferable to adjust the water content of the organic solvent, and the water content is less than 0.5%. When the water content is 0.5% or more, the light emission characteristics of the stress-stimulated luminescent material are degraded by the water in the solution.

  Moreover, in order to improve the water resistance of the stress-stimulated luminescent material of the present invention, the surface coating treatment of the stress-stimulated luminescent material can also be performed using “a metal alkoxide (a product obtained by reacting an alcohol with a metal)”.

  As the metal element constituting the “metal alkoxide”, aluminum, zirconium, titanium, and silicon (here, “silicon” which is a “metalloid element” is also included) can be used, and the type of alkoxide is used. Methoxide, ethoxide, propoxide, isopropoxide, oxyisopropoxide, butoxide and the like can be used. In addition, ethyl silicate and methyl silicate obtained by partially hydrolyzing and condensing tetraethoxysilane or tetramethoxysilane can be used.

  In particular, tetraethoxysilane, tetramethoxysilane, tetraethyl silicate, tetramethyl silicate, aluminum triisopropoxide, zirconium tetraisopropoxide, titanium tetraisopropoxide and the like are preferable.

  The addition amount of the metal alkoxide varies depending on the specific surface area of the stress light emitting material, but is 0.5 to 20% in total of the metal alkoxide in terms of each element with respect to the stress light emitting material.

  As an apparatus for mixing this stress luminescent material and metal alkoxide, various dissolvers using various blades (rotary blades), Henschel mixers, speed mixers, ball cutters, stirrers such as ball mixers, power mixers, hybrid mixers, various ball mills And kneaders, such as a corn blender, can be used. Furthermore, the surface-coated stress-stimulated luminescent material obtained is air-dried in a room temperature dryer for several hours to several days, and then dried at 60 ° C. to 200 ° C. for 1 hour to 24 hours.

  Furthermore, a method of coating an alumina film or a titanium dioxide film or the like on the surface of a stress light emitting material by a chemical vapor deposition method (CVD method), stress luminescence by vapor phase hydrolysis reaction at a temperature of 140 ° C. or less. Method of coating the surface of material with "oxide film", "protective film" consisting of metal oxide or metal hydroxide on the surface of stress-stimulated luminescent material by sol-gel reaction or neutralization reaction Metal alkoxide oligomer, an organic solvent solution of a metal alkoxide to a fluidized bed of a stress luminescent material heated to 100 to 200 ° C. (a state where a fine powder floats in a gas while moving). Or, a method of forming a metal oxide film (protective film) on the surface of a stress-stimulated luminescent material by spraying metal alkoxide itself, in a state of stress-stimulated luminescent material in a plasma state It is possible to use a method of exposing to a reactive gas and depositing an oxide film on the surface of the stress-stimulated luminescent material.

    Of course, such “fine particles P1” dispersed in “transparent resin J2” can be molded into a desired shape using an appropriate “molding die”.

  In any case, the emission of “fine particles P1” contained in “transparent resin J2” passes through “transparent resin J2” surrounding it and spreads to reach the observer's eyes Thus, the “light emitting area (area occupied by the light emitting point)” can be increased, which is preferable.

  Further, in the “stress light emitting material layers A0 to A3”, the “stress light emitting material layers A0 to A3” are produced by applying an external load and the “stress light emitting material layers A0 to A3” are deformed by the deformation. In the light emitting material layers A0 to A3 ′ ′, deformation stress is concentrated on the portion S1 of the stress light emitting material, and at the same time, visible light having a luminous intensity corresponding to the deformation stress is visible from the portion S1 When the light is emitted, "the part S1" is set so that the light of the predetermined wavelength "displays a predetermined pattern".

  Due to the "external force load" on the "stress light emitting material layers A0 to A3", the "light of a predetermined wavelength" itself or the group of "lights" emitted from each "part S1" emits "light" "Point", "light emitting area" or "light emitting pattern" appear, and their "predetermined pattern", that is, their "set of" light emitting point "or" light emitting area ", further," light emitting pattern " Appear as “a collection of”, thereby making “predetermined information” recognized.

  This is to "set that part S1" so that "the light of the predetermined wavelength" "displays" the "predetermined pattern", and the external force load is applied at each time point, respectively. In order to cause different “predetermined patterns” to appear, each portion S1 to be generated corresponding to “each“ external force load to “stress light emitting material layers A0 to A3” ”at each time is predetermined Arrange (arrange) at the position.

  That is, in each "external force load", each part S1 of a predetermined position (arrangement) emits light with a predetermined intensity, and "displays" predetermined "information" by "the pattern of light" which is an aggregate thereof. In addition, the shape of the "stress light emitting material" is set to "predetermined portion S1 of the stress light emitting material" so that the desired portion S1 is generated with respect to such individual "external force load". Is a shape having the portion S1 of which the stress concentration coefficient α is 2 or more.

  Alternatively, the shape of the "stress light emitting material" is made the shape of "stress light emitting material layer A1 or A2" so that the desired site S1 is generated for such individual "external force load", And, on the surface of the stress-stimulated luminescent material, the portion S1 has a notch K1 of a predetermined shape and / or a shape having a recess, or for such individual “external force load”. In order to generate a desired portion S1, the shape of the "stress light emitting material" is made the shape of the "fine particle P1", and the shape having a portion S1 where the stress concentration coefficient α is 2 or more " The “fine particles P1” having the “stress light emitting material” as a composition is taken as a “stress light emitting material layer A3” which is dispersed in the “predetermined transparent resin J2”.

  Here, "predetermined information" refers to characters, figures, or symbols of a predetermined size, and in particular, to a predetermined size of some "message (such as characters of" authenticity ") for authenticity determination. And so on (for example, a predetermined "character" represented by a discrete "dot"), and the character as "information". , Graphics, symbols, and any other information that can be at least visually recognized, "information that should be disclosed only to the legitimate right holder who can know the" predetermined information "" Is also suitable.

  Of course, the mere combination of the “predetermined information” and the other “information” carried by the “stress light emitting material layers A0 to A3” or the “information” of those may be synthesized by various information combining means etc. It may be as "the information to be disclosed to the legitimate right holder is formed".

  Furthermore, as "predetermined information", it may be a personal identification number, personal identification number, account number, other personal-specific numbers or symbols, lottery numbers or symbols, management numbers or symbols, etc., or simply serial numbers or symbols. When the “stress light emitting material layers A0 to A3” are produced, the ones that express their effectiveness by registration, the same number as the common key number that is the encryption key number, and even a completely random number It is set so that only the person who is permitted to know, such as the number generated so that nobody including the creator can know the contents of the number, can see it, and the other person can not easily see it. Numbers or symbols can be used.

  In addition, depending on the application of the “stress light emitting material layer A0 to A3”, not only numbers or symbols but also letters, figures, marks, others, individuals and suppliers of “stress light emitting material layers A0 to A3” are common. Anything that can be recognized (this object is all the so-called "information") can be used.

  And also the recognition method adopts a recognition method other than visual observation, for example, an optical reading method, a magnetic reading method, or any other physical or chemical reading method while having at least information that can be recognized by visual confirmation. be able to.

  Furthermore, as the "predetermined information" displayed by the "stress light emitting material layers A0 to A3" of the present invention, characters, figures, symbols, patterns, marks, shapes, three-dimensional shapes, or combinations of these, or colors and There are no particular limitations, and any other identification information such as an identification code, an identification number, an identification character, or any other means can be used.

  Examples of the identification means include visual identification, optical identification such as portable camera recognition and bar code recognition, machine identification, and other physical identification means.

  All may be identical or all individual, as long as they can be identified, or they may be individuals or businesses, or even specific to a particular industry.

  Also, as in "design", it may be the shape, pattern or color of the article (including the part of the article) or a combination thereof that gives rise to an aesthetic sensation through vision, or the like. , "Trademark", letters, graphics, symbols or three-dimensional shapes or their combinations or combinations of these with colors, and used by those who produce, certify or transfer goods as business It may be the one used by the person who provides or certifies the service as a work or the service, or the like. In addition, "title", "trade name", and even those to be collated in various scenes may be used.

  And "characters" include all typeface characters such as hiragana and slave fonts, "symbols" include special character symbols, emoticon symbols, electric character symbols, map symbols, etc., and HTML symbols Symbols used only in limited situations of limited industry, such as, are also preferable because of their speciality.

  In addition, English letters, Greek letters, and other letters used in various countries, symbols, mathematical symbols, etc. are also preferable because they can not be memorized to the extent that an illegal person peeped momentarily.

  Furthermore, by including hidden information which can not be discriminated by a mere information reading means such as visual observation or encryption information in these pieces of information, only a person who manages the operation of the "stress light emitting material layers A0 to A3" has a predetermined value. It is also preferable that the information processing means can read the hidden information and the encrypted information.

  It is preferable that automatic recognition means such as portable camera recognition be used in combination with those having special characteristics, since they may cause errors or incorrect inputs even in the case of registration or collation by authorized purchasers.

  Hereinafter, these things are generically called "number etc."

  Furthermore, “predetermined information” includes personal identification numbers, personal identification numbers, account numbers, other individual-specific numbers, etc., some individual numbers, lottery numbers, management numbers, etc., or simple serial numbers, etc. The stress light emitting material layers A0 to A3 are completely random numbers, such as ones that express their effectiveness by registration, the same number as a common key number that is an encryption key number, etc. A person who is permitted to know, such as a number that is generated when making the product so that no one including the creator knows the contents of the number etc. (means a legitimate purchaser, etc. Of course, “stress light emitting material layer Only system designers of systems using A0 to A3 and ticketers etc. of "stress light emitting material layers A0 to A3" may be included. Is set to disable Or the like can be included.

  In addition, depending on the application of the “stress light emitting material layer A0 to A3”, not only the above-mentioned number etc. but also letters, figures, marks, others, individuals and suppliers of “stress light emitting material layer A0 to A3” are commonly recognized Anything that can be done (this object is all the so-called "information") can be used.

And also as the recognition method, while having at least information that can be recognized by visual confirmation, adopt a recognition method other than visual observation, for example, an optical reading method, a magnetic reading method, or any other physical or chemical reading method. And is suitable for enhancing its anti-counterfeit properties. (The recognition method and means are not shown.)
The thickness of the “stress light emitting material layers A0 to A3” is 1.0 μm to 100 μm, particularly 3.0 μm to 30 μm, but when this thickness is less than 1.0 μm, the emission intensity is insufficient When it exceeds 100 μm, adjustment of the rigidity of “threads SL0 to SL3” becomes difficult.

  The ratio of “the thickness of the stress light emitting material layers A0 to A3” to “the thickness of the predetermined base material B0” is 1/10 to 30/10 to balance the emission intensity and the rigidity.

  Here, "paper making process 1: wiring & water squeezing" is a so-called "wire part", and is continuously made of PET (polyethylene terephthalate) fibers or a mesh woven with bronze fibers or the like. After the above-mentioned "pulp turbid solution" is homogeneous in the width direction and supplied at an appropriate concentration, speed, and angle onto a rotatable belt-like one, a coating of a predetermined thickness is obtained. Water squeezed on the wire (meaning dewatering. In the part where dewatering has progressed, dehydration is promoted by the equipped suction box <a device that sucks in water with a vacuum pump>)), A “wet paper (meaning still containing water)” for “paper Y1” of the forgery prevention paper G1 ”is formed.

Also, “paper making process 2: drying and pressing treatment” is a so-called “press part”, and
The "wet paper" peeled off from the wire is transferred to the felt, and it is put into a pressing device which applies pressure to further squeeze water and is subjected to a roll press treatment consisting of several rolls. Here, by performing sufficient pressing on "wet paper", it is possible to make "paper" with high density.

  Then, the wet paper web is dried by evaporation of water, so-called "dryer part", wound and dried while being sequentially transferred to a large number of cylinder drums heated by steam.

  Finally, the "processing and finishing process" belongs to the so-called "paper processing process", and based on its application, enters into processes such as size press treatment, coating treatment such as glossing, and calendar treatment. The coating process and the calendering process may be performed off-machine (meaning that the film is once taken up and then applied to another dedicated device).

  The “Anti-counterfeit paper G1” of the present invention can be produced by a manual making method, but in order to mass-produce it, a paper machine capable of achieving the above “paper making process”, for example, a long mesh system, twin It uses paper machines of various methods such as wire method, gap former method, circular net method, and Yankee method. In addition, a machine calendar processor can be added.

The thickness of the "anti-falsification paper G1" of the present invention, 5Myuemu～500myuemu, that is, inter alia, in the specific weight designation "Paper", a ^{52.3g / m 2 ~360g / m 2} , its size There are fixed stock certificates (Horizontal × vertical, 210 mm × 107 mm, may include fixed design printing. The same applies hereinafter.), B5 stock certificate (265 mm × 186 mm), A5 stock certificate (216 mm × 150 mm), fixed stock (210 mm × 107 mm) ), B5 stock certificate (257 mm × 182 mm), A5 stock certificate (210 mm × 148 mm), gift certificate paper (160 mm × 76 mm), and further, A series full size according to JIS P 0202, A full size, A half size, A4 size, A8 size, A0 to A which are A16 size, Kiku size, Y6 size, Hatron size, or A series or B series size according to JIS P 0138 0, or, particularly preferably in the B0～B10.

  However, it goes without saying that the thickness and size outside this range are also required depending on the application of the "forgery prevention paper G1" of the present invention.

Example 1
Softwood lumber (a mixture of spruce and pine tree) chips were disintegrated by a refiner to obtain a suspension (1) of unbleached mechanical pulp with a freeness of 600 ml (degree of beating, according to Canadian Standard). The suspension (1) is adjusted to pH 4.0 with acetate buffer, and the pulp concentration is adjusted to 3%, and then it is beaten with a single disc refiner (beating machine) until the freeness reaches 300 ml. Then, an appropriate "mixing type sizing agent" was added at an appropriate ratio to obtain a suspension (2) containing "paper pulp fibers".

  The “paper pulp fibers” at this time had an average “thickness” of 30 μm and an average “length” of 3.0 mm.

Apart from this, 1% of Eu serving as a luminescent center and 1% of boric acid are added to Sr ₃ Al ₂ O _{6 as} a matrix material, and put in a “predetermined mold”, in a hydrogen-added argon reducing atmosphere The resultant was baked at 1300 ° C. for 4 hours to obtain a “stress light emitting material layer A0” in which “length × width × thickness” forms a rectangular parallelepiped of “2 mm × 107 mm × 10 μm”. (See Figure 4)
To this “stress light emitting material layer A0” is laminated a polyethylene terephthalate film, which is a “predetermined base material B0” and “vertical × horizontal × thickness” forms a rectangular parallelepiped of “2 mm × 107 mm × 3 μm”, Crimping was performed by heating at 100 ° C. and pressurization at 10 MPa to obtain “thread SL0” of Example 1 in which “length × width × thickness” is “2 mm × 107 mm × 13 μm”. (See Figure 4)
At the time of this heating and pressurization, deformation in the thickness direction is applied to the “thread SL0” to form a shape having a deflection of 20 μm in the depth direction at “20 mm cycle” (see FIG. 4). This means that the rectangular solid “thread B0” in FIG. 4 is once formed, and is further deformed into a cross-sectional shape such as “thread SL0” in FIG.
Furthermore, using the above-mentioned suspension (2), first, "wet paper (1)" is prepared so as to have a basis weight of 30 g / m ² with a square hand-made sheet machine, The “thread B0” of Example 1 is overlapped at a predetermined position on the wet paper (1) so that the “predetermined base material B0” and the “wet paper (1)” are in contact with each other. The suspension (2) is stacked again to cover the paper (1) and the “thread SL0”, and the basis weight of “paper Y1” is 60 g / m ² , “wet paper (2 ) Was prepared. (This process is a "thread-in" process of "thread", that is, a "thread-in process in a paper-making process" process. It means that "a predetermined thickness" is set in anticipation of the drying process. )
Next, after applying drying processing at 120 ° C for 2 minutes and roll pressing treatment in a drum dryer and conditioning for 24 hours at 20 ° C and 50% conditions, the horizontal × vertical becomes a size of 210 mm × 107 mm. By cutting, “Anti-counterfeit paper G1” of Example 1 of the present invention having a basis weight of 60 g / m ² was obtained. (Refer to Fig. 1 and Fig. 4. Only part of "papermaking process" in Fig. 4 is adopted. In Fig. 1, the highest part of the deformed "thread SL0" is exposed as "thread exposed portion G3" The other part is covered with “suspension (2)” to form “thread exposed part G3.” Each of FIGS. 1 to 3 is a schematic view, and The figure which has provided thread embedded part G2 '' and 'thread exposed part G3' only in four places and three places, respectively is shown.
A “jig” (the outermost surface is mirror-finished) in which “the bottom size of the anti-counterfeit paper sheet G1” of the first embodiment is “the bottom size is 150 mm × 250 mm, and has a radius of curvature of 100 mm. Made of stainless steel as a “predetermined external load on the anti-counterfeit sheet” on the curved surface of the protruding part of the “stainless steel sheet”, the “anti-counterfeit sheet G1” is deformed when it is pressed with a finger of the hand. A portion corresponding to the vicinity of the top of the protrusion of the tool emits "green" and can be visually recognized (in particular, the emission from "the thread exposed portion G3" is strongly recognized.) This "forgery" We were able to confirm the authenticity of the prevention paper G1. (The evaluation status is not shown. The same applies below.)
This means that the "paper pulp fiber" is deformed in the "forgery prevention paper G1" by a predetermined external load (pressing with a finger) against the "forgery prevention paper G1", and the "paper pulp fiber" The deformation is transmitted to “thread SL0”, and deformation stress corresponding to the deformation of “thread SL0” is generated at a predetermined site of “stress light emitting material layer A0” of “thread SL0”, and the predetermined site It is considered that light of a predetermined wavelength ("green light") having an intensity corresponding to the deformation stress was emitted, and light of the predetermined wavelength became visible.
(Example 2)
In Example 1, 1% of Eu serving as a light emission center and 1% of boric acid are added to Sr ₃ Al ₂ O ₆ as a matrix material, and a cellulose resin is further added in a weight ratio of “matrix material / resin” And the volume ratio is 1/5. Mixed into the “predetermined mold” in a state of being stacked on a predetermined ceramic substrate, and fired for 4 hours at 1300 ° C. in a hydrogen-reduced argon reducing atmosphere, Thus, “stress light emitting material layer A0” in which “length × width × thickness” forms a rectangular parallelepiped “2 mm × 107 mm × 2.0 μm” was obtained. (See Figure 4)
To this “stress light emitting material layer A0” is laminated a polyethylene terephthalate film, which is a “predetermined base material B0” and “vertical × horizontal × thickness” forms a rectangular parallelepiped of “2 mm × 107 mm × 3 μm”, The ceramic substrate is peeled by pressure bonding by heating at 100 ° C. and pressing at 10 MPa, and the “thread of Example 2” in which “length × width × thickness” becomes “2 mm × 107 mm × 5 μm” I got "SL 0". (See Fig. 4. The ceramic plate is not shown.)
The rigidity of the “thread SL 0” at this time was 1⁄5 of the rigidity of the “paper Y 1” of the first embodiment.
Then, without performing the deformation process of “thread SL0” implemented in the first embodiment, a recess of 20 μm in depth is continuously formed on a straight line at a predetermined position on the surface of “wet paper (1)” with a period of 10 mm. Provision (direction in which “thread B 0” is inserted), and “thread SL 0” of Example 2 is superimposed thereon, and the suspension (2) is covered thereon, Example 1 and Similarly, “Anti-counterfeit paper G1” of Example 2 of the present invention was obtained. (Refer to Fig. 1 and Fig. 4. Only part of the "papermaking process" of Fig. 4 is adopted. In Fig. 1, the part of "Sled SL0" superimposed on the recessed part of the wet paper (1) It is covered with the suspension (2) and becomes "the thread embedded part G2", and the other part is the "thread exposed part G3".)
The “forgery prevention paper G1” of the second embodiment is evaluated in the same manner as the first embodiment, and good results similar to those of the first embodiment are obtained, and the “thread SL0” of the second embodiment has low rigidity. By overlapping the wet paper (1) and covering it with the suspension (2), the desired shape can be obtained (meaning that the deformation process by the heating and pressure treatment is unnecessary), "thread SL0 And the rigidity of the “forgery prevention paper G1” is more uniform in the paper surface, and is excellent in various processing suitability and printer suitability. It was guessed.
(Example 3)
In Example 1, the exposed surface of “stress light emitting material layer A0” of “thread SL0” in Example 1 is sprayed with a surface treatment agent in the following cooling step (preheating use) after baking. The surface treatment agent is dried by coating and preheating at 100 to 200 ° C. of the exposed surface, film formation and fixation (this becomes "predetermined surface treatment"), and "stress luminescence". Similar to Example 1, except that the water resistance of the material layer A0 and the water resistance of the “stress light emitting material” constituting the material layer A0 ”are improved, the“ thread SL0 ”of the third example and the same An “anti-counterfeit sheet G1” according to the third embodiment of the present invention was obtained by forming “thread SL0” into “sheet Y1”.
Surface treatment agent
3-glycidoxypropylmethyldimethoxysilane (silylating agent) 5 parts Isopropanol 20 parts Methyl ethyl ketone 10 parts Xylene 35 parts Butylcellosolve 30 parts The “anti-counterfeit paper G1” of this third embodiment and the “forgery prevention of the first embodiment” The “half-life time” of the sheet G1 was evaluated using “test” performed in accordance with the “water immersion test” in JIS K 6404-9: 1999. Even after passing twice the "half time", the light emission intensity of the "forgery prevention paper G1" of Example 3 is not halved, and the "half time" of the "forgery prevention paper G1" of Example 3 is It was judged that the water resistance was improved because it was twice as large as the “half-life” of the “anti-counterfeit paper G1” of Example 1, and it was considered to be more excellent in anti-counterfeit properties.

Further, when the “forgery prevention paper G1” of the third embodiment was evaluated in the same manner as the first embodiment, the same good results as the first embodiment were obtained.
(Example 4)
In Example 1,
As a "baking mold" provided in advance with a "cavity" having a "shape having a portion where the stress concentration coefficient α is 2 or more", the "shape of the cavity" is
A “wedge-shaped” recess is provided on one surface of “basic shape” of “2 mm × 107 mm × 10 μm” in “length × width × thickness”, as shown in FIG. A metal "baking mold 1" made of stainless steel internally affixed and having a "shape", and a press die for providing such a "wedge-shaped" recess were prepared.

Here, the “wedge shape” has a rectangular opening of 10 μm × 100 μm and a depth of 5 μm (a base of 10 μm and an isosceles triangle with two sides of 11 μm on top and bottom) ("Triangular prism shape"), this "wedge shape" is provided in a grid pattern at intervals of 3 mm in the longitudinal and lateral directions. (In Fig. 7, this is shown as "schematic", with six notches.)
In the same manner as in Example 1, other than the "basic shape" of 2 mm long × 107 mm wide × 10 μm thick, a depression having a “wedge” shape as a predetermined portion on one surface thereof “A predetermined shape cutout K1 (having a base of 10 μm and two sides having an isosceles triangle of 11 μm on the upper and lower surfaces, in the form of a triangular prism)” (in FIG. This “site S1” is provided as “the predetermined site S1”, which is “stress concentration coefficient α = 2.0 or more”, in the shape of “grid of eyes”, The “thread SL1 (laminated body of“ stress light emitting material layer A1 ”and“ predetermined base material B0 ”)” and the “thread SL1” of Example 4 of the present invention were milled into “paper Y1”. "Anti-counterfeit paper G1" of Example 4 of the present invention was obtained.

The “forgery prevention paper G1” of this Example 4 was evaluated in the same manner as in Example 1. As a result, light having a large light emission intensity could be visually recognized and the reliability of the authenticity judgment would be improved. The same good results as in Example 1 were obtained except for the above.
(Example 5)
First, a metal-made "baking mold 2" internally attached with stainless steel was prepared, in which "the shape of cavity" of "the mold for baking" is 30 mm long × 100 mm wide × 10 mm thick.

Next, add 1% of Eu to be a luminescence center and 1% of boric acid to Sr ₃ Al ₂ O ₆ which is a base material, and have a “cavity” of a rectangular solid of 30 mm long × 100 mm wide × 10 mm thick Put into mold 2 ", raise temperature up to 900 ° C gradually in a hydrogenation argon reduction atmosphere and temporarily calcinate, then continue baking in a hydrogenation argon reduction atmosphere at 1300 ° C for 4 hours Allow the material to naturally cool, take it out of the “mold 2 for firing”, and make it a “plate-like stress light-emitting material sheet” that has a “shape” of rectangular 30 mm × 100 mm × 10 mm thickness, and repeat this operation Thus, 100 “flat sheet-like stress light emitting material sheets” were obtained.

This 100 "plate-like stress light emitting material sheet" is repeatedly pulverized for 60 minutes three times using a metal ball mill (dry ball mill) at an internal volume of 200 liters and a rotational speed of 50 rpm. It has been (See Figure 8)
This “fine particle” is classified by an air classification system with a classifier equipped with a stainless steel classification rotor of 1000 revolutions / minute while controlling the particle size by laser diffraction method, and the particle size distribution width is 1 to 5 μm, average “Particulate P1” having a particle diameter D ₅₀ = 3.0 μm was obtained.

Among the "fine particles P1", "the shape (including the uneven shape of the surface)" of 100 "fine particles P1" is measured by arbitrary sampling, and "three-dimensional image data" of the "shape" is The stress concentration coefficient α is approximately 5 or more with respect to the load of the “deformation stress” that bends “fine particles P1” in “structural analysis software (stress distribution analysis software)”. Almost all the “fine particles P1” have a shape having a portion where “the stress concentration coefficient α is 2.0 or more” (this portion S1 is the position of the bottom of the concave portion of the uneven shape on the surface of “fine particles P1”. Confirmed that it would have ")". (See FIG. 8. In FIG. 8, “fine particle P1” is shown “largely” schematically and exaggerates the surface asperity shape).
Next, the following “Stress light emitting material-containing ink composition” (these mixtures are stirred using a magnetic stirrer for 1 hour so as not to change the shape of the “fine particles P1”, “fine particles P1” "Dispersed" in "transparent resin J2") on a 5.0 μm thick polyethylene terephthalate sheet "predetermined base material B0" using a stainless steel screen printing method, 10.0 μm thick Coated and dried, and the "appropriate substrate" was peeled off to give "stress light emitting material layer A3" of Example 5 of the present invention having a thickness of 6.0 μm, and a length of 5 mm and a length of 500 m. (Sled ribbon shape) to obtain “Sled SL3” of Example 5 of the present invention. (This “stress light emitting material layer A3” is a “stress light emitting material layer A3” formed by dispersing “fine particles P1 composed of a stress light emitting material in“ predetermined transparent resin J2 ”, and The “shape” of the “stress light emitting material” is the “shape” of the “fine particle P1”, and is a “shape” having a portion S1 where the stress concentration coefficient α is 2 or more.)
<Stress light emitting material 1 containing ink composition>
-"Particulate P1" 30 parts-"Transparent resin J2": acrylic resin (transmittance 95%) 50 parts-Toluene 10 parts-Butyl Cellsolve 10 parts Using "Sled SL3" of this Example 5, FIG. In the "paper making process", the paper is made into "paper Y1" (at this time, the method of providing the same "dent" in the surface of the wet paper (1) as in Example 2 was adopted), paper size It was cut to 210 mm × 107 mm to obtain “Anti-counterfeit paper G1” of Example 5 of the present invention.

Furthermore, in accordance with the method for determining the bending properties of plastic (bending test method: JIS K 7171 2008, ISO 178 2003) ("Test machine" and "Test method" are adopted. "Size and shape" of "Test piece" is It does not conform to the standard.), One side (surface) of “the forgery prevention paper G1” of the fifth embodiment is directed downward by the three-point method, and the points located at both ends of the “thread SL3” are fulcrums respectively Support at the test speed of 2 mm / min so that the central part is pushed down from the back side, against the “preventing paper for counterfeiting G1”, “deformation of 30 kPa” in the direction perpendicular to the surface as “predetermined external load” When stress is applied, “Anti-counterfeit paper G1” causes “deflection (curvature)“ deformation ”in that direction, and due to the“ deformation ”,“ thread SL3 ”and“ stress light emitting material layer A3 ”also "Mr. The “deformation stress” is concentrated on the “predetermined portion S1” of the “fine particle P1” in the “stress light emitting material layer A3”, and at the same time, the “deformation stress” is generated from the “predetermined portion S1” The light of a predetermined wavelength ("green light") having an emission intensity corresponding to "" is emitted, and light of a predetermined wavelength ("green light") becomes visible.

Specifically, when "stressed light emitting material layer A3" is "curved (deformed)", the "curved (deformed)" is transmitted to "fine particles P1" contained therein, and "fine particles P1" thereof. The same “deformation” occurs, and “deformation stress” concentrates on “predetermined portion S1 of“ fine particle P1 ”(portion of the bottom of the concave portion of the uneven shape on the surface of“ fine particle P1 ”” The "predetermined portion S1" emits light of a predetermined wavelength ("green light") having an emission intensity corresponding to the concentrated "deformation stress", and the "light" is a "transparent resin" The light passes through (transmits) the inside of the “stress light emitting material layer A3”, and the “stress light emission (light of green light)” is emitted from the inside of the “stress light emitting material layer A3”. It was visible from the front and back of the material layer A3 'and the four side surfaces of the' stress light emitting material layer A3 '. (Refer to FIG. 1 to FIG. 3 and FIG. 8. The deformed state and the light emitting state are not shown.)
In addition, the “stress light emitting material layer A3” of this Example 5 is “a jig having a bottom size of 30 mm long × 100 mm wide knurled” and a curvature radius of 60 mm (mirror finish on the outermost surface Pressed with a finger of the hand as “predetermined external load” on the curved surface of the protrusion of “made of stainless steel.” The “stress light emitting material layer A3” is deformed, and in particular, the protrusion of the jig The part corresponding to the vicinity of the part (apex) emits “green” by “deformation” and can be visually recognized, and the authenticity of “anti-counterfeit paper G1” according to the fifth embodiment of the present invention The evaluation status was not shown.

Further, when this authenticity check operation is repeated 200 times, the same "green light" can be confirmed in the same manner without changing any of them, and the forgery prevention paper G1 of Example 5 of the present invention is forged. It seemed very difficult to do.
(Example 6)
In the fourth embodiment, the "notch K1" is provided in a grid shape with a period of 0.4 mm to fill in the "image portion of a predetermined character", and "display" of the "predetermined pattern". “10 mm long × 20 mm wide,“ between ”20 mm apart,“ true ”and“ positive ”are represented, and“ stress light emitting material layer A2 ”is used in Example 6 of the present invention. It is "thread SL2". (Refer to FIG. 7. The width of the “image part” of the “character” was 2 mm. The centers of the two characters were arranged to be located at the center of the “stress light emitting material layer A2”. The "notched part K1" shown in the target is to be arranged to represent the "predetermined character". This "arrangement etc." is not shown.)
Specifically, the "display" of "predetermined pattern" at this time, for example, the inside of "line" of 2 mm in width of "true" of the character "true" of 10 mm long and 20 mm wide is provided in a grid pattern. Moreover, it is filled with a large number of "notched parts K1" and formed, and the "light emission" of the "bottom side (predetermined portion S1)" of this "notched part K1" The letter "" should be visible as "the letter of" light ".

  And "a stress light-emitting material layer A2" of this Example 6 is "a jig whose bottom size is 30 mm in length × 100 mm in width and has a radius of curvature of 60 mm" (mirror finish on the outermost surface When pressed with a finger of the hand as a “predetermined external load” against “the anti-counterfeit sheet G1” on the curved surface of the protrusion of “made of stainless steel”), “the anti-counterfeit sheet G1 of the sixth embodiment In particular, the portion corresponding to the vicinity of the protruding portion (apex) of the jig emits “green” by “the deformation” and can be visually recognized, and the “predetermined wavelength” The light (green light) becomes visible as the "predetermined pattern (two characters of" true "and" positive ")" as "display (" display "as the character of" light ")". The authenticity of “Anti-counterfeit paper G1” of Example 6 could be confirmed (evaluation Situation is not shown.).

  Furthermore, even if this authenticity confirmation operation is repeated 100 times, the "predetermined pattern" can be similarly confirmed similarly without changing, and it is possible to forge the "forgery prevention paper G1" of the sixth embodiment of the present invention, It seemed to be extremely difficult.

(Comparative example 1)
In Example 1, a “thread sheet” was prepared using “suitable ceramic material” as a substitute without including “stress light emitting material”, and was referred to as Comparative Example 1.

  When Comparative Example 1 was evaluated in the same manner as Example 1, no light emission occurred, and it could be determined that this "thread paper" was not authentic.

G1 Anti-counterfeit paper G2 thread embedded portion G3 thread exposed portion Y1 sheet A0 to A3 stress light emitting material layer B0 base material SL0 to SL3 thread J2 transparent resin P1 fine particle S1 predetermined portion K1 notched portion

Claims (5)

Anti-counterfeit paper comprising at least paper pulp fibers and threads,
The thread is formed in a strip shape in which a stress light emitting material layer containing a stress light emitting material is provided on a predetermined base material, and the thread is machined in a papermaking process of the forgery resistant paper. It has been
At the same time as the thread is deformed in the anti-counterfeit sheet due to a predetermined external force load on the anti-counterfeit sheet,
The stress light emitting material layer is deformed to generate a deformation stress corresponding to the deformation of the thread at a predetermined portion of the stress light emitting material layer, and a light emission intensity corresponding to the deformation stress from the predetermined portion Light having a predetermined wavelength is emitted, and the light having the predetermined wavelength is visible ,
The composition of the stress light emitting material layer is composed of the stress light emitting material, and the surface of the stress light emitting material layer has notches and / or recesses of a predetermined shape as the predetermined portion, and the predetermined light emitting material layer anti-falsification paper which stress concentration factor α at the site is characterized that you have a two or more. Anti-counterfeit paper comprising at least paper pulp fibers and threads,
The thread is formed in a strip shape in which a stress light emitting material layer containing a stress light emitting material is provided on a predetermined base material, and the thread is machined in a papermaking process of the forgery resistant paper. It has been
At the same time as the thread is deformed in the anti-counterfeit sheet due to a predetermined external force load on the anti-counterfeit sheet,
The stress light emitting material layer is deformed to generate a deformation stress corresponding to the deformation of the thread at a predetermined portion of the stress light emitting material layer, and a light emission intensity corresponding to the deformation stress from the predetermined portion Light having a predetermined wavelength is emitted, and the light having the predetermined wavelength is visible ,
The stress light emitting material layer is formed by dispersing fine particles containing the stress light emitting material in a predetermined transparent resin, and the shape of the fine particles of the stress light emitting material has a stress concentration coefficient α of 2 or more. a shape having a portion to be, anti-falsification paper which said portion, characterized in Rukoto such a predetermined portion of said stress luminescent material layer. In the forgery prevention paper according to claim 1 or 2 ,
The rigidity of the thread is 1/10 to 50/10 of the rigidity of the anti-counterfeit sheet. The anti-counterfeit paper according to any one of claims 1 to 3
A paper for preventing forgery characterized in that the stress light emitting material is subjected to a predetermined surface treatment to improve the water resistance of the stress light emitting material. The anti-counterfeit paper according to any one of claims 1 to 4
The anti-counterfeit paper according to claim 1, wherein the light of the predetermined wavelength can be visually recognized as displaying a predetermined pattern.

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