JP2016098454A - Form sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a "form sheet" configured to emit light with a predetermined tone when the "form sheet" is distorted in a predetermined manner by a comparably small load, the light which is usually unrecognizable, for improving designability and forgery prevention of the "form sheet."SOLUTION: "Paper pulp fibers" and a "stress luminescent material" are mixed in a "form sheet." Distortion stress applied to the "form sheet" distorts the "paper pulp fibers" included therein and at the same time the "stress luminescent material" is also distorted. Then a predetermined stress occurs in the "stress luminescent material" to generate light of a wavelength peculiar to the "material." With this, the authenticity of the "form sheet" can be determined without any confirmation lighting device but only with visual inspection, so that the "form sheet" can achieve excellent designability and forgery prevention.SELECTED DRAWING: Figure 1

Description

The present invention relates to foam paper, in particular, containing paper pulp fibers and a stress luminescent material therein, the stress luminescent material is included in contact with the paper pulp fibers,
Further, the form sheet has one or more vertical penetrating portions, oblique penetrating portions, notched portions, and / or concave portions, particularly slit-shaped penetrating portions (hereinafter collectively referred to as “specific portions”). .), And when a predetermined external force is applied to the foam paper, the foam paper is pulled, bent, bent, or twisted by the external force. Stress due to the deformation concentrates on the specific part (vertical through part, oblique through part, slit-like through part, notch part, or concave part) ("internal stress" applied to the "specific part" increases) Meaning) or the stress associated with the deformation concentrates on the paper pulp fiber in the specific part and in the vicinity (area where the stress is concentrated), and this causes the paper pulp fiber to undergo strong deformation. At the same time, the stress luminescent material that is mixed in contact with the paper pulp fiber is also subjected to a predetermined deformation stress, and light of a predetermined wavelength, depending on the magnitude of the deformation stress, The present invention relates to a foam sheet that emits (emits light) at a predetermined intensity from a predetermined part of a stress-stimulated luminescent material.

  Here, “deformation” includes “form deformation of form paper” and “deformation of stress-stimulated luminescent material”. This is called “deformation”.

  Hereinafter, “internal stress” or “deformation stress” is also simply referred to as “stress”.

  That is, by the predetermined external force load on the “foam paper” of the present invention, the “deformation” of the “foam paper” is transmitted to the “paper pulp fiber” included in the “foam paper”, which is the “stress luminescent material” "Form paper" or "form paper" is "deformed" and the "deformation" becomes "deformation" of the stress luminescent material as it is, or both. "Particulate stress luminescence in contact with" paper pulp fibers "in" one or more vertical penetrations, diagonal penetrations, notches and / or recesses, especially slit-like penetrations " “Particulate” in contact with the “material” or “paper pulp fibers” in the vicinity of the “vertical through, oblique through, notched, and / or concave, especially slit-like through” Is relatively large Concentrated in the specific part, meaning that the larger than the periphery of the particular unit.), "Internal stress", or, so that the "deformation stress" occurs.

  In addition, the “specific part” in which the stress concentration factor α (“stress concentration factor α” is described in detail below) in the “foam paper” of the present invention is 2 or more is further 10 or more, in particular, When the stress concentration coefficient α is 100 or more, the difference in the “light emission” intensity between the specific part and the peripheral area of the specific part (area far from “near”) becomes significant (“specific part” and “Contrast” at the time of light emission of the “region around the specific portion” is high).

  Of course, since the “stress concentration factor α” is an index for a material having a certain “shape (including elements related to the material)”, not only the “shape” of the “form paper” but also the “stress luminescent material”. The “predetermined part” included in the “outer shape” can also be applied, and the “stress concentration coefficient α” in the “predetermined part” is also 2 or more, further 10 or more, and particularly 100 or more. It goes without saying that it is preferable to do this.

  “Specific part of form paper” means “tensile stress”, “shear stress”, “slip stress”, etc. (“internal stress”, “deformation with physical movement”) Or “deformation stress”, or “stress” classified from “phenomenon plane”) (parts, areas, etc.), especially those “stress”. "Stress concentration degree is 2 or more" "area, part, or place (the part is smaller than the area, the part is smaller than the area, in other words, the target range becomes narrower Is).

  That is, “area, part, or location” where “stress concentration coefficient α is 2 or more” corresponding to those “stresses”.

And, this “specific part”, in particular, “the specific part having the largest stress concentration coefficient α among those“ specific parts ””, and further, “the specific part having the largest stress concentration coefficient α”, "The part where the stress concentration coefficient α is the largest" in that part and its area "depends on the direction of" deformation "in" form paper "and the magnitude and direction of" external force applied " The position (target range) changes. (Even if these “forms, areas, or places where the stress concentration factor α is the largest” are changed in the “form paper”, the “form paper” (It is still the same as having a “shape” having a “specific part” with a large stress concentration factor α.)
“Vertical penetrating part and / or oblique penetrating part”, in particular, “slit-like penetrating part”, that is, “penetrating part (a kind of“ specific part ”)” included in the “form paper” of the present invention. , An upper surface opening (front surface opening) or a lower surface opening (back surface opening) on one surface of the “form paper”, that is, the front surface, or the other surface, that is, the back surface, respectively. Even if it has any horizontal cross section of the “penetrating part” (meaning “cross section cut by a plane parallel to those“ surfaces ”), the“ cross-sectional shape ”has an upper surface opening (surface Opening) and the shape of the lower surface opening (back surface opening). ("Almost identical" means that even if there are "differences" that do not affect the object of the present invention, such as manufacturing errors, they are regarded as "identical".)
This is a “vertical penetrating part and / or an oblique penetrating part” as a “specific part”, in particular, a “slit-like penetrating part”, that is, a “penetrating part”. A “shape” provided with a “penetrating portion” in part becomes a “form of the form paper”.

  Then, by the “deformation” of the “form paper” of the present invention, the “penetration portion” itself is pulled, curved, bent, or twisted, and the “penetration portion” Stress is concentrated.

  That is, the “penetrating portion” is “a“ specific portion ”having the largest stress concentration coefficient α in“ form paper ”.

Here, when the “form paper” of the present invention includes a plurality of “penetration portions”, the “form paper” provided in the “deformation” region of the “form paper” is large. The “penetrating part” receives a larger “deformation stress” than other “penetrating parts”, that is, “penetrating parts” provided in a region where “deformation” of “form paper” is small. Become. (The stress concentration factor α in such “one deformation of the foam paper” is larger in the “penetrating portion” than the other “penetrating portion” as a value for the “one deformation of the foam paper”. With value.)
Further, even in one “penetrating portion”, when the “vertical penetrating portion: specific portion K1” is, for example, “a quadrangular prism whose upper and lower surfaces are rectangular”, the “opening on the upper and lower surfaces of the quadrangular column is defined. “Deformation that spreads in one direction (occurs by deformation that pulls“ form paper A1 ”at both ends thereof”) and “deformation that bends the square pillar at its center portion (occurs by deformation that curves“ form paper A1 ”). ) ”Etc., which means the type of“ deformation ”of the“ quadrangular column ”(meaning“ deformation ”. More specifically,“ points ”on the upper and lower surfaces of the“ quadrangular column ”and four side surfaces) By the former, it means the individual direction, size, and distribution of the “deformation vector” acting on all “points” on the surface of the “square prism”. Part of the opening on the top and bottom of the square column "(stress concentration point KS ) (See FIG. 3.), The latter is in its "center portion of the square pillar" (not shown.), So that the "stress" is concentrated.

That is, those “locations” in the “penetrating portion” are “locations where the stress concentration coefficient α is the largest” in the “specific portion (penetrating portion)”. (The stress concentration factor α determined corresponding to such “deformation” is larger in “the part of the penetration” than “the other part of the penetration”.)
Further, in the “form paper” of the present invention, in “one or more vertical through portions and / or oblique through portions”, “light of a predetermined wavelength” generated in the “through portion” In the “part”, in particular, in the “inner wall” of the “penetrating part” (in the example of the quadrangular column, it means its four side surfaces), so to speak, “repetitive reflections” occur and strengthen each other. Finally, since it is emitted from the upper and lower openings, “light” having higher directivity and higher intensity can be visually recognized.

  This phenomenon is particularly emphasized when the “inner wall” of the “penetrating portion” is a “smooth surface”.

  Such “repetitive reflection” is “effective reflection (meaning that the reflection efficiency is good)” as the distance between the side surfaces facing each other is smaller in the example of “square prism”. It is most preferable when the “opening” is “slit-shaped”, that is, when the “penetrating portion” is “slit-shaped penetrating portion” (“slit-shaped penetrating portion” is not shown). The same applies hereinafter.)

  The “slit-shaped through-hole” has a “top-opening or bottom-opening (hereinafter simply referred to as“ opening ”) shape” (therefore, the horizontal cross-sectional shape is also the same), which is close to a very flat elliptical shape. In addition, since the “both ends” have a “shape” that is “a sharp crease”, the “stress concentration coefficient α” at the “both ends” portion (the crease) is very In the “location”, strong light emission is expressed (meaning that light with high intensity is emitted), and the “side light” having a gentle curved surface emits “light of a predetermined wavelength”. Reflection is repeated while increasing directivity, resulting in “emitted light” that is very strong and has high directivity, and the visibility of the “light of the specified wavelength” can be significantly increased. And

  The “opening shape” of the “slit-shaped through portion” is 10/1 to 1000/1 in terms of the ratio of the two main axes (long axis and short axis) of the ellipse, and the “short axis”. The length (meaning the maximum width of the “slit-like opening”) is 1.0 μm to 3.0 mm.

  In particular, by setting the length of the “short axis” to 1.0 to 100 μm, the “opening” of the “form paper” of the present invention cannot be recognized on the appearance, or it is simply “one”. It can only be recognized as “there is a line of books”, and from that “part” (from “the place where there is nothing” or from “a simple line”), “light of a predetermined wavelength” appears. As something that cannot be imagined, it is possible to increase its secrecy and remarkably improve its anti-counterfeiting.

  The “opening shape” of the “penetrating portion” of the “form paper” of the present invention can be any “non-intersecting, closed two-dimensional shape”, for example, a polygon such as a triangle or a quadrangle. , Circles, ellipses, gourds and variations thereof, eg, stars, slits, and shapes that include irregular jagged curves.

  More specifically, isosceles triangles, right triangles, right isosceles triangles, other triangles, rectangles, rhombuses, parallelograms, trapezoids, isosceles trapezoids, bowls, other rectangles, regular triangles, squares, regular pentagons, etc. Includes fractal curves such as regular polygons, other polygons, star hexagons, star hexagons, star polygons, Koch curves, Sherpinski's Gasket curves, Mandelbrot set circumference curves, Hilbert curves, etc. Polygons (meaning that these unique “curves” are included in the part of the “two-dimensional curve closed without intersection” that represents the periphery of the polygons), rouleau polygons, sectors, circles, and ellipses , Lid mountain gourd shape, gourd shape such as mitsuyama gourd shape, slit shape, crescent shape, and combinations of these, as well as hiragana and katakana, alphabet and Greek It can be a character shape such as a character (a character with a white outline or a white outline around the line), a shape representing various symbols (the same).

In order to set the “stress concentration coefficient α” in the “penetrating portion” of the “form paper” of the present invention to 2 or more, as described above, the “opening shape” is set to “complex two-dimensional shape”. In particular, the stress concentration coefficient α is set to 10 or more, further to 100 by setting “a shape including a bending of 10 to 90 degrees in the two-dimensional shape” or the like. This can be done. Further, if the “shape of the opening” is “slit” in which the radius of curvature of the bent portion located at both ends is 0.01 mm or less, the stress concentration coefficient α at the “both ends” is It becomes 100 or more easily.
Furthermore, the size of the “opening” (maximum width or maximum diameter. The value of each “opening” or the sum of a plurality of “opening” values) is the width direction of the “form paper”. The area of the “opening” (including a combination of a plurality of “opening” areas) is the surface area of the “form paper” (“form” The area of the “surface” that has the minimum length in the vertical direction, including the width of the “paper”, and each individual “aperture” or series of “apertures.” ] Of 1/10 < ⁸ > to 1/2.

If the “size” or “area” exceeds ½, it becomes difficult to carry out processing as “form paper”, various types of processing, and determination by repeated deformation. Further, when the “size” or “area” is less than 1/10000 or less than 1/10 ⁸ , the visibility of “light of a predetermined wavelength” emitted from the “form paper” is lowered.

  For the purpose of concealing the existence of the “opening”, the “size (maximum width or maximum diameter)” of the “opening” is set to 100 μm to 1.0 mm (in this case, “1.0 mm "There is a place of 1.0 mm in one place, but the length of any other direction is smaller than 1.0 mm" opening ", for example," diagonal is 1.0 mm, length & width <1.0 mm " It means “opening” or the like), and the “opening” is also preferably slit-shaped (10 μm ≦ slit length = major axis length ≦ 10 mm).

  Further, “oblique” of “obliquely penetrating portion: specific portion K2” of “form paper A2” of the present invention refers to one surface of “form paper A2” as “one plane”. [Angle] with respect to “perpendicular to one plane” (the angle overlapping with the perpendicular is 0 degree), and the [angle] is 80 degrees or less, more preferably 40 degrees ≦ [angle] ≦ 60 degrees. To do.

Comparing “vertical penetrating portion: specific portion K1” and “oblique penetrating portion: specific portion K2” as “square prism shape”, respectively, “vertical penetrating portion: specific portion K1” has a “rectangular shape” on the top and bottom surfaces. The “right-angled pillars (the upper and lower surfaces and the side surfaces are orthogonal to each other)” and the “obliquely penetrating part: the specific part K2” are “slanting prisms (the upper and lower surfaces and the side surfaces are inclined). (See Fig. 3 and Fig. 4)
Thus, by making the “penetrating portion” “oblique”, the direction in which the “light of the predetermined wavelength” is emitted can be “oblique”, and the design and unexpectedness can be improved. When “form paper A2” is observed from vertically above, the openings on the upper and lower surfaces overlap (meaning that when viewed in the vertical direction, they appear to be substantially the same position), “when opened (overlapped area). ”Can prevent the background from being peeped. (See Fig. 4. If the openings on the top and bottom surfaces overlap, when the "penetration part" is "lighted", the "light emitting area" will suddenly appear in the "light emitting area". By making it “oblique” at a predetermined “angle”, the “non-light emitting area” can be reduced, and further, the entire “opening” can be reduced. , It can be considered as a “light emitting area”.)
In addition, the “notch portion” (a kind of “specific part”. Notch.) And the “recess” (a kind of “specific part”. Dent.) Included in the “form paper” of the present invention are “ The depth of 1/10 to 1/2 of the thickness of the “foam paper” is formed on the front surface and / or part of the back surface of the “foam paper” which can be regarded as a “flat plate shape”. It is obtained by providing a “notch” (notch) or “recess” (dent).

  This is a “notched portion and / or a concave portion as a“ specific portion ”, and these are provided on the surface and / or a part of the back surface of the“ flat sheet ”“ form paper ”. "Shape" is "Form paper shape".

  Of course, this “notch and / or recess” is not only the “front surface and / or back surface” of the flat “form paper” but also the “side surface (end surface) of the“ flat external shape ”. Or the slit end face) ”(in this case, the depth is set to 1/10 to 1/2 of the lateral width of the“ form paper ”).

  The shape of this “recess” is “shallow shape of bottom. For example, [(opening width W / depth D) ratio = W / D] is 20/1 to 10/1”, more preferably , “The shape of the bottom is deep. For example, when the [(opening width / depth) ratio] is 5/1 to 1/1”, “stress concentration” is present around the “bottom” of this “recess”. Occurs, and the “stress concentration coefficient α” is 2 or more.

  In addition to the “light” emitted from the “bottom” of this “concave”, the “concave” acts like a “concave mirror”, condenses the “light”, and the “light” (This means the relationship between “lamp umbrella” and “illumination light source” in “lamp-shaped illuminator”).

  Such an effect is also exhibited at the “notch”.

  The “form” of such “form paper” is, for example, when the “form paper” has a “basic shape” of a very thin flat plate cuboid (the “basic shape” itself has “ At the stage of “form paper”, the “form paper” according to the present invention does not have the “shape”, and thus does not correspond to the “form paper of the present invention.” In this sense, it is expressed as “basic shape”. As the above-mentioned “specific part”, a part of the “cuboid that is a basic shape” includes a “part where the length is ½ or less” and a “part where the width is ½ or less”. And / or “a shape” including at least one or more “parts whose thickness is ½ or less”.

For example, if a “specific part” having a thickness of ½ is provided at the center of the “basic shape” of a very thin flat plate cuboid, the “form paper” is the “cuboid”. The area of the “cross-section group” forming the “rectangle”, which is cut out by a plane group parallel to the “end (end face)”, is local (assuming that the end area is “(S) mm ² ”) Therefore, it has a “shape” obtained by deforming the “cuboid” so as to change to “(S / 2) mm ² ”, and the “local” cross-sectional area is included in the “form paper”. The “rectangular” part that is “1/2” is the “specific part”, and the “specific part” is the “specific part” that is “stress concentration coefficient α = 2.0”. .

  And if the “shape” of the “specific part” is a “U-shaped (semi-cylindrical) dent”, it can be said to be a “concave”, and the “shape” is “V-shaped or wedge ( If it is a “wedge” -shaped (triangular prism-shaped depression), it can be said to be a “notch”.

  Of course, the “specific part” may be oriented in any direction, regardless of the horizontal direction, vertical direction, or any other position, even if it is not located at the “center” of the “basic shape”. In part of the “basic shape”, a “cross section” whose cross-sectional area is less than half of the “average cross-sectional area (here, the average value of the areas of all the rectangles)” If there is a “specific part”, the “specific part” becomes a “specific part” with “stress concentration coefficient α ≧ 2”.

  Here, the “average cross-sectional area” of a certain “shape” means a direction in which a predetermined one of the various stresses generated when a predetermined external load is applied to the “shape”. Of the “area” (cross-sectional area) of all the “cross-sections” obtained by cutting out the “shape” in a plane perpendicular to the plane (in the above example, it means a plane group parallel to the “end portion (end face)”) , “Average value” in the entire “shape”.

  And, such “a shape in which there is a cross section having a cross-sectional area less than or equal to ½ of the average cross-sectional area” is “a shape having a specific portion where the stress concentration coefficient α is 2 or more”. The “specific part” having a “cross-section” is the “specific part of the foam paper”, whereby the “form of the foam paper according to the present invention has a stress concentration coefficient in the notch and / or the recess. It can be said that “α is a shape of 2 or more”.

  In addition, the “basic shape” exemplified here is not limited to the “basic shape” as described above, and it is needless to say that “any shape of the object” can be targeted (all shapes are referred to as “original shapes”). Meaning that can be assumed.)

  Furthermore, as the “shape having a specific portion where the stress concentration coefficient α is 2 or more”, taking the above “basic shape” as an example, a part of the surface of the “basic shape” has a hemispherical surface (a spherical surface). 3D curved surface cut out in one plane), a concave part shaped like an ellipsoid (3D curved surface cut out of an ellipsoidal surface in one plane), a cut with an acute “cut” shape, Or, a “shape” having a predetermined uneven shape on the surface thereof, such as a “shape” having a corner-shaped protrusion, or more generally, “in a predetermined portion in a direction in which stress acts. In other words, the change in the cross-section cut along the vertical plane is a shape in which the stress concentration coefficient α of the part is 2 or more.

  This “having a notch and / or a recess” means that at least one “notch” is present on the surface of the “thin flat plate” “foam paper”, or at least one This means that it has the above “recesses”, and further has at least one “notch and recess”.

  Here, the “notch portion” is a so-called “wedge” -shaped recess as described above.

  "Wedge shape" means that one side of a "triangular prism" (one rectangle) is located on the top surface, the other two side faces (two rectangles) and the upper and lower surfaces of the "triangular prism" (two triangles) Forms that form the “four sides” of the indented part of the “form paper”, the two triangles (cross-section) surfaces (upper and lower surfaces) and the three parallel sides connecting the three vertices It is defined that two sides are located in the opening and the other side is located in the bottom of the dent.

That is, for example, with respect to a very thin flat plate “basic shape”, a “notch portion of a predetermined shape” which is a recess having a “wedge shape” as a specific portion K3 on one surface thereof. When a specific portion K3 "(" bottom side "becomes" stress concentration point KS3 "in FIG. 5), a" shape "such as" form paper A3 "in FIG. 5 is provided. Here, FIG. 5 is a “schematic diagram”, which shows only six “notch portions” having the same triangular prism shape arranged in an orderly manner. Depending on the purpose of the “form paper A3”, the shape (three-dimensional shape), size, and base direction of each “notch portion: specific portion K3” (“base” is not limited to “straight line”, "Curve" may be used), the shape of the opening (not only "rectangular" but also other "planar shape"), size, direction (vertical direction of the opening, horizontal direction), "notch : Number of specific parts K3 ”, how to arrange“ notch parts: specific part K3 ”(not only“ ordered arrangement ”but also“ random arrangement ”, and further,“ to display a predetermined pattern as described below ” This may be changed in various ways.). (The same applies to the “concave portion”.)
Then, when “predetermined external load” is applied to the “wedge shape”, that is, when deformation is applied in the direction of opening the “two sides of the opening”, “the other side (one side of the bottom. "Spot KS3") ")" and "stress concentration coefficient α" are equal to or greater than 2 and simultaneously maximized. Furthermore, the “stress concentration coefficient α” increases as the “open angle” (corresponding to the apex angle of the triangle) at the “bottom side” becomes smaller, such as 10 degrees to 90 degrees. When the “opening angle” is less than 10 degrees, the “stress concentration coefficient α” can be extremely increased. However, in the manufacturing process of the “foam paper A3” of the present invention, the manufacturing stability is insufficient and repeated. It will be difficult to withstand deformation.

  Further, the “value” of the “stress concentration coefficient α” at the “bottom side” varies depending on the direction in which “deformation” is applied. In other words, the “value” fluctuates depending on the direction in which the “predetermined external load” is applied. For example, when the above-described “upper and lower triangles” are deformed in an opening direction, the “stress concentration at the bottom side” In the coefficient α ”, stress concentrates at the midpoint of the“ bottom side ”(not shown, but in such deformation, the“ midpoint ”becomes the“ stress concentration location KS3 ”).

  In other words, the “wedge” dent is a “third direction” determined by the “direction in the three-dimensional space” of the “predetermined external force load” (the three-dimensional space component, which is loaded on the “wedge shape”. The “light emission intensity (or distribution thereof)” and the “light emission point position (or light emission region)” change.

  This means that the “predetermined external force load” applied to the “foam paper A3” of the present invention provided with the “wedge shape” and the “notch portion” of the “wedge shape” with respect to the “form paper A3”; The “light emission” of the “form paper A3” of the present invention by the “direction in the three-dimensional space (the direction of the vector, the“ external force ”expressed by the“ three-dimensional vector ”)” for the specific part K3 ”. The state (position distribution of light emitting points and intensity distribution of individual light emitting points) "is different.

It is also preferable to determine the authenticity by changing the “direction” of the “predetermined external force load” with respect to the “form paper A3” and visually checking the change in the light emission state of the “form paper A3”. It is. ("Light emission" status and judgment status are not shown. The same applies hereinafter.)
In addition, the “wedge shape” has a “wedge shape with a rectangular bottom”, that is, a “wedge trapezoidal shape”, a polygonal pyramid such as a quadrangular pyramid and a pentagonal pyramid, a cone, an elliptical pyramid, Also included are those in which “shape” becomes “polygon such as triangle, quadrangle, circle, ellipse, and deformation thereof”.

Furthermore, in the “foam paper” of the present invention, the “recessed portion of the predetermined shape” is a recess having a “recessed shape”, a semi-cylindrical concave shape, a semi-ellipsoidal concave shape, a hemispherical concave shape, and their It can be defined as a “dent” in which the bottom surface of the recess, such as a combination, is “three-dimensional curved surface”. (Recesses are not shown. The same applies hereinafter.)
Of course, the “concave shape” is also preferably an “arbitrary three-dimensional curved surface” on the premise that the shape is “controllable” (meaning that there is manufacturing reproducibility).

  The depth of the “notch” or “recess” (hereinafter, also simply referred to as “dent”) is, for example, the surface of the “form paper” having a “thin flat plate” profile. When provided in a part, the “thickness” of the “flat plate” (meaning the “thickness” of the position where the plate is provided) is 1/10 to 4/5 deep, , “Recesses” are provided.

  In addition, the shape of the “dent” is a so-called “socket” in which the “dent” itself reflects and collects the light from the light source against the “light” emitted from the “bottom” of the “dent”. ”(Meaning a role like“ concave reflector ”), enhances the condensing and directivity of the“ light ”, and improves the visibility of the“ light ”.

  The shape of this “notch” or “recess”, ie, “dent”, is “shallow at the bottom. For example, the depth is less than 1/10 of the thickness of“ foam paper ”, Furthermore, when 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 concentration coefficient α” is less than 2.

  Or, “the shape of the bottom is deep. For example, when the depth is more than 4/5 to less than 5/5 of the thickness of the“ foam paper ”, the“ bottom ”around the“ dent ” However, due to repetitive deformation operations, the “bottom part” and the like are easily cracked, and “stable light emission of at least 100 times” cannot be secured. It cannot be secured.

  In the first place, “paper” is one of the categories of “paper”, “paperboard”, and “pulp” in the production dynamic statistics classification by the Ministry of Economy, Trade and Industry. There are four types: industrial printing paper, coated printing paper, special printing paper, and information paper.

  In other words, non-coated printing paper such as high-grade printing paper, intermediate-grade printing paper (medium quality paper and upper refill paper), lower-grade printing paper, and printing paper with high-grade printing paper and intermediate-grade printing paper as the base paper and coated with paint on the surface. Depending on the amount of paint, etc., classified as art paper, coated paper, or lightweight coated paper, etc., coated printing paper, the amount of paint is less than coated printing paper, For information paper, such as special quality printing paper, copy paper, foam paper, inkjet paper, carbonless paper, photosensitive paper, thermal paper, OCR paper, and crimped postcard paper, which are classified as high-quality colored paper and government-made postcards being classified.

  Among them, “information paper” may be classified into “four classifications” of carbonless paper, foam paper, PPC (plain paper copier) plain paper, and thermal paper.

  In any “classification”, “form paper” in the present invention, which is positioned as “one classification”, is a continuous slip for output as “paper” on which various data outputs are printed, that is, So-called computer forms, in other words, various computer-controlled printers (impact printers, non-impact printers, etc., especially laser printers, ink-jet printers, etc.), and copying machines based on various principles A form to which various information (including design) is output, which is “paper” with ruled lines indicating the output position, feed hole processing and zigzag folding (ruled lines, hole processing, and , Including “paper” in a state before folding, and “single sheets” in some cases).

  In addition, “paper” is used in part as copy paper.

  For this reason, “form paper” has “quality characteristics” essential as “form paper”, that is, “printability such as offset printing”, “printability such as NIP (non-impact printer)”, “inkjet printer, etc.” Printing ability ”, feed hole (sprocket hole) processing, sewing machine processing, zigzag folding processing, envelope processing, or“ post-adhesion pressure bonding ”processing is required.

  In order to ensure these “suitability”, “foam paper” has at least a predetermined “basis weight”, an allowable range of the “basis weight”, a predetermined “thickness”, and an allowable “thickness”. Range, predetermined "smoothness" and allowable range of "smoothness", predetermined "moisture amount" and allowable range of "moisture amount", predetermined "rigidity" and allowable range of "stiffness" The “information sheet” or the “paper” satisfies the predetermined “strength” and the allowable range of the “strength”.

  Here, “basis weight” is defined in JIS-P8124 as “predetermined basis weight” (“predetermined basis weight” is defined as “value” in which “basis weight” is an individual value. It means that it has “value”. The same applies hereinafter.) + 10% and −2%, “thickness” is a predetermined “thickness” ± 8% in JIS-P8118, and “smoothness” is JIS -In P8119, 20 sec or more on the front (front) surface, 20 sec or less on the back surface, "moisture content" is 5.0 to 7.0% in unconditioned humidity, and "ISO whiteness" is In JIS-P8148, 83% ± 2%, “Clark stiffness” is not less than a predetermined “value” in JIS-P8143, and “tensile strength” is predetermined in both “longitudinal” and “lateral” in JIS-P8113. Above “value”, tear strength is “longitudinal” in JIS-P8116. , “Horizontal” must be equal to or greater than a predetermined “value”.

For example, illustrates one of those "values", "Clark stiffness" in JIS-P8143, 30cm ^3/100 or more, "tensile strength" in JIS-P8113, the "vertical" 3.55 or higher , "Horizontal" 1.5 or higher, "Tear strength" is "Vertical" 180 or higher and "Horizontal" 210 or higher in JIS-P8116, but any of the specific "paper" satisfying these “Value” is also the “next value” of “value” of “quality specification” (“jump value”) that is one rank higher than “value” (meaning “paper” having a larger “basis weight”). "" Means no more.)

That is, when all the individual values are shown, the predetermined “basis weight” is 52.3, 60, 64, 81.4, 84.9, 96.5, 104.7, 127.9, 157 g / m. Takes a “jump value” of ³ .

  In response to this, the predetermined “thickness” also has “jump value” of 67, 81, 84, 102, 106, 119, 128, 156, and 192 μm.

  The same applies to a predetermined “rigidity” and a predetermined “strength”.

  In other words, if the “quality specification” of these “paper” is not “same” as the standard “form paper”, there will be problems such as printing defects, printing defects, processing defects, etc. in the application of the “paper”. In addition, physical properties such as durability will be significantly inferior (printers, etc. that have been “set” to fit standard “form paper”, processing devices, etc. This means that the “form paper” of the present invention can be adapted without changing those “settings”).

  Therefore, in the “foam paper” of the present invention, which includes “stress luminescent material” having a large specific gravity, “rigidity”, and “strength” that are significantly higher than “paper pulp fiber” contained in “paper”. However, in order to satisfy this “quality specification”, the “stress luminescent material” has a “predetermined shape (predetermined“ size ”or a predetermined“ shape ”)”, Therefore, it is necessary to control the state of inclusion (arrangement, distribution state, etc. in “paper”).

  Furthermore, regarding “ISO whiteness”, by setting the “value” to a predetermined value, the “color contrast” after printing such as offset printing or after printer printing is improved. In order to make the “printing finish (meaning the finishing of printing. Including the contrast between the printed part and non-printed part)” in FIG. It can be positioned as “form paper” of the ISO whiteness enhancement type, which is preferable.

  With regard to “smoothness”, the high “smoothness” enables even halftone dots and fine printed areas to be reproduced without unevenness, resulting in excellent “image reproducibility” and not only “text” but also “photographs”. Since it can be printed beautifully (printing), a higher “smoothness” can be similarly positioned as “form paper of improved smoothness type”, which is preferable.

  Although not included in the above-mentioned standards, when the “opacity” of “form paper” is improved (when it is made more “opaque” form paper), the “opacity” makes it “double-sided printing”. ”And“ double-sided printing ”(meaning that“ printing and printing on the back side ”can be seen through and does not affect“ printing and printing on the front side ”).

  Further, the “form paper” of the present invention is provided with a relatively large number of “vertical through portions, oblique through portions, cutout portions, and / or concave portions”. In various processing steps (processing steps) for providing the “penetrating portion, notch portion, and / or concave portion”, it is necessary to ensure the “processing suitability (processing suitability)”.

  This is an example of “perpendicular part”, “perforation”, “perpendicular part” and “slit-like part”, “sewing process”, and “slit process”. As an example, various drilling processes, sewing machines (folding machines, breaking machines, burst sewing machines, sheet-cutting machines, etc., including half-cut machines), slitting, etc. (In the case of laser processing, it means a laser beam), and a predetermined hole, a predetermined perforation, and a predetermined slit are provided, so in these processing, In order to maintain the “machining accuracy” and do not deteriorate the “wear resistance” of these “blades” (the “blades” are significantly scraped and consumed due to contact with the “stress luminescent material”. , That This means that it is necessary to prevent the product from having to be replaced with a significantly smaller “number of times (frequency and length)” than the predetermined “number of times of usefulness (life frequency, length of service life, etc.).” Laser processing ” In the case of “high output”, it means that the replacement of the “laser light source” will not be accelerated.) Therefore, it is important to control the “distribution” of the “stress luminescent material” in the “form paper”.

  In addition, in order to keep “smoothness”, “rigidity”, and “strength”, which are quality specifications (quality characteristics) of “form paper”, within the “acceptable range”, the “size” of “stress luminescent material” Is preferably “fine particles”, more preferably “ultrafine particles”, and “uniformly dispersed” on the “paper”.

  Moreover, because the “amount” that includes the “stress luminescent material” is also limited (of course, as described above, its “size” is also limited), so a small “amount” (and a small “shape”). In order to express “light emission” of “high brightness”, the stress emission coefficient α of the “stress emitting material” in the “stress emitting material”, that is, the “predetermined site” is 2 It is preferable to set it as above, and it is preferable to set it as 10 or more especially 100 or more.

  Then, in order to make such a printing or “white background” as a background of printing “a uniform white background without unevenness”, not only “ISO whiteness” is satisfied, but also “paper” The “color difference” E of the “color tone” of the “sizing agent” and the “color tone” of the “stress luminescent material” to be added is set to 0.5 or less.

  In the present invention, “paper pulp fiber” means “pulp fiber (hereinafter also referred to as“ pulp ”)”, which is a plant fiber separated for use in “papermaking”. , “Chemical fiber” or “artificial fiber” is not included.

  However, it is not excluded to include these “fibers” in addition to “paper pulp fibers”.

  Here, the “shape” in the form of “fiber” is a morphological property, and is “elongate”, that is, “thickness” (maximum diameter, or “width” or “thickness” of the cross section. "Length" is very large, and a so-called aspect ratio value ("thickness" vs. "length") means a ratio of about 1:50 to 1: 2000. To do.

  The “foam paper” of the present invention is a “paper” including a “stress luminescent material” made of so-called “ceramic” in addition to the “paper pulp fiber” (the composition of the “stress luminescent material”). The structure and the like will be described in detail below. In addition, the “paper pulp fiber” and the “stress luminescent material” are in contact with or entangled inside the “paper” (in this sense). The “paper pulp fiber” & “stress luminescent material” in this “paper” is also referred to as “composite” as “combined”.), A predetermined external force load on this “paper”, for example, When the “paper” is bent by “finger force” or the “paper” is pressed against the jig with an appropriate curved surface by hand, the “paper pulp fiber” in the “paper” “Deformation” is caused by the load.

  In particular, a “specific part” provided on the “paper” causes a “unique deformation” due to the position of the “specific part” or the “shape” of the “specific part” itself. Along with "inherent deformation", a very large "deformation stress (internal stress)" appears in the "specific part", and the "complex" existing in the "specific part" and the vicinity of the "specific part" The deformation of the “complex” existing in

  Then, the “deformation” of the “paper pulp fiber” when the “composite” causes “deformation” such as “curvature” is combined with the “paper pulp fiber” (partially coupled). ) ”, And“ deformation ”of the“ stress luminescent material ”, in particular, in the“ contact point ”between the“ paper pulp fiber ”and the“ stress luminescent material ”, with the physical movement, “Shear stress” and “shear stress” (hereinafter, collectively referred to as “stress”) are generated in the “stress luminescent material”.

  This "stress luminescent material" has "ceramic", especially "metal or silicon oxide, nitride, carbide or sulfide composition", and is the contact between "paper pulp fiber" and "stress luminescent material" In the same way as “hydrogen bonding” by “hydroxyl group of cellulose” at the contact point between “paper pulp fiber”, “hydroxyl group of cellulose” constituting “paper pulp fiber” and “oxide, nitride, They are “bonded” at their contacts by “hydrogen bonds” with the oxygen, nitrogen, carbon and sulfur atoms of carbides and sulfides.

  Of course, the “stress luminescent material” is also subject to the direct stress on the “stress luminescent material” caused by the “curved” of the “composite” and the “curved” of the “paper pulp fiber”. ”.

  The “stress luminescent material” used for the “foam paper” of the present invention is not “needle-like” or “strip-like” but “particle”, and the “shape” of the “particle” is “predetermined”. `` Shape '', as described above, when the pressure to the “stress luminescent material”, that is, when the “particles” are subjected to “deformation pressure”, “deformation stress corresponding to deformation of the paper pulp fiber” That is, in the “inside of the particle”, ““ tensile stress ”,“ shear stress ”or“ slip stress ”” occurs, which is a site specific to the “outer shape” of the “particle” (this is the “predetermined site”). ).), “Stress concentration” occurs, and in particular, the surface of the “particle” has a large number of “concave and convex shapes (the“ particle ”generated in the process of generating the“ particle ”. This means the original “concave shape”.) “ "Tension stress", "shear stress", or "slip stress" "causes the same" stress concentration "in the" bottom part of the recess "(this also becomes" predetermined part "), Those “parts” emit light strongly (a larger “stress” is generated in the “concave portion” than in the “convex portion” on the “particle” surface).

  That is, “parts peculiar to“ outer shape ”(meaning“ parts ”determined by“ outer shape ”) of such“ particles ”and“ recesses on the surface of the particle ” The “bottom” part ”is the“ predetermined part ”of the“ stress luminescent material ”, and the stress concentration factor α of the“ predetermined part ”is 2 or more, particularly 10 or more, and even 100 or more. It has become.

  In addition, in the “stress luminescent material”, the “contact point” with the “paper pulp fiber” is also a place that can be a “predetermined part” of the “stress luminescent material”. "" Tensile stress "," Shear stress ", or" Slip stress "" is generated as "Deformation stress corresponding to the deformation of the paper pulp fiber".

  The “stress luminescent material”, and further, each “part” of the “stress luminescent material” has an intensity proportional to each “stress magnitude” acting on the “part”, and The strength corresponding to the “direction in which the stress acts” with respect to the “structure (including composition and crystal structure) constituting the stress-stimulated luminescent material” described in detail below (this is the “strength corresponding to the deformation stress”). It emits light of a wavelength that is unique to the “structure”.

  And, this “light having a wavelength peculiar to“ the structure constituting the stress-stimulated luminescent material ”” is “light of a predetermined wavelength”, and usually in the wavelength range of “visible light”, that is, the wavelength of light, In the range of 400 nm to 800 nm, light of one wavelength is emitted corresponding to one type of “stress light emitting material”. Therefore, the observer can visually recognize the emitted “light of a predetermined wavelength”.

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

  “Conifer pulp fiber (referred to as NBKP or“ N material ”)”, which is a representative example of “paper pulp fiber” used in “foam paper” of the present invention, has a “thickness” of 30 to 30. The “length” is about 1.0 to 6.0 mm, or the “average length” as the “N material” has a “shape” of 3.0 mm.

  The Young's modulus of the “stress luminescent material” used in the “foam paper” of the present invention is much larger than the Young's modulus of the “paper pulp fiber” (there is a difference of 100 times or more). In order to satisfy the above, the “size (maximum diameter)” of the “stress luminescent material” is 1/2 or less of the “thickness” of the “paper pulp fiber”, and further 1/20 or less, and 1/50 or less of the “length” of “paper pulp fiber”, and further 1/500 or less.

  If the “thickness” exceeds 1/2 or the “length” exceeds 1/50, the “stiffness” and “strength” as “form paper” should be kept within the “quality specifications”. It becomes difficult.

  In the present invention, “the stress-stimulated luminescent material does not have a needle-like“ shape ”or a strip-like“ shape ”” means that “stress-luminescent material” has the same “shape” as “paper pulp fiber”. "Needle" means "bar" with "maximum diameter and length" equivalent to "paper pulp fiber", and "band" "shape" Has a “rectangular” “cross-section” with a “length” × “length” equal to the maximum diameter of “paper pulp fiber” and is equivalent to “paper pulp fiber” It means “an ultra-thin plate (band) flat rectangular parallelepiped” having a “length”.

  The “stress luminescent material” having such a needle-like or band-like “shape” has very large “rigidity” and “strength”, and due to its existence as a single unit, the “stiffness” of the “foam paper” and This will increase the “strength”. Furthermore, the “stiffness” and “strength” of the “composite” are significantly increased by being entangled with the “paper pulp fiber”.

  In addition, if the “foam paper” includes the “stress luminescent material” having such a needle-like or band-like “shape”, the “form paper” is subjected to the above-described processing. , "Stress luminescent material" "cutting (meaning that the" blade "directly cuts the stress luminescent material)" by the processing "blade" increases, the wear of the processing "blade" is remarkable (In the case of laser processing or the like, the laser output is increased.)

  On the other hand, the “stress luminescent material” is uniformly dispersed in the “foam paper” as the “fine particles” or “ultrafine particles” as described above. In addition to facilitating control of “strength”, it is also possible to suppress wear of such processing “blade” (because “stress luminescent material” is “small”, machining “blade” is “stress luminescent”. “Opportunities” that divide “materials” are drastically reduced or almost eliminated.

  Furthermore, by making the “stress luminescent material” as “fine particles” or “ultra fine particles” as described above, more “stress luminescent materials” are added to the “specific part” of the “foam paper” of the present invention. The “deformation stress” due to the deformation of the “specific part” is easily transmitted to the “paper pulp fiber” and the “stress luminescent material”.

The “predetermined external shape” of the “particle” in the form of “fine particles” is a “fine particle shape” having a maximum diameter of 1.0 to 20 μm and an average diameter D ₅₀ of 0.5 to 15 μm. .

Furthermore, the “predetermined external shape” of “particles” in the form of “ultrafine particles” having a maximum diameter of 0.01 to 1.0 μm and an average diameter D ₅₀ of 0.005 to 0.5 μm. It is also more preferable.

Here, in order to obtain the “predetermined shape” of the “particles” in the form of “fine particles”, a simple “crushing treatment” is applied to a relatively large “bulk” or “plate-like” “stress luminescent material”, and The particle size distribution forms a so-called “normal distribution” simply by performing a simple “classification process” after the treatment, and has an average diameter D ₅₀ as a center (here, having the maximum value of the distribution). ), Drawing a “distribution curve” with similar slopes towards both smaller and larger particle sizes (at least of its average diameter D ₅₀ ). , “Distribution” with a spread in which particles having a diameter of ± 70% or more exist significantly).

The “predetermined outer shape” of the “particles” in the form of “fine particles” of the “stress luminescent material” of the present invention is, for example, “fine particle shape” having a maximum diameter of 20 μm and an average diameter D ₅₀ of 15 μm. Then, with respect to the average diameter D ₅₀ , the distribution toward the large particle diameter is “distribution curve” (small particle diameter) in which the distribution value suddenly becomes “0” (meaning that it almost disappears) at the boundary of + 35%. The distribution toward is a “distribution” having a “spread of −70% or more” as described above.

That is, “classification process for removing“ particles ”having a maximum particle size exceeding + 35% with respect to the average diameter D ₅₀ ” (a “classification process” method for removing large “particles” exceeding a predetermined maximum particle diameter) "Stressed luminescent material", which is used to prevent "foam paper" from containing "particles" of unnecessary size, and "quality characteristics such as" smoothness ". enhance ", at the same time, by a" stress luminescent material "having a relatively large mean diameter D _50, to allow possible to increase the luminescence intensity thereof.

The “ratio between the maximum diameter and the average diameter D ₅₀ (value of“ maximum diameter ”/“ average diameter D ₅₀ ”) is set to 1.05 to 1.50. In particular, 1.20 to 1.35 is preferable.

  When this ratio exceeds 1.50, the meaning of the above-mentioned “special classification process” is diminished, and when it is less than 1.05, such classification process itself becomes difficult (repeatedly, “ "Classification" also includes the meaning that "the number of repetitions" increases extremely.) In addition, the "yield" of the resulting "stress luminescent material" will be significantly reduced. Is inappropriate.

  In the above description, it is assumed that “paper pulp fiber” and “stress luminescent material” are included in a “contact state” with each other. In the “process for producing paper”, that is, in the “paper making process”, a suspension (also referred to as slurry) of “paper pulp fiber” and “stress luminescent material” is used as a so-called “net (plastic wire or the like). ) "Is spread out and dried, and in this series of steps, the" paper pulp fiber "and" stress luminescent material "are uniformly dispersed in the suspension, and the uniform dispersion Is spread evenly and uniformly, or after thinly spreading the “paper pulp fiber”, the “stress luminescent material” is spread in a thin layer, and then again, the “paper pulp fiber” "Stress luminescent material" The individual “particles” of the glass fiber easily adhere to the surface of the “paper pulp fiber” (meaning that the “particles” are attached to the concave portions of the “fiber” surface and stay in contact with each other). , Where “paper pulp fibers” overlap each other, for example, “x” or “ki” “cross”, “paper pulp fibers” It is obtained by allowing the “particle” to enter the “intersection” and at the same time fix it.

  Then, through such “process”, “particles” of “stress luminescent material” are uniformly dispersed throughout the “form paper”.

  Here, as the “parts in contact with each other (including crossing positions; the same applies hereinafter)” increases, the light emission intensity when the “form paper” is deformed, that is, the light emission intensity at the specific portion increases. (Meaning that the emission point increases).

In addition, “deformation stress” concentrates on such “contact portion”, and as a result, the light emission intensity of the stress light-emitting material increases (means “increase in proportion to stress”) and the light emission. The “light” emitted from the part also enters the “paper pulp fiber” having transparency, and is repeatedly reflected in the “paper pulp fiber” (meaning that multiple reflection occurs). The “emission point” is expanded to the “emission area” (meaning that light is emitted from a plurality of “emission points”), and the emitted part (including “emission point” and “emission area”), and its The contrast in the peripheral area is increased, and it becomes easier to visually recognize. (This phenomenon and the repeated reflection at the “specific part” described above occur in combination.)
In the present invention, the “stress luminescent material” means “twinned pseudoelastic deformation” when “stress” is applied to the material in the vicinity of the so-called “thermoelastic martensitic transformation” accompanied by “physical deformation”. “Stress” was applied to the material accompanied by “physical deformation” represented by “Eu-added SrAl ₂ O ₄ (also referred to as“ SAOE ”)”, which is a material that is likely to occur. In this case, a material that emits light of a predetermined wavelength and whose emission intensity increases according to the applied “stress” is fired and sintered, and the above-mentioned “particle” shape or the like This is the shape.

Here, the meaning of “physical deformation” means, of course, that it is not “chemical composition change”, but “only part of the crystal structure inside the material changes its lattice structure. It shows that it is “deformation” that leads to “change in the outer shape of the entire material”. (In this way, “deformation accompanied by“ deformation of the outer shape that can be recognized in appearance ”” is called “physical deformation.” That is, deformation of the lattice structure occurs only in the microscopic region. (It means not a state but a state in which the deformation of the lattice structure propagates in the material and occurs over a large area that can be visually recognized.)
Therefore, in order to promote the “luminescence” of the “stress luminescent material” of the present invention, the “outer shape of the entire material” can be “changed” (also expressed as “movable range” as a movable region). It is important to have a configuration in which the “stress luminescent material” can move relatively freely in the “foam paper” like the “stress luminescent material” of the present invention.

  More specifically, the “form” of “foam paper” including “stress luminescent material” and “paper pulp fiber” includes “vertical through portion, oblique through portion, notch portion, and / or concave portion, in particular, Has a “shape” that includes slit-like penetrations (“specific parts”), and “physical deformation” of “form paper” causes stress concentration in these “specific parts” Depending on the “shape” of these “specific parts”, the “physical deformation” as described above occurs, and by such “physical deformation”, each of the “specific parts” is in the middle. "Spot with high stress concentration" (stress concentration spot) occurs in "Spot" with extremely high stress concentration, or "Region with high stress concentration" in the vicinity of "Spot" (Respectively in the “location” and “region”, and "Stress luminescence material" itself is subject to "physical deformation", or "physical deformation" is caused to "paper pulp fiber". Such “physical deformation” of the “material” occurs, and the stress concentration on the “predetermined portion (stress concentration portion)” in the “stress luminescent material” due to the “outline” of the “stress luminescent material” As a result, strong “luminescence” is generated from the “site”.

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

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

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

A numerical value representing this “stress concentration” state is “stress concentration coefficient α”, where α = σmax / σ ₀ (where σ ₀ is “stress” ”Is an“ average value ””, and σmax is expressed as “the maximum value of“ stress ”” generated at the stress concentration portion.

In addition, when this “stress concentration coefficient α” is applied to, for example, a part of “form paper” (partial region, meaning “a part of paper, not the whole paper”) ” “ ₀ ” is an “average value of“ stress ”” that occurs in the “part (one region)” when the “part” is regarded as the whole, and σmax is the “part (one region)” ) ”, Which means“ maximum value of “stress” ”generated at the stress concentration point (predetermined part), and correctly,“ maximum value of “stress” ”.

As a simple example, a cylindrical material (a rod-shaped material whose upper and lower surfaces are the same circle) is sandwiched between its upper and lower surfaces (the area of each surface is S square millimeters). When an external force F (N: Newton) is applied in the vertical direction at a position where the cross-sectional area becomes 1/2 of the upper surface (lower surface) at the intermediate position of the cylindrical shape (the cross-sectional area of this portion is S / 2 Σ ₀ is [(proportional constant k) × F / S] (N / mm ² ), and σmax is [(proportional constant k) × 2 F / S]. (N / mm ² ) and the stress concentration coefficient α = σmax / σ ₀ = 2.0.

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

  In order to set the “stress concentration coefficient α” of the “stress luminescent material” of the present invention to 2 or more, a part of the “stress luminescent material” having a “particulate” “outer shape” has a maximum diameter of 1 It is obtained by providing “dents” and “notches” with a depth of / 10 to 1/5.

  The shape of the “dent” is “shallow shape of bottom. For example, [(opening width / depth) ratio] is 1/5 to 1/1” or “deep bottom shape. , [(Opening width / depth) ratio] is 1/20 to 1/10 "," stress concentration "occurs around the" bottom "of this" dent ", and the" stress concentration coefficient α "Is 2 or more.

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

  The “stress light-emitting material” of the present invention has a light emission intensity that increases substantially in proportion to the amount of “stress” generated. Therefore, as the “stress concentration coefficient α” increases, the light emission increases. The strength is increased and the visibility can be improved.

  The “stress concentration coefficient α” is preferably as large as possible, and is set to 2 or more. Furthermore, 10 or more, and more preferably 100 or more is preferable because the light emission intensity of the portion can be set to “high luminance” and can be more easily recognized.

However, the larger the “stress concentration factor α”, the more “discontinuity” of the “outer shape” of the “stress luminescent material” becomes so-called “sudden”, and the “stress luminescent material” “lights”. If the “deformation” is repeated, it is easily “destructed” and no longer emits “light”. (This means that “stable light emission at least 100 times or more” is necessary to ensure the reliability of the authenticity determination, but the reliability cannot be ensured.)
Further, in the present invention, the “sizing agent” means “form paper” at the stage of “making paper”, printability as “foam paper”, smoothness, friction resistance, barrier property, folding strength, bursting strength. It is a “generic name” for materials used to improve performance such as oil resistance and chemical resistance. It suppresses the permeability of liquids such as printing ink to “foam paper” and prevents settling and bleeding. Mineral that is added or applied to prevent squeeze-through by adding opacity to the “sizing agent” and “foam paper” added for the purpose of preventing and giving a certain level of water resistance, and providing whiteness, smoothness, etc. There are “fillers” in which talc and kaolin are mainly used, “viscous agents” that are also used in “Japanese paper” and the like.

  The “color tone” of the “sizing agent” means the “color tone” of the entire “sizing agent” added to the “foam paper” of the present invention.

The “color difference”, which is the difference between the “color tone” of the entire “sizing agent” and the “color tone” of the “stress luminescent material”, is, for example, an L * a * b * chromaticity diagram (LAB color system) Is a “color difference” represented by ΔE {= (Δa ² + Δb ² + ΔL ² ) ^1/2 )}, and this “color difference” is 0.5 or less. This means that the “color tone” of the “stress luminescent material” and the “color tone” of the “sizing agent” are “same color”.

  Other color systems proposed by the International Commission on Illumination (CIE) include RGB, XYZ (Yxy), and UVW (Luv), but these are correlated and easy. Can be converted, and the converted value can also be used.

  The change in “color” is recognized as “there is a difference” when ΔE exceeds 0.5 (defined as “SLIGHT: the difference is felt slightly”). If it exceeds 5, the “difference” can be clearly seen (defined as “NOTICEABLE: the difference is felt considerably”).

  By making the “color tone” of the “stress luminescent material” and the “color tone” of the “sizing agent” “same color”, it is ensured that the “stress luminescent material” is included in the “foam paper”. It becomes possible to “hide”.

  Further, the “stress luminescent material” is formed in a “predetermined pattern”, for example, a character, figure, or symbol of a predetermined size, in particular, some “message (such as“ true ”character) for authenticity determination”. Is provided in a predetermined size (meaning that a region including “stress luminescent material”, a region not including it, a region including a large amount, and a region including a small amount are provided. The distribution of the “stress luminescent material” is uniform.) The “predetermined pattern” before the “stress luminescent material” emits light, or in the situation where the “predetermined pattern” is desired to be hidden. It is important to keep the value smaller.

  In the present specification, “part” indicating the formulation is based on mass.

(Main applications)
The fields in which the “form paper” of the present invention is used include the following.

  That is, receivables, deposit certificates, receipts, bills, checks, bankbooks, magnetic forms, transfer cards, gift certificates, coupons, bags, gift certificates, movie tickets, membership tickets, beer tickets, etc., evidence securities, etc. In the securities field, catalogs, flyers, brochures, leaflets, posters, POPs, greeting cards, postcards, stickers, invitations, invitations, reports, minutes, lists, name cards, business cards, participation certificates, manuals, manuals , Company history, public relations magazine, in-house newsletter, price list, transfer form, purchase order, production instruction, delivery slip, various slips such as sales slips, various statements such as call charge statement, salary statement, transaction statement , Various invoices, business forms, postcards and sealed forms, notes, envelopes, notepaper, notebooks, diaries, postcards, crimped postcards, stamps, direct mail, Novels, picture books, encyclopedias, other books, newspapers, including “insert (insert)” into commercial fields, such as kulet mail, wrapping paper, flexible packaging, plastic containers, paper containers, toys, or parts thereof There are publishing fields such as magazines, industry papers, maps, telephone books, textbooks, reference books, and music scores.

  In particular, “paper” used in the anti-counterfeiting field, specifically those that can cause damage to the holders or issuing companies of securities, etc. , ID cards such as employee ID cards, membership cards, admission tickets for entrance examinations, passports, banknotes, gift certificates, point cards, stock certificates, lottery tickets, horse tickets, passbooks, boarding tickets, pass tickets, air tickets, various There are admission tickets, play tickets, transportation vouchers, etc.

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

  In addition, other than these information records, proof is attached to what is often referred to as a high-end brand product, such as a high-priced product, such as a luxury watch, luxury leather product, precious metal product, or jewelry. A storage box or a case of such expensive products can also be forged. Furthermore, even if it is a mass-produced product, a product of a well-known brand such as an audio product or an appliance that certifies the product or a tag that is hung on the product is easily forged.

  In addition, the proof that is attached to a memory that records music software, video software, computer software, game software, etc., which is a copyrighted work, or those cases themselves are also subject to forgery. Can be. In addition, it is desirable that products such as printer toner, paper, and the like in which supplies to be replaced are limited to genuine materials have a function of identifying their authenticity for the purpose of preventing damage caused by forgery.

(Background technology)
In the first place, “emission” means emitting light, and in terms of “phenomenon”, burning an object, passing a large amount of current through a conductive material with high electrical resistance, and nuclear fusion, etc. The object or material is brought into a high-temperature state by causing an exothermic reaction, and the atoms and molecules constituting the object or material are vibrated at high speed to emit light corresponding to the temperature. It is also called “body radiation. Light from flames, incandescent lamps, stars, etc.”) “Luminescence (cold light) that emits light when a quantum system (such as electrons) in an excited state transitions to a lower excited state or ground state. ) ”, Electromagnetic radiation generated when a charged particle is suddenly decelerated or bent in the electric field,“ bremsstrahlung ”of a charged particle beam, the speed of the charged particle is the speed of light in the material Through the material at a faster rate There is "Chelenkov radiation" that occurs when carrying.

  This “bremsstrahlung” includes synchrotron radiation, which means that electrons are stopped by atoms in a narrow sense. The principle of artificially generating X-rays with an X-ray tube is bremsstrahlung, and bremsstrahlung is also generated in the target when high-speed electrons collide with the target. That is, when the beta ray (electron beam) is shielded with lead (target) or the like, the beta ray itself stops with lead, but at the same time, X-rays due to bremsstrahlung are also generated.

  In addition, “luminescence” means that a substance is excited by receiving energy by electromagnetic wave irradiation, electric field application, electron collision, etc., and the ratio of the number of high energy states to the number of low energy states is in a thermal equilibrium state. This is a light emission phenomenon due to spontaneous emission that occurs when the state is made larger (in contrast to this, black body radiation is a phenomenon in which a substance in a thermal equilibrium state emits light), and the number of distributions of low energy states In the inverted distribution state in which the ratio of the number of distributions of high energy states to 1 or more, light amplification 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 are collectively called “fluorescence”. Chemically, emission associated with deactivation (transition to the ground state) from excited singlet is “fluorescence”, and emission associated with deactivation from excited triplet is “phosphorescence”. The transition from this excited triplet to the ground state (ground singlet) is a forbidden transition because of its different spin multiplicity, so the excited triplet state has a long lifetime, and the excited triplet is The energy level is often lower than that of the excited singlet, so that the wavelength of “phosphorescence” tends to be longer than that of “fluorescence”.

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

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

  The above-mentioned “thermal radiation” is special and extraordinary in order to “emits light”, such as bringing the object or material into a high-temperature state or vibrating the atoms or molecules constituting the object or material at high speed. In “luminescence”, in order to excite electrons from the ground state to the excited state, excitation by light irradiation, excitation by electron beam irradiation, excitation by voltage, excitation by acoustic energy, Excitation by mechanical energy, excitation by chemical reaction, excitation by solvent, excitation by piezoelectric effect, etc. requires some process, and this process also requires sufficient “luminescence” It was necessary to apply an excessive load corresponding to it.

(Prior art)
For these “light-emitting” mechanisms, the “material” itself, that is, the “material composition” or “material structure” has a “potential light-emitting structure”, and only a relatively small stress is applied. Thus, a novel “stress luminescent material” having a novel “luminescence” mechanism capable of causing the “material” to emit light has been discovered.

  This new "stress luminescent material" is a new "luminescent material" developed by Mr. Xu et al. Of (National Institute of Advanced Industrial Science and Technology), and "elastic deformation region" with relatively small "mechanical energy" And “a material exhibiting stress luminescence”.

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

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

  The “destructive luminescence” phenomenon has been observed in a large number of material systems, and about half of the inorganic substances are said to have the property of “destructive luminescence”.

  In contrast, “deformed luminescence” has been reported to be weak emission in the “plastic deformation region” although there have been several reports of radiation-induced alkali halides and certain polymers. doing.

  In contrast, the “stress luminescent material” developed by Mr. Xu et al. Of the National Institute of Advanced Industrial Science and Technology is different from this “deformed luminescence” and “stress luminescence” in the “elastic deformation region”. It is a material which shows.

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

Typical examples of the emission center include strontium aluminate added with europium (SrAl ₂ O ₄ : Eu: green emission), zinc sulfide added with manganese as the emission center (ZnS: Mn, yellow-orange emission), and the like. is there. (See Patent Document 1.)
Then, these stress luminescent materials are made of the structure itself (all the structures are composed of “stress luminescent materials”) or a laminate in which the structure is simply stacked on another structure, etc. In addition, those in which external stress is directly applied to them and the structure itself or a laminate is simply made to emit light are disclosed. (See Patent Document 2.)
However, according to many subsequent technical disclosures including these technical disclosures, this stress light emitting structure can be produced by the “prescription”, or the stress light emitting structure alone or a laminate can be produced. It ’s not so difficult to create something that has the same effect.

  In addition, as “paper” for the purpose of preventing counterfeiting, that is, “anti-counterfeit paper”, the authenticity of such as “fluorescent ink” printing paper, securities paper with embedded hologram thread, etc., whose authenticity is determined by ultraviolet irradiation. There are many papers that can be confirmed, but these “counterfeit prevention papers” require a “light source that irradiates light” such as an “ultraviolet lamp” in order to determine their authenticity. For example, in order to confirm the authenticity of the passport, the immigration inspector makes a “judgment” under the examination table, and the authenticity is ensured in places where the illumination light does not reach or “dark”. It has the disadvantage that it is difficult to judge.

JP 2007-055144 A JP 2003-253261 A

  Accordingly, the present invention has been made to solve such problems. The purpose of the appearance is simply “form paper” or “form paper” provided with “specific parts” such as “vertical through part, oblique through part, notch part and / or concave part”. In fact, the “foam paper” contains “stress luminescent material” together with “paper pulp fiber” in a form that cannot be recognized from its appearance at all. In addition, due to a predetermined external force load on the “foam paper”, the “paper pulp fiber” is deformed. In particular, the “paper pulp fiber” in the “specific part” is largely deformed, and at the same time, “stress When “deformation stress” is generated at a predetermined portion of the “luminescent material” and light of a predetermined wavelength having an intensity corresponding to the deformation stress is emitted from the predetermined portion and becomes visible, the “form paper” "of The Tadashisei, special illumination light without providing a "Form Paper" which enables it to easily determine.

  In addition, the “stress luminescent material” has a specific shape, and is further included so as to be in contact with the “paper pulp fiber” to increase the “luminescence”, and furthermore, the “sizing agent” used for the “foam paper” "Foam paper" having a design difference and anti-counterfeiting property with a color difference of 0.5 or less.

To solve the above problem,
The first aspect of the foam paper of the present invention is:
A foam paper containing at least paper pulp fibers and a stress luminescent material, wherein the foam paper has a shape including a vertical penetrating portion, an oblique penetrating portion, a notch portion, and / or a concave portion, and the foam Due to the deformation of the foam paper caused by a predetermined external force load on the paper, deformation stress concentrates on the vertical penetrating part, the oblique penetrating part, the notch part and / or the concave part, and at the same time, the vertical penetrating part and the oblique penetrating part. The paper pulp fiber in the portion, the notch, and / or the recess is deformed in the foam paper, and the stress luminescent material has a predetermined outer shape, and the stress luminescent material has a predetermined shape. A deformation stress corresponding to the deformation of the paper pulp fiber is generated at a portion of the light, and light having a predetermined wavelength having emission intensity corresponding to the deformation stress is emitted from the predetermined portion. Te, and is characterized in that the light of the predetermined wavelength is visible.

According to the form paper of the first aspect,
A foam paper containing at least paper pulp fibers and a stress luminescent material, wherein the foam paper has a shape including a vertical penetrating portion, an oblique penetrating portion, a notch portion, and / or a concave portion, and the foam Due to the deformation of the foam paper caused by a predetermined external force load on the paper, deformation stress concentrates on the vertical penetrating part, the oblique penetrating part, the notch part and / or the concave part, and at the same time, the vertical penetrating part and the oblique penetrating part. The paper pulp fiber in the portion, the notch, and / or the recess is deformed in the foam paper, and the stress luminescent material has a predetermined outer shape, and the stress luminescent material has a predetermined shape. A deformation stress corresponding to the deformation of the paper pulp fiber is generated at a portion of the light, and light having a predetermined wavelength having emission intensity corresponding to the deformation stress is emitted from the predetermined portion. Te, wherein it is possible to predetermined wavelengths of light to provide a foam sheet, characterized in that the visible, design properties, and, it is possible to provide a foam sheet having an excellent anti-counterfeit properties.

The second aspect of the foam paper of the present invention is:
In the foam sheet according to the first aspect, the vertical penetrating portion and / or the oblique penetrating portion is a slit-like penetrating portion.

According to the form paper of the second aspect,
In the foam paper according to the first aspect, it is possible to provide a foam paper characterized in that the vertical penetrating portion and / or the oblique penetrating portion is a slit-like penetrating portion. It is possible to provide a form paper that can be made possible.

The third aspect of the foam paper of the present invention is:
In the foam paper of the first aspect or the second aspect, the shape of the foam paper is such that the stress concentration coefficient α in the vertical penetrating part, the oblique penetrating part, the notch part, and / or the concave part is 2 or more. It is the shape which becomes.

According to the form paper of the third aspect,
In the foam paper of the first aspect or the second aspect, the shape of the foam paper is such that the stress concentration coefficient α in the vertical penetrating part, the oblique penetrating part, the notch part, and / or the concave part is 2 or more. It is possible to provide a foam paper that has a shape of the above, and to provide a foam paper that can emit light more stably and with higher light emission intensity.

The fourth aspect of the foam paper of the present invention is:
In the foam paper according to any one of the first to third aspects, the predetermined shape of the stress-stimulated luminescent material has a maximum diameter of 1.0 to 20 μm and an average diameter D _50. It is characterized by having a fine particle shape of 0.5 to 15 μm.

According to the form paper of the fourth aspect,
In the foam paper according to any one of the first to third aspects, the predetermined shape of the stress-stimulated luminescent material has a maximum diameter of 1.0 to 20 μm and an average diameter D _50. It is possible to provide a foam paper characterized by a fine particle shape of 0.5 to 15 μm, to improve the suitability of its “quality characteristics”, improve the suitability for processing, and emit light intensity. It is possible to provide a foam sheet that can increase the number of sheets.

The fifth aspect of the foam paper of the present invention is:
In the foam paper according to any one of the first to fourth aspects, the foam paper includes a sizing agent, and a color tone of the sizing agent and a color tone of the stress-stimulated luminescent material included in the foam paper. The color difference is 0.5 or less.

According to the form paper of the fifth aspect,
In the foam paper according to any one of the first to fourth aspects, the foam paper includes a sizing agent, and a color tone of the sizing agent and a color tone of the stress-stimulated luminescent material included in the foam paper. It is possible to provide a foam paper having a color difference of 0.5 or less, and to provide a foam paper that is remarkably excellent in design and anti-counterfeiting properties.

  The “foam paper” of the present invention includes both “paper pulp fiber” and “stress luminescent material” in the paper making process of “paper”, so that “paper pulp fiber” and “stress luminescent material” are mutually connected. In the stage where the external force load related to the "paper" is in contact with the "paper pulp fiber" in the interior, and the "paper pulp fiber" is pulled or bent to be "deformed" The "deformation" that the "paper pulp fiber" undergoes acts as a "deformation" pressure on the "stress luminescent material" that is in contact with the "paper pulp fiber". As a result, the "stress luminescent material" Under the pressure, “deformation stress” is generated inside the “stress luminescent material”, and has a strength corresponding to the “deformation stress” (substantially proportional), and emits light of a predetermined wavelength. have.

  In particular, “vertical through portions (including slit-like through portions; the same applies hereinafter), oblique through portions (including slit-like through portions. The same applies hereinafter), notch portions, In addition, a “larger deformation pressure” is applied to the “paper pulp fiber” and the “stress luminescent material” in the “specific part” composed of the recesses and in the vicinity of the “specific part”. The “stress luminescent material” has a structure in which light having a predetermined wavelength having a higher luminescence intensity has a strength corresponding to a larger “deformation stress”.

  The “stress luminescent material” used in the “foam paper” of the present invention is not a “fibrous” (“needle” or “strip”) “shape” having the same size as the “paper pulp fiber”. It has a “predetermined shape”, that is, a “particle” -like “shape”, and further has a “fine particle” shape, in particular, an “ultrafine particle” shape.

  A large number of protrusions (convex portions) and a large number of craters (concave portions) are present on the surface of the “particle” -like “stress luminescent material”.

  In other words, the surface of each “particle” of the “stress luminescent material” has a large number of “unevenness”, and the “particle” has the above-mentioned “force from the outside” (“particle” "Deformation" pressure)), the "deformation stress" generated inside the "particle" is concentrated at the "vertex" of the convex part and the "bottom" of the concave part, In particular, the largest deformation stress (internal stress) is generated at the “bottom part of the recess” (this “predetermined part” of the “stress luminescent material” is the “stress concentration part”).

(See FIG. 1. In FIG. 1, this state is shown as a “schematic diagram” of one section of “form paper A1.” FIG. 1 is a sectional view of a portion not including “specific portions K1 to K3.” The “part” of the “bottom of the recess” of the “concave / convex” on the surface of the “stress luminescent material P1” in the form of “particles” is indicated as “stress concentration portion S1”.
Furthermore, a “dent” or “notch” having a depth of 1/10 to 1/5 of the maximum diameter is formed on a part of the “shape (outer shape)” of the “particle” -like “stress luminescent material”. Even if it is provided, “stress concentration” occurs around the “bottom” of the “dent” and around the “vertex (pointed portion of the bottom)” of the “notch”. The “part” of “is a“ stress concentration part ”. (Not shown)
In addition, stress concentration occurs at the “contact point” where the “paper pulp fiber” and the “stress light emitting material” are in contact with each other, and the “contact point” of the “stress light emitting material” is , “Stress concentration part”. (See FIG. 1. FIG. 1 is a schematic diagram showing a state in which “stress luminescent material P1” is fixed to the surface of “paper pulp fiber 1”. Although the state where the “stress light-emitting material P1” is fixed at the position where the crossing points is illustrated, this portion is not indicated as the “stress concentration portion S1”. (The light emitting material P1 ”alone indicates that it is attached to some“ material ”other than“ paper pulp fiber 1 ”.)
Then, an observer visually recognizes the emitted light having a predetermined wavelength.

  Furthermore, as described above, the “form sheet” of the present invention includes a “specific part” including “vertical through part, oblique through part, notch part, and / or concave part” (“specific part”). Means that is provided.)

  This “specific part” is provided in any “process” of the “paper making process” of the “foam paper” shown in FIG. 2, and in particular, “paper making process 1: wiring & squeezing” In the so-called “wet paper” state after the “squeezing”, a metal jig having a projection having the same shape as the desired “penetrating part” is pressed against the “wet paper”, The “wet paper” in the “pressed part” is completely pushed out (meaning “excluded” in part), and the pushed part is made into a “penetrating part” in a desired shape by drying in the next step. Also, a metal jig having a protrusion having the same shape as the desired “notch” or “recess” is pressed against the “wet paper”. However, in this case, the “pressed” Do not push the “wet paper” in the “Part” completely, but finish it as a “dent” with the desired depth. Accordingly, the "thickness direction, a portion, displaced portion" and can be obtained by a "switching chipped portion or recess portion" in the desired shape.

  Alternatively, a jig (a metal-made jig having a desired shape) or an apparatus for providing a “penetrating portion” in “paper making process 2: drying & pressing process” or the last “processing & finishing process”. (A device that applies a desired pressure to the jig and at the same time gives a desired “movement”), a jig (similar) or a device (similar) that provides a “notch or recess”. It will be provided in the desired form.

  In particular, as a jig and device for providing a “penetrating portion”, “drilling device”, “sewing machine device”, and “slitter processing device” can be used. A “folding device” and an “embossing device” can be used as the jig or device to be provided.

  Of course, as various “post processing” as “foam paper”, drilling, sewing, zigzag folding, slitting, bursting, bi-folding, tri-folding, full gluing, partial gluing, windows "Post-processing" such as opening processing, window film pasting processing, envelope processing, embossing processing, or other materials for anti-counterfeiting and other purposes such as magnetic stripes and transfer processing (all "processing" Also referred to as “processing”, and collectively referred to as “post-processing”).

  At this time, it is essential to be able to distinguish between the “specific part” for authenticity determination and these so-called “post-processing” parts.

  FIG. 6 shows a part of a so-called “continuous form” as “form paper A1”, and “feed hole HL” (“hole” shape provided by drilling as “vertical through portion: specific portion K1”). “Vertical penetration part: specific part K1” is arranged in a vertical direction in two rows in a predetermined cycle (indicated by “circles” of the same diameter in FIG. 6), provided by horizontal sewing. "Horizontal sewing machine M1" (Elongated elliptical "vertical through part: specific part K1" is arranged in the horizontal direction at a predetermined cycle. In FIG. "Vertical sewing machine M2" provided by vertical sewing processing (in the direction orthogonal to the "horizontal sewing machine", another elongated elliptical "vertical penetration part: specific part K1" is arranged at a predetermined cycle in the vertical direction. In FIG. 6, left and right, two rows are indicated by “broken lines”), and part “Slit SL” (“vertical penetrating part” and “slit-like penetrating part”: specific part) provided by litter processing is provided in one place. In FIG. 6, this is indicated by “single line” in the vertical direction. )) Is schematically illustrated.

  Other “vertical through part: specific part K1”, “oblique through part: specific part K2”, “notch part: specific part K3” and “concave part: specific part” are not provided. Also, “single sheet” as “form paper A1” and other “post-processing” states are omitted.

In particular, the “machining accuracy” of “drilling” is such that when the “hole” is a “feed hole (also referred to as sprocket hole)”, the above-mentioned various “printers” can perform continuous printing. , "Paper feeding aptitude" (meaning that "smooth feeding" without "paper folding", "meandering", "jam", etc.) and "printing position accuracy" If the “machining blade” used for drilling is heavily worn, the reliability of authenticity judgment will be greatly reduced, and not only will the replacement frequency of this “machining blade” increase rapidly, but the “machining blade” will suddenly "Paper loss" and "working time loss" due to breakage or sudden chipping, and "partial wear" occurs on the "cutting edge" of the "machining blade" It is difficult to grasp that “foam paper” including “various drilling defects” So that the results in manufacturing. (This is also true for “laser machining” without using a “machining blade”, and the occurrence of “defects” due to fluctuations in the required “high laser output” is expected.
For this reason, the degree of wear of the “machining blade” used in the “machining” described above can be grasped by the “wear speed” or the “machining blade replacement period” that becomes apparent as a result.

  That is, the “foam paper” of the present invention satisfies the above “quality specifications”, and the “consumption rate” is equivalent to “ordinary foam paper (form paper that does not contain stress luminescent material)”. Alternatively, it is necessary to set the “consumption rate” to at least twice that. In order to index this “consumption rate”, the “replacement period” of the “machining blade” is replaced with the “replacement period” of the “machining blade” when “ordinary foam paper” is used. When the “form paper” is used, the “replacement period” of the “machining blade” is the “period of 1/2 to 1/1”.

  The same applies to “sewing machine processing” and “slitter processing”.

  Furthermore, such “feed holes”, “perforations”, and “slitter lines (including“ cut lines ”that become partial slitters)”, respectively, are different from “form paper”. "Cut" ("Cut") in "Shape" ("Circular" of "Circular Hole", "Shape" of "Oval Hole", or "Shape" of "Vertical Cut") ) ”,“ Form paper feed mechanism ”such as“ printer ”, and various“ processing machines ”(folders, bag making machines, bursters, etc.) of“ form paper ” )) Is subject to various “external force loads” by the “form paper transport mechanism”, and “stress concentration” peculiar to the “feed hole”, “perforation” and “shape” of the “slitter line”. (It depends on the direction in which “stress” works.) , Of the "specifying part", respectively, to each of the "stress concentration points", so that the resulting strong "luminescence".

For example, “feed hole HL” of “form paper A1” is one of “form paper feed mechanism” of “printer”, “feed pin” (“feed pin” is inserted into “feed hole HL”, “ Along with the movement of the “feed pin”, the “form paper A1” is conveyed.) With the “contact” between the “feed pin” and the “feed hole HL”, a predetermined direction is set in the movement direction of the “feed pin”. The "deformation stress" concentrates on this "contact point" (a large external force load is applied to "one point" on the circumference of the circular hole, and the "circular" is distorted. “Stress” also works.) “Paper pulp fiber 1” in “foam paper A1” existing in the vicinity of the “contact” is deformed, and “stress in the foam paper A1” in the vicinity of the “contact” is deformed. In the “predetermined part (stress concentration part S1)” of the “luminescent material P1” A “deformation stress” corresponding to the deformation of the “paper pulp fiber 1” is generated, and light of a predetermined wavelength having a light emission intensity corresponding to the “deformation stress” from the “predetermined portion (stress concentration portion S1)”. Emits light. (See FIG. 1 and FIG. 6.)
In particular, the “shape” of the “feed hole HL” is not a mere “circle” or “ellipse”, but a “shape” having a number of “notches” on the circumference or on the circumference of the ellipse. It means a so-called “hole” with a jagged circumference, also called “Kikumaru” (not shown).), The “notch” part corresponding to that “one point” has a very large “deformation stress” As a result, strong “luminescence” is generated from the “site”.

  Then, “light emission” of a predetermined wavelength in “feed hole HL”, “sewing machine M1 or M2”, “slit SL” or the like of “form paper A1” is received by an appropriate light receiving element and used. It is determined that the “form paper A1” is authentic, or the “light emission” is detected by an appropriate “position sensor” to grasp the feeding status and processing status of the “form paper A1”. Then, by controlling the moving speed and the like of the “feed pin”, the feed accuracy and processing accuracy of the “form paper A1” are improved.

  As shown in FIG. 2, the “paper making process” for “making paper” of the “foam paper” of the present invention is typically “pulping process”, “pulp bleaching process”, “pulp selection and dewatering process”. , “Raw material adjustment step 1: Melting & beating”, “Raw material adjustment step 2: Addition of chemicals such as sizing agent”, “Paper making step 1: Wiring & squeezing”, “Paper making step 2: Drying & pressing”, and “Processing” The “stress luminescent material” is added mainly in the “raw material adjustment step 2: chemical addition such as sizing agent” step and the “papermaking step 1: wiring & squeezing”.

  Of course, in other processes, “stress luminescent material” may be added, and in this process, “paper pulp fiber” is also referred to as “layer” (“wet paper”. ")", And the "layer" of "stress luminescent material" is stacked on the "layer", and the two-layer structure of "" stress luminescent material "/" "paper pulp fiber" " Since two layers are stacked before drying, a more preferable “entanglement” state can be obtained in a boundary region where two materials are mixed.

  Further, in the same manner, ““ stress luminescent material ”/“ paper pulp fiber ”/“ stress luminescent material ”and“ “paper pulp fiber” / “stress luminescent material” / “paper pulp fiber” ” It can be a layer structure or a multilayer having more layers.

  At this time, when the “stress luminescent material” is arranged on the outside, the “light emission” is easily visible, and when the “paper pulp fiber” is on the outside, the existence of the “stress luminescent material” is easily concealed.

  As the “paper pulp fiber” used in the present invention, “pulp fiber (“ pulp ”)” which is a plant fiber separated for use in “papermaking” is used.

  Here, this "paper pulp fiber" is derived from plants, such as regenerated cellulose fiber obtained by dissolving cellulose in a solvent and fiberized again, and "corn fiber" made from "starch" of "corn" Of synthetic fibers.

  As used in the present invention, the “shape” expressed as “fiber” or “fibrous” is a morphological property and is “elongate”, that is, “thickness” (maximum diameter. "Length" is very large with respect to the cross-section "width" and "thickness"), and the aspect ratio value ("thickness" vs. "length") is 1:50 About 1 to 2000 is used.

  The shape of the “paper pulp fiber” of the present invention is the typical “conifer pulp fiber (“ N material ”)” or “hardwood pulp fiber (LBKP or“ L material ”)”, respectively. , “Thickness” is about 30 to 50 μm, “Length” is about 1.0 to 6.0 mm, or “Thickness” is about 10 to 30 μm, and “Length” is about 0.5 to 3.0 mm have.

  The “foam paper” of the present invention is a “paper” including “stress luminescent material” in addition to the “paper pulp fiber”, and the “paper pulp fiber” and the “stress luminescent material” The “paper” is entangled inside the “paper”, and the “paper” is bent by a predetermined external force load, for example, “finger force”, or the “paper” is applied to a jig having an appropriate curved surface by hand force. First, the “paper pulp fiber” in the “paper” is “deformed” by the external force load.

  The “deformation” of “paper pulp fiber” at this time can be expressed as follows.

  That is, the thickness of the “paper” is compared with the thickness of a general high-quality paper to be “100 μm thick”, and this “paper” is cut into a “30 mm (30,000 μm) long section”. , "" Thickness "is about several tens of micrometers in" Section "of" "Thickness 100 μm x Length 30,000 μm (Imaging a cross section of the paper as shown in Fig. 1)" The “fiber” having a “shape” having a “length” of several millimeters (several thousand μm) is in a state where the “fiber” is stretched, and the plurality of “fibers” are “stretched”. In this state, it is expressed as “a state in which a plurality of“ fibers ”are entangled”, and “paper pulp fiber” is “hydrogen bond” at these “contact points”. "Combined with each other." Are regarded as complex. ")" It is assumed.

  When the “fiber composite” is “curved” when the “fiber composite” is “curved” with a “predetermined external force load”, for example, by sandwiching both ends of the “fiber composite” with fingers. The individual “fibers” confined in the “fiber composite” are bent in the “curved” direction according to the “curved” direction.

Moreover, the “bond (hydrogen bond)” between “paper pulp fibers” at those “contact points” is very weak compared to general polymer chemical bonds and adhesion between resins, as described above. The “predetermined external load (ie, curvature)” easily breaks the bond, and the “paper pulp fibers” are not only “shall” but also pulled in both directions of the “section”. At the same time, it causes “physical horizontal movement”. (Meaning with macroscopic movement.)
Then, after the mutual bond is cut, the “paper pulp fiber” again absorbs “humidity” in the air, that is, absorbs moisture, and “bonds” again at “new contact”. It will be.

  As described above, the very long “fiber (paper pulp fiber)” confined in the “fiber composite (paper)” spread very thinly, when this “fiber composite” is “curved”. In response to the “curvature”, a “horizontal movement” occurs simultaneously with “being”.

  In particular, in the case of “paper pulp fiber” included in such “paper”, this “deformation” is not simply “curved”; "Deformation" (so to speak, meaning that the surface of "paper" is rubbed on the surface of the jig (meaning that it slides on the surface)) while pressing the "paper" by hand (this is "curved") In addition to the deformation stress associated with “curvature”, “shift stress” can also be generated inside the “paper”.

  When such “slip stress” is generated, the above-described “physical horizontal movement” is promoted, and the “paper” remains in a “curved” shape, and this shape is again replaced with the original. In order to return to the “flat state”, the “deformation process with a deviation stress” of “similar and in the opposite direction” is required again.

  The “stress luminescent material” used in the “foam paper” of the present invention has a ceramic, in particular, metal, or silicon oxide, nitride, carbide or sulfide composition, and includes “paper pulp fiber” and “stress In the contact point of the “luminescent material”, the “hydroxyl group of cellulose” constituting the “paper pulp fiber” and the “oxidation” are the same as the “hydrogen bond” by the “hydroxyl group of cellulose” in the contact point between the “paper pulp fiber”. That are “bonded” at the contact point by “hydrogen bonding” with an oxygen atom, nitrogen atom, carbon atom or sulfur atom of an oxide, nitride, carbide or sulfide.

  As a result, the “deformation” of the “paper pulp fiber” when the “fiber composite” is “curved” is the “deformation” of the “stress luminescent material” “bonded” to the “paper pulp fiber”. In particular, at the contact point between “paper pulp fiber” and “stress luminescent material”, “tensile stress”, “shear stress”, and “shear stress” are generated with physical movement.

Of course, the “stress” of the “stress luminescent material” is also directly applied to the “stress luminescent material” due to the “curvature” of the “fiber composite” and the “curvature” of the “paper pulp fiber”. To encourage. (In fact, the entire “composite”, which is a combination of this “fiber composite” and “stress luminescent material,” is “deformed.”)
In this “stress luminescent material”, the point of contact with the “paper pulp fiber” becomes the “predetermined part of the stress luminescent material”, and this ““ tensile stress ”,“ shear stress ”,“ slip stress ”” However, the strength is proportional to these “stress magnitudes” and, more specifically, “the structure (composition, crystal structure, etc. It emits light of a wavelength characteristic of the “structure” (meaning that there is a dependency on the direction of the stress).

  The “stress luminescent material” of the present invention includes a “three-dimensional structure” including its “composition”, and further, “elements at lattice positions with high electron density” and “low electron density” located in this “structure”. The “transition width” of the electronic state is determined by the element at the lattice position (including those having “lattice defects: no element”), and “light” having energy corresponding to this “transition width” ".

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

  Accordingly, it is possible to carry out the authenticity determination of the “foam paper” of the present invention including such “stress luminescent material” in its interior with high reliability.

  Furthermore, according to the intensity distribution of the “deformation stress” generated in the “stress luminescent material”, that is, the “deformation method” of the “stress luminescent material”, and thus the “deformation method” of the “form paper” of the present invention. Since the “light emission intensity” of “light of a predetermined wavelength” and ““ light emission distribution ”on the paper surface of“ form paper ”” differ depending on each other, authenticity determination using this property can also be performed. Of course, the “light emission” and “light emission distribution” in the above-mentioned “feed hole”, “perforation”, etc., that is, the “shape” of the “specific part” and the arrangement of the “specific part” are as described above. In addition, it can be used for authenticity determination.

If the “form paper” of the present invention is mass-produced with an appropriate paper machine, excluding the “specific part” provided in advance, the “light emission distribution” (when light is emitted) on the surface of each “form paper” The meaning of “distribution” excluding the known “specific part” (for example, the part shown in FIG. 1), although the “average light emission intensity” is controllable, the individual “form paper” "Light emission distribution" on the paper surface, for example, when the center of "form paper", which is 11 inches wide "continuous paper", has a certain "width" and sequentially emits light sequentially in its "traveling direction" The “light emission intensity curve (a graph in which the horizontal axis is“ position in the advancing direction on the paper ”and the vertical axis is“ light emission intensity ”) is a curve with relatively severe fluctuations, and the“ width ”is set. The way it fluctuates greatly changes with the Intensity curve "is, be a thing of the" intrinsic "to the individual of the" Form Paper ". (It means that artificial control is impossible until the placement and entanglement of individual “stress luminescent materials” with respect to “paper pulp fibers”.)
Furthermore, for the purpose of making such “light emission distribution” significantly different in each “foam paper”, “suspension of“ paper pulp fiber ”and“ stress light-emitting material ”in the paper manufacturing process described later A method in which the “concentration” and “suspension state” of the “stress luminescent material” in the liquid is temporally changed is also suitable.

  In addition, when the “predetermined wavelength light” is visually recognized, the authenticity is obtained by observing through an appropriate optical filter (such as a wavelength filter that allows only the “predetermined wavelength light” to pass through). It is also possible to further increase the reliability of the determination.

The light emission mechanism of this new "stress luminescent material" is a representative "stress luminescent material" by Mr. Yamada (National Institute of Advanced Industrial Science and Technology) and Mr. Matsuo, Nippon Steel Corporation. Since a certain SrAl ₂ O ₄ : Eu system has been announced in detail, only the outline will be described below. ("National Institute of Advanced Industrial Science and Technology, Production Measurement Technology Research Center, Head of Stress Luminescence Technology Team, Xuo Xu (Editorial Representative), Naohiro Ueno, Tadashi Terasaki, Hiroshi Yamada (Editorial Committee), etc. and Novel Structural Health Diagnosis ", published by NTS, Inc., August 2012").
The former host crystal is a stuffed-tridymite structure, and has become a honeycomb structure AlO ₄ tetrahedra are shaped in "corner-sharing", the large pores therein, Sr ²⁺ ions Has a structure that is arranged. Then, in the host crystal, as a luminescent center, and Eu ²⁺ ions are added, and are replaced by two types of sites of Sr ²⁺ ions described above, the Eu ²⁺ ion "4f- It is assumed that light emission occurs due to radiation transition associated with “5d electron orbit transition” (the difference in electron orbit energy at this time is the above energy E).

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

When this stress is unloaded, the “twin interface” returns to its original position. At that time, carriers are excited from Eu ²⁺ , trapped in vacancies, etc., and return to the original state. The phenomenon is going to be repeated.

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

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

  This “light with a wavelength unique to the“ structure ”constituting the stress-stimulated luminescent material” is the above-mentioned “light with a predetermined wavelength”, and is usually in the wavelength range of “visible light”, that is, the wavelength of the light. Thus, light having one wavelength is emitted corresponding to one kind of “stress light emitting material” in the range of 400 nm to 800 nm. Therefore, the observer can visually recognize the emitted “light of a predetermined wavelength”.

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

And by utilizing the high transparency of the “paper pulp fiber” itself in contact with this “stress luminescent material”, the light emitted from such “stress luminescent material” is transmitted to the “paper pulp fiber” in the vicinity thereof. It is possible to further improve the visibility by allowing the light to pass through while repeatedly reflecting inside. (When the emitted light spreads in the “paper pulp fiber” from the contact point, depending on the angle of the light and the outermost wall of the “paper pulp fiber”, the light Means repeated reflections.)
In particular, in visual confirmation outdoors, the determination reliability is higher when 10 mcd / cm ² or more is further recognized as “high luminance” and the “light emission” is used for authenticity determination. Therefore, “light emission luminance” of 100 mcd / cm ² or more is given.

  Of course, one “stress luminescent material” may contain “multiple structures (crystal structures, different luminescent central elements, etc.)” or “foam paper” with multiple types of “stress luminescent materials”. It is also possible to emit light having a plurality of wavelength regions, or to “stress light emission” in a wavelength region other than visible light (stress light emission of ultraviolet light or infrared light). The “phosphor layer (a layer containing an appropriate fluorescent material)” or “phosphor” appropriately contained in the “foam paper” of the present invention in advance with the emitted light. The “pattern layer (phosphor layer formed in a pattern)” may be “excited” to emit light in the visible light region, and as a result, visible light may be visually recognized.

  Furthermore, in the “papermaking” process, “paper pulp fibers” are produced while flowing in a certain direction, so that the “length” direction of “paper pulp fibers” can be easily aligned in this direction, and “paper flow” can be formed. , “Stress luminescent material” is likely to be distributed along this “flow line” (meaning that “stress luminescent material” “particles” are aligned in the “length” direction of “paper pulp fiber”. As a result, when the “form paper” is bent “perpendicularly” with respect to the “flow line” (the individual “stress luminescent material” is “deformed to bend”), the “flow” In the case of bending in parallel to the “eye” (almost no “deformation” occurs for each “stress luminescent material”), not only the direction of “stress” generated in the “stress luminescent material”, “Significant difference (visual distinction) against“ stress ” Meaning that kill difference.) "Can be generated.

  In the first place, "paper" is "thinly formed into a flat shape while entangled with fibers such as plants." According to the Japanese Industrial Standard (JIS), "paper" was produced by gluing plant fibers and other fibers. Defined as "thing".

  As a raw material for “broadly defined paper”, “widely defined paper” is made using almost all kinds of raw materials such as minerals, metals, animal-derived substances, or synthetic resins, as long as they are elongated fibers having a diameter of 100 μm or less. “Nonwoven fabric” or the like may be classified as a kind of “paper”.

  However, the “foam paper” of the present invention is made of “paper pulp fiber”, which is “vegetable fiber”, and “formation method” (“papermaking method”) of the “form paper” is also used. The “paper pulp fiber” is dispersed in an appropriate “water” and then spread on a “bamboo shoot” or “net”, which is made through a dehydration step, a drying step, or the like. However, this does not exclude products manufactured by a “dry process” that does not use “water”.

  In addition, some of the “stress luminescent materials” used in the “foam paper” of the present invention have “inferior water resistance properties”. It is also preferable to carry out a surface treatment such as crystallization to prevent the crystal structure of the “stress luminescent material” from being destroyed by water or loss of luminescent property.

  Furthermore, it is good also as what formed the coating film of the thermoplastic resin or the thermosetting resin so that the surface treatment surface might be covered. In particular, cellulose resins such as methyl cellulose, ethyl cellulose, cellulose nitrate, and cellulose acetate propionate, which are easily entangled with “paper pulp fibers”, are preferable.

  As the surface treatment agent, at least any acidic group of phosphoric acid group, phosphorous acid group, sulfonic acid group, carboxylic acid group, and silanol group, or a compound containing an ester thereof, these surface treatments are used. The agent can be applied by a method of reacting with a stress-stimulated luminescent material.

  For example, a method of dissolving the surface treatment agent in an organic solvent, adding a stress-stimulated luminescent material to the solution, and stirring the solution can be suitably used.

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

  By improving the water resistance of such a “stress luminescent material”, it is possible to prevent a decrease in luminescent performance in the “water” treatment step in the paper making process described above, and further, the water resistance as “foam paper” And weather resistance can be improved.

  As a raw material of “paper pulp fiber” used for “foam paper” in the present invention, “wood” itself, “imported wood chip”, “non-wood plant”, which are raw materials of so-called “Japanese paper” and “Western paper”, “Waste paper” can be used, and “wood pulp” such as “wood pulp”, walla pulp, kenaf pulp, “waste paper pulp”, etc. obtained by “pulping” them can be used.

  Or, according to the classification according to the “pulping” method, “mechanical pulp (MP)” such as “crushed wood pulp (GP)” and “refiner ground pulp (RGP)” and “craft pulp (KP)” Chemical pulp (CP) "can be used.

In the “stress luminescent material” of the present invention, as described above, in the vicinity of the “thermoelastic martensitic transformation”, when “stress” is applied to the material accompanied by “physical deformation”, “twinned pseudoelasticity” A material that is prone to “deformation”, such as “Eu-added SrAl ₂ O ₄ (SAOE)”, etc. The material emits light of the wavelength of, and its emission intensity increases according to the applied “stress”. The material is fired and sintered to have a predetermined shape such as the above-mentioned “fiber” shape. Is used.

Here, "loading the material with 'stress' with 'physical deformation'" means
When the “predetermined external force load on the foam paper” is transferred to the “external force load on the“ paper pulp fiber ”” and further to the “external force load on the“ stress luminescent material ” In addition, “stress strain” occurs in the “stress luminescent material”, and the “stress luminescent material” itself causes “physical“ deformation ”=“ stress strain ”.

In other words, the “stress light-emitting material” of the present invention, when an external force load is applied, in the so-called “stress-strain diagram”, “the region that changes linearly in the elastic region (stress-strain diagram. When the load is removed, it tries to return to the original state.) (This behavior is so-called “elastic deformation”.)
The “stress luminescence” of the “stress luminescent material” of the present invention utilizes a phenomenon that occurs in this “elastic deformation” region, and the luminescence phenomenon is stabilized from several hundred times to several tens of thousands of times. It is suitable for the purpose of judging the authenticity by visually recognizing this “light emission”, that is, for the purpose of repeatedly performing this “light emission” and “determination”.

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

  More specifically, although it is merely “an explanation for making it easy to capture a“ conceptual image ”of“ how the crystal structure changes ””, it can be compared as follows.

  That is, “tetragonal crystal” which is one of the crystal lattices causes “with physical deformation”, for example, “phase transformation with shear deformation in one axial direction of tetragonal crystal”. In appearance, as if it were “deformed” as “triclinic”, or in the state where multiple crystal structures overlapped in layers, it caused “slip deformation” between these crystal layers. The “material” as a whole can be compared to a deformation that causes a “macroscopic deformation (measurable or visible level of deformation)”. (It is only an image.)

  When the above-mentioned “physical deformation” exceeds the so-called “yield point” and reaches the “plastic zone” in the “stress-strain diagram”, the “material” changes depending on the external force load. Since it will only stretch, it will continue to “elongate” until the “material” “breaks”, and it will no longer be able to emit light repeatedly, so such deformation in the “plastic zone” is the “deformation” of the present invention. No.

  Further, “increasing the internal stress of the material while hardly changing the material shape” does not fall under the “deformation” of the present invention.

  For example, “Stress strain” does not occur even when an external pressure of several hundred N (Newton) is applied to the outer surface of the material to increase the internal stress of the material, and almost no “material shape”. In the “unchanged state”, the crystal structure itself (lattice shape, etc.) inside the material and the deformation to the crystal wall (wall (boundary surface) between one crystal structure and another crystal structure) It is considered that no movement occurs, in other words, "the state in which these structures are able to withstand a large applied pressure while maintaining the spacing between the atoms constituting the lattice and their arrangement", and therefore Unlike the “external force load and its deformation” of the present invention, there is no change in the “electronic state” assumed from the atomic arrangement or the like (therefore, there is no light emission due to electronic transition). No “light emission” occurs.

  The “stress luminescent material” of the present invention has a basic structure in which alkali metal ions or alkaline earth metal ions are inserted into a space of a host structure formed by a plurality of molecules having a polyhedral structure. Part is formed by a plurality of molecules having a tetrahedral structure of stress-stimulated luminescent material, AlO-like structure, and SiO-like structure substituted by at least one kind of metal ion among rare earth metal ions and transition metal ions A stress-stimulated luminescent material in which a luminescence center is inserted into a basic structure having a three-dimensional structure and an asymmetric flexible frame structure, and the formation of strain energy, thereby generating heat due to piezoelectric effects, lattice defects, and deformation Stress-stimulated luminescent materials that emit light by such mechanisms, mixed stress-stimulated luminescent materials composed of a mixture of multiple crystal structures, and the generation of these stress materials. Luminance increased by several hundred times, high luminous intensity stress luminescent material, ultraviolet (infrared light) luminescent stress luminescent material that emits light outside the visible light range, or ultrafine particles dispersed in transparent resin In addition, a stress-stimulated luminescent material or the like having a “predetermined shape such as particles” can be used.

  In order to make the “stress luminescent material” of the present invention into a desired shape, that is, “particulate”, using these materials, the powder mixture with the adjusted material composition is used as it is or as appropriate. It can be obtained by being dispersed and mixed in a resin material, put in a “mold” having a predetermined shape, fired and sintered.

  Alternatively, on the “resin plate that can be burned off during firing”, the above powder mixture itself or the above resin material dispersion mixture is formed into fine dots and then fired and sintered in the same manner. Can do.

  Of course, it is possible to adopt a simple “crushing (pulverization) method”, but the crushing (pulverization) product is more uniform in the “shape (outer shape)” and dimensions than those produced by the above method. The accuracy and, in addition, the controllability of the “uneven shape” on the surface tends to be slightly inferior, so in this method, a “thin sheet-like molded product” having a thickness close to the desired shape is sintered. It is preferable to crush (pulverize) after the treatment.

  In addition, by using a “stress luminescent material having a stress concentration coefficient α of 2 or more” as the “stress luminescent material” of the present invention, the “luminescence” intensity is increased and the reliability of the visual judgment is ensured. can do.

  In order to set the “stress luminescent coefficient α” of the “stress luminescent material” of the present invention to 2 or more, a part of the “stress luminescent material” having an outer shape of “particulate” is 1/10 to 10 times the diameter. A “dent” or “notch” with a depth of 1/5 is provided. A plurality of “dents” and “notches” may be provided within a range in which the repeated luminescent property of the “stress luminescent material” can be maintained, or within a range in which “processing for that purpose” can be performed.

  The shape of this “dent” is either “shallow shape at the bottom” or “depth shape at the bottom”, and “stress concentration” occurs around the “bottom” of this “dent”. The “stress concentration coefficient α” is 2 or more.

  Furthermore, if the ratio of [opening width of dent / depth of dent] is [<1/20], it can be shaped almost like a “fissure”, and its “bottom” is a “sharp blade” The “stress concentration coefficient α” at the “bottom part” is 100 or more.

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

  In order to provide a desired “dent” or “notch” in such a “stress luminescent material”, such a “dent” is previously placed on the above “molding die” or “on the resin plate that burns down during firing”. And a method of providing a portion corresponding to the “notch” portion.

  Further, in the case of providing a “through hole” or a very “sharp gap”, a method is used in which “resin that is burned off during firing” is packed in that portion.

  The “stress light-emitting material” of the present invention has a light emission intensity that increases substantially in proportion to the amount of “stress” generated. Therefore, as the “stress concentration coefficient α” increases, the light emission increases. The strength is increased and the visibility can be improved.

  The “stress concentration coefficient α” is preferably as large as possible, and is set to 2 or more. Furthermore, 10 or more, more preferably 100 or more is preferable because the emission intensity can be “high luminance”.

  Further, by using the “stress luminescent material” having a large “stress concentration coefficient α” in this way, the “size” of the “stress” applied to the “stress luminescent material” is, for example, JIS X 6305 (2010: ISO / IEC 10373-1) “Identification card test method-Part 1: General characteristics”, “Load (F) of 0.7 N is applied to the entire area within 3 mm on the right side of the card for 1 minute. "Large stress load (estimated to be about 10 MPa)", but not "large" that can be bent lightly with the observer's "hand", sufficient light emission can be obtained. Such a stress load can be set to 5 kPa to 1 MPa, preferably 5 kPa to 100 kPa.

  However, as described above, the greater the “stress concentration factor α”, the more “discontinuity” of the “shape” of the “stress luminescent material” becomes so-called “sudden”, and the “stress luminescent material” When “deformation” for “light emission” is repeated, it is easily “destructed” and no longer “light emission”. Therefore, it is inappropriate that the “stress concentration coefficient α” exceeds 1000.

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

  By this method, it is possible to estimate which part of the “stress concentration coefficient α” is increased when an external force of which direction is applied from which direction to the “stress luminescent material”. For the “form paper” of the present invention itself, the strength and direction of the pulling force of the “form paper”, the magnitude and direction of the bending force, and the stress concentration in the “form paper” with respect to the magnitude and direction of the twisting force It becomes possible to estimate the trend.

  In this way, by analyzing the stress concentration tendency of the “form paper” of the present invention, and further by analyzing the “shape” of the “stress luminescent material” included therein and the arrangement thereof, finally, The “stress” of the “stress concentration portion” of the “stress luminescent material” is estimated.

  In the present invention, the “color tone” of the “stress luminescent material” is 0.5 or less in terms of the “color difference” from the “color tone” of the “sizing agent” used in the “foam paper”. The presence of “stress luminescent material” in the “paper” can be concealed.

  Various chemicals and additives used in the “paper making” process of “foam paper”, that is, “sizing agent” as a general term for these additives used in the “foam paper” of the present invention includes the “paper making”. In the “process”, chemicals added to improve the ratio (yield) of “paper pulp fibers” and mineral fillers remaining on the “wire (wire)”, mainly aluminum sulfate, polyacrylamide, etc. Polymers, starches, and also carboxymethylcellulose and inorganic colloidal silica are used as a retention agent, a chemical added to improve water drainage and improve drying properties in the “papermaking process”. Imine, polyacrylamide, cationized starch, etc. used, drainage improver, added to add strength to “paper” Urea formaldehyde resin, melamine formaldehyde resin, polyamide polyamine epichlorohydrin, polyvinylamine, etc. used in the formula, wet paper strength enhancer to give strength in wet and wet state, cationized starch, cationic and amphoteric Polyacrylamide copolymer, etc., to increase the strength of paper in the normal dry state, dry paper strength enhancer, used in the surface method, coated on the surface of the paper, such as modified starch, polyacrylamide, polyvinyl alcohol Or by spraying, the paper strength enhancer, the “paper pulp fiber” of “Machine-made Japanese paper” is dispersed in water, and the natural “Nelori” such as troro-aoi which has the effect of preventing the adhesion of the stacked paper ”, Synthetic adhesives such as polyacrylamide (synthetic paste), rosin soap, al By means of gate roll coater or liquid film transfer, such as ketene dimer, alkenyl succinic anhydride, polyvinyl alcohol, etc., internally added type, oxidized starch, styrene / acrylic copolymer (copolymer), styrene / methacrylic copolymer, etc. It is a surface method to be applied, and is used to reduce the size and pulp weight added to the "paper" for the purpose of suppressing the penetration of liquids such as ink, preventing set-off and bleeding, and providing a certain level of water resistance. In order to maintain the opacity and printing performance while corresponding to weight reduction, surfactants such as fatty acid ester emulsions are effective by submerging part of the fiber surface while also increasing drainage. , A bulking agent that is added for the purpose of reducing the density of “paper” and increasing its volume. Mineral powder blended or applied to give batter, whiteness, smoothness, etc., mainly talc, kaolin (white clay), calcium carbonate, titanium oxide, barium sulfate, etc. Silica (white carbon), urea resin is also used as an organic filler, filler, further, kaolin, calcium carbonate or organic white pigment is used as a pigment, and synthetic rubber latex mainly composed of butadiene is used as a binder, Apply a paint liquid containing a white pigment on the surface of paper to increase whiteness, smoothness, printability and water resistance, and add starch, casein, carboxymethylcellulose, etc. And coating chemicals used as a modifier.

  As the “color tone” of the “sizing agent”, the entire “color tone” of the “sizing agent” added to the “foam paper” of the present invention is used.

  By changing the “color tone” of this “stress luminescent material” and the “color tone” of the “sizing agent” to “same color”, the fact that the “stress luminescent material” is included in the “form paper” is “hidden” It becomes possible to do. Accordingly, the color difference ΔE is set to 0.5 or less, and more preferably 0.3 or less.

Specifically, first, measure the “color tone” of the “prototype paper” created without including the “stress luminescent material” (the paper pulp fiber is basically “transparent”; “Sizing agents” can be used together.), “Sheets” made of a stress-stimulated luminescent material having a “color tone” with which the color difference from this color tone is 0.5 or less is selected. The composition of the “stress luminescent material” used in the above is defined. (More strictly, the color tone of “paper pulp fiber and sizing agent combined” is compared with the color tone of “paper pulp fiber, sizing agent combined with stress luminescent material”.)
This color difference can be measured using a spectral color difference meter, a spectral color meter, a spectral color meter, a minute surface spectral color difference meter, an optical fiber spectral color difference meter, or the like.

  In addition, the “stress luminescent material” is in a “predetermined pattern” shape, for example, a character, figure, or symbol of a predetermined size, in particular, some “message (such as a“ authentic ”character”) for authenticity determination. In a stage where a predetermined size is provided and the “predetermined pattern” is to be emitted before the “stress luminescent material” emits light, and in the situation where the presence of the “predetermined pattern” is desired to be hidden, It is desirable to reduce this “color difference”.

  Such a “predetermined pattern” is commonly recognized not only by numbers or symbols but also by characters, figures, marks, etc., individuals, and suppliers of the “form paper” depending on the use of the “form paper”. Anything that can be used (this object is all so-called “information”) can be used.

  And the recognition method can employ | adopt recognition methods other than visual observation, for example, an optical reading method, having the information which can be recognized at least by visual confirmation.

  In particular, as the “predetermined pattern”, it is also preferable to adopt the “form paper” type, model number, manufacturer name, and date of manufacture to ensure traceability of the “form paper”.

  In addition, “form paper” manufactured for use for a limited purpose or purpose, such as “information” according to the purpose or purpose, such as logos, seals, and other characters that are distinguishable from other companies. , Graphics, symbols, etc., ie, brand logo display, publishers, authors, game console operators, luxury brands, security companies, ticket issuers and issuers, delivery and delivery companies, sales companies, and other related organizations Information, including authenticity characters and symbols, etc., and the logo, characters, graphics, symbols, etc. add value to the paper and provide reliability such as quality assurance. Something that can be enhanced (what you prove) can be used.

  Furthermore, it is simply a serial number or symbol that manifests its effectiveness by registration, the same number, such as a common key number that is an encryption key number, or a completely random number, Those who are allowed to know such as numbers that are devised so that nobody including the creator knows the contents of the number (a regular purchaser etc. is used. System designers, publishers of products that apply “form paper”, etc. may be included, and only others can see, and others are set so that they cannot physically see Numbers or symbols may be used.

  As a method for confirming such a “hidden pattern”, a “jig” having a predetermined shape, for example, “kamaboko type with a bottom size of 30 to 50 mm × width 50 to 100 mm” is used. Then, the method of causing the observer to press the “foam paper” of the present invention on the curved surface of the protrusion of the “jig” having a curvature radius of 10 mm to 100 mm by the observer with the finger of the hand. Can be adopted.

  Furthermore, it is preferable that the character size of the “hidden pattern” to be confirmed is 5-10 mm long × 10-30 mm wide so that it can be read on the curved surface of the “jig” and is more stable. Enable authenticity determination.

  For example, the character size of the “hidden pattern” is 10 mm × 20 mm wide (“horizontal” with an aspect ratio of ½), and “the radius of curvature is 60 mm and the bottom size is 30 mm vertical × horizontal. An observer presses the “form paper” of the present invention on the curved surface of a 50 mm kamaboko-shaped jig, and pulls both ends of the “form paper” downward. In this state, it is moved so as to be rubbed against the jig (also expressed as “squeezing” operation of the paper), and the emitted “hidden pattern” -like characters are visually recognized and determined.

  In addition, for the “form paper” of the present invention, as one of the “perpendicular through portions”, the processing tool when performing the drilling process is a double-edged, single-edged, double-edged, single-edged double-edged blade, Use a blade with a “blade edge” such as a scissors, and change the “shape” of the “blade” into a desired “shape” such as a circle or a square. The material composition of the “blade” is SK60 or other SK. Series (carbon tool steel), SKS (a kind of alloy tool steel, tungsten steel) 4 etc. SKS series, SKD (a kind of alloy tool steel, die steel) 11 etc. SKD series, SKT (alloy tool) SKT series such as 4 (Rockwell hardness HRC: 42 or more), SKH (high-speed tool steel or high-speed steel, the same applies hereinafter) 3, SKH series such as SKH10, SKH51, SKH59 , SUS (stainless steel, SUS series such as 440C, etc., austenitic stainless steel, WC-Co (tungsten carbide-cobalt) alloy (Rockwell hardness HRA: 80-94, bending strength: 2-5 GPa, Young's modulus: 500 A cemented carbide such as ˜700 GPa) can be used.

  In particular, a cemented carbide is preferable because of its hardness and durability.

  And, as the “shape” of the “hole (through hole)” (the shape of the “opening” of the “vertical through portion”), the “round”, “ellipse”, “triangle”, Alternatively, various “shapes” such as “rectangle” can be used, but examples of “sprocket holes (feed holes)” that are “holes (through holes)” most used in “continuous forms” are shown below.

  Its dimensions and accuracy are in accordance with JIS C6283. The diameter of the “feed hole” is 4.0 ± 0.1 mm “circular” (however, the “periphery of the hole” is “toothed (notched. Kikumaru). This value corresponds to the minimum diameter, and the maximum diameter does not exceed 4.5 mm.), And the distance between the centers of the “feed holes” is 12.70 mm ± 0.05 mm, the position of the “feed hole” is provided in the left and right margins of the “continuous slip”, and the distance from the center line of the “feed hole” to the corresponding edge is 6. 0 ± 0.7 mm.

  Another example of the “hole” is a so-called “punch hole”. One of the “punch holes”, “2 holes (JIS S6041)”, has a “hole” diameter of 5.5. The position of “circle” and “hole” of ˜6.5 mm is 11 to 13 mm from the nearest end of “form paper”, and the distance between “holes” is 79.5 as the distance between the centers of “holes”. ˜80.5 mm.

  Other “standard“ hole ””, “don hole (26 holes, 30 holes, etc.)”, “computer hole”, “square hole”, and “needle hole”, etc., “form paper” of the present invention Can be provided.

  Further, in the “sewing processing” that can be performed on the “form paper” of the present invention, the “sewing blade” has a spring blade and a flexible die (a “blade” provided on a resin plate). Ordinary sewing machine, micro sewing machine, jump sewing machine (stop sewing machine, L-shaped sewing machine, T, etc.) using a rotary die (having a "blade" on the surface of a rotating roll. High-speed continuous machining is possible.) Character sewing machines, etc.), slitter sewing machines, square sewing machines, and the like.

  The “cutting edge” of the “sewing machine blade” is the same as the above-described drilling tool, and the material can be the same as that of the above-described drilling tool. From the durability of "", a Rockwell hardness of HRC = 30 to 60 can be used. In addition, it is also preferable to dispose a material having higher hardness or a material having releasability on the “top portion of the blade edge” in order to improve the durability.

  “Thickness of the sewing machine blade” is 0.5 to 5 mm, and its cross-sectional shape is not “square” but “elliptical” (no “corner” anywhere, gentle “curve” In particular, a "tapered shape" is preferable so that the curvature R of the "rounded corner" is 1/2 to 1/10 of the "thickness". .

  If the cross-sectional shape of the “sewing blade” is “square” (that is, the shape of the “opening” of the “vertical penetrating part” is actually a “sharp angle” with four corners orthogonal to each other. "Square" means that a very large stress (theoretically "infinite size") is generated at the "corner". “Tear” starting from “corner” is likely to occur, and is not suitable for “authentication determination” which is the object of the present invention.

  As the perforation that is the “blade edge shape”, as “cut / uncut”, as a normal perforation blade, [1/1] (unit: mm, the same applies hereinafter), “2/3”, “2” / 1 "," 2 / 1.5 "," 2.5 / 3 "," 2.5 / 1 "," 2.5 / 1.5 "," 2.5 / 2 "," 3/1 ”,“ 3 / 1.5 ”,“ 3/2 ”,“ 3 / 2.5 ”, etc. As micro-sewing blades,“ 0.2 / 0.1 ”,“ 0.2 / 0.15 ”, etc. Can be used.

  Also, as “perforation”, “horizontal internal sewing machine” (a type of horizontal sewing machine, for example, cut / uncut = 3/1 and 10 mm on the left and right of the sewing machine), “folding sewing machine”, and “continuous form”. (A kind of horizontal sewing machine. For example, cut / uncut = 2.5 / 1) and “vertical internal sewing machine” (a kind of vertical sewing machine. For example, cut / uncut = 2/1) can be provided.

  Furthermore, “pushing” may be applied using a “push blade” (a “notch” or “concave”).

  In addition, two folds, three folds, three folds inside, outside folds, bellows folds, kannon folds, kannon folds, cross folds, letter folds, map folds, combination folds, direct mail folds, four folds , “Folding” such as mini folding (“Instruction Manual”, “Nosho” etc.), etc. (folded part becomes “recessed part”), and slitter processing (“slit-shaped through part”) ), Burst processing, full gluing processing, partial gluing processing, window opening processing, window film pasting processing, envelope processing, embossing (embossed part becomes “concave part”), magnetic stripe, etc. “Post-processing” such as pasting and transfer processing of various target materials can be performed.

  Moreover, it is also possible to perform the above-mentioned various “post treatments” on the “foam paper” of the present invention using a “laser processing machine” which is a machine tool using an invisible laser.

  In this case, since it is not necessary to consider the significant wear of the various “blades” described above (however, the “laser light output” needs to be higher), it is particularly preferable.

  However, the “stress luminescent material” used in the “foam paper” of the present invention has a high refractive index as a material, and reflects the “laser light” for processing at a high reflectance on the surface of the “stress luminescent material”. Therefore, in order to suppress such a “reflection phenomenon”, the surface of the “stress luminescent material” is made highly scattering (“increase the irregular shape”. Increase the “number of irregularities” on the surface, In addition, it means that the “undulations” become intense.) Or, “stress light-emitting material” is “fine-grained” to increase the “transmittance” of “laser light” and its “laser processability” It is preferable to improve.

  As this “laser processing machine”, a gas type laser processing machine and a solid type laser processing machine can be used. As a gas type laser processing machine, an average output is several W to several tens KW, a continuous output type. Alternatively, a pulse oscillation type or a fiber laser type carbon dioxide gas laser (oscillation wavelength: 9 to 11 μm. Therefore, “low reflectivity” or “transmission” with respect to this “wavelength” is required. As a solid-state laser processing machine, a YAG (Y: yttrium, AL: fiber laser type) having an average output number of W to several KW, a continuous output type or a pulse oscillation type, and a fiber laser type. Aluminum: Garnet: laser (oscillation wavelength: 1.1 μm. “Harmonics” can also be used.), Yb: YAG fiber laser with an average power of W to several tens of KW ( (Diode Pumped Solid State <DPSS> laser, Nd: YAG fiber laser, etc.).

  Depending on the content of the “post-processing”, the average output of the laser beam, the spot diameter of the laser beam, the focal length and depth of the optical system, and the peak output, average output, repetition frequency, and duty of the laser pulse Adjust the ratio.

  In addition to the above, “vertical through portions (including slit-like through portions), oblique through portions (including slit-like through portions), cutout portions, and concave portions” use the above-described jigs and devices. Can be provided.

According to the “form paper” of the present invention,
In terms of appearance, simply use “form paper” or simply “form paper” with “specific parts” such as “vertical through, oblique through, notched, and / or concave”. In fact, the “form paper” contains “stress luminescent material” together with “paper pulp fiber” in a form that cannot be recognized from its appearance at all. The “paper pulp fiber” is deformed by a predetermined external force load on the “foam paper”, in particular, the “paper pulp fiber” in the “specific part” is largely deformed, and at the same time, the “stress luminescent material” The authenticity of the “form paper” is generated when a “deformation stress” is generated in a predetermined portion, and light of a predetermined wavelength having an intensity corresponding to the deformation stress is emitted from the predetermined portion and is visible. Special Without illumination light, it made it possible to easily determine "foam sheet" is provided.

  In addition, the “stress luminescent material” has a specific shape, and is further included so as to be in contact with the “paper pulp fiber” to increase the “luminescence”, and furthermore, the “sizing agent” used for the “foam paper” "Foam paper" having a design difference and an anti-counterfeiting prevention property are provided.

These are partial cross-sectional views of “form paper A1” showing an embodiment of the present invention.

(A partial sectional view of a portion not including “specific portions K1 to K3” is shown. “Form paper A1” includes “paper pulp fiber 1” and “stress luminescent material P1”. The situation where the “stress light-emitting material P1” is in contact with the “stress-concentrated portion S1 (predetermined part)” and the “paper pulp fiber 1” and the “stress-light-emitting material P1” are shown schematically. And this contact can also be a stress concentration part.)
FIG. 4 is a diagram showing a flow of a “paper manufacturing process” for manufacturing “form paper A1” according to an embodiment of the present invention.

(The process of providing “specific parts K1 to K3” is included in the first papermaking process, the second papermaking process, or the processing and finishing process.)
These are figures of "form paper A1" which shows one Example of this invention.

(In the center of the thin flat “form paper A1”, a “shape” is formed in which “vertical penetration part: specific part K1” is provided. “Stress in this“ vertical penetration part: specific part K1 ” The position of the “concentrated portion KS1” changes depending on the “external force load” applied to the “form paper A1”, but in FIG. 3, a square shape that is the shape of the “opening” of the “vertical through portion: specific portion K1” This figure is a “schematic diagram.” This figure is a “schematic diagram.” Only three “vertical penetrating parts: specific part K1” having the same “rectangular prism shape”. (The paper pulp fiber 1 ”and the“ stress luminescent material P1 ”are omitted. The same applies to the following figures.)
These are figures of "form paper A2" showing other examples of the present invention.

(In the center of the thin flat “form paper A2”, a “shape” is formed in which “an oblique through portion: specific portion K2” is provided. “Stress in the“ oblique through portion: specific portion K2 ” The location of the “concentrated portion KS2” changes depending on the “external force load” applied to the “form paper A2”. In FIG. 4, the square portion that is the shape of the “opening” of the “obliquely penetrating portion: the specific portion K2” is used. This figure is a “schematic diagram.” This figure is a “schematic diagram.” Only three “diagonal penetrating parts: specific part K2” having the same “quadrangular prism shape” are orderly arranged. Shows what was placed.)
These are figures of "form paper A3" which shows another example of the present invention.

(It forms a “shape” in which a predetermined shape of “notch portion: specific portion K3” is provided on one surface of a thin flat-plate “form paper A3”. : “Bottom” of “Specific part K3 (wedge shape)” becomes “Stress concentration point KS3.” This figure is a “schematic diagram” and shows “notch part: specific part K3” having the same triangular prism shape. Only 6 are shown in an orderly arrangement.)
These are the figures which looked down at "form paper A1" of one example of the present invention.

              ("Form paper A1" which is a "continuous form", "feed hole HL" provided by drilling, "horizontal sewing machine M1" provided by horizontal sewing, "vertical sewing machine M2" provided by vertical sewing, In addition, “slitting state” of “slit SL” provided by slitting is schematically illustrated, “single sheet” as “form paper A1” and other processed states are omitted. doing.)

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
(Paper pulp fiber and sizing agent)
“Paper pulp fiber 1” used for “foam paper A1” (or foam paper A2 or A3, hereinafter the same) of the present invention is a “pulping process” in the papermaking process of FIG. It can be obtained through “pulp bleaching step”, “pulp selection & dehydration step” and “raw material adjustment step 1: melting & beating” step. (See FIGS. 1 to 5. In FIG. 1, no sizing agent is shown.)
“Paper pulp fiber 1” is mainly made of “wood”, “imported wood chips”, and “waste paper”. From the viewpoint of suppressing deforestation by “papermaking”, kenaf, sugar cane, bamboo In some cases, "non-wood plants" are used.

  The “non-wood plant” is called “linen pulp”, which has been the main raw material for paper since ancient times, and has been used as the main raw material for “wasaki”, Ganpi, Mitsumata, Mayumi, and “Japanese paper”. It is easy to grow, bamboo, which is the raw material of “bamboo paper”, and the main ingredients of rice straw, wheat straw, flax and old paper, which are relatively weak because the fiber is too thin and short. Linters made from short fibers such as rag pulp and cotton wool with relatively long “fibers” can also be made by using short fibers (linters) such as wool generated during processing of raw materials as raw materials. Cotton, the raw material for pulp, sugarcane, the raw material for bagasse pulp, and Manila Asa, the raw material for Abaca pulp, which has relatively long and thin fibers and can produce supple and strong paper. Close to the tree 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.

  As a raw material of “paper pulp fiber 1”, “N material”, which is “softer” than “L material”, is preferable, and a material which is a raw material of “Japanese paper” is particularly preferable for the purpose of the present invention. Among the above-mentioned “non-wood plants”, in the same sense, “Manila Asa” and “Oil Palm” having high strength, long fibers and “flexibility” are preferable.

  “Paper paper” dissolves in water and uses chemicals such as mechanical force, gravity, and surfactants to remove foreign substances (metal, film, adhesive resin, printing ink, copy toner, etc.). Etc.) is added, bleached to increase whiteness according to the application, dehydrated and dried to make “Paper Pulp Fiber 1”, its recovery route, the type of “paper” to be recovered, Since its composition and quality are greatly affected by the state of separation, it is somewhat inappropriate as a material for the “foam paper A1” of the present invention, but it can be used because of its low cost.

  Further, metal fibers and resin fibers (polymer fibers, aramid fibers, etc.) are used to reinforce the strength of the “foam paper A1” of the present invention (the “foam paper A1” is torn or deteriorated by repeated deformation). It is preferable to add 5% to 20% with respect to “paper pulp fiber 1” for the purpose of preventing and promoting the restoration to the original shape. When the added amount is less than 5%, this “reinforcing” effect is insufficient. When the added amount exceeds 20%, entanglement and binding between “paper pulp fiber 1” and “stress luminescent material P1” are inhibited. Will be.

  As "wood", conifers such as fir and pine ("N wood") and broadleaf trees such as eucalyptus and poplar ("L wood") are used. In hardwood, wood fiber cells are mainly used. Since the fibers of conifers are thicker and longer than the fibers of hardwoods, “foam paper A1” manufactured from conifers is a stronger “paper”. Most of the “information paper” is made from hardwood.

  Imported wood chips are imported from the United States, Australia, New Zealand, Chile, China, etc., and are made from the remainder of lumber backboards, thinned wood, waste wood, etc. Use planted wood produced from eucalyptus and acacia wood.

  “Plant fiber” that is the raw material of “paper pulp fiber 1” is mainly composed of “cellulose”, and when subdivided, it is divided into “cellulose”, “hemicellulose”, and “lignin”, and “cellulose” is a skeleton. "Hemicellulose" promotes connection, and "lignin" is responsible for void filling.

Among them, “cellulose” has a very large number of “OH groups” in its structure, and therefore has a property of being linked by “hydrogen bonding”. With this “hydrogen bond”, further, with the help of moisture (H—OH) contained in “foam paper A1”, “paper pulp fiber 1” is bonded at the intersections thereof. Are doing (sticking together). (In FIG. 1, the joint portion of the “paper pulp fiber 1” is not marked specially.)
“Paper pulp fiber 1” is a material obtained by pulping (pulverizing) pulp fibers (cell wall units) from “plant fibers” after pulping to remove lignin and hemicellulose as a matrix.

  Since the “paper pulp fiber 1” has a large number of hydroxyl groups on its surface, when it is dried, it forms hydrogen bonds and self-adheses or bonds with the “stress luminescent material P1” to become “foam paper A1”. . After drying, it contributes to the deformation and restoration of “foam paper A1” mainly by the swelling ability of “paper pulp fiber 1” and mutual adaptability.

  The “paper pulp fiber 1” is further “defibrated” using various techniques to extract “cellulose nanofibers”, and “transparent paper” is extracted using these “cellulose nanofibers”. The technology to make has already been disclosed.

  Such a “cellulose nanofiber” is added to the “paper pulp fiber 1” in an amount of 1% to 20% to increase the transparency of the “foam paper A1”, and thus the light emission of the “stress luminescent material P1”. It is also preferable to promote the light emission of “form paper A1” based on the above.

  In addition, “pulp” as a raw material of “paper pulp fiber 1” is classified into mechanical pulp (MP: mechanical pulp) made by a method of crushing wood with physical force according to its production method, There is a chemical reaction classified into chemical pulp (CP: chemical pulp) that can be obtained by a method of decomposing crushed chip wood and separating (cooking) lignin and the like.

  This "mechanical pulp" includes groundwood pulp (GP, Ground Pull), refiner ground pulp (RGP, Refiner GP), thermomechanical pulp (TMP, Thermo-MP), chemithermomechanical pulp (CTMP, Chemi-TMP), etc. When “mechanical pulp” is the main component, “foam paper A1” becomes a relatively rigid “paper”.

  “Chemical pulp” includes kraft pulp (KP, Kraft Pulp), sulfide pulp (SP, Sulfide Pulp), alkaline pulp (AP, Alkaline Pulp) and the like. “Paper pulp fiber 1” obtained from “chemical pulp” is “flexible” because it contains cellulose of considerably high purity, and “entangled” with “supple”, so the strength as “foam paper A1” is strong, Is preferred.

  In the “pulping process” in the paper making process of FIG. 2, for example, when “wood” is used as a raw material, bark is removed from the “wood” and pulverized into a so-called “chip shape”. This is a process in which “wood” is made into “pulp” one by one by heat treatment at high temperature in an aqueous solution of sodium or sodium chloride.

  The next “pulp bleaching step” is a step of “white” pulp by bleaching this “pulp” with a bleaching agent such as chlorine dioxide.

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

  In the “pulp selection and dehydration process”, the “pulp” is removed by using a cleaner or the like to remove the “undissolved fibers” and “dust” contained in the “pulp”, and a “pulp sheet” is obtained. It is a process.

  Furthermore, in the “raw material adjustment 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 in a sufficient amount of water. In the state, put the melt of pulp between two metal blades (double disc refiner), put it through an appropriate beating machine (refiner), and cut the “pulp” to an appropriate size and at the same time make it fluffy (fibrils) ), A process for facilitating the connection between the fibers.

Through these “pulping step”, “pulp bleaching step”, and “pulp selection & dehydration step”, “paper pulp fiber 1” used for “foam paper A1” of the present invention is obtained. (See Figure 2.)
The sizing agent used in the “foam paper A1” of the present invention was obtained through “pulp selection and dehydration step” in “raw material adjustment step 2: addition of sizing agent etc.” in the paper making step of FIG. It is added to the paper pulp fiber 1 ”at an appropriate ratio.

As described above, the “sizing agent” includes a retention agent, a drainage improver, a paper strength enhancer, a viscosity agent, a sizing agent, a bulking agent, a filler, and a coating chemical. Depending on the use of the “foam paper A1” of the invention, each is added in an appropriate ratio and by an appropriate method. (Not shown)
The “paper pulp fiber 1” of the present invention is “white” in the bleaching step described above, because the surface thereof is rough, and the material itself has high “transparency”. Have

  Therefore, since it is this “sizing agent” that influences the “color tone” of the “form paper A1” of the present invention, the “color tone” of this “sizing agent” and the “stress luminescent material P1” of the present invention. By setting the color difference from “color tone” to 0.5 or less, it is possible to conceal “stress luminescent material P1” present in “form paper A1” of the present invention.

  Among the above-described “sizing agents”, many are colorless and transparent, and the color tone of “paper strength enhancer”, “sizing agent”, and “filler” is important in practice.

  In any case, in order to securely conceal “stress luminescent material P1”, prepare “paper” including this sizing agent and excluding “stress luminescent material P1”. “Color tone” is measured, and “stress light-emitting material P1” having a “color difference” of 0.5 or less is selected.

Furthermore, in order to ensure the “hiddenness”, that is, to make this “color difference” 0.3 or less, when preparing the “form paper A1” of the present invention, as a preparation stage, A plurality of “stress luminescent materials P1” are formed in a “pattern shape such as a belt-like shape”, and a “band-like” formation portion and a portion without “stress luminescent material P1” (a portion other than the “band-like” formation portion) The “color difference” is measured by the above color difference meter, and the optimum “stress luminescent material P1” is selected.
(Stress light emitting material)
As the “stress luminescent material P1” used in the “form paper A1” of the present invention, the following can be used. (See Figure 1)
(1) An alkali metal ion and / or an alkaline earth metal ion has a basic structure inserted in a space of a base crystal formed by a plurality of molecules of a polyhedral structure, and is inserted into the space. At least one of the alkali metal ions and / or alkaline earth metal ions is selected from the group consisting of rare earth metal ions, transition metal ions, group III metal ions, and group IV metal ions A stress-stimulated luminescent material P1 that is replaced by seed metal ions.

The stress-stimulated luminescent material P1 is a base crystal that is a basic structure thereof.
Triclinic structure belonging to the P-1 space group, in particular, anorthite-like structure, and structure similar to the anorthite structure as long as alkali metal ions and alkaline earth metal ions can be inserted into the three-dimensional structure space Including (similar compositions),
A tetragonal structure belonging to the P-42m space group, in particular, an akermanite-like structure, and an akermanite within a range in which alkali metal ions and alkaline earth metal ions can be inserted into the space of the host crystal. Including structures similar to structures (similar compositions),
The trigonal structure belonging to the R-3 space group, in particular, the feldspar structure having the aluminosilicate composition, and the tetrahedral structure of SiO molecules and AlO molecules are the smallest units, and these molecules are all A three-dimensional structure in which a plurality of vertices are connected together and an alkali metal or a space (gap) formed in the three-dimensional structure. With an alkaline earth metal inserted,
Feldsparoid structures such as leucite KAlSiO, nepheline NaAlSiO, and compositions similar in crystal structure to these compositions, etc.
And this basic structure uses what is shown by any one of the following general formula (1)-general formula (6).

_{That, 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 -xyAl 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 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, the base crystal of the stress-stimulated luminescent material P1 of (1) exhibiting ultraviolet light emission has the general formula M ₁ -xyNxQyAl ₂ Si ₂ O ₈ (7) (where M and N in the formula are respectively In the anorthite structure, it is Ca, Sr, Mg, or Ba, in the feldspar structure, it 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. An ion and a number satisfying 0 ≦ X ≦ 0.8 and 0.001 ≦ y ≦ 0.1.)
Furthermore, in the host crystal of the stress-stimulated luminescent material P1, Ca is selected as the alkaline earth metal ion, and a part of the Ca site is substituted with Ce as the rare earth metal ion, that is, the general formula (8) , Ca ₁ -yQyAl ₂ Si ₂ O ₈ (8) (wherein Q is Eu or another emission center ion, and y is a number satisfying 0.001 ≦ y ≦ 0.1. In addition, the general formula (8) can be expressed as Ca ₁ -mCemAl ₂ Si ₂ O ₈ (wherein m is a number satisfying 0.001 ≦ m ≦ 0.1). Can be used.

And as the light emission center of this stress light emitting material P1,
As rare earth metal ions, europium (Eu), dipsirosium (Dy), lanthanum (La), gadolinium (Gd), cerium (Ce), samarium (Sm), yttrium (Y), neodymium (Nd), terbium (Tb) Ions of praseodymium (Pr), erbium (Er), thulium (Tm), ytterbium (Yb), scandium (Sc), promethium (Pm), holmium (Ho), lutetium (Lu), etc.
Further, as transition metal ions, chromium (Cr), manganese (Mn), iron (Fe), antimony (Sb), titanium (Ti), zirconium (Zr), vanadium (V), cobalt (Co), nickel ( Illustrative are ions such as Ni), copper (Cu), zinc (Zn), niobium (Nb), molybdenum (Mo), tantalum (Ta), tungsten (W) and the like. Further, ions of aluminum (Al), gallium (Ga), indium (In), thallium (Tl), or the like can be used as group III metal ions.

  In addition, group IV metal ions include germanium (Ge), tin (Sn), lead (Pb), and the like, and further rare earth metal ions, transition metal ions, group III metal ions, and IV Selected from the group of metal ions, and the content of the rare earth metal ion and transition metal ion, in other words, the content of the luminescent center is 0.1 mol% or more and 20 mol% Those within the following range, preferably those within the range of 0.2 mol% or more and 10 mol% or less, and particularly preferably those within the range of 0.5 mol% or more and 5 mol% or less can be used.

Here, the content is 0. If the amount is less than 1 mol%, efficient light emission cannot be obtained.
(2) Alkali is introduced into the space of the base crystal formed by a plurality of molecules having at least an AlO-like structure and a tetrahedral structure of an SiO-like structure sharing a vertex atom of the tetrahedral structure. It has a basic structure in which at least one of a metal ion and an alkaline earth metal ion is inserted, and the base crystal further has an asymmetric framework structure, and an alkali metal inserted into the space A stress-stimulated luminescent material P1 in which at least a part of at least one of ions and alkaline earth metal ions is substituted with at least one metal ion of rare earth metal ions and transition metal ions, and in particular at least AlO A three-dimensional structure (three-dimensional frame structure) formed by a plurality of molecules having a tetrahedral structure of SiO-like structure and SiO-like structure; By having a structure in which a light emitting center is inserted into a basic structure having a flexible frame structure, the “foam paper A1” of the present invention including the stress light emitting material P1 can be lightly deformed by hand. Those that can emit light.

  The stress-stimulated luminescent material P1 has a flexible three-dimensional frame structure and an asymmetric flexible framework structure at the same time, so that in addition to the three-dimensional frame structure, “spontaneous strain” or “elastic anisotropic” Such a host crystal is easily distorted and easily converts the strain energy into a change in the electronic structure of the luminescent center at the center of the frame. It has become.

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

  The ion to be substituted at this time is not particularly limited as long as the crystal structure of the base crystal (asymmetrical flexible three-dimensional frame structure) can be maintained. Examples of the ion to be substituted include, for example, an alkali metal ion inserted in a space formed in the parent crystal and a rare earth metal ion or a transition metal ion having an ion radius different from that of the alkaline earth metal ion. Is preferred. As a result, the base crystal can be easily distorted, and the stress-stimulated luminescent material P1 exhibiting stronger light emission can be provided. Note that the rare earth metal ion or transition metal ion here is for making the base crystal easily distorted, and may not function as the emission center described later.

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

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

More specifically, the stress-stimulated luminescent material P1 exhibiting particularly strong blue light emission includes the following M ₁ -x-yNxQyAl ₂ Si ₂ O ₈ (9) and X ₁ -x-yYxQyAl ₂ -xSi ₂ + xO. ₈ (10) (wherein M and N in the formula are each a divalent metal ion, at least one of them is Ca, Sr, Mg or Mn, and X and Y are monovalent A metal ion, at least one of which is Li, Na, or K, Q is a rare earth metal ion or a transition metal ion, and satisfies 0 ≦ X ≦ 0.8 and 0.001 ≦ y ≦ 0.1 It is preferable that the luminescent material represented by

  However, in the case of an alkaline earth metal as in the formula (9), Al and Si remain 2 respectively and do not change according to the formula X. On the other hand, in the case of an alkali metal as in the formula (10), in order to balance the charge, the number of monovalent alkali metals increased by X, the number of tetravalent Si increased to (2 + X), and 3 Al is reduced (2-X).

Further, in the stress-stimulated luminescent material P1, the stress-stimulated luminescent material P1 in which Ca is selected as the alkaline earth metal and a part of the Ca site is replaced with at least one kind of luminescent center is more preferable. That is, Ca ₁ -yQyAl ₂ Si ₂ O ₈ (11) (wherein Q is Eu and at least one of other emission centers, and y is 0.001 ≦ y ≦ 0.1. It is the 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 emission center is E _In the case of a mixture of _U and other luminescent center ions, the content (m) of the mixture as the luminescent center may be in the range of 0 to 0.2.

Such a stress-stimulated luminescent material P1 can exhibit blue light emission particularly strongly. In the formula (11), it is preferable that the emission center (Q) contains at least Eu. Furthermore, in the formula (11), it is preferable that at least Eu is contained as the rare earth metal ion of the emission center. For example, it is more preferable that the emission center is only Eu or a mixture of Eu and Dy. Thus, if Eu is contained as the emission center, the stress-stimulated luminescent material P1 that exhibits blue emission particularly strongly can be obtained.
(3) A stress-stimulated luminescent material P1 that satisfies the conditions for emitting light by strain energy, that is, a stress-stimulated luminescent material P1 that emits light by a mechanism such as piezoelectric effect, lattice defects, and heat generation due to deformation by forming strain energy.

  By using the stress-stimulated luminescent material P1, the “foam paper A1” of the present invention including the stress-stimulated luminescent material P1 can be made to emit light simply by lightly deforming it by hand.

  Light emission due to this piezoelectric effect is caused by the addition of strain-forming force, resulting in strain energy in the “material”, and electricity is generated by the piezoelectric effect associated with the strain energy, thereby causing “electroluminescence”. .

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

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

  In the stress-stimulated luminescent material P1, 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 defect center in the base material contained in the stress-stimulated luminescent material P1. It may be added as the central ion of the cation.

In such a stress-stimulated luminescent material P1, as will be described later, various “metal elements” are added so that metal ions replace Sr sites and Al sites in the α-SrAl ₂ O ₄ phase crystal material.

When the material is deformed due to the formation of strain, light emission due to heat generation generates heat, and thermoluminescence (thermoluminescence) occurs due to heat generation (temperature increase), resulting in “light emission”. Here too, α-SrAl ₂ O ₄ can be mentioned as the base material.
(4) A stress-stimulated luminescent material P1 containing a “mixed phase” formed by mixing (mixing) a plurality of crystal structures. In other words, by using a “mixed phase” in which a plurality of crystal structures are mixed, a light-emitting material capable of visually observing high-efficiency (high-intensity) red stress emission, which could not be realized with a single crystal structure. .

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

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

Some of the metal ions constituting the mixed crystal may be substituted with other metal ions. In this case, it is preferable that another metal ion different from the metal ion constituting the mixed crystal is Te ion. As a result, the intensity of red light emission of the stress-stimulated luminescent material P1 can be greatly improved. ("High brightness red stress luminescent material")
The Te ions are preferably in the range of 0.1 mol or more and 5 mol or less with respect to 100 mol of metal ions constituting the mixed crystal.

  Further, the stress luminescent material P1 is composed of tetragonal barium titanate, orthorhombic calcium titanate, rhombohedral magnesium titanate, and cubic strontium titanate. Among them, at least two kinds or more may be included, and in this case, a part of the metal ions constituting the mixed crystal may be replaced with other metal ions.

The stress-stimulated luminescent material P1 has a 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 ≦ 0.05, 0.005 ≦ y ≦ 0.995, A ′ is Dy, La, Gd, Ce, Sm, Y, Nd, Tb, Pr, Or a rare earth element selected from the group consisting of Er).

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

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

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

  The stress-stimulated luminescent material P1 emits light by applying a mechanical external force such as stress, shear force, impact force, pressure, etc., and the luminescence intensity generally increases as the applied external force increases.

Furthermore, as “stress luminescent material P1” that can be used for “foam paper A1” of the present invention,
(5) As a base crystal, an oxide or composite oxide of at least one metal belonging to groups 2A, 3A, 4A, and 3B of the periodic table, particularly MgO, SrO, CaO, ZrO ₂ , CeO ₂ , metal oxides selected from HfO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , Cr ₂ O ₃ , and Ti ₂ O ₃ , or composite oxides thereof, among others, spinel structure, fluorite One having a structure, a yttria structure, a corundum structure, or a β-alumina structure, particularly selected from ZrO ₂ , CeO ₂ , HfO ₂ , Y ₂ O ₃ , Cr ₂ O ₃ , and Ti ₂ O ₃ And having a crystal structure selected from a fluorite structure, a yttria structure, and a corundum structure,
The emission center has an unstable 3d, 4d, 5d, or 4f electron shell, and can generate a radiative transition in the electron shell, and a transition metal ion, particularly a first ionization At least one metal ion selected from rare earth metal ions and transition metal ions having an energy of 8 eV or less, in particular, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, in particular, a rare earth metal ion selected from Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy, Or Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, especially A transition metal ion selected from V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ta, and W.
(6) the host crystals, oxides of FeS ₂ structure, sulfides, carbides, and, one or more of nitrides, in particular, Sr ₃ Al ₂ O ₆ of FeS ₂ structure or,, Ca ₃ Al ₂ O ₆ In which the emission center is the same as in (5) above.
(7) The base crystal is selected from among spinel-structured MgAl ₂ O ₄ and CaAl ₂ O ₄ , corundum-structured Al ₂ O ₃ , and β-alumina-structured SrMgAl ₁₀ O ₁₇ , One type of metal oxide or composite oxide is used, and its emission center is the same as in (5) above.
(8) A base material mainly comprising a composite of at least one metal oxide selected from Y, Ba, and Mg and an oxide of Si as a base crystal, and in particular, , Y ₂ SiO ₅ , BaSi ₂ O ₅ , and Ba ₃ MgSi ₂ O ₈ , which uses at least one complex oxide, the emission center of which is the above (5) The same thing.

In particular, a rare earth element that emits light when electrons excited by mechanical energy return to the ground state, or a light emission center composed of one or more transition metals is added.
(9) The base crystal is composed of CaYAl ₃ O ₇ , Ca ₂ Al ₂ SiO ₇ , Ca ₂ (Mg, Fe) Si ₂ O ₇ , Ca ₂ B ₂ SiO ₇ , CaNaAlSi ₂ O ₇ , Ca ₂ MgSi having a melilite structure. ₂ O ₇ , (Ca, Na) ₂ (Al, Mg) (Si, Al) ₂ O ₇ , and Ca ₂ (Mg, Al) (Al, Si) From one or more kinds of oxides of SiO ₇ And a light emitting center similar to the above (5).
(10) A compound represented by MN ₂ O ₄ (M and N are selected from the group of Mg, Sr, Ba, Zn, and the group of Ga and Al, respectively) Oxides composed of the above metal elements), and those using a luminescent center element with a mole percentage of 0.001 to 20% represented by M, in particular 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, the base material is composed of a compound having a spinel structure, An oxide containing a pseudo-spinel or inverse spinel structure, the emission center of which is the same as in (5) above.
(11) a compound represented by MN ₂ O ₄ (M and N are at least one metal element selected from the group of Mg, Sr, Ba, Zn and the group of Ga, Al, respectively) A material having a lattice defect of 0.0001 to 20 mol% with respect to M or N, using a configured oxide as a base material.
(12) In the base crystal, (A) General formula xM1O.yAl ₂ O ₃ .zSiO ₂ (M1 in the formula is Ca, Ba, or Sr, a part of which is Na, K, and Mg. least may be replaced by one in the, x, y, and, z is aluminosilicate represented by a is) number of 1 or more, (B) the general formula xM2O · yAl ₂ O ₃ (in the formula M2 is Ca or Ba, part of which may be replaced with at least one of Mg and La. X and y are the same as described above.) , (C) the general formula xM3O · ySiO ₂ (M3 in the formula, Ca, or a Sr, partially, Na, Mg, Zn, be , Mn, Zr, Ce, and, in the Nb It may be replaced with 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 Nb, and x and y have the same meaning as described above) or niobate, (E) General formula xM5O · yGa ₂ O ₃ (wherein M5 is Ca, Ba or Sr, part of which may be replaced by La. X and y are as defined above), And at least one oxide selected from ZrO ₂ , in particular, a general formula xSrO ₂ · y Al ₂ O ₃ · z S i O ₂ (wherein part of Sr is Na, K , And even if it is replaced by at least one of M g 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, Z r, C e, and N b may be substituted with at least one selected from the group consisting of x r and y as described above), or a general formula xSrO · yM4O ₁₁ (wherein M is at least one of Ta and Nb, and x and y are the same as described above.), And a base material made of a strontium complex oxide having a composition represented by: xSrO · yAl ₂ O ₃ · zSiO ₂ , (Sr, K ₂ , Na 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 ( g, Al) (Al, Si ) such as _{SiO 7, Sr 2 Al 2 SiO} 7, SrNa 2 Al 4 Si 4 O 16 can be given, elements in parentheses are those that can be replaced with each other.

Further, as xSrO · ySiO ₂ , Sr (Zn, Mn, Fe, Mg) Si ₂ O ₆ , Sr ₂ (Mg, Fe) Si ₂ O ₇ , Sr ₂ B ₂ SiO ₇ , Sr ₂ BeSi ₂ O ₇ , Sr ₂ MgSi ₂ O ₇ , Sr ₂ Na ₄ CeFeNb ₂ Si ₈ O ₂₈ , Sr ₃ Si ₂ O ₇ , SrFeSi ₂ O ₆ , SrMgSi ₂ O _6, etc., or xSrO · yM4O ₁₁ as Sr (Ta, Nb) ₄ O ₁₁
Particularly, those having high emission intensity are Sr (Ta, Nb) ₄ O ₁₁ , Sr (Zn, Mn, Fe, Mg) Si ₂ O ₆ , Sr ₂ (Mg, Al) (Al, Si) SiO ₇ , Sr. ₂ Al ₂ SiO ₇ , Sr ₂ MgSi ₂ O ₇ , Sr ₂ Na ₄ CeFeNb ₂ S ₈ O ₂₈ , and SrMgSi ₂ O _6, and SrGa ₁₂ O ₁₉ and SrLaGa ₃ O ₇ .

  These oxides are represented by point groups (in the simplified expression index) 1, -1, 2, 2 / m, 6 / m, m3m, (-4) 2m, 622 in terms of crystal structure. In which the emission center has an unstable 3d, 4d, 5d, or 4f electron shell and can cause a radiative transition in the electron shell. Rare earth metal ions and transition metal ions, in particular, at least one metal ion selected from among rare earth metal ions and transition metal ions whose first ionization energy is 8 eV or less, in particular, Sc, Y La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, in particular, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Selected from Tb and Dy Earth metal ions, or Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W , Re, Os, Ir, Pt, Au, in particular, a transition metal ion selected from V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ta, and W.

As the “stress luminescent material P1” that can be used for the “form paper A1” of the present invention,
A strontium represented by a composition formula, SrMgAl ₆ O ₁₁ , SrLaAl ₃ O ₇ , or SrYAl ₃ O ₇ , and an aluminum-containing composite metal oxide as a base material, and europium as a luminescent center.
(13) to the luminescent center, at least, comprise a europium (Eu), composition formula _{(1) (Eu 1 -xA'x)} yB '1 -yAl 2 O 4 or a composition formula (2) (Eu ₁ -xa 'x) B' ₁ -yMgAl ₁₀ O ₁₇ {wherein A 'is a rare earth metal, B' is an alkaline earth metal of any one of strontium (Sr), barium (Ba), or calcium (Ca) In which 0 ≦ x ≦ 0.99 and 0.001 ≦ y ≦ 0.550}.
(14) In the base crystal, the general formula xBaO.yAl ₂ O ₃ .zSiO ₂ (Ba in the formula may be partially replaced by at least one of Na, K, and Mg, x, y, and z are numbers of 1 or more), xBaO · yAl ₂ O ₃ (in the formula, a part of Ba may be replaced by Mg, and x and y are the same as above) ), Or xBaO · ySiO ₂ (in which Ba is partially substituted with at least one of Mg, Fe, Mn, Zn, and Be, and x and y are The same as the above) at least one oxide selected from barium composite oxides having the composition represented by:
Here, as 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 ,
As xBaO · ySiO ₂ , for example, Ba (Zn, Mn, Fe, Mg) Si ₂ O ₆ , Ba ₂ (Mg, Fe) Si ₂ O ₇ , Ba ₂ BeSi ₂ O ₇ , Ba ₂ MgSi ₂ O ₇ , Ba ₂ MgSiO ₇ , etc.
Those having particularly high emission intensity are Ba ₂ Al ₂ SiO ₇ , Ba ₂ MgSi ₂ O ₇ , BaAl ₂ Si ₂ O ₈ , and BaAl ₈ O ₁₃ .

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

Alternatively, a light-emitting material in which the above light-emitting material is a light-emitting material that exhibits red light emission and a light-emitting material in which the light emission intensity is proportional to the magnitude of a mechanical external force applied to the light-emitting material can be used. .
(15) In a space of a matrix structure formed by a plurality of molecules having at least an AlO ₄ -like structure and a tetrahedral structure of SiO ₄ -like structure sharing and bonding atoms at the apexes of the tetrahedral structure , Having a basic structure in which at least one of alkali metal ions and alkaline earth metal ions is inserted, and the base structure further has an asymmetric framework structure, and alkali metal ions inserted into the space And at least one of the alkaline earth metal ions is substituted with at least one kind of metal ions of rare earth metal ions and transition metal ions, and the basic structure is 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, and 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 , Mg0.2Sr0.77Eu0.01Dy0.02Al ₂ Si ₂ O ₈ , or , Ba0.2Sr0.77Eu0.01Dy0.02A A stress-stimulated luminescent material P1 having a composition represented by l ₂ Si ₂ O ₈ .
(16) An oxide having a tetragonal structure represented by the general formula CaM1Al ₃ O ₇ (M1 represents Y, La, or Gd) and Eu ² +, and formed from a raw material of the oxide Stress-stimulated luminescent material P1 further including an oxide crystal having a lattice defect structure in which an atom represented by M1 is deficient.

Then, the Eu ² +, for that oxide 100 mol, containing 0.01 mol to 20 mol, further, the material forming the impurity phase, 0.1 mol to 80 mol, relative to the oxide 100 mol A stress luminescent material. In particular, the stress luminescent material P1 whose oxide is CaYAl ₃ O ₇ and whose 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 includes at least one compound selected from the group consisting of metal oxides, metal nitrides, and metal sulfides. In particular, the metal oxides include aluminate and aluminosilicate. Using at least one compound selected from the group consisting of acids, the emission center of which further includes at least one element of transition metals (excluding rare earth metals), Si, and Sn; At least a part is contained in the matrix material in a non-solid solution state. Further, the element is in the form of particles and is present on the surface of the matrix material (matrix crystal), and the content of the element is 0.1 to 90 mol%, in particular 10 to 90 mol%, or 0.1 to 10 mol%, and the elements are Zr, Ti, V, Cr, Mn, Fe, Co, Ni Cu, Zn, Hf, At least one metal selected from the group consisting of Nb, Mo, Ta, and W.
(18) (ZnO) 0.6 (MnS) 0.4-x (MnTe) x (0.001 ≦ x ≦ 0.05), in particular, a crystalline phase of a wurtzite type zinc oxide, cubic crystal, Or a mixed phase comprising at least two kinds of crystal phases selected from a wurtzite-type zinc sulfide crystal phase and a cubic manganese oxide crystal phase, and constituting the mixed phase Stress-stimulated luminescent material P1 in which a part of metal ions is replaced with Te ions. Furthermore, it has a plurality of crystal phases having different sizes, the crystal phase of manganese oxide has a large particle size, and the crystal phase of zinc sulfide and the crystal phase of zinc oxide are configured with a small particle size. The crystal phase of the small particle size is uniformly dispersed among the particles of the crystal phase of the large particle size, and in particular, it exhibits red light emission and has a mechanical external force with a load of light emission intensity. Proportional, stress luminescent material P1.
(19) A stress-stimulated luminescent material P1 containing monoclinic LiSrPO ₄ : Eu ² +. In particular, it is formed of a phosphor further containing hexagonal LiSrPO ₄ : Eu ² +, a phosphor composed of monoclinic LiSrPO ₄ : Eu ² +, or a matrix structure composed of orthorhombic LiBaPO ₄ . LiBaPO ₄ : Eu ² + in which europium (Eu) ions are inserted as the emission center in the space, and the content of the emission center is 2.0 to 3.5 mol% LiBaPO ₄ : Eu ² + A luminous body consisting of

Further, as the “stress luminescent material P1” (hereinafter also referred to as “high luminance stress luminescent material P1”) capable of emitting light with high luminance, it is preferable to use the following.
(20) An alkaline earth metal deficient type composed of an alkaline earth metal oxide and an aluminum oxide and lacking the composition ratio of alkaline earth metal ions therein, and having the formula MxAl ₂ O ₃ + x, MxQAl ₁ 0O 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 [where M, Q, and L is Mg, Ca, Sr or Ba, respectively, x is 0.8 ≦ x ≦ 0.99, x ₁ and x ₂ are 0.8 ≦ (x ₁ + x ₂ ) ≦ 0.99 Is emitted when the carrier excited by mechanical energy returns to the ground state, and is composed of at least one kind of aluminate having a non-stoichiometric composition whose main component is a compound represented by A material having lattice defects, or a rare earth metal ion in the base material, 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, a substance composed of an aluminate having lattice defects has an alkaline earth metal ion content of 1 to 20 mol% less from the stoichiometric composition ratio, and the rare earth metal ion and transition metal are contained in this substance. A high-intensity stress luminescent material P1 containing 0.01 to 10 mol% of at least one metal ion selected from ions as a central ion of a luminescent center.
(21) General formula xM1Al. (1-x) M2A2 (wherein M1 and M2 are selected from Zn, Mn, Cd, Cu, Eu, Fe, Co, Ni, Mg, and Ca) At least one atom, and A1 and A2 are at least one atom selected from chalcogens, which are different from M1A1 and M2A2, and x is greater than 0 and less than 1 A high intensity stress luminescent material P1 in which the composite semiconductor crystal has a coexistence structure of a wurtzite structure and a zincblende structure.

Furthermore, M1 is Mn or Eu, A1 and A2 are the same chalcogen, or M2 is composed of Zn and Cd or Zn and Cu. Among them, general formula xMA. (1-x) MnA (wherein M is Zn or Zn partially replaced by Cu, A is chalcogen, x is a number greater than 0 and less than 1) And a high intensity stress luminescent material P1 made of a composite semiconductor crystal having a crystal grain size of 20 nm or less. In particular, the high intensity stress light emitting material P1 in which A is S or Te.
(22) A stress-stimulated luminescent material containing a first aluminate having a monoclinic crystal structure, wherein the matrix material of the first aluminate is α-SrAl ₂ O ₄ , More than one kind of metal ion is added to the base material as a central ion of the defect center, and the added central ion replaces at least the Sr site of α-SrAl ₂ O _4. Both high and small ionic diameters are added, and the metal ions having an ionic diameter smaller than Sr are Eu and the high-intensity stress luminescent material P1, in particular, the second crystal whose crystal structure is not a single crystal. Lattice defects are formed in the crystal structure having spontaneous polarizability of the base material by addition of central ions, and the tunnel structure is included in the crystal structure. G The high-brightness stress luminescent material P1 in which elements arranged in the channel are arranged by ionic bonds, and metal ions having an ion diameter smaller than that of Sr are Mg, Na, Zn, Cu, Eu, Tm, Ho, Dy, At least one selected from the group consisting of Sn, Mn, Nd, Pr, and Ca is used, and a high-intensity stress luminescent material P1, in which Ba and / or K is used as a metal ion having an ionic diameter larger than that of Sr, In addition, the metal ion substituting the Sr site of α-SrAl ₂ O ₄ is added in an amount of 0.1 to 40 mol% based on Sr, and the addition amount of all metal ions is determined from the stoichiometry. it is small, central ions, that by replacing 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, the B is used, the metal ions added as the central ion is, there is a large ion diameter than Al, the Ga, In is used, is added as a central ion, α-SrAl ₂ O ₄ The metal ion substituting the Al site is added in an amount of 0.1 to 20 mol% based on Al, and at least two types of metal ions having different valences are added as the metal ion added as the central ion. A high-intensity stress luminescent material P1 characterized by adding, emitting light in proportion to the strain energy density of the material, and the like.

Moreover, the following can also be used as the “stress light-emitting material P1” that enables light emission in the ultraviolet region (light wavelength: 200 nm to 400 nm).
(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 matrix structure, and the above M or N A stress-stimulated luminescent material P1 that is partially substituted with at least one of rare earth ions or group III metal ions.

In particular, the stress-stimulated luminescent material P1 that is Na ₁ -xQxLa (PO) ₄ (wherein Q is a Ce ion or a Tl ion, and 0.01 ≦ x ≦ 0.2).
(24) It has a basic structure in which alkaline earth metal ions are inserted in a space of a matrix structure formed by a plurality of molecules of a polyhedral structure, and a part of the alkaline earth metal ions inserted in the space , A stress-stimulated luminescent material P1 substituted with Ce ions, the basic structure of which is spontaneously strained, and the polyhedral structure molecule is a tetrahedral structure of at least one of AlO ₄ and SiO _4. The basic structure is represented by the general formula MxN ₁ -xAl ₂ Si ₂ O ₈ (wherein M and N are divalent metal ions, at least one of is Ca or Sr, is 0 ≦ x.), the stress luminescent material P1 _{is, Ca0.2Sr0.77Ce0.005Dy0.02Al 2 Si 2 O 8,} Ca0.2Sr0.79Ce0.005Tb0.00 _{Al 2 Si 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 A stress-stimulated luminescent material P1 having a composition represented by ₂ Si ₂ O ₈ .
(25) A structure represented by a general formula MN (PO ₃ ) ₄ (wherein M is a Na ion and N is a La ion) is a base structure, and a part of M is a rare earth The rare earth ion that is substituted by at least one of ions or group III metal ions and that is substituted for a part of M is a rare earth ion selected from the group consisting of Eu, Dy, Ce, and Tb. The group III metal ion substituted for a part of M is a Tl ion.

  For the “stress luminescent material P1” of the present invention, a material corresponding to the above-described composition is prepared, that is, for each matrix crystal material, an oxide containing an element serving as a corresponding luminescent center is used as its metal. In an inert atmosphere such as nitrogen gas, they are mixed at a predetermined ratio in terms of atoms (generally, a predetermined value in the range of 0.1 to 100 mol with respect to 100 mol of the base crystal material). Then, after gradually raising the temperature to a temperature in the range of 900 to 1100 ° C., it can be obtained by firing at a temperature in the range of 1200 to 1500 ° C. in a reducing atmosphere such as hydrogen-containing argon gas.

  Here, in order to make the “stress luminescent material P1” of the present invention a predetermined “outer shape”, a “molding die (including a firing die. The same applies hereinafter.) Having a desired shape in advance. A material made of a ceramic material with relatively little deformation at a high temperature is selected.) The above-mentioned material is put in, subjected to predetermined firing, and then taken out from the “mold”.

  However, in order to smooth the surface of the “stress luminescent material P1” of the present invention, a metal material having a high melting temperature (the metal material has higher surface smoothness than the ceramic material, and after the “firing” Means that the surface thereof becomes the surface of the “stress light-emitting material P1”).

  In addition, at a high temperature described above, a flat “with sufficient heat resistance” using a resin material such as a cellulose-based resin material or an acetylcellulose-based resin material that is completely burned down and hardly adheres to the fired product. On the “ceramic plate”, a resin coating film is formed with an appropriate thickness, and at that time, on the surface of the resin coating film, a concave portion (microscopic shape) corresponding to a desired shape (“outer shape of stress luminescent material P1”) is formed. The material prepared as described above is put into the concave portion and fired in the same manner as above to burn off the resin coating, and at the same time, on the "ceramic plate" It is also preferable to adopt a method of leaving the “stress luminescent material P1” having a shape.

  Here, in order to improve the water resistance of the stress-stimulated luminescent material P1, it is also preferable to subject the stress-stimulated luminescent material P1 to a surface treatment.

  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 an appropriate amount of the above-described amount according to the purpose is added to the solution. The stress-stimulated luminescent material P1 is added, and the mixture is stirred for an appropriate time using an appropriate stirring device such as a dissolver or a mixer, and then dried under appropriate conditions.

  At this time, it goes without saying that conditions are set so as to maintain the “outer shape” of the stress-stimulated luminescent material P1 without breaking it.

  For the purpose of further improving the water resistance, it is also preferable to mix an appropriate amount of a thermoplastic resin or a thermosetting resin for forming a “film” for the stress-stimulated luminescent material P1 at the same time with the above-described solution. .

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

  Thermoplastic resins include acrylic acid ester resins, ie, polymethyl methacrylate, polymethyl acrylate, polybenzyl methacrylate, polybutyl acrylate, polyisobutyl acrylate, etc., and cellulose resins, ie, cellulose nitrate, methyl cellulose, ethyl cellulose, cellulose acetate Pionates, etc., vinyl resins, that is, polyvinyl acetate, polyvinyl chloride / vinyl acetate, acrylamide resins, polystyrene resins, etc., and thermosetting resins include unsaturated polyester resins, acrylic urethane resins, epoxy Examples thereof include a modified acrylic resin, a melamine resin, an epoxy-modified unsaturated polyester resin, an alkyd resin, a phenol resin, a silicon resin, or a fluorinated resin.

As the surface treatment agent, typically, a silylating agent or a silane coupling agent is used. As the silylating agent or silane coupling agent,
Having a vinyl group, vinyltrimethoxysilane, vinyltriethoxysilane, etc., having an epoxy group, 3-glycidoxypropylmethyldimethoxysilane, etc., having a styryl group, P-styryltrimethoxysilane, etc., having an acrylic group, 3-acryloxypropyltrimethoxysilane, etc., having a methacryl group, 3-methacryloxypropyltrimethoxysilane, etc., having an isocyanate group, 3-isocyanatopropyltriethoxysilane, etc. 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, 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%. Water content is 0. In the case of 5% or more, the light emission characteristics of the stress-stimulated luminescent material P1 deteriorate due to moisture in the solution.

  In addition, in order to improve the water resistance of the stress-stimulated luminescent material P1 of the present invention, the surface coating treatment of the stress-stimulated luminescent material P1 can also be performed using “metal alkoxide (a metal reacted with alcohol)”.

  As the metal element constituting the “metal alkoxide”, aluminum, zirconium, titanium, and silicon (here, “semi-metal element”, “silicon” is also included) can be used. For example, methoxide, ethoxide, propoxide, isopropoxide, oxyisopropoxide, butoxide and the like can be used. Further, tetraethoxysilane or ethyl silicate and methyl silicate obtained by partially hydrolyzing and condensing 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-stimulated luminescent material P1, but is 0.5 to 20% in total in terms of each element of the metal alkoxide with respect to the stress-stimulated luminescent material P1.

  As an apparatus for mixing the stress luminescent material P1 and the metal alkoxide, various dissolvers using various blades (rotating blades), Henschel mixers, speed mixers, ball cutters, power mixers, hybrid mixers and other stirrers, A kneading machine such as a ball mill and a cone blender can be used. Further, the surface-coated stress-stimulated luminescent material P1 obtained is air-dried for several hours to several days in a normal temperature drier, and then dried at 60 to 200 ° C. for 1 to 24 hours.

  Furthermore, a chemical vapor deposition method (C V D method) is a method in which the surface of the stress-stimulated luminescent material P1 is coated with an alumina coating or a titanium dioxide coating, or a vapor hydrolysis reaction at a temperature of 140 ° C. or lower. The surface of the stress-stimulated luminescent material P1 is coated with an “oxide film” by a sol-gel reaction or neutralization reaction, and the surface of the stress-stimulated luminescent material P1 is made of metal oxide or metal hydroxide. A method of forming a “protective film”, a metal alkoxide oligomer in a fluidized bed of a stress-stimulated luminescent material P1 heated to 100 to 200 ° C. (a state in which fine powder is suspended while moving in a gas), Method of forming a metal oxide film (protective film) on the surface of the stress luminescent material P1 by spraying an organic solvent solution of the metal alkoxide or the metal alkoxide itself, stress Exposing the optical material P1 in the reactive gas in a plasma state, it may be employed a method such as depositing a oxide film on the surface of the stress luminescent material P1.

Further, the material having the above composition is made into “fine particles” by using a predetermined method, and further made into “ultrafine particles” to form “stress luminescent material P1” having a “predetermined shape”. (Hereinafter, “fine particles” and “ultra fine particles” are also referred to as “fine particles”.)
Further, after the “stress luminescent material P1”, which has been made into “fine particles” or “ultrafine particles”, is mixed into an appropriate resin material, in particular, “paper pulp fiber 1” that is easily hydrogen-bonded. Using an appropriate printing method such as stainless screen printing or intaglio printing, the film is formed on an appropriate peelable film, dried and then peeled off from the appropriate peelable film. P1 "is also preferable.

  Of course, such “mixed fine particles or the like in a resin material” can be molded into a desired shape using an appropriate “mold”.

  In either case, the light emission of the fine particles contained in the resin material passes through the resin material enclosing it and spreads to reach the eyes of the observer. "Is preferable because it can be increased.

  In particular, the “stress luminescent material P1” of “fine particles” or “ultrafine particles” is obtained by physically crushing “stress luminescent material flat plate” or “stress luminescent material lump” into “fine particles”, or , “Ultrafine particles” (this is “micronization” or “ultrafine particleization”), but during the pulverization, for example, using an impact pulverizer, “microparticles” or “ The desired particle size (particle size) is controlled by the “classifier” while controlling the “ultrafine particles” to have a relatively irregular shape and suppressing the collision between the pulverized fine particles or the ultrafine particles. “Fine particles” or “ultrafine particles” having the desired shape of the distribution) are produced.

  Furthermore, “a composition for“ stress luminescent material ”before firing” (hydroxide containing a predetermined ratio of each element to be a desired “stress luminescent material” by a predetermined “baking” procedure. , Hydrates, oxides, complex oxides, nitrates, hydrochlorides, carbonates, acetates, sulfates, and other raw materials and their mixtures, also called “precursors.” Also, the luminescent center element is doped. It can also be added separately by means, etc. These mixtures, and also powder mixtures or powder mixtures, when directly “baked”, will become “stress luminescent materials”). "Resin that is easily decomposed by firing" such as a resin (so-called "ceramics" resin. When fired, the resin component becomes carbon dioxide gas or water and burns almost completely. "soot And “residues” are relatively small.) The individual “stressed luminescent materials before firing” are so-called “individually dispersed as individual particles” (this resin By the predetermined firing, the “stress luminescent material P1” is fired in the “individually dispersed state as individual particles”. Sintering is also preferable because it enables the individual shapes after firing to be more complicated.

  Furthermore, spray pyrolysis method, sol-gel method, flux feeder method and the like can also be used, but these methods are particularly directly from “composition for“ stress luminescent material ”before firing”, An “ultrafine particle” -like “stress luminescent material P1” can be produced, and the “particle diameter (distribution)” is excellent in controllability, which is preferable.

  Of course, in order to change the “shape” of the fine particles to the desired “shape”, the “firing” (made of metal or ceramics) having the desired “shape” as the internal shape is used in the “firing” described above. A method of filling the previous “stress luminescent material” composition (or filling with the molding die at the same time as molding) and taking out from the molding die after firing can also be employed.

  The more the "shape" of the "fine particles" or "ultrafine particles" is irregular, and the more the surface of the "fine particles" or "ultrafine particles" is rougher, ”Or“ ultrafine particles ”, it is possible to have a wide range of“ locations ”where“ stress concentration coefficient α> 2 ”that can be defined in the same manner, and the“ fine particles ”or“ It is also possible to have a shape in which the “stress concentration coefficient α” on the surface of the “ultrafine particle” is very large (α ≧ 500).

  Such “fine particles” or “ultrafine particles” are originally “stress luminescence” obtained by firing the composition for “stress luminescent material” under predetermined conditions to obtain “flat plate shape” or “lumb shape”. The “material” is “particulate” or “ultrafine particle” using a predetermined pulverization means, classification means or the like.

Alternatively, the “micronized” powder, that is, the “micronized powder” is temporarily changed to an appropriate “transparent resin” (particularly, the volume elastic modulus of the “resin” is the “micronized powder”. If it is larger than the bulk modulus of elasticity, the “deformation” loaded on the resin is transmitted directly to the “micronized powder.” The composition of the “transparent resin” and the “stress luminescent material” (The ratio is 10/1 to 1/10.) There is a predetermined correlation between the bulk modulus and the other constants, Young's modulus, Poisson's ratio, rigidity, and lame first constant. What was dispersed in the form of pellets and the like was again pulverized and classified to “fine particles”. (Here, the “particulate stress light emitting material P1” of the present invention is composed of the “particulated powder” and the “transparent resin” obtained.)
Further, during the treatment, if the treatment is performed while suppressing the collision between the fine particles (if the fine particles after pulverization collide with each other, the surface of the fine particles gradually becomes smooth), those “fine particles”. The “shape” itself forms a complex “shape”, and the surface of the “fine particles” also has a very random uneven shape (if the period and depth of the unevenness are small, the nano-size is extremely From a fine one to a large one, it can be maintained at random, even from a few micrometer size to its distribution width.

  The “particulate stress luminescent material” is further made into “ultrafine particles” by using a predetermined pulverization means, classification means, etc., to obtain “ultrafine particle stress luminescent material P1”. As described above, once the “stress luminescent material” is dispersed in the “transparent resin”, the “transparent resin containing the“ particulate stress luminescent material ”” is once again converted into the predetermined pulverizing means and classification. “Ultrafine particles” may be used by using means or the like (the “ultrafine particle-like stress luminescent material P1” at this time is covered with the “transparent resin”).

  In any case, “stress luminescent material P1” in the form of “fine particles” or “stress luminescent material P1” in the form of “ultrafine particles” is covered with “transparent resin”. The difference between “refractive index of stress-stimulated luminescent material”, “refractive index of transparent resin”, and “refractive index of paper pulp fiber 1” is 0.03 or less, and particularly 0.01 or less. Thus, the “transmittance” of the “interface” at these contacts can be increased, and the reflectance of the “interface” can be decreased.

  That is, it is possible to increase the “transparency” of those “interfaces”, suppress “reflection”, and improve the light emission visibility of the “stress luminescent material P1”.

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

  Among them, it is a typical pulverizer for obtaining fine particles, and a ball made of metal is packed in a cylinder that is slightly tilted or horizontally rotated, In a ball mill in which grinding is performed by friction, a dry ball mill or a wet ball mill (both have an internal volume of 100 to 10000 liters and a rotational speed of 10 to 50 revolutions / minute) are preferably used.

  The rod mill uses a rod (metal cylinder) instead of a ball as a grinding medium, and pulverizes the crushed material by impacting the rod with a rotating drum (body). In particular, the impactor mill is a fine pulverizer that rotates impact teeth at high speed and pulverizes the raw material by impact force. The impactor mill rotates a rotating disk having a diameter of 100 to 1000 mm at a high speed of 500 to 10,000 rotations / minute. Alternatively, the shape of the ultrafine particles itself is a complicated shape, and the surface of the fine particles and the ultrafine particles are likely to be rough uneven shapes, which is preferable.

  Further, once the “stress luminescent material” is changed to “fine particle”, and further to “ultrafine particle (average particle diameter is 0.005 to 0.5 μm, particularly 0.05 to 0.5 μm) Is referred to as “ultrafine particles. Larger particles are“ fine particles. ”) Using a“ granulating ”means such as a granulator, the“ bonding between “ultrafine particles” is strong. By using “secondary aggregates”, “stress luminescent material P1” in the form of “fine particles” having “indefinite shape” and “complex shape” can be obtained.

  Such a granulator is an apparatus that consolidates “powder” and “fine particles” into “granular”, and is also called a pelletizer because it can produce “granular” pellets.

  And in this `` granulation '' method, self-supporting granulation swivel type (rotor type), kneading type, stirring type, rolling type, fluidized bed type, forced granulation compression type (roll press type), There are a twin screw extrusion method, a wet extrusion method, and a combination of these, and there are also models that perform mixing, dispersion, and granulation continuously.

"Stress luminescent material P1"("stress luminescent material" 100% composition, "stress luminescent material" composed of a plurality of stress luminescent materials, "micronized" or "ultrafine" by such pulverization means The composite of the material ”and the composition composed of“ stress luminescent material and transparent resin ”are selected using a classifying means, or granulated using a granulating means, further, sorted using a classification means, in maximum diameter, 1.0Myuemu～20myuemu, preferably, a "particulate P1" of 1.0Myuemu～10myuemu, and an average diameter D _50, 0.5μm~15μm, Preferably, a “fine particle stress luminescent material P1” of 0.5 μm to 5 μm is used.

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

  In such a particle size distribution measurement method, an X-ray transmission type sedimentation method in which the concentration of particles in the dispersion medium is directly measured using a finely focused X-ray beam, and the particles pass through a pore detection area. An electrical detection band 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 passed through the flow cell. Light is applied from the light source to the flow cell, An image analysis method in which a projected image of a particle passing through the cell is photographed with a high-sensitivity CCD camera, the particle image is digitally converted, and the particle equivalent circle diameter, shape information, and the like are obtained by an analysis program process. (Use dozens of shape parameters and image analysis models such as circular model, fiber model, rectangular model, polygonal model, ellipse model, irregular model) "Brownian motion" in particle suspension Do Particles are irradiated with laser light, and the dynamic light scattering method is used to measure the particle diameter from the scattered light from the moving particles. Light diffraction / scattering phenomenon by irradiating the particles with laser light. The intensity pattern of the diffracted / scattered light depends on the particle size, and different intensity patterns (intensity distributions) are observed depending on the angle of diffraction / scattered light. , Laser diffraction scattering method to obtain particle size distribution using Mie scattering theory, when air is passed through the packed bed of powder, the finer the powder particles, the more difficult it is to flow, and the particle size of the powder and fluid permeation An air permeation method or the like for determining the specific surface area of the powder from the correlation with the properties can be used.

  The “form” of the “fine-particle or ultrafine-particle stress luminescent material P1” used for the “foam paper A1” of the present invention is “a large number” included in the “foam paper A1” of the present invention. This means an “average shape of the stress-luminescent material P1 in the form of fine particles or ultrafine particles”, and is defined as a “shape” that can be determined by a so-called optical fine particle shape measuring device or the like. Of course, this “sampling measurement” condition is specifically included, for example, by cutting out an arbitrary area of 10 mm in length × 10 mm in the “form paper A1” of the present invention and using an appropriate solvent or the like. It is also possible to extract all of the particulate or ultrafine stress light emitting material P1 "and perform the above measurement.

The “particulate” “stress luminescent material P1” of the present invention thus obtained is used in the “pulp process” (see FIG. 2) in the “paper pulp fiber 1” for producing the “paper pulp fiber 1” described above. In the “selection & dehydration process”, further, at the stage of the “pulp suspension”, which is the state before the dehydration process, the “pulp suspension” is “mixed” at a predetermined ratio, and in FIG. The remaining “papermaking process”, “raw material adjustment process 2: addition of chemicals such as sizing agent”, “papermaking process 1: wiring & squeezing”, “papermaking process 2: drying & pressing”, and “processing & finishing” Through the “process”, “foam paper A1” of the present invention is obtained. (See FIG. 1 and FIG. 2. In FIG. 1, no sizing agent is shown.)
At this time, the ratio of the “stress luminescent material P1” to the “paper pulp fiber 1” is 0.5 to 30%, particularly 1 to 10% with respect to 100% of the “paper pulp fiber 1”. The appropriate ratio is set according to the quality specification of the “form paper A1” of the present invention and the purpose of use.

  When the ratio of the “stress luminescent material P1” is less than 0.5%, sufficient light emission that is visible cannot be obtained when a predetermined external load is applied to the “form paper A1”, and exceeds 30%. As a result, the rigidity of the “form paper A1” becomes too strong, or the specific gravity of the “form paper A1” becomes too high, making it difficult to achieve quality specifications.

  Here, “paper making step 1: wiring & squeezing” is a so-called “wire part”, which is a mesh (wire) woven with PET (polyethylene terephthalate) fiber or bronze fiber, etc., continuously. After the above-mentioned “pulp turbidity liquid” is homogeneous in the width direction and supplied at an appropriate concentration, speed, and angle on the belt-like one that can be rotated, after the coating film has a predetermined thickness , Squeezing water on the wire (meaning dehydration. In the part where dehydration has progressed to some extent, dehydration is promoted by the equipped suction box (device that sucks water with a vacuum pump)). A “wet paper (meaning still containing water)” for the foam paper A1 ”is formed.

“Paper making process 2: drying & pressing” is a so-called “press part”,
The “wet paper” peeled off from the wire is transferred to the felt, enters a press device that applies pressure to further squeeze the water, and is subjected to a roll press process consisting of several rolls. Here, the density of the “form paper A1” can be adjusted by appropriately pressing the “wet paper”.

  Next, the wet paper is dried by evaporation of moisture, so-called “dryer part”, wound and dried while being successively transferred to a number of cylinder drums heated by steam.

  Finally, the “processing & finishing process” belongs to the so-called “processing process of the foam paper A1 (the processing process different from the“ post-processing ”described above).” It enters into processes such as coating processing such as dispensing and calendar processing. The coating process and the calendar process may be performed off-machine (meaning once wound up and then applied to another dedicated apparatus).

  The “foam paper A1” of the present invention can be produced by a manual method, but in order to produce in large quantities while satisfying the quality specifications, a paper machine capable of achieving the above “paper making process”, for example, , Paper machines of various systems such as a long net system, a twin wire system, a gap former system, a round net system, and a Yankee system are used. Furthermore, a machine calendar processing machine can be added.

Example 1
A softwood (mixed material of Nidomatsu and Todomatsu) chips was defibrated by a refiner to obtain a suspension (1) of unbleached mechanical pulp having a freeness of 600 ml (beating degree, according to Canadian Standard). The suspension 1 was adjusted to pH 4, 0 with an acetate buffer and the pulp concentration was adjusted to 3%, and then beaten with a single disc refiner (beater) until the freeness reached 300 ml. A suspension (2) containing “paper pulp fiber 1” was obtained.

  The “paper pulp fiber 1” at this time had an average “thickness” of 30 μm and an average “length” of 3.0 mm.

  Apart from this, the “hollow shape” of the “mold” for firing (the shape of the “space” inside the “mold”) is a “shape” of 30 mm in length, 100 mm in width, and 5.0 mm in thickness. A metal “firing die (1)” with stainless steel attached inside was prepared.

Next, 1% Eu and 1% boric acid are added to Sr ₃ Al ₂ O ₆ which is the base material, and the rectangular “cavity” of 30 mm length × 100 mm width × 5.0 mm thickness is added. In the hydrogenation argon reduction atmosphere, the temperature is gradually raised to 900 ° C. and temporarily calcined, and then in the hydrogenation argon reduction atmosphere at 1300 ° C. It is fired for 4 hours, allowed to cool naturally, and taken out from the “baking mold (1)”, and has a “shape” of a rectangular parallelepiped of 30 mm long × 100 mm wide × 5.0 mm thick. This operation was repeated to obtain 100 “flat-stressed luminescent material sheets (H1)” having the same shape. (Here, even if 100% of the “stress luminescent material” is filled to match the shape inside the “firing mold”, that is, the space inside the “mold”, The “light emitting material” shrinks, and the “shape” of the “stress light emitting material” is finished as a “shape” that is considerably smaller than the inner shape of the “firing mold”. Of course, it is possible to define the shape inside the “firing mold” in anticipation of this “shrinkage”.)
These 100 “flat stress-stimulated luminescent material sheets (H1)” were pulverized three times for 60 minutes using a metal ball mill (dry ball mill) with an internal volume of 200 liters and a rotation speed of 50 revolutions / minute. "Particulate".

This “particle” is classified by a classifier equipped with a stainless steel classifying rotor with an air classification type while controlling the “particle size” (particle diameter) by the laser diffraction method, and the particle size distribution. A “particulate stress luminescent material P1” having a width (maximum diameter distribution width of particles) of 1 to ₅₀ μm and an average particle diameter (average diameter of particles) D ₅₀ = 30 μm was obtained. (See FIG. 1. In FIG. 1, the “particulate stress-stimulated luminescent material P1” is “schematically” large and the surface irregularities are exaggerated.)
From the “particulate stress luminescent material P1”, 100 “particulate stress luminescent materials P1” were measured by arbitrary sampling, and the “shape (external shape including the uneven shape of the surface)” was measured. The “3D image data” of “shape” is applied to “structural analysis software (stress distribution analysis software)”, and any “particulate stress luminescent material P1” bends the “particulate stress luminescent material P1”. For the load of “deformation stress”, the stress concentration coefficient α is approximately 5 or more, and almost all of the “particulate stress luminescent material P1” has a portion where the “stress concentration coefficient α is 2.0 or more. It was confirmed that the shape (the stress concentration portion S1 in this case was the position of the bottom of the concave portion of the concave and convex shape on the surface of the “particulate stress luminescent material P1”) ”. (The confirmation status is not shown.)
Then, 20 parts of the “stress luminescent material P1” was mixed with 100 parts of the “paper pulp fiber 1” of the suspension (2) to obtain a suspension (3).

Furthermore, 1 part of an appropriate sizing agent was added to the suspension (3), and a “wet paper” was prepared with a square handsheet sheet machine so that the basis weight was 64 g / m ² ( It means “predetermined thickness” in anticipation of the drying process.), Dried at 120 ° C. for 2 minutes while adjusting the press pressure in a drum dryer, and at 24 ° C. under conditions of 20 ° C. and 50%. After humidity control, cut to 279.4 mm wide (11 inch wide) x 838.2 mm long (33 inch long) size, and the left and right ends in the width direction were “diameter 60 mm, cutting edge with one edge. And a slitter process using a slitter blade using super high speed steel, and the width was 279.4 mm (11 inches wide).

Then, “feed hole HL” which is “vertical through portion: specific portion K1” is formed at a predetermined position on the inner side from both slit end faces, and “in the shape of“ opening ”of“ vertical through portion: specific portion K1 ”. There is a “sprocket hole (feed hole)” with a “hole diameter of 4.0 mm” according to the specified standard. By using steel.), Two rows are provided at a predetermined cycle, and the other “two vertical perforations: specific portion K1”, “two types of perforations”, are first “sewing blades” with the following specifications. Is used to apply a “folding horizontal sewing machine M1” with a period of 279.4 mm (11 inches) by a sewing machine, and then, at a predetermined position on the inner side from the end surfaces of both slits, Uncut = 3mm / 1.5mm ", other specifications are above Using a "sewing machine blade" which was the same as, the "vertical sewing machine M2" is subjected at sewing machine, to obtain a "Form Paper A1" in Example 1 of the present invention. (See FIGS. 1, 3, and 6. The “form paper A1” in Example 1 does not have the “slit SL” shown in FIG. 6.)
<Specifications of “sewing blade” of horizontal sewing machine M1 for folding>
"Cut / Uncut": "2mm / 1mm"
“Thickness”: 2 mm
“Cross-section four-corner finish”: Rounded corner with a radius of 0.3 mm “Blade edge specification”: Double-blade “Material”: Alloy tool steel The quality specification (quality characteristics) of “foam paper A1” in Example 1 is thick. in the 84 .mu.m, and a basis weight 64 g / m ^2, smoothness (Table) 25, smoothness (back) 14, Clark stiffness (vertical) 70cm ^3/100, Clark stiffness (transverse) 35 cm ^3/100, tensile strength ( Length) 4.5, tensile strength (width) 2.5, tear strength (length) 220, tear strength (width) 240, ISO whiteness 85%. (In a normal press pressure, the pressure was reduced when the thickness was about 70 μm, and the thickness was adjusted. See FIGS. 1 and 2. The sizing agent is not shown in FIG. Only part of the process is adopted.)
The “foam paper A1” of Example 1 is a “kamaboko type with a bottom size of 30 mm in length × 100 mm in width” and a curvature radius of 60 mm. “Jig (made of stainless steel with a mirror-finished outermost surface). ) ”On the curved surface as a“ predetermined external force load on the foam paper A1 ”, the“ form paper A1 ”is deformed when it is pressed with a finger of a hand, and in particular, near the protruding portion (vertex) of the jig. The “feed hole HL” as “vertical through portion: specific portion K1”, “folding horizontal sewing machine M1” as “vertical through portion: specific portion K1”, or “vertical through portion: When “vertical sewing machine M2” as “specific part K1” is positioned, they emit strong “green” light and can be visually confirmed, and the authenticity of “form paper A1” can be confirmed. . (The evaluation status is not shown.)
This is because the “paper pulp fiber 1” is deformed in the “foam paper A1” by a predetermined external force load (pressing with a finger of the hand) on the “foam paper A1”, and the “stress luminescent material P1. The “stress concentration portion S1 (predetermined part)” of “is a deformation stress corresponding to the deformation of the“ paper pulp fiber 1 ”and a predetermined wavelength having a strength corresponding to the deformation stress from the predetermined part. Light ("green light"), and in particular, in the "vertical through part: specific part K1", in the "thickness direction of the cylindrical hole" of the "feed hole HL", respectively. "Middle part" (stress concentration location), "Folding horizontal sewing machine M1""Middle part in the thickness direction of the elliptical columnar hole" (same as on the left), "Vertical sewing machine M2""Oval columnar hole thickness" The central part of the direction "(left) emits particularly intense light, It was considered to be the light of the wavelength has become visible.

Similarly, using a mass production type paper manufacturing apparatus, the long “foam paper A1” of Example 1 and the long “foam paper” of Comparative Example 1 (below) are manufactured, respectively. The durability of the “blade” in “drilling” and “sewing” is set to “amount that can be processed” by the blade before replacement when the blade is replaced under the same setting (the above setting) (machining) The ratio is 95/100 and 98/100 respectively, and the “processable amount” tends to decrease slightly (the number of possible processing meters is short). However, it did not affect the “mass productivity”, and “blade wear” was sufficiently suppressed, and was judged to be a good result. (The evaluation status is not shown. The same applies hereinafter.)
(Example 2)
In the first embodiment, the “feed hole HL” is not processed perpendicularly to the surface of the “form paper A1”, but is inclined by 45 degrees in the vertical direction with respect to the vertical line with respect to the surface. Is changed from “right cylindrical shape” to “oblique cylindrical shape” and “feed hole HL” as “obliquely penetrating portion: specific portion K2”. “Form paper A2” of Example 2 was obtained. (See FIG. 1, FIG. 4, and FIG. 6.)
The “form paper A2” of Example 2 was evaluated in the same manner as in Example 1. As a result, the “center portion in the thickness direction of the oblique cylindrical hole” (stress concentration portion KS2) of the “feed hole HL” was particularly large. Good results similar to those of Example 1 were obtained except that the light was emitted strongly.

(Example 3)
In Example 1, instead of “folding horizontal sewing machine M1” as “vertical penetrating part: specific part K1”, a long and narrow rectangular opening of 10 mm in width and 0.1 mm in length and having a depth of 30 μm is used. The “form” according to the third embodiment of the present invention is the same as the first embodiment except that the “wedge shape” is provided with a “notch portion: specific portion K3” in which the wedge shape is regularly arranged in a horizontal line with an interval of 1 mm. Paper A3 "was obtained. (See FIG. 1, FIG. 5, and FIG. 6.)
This “notch portion: specific portion K3” is formed on “wet paper” and “metal flat plate” in “paper making step 1: wiring and squeezing” in “paper making step” of “form paper A3”. The above-mentioned “wedge shape” was turned upside down to form a protrusion and pressed by a jig arranged in a horizontal row. (In FIG. 5, this is “schematically” indicated by six “cutout portions K3”.)
By adopting this method, the “bottom edge” of each “wedge shape” of the “form paper A3” (this is the stress concentration point KS3) becomes “a plane perpendicular to one side of a triangular prism. It was not a “sharp corner” but a gentle “curved surface”.

The “form paper A3” of Example 3 was evaluated in the same manner as in Example 1. As a result, the “bottom part” (stress concentration part KS3) of the “notch part: specific part K3” emitted light particularly strongly. Good results similar to those of Example 1 were obtained.
Example 4
In Example 1, “slit SL” having “vertical through portion: specific portion K1” and “slit-shaped through portion: specific portion” having an opening shape of “width 0.1 mm × length 30 mm” The “foam paper A1” of Example 4 of the present invention was obtained in the same manner as in Example 1 except that the spot diameter of the 10 KW output carbon dioxide gas laser was reduced and the power was adjusted to provide one place. It was. (See FIG. 1 and FIG. 6.)
By adopting this method, both ends of the opening of the “slit SL” on the “form paper A1” do not become “sharp angles that are orthogonal to each other like the four corners of a square”, and are gentle. It was a “curved surface”, and the “side surface” in the “slit SL” was a relatively smooth surface.

The “form paper A1” of Example 4 was evaluated in the same manner as in Example 1. As a result, “slit-shaped through portions: specific portions” “both ends of the opening” emitted particularly intense light, and “slit SL”. In “side surface” of “”, the same good results as in Example 1 were obtained except that the emitted light was repeatedly reflected, and the emitted light had directivity and high intensity.
(Example 5)
In the first embodiment, the shape of the “opening” of the “vertical through portion: the specific portion K1” is set as the “feed hole HL” that is “vertical through portion: the specific portion K1” and the diameter of the “hole” is 4.0 mm ( "Kikumaru" specification. The area around the "hole" is a so-called "jagged" shape.)) Except that a "sprocket hole (feed hole)" is used. “Form paper A1” of Example 5 was obtained. (See FIG. 1, FIG. 3, and FIG. 6.)
At this time, ““ vertical penetrating portion: specific portion K1 ”is a“ polygonal column ”whose opening shape is“ Kikumaru ”, and“ stress concentration point KS1 ”of the“ polygonal column ” The “side portion” of the “side surface” of the “polygonal column” is “the central portion in the thickness direction”, and the “stress concentration coefficient α” is 15.

When the “form paper A1” of Example 5 was evaluated in the same manner as in Example 1, the central portion (stress concentration portion KS1) in the thickness direction of “vertical through portion: specific portion K1” had a larger light emission intensity. Good results similar to those of Example 1 were obtained except that the light emission was considered to be improved.
(Example 6)
In Example 1, 1% Eu and 1% boric acid are added to Sr ₃ Al ₂ O ₆ which is a base material, and a rectangular parallelepiped “30 mm long × 100 mm wide × 0.1 mm thick” In a “firing mold (2)” having a “cavity”, the temperature is gradually raised to 900 ° C. in a hydrogenated argon reducing atmosphere, and after preliminary firing, 1300 in a hydrogenated argon reducing atmosphere. Baked at 4 ° C. for 4 hours, allowed to cool naturally, and taken out from the “baking mold (2)”, and has a “shape” of a rectangular parallelepiped of 30 mm long × 100 mm wide × 0.1 mm thick. The stress-stimulated luminescent material sheet (H2) ”was used, and the 100“ flat-stressed luminescent material sheets (H2) ”were used with a metal ball mill (dry ball mill) with an internal volume of 100 liters and a rotational speed of 50 revolutions / minute. And crush 60 minutes for 5 times (The diameter of the metal ball mill was gradually reduced each time it was repeated.) The average diameter of 10 μm was made “fine particles”, and a classifier for removing particles larger than 15 μm in diameter was passed three times to obtain a maximum diameter of 3 μm. The “stress luminescent material P1” of Example 6 having a “fine particle shape” of 15 μm and an average diameter D ₅₀ of 12 μm was obtained, and “Suspension (2) of Example 1” In the same manner as in Example 1, except that 10 parts of the “stress luminescent material P1” was mixed with 100 parts of the paper pulp fiber 1 to obtain “Suspension (3) of Example 6”. “Form paper A1” of Example 6 of the present invention was obtained.

(See FIGS. 1, 3, and 6. “Form paper A1” in Example 6 does not have the “slit SL” shown in FIG. 6.)
The quality specifications (quality characteristics) of the “foam paper A1” in Example 6 are as follows: basis weight 64 g / m ² , thickness 84 μm, smoothness (front) 27, smoothness (back) 16, Clark stiffness (vertical) 65cm ^3/100, Clark stiffness (transverse) 33cm ^3/100, tensile strength (vertical) 4.2 tensile strength (lateral) 2.2, tear strength (vertical) 200, tear strength (horizontal) 225, ISO whiteness It was 83%, and it was easy to adjust the quality specifications (quality characteristics) to the quality specifications (quality characteristics) of “foam paper” (see Comparative Example 1) that does not include “stress luminescent material P1”. (This means that it is easy to match the “quality characteristics” of the “form paper” in Comparative Example 1. See FIG. 1 and FIG. 2. In FIG. 1, no sizing agent is displayed. Only part of the papermaking process is used.)
Then, when “foam paper A1” of Example 6 was evaluated in the same manner as in Example 1, the amount of “stress luminescent material P1” added was set to “1/2” (20% → 10%) of Example 1. In spite of the fact that the light emission intensity was almost the same as in Example 1 and the so-called “light emission efficiency” was thought to have increased, the same good results as in Example 1 were obtained.
(Example 7)
In Example 1, 1% Eu and 1% boric acid were added to Sr ₃ Al ₂ O _{6 as} a base material, and a rectangular parallelepiped having a length of 1.0 mm × width 1.0 mm × thickness 10 μm. The “cavities” are placed in a “firing mold (3)” having 10 in the vertical direction and 20 in the horizontal direction (200 in total), and gradually increased to 900 ° C. in a hydrogenated argon reducing atmosphere. And then calcined in a hydrogenated argon reducing atmosphere at 1300 ° C. for 4 hours, naturally cooled, taken out from the “firing die (3)”, and vertically 1 The plate-shaped stress light-emitting material sheet (H3) has a rectangular “shape” of 0.0 mm × width 1.0 mm × thickness 10 μm. The 2000 “plate-shaped stress light-emitting material sheets (H3)” A metal ball mill with an internal volume of 30 liters and a rotation speed of 50 rev / min Using a dry ball mill.), 60 minutes of pulverization was repeated 10 times (the diameter of the metal ball mill was gradually reduced each time) to obtain a “fine particle shape” having an average diameter of 2 μm, which was larger than 1 μm in diameter. The “stress luminescent material P1” of Example 7 having an “ultrafine particle shape” having a maximum diameter of 1.0 μm and an average diameter D ₅₀ of 0.3 μm is passed through a classifier for removing fine particles five times. 10 parts of the “stress luminescent material P1” are mixed with 100 parts of the “paper pulp fiber 1” of the “suspension (2) of Example 1” to obtain “the suspension of Example 7”. A “foam paper A1” of Example 7 of the present invention was obtained in the same manner as in Example 1 except that the “turbid liquid (3)” was used. (See FIGS. 1, 3, and 6. “Form paper A1” in Example 7 does not have “slit SL” shown in FIG. 6.)
The quality specifications (quality characteristics) of the “foam paper A1” of Example 7 are as follows: basis weight 64 g / m ² , thickness 84 μm, smoothness (front) 30, smoothness (back) 18, Clark stiffness (vertical) 65cm ^3/100, Clark stiffness (transverse) 30 cm ^3/100, tensile strength (vertical) 4.0, tensile strength (horizontal) 2.0, tear strength (vertical) 190, tear strength (horizontal) 220, ISO whiteness 83%, and it was easier to adjust the quality specifications (quality characteristics) to the quality specifications (quality characteristics) of “foam paper” (see Comparative Example 1) that does not include “stress luminescent material P1”. In addition, good results similar to those of Example 1 were obtained except that the emission intensity was slightly higher than that of Example 1 and the “light emission efficiency” was considered to have further increased. (See FIG. 1 and FIG. 2. In FIG. 1, no sizing agent is shown. Only part of the “paper making process” in FIG. 2 is employed.)
(Example 8)
In Example 1, 1% Eu and 1% boric acid are added to Sr ₃ Al ₂ O ₆ which is a base material, and 1/8 slices of two spheres having a diameter of 100 μm are obtained. The joined shape (so-called “gourd shape”. The part of the “joint surface (constriction)” becomes the “stress concentration portion S1”. The “stress concentration coefficient α” of the “stress concentration portion S1” is “two stresses”. The “deformation stress generated when pulling the sphere” is 10, and the “deformation stress generated when twisting two spheres” is the “stress concentration portion S1” at the outer periphery of the joint surface. The “stress concentration coefficient α” was 30 or more.) “Caving mold (4) having 20“ cavities ”in the vertical direction and 40 in the horizontal direction (800 in total). ) "And gradually raise the temperature to 900 ° C in a hydrogenated argon reducing atmosphere. After calcining, it is subsequently calcined at 1300 ° C. for 4 hours in a hydrogenated argon reducing atmosphere, allowed to cool naturally, and taken out from the “firing mold (4)” to have a “gourd shape” , “Stress luminescent material P1 in particulate form of Example 8 having a stress concentration coefficient α of 2 or more” (“gourd form” particulate form having a maximum diameter of 175 μm) and “hanging of Example 1 Except for adding 5 parts of the “stress luminescent material P1” to 100 parts of “paper pulp fiber 1” of the “turbid liquid (2)” to obtain “suspension (3) of Example 8”. In the same manner as in Example 1, “Form Paper A1” of Example 8 of the present invention was obtained. (Refer to FIG. 1, FIG. 3 and FIG. 6. “Form paper A1” in Example 8 does not have “slit SL” shown in FIG. 6. In FIG. Not shown.)
The quality specifications (quality characteristics) of the “foam paper A1” of Example 8 are 84 μm in thickness, 64 g / m ^{2 in} basis weight, smoothness (front) 20, smoothness (back) 10, and Clark stiffness ( vertical) 80 cm ^3/100, Clark stiffness (transverse) 40 cm ^3/100, tensile strength (vertical) 5.0, tensile strength (horizontal) 3.0, tear strength (vertical) 250, tear strength (horizontal) 280, ISO Good results similar to those of Example 1 were obtained except that the whiteness was 82% and the emission intensity was higher than that of Example 1 and the “light emission efficiency” seemed to be significantly increased. . (See FIG. 1 and FIG. 2. In FIG. 1, no sizing agent is shown. Only part of the “paper making process” in FIG. 2 is employed.)
Example 9
As the sizing agent, “kaolin (white clay)” having a particle size of 1 to 10 μm and having a “color tone” of 0.4 from the color tone of the “stress luminescent material P1” of Example 1 was used. Except for this, “Form paper A1” of Example 9 of the present invention was obtained in the same manner as Example 1. (See FIG. 1. In FIG. 1, the display of the “sizing agent” used is omitted.)
When the appearance of the “form paper A1” in Example 9 was observed, it was only recognized as “white paper”, and the “stress luminescent material P1” was mixed in the “paper”. The same good results as in Example 1 were obtained except that could not be imagined. (The evaluation status is not shown.)
(Comparative Example 1)
In Example 1, a “foam paper” was produced without including the “stress light-emitting material P1”.

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

A1 to A3 Foam paper 1 Paper pulp fiber P1 Stress luminescent material S1 Stress concentration part HL Feed hole M1 Horizontal sewing machine M2 Vertical sewing machine SL Slit KS1, KS2, KS3 Stress concentration part K1, K2, K3 Specific part

Claims (5)

A foam paper comprising at least paper pulp fibers and a stress-luminescent material,
The shape of the form paper is a shape including a vertical penetrating part, an oblique penetrating part, a notch part, and / or a concave part,
Due to the deformation of the foam paper caused by a predetermined external force load on the foam paper, deformation stress concentrates on the vertical penetrating part, the oblique penetrating part, the notch part, and / or the concave part, and at the same time, the vertical penetrating part, The paper pulp fiber in the oblique penetration part, the notch part and / or the concave part is deformed in the foam paper,
and,
The stress luminescent material has a predetermined outer shape, and a deformation stress corresponding to the deformation of the paper pulp fiber is generated in a predetermined portion of the stress luminescent material, and the deformation stress is generated from the predetermined portion. A foam paper characterized in that light of a predetermined wavelength having a light emission intensity corresponding to the light is emitted, and the light of the predetermined wavelength is visible.
The form paper according to claim 1,
The form paper characterized in that the vertical penetrating part and / or the oblique penetrating part is a slit-like penetrating part.
In the foam paper according to claim 1 or 2,
The form paper has a shape in which the stress concentration coefficient α in the vertical through portion, the oblique through portion, the cutout portion, and / or the concave portion is 2 or more.
In the form paper according to any one of claims 1 to 3,
The predetermined outer shape of the stress-stimulated luminescent material has a fine particle shape having a maximum diameter of 1.0 to 20 μm and an average diameter D ₅₀ of 0.5 to 15 μm. .
  The foam paper according to any one of claims 1 to 4, wherein the foam paper includes a sizing agent, a color tone of the sizing agent, and a color tone of the stress-stimulated luminescent material included in the foam paper. The form paper has a color difference of 0.5 or less.

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