TW548192B - Multi-color change material and observation method therefor - Google Patents

Abstract

A multi-color change material according to the present invention is characterized in that it is formed of a selectively permeable layer, which is formed by a multi-layer structure multiple laminated with more than two kinds of materials with different refractive indices, with higher permeability of linear light incident from approximately vertical direction as well as with higher scattering reflectivity of visible light, and a colored pigment layer which underlies the foregoing selectively permeable layer. Said selectively permeable layer in the foregoing multi-color change material preferably contains a pearl agent. Further, an observation method of the present invention is characterized in that the observation is conducted by irradiating the multi-color change material formed of a selectively permeable layer, which is formed by a multi-layer structure multiple laminated with more than two kinds of materials with different refractive indices, with higher permeability of linear light incident from approximately vertical direction as well as with higher scattering reflectivity of visible light, and a colored pigment layer which underlies the foregoing selectively permeable layer, so as to change the color into the hue different from that of the multi-color change material under visible light.

Description

548192 V. Description of Invention (1) [Background of the Invention: This application claims the priority of Japanese Patent No. 2 0 1-2 1 6 8 7 5 in the Japanese patent filed on July 17, 2001. However, this specification FN includes its content. [Technical field: The present invention relates to a color-changing material that exhibits different color tones due to the light irradiated and its observation method, and particularly to the improvement of the composition of the material and its observation method. [Technical background: For the purpose of designing the appearance of the pattern or preventing forgery, a variety of materials with color change properties have been developed. Such materials can be exemplified: if the white light is irradiated, the color rainbow hologram film that reproduces the three-dimensional image (rainbow) ho] ogram fi 1 m) or mica-coated pearlite coated with titanium oxide, a powder that interferes with multilayer deposition of films with controlled refractive index and film thickness. In addition, in recent years, commodities developed by combining the above materials to give design to the design and strengthen the prevention of counterfeit S have also appeared. For example, as a technique using a retroreflective material and a precious pearl pigment with multiple color changing properties, there may be mentioned Japanese Patent Publication No. 2000--8 1 8 31. The technology described here is provided on the retroreflective material with an interfering substance layer that interferes with incident light to change color due to polychromic pearl agent. Under normal light such as sunlight or illumination light due to light, The incident color of the retroreflective material from various directions cannot be observed due to the interference color of the interfering material layer, so that the light traveling in the same direction (referred to as straight light: from the light incident direction, the interference

313810.ptd Page 10 548192 V. Description of the invention (2) The material layer can observe the interference color caused by the interference of light. However, articles using retroreflective materials are difficult to make thin. Fig. 4 is a schematic explanatory diagram of a conventional retroreflective material. The retro-reflective material 100 described in the figure is made of a plurality of glass beads 104 arranged on the substrate 1 102 to impart retroreflectivity, and the thickness of the resin layer 106 fixing f glass beads is adjusted to Adjust the focal length of the glass beads to make it possible to observe characters written on the substrate 102 and return the incident light 1 0 to the slightly incident light entering direction to obtain the feedback light n 0. And it is composed of the substrate 102 and the resin layer! The interfering layer 1 1 2 which is discolored due to the interference of light, which is set between 〇6, is a special method to change the color.

In this way, the retro-reflective material 100 is provided with a glass bead layer for the purpose of imparting retroreflectivity to light, and the diameter of the glass beads, such as the particle size of toilet materials, is very large when compared. # 以Make it thin. -Furthermore, when manufacturing the aforementioned retro-reflective material, since the substrate interferes with the Wu layer, Ya sets a resin layer under the square shirt which can ensure the focal length of the glass beads, and furthermore, it is given by glass in the resin layer. … There are also steps in the operation: There are also many steps in the dense operation, so that:

[Revelation of the invention] The problem of the door brigade. The present invention is developed by the developer of the subject of the aforementioned conventional technology, which can be made into a thin film and can be relatively easily manufactured in a generally strong color, which can be recognized under linear light, and a method for providing 颧 = recognition material. for purpose. /, Rules / 丁, rules

3l3810.ptd Page 11 548192 V. Description of the invention (3) In order to achieve the aforementioned object, the polychromic material of the present invention is characterized by a multilayer structure formed by stacking two or more substances with different refractive indices from a multilayer structure. A light penetrating light incident in a slightly perpendicular direction has a high transmittance, and usually has a selective transmission layer with a high scattering reflectance of light, and a colored pigment layer disposed under the selective transmission layer. In the polychromic material of the present invention, the selective penetration layer preferably contains a pearl agent. In the polychromic material of the present invention, the selective penetration layer preferably contains a hologram and / or a light diffracting recording body, and a pearl agent formed from a lower layer of the hologram and / or a light diffracting recording body. A layer of pearl agent. In addition, in the polychromic material of the present invention, it is preferable that the pearl agent forming the selective penetration layer is made of light-interfering powder, and the light-interfering powder system is laminated in multiple ways to form the aforementioned selection. Sexual penetration. Moreover, in the polychromic material of the present invention, it is preferred that the pearl agent made of the light-interfering powder has a light transmittance of 40% or more in a wavelength range of 4 20 nm to 7 0 nm. When the brightness measured by coating the pearl agent on black paper is marked with the La b value of Hunter, it can meet the following relationship. ((a4〇-a〇) 2 + (b4〇-b〇) 2) 1 / ^ 13 (Here, a4〇 and b4 represent the a value and the b value of the Lab value measured at a light receiving angle of 40 degrees And aG and b represent the a value and the b value of the Lab value measured at the position where the light receiving angle is 0 degrees.) Also, in the polychromic material of the present invention, it is preferable that the colored pigment layer is composed of an inorganic pigment and an organic dye. , Or if you change the direction of incident light

Page 12 313810.ptd 548192 V. Description of the invention (4) Any one of polychromatic pigments of various colors, or a plurality of pigments and dyes. In addition, the multi-color-change material of the present invention is preferably one that is attached to or formed integrally with a substrate or article such as paper or film. Moreover, the observation method of the present invention is characterized in that, for a multilayer structure formed by stacking two or more substances with different refractive indexes, a linear structure incident from a substantially perpendicular direction has a high transmittance and a normal light scattering. The selective transmissive layer with higher reflectance and the multi-color changing material formed by the colored pigment layer disposed under the selective transmissive layer are irradiated with straight light to change the color to a color tone different from that under ordinary light. Observer. Further, in the observation method of the present invention, it is preferable to irradiate linear light from a slightly vertical direction of the polychromic material, and perform observation in a slightly vertical direction of the polychromic material. [Best Mode for Carrying Out the Invention] Hereinafter, a polychromic material of the present invention will be described in detail with reference to one embodiment of the present invention. Fig. 1 is a schematic cross-sectional view showing an embodiment of a multi-color-change material according to the present invention. The multi-color changing material 2 shown in the figure is attached to the substrate 4 and a multilayer structure in which two or more substances having different refractive indices are laminated in a multiple manner forms a line of light incident from a substantially perpendicular direction. A selective transmission layer 6 having a high transmittance, usually a high scattering reflectance of light, and a colored pigment layer 8 disposed under the selective transmission layer. The selective transmission layer 6 is laminated in multiple ways by using two or more substances with different refractive indices, and only the vertical direction of the multi-color-changing material is determined.

313810.ptd Page 13 548192 V. Description of the invention (5) and comparatively strong light incident on the near side pass through, but incident light at an angle away from the vertical direction of the polychromic material plays a role of reflection. In addition, in the multi-color-changing material of the present invention, since the selective transmission layer has a hue observed under normal light and a hue change observed under linear light, many of the present invention are observed by irradiating straight light When changing color materials, the color tone different from the color tone observed under normal light will be observed. Therefore, if it is a structure that adjusts the color tone in advance so that you can observe different patterns, patterns, and text, it can be improved. The design is pattern-proof, and since specific information is displayed only when the linear light is irradiated, it can be used for preventing forgery. Thus, since the color tone will change smoothly due to the light irradiated, it is preferable that the selective transmission layer contains a pearl agent capable of changing the color tone due to the interference of light. In addition, as the selective penetrating layer, a pearl agent may be used, and a transparent or translucent film capable of reproducing an image formed by a hologram and / or a light diffracted recording body may be used, and these are used to form a selection When the layer penetrates sexually, the design of the multi-color-changeable material can be significantly improved. Such an image reproduction body can be exemplified by a rainbow hologram capable of reproducing a stereoscopic image with white light, or a general hologram recording body capable of reproducing an image with laser light. In addition, although it has been briefly explained in the aforementioned conventional technology, the name of light used in this specification is defined here. In this manual, two kinds of light are mainly used, one is called normal light, and the other is called linear light. Usually light refers to sunlight or light environment using general lighting.

313810.ptd Page 14 548192 V. Description of the invention (6) Light, in particular, there is light of various wavelengths, and the direction of the aforementioned light is also the meaning of light in various directions. In contrast, linear light refers to the light in the same direction despite the existence of various wavelengths of light. Here, coherent light, such as laser light, can be described as a special form of linear light. In this context, laser light can also be included in linear light. The names of other lights, such as white light, are used in the same meaning as in general interpretation. When two types of light as defined above are irradiated to the multi-color-change material of the present invention as shown in Fig. 1, the following phenomenon occurs. Under ordinary light, for multi-color-change materials, light is incident from various directions, and it is difficult to cause interference on the pearl agent used in the selective transmission layer. At the same time, when holography and / or light diffraction recording is used, Due to the high brightness of the reproduced holographic image, the interference color of the selective penetration layer will be more difficult to identify. On the other hand, 'under the linear light', since highly directional light is irradiated from one direction, when viewed in the reflection direction reflected by the light, the pearl agent contained in the selective penetrating layer is strongly generated. The interference of light from the bow will cause the interference color to be observed as it would not be observed under normal light. ° In addition, the multi-color-change material of the present invention is preferably a color-reflecting light feedback which is different from the color tone of incident light. When such a multi-color-change material is used, different color tones can be observed under normal light and linear light, and as a result, higher pattern design can be imparted. The selective penetration layer of the polychromic material of the present invention having these properties,

313810.ptd Page 15 548192 V. Description of the invention (7) Che Jiajia The pearl agent for forming the selective penetrating layer is made of light interference powder and the light interference powder system is laminated in a multilayer manner. Those forming the aforementioned selective penetration layer. In order to explain the selective penetrating layer structure of the polychromic material of the present invention ', a cross-sectional view of one embodiment of the polychromic material of the present invention is shown in FIG. 2 as an enlarged selective penetrating layer structure. Here, the corresponding components in FIG. 1 corresponding to the same constituent elements are assigned the same reference numerals and descriptions thereof will be omitted. Among the multi-color-change materials shown in the figure, the 'selective transmissive layer 6 is a layer of light coated with mica, silicon dioxide, and titanium dioxide on the mica that becomes the mother core. The interference powder forms a pearl agent layer 10 in which the light interference powder is laminated in a multilayer manner. A colored pigment layer 8 is provided under the pearlizer layer. That is, the present embodiment in which the incident light 14 is incident on these structures passes through the hologram and / or light diffractive recording layer 12 made of a transparent or translucent film and enters f into the pearlizer layer 10, But the incident light is due to the powder inside the pearl agent layer. The layered structure of P is at the boundaries of the layers, and the powder really penetrates simultaneously. Qian, it was observed that the penetrated light was reflected at 2Λ 'and then at the boundaries of the layers inside the powder' and at the powder and powder ^ meaning boundary and penetrated the pearl agent layer 10 at the same time, and then passed through a transparent or translucent soft sheet The resulting hologram and / or light diffracted recording body layer 12. When the incident light 14 is normal light, because the direction of the light is not consistent, clear interference light cannot be seen on the pearlizer layer 10, and the incident light is reflected by the colored pigment layer 8 and then penetrates the pearl. The reason for the agent layer 10 is that the appearance and color of the powder as the mixed pearl agent layer 10 can be observed.

313810.ptd Page 16 548192 V. Description of the invention (8) The hue of the hue of the pigment layer 12. In contrast, if the incident light 14 is a straight line ^, due to the μ-, the powder of the pearl agent layer 1G causes interference ... 'As a result, the appearance color of the mixed pearl agent layer can be observed. The accent color ...: The hue of the hue of = 8. If you want to observe the selective transmission layer color ^ 400 lux (lux) or more. It is known that the illuminance of the linear light emitted here is here. In order to display the information in such a way that the linear light is irradiated, the powder of the agent is preferably a spherically-converted particle diameter of bm to 10 μm, more = k To 60 / zm. When k is called, it is difficult to produce interference color, and when = 100 // m, the directivity of the powder is reduced, so that the reflectivity is too low to obtain uniform interference in the plane of straight light. It is estimated that the thickness of the pearlizer layer formed by using powders of these particle sizes is more preferably 5 # n ^ 20 // m than 1 // m to 50 / z m '. When 1 // m or less, it is difficult to observe the interference color of the pearlescent layer JF passing through the linear light JF, and it is difficult to observe the colored pigment layer 8 under ordinary light under super light. In addition, in the polychromic material of the present invention, when the coating film is formed, the transparency of the pearl agent forming the selective transmission layer 6 is at a light transmittance of a wavelength of 4 2 0 to 7 000 nm = f It is preferably 40% to 90%. When it is 40% or less, the straight line = when the colored pigment layer 8 is observed under normal light, and when it exceeds 90%, it is difficult to observe the interference color of the pearlizer layer 10 under linear light. With Ni ^, ί: In terms of the brightness of the Daiji pearl agent, ‘1 part by weight of the pearl agent, Tron lacquer C product name’, 5 parts by weight of M made by Musashi Paint Co., Ltd.

Page 17 548192 V. Description of the invention (9) Mix 'coated on black paper with a thickness of 1 0 1 // m, after fully drying at room temperature, use CM- 100 0 0% trade name, Minota (Manufactured by Camera Co., Ltd.) When the 'measured luminance' in color measurement is marked with Hunter Lab value, the peak wavelength of the interference color is between 400 nm and 4500 nm (violet), preferably (a2 + b2) " 20, the peak wavelength of the interference color is from 45nm to 500nm (blue), preferably (a2 + b2) 1/2 g 30, and the peak wavelength of the interference color is from 50011111 to 55nm (Green) under (a2 + b2) " k 15 'peak wavelength of interference color is 55〇1111] to 6 ^ two to two (a; + b2) 1,13, edge wavelength of interference color is 6 center 7 Under 0 0 · (board to red), (aHb2) 丨 ⑨20 is preferred. If it can be related, when the linear light is irradiated, the dry shoulder of the pearl layer can be well observed. Clarity ^ In the present invention, the powder used as the pearl agent layer is preferably a < transparent Φ :, ϊj color changeable powder. For example, 'preferably the layered person of muscovite, two ,, moon, mother (sericite), kaolin, talc, etc. is a controversial, plate-like oxidation " and so on. Ethylene glycol ester) resin film, acrylic resin film, etc. scale powders, etc. are used as the core, and metal oxides such as aluminum oxide, metal oxide can be exemplified by titanium dioxide, iron oxide, oxygenated oxygen Bell diamond titanate, etc., but as long as it can show interference color gold flake powder: Asia is not limited to these. The inorganic salts of these metal oxides can be skin-coated 'according to the organic salts of these metal oxides or PVD (physical neutralization and hydrolytic decomposition method; or deposition such as CVD (chemical deposition) / deposition) get on. In addition, those who use inflammation + > horse colored pigment layer can be exemplified by polychromic powder, inorganic

Page 18 548192 V. Description of the invention (10) Toner powder, organic pigment, metal powder, fluorescent pigment, ink, coating, and mixture thereof. Polychromatic powder can be exemplified by muscovite Λ 垔 Φ mica, sericite, ridge Lamellar compounds such as soil talc, plate-like silicon oxide, plate-like titanium oxide, plate-like alumina, and other plate-like oxide PET resin films, organic molecular foils such as acrylic resin films, and scaly powders are used as mother cores. The powder whose surface is covered with a metal oxide is not limited to these as long as it is a metal oxide capable of exhibiting interference colors. Inorganic colored powder can be exemplified by iron red, yellow iron oxide, Iron pigments such as black iron oxide, titanium yellow titanium oxide, titanium cobalt green, and other titanium pigments. Cobalt blue, cobalt, aluminum blue, cerium blue, Cerulean blue,% deep cobalt violet and other cobalt pigments. Spinel (Spinel) structure of the inorganic colored powder, but as long as it is an inorganic colored powder, it is not limited to these. O organic pigments can be exemplified by azo dyes, xanthene dyes quinoline Organic dyes such as diphenyl methane-based dyes, anthraquinone dyes, or organic red pigments such as Permanent Red Herlington CN and phthalocyanine blue β-carotene Natural pigments such as K, Carthamin, and Carmine (: Cochen i: 1 le), but as long as they are organic pigments, they are not limited to these. 0 Metal powders can be exemplified by aluminum titanium, Silver and copper are not limited to these as long as they are non-ferrous metal powders. In addition, fluorescent pigment oil ink Λ coating can be used by the general marketer 1 as long as it does not hinder the discoloration of the irradiated light by the selective penetrating layer.

313810.ptd Page 19 548192 V. Description of the Invention (11)

Sexual people can use it without limitation. Such a multi-color-changing material of the present invention, the color presented by the selective transmission layer, can be changed due to the irradiated light. Because it is made only when the linear light is irradiated, the design is beyond The structure of the information can therefore give play to the Hungarian selective penetration layer. It is better to be fitted or integrally formed on paper counterfeit and prevent counterfeiting. '& cymbals and other substrates or objects, such as the original can view patterns and other discoloration to have a regression line of light, the angle of incidence into the penetrating layer, if you need to check the method from a distance. When the reflection is no longer visible, the more variable than the one described above, the specific resource selected and the normal light are detected, and the reflective ones are reflected by straight light. The color change must be more difficult when the color is changed from far away from the multi-line. Because of the light, colored pigments are better unknown from the nature. Therefore, there will be many color change materials to find the direct selectivity, even the layer. Because of the color powder of the invention, the color of the layer is preferably the same color changing material. For example, when the color changing material is irradiated with the light displayed directly on the color changing material, the layer is reversely penetrated by the vertical light of the vertical axis. In this light, the changeable color material 1 can be observed only because of the change in light, and the irradiated person can be observed. When selectively penetrating the incident incident light of the multi-color change of the invention, if the direction of the reflection of the text information to be reflected is irradiated with the angle of the linear axis, the angle of observation is farther from the vertical. When the vertical axis of many materials forms a straight line of light, the characters, patterns, or straight lines of light make their layers not the same as the selective anti-observation pattern or pattern with the right angle of the material. Therefore, when it ’s time to observe, it ’s only when the observation operation is more complex.

Less than h ^: bright color change f irradiates straight light. At this time, the observer also observes the vertical axis of the material at an angle of 30. ， ^ ^ 4 is the multi-color-changing material of the present invention _ more than 20 〇 From the other, let's talk about people. π TT w and the properties of various pearl agents which are more suitable for pearl discoloration materials are used to check the discoloration and the transmittance of the powder as shown in the powder. The cross color is checked. ~ Degree ▲ is a complex compound that mixes 1 mile of light interference powder, lacquer (trade name, manufactured by Musashi Coatings Co., Ltd.) is uniform, / Tron cleaner, coated with rods, and robbed-uniformly knife knife ~ Pearl pearl PET film (^ ^ C〇 ^ ter) was prepared, coated in various thicknesses at Λ pair temperature for ^ 3 minutes, and this film was prepared. As described in Figure 3, GCMS was measured using variable angle spectrometry. -3 type TM (trade name, manufactured by Murakami Color Technology Research Institute), which fixes the original light j at an incident angle from the vertical axis of the film 32 as a measurement target to-^ production, and the light receiving angle becomes 0 degrees The measurement of the Lab value is performed at the position 34 and the position 36 of the j η :. _ Further, as the light-interfering powder to be measured, those having interference colors of yellow, red, purple, blue, and green are used. The thickness of the pearl agent coated on the PET film is used to make the gap of the bar coating machine to be 0.025mm, 0.050mm, 0.101mm, and 0.204mm. These dry coating films have a film thickness of about 4 // m, about 8 // m, about 16 // m, and about 32 // m, respectively. The measurement results are shown below.

313810.ptd Page 21 548192 V. Description of the invention (13) [Table 1] Lab value when the gap of yellow light interference powder bar paint machine is affected by _ A ^ l5_Lab value when the light angle is 40 degrees (a40 ~ a〇) + (^ 4〇- ^ 〇) {(a4〇-a〇) 2+ (b40-b0) 2}, / 2 Yiguang b〇 乙 40 a4〇b4〇0.025mm 29.86 ^ _ ^ 0.82 -0.91 191.41- 5.80 59.53 3677.7940 60.64481841 0.050mm 35T〇Γ ~~ -2.55 194.67 -7.71 65.30 4645.4834 68.15778312 0.101 mm 4 ^ 38 ^ -1.36 u-- -2.10 196.33 -11.31 79.01 6677.8346 81.71801882 0.204mm 55.7Γ ~~--1.80 ----- --1.08 198.71 -14.47 94.12 9223.5689 96.03941326 ------ [Table 2] Lab value at 0 ° light receiving angle for red light interference powder bar coating machine Lab value at 40 ° light receiving angle Lab value \ 2 1 / 1 * U {(a4〇-a0) 2+ (b40-b0) ·} 丨 / _ L〇b〇L4〇3 * 40 ^ 40 (a40-a〇) + (〇4〇D〇j 0.025mm 19.35 3.34 ------- -5.72 172.14 17.99 9.84 456.7361 21.37138507 U, U50mm 27.65 3.71 -7.28 158.28 33.30 8.37 1120.4906 33.47373000 0.101mm 34.88 5.08 -7.83 82.00 36.54 3.47 1117.4216 33.42785665 0.204mm 47.87 6.12 -6.64 13.29.96 63.96 63.96 3687.3745 60.72375565 [Table 3] Lab value at a light receiving angle of 0 degrees for a purple light interfering powder bar coating machine Lab value (a4〇-a〇)-+ (b40-b〇)-~~ * ------- Π Π 0 < w — L〇a〇b〇L40 a4〇 ^ 40 {(a4〇-a0) 2+ (b40-b0) 2}, / 2 υ.υζ jmm Π Π ... 23.77 4.66 -9.89 164.89 28.63 -21.28 704.2930 26.53851917 u.ujumin Π 1 Λ 1-27.71 4.30 ~ -10.43 155.55 —37.05 -31.99 1537.3961 39.20964295 —yj. UJlmm Π 0 A / 1 34.48 5.51 -11.80 148.8T ~ 49.28 -42.13 2835.7218 53.25149575 — U-2U4mm 46.38 5.55 -10.38 135.25 ~~ 78.71 -58.73 7690.1081 87.69326143 [Table 4] Lab value when the light receiving angle of the blue light interference powder bar painter is 0 degrees and the light receiving angle is 40 degrees Lab value (a40-a0)-+ (b40-b0)-{(a40-a0) 2+ (b40-b0) 2}, / 2 L〇b〇B 40 ^ 40 b40 0.025mm 19.43 -0.34 -10.01 160.72 11.57 -30.60 543.8506 23.32060462 ___ 2i〇50mm 28.22 -0.54 -12.61 157.78 16.41 -56.41 2205.7425 46.96533296 〇101mm 34.56 -1.09 -14.65 152.50 21.57 -81.09 4927.7492 70.19792874 0.204mm 48.36 "-2.94 -14. 40 134.32 23.36 -92.39 6774.1301 82.30510373 Page 22 313810.ptd 548192 V. Description of the invention (14) [Table 5] Lab value when the light receiving angle of the green light interference powder bar coating machine is 0 degrees and the light receiving angle is 40 degrees Lab value (a40-a〇)-+ (b40-b0)-{(a4〇-a〇) 2+ (b40-b0) 2} I / 2 L〇a〇b〇 B 4〇a40 ^ 40 0.025 mm 27.49 -5.76 -2.59 169.05 -25.23 5.11 438.3709 20.93730881 0.050mm 35.54 -6.81 -3.66 172.16 -48.94 6.69 1882.0594 43.38270854 0.101mm 41.02 -7.47 -3.81 165.83 -54.13 7.24 2299.2581 47.95057977 0.204mm 57.10 -2.67 -9.07 -2.67 -9.07 -2.67 -2.67 -2.68- 66.17307685 According to the above results, it is known that the pearl agent used in the present invention and the light-interfering powder used in the pearl agent are preferably the Lab value measured in the aforementioned angle-varying gloss measurement can meet 20 ^ {(a4〇- a〇) 2+ (b4〇-b〇) 2} 1/2 < 80 (Here, a 4〇 and b 4 represent positions at a light receiving angle of 40 degrees (position 3 shown in FIG. 3 6 ) A and b values of the measured L ab values, a 0 and b 0 represent the Lab measured at the position (position 34 shown in FIG. 3) at a light receiving angle of 0 degrees Values of a and b. ). When it is larger than this, it is difficult to observe the colored pigment layer under the selective penetration layer, and when it is smaller, sufficient discoloration is not obtained. Next, the transmittance was checked. Measurement of transmittance '1 part by weight of light-interfering powder was uniformly dispersed and mixed with 15 parts by weight of Nitlon varnish (trade name, manufactured by Musashi Paint Co., Ltd.) to make a pearl agent, which was painted with a bar. The machine is coated on transparent PET film (thickness 100 // m) in various thicknesses, and dried at room temperature for 30 minutes to prepare the measurement target.

Page 23 313810.ptd 548192 r ~ ------------ 5. Description of the invention (15) Film. The transmittance of this film was measured using a visibility measuring device (h a z e m e t er) HR 1 0 0 TM (trade name: manufactured by Murakami Color Technology Research Institute). The light source was a C light source (J I S K 7 3 6 1). In this measurement, the light-interfering powders to be measured are those having interference colors of yellow, red, purple, blue, and green. The thickness of the pearl agent coated on the transparent PET film is made into a bar. The gaps of the paint machine are 0 mm, 50 mm, 0.5 mm, 0.1 mm, and 2.04 mm. The thickness of these dry coating films is the same as that of the discoloration measurement described above, and is about 4 V π, about 8 // m, about 16 // m 'and about 3 2 // m, respectively. The measurement results are shown below. [Table 6] Full light transmittance 1¾7 lacquered 3 rooms $ 0.025mm

From the above results, it can be known that the pearl interference agent used in the present invention and the light-interference powder used by the pearl agent are preferably more than a predetermined transmittance τ in the above-mentioned transmittance measurement which can be more than 40%, and more preferably 50% $ τ $ 90% test coating. If it is larger than this, there is interference in the layer, and if it is larger than this, it is small to the colored pigment layer. It is difficult to observe the pearl when it is irradiated with straight light, and it ’s difficult to see the pain when it is exposed to normal light.

31381〇.ptd

548192 V. Description of the invention (16) The following is an example of the manufacture of light-interfering powders suitable for use in Sheming. Li-Ill system i 11 Potassium mica (10 to 6 «0100g suspended in 2 liters of deionized water. Heat the suspension at 7 5 C, adjust to p H i · 8 using dilute hydrochloric acid, First, ^ I1 ™! / Min was added to the SnC1 solution (derived from SnCl4 • g in deionized water and 0.75 g of hydrochloric acid) and covered with Sn0. 32% sodium hydroxide was used to maintain a certain pH. Disturb for 15 minutes'. Then, at the same pH / temperature condition, push it at 1.5 liters / add TiC1 solution (TiCl4 4．00g / 1), use 32% hydrogen end point. ϊ Γ Hold Γ fixed, covered with Ti0 miscellaneous lines. Achieve 2 times of thin green solution ^ whole coating 'Continue to stir for 15 minutes, then use sodium hydroxide for 10 minutes: within 15 minutes) " is 8. 〇 ， Then, continue stirring

Then, yT solution (obtained from SiO 27 ^ weekly PH at a rate of 3ml / min by adding sodium silicate to dissolve Si. 2 / of sodium silicate 7. 3g and deionized water 80ml), in Within 1 f 8 continued, 15 minutes, * adjusted with dilute hydrochloric acid (approximately, after and added in the same way as before; break was broken / broken ff 2 Ti〇2t. 3 times to achieve the green comparison end of the filtration, washing, Yes 磬 Continue stirring for 15 minutes, then, attract the pigment ^, dry, and calcinate at 850 ° C for 30 minutes. 1st layer 2nd layer 3rd layer about 170 nm about 8 5 nm Approx. 2 6 0nm

3l3810.ptd Page 25 1 The pigment has a strong green interference color. The sections of the Ti0 layer are as follows. 548192 V. Description of the invention (17) The thickness of the intermediate layer of S i 0 2 is about 5 nm. In addition, in this manufacturing example, it is a manufacturing method of a powder having a green interference color. However, in the aforementioned manufacturing example, if the thickness of the Ti layer covered is adjusted, yellow, red, purple, and blue colors can also be manufactured. Different colors and other colors interfere with the powder. Example 1 First, a transparent rainbow holographic film with a thickness of 38 // in that can reproduce stereoscopic images in white light is used as a pearl agent layer with high transparency and a multi-chromic powder having high brightness. The pearl agent with white appearance and purple interference color obtained in Example 1 was dispersed in Nitlon varnish, painted with a gap of 0.11 mm, and dried at 70 ° C for 20 minutes to form a selection. Sexual penetration layer. Next, as a colored pigment layer, Plibel BPTM (trade name, manufactured by Shiseido, a polychromic pearl agent with an appearance color of blue and a purple interference color) was dispersed in the Nitlon varnish with a gap of 0. 1 0 1 mm is applied under the selective penetration layer, dried at 70 ° C for 20 minutes, and then pigment-grade titanium oxide is dispersed in the Nitlon varnish with a gap of 0.1 1 0 mm for painting and drying at 70 ° C for 20 minutes. From the above steps, the polychromic material of the present invention (Example 1) was prepared. ° Example 2 First, a layer of transparent rainbow holographic film with a thickness of 19 // m which can reproduce a three-dimensional image with white light was used as a pearl. Polychromatic powder with high transparency in the agent layer and high brightness, and the appearance obtained in Production Example 1

313810.ptd Page 26 548192 V. Description of the invention (18) The pearl agent with white color and purple interference color is dispersed in Nitlon varnish, painted with a gap of 0.1 mm, at 70 ° Dry at C for 20 minutes to form a Θ selective transmission layer. Then, 'as a colored pigment layer, spinel blue (C0A 1220J was dispersed in Nitlon varnish, and the layer under the selective penetration layer was coated with a gap of 0.1 · 0 mm' at 70 C After drying for 20 minutes, the pigment-grade titanium oxide was dispersed in Nitlon varnish, coated with a gap of 0.1 · 0 丨 mm, and dried at 70 ° c for 20 minutes. $ From the above steps To obtain the polychromic material of the present invention (Example 2) ° ^ ^ 'Regarding the pearl agent layer and the colored pigment layer, in the polychromic material of the present invention prepared by using the several materials described in Example κ In order to confirm the discoloration under normal light and linear light with the combination of these materials, the following comparative examples are also prepared during the test, and the same experiment is performed. Comparative Example 1 White light reproduces a stereoscopic image with a thickness of 3 8 // m. Transparent color = full ^ under the photographic film. The color of Priebel Bp TM (trade name, manufactured by Shiseido Corporation) is blue and it can show purple interference. Multi-color discoloration pearl agent) dispersed in Nitroon varnish with a gap of 0 · 1 0 1 mm for coating, dried at 70 C for 20 minutes, and then dispersing pigment-grade titanium oxide in Nitlon varnish, 'coated with a gap of 0 · 1 0 1 mm, and dried at 70 ° C In 20 minutes, Comparative Example 1 was prepared. Comparative Example 2

313810.ptd 548192 V. Description of the invention (19) Under the layer of transparent rainbow holographic Zhao 4-phase film with a thickness of 38 // m which can reproduce stereoscopic images with white light, Priepel BPTM (trade name, appearance of Shiseido Corporation) The polychromic pearl agent whose color is blue and showing purple interference color) is dispersed in Nitlon varnish, coated with a gap of 0.22 mm, and dried at 70 ° C for 20 minutes, and then Pigment-grade titanium oxide was dispersed in Nitroon varnish, coated with a gap of 0_101 mm, and dried at 70 ° C for 20 minutes to obtain Comparative Example 2 c) Comparative Example 1— in white light The lower layer of a transparent rainbow holographic film with a thickness of 19 // m is reproduced. The spinel monitor (CoA 1 20 4) is dispersed in the nitron varnish with a gap of 0.101n [im, After drying at 70 ° C for 20 minutes, the pigment-grade titanium oxide was dispersed in Nitlon varnish, and coated with a gap of 0.1 · 0.1 mm, and dried at 70 ° C for 20 minutes. . Comparative Example 4 A spinel monitor (CoA 1 20 4) was dispersed in a Nitlon varnish with a gap of 0 · under a transparent rainbow holographic film having a thickness of 19 / m which can reproduce a stereoscopic image in white light. 2 0 2 mm for painting, • After drying at 7 ° C for 20 minutes, disperse pigment-grade titanium oxide in Nitlon varnish, and paint with a gap of 0 · 1 0 1 mm, at 7 0 ° Dry for 20 minutes at C. In the experiment, each sample formed in the above manner was subjected to an experiment by visual observation under normal light and linear light. Evaluation method Generally under light

313810.ptd Page 28 548192 V. Description of the invention (20) As normal light, observe each sample under diffused light, and determine whether it has been discolored in a selective penetrating layer that cannot be identified under the holographic film. Evaluation. ◦: Discoloration of the selective transmission layer cannot be discerned △: Discoloration of the selective transmission layer cannot be discerned X: Discoloration of the selective transmission layer can be discerned Straight line light is irradiated from the vertical direction of each sample under the linear light of the discernable transmission layer and visually observed Each sample was observed in a slightly vertical direction, and whether or not a discoloration pattern constituting a selective penetrating layer capable of recognizing the lower layer of the holographic film was evaluated. 〇: Discoloration of the selective penetration layer can be identified △: Discoloration of the selective penetration layer is difficult to discern X: Discoloration of the selective penetration layer cannot be discerned, [Table 7]

Example 1 under normal light under linear light Example 1 〇 Example 2 〇 Comparative Example 1 ΔΔ Comparative Example 2 Δ Δ〇 Comparative Example 3 〇 · Comparative Example 4 〇X As shown in Table 7, high transparency is not required and has Comparative Example 1 consisting of a pearl agent with high brightness and a pearl agent with low light interference only shows good results because it cannot recognize discoloration under normal light, but in a straight line

313810.ptd 548192 V. Description of the invention (21) The discoloration caused by the interference of the pearl agent under the light The discoloration caused by the low luminosity of the light is less improved under the light interference line light. The results in Comparative Example 3 of the penetrating layer were good, but even appropriate. In addition, the pigment layer improves the characteristics of the sample. In contrast, in the selective transmission layer, a transparent pearlescent interference color cloth is used to irradiate ((a 40-a 〇) 2+ (b 40-b 0) 2) on black paper and change the color in a linear light. The examples described in the present invention are as follows. As described above, this light exhibits good discoloration resistance or anti-counterfeit and anti-counterfeit layers. At the same time, it can be made into a thin film with a small particle size. However, the peak wavelength of the color in the present invention is not less than 45 nm. 〇〇nm, not suitable due to sufficient. In Comparative Example 2, the layer thickness of the pearl agent was doubled, and although it was straight, it was possible to identify the interference due to interference to some extent. Perturbative pearl agent is only composed of pigments. • π cannot recognize discoloration under normal light, but it shows that the discoloration is still unrecognizable when irradiated with straight light. In Comparative Example 4, which did not double the layer thickness, it still failed. Example 'f. Examples 1 and 2 of the present invention are based on the selection of pearl agents with the same clarity and high brightness, and the front peak wavelength is from 40 nm to 4500 nm, and the brightness measured during coating is in order to meet 17 For 20 people, it is difficult to recognize and show clear and good discoloration under ordinary light. The polychromic material is not limited to the polychromic material issued here: The polychromic material in is due to the irradiation. J can use such discoloration to judge the artwork. Furthermore, due to the formation of the selective T: Zhu agent, the material can be manufactured in relatively simple steps. The observation method of the body's multi-color changing materials can be obtained by directly

Brother 30, page 548192 V. Description of the invention (22) The color of the light is different from that under normal light. In addition, such a discoloration property can be used to judge a fake.

313810.ptd Page 31 548192 Brief description of drawings [Simplified description of drawings] Fig. 1 is a schematic cross-sectional view of one embodiment of the multi-color-change material of the present invention. Fig. 2 is an enlarged cross-sectional view of an embodiment of the polychromic material according to the present invention in a selective penetration layer structure. Fig. 3 is an explanatory diagram illustrating a method for measuring discoloration shown by a pearl agent used in the present invention and a light-interfering powder used in the pearl agent. FIG. 4 is a schematic explanatory diagram of a conventional retroreflective material. [Explanation of component symbols] 2 Polychromic material 4 Substrate 6 Selective transmission layer 8 Colored pigment layer 10 Pearl agent layer 12 Diffraction recorder layer 14 Incident light 30 Light source 32 Film 34 Position at a light receiving angle of 0 ° 36 Light receiving angle- 4 Position at 5 degrees 100 Retroreflective material 102 Substrate 104 Glass beads 106 Resin layer 108 Incident light 110 Feedback light 112 Interfering substance layer

313810.ptd Page 32

Claims (1)

548192 6. Scope of patent application 1. A multi-color-change material, which is characterized by a multilayer structure in which two or more substances with different refractive indices are laminated by a multilayer method to form a linear light incident from a slightly perpendicular direction, and has a high transmittance. Usually, a selective transmission layer having a high scattering reflectance of light, and a colored pigment layer disposed under the selective transmission layer. 2. The polychromic material according to item 1 of the patent application, wherein the selective penetrating layer contains a pearl agent. 3. The polychromic material according to item 2 of the patent application scope, wherein the selective transmission layer contains a hologram and / or light diffracting recording body, and a layer formed by the foregoing hologram and / or light diffracting recording body. A pearl agent layer made of pearl agent. 4. If the multi-color-change material of the second or third item of the scope of patent application, the pearl agent forming the selective penetrating layer is made of light interference powder, and the light interference powder system is The above-mentioned selective penetration layer is formed by laminating the layers. 5. The polychromic material according to item 4 of the scope of patent application, in which the pearl agent made of the light-interfering powder is 4 in the wavelength range of 4 2 0 nm to 7 0 0 nm. 0% or more, and when the brightness measured by coating the above-mentioned pearl agent on black paper is marked with the Lab value of Hunter, it can satisfy the following relationship: ((a 4〇_ a 〇) H (b 4〇 ~ b 〇) 2) 13 (Here, a4G and b4 represent the a and b values of the Lab value measured at the light receiving angle of 40 degrees, and aG and b represent the Lab measured at the light receiving angle of 0 degrees. Value a and b)). 313810.ptd Page 33 548192 6. Application scope of patent 6. A kind of multi-color-change material, which is characterized in that the multi-color-change material in any one of the first to fifth scope of patent application, the colored pigment layer is composed of Inorganic pigments, organic dyes, or any of a variety of color-changing pigments that can exhibit various colors if the direction of incident light is changed, or a plurality of pigments and dyes. 7. A multi-color-changeable material, characterized in that the multi-color-changeable material of any one of items 1 to 6 of the scope of patent application is attached or integrally formed on a substrate or article such as paper or film. 8. An observation method, characterized in that the transmittance of linear light incident from a slightly perpendicular direction is high and the light is normally scattered and reflected from a multilayer structure in which a multilayer structure in which two or more substances with different refractive indexes are laminated by a multilayer method is used. The selective penetration layer with a higher rate and the multi-color changing material formed by the colored pigment layer disposed under the selective penetration layer are irradiated with straight light to change the color to a color tone different from that under ordinary light. Observer. 9. The observation method according to item 8 of the scope of patent application, wherein the linear light is irradiated from a slightly vertical direction of the polychromic material, and the observer is observed in the slightly vertical direction of the polychromic material. 3i3810.ptd Page 34