WO2003008330A1

WO2003008330A1 - Multi-discoloring material and observation method therefor

Info

Publication number: WO2003008330A1
Application number: PCT/JP2002/007240
Authority: WO
Inventors: Masayoshi Wada; Kenichi Sakuma; Tsuyoshi Miyamoto; Yukie Yoda; Asa Kimura
Original assignee: Shiseido Co., Ltd.
Priority date: 2001-07-17
Filing date: 2002-07-17
Publication date: 2003-01-30
Also published as: JPWO2003008330A1; TW548192B

Abstract

A multi-discoloring material characterized by comprising a selectively transmitting layer consisting of a multi-layer structure formed by laminating at least two substances different in refractive index in layers and being high in transmittance to a linear light beam incident from an almost vertical direction and also high in scattering reflectance to a regular light, and a colored pigment layer disposed on the lower layer of the selectively transmitting layer, the selectively transmitting layer preferably containing a pearl agent. An observation method characterized by irradiating the multi-discoloring material with a linear light beam to observe the material discolored to a tone of color different from that under a regular light.

Description

Description Multicolor material and method for observing the same This application claims the priority of Japanese Patent Application No. 2001-216875 filed on Jul. 17, 2001, which is incorporated herein.

[Technical field]

The present invention relates to a discolored material exhibiting a different color tone depending on irradiated light and a method for observing the material, and particularly to an improvement in the composition of the material and a method for observing the material.

[Background technology]

Many materials having discoloration properties have been developed for the purpose of appearance design or to prevent forgery or falsification. Examples of such materials include a rainbow hologram film that reproduces a three-dimensional image while shining iridescent when illuminated with white light. A pearlescent agent coated with titanium oxide on mica, a multi-layer deposition with a controlled refractive index and film thickness. Examples include powders that cause interference by a film.

In recent years, there has been seen a combination of these materials for the purpose of imparting designability and further preventing forgery and falsification. For example, Japanese Patent Application Laid-Open No. 2000-81831 discloses a technique using a retroreflective material and a multicolored pearl pigment. In the technology described here, the retroreflective material is provided with an interfering substance layer that changes the color by causing interference with incident light using a multicolored pearlescent agent, and is used to control sunlight and illumination light. Under such normal light, light enters the retroreflective material from various directions, so that no interference color due to the interference substance layer is observed, and when light with a uniform traveling direction (referred to as linear light) is irradiated. However, interference colors due to light interference were observed in the interference substance layer from almost the light incident direction.

However, it was difficult to reduce the thickness of articles using retroreflective materials.

Fig. 4 shows a schematic explanatory diagram of a conventional retroreflective material.

The retroreflective material 100 shown in FIG. The retroreflectivity is given by the beads 104, and the focal length of the glass beads is adjusted by adjusting the layer thickness of the resin layer 106 to which the glass beads are fixed, and is described on the substrate 102. When characters and the like can be observed, the incident light 108 is fed back substantially in the direction of the incident light, and the return light 110 is obtained. Then, the color is changed by means such as providing an interference substance layer 112 that changes color by light interference between the substrate 102 and the resin layer 106.

In this way, the retroreflective material 100 is provided with a glass bead layer 104 or the like in order to provide retroreflectivity of light, and the diameter of the glass beads is very large compared to the particle size of the interfering substance. It was large and it was difficult to reduce the film thickness.

Further, when manufacturing the retroreflective material, an interfering substance layer is provided on a substrate, and a resin layer is provided thereon while adjusting the focal length of the glass beads so as to maintain the focal length. Further, glass beads are provided on the resin layer. Are manufactured by spraying them so that they are in a single layer, and fixing them so that the adjusted focal length is not lost.Each process requires precise work, and the number of processes increases the cost. There was also a problem of doing so.

[Disclosure of the Invention]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is capable of being formed into a thin film and relatively easily manufactured. It is an object to provide a material that can be recognized and to provide a method for observing the material.

In order to achieve the above object, the multicolor material according to the present invention has a multilayer structure in which two or more substances having different refractive indices are multiplexly laminated, and has a high transmittance of linear light incident from a substantially vertical direction, It is characterized by comprising: a selective transmission layer having a high scattering reflectance of ordinary light; and a colored pigment layer disposed below the selective transmission layer.

Further, in the multicolor-changeable material of the present invention, the selectively permeable layer preferably contains a pearl agent.

Further, in the multicolor material according to the present invention, the selective transmission layer is a pearl agent layer comprising a hologram and / or optical diffraction recording material and a pearl agent formed below the hopper gram and / or optical diffraction recording material. It is preferable to include Further, in the multicolor-changeable material of the present invention, the pearl agent forming the selective transmission layer is made of a light-interfering powder, and the light-interfering powder is multiply laminated to form the selective transmission layer. Preferably, it is formed.

Further, in the multicolor-changeable material of the present invention, the pearl agent comprising the light coherent powder has a transmittance of light of 40% or more in a wavelength range of 420 nm to 700 nm, and It is preferable that the following relationship be satisfied when the luminance measured by applying the agent on black paper is represented by the hunter's Lab value.

((a _{J 0} -a _o ) ² + (b— _{1 0} — b ₀ ) ^ ² ≥ 1 3

(However, a ₀ and b ₄₀ are the a and b values of the L ab value measured at the position of the acceptance angle of 4 °, a. And b are the L values measured at the position of the acceptance angle of 0 °. The a value and the b value of the ab value shall be indicated.)

Further, in the multicolor-changeable material of the present invention, the colored pigment layer may be any of a non-pigment, an organic dye, or a multicolor-changeable pigment that exhibits various colors when the incident direction of light is changed, or a plurality of these pigments and dyes Preferably, it consists of

It is also preferable that the multicolor-changeable material of the present invention is adhered or integrally formed on a substrate or an article such as paper or film.

In addition, the observation method of the present invention has a multilayer structure in which two or more substances having different refractive indexes are multiplexed and stacked, and has a high transmittance of linear light incident from a substantially vertical direction, and a high scattering reflectance of ordinary light. A multicolor material composed of a selective transmission layer, a colored pigment layer disposed below the selective transmission layer, and a linear light is irradiated with a linear light to change the color to a color tone different from that under normal light. And features.

Further, in the observation method of the present invention, it is preferable that the linear light is irradiated from a substantially vertical direction of the multicolored material, and the multicolored material is observed in a substantially vertical direction.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of one embodiment of the multicolor material according to the present invention.

FIG. 2 is a cross-sectional view of an embodiment of the multicolor material according to the present invention in which the configuration of the selective transmission layer is enlarged.

Fig. 3 shows the pearl agent used in the present invention and the light interference powder used in the pearl agent. It is explanatory drawing for demonstrating the measuring method of discoloration.

FIG. 4 is a schematic explanatory view of a conventional retroreflective material.

[Best Mode for Carrying Out the Invention]

Hereinafter, the multicolor material of the present invention will be described in detail with reference to an embodiment of the present invention.

FIG. 1 shows a schematic cross-sectional view of one embodiment of the multicolor material according to the present invention. The multicolor material 2 shown in the figure is adhered to the base 4 and has a multilayer structure in which two or more substances having different refractive indices are multiply laminated, and the transmittance of linear light incident from a substantially vertical direction is increased. It comprises a selective transmission layer 6 having a high scattering reflectance of ordinary light and a colored pigment layer 8 disposed below the selective transmission layer.

The selective transmission layer 6 transmits only light of relatively high intensity that is incident from the vertical direction of the multicolor material and from the vicinity thereof by multiplexing two or more substances having different refractive indexes. Light incident at an angle that deviates greatly from the vertical direction of the multicolor material acts to be reflected.

In the multicolor material according to the present invention, the selective transmission layer changes the color tone observed under normal light and the color tone observed under linear light. When the pigment material is observed, it is observed in a color tone different from that normally observed under light. Therefore, by adjusting the color to be changed in advance so that different patterns, patterns, characters, etc. can be observed, the design can be further enhanced, and only when irradiated with linear light. In order to display specific information, it can be used to prevent counterfeiting.

In order to more suitably change the color tone by the light irradiated as described above, the selective transmission layer preferably contains a pearl agent that changes the color tone by light interference.

In addition, it is possible to use a transparent or translucent film capable of reproducing an image composed of a hologram and / or an optical diffraction recording material together with a pearl agent for the selective transmission layer. When a transparent layer is formed, the design of the multicolor material can be significantly improved. Examples of such an image reproducing body are a rainbow hologram that can reproduce a stereoscopic image with white light, and a general aperture that can reproduce an image with laser light. Recording medium.

Although briefly described in the prior art, the name of light used in this specification is defined here. In this specification, two main types of light are used. One is called ordinary light, and the other is called linear light.

Ordinary light is light in sunlight or light environment by general lighting. Specifically, light of various wavelengths exists and the light travels in various directions. To say.

On the other hand, linear light refers to light in which light of various wavelengths exists but whose traveling directions are aligned. Coherent light such as laser light can be said to be a special form of linear light. In this sense, laser light is also included as straight light.

Other names of light such as white light are used in the same meaning as those generally interpreted. ·

When the two kinds of light defined as above are irradiated on the multicolor-changeable material of the present invention as shown in FIG. 1, the following behavior is exhibited.

Under normal light, light enters the multicolor material from various directions, making it difficult for the pearling agent used in the selective transmission layer to interfere with the light, and when using holograms and Z or optical diffraction recording materials. Since the brightness of the reproduced hologram image and the like is high, the interference color of the selective transmission layer becomes more difficult to recognize.に対して On the other hand, under linear light, highly directional light is emitted from one direction, so when observed in the reflection direction where the light is reflected, the light interference power S It occurs strongly and makes it possible to observe interference colors that could not be observed under normal light.

It is preferable that the multicolor material in the present invention returns colored light having a color tone different from the color tone of the incident light. When such a multicolored material is used, different color tones are observed under normal light and under linear light, so that it is possible to impart higher designability.

In the selective transmission layer of the multicolor material of the present invention having such properties, the pearl agent forming the selective transmission layer is made of light coherent powder, and the light coherent powder is Multiple layers Preferably, the selectively permeable layer is formed.

FIG. 2 is a cross-sectional view of an embodiment of the multicolor material according to the present invention in which the configuration of the selective transmission layer is enlarged to explain the structure of the selective transmission layer of the multicolor material according to the present invention. In the figure, components corresponding to the same components as those in FIG. 1 are denoted by the same reference numerals, and description thereof is omitted.

The multicolor material 2 according to the embodiment of the present invention shown in FIG. 1 is composed of a selectively permeable layer 6, a light interference powder coated on a mica serving as a mother nucleus in the order of titanium dioxide, silica, and titanium dioxide. And a pearl agent layer 10 in which the light coherent powder is multiply laminated is formed. A colored pigment layer 8 is provided below the pearl agent layer 10.

When the incident light 14 enters the present embodiment having such a configuration, it passes through the hologram made of a transparent or translucent film and the Z or optical diffraction recording layer 12 and enters the pearl agent layer 10. The incident light is transmitted while being reflected at the boundary between each layer and the boundary between the powder and the powder due to the layered structure inside the powder of the pearl agent layer. Then, the transmitted light is reflected by the colored pigment layer 8, transmitted through the pearl agent layer 10 again while being reflected at the boundaries between the layers inside the powder and at the boundaries between the powders, and again transparent or semi-transparent. It is observed through the hologram made of a transparent film and the Z or optical diffraction recording layer 12.

When the incident light 14 is ordinary light, since the traveling directions of the light are not the same, clear interference light in the pearl agent layer 10 is not recognized, and the incident light is reflected by the colored pigment layer 8 and becomes pearl again. As a result, the color of the powder of the pearl agent layer 10 and the color tone of the colored pigment layer 12 are observed as a mixed color.

On the other hand, when the incident light 14 is linear light, the traveling directions of the light are the same. The interference of the powder of the pearl agent layer 10 occurs, and the interference color is observed. As a result, the appearance color of the powder of the pearl agent layer 10, the color tone emphasized by the interference, and the color pigment layer 8 The color tone will be observed as a mixed color tone. In order to discolor the selective transmission layer and to observe the colored pigment layer well, it is preferable that the illuminance of the irradiated linear light be 40 Olux or more.

In order to display information by irradiating linear light in this way, the powder used as a pearling agent has a spherical equivalent particle diameter of 1 μπ! It is preferably from 100 to 100 μm, more preferably from 5 μm to 60 / im. If it is less than 1 μm, it becomes difficult to produce interference colors, If it exceeds 100 / m, the orientation of the powder will be reduced, and the reflectivity will be too low to obtain uniform interference in the plane of linear light.

The thickness of the pearl agent layer formed by using powder having such a particle size is 1 m to 50 μm, and more preferably 5 μm to 2 Q!丄 m is preferred. If it is less than 1 μm, it becomes difficult to observe the interference color of the pearl agent layer 1 ° with linear light, and if it exceeds 50 μm, it becomes difficult to observe the colored pigment layer 8 with ordinary light.

In the multicolor material of the present invention, the transparency of the pearl agent forming the selective transmission layer 6 is such that when formed into a coating film, the transmittance of light in a wavelength range of 420 nm to 700 nm is improved. It is preferably from 40% to 90%. If it is less than 40%, it becomes difficult to observe the colored pigment layer 8 with ordinary light, and if it exceeds 90%, it becomes difficult to observe the interference color of the pearl agent layer 10 with linear light.

Then, the luminance of such a pearl agent (manufactured by Musashi paint) Pearl agent 1 part by weight two Torontari Arakka ^TM 1 5 parts by weight were mixed and stirred, was applied in a thickness of 1 0 1 Myuitaarufa black paper, After drying to room temperature at room temperature and measuring the color with CM- ¹⁰⁰⁰⁰ 0 (Minolta Camera Mori), the measured brightness is the interference color when expressed in Hunter's ^Lab value. (A ² + b ² ) ¹ ' ² ≥ 20 when the peak wavelength of the wavelength is 400 nm to 450 nm (purple), the peak wavelength of the interference color is 450 nm to 500 nm (blue) Then, the peak wavelength of the (a ² + b ² ) ^^ S CK Chihiro color is 500 11 n! In ~ 5 5 0 nm ^{^{(green), (a 2 + b 2}} ) the ^{1 2} 1 5, the peak wavelength of the interference Wataruiro is 5 5 0 nm~6 0 0 nm ^{^{(yellow), (a 2 + b 2}} ) ^{1 2} in ≥ 1 3, the peak wavelength of the interference color 6 00 nm~7 0 0 nm (orange-red), it is preferable that a ^{^{^{(a 2 + b 2) 1}}} 2 ≥ 2 0. If such a relationship can be satisfied, the interference of the pearl agent layer can be favorably observed when irradiating linear light.

In the present invention, as the powder used in the pearl agent layer, it is preferable to use a discolorable powder having high transparency and high brightness. For example, lamellar compounds such as muscovite, biotite sericite, force-oliminite, talc, plate-like silica, plate-like titanium oxide, plate-like acid such as plate-like alumina, PET resin film, acrylic resin It is preferable to coat with a metal oxide a multi-layer using scaly powders such as organic polymer foil such as a film as a mother nucleus.

Examples of the metal oxide to be coated include titanium dioxide, iron oxide, silicon oxide, aluminum oxide, cobalt oxide, lithium cobalt titanate, and the like. The metal oxide is not particularly limited as long as it can be realized. The coating of these metal oxides on the flaky powder can be carried out by heating or neutralizing and hydrolyzing the organic or inorganic salts of these metal oxides, or by vapor deposition such as CVD or PVD. Examples of the material used in the colored pigment layer include polychromatic powder, inorganic colored powder, organic pigment, metal powder, fluorescent pigment, ink, paint, and a mixture thereof.

Examples of multicolor-changeable powders include layered compounds such as muscovite, biotite, sericite, olizonite, and talc, plate-like oxides such as plate-like silica, plate-like titanium oxide, and plate-like alumina, and PET resin. Films and powders in which the surface of the powder is coated with a metal oxide using scaly powder such as an organic polymer foil such as an acrylic resin film as a mother nucleus. It is not particularly limited to these.

Inorganic colored powders include iron pigments such as red iron oxide, yellow iron oxide and black iron oxide, titanium pigments such as titanium yellow, titanium oxide, and titanium cobalt green, cobanoleto blue, cobanoletanomiriphonore, kononoreto In addition to cobalt-based pigments such as green, cenorerian bonore, and cono-norreno-diolet deep, inorganic colored powders having a svinenole type structure are exemplified, but the inorganic colored powders are not particularly limited as long as they are inorganic colored powders.

Organic dyes include organic dyes such as azo dyes, xanthene dyes, quinoline dyes, triphenylmethane dyes, anthraquinone dyes, and organic pigments such as permaton red, helindon pink CN, and phthalocyanine blue; And natural dyes such as calsamine and cochineal. However, organic dyes are not particularly limited thereto.

Examples of the metal powder include aluminum, titanium, gold, silver, copper and the like, but are not particularly limited as long as they are colored metal powders.

Commercially available fluorescent pigments, inks and paints can be used as long as they do not impair the discoloration exhibited by the selective transmission layer to the irradiated light. Yes, there is no particular limitation.

As described above, the multicolored material of the present invention can change the color presented by the selective transmission layer depending on the irradiated light, so that the design can be improved, and the selective transmission can be achieved only when linear light is irradiated. Adhering to or integrating with a substrate or article, such as paper or film, because it is effective to distinguish counterfeit products and prevent counterfeit alteration by configuring so that specific information appears on the layer Preferably, it is formed.

The polychromatic powder as described above can change the color of the selective transmission layer and observe specific information such as characters, pictures, and patterns only when irradiated with linear light. It is preferable to irradiate and change the color to a color tone different from that under normal light for observation. The selective transmission layer of the multicolor material of the present invention does not have retroreflective properties. Therefore, when the multicolor material of the present invention is irradiated with linear light, the linear light is reflected at the same reflection angle as the angle of incidence incident on the multicolor material. Therefore, in order to observe the change in the color of the selective transmissive layer and the appearance of character information, pictures, patterns, etc., when it is irradiated with linear light, the light irradiated with the linear light is reflected in the direction in which it is reflected. Observations must be made. Then, when linear light is irradiated from an angle that is significantly off the vertical axis of the multicolored dye, the observer must also observe at an angle that is significantly off the vertical axis of the multicolored material. In the method, it is relatively difficult to find the angle at which the linear light is reflected, and the operation is complicated. Furthermore, since the selective transmission layer reflects incident light as it deviates greatly from the vertical direction, even if it is linear light, the colored pigment layer cannot be observed once the critical angle is exceeded. Therefore, when observing the polychromatic material of the present invention, it is preferable to irradiate the linear light at an angle of 30 °, more preferably 20 ° or less, from the vertical axis of the multicolor material of the present invention. At this time, it is preferable that the observer also observes the multicolored material of the present invention at an angle of 30 ° or even 20 ° or less from the vertical axis of the multicolored material of the present invention. Here, characteristics of various pearling agents suitably used in the multicolor material of the present invention and the light-interfering powder used in the pearling agent were examined for the characteristics of discoloration and transmittance.

First, the discoloration was examined.

Variable glossiness measurement

One part by weight of Hikari Senshin Powder and 15 parts by weight of -Tron Lacquer (Musashi Paint) are uniformly dispersed and mixed to form a pearl agent, and a bar coater is applied to a transparent PET film (thickness Ι Ο Ομπα). Each sample was coated at each thickness and dried at room temperature for 30 minutes to prepare a finolem to be measured.

As shown in Fig. 3, this film was ^{subjected to a goniospectrophotometer GCM} S-3 Using a light source 30 (manufactured by Murakami Color Research Laboratory), the light source 30 is fixed so that the angle of incidence is 1 45 degrees from the vertical axis of the film 32 to be measured. The ab value was measured at position 36, which is the degree.

In addition, as the light interference powder to be measured, those having interference colors of yellow, red, green, blue, and green were used. The thickness of the pearl coating applied to the transparent PET film was set at 0.025 mm, 0.050 mm, 0.101 mm, and 0.204 mm for the Perco overnight clearance. The thickness of these dried coatings was about 4 xm, about 8 zm, about 16 / zm, and about 32 mm, respectively.

The measurement results are shown below.

[table 1]

Yellow light interference powder

[Table 2]

Red light coherent powder

[Table 3]

Tinted light interference powder

Replacement form (Rule 26)

[Table 4]

[Table 5]

Green light interference powder

Considering the above results, the pearl agent used in the present invention, and the light interference powder used in the pearl agent, the Lab value measured in the gonio gloss measurement,

20≤ {(a ₄₀ -a ₀ ) ² + (b ₄₀ -b ₀ ) ² } ^1/2 times 80

(However, a _4t) b _{4 (),} the position of the light receiving angle of 40 degrees (the position 36 shown in FIG. 3) a value of the measured L ab value each smell and b values, a ₀ b. Indicates the a and b values of the Lab value measured at a light receiving angle of 0 degrees (position 34 shown in FIG. 3). )

It is preferable that the coating be performed so as to satisfy the following.

If it is larger than this, the colored pigment layer below the selective transmission layer becomes difficult to observe, and if it is smaller than this, sufficient discoloration cannot be obtained. Subsequently, the transmittance was examined. Replacement form (Rule 26) , Ten, lamrrm υ ^ .υο.υ

12 Transmittance measurement

One part by weight of the light coherent powder and 15 parts by weight of NITRON lacquer (Musashi Paint) are uniformly dispersed and mixed to form a pearl agent, which is then transferred to a transparent PET film (100 m thick) by Barco. First, the film was coated at each thickness and dried at room temperature for 30 minutes to prepare a film to be measured. The transmittance of this film was measured using a haze meter HR100 ™ (manufactured by Murakami Color Research Laboratory). The C light source (JI SK7361) was used as the light source.

Also in this measurement, as the light interference powder to be measured, a powder having interference colors of yellow, red, green, blue and green was used. The thickness of the pearl coating applied to the transparent PET film is as follows: Barco overnight clearance 0.025 mm, 0.05 Omm, 0.10 oo

lmm and 0.204 mm. These dried coating film thicknesses were about 4 rn, about 8 m, about 16 mm, and about 32 m, respectively, as in the measurement of discoloration.

The measurement results are shown below.

[Table 6]

Total light transmittance

-Coater- Yellow interference Red interference Blue interference Blue interference Green interference

Clearance powders Powdery powders Powdery powders Powdery powders

0.025 Marauder 77.3% 87.8% 87.7% 87.5¾ 81.5%

0.050 Awakening 67.1% 83.1% 84.2% 80.3¾ 71.5¾

0. 101 Maraud 58. 3% 79. 1¾ 76. 0% 63.7%

0. 204 Bandits 42. 3% 70.1% 73. 1¾ 66. 4% 48.7%

Considering the above results, the pearl agent used in the present invention, and the light interference powder used in the pearl agent, the transmittance measured in the transmittance measurement is 40% or more, more preferably 50% ≤ It is preferable that the coating be performed so as to satisfy τ ≦ 90%.

If it is larger than this, it is difficult to observe the interference of the pearl agent layer when irradiated with linear light, and if it is smaller than this, it becomes difficult to observe the colored pigment layer when irradiated with ordinary light.

As an example of the production of the optical coherent powder suitably used in the present invention as in the above, the following replacement paper (Rule 26) It looks like below.

Production example of optical coherent powder 1

Suspend 100 g of potash mica (10-60 μm) in 21 deionized water. The suspension was heated to 75 ° C, adjusted to p H 1. 8 with dilute hydrochloric acid, first, S in S n C 1 ₄ solution (de I O emissions Water 100 m] n C 1 j 2. 2 g coated with S N_〇 ₂ and obtained from concentrated hydrochloric acid 0. 75 g) 3. the addition in 3 m 1 / min. Keep pI-I constant using 32% sodium hydroxide solution.

Continued for 1 5 minutes question stirred, then, the same pH / temperature conditions, T i C 1 ₄ solution (T i C 14

Add 400 g / 1) in 1.5 ml and coat with TiO ₂ by keeping the pH constant with 32% sodium hydroxide solution. After reaching the second green endpoint, the coating was discontinued, stirring was continued for 15 minutes, the pH was adjusted to 8.0 with dilute sodium hydroxide solution (in about 15 minutes), and then stirred. 'Continue stirring for another 10 minutes.

_ Then, the addition of sodium silicate solution without adjusting the Ri- gamma a (obtained from S i 0 ₂ 27% of silicate sodium © beam 7. 3 g and deionized water 80 m l) in 3m 1 / min covering the S i 0 ₂ by. Thereafter, stirring continued for 15 minutes, adjusting the p H to 1.8 by dilute hydrochloric acid (about 1 0 min), and in the same way as described above T i C 1 ₄ solution second T i 0 More adding Coat _two layers. After reaching the third green comparison end point, the coating is interrupted, stirring is continued for 15 minutes, then the pigment is suctioned off, washed, dried and calcined at 850 ° C for 30 minutes.

The pigment obtained has a strong green interference color. Each part of the Ti 0 ₂ layer is as follows.

First layer: about 170 nm

Second layer: approx. 8511 m

The whole layer: about 26011 m

The thickness of the 5 i O 2 interlayer is about 5 nm.

In the present manufacturing example, it has been made in the production method of a powder having green SenWataruiro, in the above production example, by adjusting the thickness of T i 0 ₂ layers of coating, yellow, red,蓳It is also possible to produce powders with different interference colors, such as color, blue and the like. Example 1

First, a transparent rainbow holo that reproduces stereoscopic images with 38 / zm thick white light

Underneath the film, as a pearl agent layer, a multi-coloring powder having high transparency and high luminance, the pearl agent having a white appearance color obtained in Production Example 1 and exhibiting a purple interference color is used. It was dispersed in a top lacquer, coated with a clearance of 0.10 lmm, and dried at 70 ° C for 20 minutes to form a selectively permeable layer.

Next, Shiseido's Preveil BP ™ (a multicolor-changing pearl agent that exhibits a blue and purple interference color) as a colored pigment layer is dispersed in nitrone lacquer and selectively permeated at a clearance of 0.10 lmm. After applying to the lower layer and drying at 70 ° C for 20 minutes, further disperse pigment grade titanium oxide in ditron lacquer, apply with 0.10mm clearance and dry at 70 ° C for 20 minutes I let it.

Through the above steps, the multicolor-changeable material of the present invention (Example 1) was obtained. Example 2

First, as a pearl agent layer under the transparent rainbow hologram film that reproduces a stereoscopic image with white light with a thickness of 19 μπι, a multi-color powder with high transparency and high brightness was produced in Production Example 1. The resulting pearlescent agent, which exhibits a white and purple interference color, is dispersed in a two-tone lacquer, coated with a 0.10 mm clearance, and dried at 70 ° C for 20 minutes to be selective. A transmission layer was formed.

Subsequently, Supineruburu one as colored pigments layer _{_{(C o A 1 2 0 4}} ) dispersed in nits port Nrakka was coated on the lower layer of the selectively permeable layer in clearance 0. 101 mm, 2 0 min 70 After drying, pigment-grade titanium oxide is further dispersed in a ditron lacquer and applied with a clearance of 0.1 mm. C was dried for 20 minutes.

Through the above steps, a multicolored material of the present invention (Example 2) was obtained.

Thus, for the pearl agent layer and the colored pigment layer, in the multi-color-change material of the present invention obtained in the above-mentioned example using several substances, the combination of these materials changes color under normal light and under linear light. It was decided to conduct an experiment to confirm the sex.

At the time of the experiment, the following comparative example was prepared and the experiment was performed in the same manner. Comparative Example 1

Transparent rainbow holo that reproduces stereoscopic images with 38 μm thick white light

In the lower layer, Shiseido's Preveil BP ™ (a multicolor pearlescent agent that has a blue appearance and develops a purple interference color) is dispersed in a double-coated lacquer and coated with a clearance of 0.11 mm. After drying at 20 ° C. for 20 minutes, pigment-grade titanium oxide was further dispersed in a nitrone lacquer, coated with a clearance of 0.11 mm, and dried at 70 for 20 minutes to obtain Comparative Example 1 i-. Comparative Example 2

Under the transparent rainbow hologram film that reproduces stereoscopic images with 38 μm thick white light, Shiseido's Preveil BP ™ (a multicolored pearl agent with a blue appearance color and a purple interference color) is used as an etron. Disperse in lacquer, apply with a clearance of 0.202 mm, dry at 70 ° C for 20 minutes, and further disperse pigment grade titanium oxide in a ditron lacquer and apply a clearance of 0.101 mm After drying at 70 ° C. for 20 minutes, Comparative Example 2 was obtained. Comparative Example 3

Lower spinel blue transparent rain Po hologram film for reproducing a stereoscopic image with white light with a thickness of 1 9 μΐη a (C oA l ₂ Oj) dispersed in nitrone lacquers and coating with clearer Nsu 0. 10 1 mm After drying at 70 ° C for 20 minutes, pigment-grade titanium oxide was further dispersed in a ditron lacquer, coated with a clearance of 0.10 mm, and dried at 70 ° C for 20 minutes. Comparative Example 4

Lower spinel blue transparent rainbow hologram film to play standing ί present image with white light with a thickness of 1 9 m and (C oA l ₂ 0 ₄₎ distributed in two Tron lacquers, coating with clearer Nsu 0. 202 mm After drying at 70 for 20 minutes, pigment grade titanium oxide was further dispersed in ditron lacquer and coated with a clearance of 0.11 mm. C was dried for 20 minutes. An experiment was performed by visually observing each sample formed as described above under normal light and linear light.

Evaluation method

Under normal light

Each sample was observed under diffused light as normal light, and it was evaluated whether or not the discoloration of the selective transmission layer below the hologram film was configured to be unrecognizable. 〇: Discoloration of selective transmission layer cannot be recognized

Δ: Discoloration of the selective transmission layer is difficult to recognize

X: Discoloration of selective transmission layer can be recognized

Under straight light

Each sample is irradiated with linear light from the vertical direction, and each sample is visually observed from the substantially vertical direction to evaluate whether or not it is configured to recognize the discoloration of the selective transmission layer below the hologram film. went.

〇: Discoloration of selective transmission layer can be recognized

Δ: Discoloration of the selective transmission layer is difficult to recognize

X: Discoloration of the selective transmission layer cannot be recognized

The results are shown in Table 7 below.

[Table 7]

As shown in Table 7, without using a pearlescent agent with high transparency and high brightness, In Comparative Example 1, which was composed of only the pearlescent agent having relatively low light sensitivity, no discoloration was recognized under normal light and good results were obtained. The peak wavelength is 450 η π! Although it is at 5500 nm, discoloration due to interference was not sufficient and was not preferable. In Comparative Example 2, the layer thickness of the light-interfering pearlescent agent having a relatively low luminance was doubled, but the discoloration due to interference was small even under normal light, although some improvement was observed under linear light. It was recognized and was not preferred.

In Comparative Example 3, in which the selective transmissive layer was formed using only the pigment without using the light-interfering pearlescent agent, no discoloration was recognized under normal light, and the linear light having good results was obtained. Irradiation was not preferable because no discoloration was recognized. In Comparative Example 4 in which the thickness of the pigment layer was doubled, the characteristics of the sample were not improved.

In contrast to such comparative examples, Examples 1 and 2 of the present invention use a pearl agent having high transparency and high luminance in the selective transmission layer, and the pearl agent has a peak wavelength of interference color of 40%. It is between 0 nm and 450 nm, and the brightness measured when applied to black paper and irradiated with light is ((a _.10 -a ₀ ) ² + (b ₀ -b ₀ ) ² ) ^Since it satisfies 220, no discoloration was recognized under normal light, and a good and good discoloration was shown under linear light.

It should be noted that the multivariable dye in the present invention is not limited to only the examples described here.

As described above, the multicolor-change material according to the present invention exhibits good color change due to irradiation light. By utilizing such discoloration properties, it can be used for improving design properties, preventing forgery and falsification, and discriminating forged products. Furthermore, since the selectively permeable layer can be formed by a pearl agent having a small particle diameter, the element can be made thinner, and can be manufactured by a relatively simple process.

In the method for observing a multicolored material according to the present invention, a color different from that under normal light can be observed by irradiating linear light. Then, it is possible to discriminate a counterfeit product by using such discoloration.

Claims

The scope of the claims

1. A selective transmission layer, which has a multilayer structure in which two or more substances with different refractive indices are stacked in multiple layers, has a high transmittance of linear light incident from a substantially vertical direction, and a high scattering reflectance of ordinary light, A colored pigment layer disposed below the selective transmission layer,

Multicolored material characterized by consisting of

2. The multicolor-changeable material according to claim 1, wherein the selectively permeable layer contains a pearl agent.

3. The multicolor material according to claim 2, wherein the selective transmission layer comprises a hologram and / or an optical diffraction recording material;

A pearl agent layer comprising a pearl agent formed below the hologram and / or the optical diffraction recording medium;

A multicolored material characterized by containing

4. The multicolor material according to claim 2 or 3, wherein the pearl agent forming the selective transmission layer is made of a powder having a light scattering property.

The multicolor-changeable material, wherein the light-interfering powder is laminated in multiple layers to form the selective transmission layer.

5. The multicolor material according to claim 4, wherein the pearl agent comprising the light coherent powder has a transmittance of light of 40% or more in a wavelength range of 420 nm to 700 nm, and the pearl agent. Is a multi-colored material characterized by satisfying the following relationship when the luminance measured by coating on black paper is expressed by the hunter's Lab value.

((a. ₁₀ -a ₀ ) ² + (b, ₀ -b ₀ ) ² ) ^{1 2} ≥ 1 3

(However, a and b ₀ are the a values of the L ab values measured at the position with a light receiving angle of 40 degrees, b values, a, and b are the L ab values measured at the position with a light receiving angle of 0 degrees. The a and b values of are shown below.)

6. The multicolor-changeable material according to any one of claims 1 to 5, wherein the colored pigment layer is an inorganic pigment, an organic dye, or a multicolor-changeable pigment that exhibits various colors when a light incident direction is changed. Or a multicolor pigment comprising a plurality of these pigments and dyes.

7. The multicolor-changeable material according to any one of claims 1 to 6, wherein the material is a substrate such as paper or film. Or a multi-colored dye, which is adhered or integrally formed on an article or an article.

8. A selective transmission layer, which has a multilayer structure in which two or more substances having different refractive indices are laminated in a multi-layer manner, has a high transmittance of linear light incident from a substantially vertical direction, and a high scattering reflectance of ordinary light, A colored pigment layer disposed below the selective transmission layer,

An observation method characterized by irradiating a linear light to a multi-colored material composed of and changing the color to a color tone different from that under normal light for observation.

9. The observation method according to claim 8, wherein linear light is irradiated from a substantially vertical axis direction of the multicolored material, and observation is performed in a substantially vertical axis direction of the multicolored material.