JP4752423B2 - Authenticity indicator - Google Patents

Description

  The present invention relates to an authenticity display body that displays authenticity of an article or the like.

Conventionally, as one of the measures to prevent forgery of cards, passports, identification cards, gift certificates, etc., and to prevent counterfeit goods, pirated goods, etc., the authenticity of articles etc. is displayed with hologram labels using relief holograms, etc. The technique of sticking to a target object as an authenticity display body is used.
However, this type of hologram is likely to be overlooked in actual operation because forgery of forgery technology in recent years and the availability of hologram material has become easier, and a hologram label that looks similar to this is forged. there were.

Further, as a counterfeit prevention measure, a method of attaching a liquid crystal film using a cholesteric liquid crystal whose reflection color changes depending on the viewing angle as an authentic display is also used. However, in recent years, forgery techniques have also become more sophisticated, and even an authentic display using cholesteric liquid crystals may be forged.
Therefore, it is considered that the anti-counterfeiting effect is improved if the hologram label and the liquid crystal film are used in combination, but there is a problem that the number of work steps increases when these are prepared and attached to the object.

Patent Document 1 discloses a method of providing a reflective layer of cholesteric liquid crystal on the reflective surface of a relief hologram.
However, in the identification medium shown in Patent Document 1, the cholesteric liquid crystal has only a function as a reflection layer that reflects incident light to the relief hologram, and forms an identification image for identifying whether the light is genuine. Is only a relief hologram and does not improve the forgery prevention effect. Further, the relief hologram has begun to be forged as described above, and there has been a problem that the effect of preventing forgery is insufficient.

Furthermore, even if an authentic display that is difficult to counterfeit is used, if the authentic display itself is obtained, peeled off from the pasted part, and attached to another article, the authentic display itself is authentic. Therefore, there is a problem that it is extremely difficult to determine whether there is an unauthorized intention.
Japanese Patent No. 3655287

  An object of the present invention is to provide an authentic display that is difficult to counterfeit, has high discrimination and designability, and can prevent intentional replacement for the purpose of alteration or the like.

The present invention solves the above problems by the following means. In addition, in order to make an understanding easy, although the code | symbol corresponding to the Example of this invention is attached | subjected and demonstrated, it is not limited to this.
The invention of claim 1, possess a liquid crystal layer having cholesteric regularity having a first authenticity determination function using the reflected light (12), the second authenticity determination function using the reflected light, specific An authentic display body obtained by laminating a Lippmann hologram layer (15) that diffracts light in the wavelength region, and a sticking layer (18) that can be stuck to an object includes the liquid crystal layer and the Lippmann hologram An anti-replacement structure (12, 14) that is formed on the back side of the layer and prevents the object other than the object from being attached after being attached to the object by the adhesive layer. , 15,18,101a, 102a, 103a, 104a ) Bei give a, a wavelength region where the liquid crystal layer corresponding to a half-value width in the wavelength region of light reflected, the wavelength of light the Lippmann hologram layer is reflected In the wavelength region corresponding to a half-value width range, that does not overlap, it is authentic display body characterized by (101, 102, 103, 104).
According to a second aspect of the present invention, in the authenticity display body according to the first aspect, in addition to the liquid crystal layer (12) and the Lippmann hologram layer (15), the anti-replacement structure constitutes an authenticity display body. An authentic display body (101, 102, 103, 104) characterized in that the liquid crystal layer and / or the Lippmann hologram layer has a breaking strength smaller than the peel strength between the layers including the above layer.
According to a third aspect of the present invention, in the authentic display according to the first or second aspect, the breaking strength of the liquid crystal layer (12) and / or the Lippmann hologram layer (15) constitutes the authentic display. An authenticity display body (101, 102, 103, 104) characterized by being smaller than the breaking strength of other layers.
According to a fourth aspect of the present invention, in the authenticity display body according to any one of the first to third aspects, the anti-replacement structure is provided adjacent to the observation side of the Lippmann hologram layer . A peeling strength between the hologram observation side layer and the Lippmann hologram layer is a hologram observation side peeling strength, and a hologram backside layer provided adjacent to the backside opposite to the observation side of the Lippmann hologram layer; The Lippmann hologram layer (15) having a rupture strength smaller than the hologram observation side peel strength and the hologram backside peel strength when the peel strength between the Lippmann hologram layer is the hologram backside peel strength. The authenticity display body (101, 102, 103, 104) characterized by the above.
According to a fifth aspect of the present invention, in the authentic display according to the fourth aspect, the hologram observation side peel strength and / or the hologram back side peel strength is partially (14a) peel strength so as to form a pattern. An authentic display (101) characterized in that the Lippmann hologram layer breaks into the pattern when the hologram observation side layer and the hologram back side layer are peeled off. is there.
According to a sixth aspect of the present invention, in the authentic display according to the fourth or fifth aspect, the Lippmann hologram layer (15) contains 10 to 100 parts by weight of fine particles with respect to 100 parts by weight of the photosensitive material. It is an authenticity display body (101, 102, 103, 104) characterized by
The invention according to claim 7 is the authentic display body according to claim 6, wherein the fine particles are inorganic fine particles (101, 102, 103, 104).
According to an eighth aspect of the present invention, in the authenticity display body according to the sixth aspect of the present invention, there is provided an authenticity display body (101, 102, 103, 104) characterized in that the fine particles are plastic fine particles.
According to a ninth aspect of the present invention, in the authenticity display body according to the first aspect, in addition to the liquid crystal layer (12) and the Lippmann hologram layer (15), the anti-replacement structure constitutes an authenticity display body. These are bonding layers (18, 24) which are provided at any position between the layers including the layers of and join the layers on both sides thereof, and the bonding layers are observed when the bonding layer portion is peeled off. A first portion that is stronger than the bonding strength on the back side and remains in the observation side layer; a second portion that has a bonding strength on the observation side that is weaker than the bonding strength on the back side and remains in the layer on the back side; It is an authenticity display body (101, 102, 103, 104) characterized by having
The invention of claim 10 is the authentic display of claim 9, wherein the layer provided on the observation side of the bonding layer and / or the layer provided on the back side of the bonding layer includes The authenticity display body (101, 102, 103, 104) is characterized in that layers (18a, 24a) that weaken the bonding strength with the bonding layer are partially provided.
The invention according to claim 11 is the authentic display according to claim 9, wherein the layer provided on the observation side of the bonding layer and / or the layer provided on the back side of the bonding layer includes An authentic display body characterized in that a layer for enhancing the bonding strength with the bonding layer is partially provided.
According to a twelfth aspect of the present invention, in the authenticity display body according to the first aspect, in addition to the liquid crystal layer (12) and the Lippmann hologram layer (15), the anti-replacement structure constitutes an authenticity display body. The Lippmann hologram layer (15), which is provided at any position between the respective layers including the layer, and has a tensile strength of 1% smaller than the bonding strength of the bonding layer bonding the layers. Sex display (101, 102, 103, 104).
The invention according to claim 13 is the authentic display according to claim 1, wherein the anti-replacement structure includes each layer including the liquid crystal layer and the Lippmann hologram layer and other layers constituting the authentic display. It is an authentic display body (101, 102, 103, 104) characterized by being a notch (101a, 102a, 103a, 104a) formed in any of the above.
According to a fourteenth aspect of the present invention, in the authenticity display body according to the thirteenth aspect, the cut (101a, 102a, 103a, 104a) is formed between the liquid crystal layer (12) and the Lippmann hologram layer (15). An authenticity display body (101, 102, 103, 104) characterized by being formed on at least one side.
According to a fifteenth aspect of the present invention, in the authentic display according to any one of the first to fourteenth aspects, a peelable peeling member (19) is laminated on the back side of the adhesive layer. It is an authenticity display body (101, 102, 103, 104) characterized by

According to the present invention, the following effects can be obtained.
(1) possess a liquid crystal layer having cholesteric regularity having a first authenticity determination function using the reflected light, the second authenticity determination function using the reflected light, diffracted light of a particular wavelength region The liquid crystal layer and the volume type are provided with an anti-replacement structure that prevents the object from being replaced with an object other than the object after being laminated to the object by the adhesive layer. It is possible to display the authenticity by both the hologram and the anti-counterfeiting effect, and it is possible to prevent the reuse of the authentic display that is extremely difficult to forge.

(2) The anti-replacement structure is a liquid crystal layer and / or a Lippmann hologram layer whose breaking strength is smaller than the peel strength between layers including the liquid crystal layer and the Lippmann hologram layer and other layers constituting the authentic display body. Therefore, when peeling from the object, at least one of the liquid crystal layer or the Lippmann hologram layer , which is difficult to forge, is reliably destroyed, and reuse can be prevented.

(3) Since the breaking strength of the liquid crystal layer and / or the Lippmann hologram layer is smaller than the breaking strength of the other layers constituting the authentic display, the other layers constituting the portion other than the joint portion are broken and peeled off. Can be prevented from being reused.

(4) Since the Lippmann hologram layer has a smaller breaking strength than the hologram observation side peeling strength and the hologram backside peeling strength, the Lippmann hologram layer is surely broken when the authentic display is peeled off, thereby preventing reuse. .

(5) When peeling between the hologram observation side layer and the hologram back side layer, the hologram observation side peel strength and / or the hologram back side peel strength are partially different so as to form a pattern. In addition, since the Lippmann hologram layer breaks into a pattern, it can be easily determined that the layer has been peeled off, and reuse can be prevented.

(6) Lippmann hologram layer, since the fine particles containing 10 to 100 parts by weight with respect to the photosensitive material 100 parts by weight, intentionally defects Lippmann hologram layer without impairing the required functions of the Lippmann hologram layer It can be formed, brittleness can be imparted to the Lippmann hologram layer , and the breaking strength can be lowered. Therefore, it can be easily weakened and reuse can be prevented.

(7) microparticles, since it is the inorganic fine particles can be formed intentionally defects Lippmann hologram layer, a Lippmann hologram layer can impart brittleness, can be reduced breaking strength.

(8) microparticles, since plastic particles, can be formed intentionally defects Lippmann hologram layer, a Lippmann hologram layer can impart brittleness, it can be reduced breaking strength.

(9) The bonding layer has a first portion in which the bonding strength on the observation side is stronger than the bonding strength on the back surface side when the bonding layer portion is peeled off, and the bonding strength on the observation side is the back surface. Since it has a second portion that is weaker than the bonding strength on the side and remains in the layer on the back surface side, it can be easily determined that it has been peeled off, and reuse can be prevented.

(10) Since the bonding portion on the observation side of the bonding layer and / or the bonding portion on the back surface side of the bonding layer is partially provided with a layer that weakens the bonding strength with the bonding layer, the observation side The first portion remaining in the layer and the second portion remaining in the back side layer can be more reliably formed, and reuse can be prevented.

(11) Since the bonding portion on the observation side of the bonding layer and / or the bonding portion on the back surface side of the bonding layer is partially provided with a layer that increases the bonding strength with the bonding layer, the observation side The first portion remaining in the layer and the second portion remaining in the back side layer can be more reliably formed, and reuse can be prevented.

(12) Since a Lippmann hologram layer having a tensile strength that is 1% smaller than the bonding strength of the bonding layers that bond each layer is provided, the Lippmann hologram layer is discolored when an attempt is made to peel off the authentic display body, thereby preventing reuse. it can.

(13) Since a cut is formed in any one of the layers including the liquid crystal layer and the Lippmann hologram layer and other layers constituting the authentic display body, the authentic display body is removed when the authentic display body is peeled off. It is destroyed so that it can be divided, preventing reuse.

(14) Since the cut is formed in at least one of the liquid crystal layer and the Lippmann hologram layer , at least one of the liquid crystal layer and the Lippmann hologram layer , which is difficult to forge, is reliably destroyed and reused. It can be prevented.

(15) Since a peelable peeling member is laminated on the back side of the adhesive layer, it can be provided as a label and is easily distributed. Moreover, it can be affixed to various objects as an authenticity display.

  An object of the present invention is to provide a liquid crystal layer and a Lippmann hologram layer, which are difficult to forge, have high distinguishability and high designability, and provide an authentic display that can prevent deliberate replacement for the purpose of alteration or the like. This is realized by providing an anti-replacement structure that prevents re-deposition after being laminated to an object.

FIG. 1 is a diagram showing a layer structure of a specific example 1 of the embodiment of the authenticity display according to the present invention.
The authentic display body 101 includes a protective layer 11, a liquid crystal layer 12, a Lippmann hologram layer 15, an adhesive layer (sticking layer) 18, a separator 19, and the like.

First, the liquid crystal layer 12 and the Lippmann hologram layer 15 will be described, and the other layers will be described later.
FIG. 2 is a view of the liquid crystal layer and the Lippmann hologram layer as viewed from the observation side. FIG. 2A is a view in which only the liquid crystal layer is viewed, FIG. 2B is a view in which a part of the liquid crystal layer is viewed through a circularly polarizing plate, and FIG. 2C is a Lippmann hologram. FIG. 2D is a view of the liquid crystal layer and the Lippmann hologram layer laminated, and FIG. 2E is a view of the liquid crystal layer shown in FIG. 2D. It is the figure which looked at a part of what laminated | stacked the Lippmann hologram layer through the circularly-polarizing plate.
The liquid crystal layer 12 is a layer having cholesteric regularity and having a first authenticity determination function using reflected light. The liquid crystal layer 12 is light in a specific wavelength region, reflects only circularly polarized light in one direction, and transmits light outside the wavelength region and circularly polarized light in the reverse direction.

The liquid crystal layer 12 is composed of a liquid crystalline composition having cholesteric regularity, a roll base method, a gravure coat method, a bar coat method, etc. After coating using, an alignment treatment is performed to align cholesteric liquid crystal molecules and to fix the cholesteric liquid crystal structure.
The liquid crystal molecules in the liquid crystal layer 12 have a physical molecular arrangement in a spiral structure in which the director of the liquid crystal molecules rotates. The liquid crystal layer 12 has a polarization separation characteristic that separates a unidirectional circularly polarized component and a reversely polarized circularly polarized component based on the physical molecular arrangement of the liquid crystal molecules. That is, in the liquid crystal layer 12, the incident non-polarized light is separated into two polarization states (right circularly polarized light and left circularly polarized light), one of which is reflected and the other is transmitted. This phenomenon is known as circular dichroism, and when a spiral direction in the spiral structure of liquid crystal molecules is appropriately selected, a circularly polarized component having the same optical rotation direction as this spiral direction is selectively reflected.

In the present embodiment, the wavelength region (selected wavelength region) of light reflected by the liquid crystal layer 12 is 605 to 675 nm in the wavelength region corresponding to the half width, and the reflected light looks red. This wavelength region will be described later with reference to FIG. The light reflected by the liquid crystal layer 12 is right circularly polarized light.
The liquid crystal layer 12 is uniformly formed on the entire surface on the observation side of the support base material layer (easily adhesive PET layer) 13 and looks red when viewed from the front (in FIG. 2, the liquid crystal layer 12 is red). Visible state is shown by shading).

As the liquid crystalline composition applied on the support base layer 13, chiral nematic liquid crystal or cholesteric liquid crystal exhibiting cholesteric regularity can be used. Such a material is not particularly limited as long as it is a liquid crystal material capable of forming a cholesteric liquid crystal structure, and in particular, a polymerizable liquid crystal material having a polymerizable functional group at both ends of the molecule. It is preferable for obtaining an optically stable liquid crystal layer 12 after curing.
Hereinafter, the case where a chiral nematic liquid crystal is used as the liquid crystalline composition will be described as an example. The chiral nematic liquid crystal is a mixture of a polymerizable liquid crystal material exhibiting nematic regularity and a chiral agent. Here, the chiral agent is for controlling the helical pitch length of the polymerizable liquid crystal material exhibiting nematic regularity so that the liquid crystalline composition exhibits cholesteric regularity as a whole. In addition, a photopolymerization initiator and an appropriate additive are added to such a liquid crystalline composition.

上記一般式（１）において、Ｒ１及びＲ２はそれぞれ水素又はメチル基を示すが、液晶相を示す温度範囲の広さからＲ１及びＲ２はともに水素であることが好ましい。Ｘは水素、塩素、臭素、ヨウ素、炭素数１〜４のアルキル基、メトキシ基、シアノ基、ニトロ基のいずれであっても差し支えないが、塩素又はメチル基であることが好ましい。また、上記一般式（１）において、分子鎖両端の（メタ）アクリロイロキシ基と芳香環とのスペーサーであるアルキレン基の鎖長を示すａ及びｂは、それぞれ個別に２〜１２の範囲で任意の整数をとり得るが、４〜１０の範囲であることが好ましく、６〜９の範囲であることがさらに好ましい。ａ＝ｂ＝０である一般式（１）の化合物は、安定性に乏しく、加水分解を受けやすい上に、化合物自体の結晶性が高い。また、ａ及びｂがそれぞれ１３以上である一般式（１）の化合物は、アイソトロピック転移温度（ＴＩ）が低い。この理由から、これらの化合物はどちらも液晶相を示す温度範囲が狭く好ましくない。 Examples of polymerizable liquid crystal materials exhibiting nematic regularity include, for example, compounds represented by the following general formula (1) and compounds represented by the following formulas (2-i) to (2-xi). Can be mentioned. These compounds can be used alone or in combination.

In the general formula (1), R1 and R2 each represent hydrogen or a methyl group, but it is preferable that both R1 and R2 are hydrogen because of the wide temperature range showing the liquid crystal phase. X may be hydrogen, chlorine, bromine, iodine, an alkyl group having 1 to 4 carbon atoms, a methoxy group, a cyano group, or a nitro group, but is preferably a chlorine or methyl group. Moreover, in the said General formula (1), a and b which show the chain length of the alkylene group which is a spacer of the (meth) acryloyloxy group and aromatic ring of both ends of a molecular chain are arbitrary in the range of 2-12, respectively. Although it can take an integer, it is preferably in the range of 4 to 10, and more preferably in the range of 6 to 9. The compound of the general formula (1) in which a = b = 0 is poor in stability, easily subjected to hydrolysis, and the compound itself has high crystallinity. In addition, the compound of the general formula (1) in which a and b are each 13 or more has a low isotropic transition temperature (TI). For this reason, both of these compounds are not preferable because the temperature range in which the liquid crystal phase is exhibited is narrow.

  In the above, examples of polymerizable liquid crystal monomers have been described as polymerizable liquid crystal materials exhibiting nematic regularity, but not limited thereto, polymerizable liquid crystal oligomers, polymerizable liquid crystal polymers, liquid crystal polymers, etc. It is also possible to use it. Such a polymerizable liquid crystal oligomer, polymerizable liquid crystal polymer and liquid crystal polymer can be appropriately selected from those conventionally proposed.

On the other hand, a chiral agent is a low molecular compound having an optically active site, and is mainly a compound having a molecular weight of 1500 or less. The chiral agent is mainly used for the purpose of inducing a helical structure in the positive uniaxial nematic regularity expressed by the polymerizable liquid crystal material exhibiting nematic regularity.
As long as this purpose is achieved, it is compatible with a polymerizable liquid crystal material exhibiting nematic regularity in a solution state or a molten state, without impairing the liquid crystal property of the polymerizable liquid crystal material exhibiting nematic regularity, The kind of the low molecular compound as the chiral agent is not particularly limited as long as it can induce a desired helical structure.

  In addition, the chiral agent used for inducing a helical structure in the liquid crystal in this way needs to have at least some chirality in the molecule. Accordingly, the chiral agent used herein includes, for example, a compound having one or more asymmetric carbons, a compound having an asymmetric point on a heteroatom such as a chiral amine or a chiral sulfoxide, or cumulene. And compounds having an optically active site having axial asymmetry such as binaphthol. More specifically, a commercially available chiral nematic liquid crystal (for example, chiral dopant liquid crystal S-811 (manufactured by Merck)) can be mentioned.

上記一般式（３）又は（４）において、Ｒ４は水素又はメチル基を示す。Ｙは上記に示す式（ｉ）〜（ｘｘｉｖ）の任意の一つであるが、中でも、式（ｉ）、（ｉｉ）、（ｉｉｉ）、（ｖ）及び（ｖｉｉ）のいずれか一つであることが好ましい。また、アルキレン基の鎖長を示すｃ及びｄは、それぞれ個別に２〜１２の範囲で任意の整数をとり得るが、４〜１０の範囲であることが好ましく、６〜９の範囲であることがさらに好ましい。ｃ又はｄの値が０又は１である上記一般式（３）又は（４）の化合物は、安定性に欠け、加水分解を受けやすく、結晶性も高い。一方、ｃ又はｄの値が１３以上である化合物は融点（Ｔｍ）が低い。これらの化合物では、ネマチック規則性を示す重合性の液晶材料との間の相溶性が低下し、濃度によっては相分離等が起きるおそれがある。 However, depending on the properties of the selected chiral agent, the nematic regularity formed by the polymerizable liquid crystal material exhibiting nematic regularity, the orientation deterioration, or the liquid crystallinity when the chiral agent is non-polymerizable. There exists a possibility of causing the fall of the sclerosis | hardenability of a composition, and the fall of the reliability of the film after hardening. Furthermore, the use of a large amount of a chiral agent having an optically active site leads to an increase in the cost of the liquid crystal composition. Therefore, when a polarization selective reflection layer having a cholesteric regularity with a short helical pitch length is formed, a chiral agent having an optically active site to be contained in the liquid crystalline composition has a large effect of inducing a helical structure. It is preferable to select an agent. Specifically, it is preferable to use a low molecular compound having axial asymmetry in the molecule as represented by the following general formula (3), (4) or (5). .

In the general formula (3) or (4), R4 represents hydrogen or a methyl group. Y is any one of formulas (i) to (xxiv) shown above, and among them, any one of formulas (i), (ii), (iii), (v), and (vii) Preferably there is. Moreover, although c and d which show the chain length of an alkylene group can each take arbitrary integers in the range of 2-12, it is preferable that it is the range of 4-10, and is the range of 6-9. Is more preferable. The compound of the above general formula (3) or (4) in which the value of c or d is 0 or 1 lacks stability, is susceptible to hydrolysis, and has high crystallinity. On the other hand, a compound having a value of c or d of 13 or more has a low melting point (Tm). In these compounds, compatibility with a polymerizable liquid crystal material exhibiting nematic regularity is lowered, and phase separation or the like may occur depending on the concentration.

  In addition, such a chiral agent does not need to have polymerizability in particular. However, when the chiral agent has polymerizability, it is polymerized with a polymerizable liquid crystal material exhibiting nematic regularity, and the cholesteric regularity is stably fixed, so in terms of thermal stability, etc. Highly preferred. In particular, it is preferable to have a polymerizable functional group at both ends of the molecule in order to obtain the liquid crystal layer 12 having good heat resistance.

The amount of the chiral agent contained in the liquid composition, the optimum value is determined in consideration of the induced power and finally obtained benzalkonium cholesteric liquid crystal structure of the helical structure and the like. Specifically, although it varies greatly depending on the material of the liquid crystal composition used, 0.01 to 60 parts by weight, preferably 0.1 to 40 parts by weight, per 100 parts by weight of the total amount of the liquid crystal composition. More preferably, it is selected in the range of 0.5 to 30 parts by weight, most preferably 1 to 20 parts by weight. When the content of the chiral agent is less than the above range, sufficient cholesteric regularity may not be imparted to the liquid crystal composition. When the content exceeds the above range, the alignment of the liquid crystal molecules is inhibited. There is a risk of adverse effects when cured by actinic radiation.
Furthermore, the liquid crystalline composition can be applied as it is on the support base layer 13, but it is dissolved in an appropriate solvent such as an organic solvent for the purpose of adjusting the viscosity to a coating apparatus or obtaining a good alignment state. You may make it ink.

  Such a solvent is not particularly limited as long as it can dissolve the polymerizable liquid crystal material as described above, but is preferably one that does not erode the support base material layer 13. Specific examples include acetone, 3-methoxybutyl acetate, diglyme, cyclohexanone, tetrahydrofuran, toluene, xylene, chlorobenzene, methylene chloride, and methyl ethyl ketone. The degree of dilution of the polymerizable liquid crystal material is not particularly limited, but it is 5 to 50%, more preferably 10 in consideration of the liquid crystal itself being a material with low solubility and high viscosity. It is preferable to dilute to about 30%.

(Orientation process)
In the coating process described above, after the liquid crystal composition is coated on the support base layer 13 and the liquid crystal layer 12 is formed, in the alignment process, the liquid crystal layer 12 is held at a predetermined temperature at which the cholesteric liquid crystal structure appears. The liquid crystal molecules in the liquid crystal layer 12 are aligned.
FIG. 3 is a diagram illustrating a cholesteric liquid crystal structure.
In FIG. 3, the light incident on the liquid crystal layer 12 is a light beam 31R, and the reflected light is a light beam 33 in FIG. 3A and a light beam 36 in FIG. In FIG. 3A, the directions of the reflected light vary, and in FIG. 3B, the principal ray directions of the reflected light are aligned.
The cholesteric liquid crystal structure to be finally obtained in the present embodiment has a case where the directions of the spiral axes L of the plurality of spiral structure regions 30 vary in the layers as shown in FIG. In some cases, the planar alignment state is as shown in FIG. 3B. In either case, alignment treatment is required. That is, in the former, an alignment process that forms a plurality of helical structure regions 30 in the cholesteric liquid crystal structure is necessary, and in the latter, an alignment process that forms a plurality of helical structure regions 30 in the cholesteric liquid crystal structure. In addition, an alignment process is required to align the directors of liquid crystal molecules having a cholesteric liquid crystal structure in a certain direction on the support base layer 13.

  Here, when the liquid crystal layer 12 formed on the support base material layer 13 is maintained at a predetermined temperature at which the cholesteric liquid crystal structure is expressed, the liquid crystal layer 12 exhibits a liquid crystal phase, and the liquid crystal molecules themselves are self-integrated by the self-integrating action. A helical structure is formed by rotating the director of the molecule. If the liquid crystal layer 12 is not diffusive, the directors of liquid crystal molecules having a cholesteric liquid crystal structure are aligned on the support base layer 13 in a certain direction. The cholesteric liquid crystal structure expressed in such a liquid crystal phase state can be fixed by curing the liquid crystal layer 12 by a method as described later.

Such an alignment treatment step is usually performed together with a drying treatment for removing the solvent when the solvent is contained in the liquid crystalline composition applied on the support base material layer 13. In order to remove the solvent, a drying temperature of 40 to 120 ° C., preferably 60 to 100 ° C. is suitable, and the drying time (heating time) should be such that the cholesteric liquid crystal structure appears and the solvent is substantially removed. For example, 15 to 600 seconds are preferable, and 30 to 180 seconds are more preferable.
When it is found that the orientation state is insufficient after drying, the heating time may be appropriately extended. In addition, when using the vacuum drying method in such a drying process, it is preferable to perform a separate heat treatment for the alignment process.

(Curing process)
After aligning the liquid crystal molecules in the liquid crystal layer 12 in the alignment process described above, the liquid crystal layer 12 is cured in the curing process to fix the cholesteric liquid crystal structure expressed in the liquid crystal phase.
As a method used in the curing treatment step, (1) a method of drying a solvent in the liquid crystalline composition, (2) a method of polymerizing liquid crystal molecules in the liquid crystalline composition by heating, and (3) by irradiation with radiation. A method of polymerizing liquid crystal molecules in the liquid crystal composition, and (4) a method combining these methods can be used.

  Among these, the method (1) is a method suitable when a liquid crystal polymer is used as a polymerizable liquid crystal material exhibiting nematic regularity contained in the liquid crystal composition that is a material of the liquid crystal layer 12. In this method, the liquid crystal polymer is applied to the support base material layer 13 in a state where it is dissolved in a solvent such as an organic solvent. In this case, the cholesteric regularity can be obtained only by removing the solvent by a drying treatment. The solidified liquid crystal layer 12 is formed. In addition, about the kind of solvent, drying conditions, etc., what was described in the apply | coating process and orientation process mentioned above can be used.

The method (2) is a method in which the liquid crystal layer 12 is cured by thermal polymerization of liquid crystal molecules in the liquid crystal composition by heating. In this method, since the bonding state of the liquid crystal molecules changes depending on the heating (baking) temperature, if there is temperature unevenness in the surface of the liquid crystal layer 12 during heating, physical properties such as film hardness and optical characteristics are uneven. Here, in order to keep the film hardness distribution within ± 10%, the heating temperature distribution is also preferably within ± 5%, and more preferably within ± 2%.
The method for heating the liquid crystal layer 12 formed on the support base layer 13 is not particularly limited as long as the uniformity of the heating temperature can be obtained, and can be held in close contact with the hot plate, A method can be used in which a slight air layer is provided between the layers and held in parallel with the hot plate. Further, it may be a method in which the entire specific space such as an oven is heated or passed through the apparatus. When a film coater or the like is used, it is preferable that the drying zone is lengthened so that a sufficient heating time can be taken.
In general, a heating temperature of 100 ° C. or higher is required as the heating temperature, but it is preferably about 150 ° C. due to the heat resistance of the support base material layer 13. However, if a film or the like specialized for heat resistance is used as the material of the support base material layer 13, heating at a high temperature of 150 ° C. or higher is also possible.

  The method (3) is a method of curing the liquid crystal layer 12 by photopolymerizing liquid crystal molecules in the liquid crystalline composition by irradiation with radiation. In this method, an electron beam, ultraviolet rays, or the like can be used as appropriate depending on conditions. Usually, ultraviolet rays are preferably used from the viewpoint of easiness of the apparatus, and the wavelength thereof is 250 to 400 nm. Here, when ultraviolet rays are used, it is preferable that a photopolymerization initiator is added to the liquid crystalline composition.

Examples of the photopolymerization initiator added to the liquid crystal composition include benzyl (also referred to as bibenzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoyl benzoic acid, benzoyl methyl benzoate, 4-benzoyl-4'- Methyl diphenyl sulfide, benzyl methyl ketal, dimethylaminomethyl benzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3'-dimethyl-4-methoxybenzophenone, methylobenzoylpho Mate, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- ON, 1- ( -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxy Examples include thioxanthone. In addition to the photopolymerization initiator, it is possible to add a sensitizer as long as the necessary function of the liquid crystal layer 12 is not impaired.
The addition amount of the photopolymerization initiator added to the liquid crystal composition is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. Is preferred.
The liquid crystal layer 12 can be laminated (fixed) on the support base material layer 13 by performing a series of steps as described above (application step, alignment treatment step, and curing treatment step).

The liquid crystal layer 12 of the present embodiment uses a material that scatters and reflects incident light to reduce the angle dependency that the color changes depending on the viewing angle. However, the present invention is not limited to this, and a material that regularly reflects incident light is used. May be.
Further, since the liquid crystal layer 12 reflects only the right circularly polarized light, for example, as shown in FIG. 2B, the liquid crystal layer 12 is visually observed through a circularly polarizing plate 50 that transmits only the left circularly polarized light. In this case, the liquid crystal layer 12 cannot see the reflected color.

The Lippmann hologram layer 15 is a volume hologram layer having a second authenticity determination function using reflected light, and interference fringes are recorded in the layer.
The Lippmann hologram layer 15 can switch an image by moving viewpoints in two directions, ie, an up-down direction and a left-right direction, and can reproduce a three-dimensional image or a deep image.

A conventionally known volume hologram recording material can be used as the hologram material. Specific examples include silver salt sensitive materials, dichromated gelatin, photocrosslinked polymers, and photopolymers. In particular, a photopolymer can produce a volume hologram only by a dry process as compared with other materials, and is an excellent material for mass production.
The photopolymer used in the hologram material of the present embodiment has at least one photopolymerizable compound and a photopolymerization initiator.
Hereinafter, each constituent material of the photopolymer for volume hologram recording will be described.

(1. Photopolymerizable compound)
The photopolymerizable compound used in this example will be described. As a photopolymerizable compound in a present Example, a radical photopolymerizable compound may be sufficient and a photocationic polymerizable compound may be sufficient. Hereinafter, the description will be divided into a photoradical polymerizable compound and a photocationic polymerizable compound.
(A. Photoradical polymerizable compound)
As a radical photopolymerizable compound used in this example, when forming a volume hologram using the resin composition for volume hologram of the present invention, for example, from a radical photopolymerization initiator described later by laser irradiation or the like. The compound is not particularly limited as long as it is a compound that is polymerized by the action of the generated active radical, but a compound having at least one addition-polymerizable ethylenically unsaturated double bond can be used. For example, an unsaturated carboxylic acid, an unsaturated carboxylate, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, an amide bond between an unsaturated carboxylic acid and an aliphatic polyhydric amine compound, and the like can be given. . Specific examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound are shown below.

  Acrylic esters include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylol Methylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Dipentaerythritol diacrylate, Pentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, 2-phenoxyethyl Acrylate, phenol ethoxylate monoacrylate, 2- (p-chlorophenoxy) ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenylethyl acrylate, (2-acryloxyethyl) ether of bisphenol A, ethoxylated bisphenol A diacrylate, 2- (1-naphthy Oxy) ethyl acrylate, o-biphenyl acrylate, 9,9-bis (4-acryloxydiethoxyphenyl) fluorene, 9,9-bis (4-acryloxytriethoxyphenyl) fluorene, 9,9-bis (4- Acryloxydipropoxyphenyl) fluorene, 9,9-bis (4-acryloxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4-acryloxyethoxy-3-ethylphenyl) fluorene, 9,9- Examples thereof include bis (4-acryloxyethoxy-3,5-dimethyl) fluorene.

A sulfur-containing acrylic compound can also be used. For example, 4,4′-bis (β-acryloyloxyethylthio) diphenyl sulfone, 4,4′-bis (β-acryloyloxyethylthio) diphenyl ketone, 4,4′-bis (β-acryloyloxyethylthio) 3,3 ′, 5,5′-tetrabromodiphenyl ketone, 2,4-bis (β-acryloyloxyethylthio) diphenyl ketone and the like can be mentioned.
Further, as the methacrylic acid ester, among the compound names exemplified in the above-mentioned acrylic acid ester, “acrylate” is converted to “methacrylate”, “acryloxy” is converted to “methacryloxy”, and “acryloyl” is converted to “methacryloyl”. The exemplified compounds are exemplified.
Furthermore, the said photoradically polymerizable compound may be used 1 type or in combination of 2 or more types.

(B. Photocationic polymerizable compound)
The photocationically polymerizable compound used in the present example is a compound that undergoes energy irradiation and undergoes cationic polymerization with a Bronsted acid or a Lewis acid generated by the decomposition of a photocationic polymerization initiator described later. For example, cyclic ethers such as epoxy ring and oxetane ring, thioethers, vinyl ethers and the like can be mentioned.
Examples of the compound containing the epoxy ring include polyalkylene glycol diglycidyl ether, bisphenol A diglycidyl ether, glycerin triglycidyl ether, diglycerol triglycidyl ether, diglycidyl hexahydrophthalate, trimethylolpropane diglycidyl ether, allyl glycidyl ether. , Phenyl glycidyl ether, cyclohexene oxide and the like.
Moreover, the said photocationic polymerizable compound may be used 1 type or in combination of 2 or more types.
Furthermore, the photo radical polymerizable compound and the photo cation polymerizable compound may be used alone or in combination of two or more.

Here, when a volume hologram is formed using the above-mentioned volume hologram resin composition, for example, the surface of the target image is irradiated with a laser to polymerize a radically polymerizable compound, and then the entire surface is formed. It is carried out by polymerizing an uncured substance such as a photocationically polymerizable compound by irradiating energy. In addition, the laser etc. at the time of forming an image and the energy irradiated with energy on the entire surface are usually of different wavelengths, and the photo-cationic polymerizable compound used in this example is an image forming laser, It is preferable that the compound does not polymerize due to the above.
In addition, such a photo-cationic polymerizable compound is preferably in a liquid state at normal temperature because the polymerization of the photoradical polymerizable compound is preferably performed in a composition having a relatively low viscosity.

(C. Other)
The photopolymerizable compound used in this example may be used in a proportion of 10 to 1000 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the binder resin described below.
Here, the volume hologram forms an interference fringe by polymerizing a photopolymerizable compound with, for example, laser light or light having excellent coherence, and forms an image. Therefore, in the case where the volume hologram resin composition contains a radical photopolymerizable compound and a cationic photopolymerizable compound, those having different refractive indexes are selected and used. The rate may be large. In the present example, the average refractive index of the photoradically polymerizable compound is preferably larger than that of the photocationically polymerizable compound from the viewpoint of material selectivity. It is preferably greater than 02.
This is because when the difference in the average refractive index between the photo radical polymerizable compound and the photo cationic polymerizable compound is lower than the above value, the refractive index modulation becomes insufficient, and it is difficult to form a high-definition image. Because there is a possibility of becoming. The average refractive index here means the average value of the refractive index measured for the polymer after polymerizing the photocationically polymerizable compound or the photoradical polymerizable compound. Here, the refractive index is a value measured by an Abbe refractometer.

(2. Photopolymerization initiator)
Next, the photoinitiator used for a present Example is demonstrated. As a photoinitiator in a present Example, a kind changes with photopolymerizable compounds mentioned above. That is, when the photopolymerizable compound is a photoradical polymerizable compound, the photopolymerization initiator selects a photoradical polymerization initiator, and when the photopolymerizable compound is a photocationic polymerizable compound, the photopolymerization initiator. It is necessary to select a photocationic polymerization initiator. Hereinafter, the radical photopolymerization initiator and the photocationic polymerization initiator will be described separately.

(A. Photoradical polymerization initiator)
As the radical photopolymerization initiator used in this example, an active radical is generated by, for example, a laser irradiated when a volume hologram layer is formed using the volume hologram resin composition of this example. The initiator is not particularly limited as long as it is an initiator capable of polymerizing the radical photopolymerizable compound. For example, imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like can be used. Specifically, 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name Irgacure 651, manufactured by Ciba Specialty Chemicals) ), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Product name: Irgacure 369, manufactured by Ciba Specialty Chemicals), screw (η 5-2,4-Cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (trade name Irgacure 784, Ciba Specialty Chemicals Co., Ltd. )) And the like.

(B. Photocationic polymerization initiator)
The photocationic polymerization initiator used in this example is not particularly limited as long as it generates Bronsted acid or Lewis acid by energy irradiation and polymerizes the photocationic polymerizable compound. When the volume hologram resin composition contains a radical photopolymerizable compound and a cationic photopolymerizable compound, the cationic photopolymerizable compound is a polymer that specifically polymerizes the radical photopolymerizable compound, for example, light having excellent laser or coherence. It is preferable that the light is exposed to the energy irradiated to the entire surface after the reaction. Thereby, when the photo radical polymerizable compound is polymerized, the photo cation polymerizable compound can be allowed to exist with little reaction, and a large refractive index modulation in the volume hologram can be obtained.
Specifically, sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, (η6-benzene) (η5-cyclopentadienyl) iron ( II) etc. are exemplified. Furthermore, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide and the like can also be used.

(C. Other)
In this example, as the radical photopolymerization initiator and the cationic photopolymerization initiator, aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron Examples include arene complexes. Specifically, chlorides of iodonium such as diphenyliodonium, ditolyliodonium, bis (pt-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate, hexafluoroantimony Iodonium salts such as nate salts, chlorides of sulfonium such as triphenylsulfonium, 4-t-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromides, borofluoride salts, hexafluorophosphate salts, hexafluoroantimonate salts Sulfonium salts such as 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-methyl -4,6- Scan (trichloromethyl) -1,3,5-2,4,6-substituted-1,3,5-triazine compounds such as triazine.
Moreover, said photoinitiator may be used 1 type or in combination of 2 or more types.
Further, the photopolymerization initiator is used in a proportion of 0.1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the binder resin described later.

(3. Additives)
Next, additives that can be added to the volume hologram resin composition of the present example will be described.
(A. Sensitizing dye)
In this example, it is preferable that the volume hologram tree composition contains a sensitizing dye. Many of the above photopolymerizable compounds and photopolymerization initiators are active with respect to ultraviolet rays, but addition of a sensitizing dye makes them also active with visible light and can record interference fringes using visible laser light. This is because it becomes possible.
Such a sensitizing dye is selected in consideration of the wavelength of the laser beam used when recording interference fringes, but is not particularly limited. For example, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, coumarin dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium System dyes, cyclopentanone dyes, cyclohexanone dyes, and the like can be used.

Examples of the cyanine dye and merocyanine dye include 3,3′-dicarboxyethyl-2,2′-thiocyanine bromide, 1-carboxymethyl-1′-carboxyethyl-2,2′-quinocyanine bromide, 1 , 3′-diethyl-2,2′-quinothiocyanine iodide, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolidelidene) ethylidene] -2-thioxo-4-oxazolidine, etc. Is mentioned.
Examples of the coumarin dyes and ketocoumarin dyes include 3- (2′-benzimidazole) 7-N, N-diethylaminocoumarin, 3,3′-carbonylbis (7-diethylaminocoumarin), and 3,3′-. Examples include carbonylbiscoumarin, 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin), and the like.

A sensitizing dye having an absorption wavelength in the visible light region requires high transparency when used with a volume hologram layer provided closer to the observation side than the liquid crystal layer. Those which become colorless by being decomposed by a subsequent post-process, heating or ultraviolet irradiation are preferred. As such a sensitizing dye, the above-mentioned cyanine dye is preferably used.
The sensitizing dye is used in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the binder resin described below.

(B. Binder resin)
In the present embodiment, it is preferable that the volume hologram resin composition contains a binder resin. By containing the binder resin, the film formability and the film thickness uniformity can be improved, and the recorded interference fringes can be stably present.
Examples of such a binder resin include polymethacrylic acid ester or a partially hydrolyzed product thereof, polyvinyl acetate or a hydrolyzed product thereof, polyvinyl alcohol or a partially acetalized product thereof, triacetyl cellulose, polyisoprene, polybutadiene, polychloroprene, and silicone. Rubber, polystyrene, polyvinyl butyral, polyvinyl chloride, polyarylate, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinyl carbazole or derivatives thereof, poly-N-vinyl pyrrolidone or derivatives thereof, co-use of styrene and maleic anhydride Examples thereof include polymers or half esters thereof. And at least one monomer selected from the group consisting of copolymerizable monomers such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, acrylonitrile, ethylene, propylene, vinyl chloride, and vinyl acetate A copolymer obtained by polymerizing can also be used. Furthermore, a copolymer obtained by polymerizing a monomer having a functional group capable of being thermally cured or photocured in the side chain can also be used. Furthermore, 1 type, or 2 or more types of mixtures can also be used.

As the binder resin, an oligomer type curable resin may be used. For example, the epoxy compound etc. which are produced | generated by the condensation reaction of various phenol compounds, such as bisphenol A, bisphenol S, novolak, o-cresol novolak, p-alkylphenol novolak, and epichlorohydrin, are mentioned.
Furthermore, as the binder resin, an organic-inorganic hybrid polymer using a sol-gel reaction can also be used. For example, the copolymer of the organometallic compound which has a polymeric group represented by following General formula (6), and a vinyl monomer is mentioned.
Rm M (OR ′) n (6)
Here, M is a metal such as Si, Ti, Zr, Zn, In, Sn, Al, Se, R is a vinyl group or (meth) acryloyl group having 1 to 10 carbon atoms, and R ′ is a carbon number having 1 to 10 carbon atoms. Represents an alkyl group, and m + n is the valence of the metal M.

Examples of organometallic compounds when using Si as the metal M include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane, vinyltriallyloxysilane, vinyltetraethoxysilane, vinyltetramethoxysilane, acryloxy Examples include propyltrimethoxysilane and methacryloxypropyltrimethoxysilane.
Examples of the vinyl monomer include acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester.

Here, the volume hologram is formed by recording interference fringes as refractive index modulation or transmittance modulation. Therefore, it is preferable that the refractive index difference between the binder resin and the photopolymerizable compound is large. In this example, in order to increase the difference in refractive index between the binder resin and the photopolymerizable compound, an organometallic compound represented by the following general formula (7) is added to the volume hologram resin composition. You can also.
M (OR ") k (7)
Here, M represents a metal such as Ti, Zr, Zn, In, Sn, Al, and Se, R ″ represents an alkyl group having 1 to 10 carbon atoms, and k represents the valence of the metal M.

When the compound represented by the general formula (7) is added to the volume hologram resin composition, a network structure is formed with the binder resin by a sol-gel reaction in the presence of water and an acid catalyst. In addition to increasing the rate, it has the effect of improving the toughness and heat resistance of the film. Therefore, in order to increase the refractive index difference from the photopolymerizable compound, it is preferable to use a metal M having a high refractive index.
The binder resin is usually used in the volume hologram composition in the range of 15 to 50% by weight, preferably in the range of 20 to 40% by weight.

Next, formation of the volume hologram layer will be described.
For the formation of the volume hologram layer, first, the resin composition for volume hologram is applied on, for example, a target substrate film by a general coating means, and dried as necessary to form a volume hologram. Layer. Further, the volume hologram forming layer may be formed, for example, by injecting a volume hologram resin composition between two substrates such as a glass plate. Next, the above-described photopolymerizable compound is polymerized on the volume hologram forming layer by exposure with a laser beam (light having excellent coherence (for example, light having a wavelength of 300 to 1200 nm)) that is usually used in a holographic exposure apparatus. The interference fringes of the target image are recorded. Thereby, a volume hologram layer is formed.

The volume hologram resin composition may be used with a solvent, if necessary, at the time of coating. Examples of such solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4- Dioxane, 1,2-dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol and the like can be used. These solvents may be used alone or in combination of two or more.
Moreover, as a coating method of the volume hologram resin composition, methods such as a spin coater, a gravure coater, a comma coater, and a bar coater can be used.

The coating amount of the volume hologram resin composition is appropriately selected depending on the use and type of the volume hologram layer, but is usually in the range of 1 to 100 g / m ² , preferably ^{2 to} 40 g / m ^2. The film thickness of the volume hologram forming layer is usually 1 to 100 μm, preferably 2 to 40 μm. Furthermore, the film thickness of the volume hologram layer formed by curing the volume hologram resin composition is preferably in the range of 1 to 100 μm, more preferably 10 to 40 μm.

  The volume-type hologram forming layer is polymerized with the above-described photopolymerizable compound by exposure with laser light (light with excellent coherence (for example, light having a wavelength of 300 to 1200 nm)) that is usually used in a holographic exposure apparatus, Record the interference fringes of the desired image. As the laser beam, a visible laser, for example, an argon ion laser (458 nm, 488 nm, 514.5 nm), a krypton ion laser (647.1 nm), a helium-neon laser (633 nm), a YAG laser (532 nm), or the like is used. Can do.

As a method for recording the interference fringes of the image, a conventionally known method can be used. For example, an interference pattern of an image is recorded by bringing the original plate into close contact with the volume hologram forming layer and performing interference exposure from the base film side using ionizing radiation such as visible light, ultraviolet light, or electron beam.
Further, in order to accelerate the refractive index modulation and complete the polymerization reaction of the photopolymerizable compound or the like, after the interference exposure, treatments such as full exposure with ultraviolet rays and heating can be appropriately performed.

  The Lippmann hologram layer 15 which is a volume hologram layer formed as described above diffracts light in a specific wavelength region. In this embodiment, the selected wavelength region of the Lippmann hologram layer 15 is 523 to 543 nm in the wavelength region corresponding to the half width. Therefore, the image reproduced by the Lippmann hologram layer 15 appears green.

Here, the relationship between the wavelength region of light reflected by the Lippmann hologram layer 15 and the wavelength region of light reflected by the liquid crystal layer 12 described above will be described.
FIG. 4 is a diagram illustrating the wavelength region of light reflected by the Lippmann hologram layer and the liquid crystal layer.
A curve H in FIG. 4 shows the wavelength distribution of the reflected light amount reflected by the Lippmann hologram layer 15, and a curve C shows the wavelength distribution of the reflected light amount reflected by the liquid crystal layer 12.
The half width shown above is the width of the wavelength region that is half (A / 2) of the peak value A of the reflected light amount, taking the case of the Lippmann hologram layer 15 as an example, and the range shown in the region D (Half width 20 nm). Accordingly, the amount of reflected light in the wavelength range of 523 to 543 nm corresponding to this half-value width increases, and even if reflected light in a wavelength region other than green is included, the whole appears green.
On the other hand, in the liquid crystal layer 12, the half-value width shown in the region E which is half (B / 2) of the peak value B of the reflected light amount is 70 nm, and the reflected light amount in the wavelength region 605 to 675 nm increases and becomes red. I can see it.
Accordingly, the wavelength region of light reflected by the liquid crystal layer 12 and the wavelength region of light reflected by the Lippmann hologram layer 15 do not overlap at all with the wavelength region corresponding to the half width. Thereby, the reflected light of the liquid crystal layer 12 and the reflected light of the Lippmann hologram layer 15 are observed in different colors (in this embodiment, red and green), and both can be clearly distinguished and visually recognized.
In a region other than the region corresponding to the half-value width, even if the wavelength region of the light reflected by the liquid crystal layer 12 and the wavelength region of the light reflected by the Lippmann hologram layer 15 overlap, the region corresponding to the half-value width If they do not overlap, the reflected lights of both can be observed as different colors.

(About shifting the selected wavelength range of reflected light)
FIG. 5 is a diagram for explaining the reason why the selected wavelength regions of the liquid crystal layer and the Lippmann hologram layer are shifted.
In FIG. 5, layers other than the liquid crystal layer 12 and the Lippmann hologram layer 15 are omitted for the sake of brevity.

  Even if the selected wavelength regions of the liquid crystal layer 12 and the Lippmann hologram layer 15 are the same or there is a shift, when there is a large overlap of the selected wavelength regions, the light in the wavelength region that can be reflected by the Lippmann hologram layer 15 is About half of the amount of light is reflected by the liquid crystal layer 12 provided on the observation side. Therefore, the light incident on the Lippmann hologram layer 15 is halved, and the image of the Lippmann hologram layer 15 becomes dark. In addition, since the reproduced image is similar to the color reflected and observed by the liquid crystal layer 12 and the color of the Lippmann hologram image, the image of the Lippmann hologram layer 15 becomes very unclear.

However, in the case of this embodiment in which the liquid crystal layer 12 and the Lippmann hologram layer 15 have different selection wavelength regions, first, as shown in FIG. 5A, the liquid crystal layer 12 reflects the incident light (light ray A). Light in the possible wavelength region (light ray B) is reflected by the liquid crystal layer 12 and reaches the observer O. Of the light transmitted through the liquid crystal layer 12 (light ray C), light in a wavelength region that can be reflected by the Lippmann hologram layer 15 is reflected by the Lippmann hologram layer 15 (light ray D), and an image is reproduced. Observable.
Therefore, as shown in FIG. 2D, both the red reflected light (ray B in FIG. 5) from the liquid crystal layer 12 and the green image (light D in FIG. 5) of the Lippmann hologram layer 15 are visible. Become. Further, since the selected wavelength regions of the two layers are different, the reflected light from the liquid crystal layer 12 and the image from the Lippmann hologram layer 15 can be clearly observed.
Further, even when the selected wavelength regions of the two layers partially overlap, the reflected light of the liquid crystal layer 12 and the image of the Lippmann hologram layer 15 can be clearly obtained if the regions corresponding to the half widths do not overlap.

(Authenticity judgment method etc.)
According to the present embodiment, the liquid crystal layer 12 and the Lippmann hologram layer 15 are different in the wavelength range of the reflected light. Therefore, when the liquid crystal layer 12 and the Lippmann hologram layer 15 are laminated as in this embodiment, the reflected light from each layer can be clearly seen as shown in FIG.
Further, since the liquid crystal layer 12 reflects right circularly polarized light, for example, when viewed through a circularly polarizing plate 50 that transmits left circularly polarized light, as shown in FIG. Although the reproduced image of the layer 15 is visible, the red reflected color from the liquid crystal layer 12 becomes invisible. Due to this feature, for example, the circularly polarizing plate 50 is used even when the authentic display body is forged using a film that reflects light of the same color as the light reflected by the liquid crystal layer 12 of this embodiment. Thus, the authenticity can be determined.
In the above determination method, even when the wavelength region of the light reflected by the liquid crystal layer 12 and the wavelength region of the light diffracted by the Lippmann hologram layer 15 overlap, the size of the half width of the two lights and the light use efficiency are different. Therefore, as in the case where the wavelength regions are completely different, it is possible to recognize the two lights individually. Moreover, in order to improve visibility, the angles at which the two lights can be observed can be made different from each other.

  Furthermore, the relief hologram can switch images by moving the viewpoint in the left-right direction, whereas the Lippmann hologram layer 15 can switch images by moving the viewpoint in the left-right direction and the up-down direction. It is possible to reproduce an image with a three-dimensional effect and depth. The Lippmann hologram layer 15 requires advanced technology and special equipment for its production and replication, and the material used is also special, and its distribution is managed. Therefore, the Lippmann hologram layer 15 is difficult to forge.

  Furthermore, the authenticity display body 101 in which the liquid crystal layer 12 and the Lippmann hologram layer 15 are laminated to form an integral display body 101 facilitates the pasting operation. In addition, when authenticity is determined, authenticity determination using both the liquid crystal layer 12 and the Lippmann hologram layer 15 can be performed, and the forgery prevention effect can be further enhanced.

The layer structure of the embodiment of the authentic display according to the present invention is shown as a specific example below.
Specific Example 1 and Specific Example 2 show the layer structure of an authentic display that can be used as a label that can be easily attached to an object.
(Layer structure of Example 1)
The layer structure of Example 1 of the embodiment of the authentic display according to the present invention will be described with reference to FIG.
From the observation side to the back side, the authentic display body 101 includes a protective layer 11, a liquid crystal layer 12, a supporting base material layer (easily adhesive PET layer) 13, an adhesive layer 14, a Lippmann hologram layer 15, an adhesive layer 16, and a base material layer. 17, an adhesive layer (sticking layer) 18, and a separator 19 are laminated in this order.
The protective layer 11 is a layer that protects the surface of the authentic display body 101 and is laminated on the most observation side. Since the protective layer 11 is substantially transparent, the reflected light of the cholesteric liquid crystal layer 12 and the image of the Lippmann hologram layer 15 can be visually observed through the protective layer 11 to determine authenticity.
Since the protective layer 11 needs to exhibit the polarization separation function of the liquid crystal layer 12 without disturbing the polarization of the incident light from the observation side, it is desirable to use a material with little birefringence. For example, a film made of TAC (triacetyl cellulose), a polycarbonate polymer, a cycloolefin polymer, or the like can be used.

  In addition, for example, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, polymethacrylate resin, polyvinyl chloride resin, cellulose resin, silicone resin, chlorinated rubber, casein, various surfactants, metal oxides, etc. From one or a mixture of two or more kinds, or a curable resin such as an ionizing radiation curable resin or a thermosetting resin that reacts with ultraviolet rays or electron beams, etc., is applied by a generally known method. May be used.

The support base material layer 13 is an easy-adhesion PET layer formed of polyethylene terephthalate (PET) and having an easy adhesion property, and is a layer that serves as a support base material for the liquid crystal layer 12. This support base material layer 13 is substantially transparent.
As a supporting substrate for the liquid crystal layer 12, polycarbonate polymer, polyester polymer such as polyethylene terephthalate, polyimide polymer, polysulfone polymer, polyethersulfone polymer, polystyrene polymer, polyethylene or polypropylene Film made of thermoplastic polymer such as polyolefin polymer, polyvinyl alcohol polymer, cellulose acetate polymer, polyvinyl chloride polymer, polyacrylate polymer, polymethyl methacrylate polymer, etc. be able to.

In addition, when laminating the liquid crystal layer 12 on the support base material layer 13, as described above, after applying a liquid crystalline composition exhibiting cholesteric regularity, it is common to perform an alignment treatment and a curing treatment. is there.
In this case, if the liquid crystal layer 12 is made diffusive, it is necessary to control so that the cholesteric liquid crystal structure does not become a planar alignment state. Therefore, it is preferable to use the support base layer 13 that does not have alignment ability on the surface on which the liquid crystalline composition is applied.
However, even if the material on the surface of the support base layer 13 on which the liquid crystalline composition is applied has an orientation ability on the surface, such as a stretched film, the support base layer 13 The surface of the stretched film as a surface is subjected to surface treatment, or the liquid crystal composition material, the process conditions for aligning the liquid crystal composition, and the like are controlled, so that the liquid crystal layer 12 has a cholesteric liquid crystal structure. It is possible to control so that the planar alignment state does not occur.

Further, when the surface of the support base material layer 13 on which the liquid crystalline composition is applied has orientation ability, an intermediate layer such as an easy adhesion layer is provided between the liquid crystal layer 12 and the support base material layer 13. By providing a layer, it is possible to control the alignment state of the cholesteric liquid crystal structure so that the directors of the liquid crystal molecules in the vicinity of the interface with the intermediate layer in the cholesteric liquid crystal structure are directed in a plurality of directions.
In addition, when providing intermediate | middle layers, such as an easily bonding layer, the adhesiveness between the liquid crystal layer 12 and the support base material layer 13 can also be improved. In addition, as such an intermediate | middle layer, what is necessary is just to be able to acquire high adhesiveness with respect to both the material of the liquid crystal layer 12, and the material of the support base material layer 13, and generally using what is marketed can be used. it can. Specifically, for example, PET film A4100 with an easy-adhesion layer manufactured by Toyobo Co., Ltd., and easy-adhesive materials AC-X, AC-L, and AC-W manufactured by Panac Co., Ltd. may be used.

The adhesive layer 14 is substantially transparent and is a layer formed by applying an adhesive. On the bonding surface of the adhesive layer 14 with the Lippmann hologram layer 15, an adhesive strength reduction portion 14a that partially weakens the adhesive strength between the two layers is formed. In this specific example, an adhesive layer using an adhesive is used, but a heat seal layer using a heat seal that exhibits adhesiveness when heated and pressurized may be used.
The adhesive layer 16 is a layer formed by applying an adhesive.
The base material layer 17 has a Lippmann hologram layer 15 formed on the observation side through an adhesive layer 16. In this embodiment, it is made of transparent polyethylene terephthalate (PET).
The pressure-sensitive adhesive layer 18 is a layer formed by applying a pressure-sensitive adhesive, and is a sticking layer that allows the authentic display body 101 to be easily attached to an object. An adhesive strength reduction portion 18a that partially weakens the adhesive strength between the two layers is formed on the bonding surface of the adhesive layer 18 with the base material layer 17. Further, the adhesive strength between the pressure-sensitive adhesive layer 18 and the object T (see FIG. 6) is set to be stronger than the breaking strength and the adhesive strength of all layers of the authenticity display body 101.
The separator 19 is a peelable peeling member laminated on the back side of the adhesive layer 18.

  FIG. 6 is a view showing a state in which the authenticity display body 101 is attached to the object T. As shown in FIG. 6, the authenticity display body 101 is used by peeling the separator 19 and attaching it to the object T using the adhesive force of the adhesive layer 18. When the authentic display body 101 is to be peeled off from the state where it is attached to the object T, it can be assumed that the authentic display body 101 is peeled off at positions L1 to L4 shown in FIG. Therefore, in the first specific example, the notch 101a is provided, and the relationship between the breaking strength of each layer and the peeling strength of the joint portion between each layer is set to a specific magnitude relationship, and peeling is performed at any of these positions. Even if it is done, it is equipped with an anti-replacement structure that prevents reuse. In the following, this anti-replacement structure will be specifically described.

(Cut)
The notch 101a of the specific example 1 is formed from the protective layer 11 to the base material layer 17, but since the notch 101a is not formed for the adhesive layer 18, when pasting on the object T, It will not be cut by the notch 101a. However, since the adhesive layer 18 is attached to the object T even if the authentic display 101 is to be peeled off after being attached to the object T, the liquid crystal layer 12 and the Lippmann hologram are used. The authenticity display body 101 including the layer 15 is broken, that is, cut or deformed. The cut and deformed Lippmann hologram layer 15 does not return to the state before being peeled off even if it is reapplied, and it can be confirmed that it has been reapplied by the Lippmann hologram layer 15 discolored by the joint and deformation. The effect of preventing replacement by the notch 101a is effective even if the effect is removed from any of the positions L1 to L4 shown in FIG.

  The notch 101 a provided in the authentic display body 101 may be provided in at least one layer constituting the authentic display body 101. By providing such a notch, the Lippmann hologram layer 15 can be cut or deformed when the authentic display body 101 once pasted is to be peeled off for abuse or the like. In the present embodiment, providing this notch makes it extremely difficult to peel off the authentic display body 101 without cutting or deformation of the liquid crystal layer 12 and the Lippmann hologram layer 15, and this cutting or deformation is an authentic display. It is excellent in that it is generated without being affected by the adhesion of the body 101. When the authentic display body 101 once peeled off is reapplied, it can be easily recognized that the liquid crystal layer 12 and the Lippmann hologram layer 15 are reapplied by cutting or deforming, thereby preventing forgery of the object. Can be useful.

  The layer for providing the cut may be any of the layers constituting the authentic display body 101. Preferably, it can be provided on the liquid crystal layer 12, the Lippmann hologram layer 15, the protective layer 11, and the like. The notch may be penetrated or partially in the middle of the layer (so-called half cut). The shape of the cut is not particularly limited as long as it promotes the cutting of the authentic display body 101 or the deformation of the Lippmann hologram layer 15. For the purpose of merely preventing the reuse of the authenticity display body 101, the cuts are preferably finer, such as the shape of an eyelid. However, if the cut is too fine, the visibility of the hologram pattern is hindered. Therefore, the fineness of the cut is set so as not to hinder the visibility according to the pattern. Further, when it is necessary to completely peel off the hologram laminate, it is preferable to roughen the cut and simplify it because it becomes easier to peel off the hologram laminate. Moreover, it is preferable to provide the part of a notch in the part where force is applied when it tries to peel off, such as near the place to peel off.

FIG. 7 is a diagram showing an example of the notch 101 a formed in the authenticity display body 101.
FIG. 7 (a) shows a small cut around the authentic display 101, FIG. 7 (b) shows a small cross cut on the authentic display 101, and FIG. 7 (c) shows a hologram. FIG. 7D shows a case where a cut is made in accordance with the pattern. FIG. 7D shows a case where a cut is made at the four corners of the square when the authentic display 101 is a square. FIG. FIG. 7F shows a case where a sharp cross-cut is made around the authenticity display body 101. FIG.

(Partial residue of adhesive layer)
FIG. 8 is a diagram showing a case where the authenticity display body 101 is peeled off at a position L1 in FIG.
As described above, the adhesive strength reduction portion 18a that partially weakens the adhesive strength between the two layers is formed on the bonding surface of the adhesive layer 18 with the base material layer 17, and the authentic display body 101 is peeled off. Sometimes, the adhesive layer 18 is formed such that a part of the adhesive (first part) is removed together with the authenticity display body 101 and the other part (second part) remains on the object T. .
In order to set the peel strength (adhesive strength) between each of the adhesive layers 14, 16, and 18, use different adhesives with different adhesives, or use different adhesive strengths. Use different pressure-sensitive adhesives, and use two types of mixed adhesives with different mixing ratios, so that an appropriate difference in adhesive strength occurs, or the pressure-sensitive adhesive as the main component is common As described above, any method may be used such as changing the addition amount of a crosslinking agent such as an isocyanate-based crosslinking agent or a tackifier resin to increase or decrease the adhesive strength.

In addition, the formation of the adhesive strength reduction portion 18a is performed by using a coating material that gives releasability to the back surface side (adhesive layer 18 side) of the base material layer 17, for example, a binder resin that is adhesive to the base material layer 17. An adhesive strength reduced portion 18a is formed by applying or printing in a pattern a material having a peelability such as wax or silicone added to a paint as a main component, and an adhesive layer is formed on the adhesive strength reduced portion 18a. This is done by a method that prevents 18 from being sufficiently adhered. On the contrary, using a paint containing a substance that acts as a primer to increase the adhesive strength between the two, by applying or printing in a pattern, by the method of sufficiently adhering the adhesive layer 18 in the application portion, A method of applying or printing a component for crosslinking the pressure-sensitive adhesive in a pattern on the substrate layer 17 side can also be performed. In any case, the pattern can be provided in the form of dots, stripes, lattices, symbols, other patterns, or letters. It is desirable to provide words that can be seen to be peeled off, such as “opened” and English “VOID” (= invalid meaning). The adhesive layer 18 may be arbitrarily colored with a colorant such as a pigment or a dye.
Furthermore, a method of irradiating ionizing radiation such as ultraviolet rays or electron beams in a pattern and partially performing crosslinking may be used. The adhesive strength may be partially increased.
When the adhesive layer 18 and the base material layer 17 are bonded to each other, when a portion having sufficient adhesive strength and a portion having insufficient adhesive strength are set, the adhesive layer 18 is divided into a portion having sufficient adhesive strength and a portion having insufficient adhesive strength. If the pattern of the force-reducing portion 18a can be visually recognized, a person who tries to remove it for an unauthorized purpose will be more vigilant, and attention should be paid not to cause visibility due to a difference in refractive index.

  As shown in FIG. 8, when the authenticity display body 101 is peeled off, the adhesive layer 18 is peeled off between the layers in the portion not corresponding to the adhesive strength reduction portion 18a, and the peeled surface is on either side. Since it is a rough surface, a whitish visible pattern is formed on either side, and it can be seen that the authentic display 101 has been peeled off. Is not eliminated, it is possible to prevent the adhesive strength reduction portion 18a from being peeled off and transferred to another.

(1% tensile strength of Lippmann hologram layer 15)
In the authenticity display body 101, the above-described cuts 101a and the adhesive layer 18 are partially left to prevent reuse even when peeled off at the position L1 in FIG. Even if there is a person who wipes off the remaining pressure-sensitive adhesive and tries to put the position cut from the notch 101a on another article, the Lippmann hologram layer 15 and the pressure-sensitive adhesive layers 14, 16, 18 are as follows. By making such a constant relationship, it is possible to prevent unauthorized intentions.

  The Lippmann hologram layer 15 made of a volume hologram is not so strong, and is easy to stretch when pulled, and is somewhat soft, so this is utilized. Specifically, the adhesive strength between the supporting base material layer 13 and the Lippmann hologram layer 15, the adhesive strength between the Lippmann hologram layer 15 and the base material layer 17, and the adhesive strength between the base material layer 17 and the object T are defined as Lippmann. It is set to 1% tensile strength of the hologram layer 15 (tensile force required to stretch the Lippmann hologram layer 15 by 1%) or more, and when the Lippmann hologram layer 15 is peeled off, the Lippmann hologram layer 15 is stretched. . If the height and width of the authentic display 101 is 2 cm, it is 0.2 mm even if it is extended by 1%, so it is difficult to recognize the change in size with the naked eye unless precise measurement is performed. Since the hologram has several interference fringes in the thickness direction, the distance between the interference fringes becomes narrower when the hologram is stretched, the color of the entire hologram shifts to the blue side, and the extension is visually recognized as a color change. , You can see that it was peeled off.

  The color change of the Lippmann hologram layer 15 is also caused by the solvent. When the adhesive that has been peeled off is to be wiped off with a solvent, the solvent penetrates into the Lippmann hologram layer 15 and swells the Lippmann hologram layer 15. As a result, the interval between the interference fringes is widened. The color is shifted to the red side, and the elongation is visually recognized as a change in color. Thus, the Lippmann hologram layer 15 has a built-in property that can serve as a forgery prevention measure.

(Fracture of Lippmann hologram layer 15)
FIG. 9 is a diagram showing a case where the authenticity display body 101 is peeled off at the position L2 or L3 in FIG.
The breaking strength of the Lippmann hologram layer 15 is smaller than the peeling strength between the supporting base material layer 13 and the Lippmann hologram layer 15 by the adhesive layer 14 (hologram observation side peeling strength), and the Lippmann hologram layer 15 by the adhesive layer 16 It is set smaller than the peel strength between the base material layer 17 (hologram back side peel strength). Further, the breaking strength of the Lippmann hologram layer 15 is smaller than the breaking strength of the adhesive layer 14 and the adhesive layer 16 itself. Therefore, if the peeling is attempted at the positions L2 and L3 in FIG. 6, the Lippmann hologram layer 15 is always accompanied by the cohesive failure, and the reuse of the authentic display body 101 can be prevented.
In addition, an adhesive strength reduction portion 14a that partially weakens the adhesive strength between the two layers is formed on the bonding surface of the adhesive layer 14 with the Lippmann hologram layer. 15 peels cleanly. However, the Lippmann hologram layer 15 is broken at portions other than the adhesive strength reduction portion 14a. The effect of preventing the reuse of the authentic display body 101 is further enhanced by forming the adhesive strength reduction portion 14a in the same pattern as the adhesive strength reduction portion 18a described above.
Note that the breaking strength and peel strength cannot be directly compared in numerical values, but the respective breaking strengths and interlayer peel strengths are obtained, and the magnitudes of the break strength and peel strength are determined in accordance with the case where the above-described peel situation is possible. The relationship should be determined experimentally. The points defined in this way are the same in other parts of the present invention.

(Break strength, peel strength, 1% tensile strength measurement method)
The breaking strength, peel strength, and 1% tensile strength in the present invention were measured under the following conditions using an INSTRON 5565 tester INSTRON 5565 according to JIS K7127-1989.

(Breaking strength)
A stress-strain curve (SS curve) was recorded, and the breaking strength was determined from this curve.
Measurement atmosphere: 25 ° C
Test piece: 25 mm width Pulling speed: 2 mm / min

(Peel strength)
The load-peeling distance curve was recorded, and the peel strength was determined from the load in the region where the load became constant after peeling.
Measurement atmosphere: 25 ° C
Peeling direction: 180 ° peeling Test piece: 25 mm width Peeling speed: 300 mm / min

(1% tensile strength)
From the stress-elongation curve, the 1% tensile strength was determined from the stress when the elongation was 1%.
Measurement atmosphere: 25 ° C
Sample piece: 25 mm width Pulling speed: 2 mm / min

  Here, in order to reduce the breaking strength of the Lippmann hologram layer 15 to the extent described above, for example, fine particles having an average primary particle size of 0.001 to 20 μm, preferably 0.01 to 5 μm, for the purpose of weakening. 10 to 100 parts by weight, preferably 30 to 60 parts by weight, based on 100 parts by weight of the photosensitive material.

  The fine particles are not particularly limited as long as they have the above-mentioned particle diameter, and examples thereof include calcium carbonate, talc, china clay, kaolin, microsilica, titanium dioxide, glass flakes, asbestos, wax stone powder, and silica. Inorganic fine particles such as stone powder, barium sulfate, shellben, chamotte, polyethylene resin, polypropylene resin, (meth) acrylic resin, polyvinyl chloride resin, polyamide resin, polyimide resin, polycarbonate resin, epoxy resin, fluorine resin Examples of plastic fine particles containing urethane and copolymers thereof, and phosphors that emit fluorescence when irradiated with ultraviolet light include so-called synthetic resin-specific daylight fluorescent pigments. Examples of such daylight fluorescent pigments include fluorescent dyes such as Briliantsulfoflavine FF (CI56205), Basic yellow (CI46060), Eosine (CI45380), Rhodamine 6G (CI45160), Rhodamine B (CI45170) and the like. Methacrylic acid ester, polyvinyl chloride, polyvinyl chloride vinyl acetate copolymer, polyamide resin, alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, benzoguanamine resin, and their co-condensation polymers uniformly in the carrier resin After being dissolved, it is granulated to the above-mentioned particle size. However, in this case, it is necessary that the fluorescent pigment carrier resin is not compatible with the hologram recording material or the solvent used when forming the hologram layer.

When the average primary particle size of the fine particles is smaller than the above range, it is insufficient for brittle fracture of the Lippmann hologram layer 15, and when the average primary particle size is larger than the above range, Undesirably, noise is generated during hologram recording. On the other hand, when the content is less than 10 parts by weight, the purpose of brittle fracture cannot be achieved, and when the content is more than 100 parts by weight, noise occurs during hologram recording, which is not preferable.
When a fluorescent pigment is contained in the Lippmann hologram layer 15, in addition to weakening the Lippmann hologram layer 15, it is possible to further enhance security in the intrinsic display body by using fluorescence caused by ultraviolet irradiation.

  Here, the average primary particle size is generally used to indicate the particle size of the particles, and in this embodiment, is a value measured by a laser method. The laser method is a method of measuring an average primary particle size, a particle size distribution, and the like by dispersing particles in a solvent and finely calculating scattered light obtained by applying a laser beam to the dispersion solution. Here, the average primary particle size is a value measured using a particle size distribution meter Microtrac UPA Model-9230 manufactured by Leeds & Northrup as a particle size measuring device by a laser method.

(Fracture of the liquid crystal layer 12)
FIG. 10 is a diagram showing a case where the authenticity display body 101 is peeled off at a position L4 in FIG.
The breaking strength of the liquid crystal layer 12 is smaller than the peeling strength at which the bonded portion between the protective layer 11 and the liquid crystal layer 12 is peeled off, and more than the peeling strength at which the bonded portion between the liquid crystal layer 12 and the supporting base material layer 13 is peeled off. small. Therefore, if the peeling is attempted at the position L4, the liquid crystal layer 12 is always broken, and it is not possible to reuse only the liquid crystal layer 12.

As described above, according to the first specific example, the authenticity display body 101 is used as a label having a function of displaying authenticity by the liquid crystal layer 12 and a function of displaying authenticity by the Lippmann hologram layer 15. be able to.
Moreover, since the authenticity display body 101 can be provided as a label, it can be used by being affixed to various objects.

Since the liquid crystal layer 12 is provided on the observation side with respect to the Lippmann hologram layer 15, it can be provided so as to prevent replication at a laser light source and an incident angle that match the replication conditions of the Lippmann hologram layer 15.
For example, when the Lippmann hologram layer 15 is a hologram (green) that can be duplicated at an incident angle of 30 °, if the liquid crystal layer 12 that reflects light at an incident angle of 30 ° is provided, the reflected light of the liquid crystal layer 12 is also recorded. Therefore, the Lippmann hologram layer 15 cannot be duplicated.
In addition, the liquid crystal layer 12 has a phase difference at an oblique incidence regardless of the reproduction wavelength, and by increasing the thickness of the liquid crystal layer 12, light incident on the Lippmann hologram layer 15 and light reflected from the Lippmann hologram layer 15 are reflected. The phase difference generated between them can be increased. This produces an effect of making it difficult to reproduce, because a phase difference is generated even when the reproduction incident light from a specific angle is not reflected by the liquid crystal layer 12.

  Furthermore, when replication is attempted with linearly polarized light, the liquid crystal layer 12 functions as a phase shifter for incident light that is angled from the normal, and the phase of the incident light is shifted. Furthermore, the light diffracted by the Lippmann hologram layer 15 is out of phase again when passing through the liquid crystal layer 12. For example, when the phase is shifted by λ / 10 or more, replication becomes difficult. When the phase is λ / 2, the phase is inverted, so that no interference occurs. Therefore, it cannot be duplicated.

In addition, a part of the incident light incident on the cholesteric reflecting surface is reflected in the first place, so that an image of the liquid crystal layer 12 is recorded. Thus, the duplicated holograms are not identical because the reflection component by the liquid crystal layer 12 is recorded in addition to the desired image. Therefore, it is possible to obtain an authentic display that is more difficult to forge.
In addition, since the wavelength regions of the light reflected by the liquid crystal layer 12 and the Lippmann hologram layer 15 are different from each other, the visibility of both reflected light is good. Since the appearance of light is clearly different, authenticity can be easily and reliably determined.

  Then, the relationship between the breaking strength and the peeling strength of each layer is set to a specific relationship, and by providing the notch 101a, it is impossible to reuse even if the layer is peeled off at any position.

(Modification of specific example 1)
In the specific example 1 described above, breakage from the notch 101a, breakage of the liquid crystal layer 12, breakage of the Lippmann hologram layer 15 or pattern breakage, discoloration due to deformation of the Lippmann hologram layer 15, pattern breakage of the adhesive layer 18, etc. Although a large number of anti-replacement structures are provided, these may be selectively used as appropriate even if not all of them are provided. Hereinafter, the modification is shown as specific example 1-1-specific example 1-7.

(Specific Example 1-1)
The following composition (volume hologram recording solution) on a polyethylene terephthalate film (Lumirror T60; manufactured by Toray Industries, Inc.) having a thickness of 50 μm as a first film
Polymethyl methacrylate (weight average molecular weight 200,000): 100 parts by weight 9,9-bis (4-acryloxydiethoxyphenyl) fluorene: 80 parts by weight 1,6-hexanediol diglycidyl ether: 70 parts by weight Diphenyliodonium hexafluoroantimonate: 5 parts by weight 3,9-diethyl-3′-carboxymethyl-2,2′-thiacarbocyanine iodonium salt: 1 part by weight Fine particles (colloidal silica; average primary particle size 20 nm) : 5 parts by weight Solvent (methyl ethyl ketone / 1-butanol = 1/1 (weight ratio)): 200 parts by weight of a volume hologram recording solution was applied to a film thickness of 10 μm after drying. Separator film with a thickness of 50 μm (SP-PET; Tosero Co., Ltd.) The laminate A for forming a hologram comprising the first film / the volume hologram recording layer / the first separator film was prepared.

The first separator film is peeled from the laminate A, the volume hologram recording layer surface is brought into intimate contact with the hologram master, and laser light (532 nm) is incident at 80 mJ / cm ² from the first film side to produce volume hologram recording. A volume hologram was recorded on the working layer. After recording, the laminate A is peeled off from the hologram master, and a polyethylene terephthalate film (Lumirror T60) having a thickness of 50 μm is bonded to the volume hologram layer surface as a ^second film. As a result, a laminate B composed of a first film / volume hologram layer / second film having a diffraction center wavelength at 533 nm was obtained.

A main agent (95) composed of an ultraviolet-curable nematic liquid crystal on an easy-adhesion-treated surface of a polyethylene terephthalate film (Cosmo Shine A4100; manufactured by Toyobo Co., Ltd.) having a single-sided 50 μm thickness as a third film. Cholesteric liquid crystal solution in which a polymerizable chiral agent (4.2 parts by weight), a photopolymerization initiator (5 parts by weight; manufactured by Ciba Specialty Chemicals) and cyclohexanone are mixed with 8 parts by weight is dried to a film thickness of 4 μm. Then, it was heated in an oven to perform orientation treatment (drying treatment). Thereafter, a laminate composed of a cholesteric liquid crystal layer / third film having a reflection center wavelength of 630 nm by irradiating the cholesteric liquid crystal layer with 1000 mJ / cm ² of ultraviolet light at 365 nm in a nitrogen atmosphere to cure the cholesteric liquid crystal layer. C was obtained. Furthermore, on the cholesteric liquid crystal layer of the laminate C, the following composition (protective layer solution)
Polymethyl methacrylate (weight average molecular weight 100,000): 100 parts by weight Methyl ethyl ketone: 400 parts by weight of a protective layer solution is applied to a film thickness of 2 μm after drying and dried in an oven to form a protective layer / cholesteric liquid crystal A laminate D composed of a layer / third film was obtained.

Next, the following composition (adhesive layer solution) is formed on a separator film (SP-PET) having a thickness of 50 μm as a second separator film.
Acrylic adhesive (Nissetsu PE-118; manufactured by Nippon Carbide Industry Co., Ltd.): 100 parts by weight Isocyanate-based crosslinking agent (Nissetsu CK-101; manufactured by Nippon Carbide Industry Co., Ltd.): 2 parts by weight Solvent (methyl ethyl ketone / toluene / ethyl acetate = 2/1/1 (weight ratio): 60 parts by weight of an adhesive layer solution was applied to a film thickness of 20 μm after drying, and then dried in an oven to form a first adhesive layer Then, another separator film (SP-PET) having a thickness of 38 μm was bonded as a third separator film on the first adhesive layer, and the second separator film / first adhesive layer / third The laminated body E which consists of a separator film was obtained At this time, the 3rd separator film used the thing whose peeling strength is larger than the 2nd separator film.

  Further, the same adhesive layer solution as the first adhesive layer was applied on a polyethylene terephthalate film (Lumirror T60) having a thickness of 50 μm as a fourth film, and then dried to a thickness of 20 μm. A layer was obtained. Thereafter, a separator film having a thickness of 38 μm was bonded onto the second adhesive layer as a fourth separator film. Thereafter, the third adhesive layer and the fifth separator film are bonded to the other surface of the fourth film in the same manner, and the fourth separator film / second adhesive layer / fourth film / A laminate F composed of the third adhesive layer / the fifth separator film was obtained.

  After preparing the laminated bodies B, D, E, and F, the first adhesive layer exposed by peeling the second separator film of the laminated body E and the third film of the laminated body D were bonded together, and then obtained. The separator film 3 of the laminate and the first film of the laminate B were peeled off, and the first adhesive layer and the volume hologram layer were bonded together. Thereafter, the second film of the obtained laminate and the fourth separator film of the laminate F are peeled off, and the second adhesive layer is bonded to the other surface of the volume hologram layer, so that the protective layer 11 / liquid crystal Layer (cholesteric liquid crystal layer) 12 / support base layer (third film) 13 / adhesive layer (first adhesive layer) 14 / Lippmann hologram layer (volume hologram layer) 15 / adhesive layer (second adhesive layer) ) Authentic display body 101-1 (not shown) comprising 16 / base material layer (fourth film) 17 / adhesive layer (third adhesive layer) (sticking layer) 18 / separator (fifth separator film) 19) )

The separator (fifth separator film) 19 of the obtained authentic display body 101-1 was peeled off and bonded to the object. When this was observed through a circularly polarizing plate 50 that transmits right-circularly polarized light, both the pattern of the Lippmann hologram layer (volume hologram layer) 15 and the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 could be observed. On the other hand, when observed through a circularly polarizing plate that transmits left circularly polarized light, the pattern of the Lippmann hologram layer (volume hologram layer) 15 was observed, but the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 Could not be observed.
Further, when the attached authentic display 101-1 was peeled off from the object, the Lippmann hologram layer (volume hologram layer) 15 was agglomerated and destroyed, and the Lippmann hologram layer was formed on both the object side and the peeled side. (Volume type hologram layer) 15 remained. At this stage, an attempt was made to return the peeled side to the original state, but the peeled trace remained, and it was clear that the side was peeled off.

(Specific example 1-2)
Authentic display 101-2 in the same manner except that the fine particles in the volume hologram recording solution of Example 1-1 were fluorine-based particles (a polymer of FM108 manufactured by Kyoei Chemical Co .; average primary particle size 500 nm). (Not shown) was obtained.
The separator (fifth separator film) 19 of the obtained authentic display body 101-2 was peeled off and bonded to the object. When this was observed through a circularly polarizing plate 50 that transmits right-circularly polarized light, both the pattern of the Lippmann hologram layer (volume hologram layer) 15 and the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 could be observed. On the other hand, when observed through a circularly polarizing plate that transmits left circularly polarized light, the pattern of the Lippmann hologram layer (volume hologram layer) 15 was observed, but the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 Could not be observed.
Further, when the attached authentic display 101-2 is peeled off from the object, the Lippmann hologram layer (volume hologram layer) 15 is agglomerated and destroyed, and the Lippmann hologram layer is formed on both the object side and the peeled side. (Volume type hologram layer) 15 remained. At this stage, an attempt was made to return the peeled side to the original state, but the peeled trace remained, and it was clear that the side was peeled off.

(Specific Example 1-3)
Authentic in the same manner except that the fine particle in the volume hologram recording solution of Example 1-1 is not added, and the ultraviolet ray irradiation amount applied to the cholesteric liquid crystal layer in preparing the laminate C is set to 5000 mJ / cm ^2. Sexual display body 101-3 (not shown) was obtained.
The separator (fifth separator film) 19 of the obtained authentic display body 101-3 was peeled off and bonded to an object. When this was observed through a circularly polarizing plate 50 that transmits right-circularly polarized light, both the pattern of the Lippmann hologram layer (volume hologram layer) 15 and the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 could be observed. On the other hand, when observed through a circularly polarizing plate that transmits left circularly polarized light, the pattern of the Lippmann hologram layer (volume hologram layer) 15 was observed, but the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 Could not be observed.
Further, when the attached authentic display body 101-3 was peeled off from the object, the liquid crystal layer (cholesteric liquid crystal layer) 12 was agglomerated and destroyed, and the liquid crystal layer (cholesteric liquid crystal) was formed on both the object side and the peeled side. Layer) 12 has remained. At this stage, an attempt was made to return the peeled side to the original state, but the peeled trace remained, and it was clear that the side was peeled off.

(Specific Example 1-4)
The 1st film of the laminated body B of the specific example 1-1 was peeled, and what added 8% of silicone with respect to 100 weight part of acrylic resin-type binder on the exposed volume type hologram layer by gravure printing. Then, a predetermined pattern printing was performed to obtain a laminate G composed of a pattern printing layer / volume hologram layer / second film.
Using the laminates D, E, F, and G in the same manner as in Example 1-1, protective layer 11 / liquid crystal layer (cholesteric liquid crystal layer) 12 / support base layer (third film) 13 / adhesive layer (First adhesive layer) 14 / Adhesive strength reduced portion (pattern printing layer) 14a / Lippmann hologram layer (volume hologram layer) 15 / Adhesive layer (second adhesive layer) 16 / Base material layer (fourth film) ) 17 / adhesive layer (third adhesive layer) (sticking layer) 18 / separator (fifth separator film) 19 authentic display body 101-4 (not shown) was obtained.

The separator (fifth separator film) 19 of the obtained authentic display body 101-4 was peeled off and bonded to the object. When this authentic display body 101-4 was observed, the pattern printing of the adhesive force reduced portion (pattern printing layer) 14a applied to the Lippmann hologram layer (volume hologram layer) 15 was not observed. Further, when this is observed through a circularly polarizing plate 50 that transmits right-circularly polarized light, both the pattern of the Lippmann hologram layer (volume hologram layer) 15 and the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 are observed. On the other hand, when observed through a circularly polarizing plate that transmits left circularly polarized light, the pattern of the Lippmann hologram layer (volume hologram layer) 15 was observed, but from the liquid crystal layer (cholesteric liquid crystal layer) 12 The reflected light could not be observed.
Further, when an attempt was made to peel off the attached authenticity display body 101-4 from the object, the Lippmann hologram layer (volume hologram layer) 15 remained on the object side in a pattern, and similarly on the peeled side. The Lippmann hologram layer (volume hologram layer) 15 remained in a pattern. At this stage, an attempt was made to return the peeled material to its original state, but the pattern of the Lippmann hologram layer (volume hologram layer) 15 did not disappear.

(Specific Example 1-5)
When producing the laminated body F of Example 1-1, before forming the third adhesive layer, silicone is added to the acrylic resin binder 100 on the surface of the fourth film on which the second adhesive layer is not formed. After applying a predetermined pattern printing by gravure printing with 8% added to parts by weight, the following composition (colored adhesive layer solution) is used instead of the third adhesive layer
Acrylic adhesive (Nissetsu PE-118; manufactured by Nippon Carbide Industry Co., Ltd.): 100 parts by weight Isocyanate-based crosslinking agent (Nissetsu CK-101; manufactured by Nippon Carbide Industry Co., Ltd.): 2 parts by weight Black dye (Kayaset Black KR; manufactured by Nippon Kayaku Co., Ltd.): 5 parts by weight Solvent (methyl ethyl ketone / toluene / ethyl acetate = 2/1/1 (weight ratio): 55 parts by weight of colored adhesive layer The protective layer 11 / liquid crystal layer (cholesteric liquid crystal layer) 12 / support substrate layer (third film) 13 / adhesive layer (first adhesive layer) 14 / Lippmann hologram layer ( Volume hologram layer) 15 / adhesive layer (second adhesive layer) 16 / base material layer (fourth film) 17 / adhesive strength reduced portion (pattern printing layer) 18a / adhesive layer (colored adhesive layer) (sticking layer) 18 / Sepa Chromatography to obtain data (the fifth separator film) 19 made of authenticity display body 101-5 (not shown).

The separator (fifth separator film) 19 of the obtained authentic display body 101-5 was peeled off and bonded to the object. When this authentic display body 101-5 was observed, the pattern printing of the adhesive force reduced portion (pattern printing layer) 18a applied to the fourth film was not observed. When this was observed through a circularly polarizing plate 50 that transmits right-circularly polarized light, both the pattern of the Lippmann hologram layer (volume hologram layer) 15 and the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 could be observed. On the other hand, when observed through a circularly polarizing plate that transmits left circularly polarized light, the pattern of the Lippmann hologram layer (volume hologram layer) 15 was observed, but the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 Could not be observed.
Moreover, when it tried to peel off the affixed authentic display body 101-5 from the object, the pressure-sensitive adhesive layer (colored pressure-sensitive adhesive layer) (sticking layer) 18 remained on the object side in a pattern, and also on the peeled side. Similarly, an adhesive layer (colored adhesive layer) (sticking layer) 18 remained in a pattern. At this stage, an attempt was made to return the peeled material to its original state, but the pattern of the adhesive layer (colored adhesive layer) (sticking layer) 18 did not disappear. .

(Specific Example 1-6)
An authentic display 101-6 (not shown) is obtained in the same manner except that Omnidex 706 (manufactured by DuPont) is used as the volume hologram recording solution of Example 1-4 (but no fine particles are added). It was.
The separator (fifth separator film) 19 of the obtained authentic display body 101-6 was peeled off and bonded to the object. When this authentic display body 101-6 was observed, the pattern printing of the adhesive force reduced portion (pattern printing layer) 14a applied to the Lippmann hologram layer (volume hologram layer) 15 was not observed. When this was observed through a circularly polarizing plate 50 that transmits right-circularly polarized light, both the pattern of the Lippmann hologram layer (volume hologram layer) 15 and the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 could be observed. On the other hand, when observed through a circularly polarizing plate that transmits left circularly polarized light, the pattern of the Lippmann hologram layer (volume hologram layer) 15 was observed, but the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 Could not be observed.

  Further, when an attempt was made to peel off the attached authenticity display body 101-6 from the object, the Lippmann hologram layer (volume hologram layer) 15 remained on the object side in a pattern, and similarly on the peeled side. The Lippmann hologram layer (volume hologram layer) 15 remained in a pattern. At this stage, an attempt was made to restore the peeled material, but the pattern of the Lippmann hologram layer (volume hologram layer) 15 did not disappear, leaving a trace of peeling. Furthermore, even if the Lippmann hologram layer (volume hologram layer) 15 remaining on the object is to be peeled off, the Lippmann hologram layer (volume hologram layer) 15 is stretched and discolored so that it cannot be reused. .

(Specific Example 1-7)
An authenticity display body 101-7 (not shown) is obtained by putting the notch described in 101a of FIG. 7B into the authenticity display body 101-6 obtained in the specific example 1-6 with a full cutting blade. It was.
The separator (fifth separator film) 19 of the obtained authentic display body 101-7 was peeled off and bonded to the object. When this authentic display 101-6 was observed, a trace of the cut was seen, but the pattern printing of the reduced adhesive force portion (pattern printing layer) 14a applied to the Lippmann hologram layer (volume hologram layer) 15 was performed. Not observed. When this was observed through a circularly polarizing plate 50 that transmits right-circularly polarized light, both the pattern of the Lippmann hologram layer (volume hologram layer) 15 and the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 could be observed. On the other hand, when observed through a circularly polarizing plate that transmits left circularly polarized light, the pattern of the Lippmann hologram layer (volume hologram layer) 15 was observed, but the reflected light from the liquid crystal layer (cholesteric liquid crystal layer) 12 Could not be observed.

  Further, when an attempt was made to peel off the attached authenticity display body 101-7 from the object, the authenticity display body 101-7 was broken at the cut portion, and reuse was impossible. Further, if the authentic display 101-7 remaining on the object is further peeled off, the Lippmann hologram layer (volume hologram layer) 15 remains on the object side in a pattern, and the Lippmann hologram layer is similarly formed on the peeled side. (Volume type hologram layer) 15 remained in a pattern. At this stage, an attempt was made to restore the peeled material, but the pattern of the Lippmann hologram layer (volume hologram layer) 15 did not disappear, leaving a trace of peeling. Furthermore, even if the Lippmann hologram layer (volume hologram layer) 15 remaining on the object is to be peeled off, the Lippmann hologram layer (volume hologram layer) 15 is stretched and discolored so that it cannot be reused. .

(Layer structure of Example 2)
FIG. 11 is a diagram showing a layer configuration of a specific example 2 of the embodiment of the authenticity display according to the present invention.
The authentic display body 102 of the specific example 2 includes a protective layer 11, a liquid crystal layer 12, a supporting base material layer (double-sided easy-adhesion PET layer) 20, a Lippmann hologram layer 15, an adhesive layer 16, and a base material from the observation side to the back side. The layer 17, the adhesive layer (sticking layer) 18, and the separator 19 are laminated in this order.
In the authenticity display body 102, a cut 102a is formed as in the first specific example.
In addition, since the double-sided easy-adhesion PET film is used as the support base material layer 20 in the authentic display body 102, a portion corresponding to the adhesive strength reduction portion 14a of the specific example 1 is not formed. For the portion, the breaking strength and peel strength are set in the same manner as in Example 1.

The support base material layer 20 is not limited to the double-sided easy-adhesion PET film, and an easy-adhesion PET film is used as the support base material layer 20, and a substantially transparent adhesive between the easy-adhesion PET film and the Lippmann hologram layer 15. An adhesive layer may be formed by applying an agent, and the Lippmann hologram layer 15 may be provided.
According to the second specific example, the authentic display body 102 has good visibility of both reflected light because the liquid crystal layer 12 and the Lippmann hologram layer 15 reflect different wavelength regions, and the circularly polarizing plate Since the appearance of the reflected light of the liquid crystal layer 12 is clearly different when viewed through 50, the authenticity can be easily and reliably determined.
It is also possible to prevent the authentic display 102 from being peeled off and reused.

(Layer structure of Example 3)
FIG. 12 is a diagram showing a layer configuration of a specific example 3 of the embodiment of the authenticity display body according to the present invention.
The authentic display body 103 of the specific example 3 includes an untreated PET layer 21, a peelable protective layer 22, a Lippmann hologram layer 15, an adhesive layer 14, a liquid crystal layer 12, a supporting base layer (easy adhesion) from the observation side to the back side. A PET layer 13, an adhesive layer (sticking layer) 24, and a separator 25 are laminated in this order.
The breaking strength of the Lippmann hologram layer 15 is smaller than the peeling strength at which the bonded portion between the peelable protective layer 22 and the Lippmann hologram layer 15 is peeled off, and further, the peeling at which the bonded portion between the Lippmann hologram layer 15 and the adhesive layer 14 is peeled off. Less than strength. Therefore, when the authentic display body 103 is peeled off at a layer portion close to the Lippmann hologram layer 15, the Lippmann hologram layer 15 is broken, and reuse of the Lippmann hologram layer 15 can be prevented.
The breaking strength of the liquid crystal layer 12 is smaller than the peel strength at which the bonded portion between the adhesive layer 14 and the liquid crystal layer 12 is peeled off, and the peel strength at which the bonded portion between the liquid crystal layer 12 and the supporting base material layer 13 is peeled off. Smaller than. The breaking strength of the liquid crystal layer 12 and the Lippmann hologram layer 15 is smaller than the breaking strength of the adhesive layer 14 itself. Therefore, if the authentic display body 103 is peeled off at a layer portion close to the liquid crystal layer 12, the liquid crystal layer 12 is broken and the reuse of the liquid crystal layer 12 can be prevented.
The pressure-sensitive adhesive layer 24 is a layer corresponding to the pressure-sensitive adhesive layer 18 in the specific example 1, and the adhesive strength between both layers is partially applied to the bonding surface of the pressure-sensitive adhesive layer 24 to the support base material layer 13 as in the specific example 1. A weakened adhesive strength reduction portion 24a is formed. Further, the adhesive strength between the adhesive layer 24 and the object T is set to be stronger than the breaking strength and the adhesive strength of all the layers of the authenticity display body 103. Therefore, even if the adhesive layer 24 is to be peeled off, a pattern corresponding to the pattern of the adhesive strength reduction portion 24a remains on the authentic display body 103, and reuse can be prevented.

According to the third specific example, since the Lippmann hologram layer 15 is provided closer to the observation side (light incident side) than the liquid crystal layer 12, the Lippmann hologram layer 15 may be duplicated, but the liquid crystal layer 12. The polarization function by is difficult to replicate. Therefore, when viewed through the circularly polarizing plate, the appearance of the reflected light from the liquid crystal layer 12 does not change, and only the lost function of the liquid crystal layer 12 can be duplicated. Authenticity can be easily determined.
Further, in the Lippmann hologram layer 15, light transmitted through the Lippmann hologram layer 15 is reflected by the liquid crystal layer 12, and an image of the liquid crystal layer 12 is recorded. Therefore, the duplicated hologram records the reflection component by the liquid crystal layer 12 in addition to the desired image, and therefore is not the same. Therefore, it is possible to obtain an authentic display that is more difficult to forge.
Further, since the wavelength regions of the light reflected by the liquid crystal layer 12 and the Lippmann hologram layer 15 are different from each other, the visibility of the reflected light from both is good. Since the appearance is clearly different, authenticity can be easily and reliably determined.
Furthermore, it is possible to prevent the authentic display 103 from being peeled off and reused.

(Layer structure of Example 4)
FIG. 13 is a diagram showing a layer configuration of a specific example 4 of the embodiment of the authenticity display body according to the present invention.
The authentic display body 104 of the specific example 4 includes a protective layer 11, a Lippmann hologram layer 15, a support base layer (easy adhesion PET layer) 13, a liquid crystal layer 12, and a support base layer (easy adhesion) from the observation side to the back side. A PET layer 13, an adhesive layer (sticking layer) 18, and a separator 19 are laminated in this order.
The breaking strength of the Lippmann hologram layer 15 is smaller than the peeling strength at which the bonded portion between the protective layer 11 and the Lippmann hologram layer 15 is peeled off, and further, the peeling at the bonded portion between the Lippmann hologram layer 15 and the supporting base material layer 13 is peeled off. Less than strength. Therefore, if the authentic display body 104 is peeled off at a layer portion close to the Lippmann hologram layer 15, the Lippmann hologram layer 15 is broken, and reuse of the Lippmann hologram layer 15 can be prevented.
Further, the breaking strength of the liquid crystal layer 12 is smaller than the peel strength at which the joint portions with the supporting base material layer 13 on both sides of the liquid crystal layer 12 are peeled off. Therefore, if the authentic display body 104 is peeled off at a layer portion close to the liquid crystal layer 12, the liquid crystal layer 12 is broken and the reuse of the liquid crystal layer 12 can be prevented.
Similar to Example 1, the adhesive layer 18 is formed with an adhesive strength reduction portion 18a that partially weakens the adhesive strength between both layers on the bonding surface of the adhesive layer 18 to the support base material layer 13. Further, the adhesive strength between the pressure-sensitive adhesive layer 18 and the object T is set to be stronger than the breaking strength and the adhesive strength of all the layers of the authenticity display body 104. Therefore, even if the adhesive layer 18 is to be peeled off, a pattern corresponding to the pattern of the adhesive strength reduction portion 18a remains on the authentic display body 104, and reuse can be prevented.

According to the fourth specific example, since the wavelength regions of the light reflected by the liquid crystal layer 12 and the Lippmann hologram layer 15 are different, the visibility of both reflected light is good. Since the appearance of the 12 reflected lights is clearly different, the authenticity can be easily and reliably determined.
Moreover, the support base material layer 13 can be used as an authentic display body without disturbing the polarization function of the liquid crystal layer 12 by using a thin film.
Furthermore, two support base material layers 13 may be stacked to make the anisotropy direction orthogonal to suppress the birefringence effect of the support base material layer 13 on the liquid crystal layer 12.
Furthermore, it is possible to prevent the authentic display 104 from being peeled off and reused.

(Modification)
The present invention is not limited to the embodiments described above, and various modifications and changes are possible, and these are also within the equivalent scope of the present invention.
(1) In this embodiment, an example in which breakage due to notch, breakage of the liquid crystal layer, breakage of the Lippmann hologram layer, and partial residual of the adhesive layer are all illustrated is not limited to this, but is appropriately selected from these And you may employ | adopt as a replacement prevention structure.

(2) In this embodiment, an example in which chiral nematic liquid crystal is used as the liquid crystal layer having cholesteric regularity has been described. However, the present invention is not limited thereto, and for example, cholesteric liquid crystal or the like may be used.

(3) In the present embodiment, the liquid crystal layer 12 is applied uniformly over the entire surface of the layer serving as the support substrate. However, the present invention is not limited to this, and a pattern such as a character or pattern is formed and applied. Thus, the design property may be improved. As a method for forming a pattern on the liquid crystal layer 12, for example, a technique disclosed in Japanese Patent Application Laid-Open No. 2004-133179 can be used. The pattern of the liquid crystal layer 12 may be large enough to be visually confirmed as a lattice pattern, or may be small enough not to be visually confirmed as a lattice pattern.

(4) In this embodiment, the authenticity display body may be provided with a primer layer by applying a primer in order to improve the adhesion between the layers, thereby improving the adhesion.

(5) In the specific example 1 and the specific example 2 of the present embodiment, the example in which the adhesive layer 16 and the base material layer 17 are provided on the back side of the Lippmann hologram layer 15 is shown. May be provided.

(6) In the present embodiment, a barrier layer may be provided on the back side (opposite the observation side) from the Lippmann hologram layer 15. Depending on the combination of the resin composition forming the Lippmann hologram layer 15, the separator, the heat seal layer, etc., the low molecular weight component may be transferred from the Lippmann hologram layer 15 to other layers over time, resulting in recording. In some cases, the peak wavelength of the generated hologram shifts to the blue side (short wavelength side), and when it shifts to a separator or the like, its peelability may be changed. Therefore, by providing a barrier layer, these obstruction factors may be eliminated, and the durability as an authentic display body may be improved.
The material used for such a barrier layer is not particularly limited as long as it is a material that exhibits its barrier properties, but the object can usually be achieved by using a transparent organic resin material. Among them, a solvent-free trifunctional or higher functional group, preferably a hexafunctional or higher functional ionizing radiation curable epoxy-modified acrylate resin, urethane-modified acrylate resin, acrylic-modified polyester resin, etc. that reacts with ionizing radiation such as ultraviolet rays and electron beams is used. Can do. In particular, urethane-modified acrylate resins are preferably used because of their high barrier properties.
Further, as these ionizing radiation curable resins, those having a molecular weight in the range of 500 to 2,000 are preferably used in consideration of coating suitability, hardness of the finally obtained barrier layer, and the like. Moreover, since the coating of the barrier layer is basically a solventless system, it can be laminated on any layer of the Lippmann hologram layer, the separator, and the heat seal layer.
Moreover, when the adhesiveness of each layer is weak, the layer etc. which have the function to improve adhesiveness may be formed.

(7) In the present embodiment, the label type authenticity display body has been described as an example. However, the present invention is not limited thereto, and for example, a transfer foil type authenticity display body is provided. be able to.

It is a figure which shows the layer structure of the specific example 1 of the Example of the authenticity display body by this invention. It is the figure which looked at the liquid crystal layer and the Lippmann hologram layer from the observation side. It is a figure explaining a cholesteric liquid crystal structure. It is a figure explaining the wavelength range of the light which a Lippmann hologram layer and a liquid crystal layer reflect. It is a figure explaining the reason which shifted the selection wavelength area | region of a liquid crystal layer and a Lippmann hologram layer. FIG. 3 is a diagram showing a state where an authenticity display body 101 is attached to an object T. It is the figure which showed the example of the notch | incision 101a formed in the authenticity display body 101. FIG. It is a figure which shows the case where the authenticity display body 101 is peeled in the position L1 in FIG. It is a figure which shows the case where the authenticity display body 101 is peeled in the position L2 or L3 in FIG. It is a figure which shows the case where the authenticity display body 101 is peeled in the position L4 in FIG. It is a figure which shows the layer structure of the specific example 2 of the Example of the authenticity display body by this invention. It is a figure which shows the layer structure of the specific example 3 of the Example of the authenticity display body by this invention. It is a figure which shows the layer structure of the specific example 4 of the Example of the authenticity display body by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Protective layer 12 Liquid crystal layer 13 Support base material layer 14 Adhesive layer 15 Lippmann hologram layer 16 Adhesive layer 17 Base material layer 18 Adhesive layer 19 Separator 101,102,103,104 Authentic display body

Claims (15)

A liquid crystal layer having cholesteric regularity having a first authenticity determination function using reflected light;
The reflected light second possess authenticity determination function using a Lippmann hologram layer for diffracting light in a specific wavelength region,
An authenticity display body in which
An adhesive layer that can be attached to an object is formed on the back side of the liquid crystal layer and the Lippmann hologram layer ,
E Bei the Re-sticking preventing structure for preventing the paste replacing it with respect to objects other than the object after being adhered to the object by the sticking layer,
The wavelength region corresponding to the half-value width in the wavelength region of light reflected by the liquid crystal layer and the wavelength region corresponding to the half-value width in the wavelength region of light reflected by the Lippmann hologram layer are not overlapped;
An authenticity display body characterized by In the authenticity display body according to claim 1,
The anti-replacement structure includes the liquid crystal layer and / or the Lippmann hologram having a rupture strength smaller than the peel strength between the layers including the liquid crystal layer and the Lippmann hologram layer and other layers constituting the authentic display. Be a layer ,
An authenticity display body characterized by In the authenticity display body according to claim 1 or 2,
The breaking strength of the liquid crystal layer and / or the Lippmann hologram layer is smaller than the breaking strength of the other layers constituting the authentic display;
An authenticity display body characterized by In the authenticity display body according to any one of claims 1 to 3,
The Re-sticking prevention structure, the peel strength between the adjacent hologram viewing side layer provided the Lippmann hologram layer on the observation side of the Lippmann hologram layer and holographic viewing side peel strength, the observation of the Lippmann hologram layer When the peeling strength between the hologram back side layer and the Lippmann hologram layer provided adjacent to the back side opposite to the side is the hologram back side peeling strength, the hologram observation side peeling strength and the The Lippmann hologram layer has a breaking strength smaller than the hologram back side peel strength,
An authenticity display body characterized by In the authenticity display body according to claim 4,
The hologram observation side peel strength and / or the hologram back side peel strength have partially different peel strengths so as to form a pattern, and peel off between the hologram observation side layer and the hologram back side layer. Sometimes, the Lippmann hologram layer breaks into the pattern,
An authenticity display body characterized by In the authenticity display body according to claim 4 or 5,
The Lippmann hologram layer contains 10 to 100 parts by weight of fine particles with respect to 100 parts by weight of the photosensitive material,
An authenticity display body characterized by In the authenticity display body according to claim 6,
The fine particles are inorganic fine particles;
An authenticity display body characterized by In the authenticity display body according to claim 6,
The fine particles are plastic fine particles;
An authenticity display body characterized by In the authenticity display body according to claim 1,
The anti-replacement structure is provided at any position between layers including the liquid crystal layer and the Lippmann hologram layer and other layers constituting the authentic display, and a bonding layer for bonding the layers on both sides thereof And
The bonding layer includes a first portion in which the bonding strength on the observation side is stronger than the bonding strength on the back side when the bonding layer portion is peeled off, and the bonding strength on the observation side is the back side. Having a second portion that is weaker than the bonding strength of and remains in the layer on the back surface side,
An authenticity display body characterized by In the authenticity display body according to claim 9,
A layer that weakens the bonding strength between the bonding layer and the bonding portion on the observation side of the bonding layer and / or the bonding portion on the back surface side of the bonding layer is partially provided;
An authenticity display body characterized by In the authenticity display body according to claim 9,
A layer for enhancing the bonding strength between the bonding layer and the bonding portion on the observation side of the bonding layer and / or the bonding portion on the back surface side of the bonding layer is partially provided;
An authenticity display body characterized by In the authenticity display body according to claim 1,
The anti-replacement structure is provided at any position between the layers including the liquid crystal layer and the Lippmann hologram layer and other layers constituting the authentic display, and is bonded by a bonding layer that bonds the layers. The Lippmann hologram layer having a tensile strength of 1% smaller than the strength,
An authenticity display body characterized by In the authenticity display body according to claim 1,
The anti-replacement structure is a notch formed in any of the layers including the liquid crystal layer and the Lippmann hologram layer and other layers constituting the authentic display,
An authenticity display body characterized by In the authenticity display body according to claim 13,
The notch is formed in at least one of the liquid crystal layer and the Lippmann hologram layer ;
An authenticity display body characterized by In the authenticity display body according to any one of claims 1 to 14,
A peelable peelable member is laminated on the back side of the adhesive layer,
An authenticity display body characterized by

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