CN101622582A - Method for manufacturing volume hologram laminate - Google Patents

Abstract

The main object of the present invention is to provide a volume hologram laminate manufacturing method capable of manufacturing a volume hologram laminate capable of reproducing a hologram image at an arbitrary wavelength by a simple process. The present invention solves the above problems by providing a volume hologram laminate manufacturing method comprising: a hologram imaging step of recording a volume hologram on a volume hologram layer using a substrate for forming a volume hologram, the substrate having a base material, a volume hologram layer formed on the base material and containing a photopolymerizable material, and a resin layer located on the base material and containing a resin and a polymerizable compound so as to be in contact with the volume hologram layer; a substance transfer step of transferring the polymerizable compound to the volume hologram layer; a post-treatment step of polymerizing the polymerizable compound.

Description

Method for producing a volume hologram laminate

technical field

The present invention relates to a method of manufacturing a volume hologram laminate including a volume hologram layer on which a volume hologram is recorded. The present invention also relates to a volume hologram laminate including a volume hologram layer on which a volume hologram is recorded, and a volume hologram transfer foil and a volume hologram label using the volume hologram laminate. Furthermore, the present invention relates to a volume hologram laminate excellent in anti-counterfeiting (prevention of reuse) and design, and a method for producing the same.

Background technique

A hologram is obtained by interfering two lights of equal wavelength (object light and reference light), thereby recording the wavefront of the object light on a photosensitive material as interference fringes. When the interference fringes are recorded, the reference light and light under the same conditions When they meet, the diffraction phenomenon caused by interference fringes occurs, and the same wavefront as the original object light can be reproduced. Such holograms are classified into several types (surface relief type holograms, volume type holograms, etc.) according to the recording method of interference fringes.

Here, the above-mentioned surface relief hologram is a hologram formed by providing a fine concave-convex pattern on the surface of the hologram layer. On the other hand, the above-mentioned volume hologram is formed by three-dimensionally recording interference fringes generated by light interference as fringes with different diffraction indices in the thickness direction to form a hologram.

The above-mentioned volume type hologram can be mass-produced industrially using a hologram original plate, and has the advantage of excellent industrial productivity compared with the above-mentioned relief type hologram, but the wavelength of the laser light used industrially is limited, which is the current situation. Therefore, the wavelength of light for reproducing a holographic image of an industrially mass-produced volume hologram is also limited, and thus it is difficult to reproduce a bright holographic image in an everyday hologram utilization method.

To deal with this problem, in recent years, when producing volume holograms, the following method is used, that is, by performing subsequent processing on the volume hologram layer on which interference fringes are recorded, the period of the originally recorded interference fringes is changed to make the hologram A method in which the image reproduction wavelength is different from the wavelength of light used to record interference fringes.

That is to say, since the reproduction wavelength of the volume hologram is consistent with the period of the interference fringes recorded on the hologram layer, the period of the interference fringes can be changed to that used in daily use by changing the period of the interference fringes recorded on the hologram layer afterwards. Light with very high frequencies has the same wavelength. Such a method of subsequently changing the period of the interference fringes recorded on the hologram layer is useful for producing a volume hologram layer capable of reproducing a bright hologram image in a daily use method.

Several methods are known as a method for changing the reproduction wavelength of a hologram image after the event, and the method described in Patent Document 1 can be cited as a general method. Patent Document 1 discloses that the monomer and/or plasticizer are transferred to the volume hologram by bringing a layer containing the monomer and/or plasticizer into contact with the volume hologram layer on which interference fringes are recorded, and performing heat treatment or the like. layer, a method of increasing the period of interference fringes. This method is useful in that the period of interference fringes can be increased reliably and the reproduction wavelength can be shifted to a longer wavelength direction. However, on the other hand, there is a problem that the variable period of the interference fringe is small or the process is complicated.

Furthermore, the volume hologram is a method capable of recording information in the thickness direction and also recording and reproducing a three-dimensional image. Since it is represented by the interference color of light, it has an appearance that is difficult to obtain by other image forming methods. The manufacturing method of the volume hologram itself is known, but the simulation of the volume hologram is difficult because the precision operation of the optical machine is required for the manufacture. Using the above-mentioned characteristics of the volume hologram, it is used in the identity Anti-simulation of certificates, bank cards, etc. For this anti-simulation technology, the inventors of the present invention, for example, as shown in Patent Document 2 and Patent Document 3, can not peel off the volume hologram layer from the ID card on which the volume hologram layer is pasted, even if the volume hologram is peeled off. Various researches on anti-counterfeiting that have been destroyed, but when using the volume hologram laminate recorded with the volume hologram as the original plate, it is possible to simulate the volume hologram when contact replication is attempted using a single-wavelength laser, and it is expected to develop a volume hologram that is difficult to simulate Figure volume hologram overlay.

Patent Document 1: Japanese Patent Application Laid-Open No. 3-46687

Patent Document 2: Japanese Patent Laid-Open No. 63-284586

Patent Document 3: Japanese Patent Laid-Open No. 2002-358018

Contents of the invention

The present invention has been made in view of the above problems, and provides a method for manufacturing a volume hologram laminate capable of reproducing a hologram image at an arbitrary wavelength with a simple process; a bright hologram image can be reproduced by controlling the reproduction wavelength, and a simple method can be used. A volume hologram stack produced by a process; and a volume hologram stack that is difficult to simulate a volume hologram even if contact replication is attempted with a single-wavelength laser, and its manufacturing method that can be produced by a simple process.

In order to solve the above-mentioned problems, the present invention provides a method for manufacturing a volume hologram laminate, which is characterized by including the step of recording a volume hologram on the volume hologram layer by using a volume hologram forming substrate. A step wherein the substrate for forming a volume hologram has a base material, a volume hologram layer formed on the base material and containing a photopolymerizable material, and a volume hologram layer located on the base material and in contact with the volume hologram layer. A formed resin layer containing a resin and a polymerizable compound; a substance transfer step of moving the aforementioned polymerizable compound to the aforementioned volume hologram layer; and a post-treatment step of polymerizing the aforementioned polymerizable compound.

According to the present invention, by using a substrate laminated such that the resin layer and the volume hologram layer are in contact as the volume hologram forming substrate, in the hologram imaging step, volumetric holograms are recorded on the volume hologram layer. After the hologram is formed, the period of the interference fringes constituting the volume hologram can be arbitrarily changed afterwards by moving the polymerizable compound from the resin layer to the volume hologram layer in the substance transfer step.

Therefore, according to the present invention, a volume hologram laminate capable of reproducing a hologram image at an arbitrary wavelength can be produced by a simple process.

In the present invention, the polymerizable compound is preferably a substance that migrates from the volume hologram layer. By making the above-mentioned polymerizable compound a compound that migrates from the above-mentioned volume hologram layer, for example, after laminating a resin layer composed of only the above-mentioned resin on the above-mentioned volume hologram layer, the polymerizable compound contained in the above-mentioned volume hologram layer is migrated. Up to the resin layer, the volume hologram-forming substrate used in the present invention can be produced. The reason for this is that the method for producing a volume hologram laminate of the present invention can be carried out in a simpler manner. The reason for this is that, by making the polymerizable compound a compound that migrates from the volume hologram layer, it is easy to transfer the polymerizable compound to the volume hologram layer in the substance transfer step.

In the present invention, the photopolymerizable material includes a radical polymerizable compound and a cation polymerizable compound, and the polymerizable compound is preferably the cation polymerizable compound. The reason for this is that the volume hologram laminate manufactured by the present invention can reproduce a hologram image with high contrast.

In addition, by making the polymerizable compound contained in the resin layer coincide with the constituent substances of the photopolymerizable material contained in the volume hologram layer, the volume hologram laminate can be produced in a simpler process according to the present invention.

In order to solve the above-mentioned problems, the present invention provides a volume hologram laminate having a base material and a volume hologram laminate part formed on the above-mentioned base material and containing a photopolymerizable compound and formed by forming an interference layer. A volume hologram layer in which a volume hologram is recorded with fringes, and a resin layer containing a transparent resin formed in contact with the volume hologram layer, wherein interference fringes are formed on the resin layer.

According to the present invention, interference fringes are also formed on the resin layer, and by arbitrarily controlling the period of the interference fringes formed on the volume hologram layer and the resin layer, a volume hologram capable of reproducing a bright hologram image at an arbitrary wavelength can be obtained. laminated body. In addition, according to the present invention, by forming the above-mentioned resin layer in contact with the above-mentioned volume hologram layer, for example, after forming the volume hologram layer directly on the above-mentioned resin layer, by simultaneously recording interference fringes on these layers, it is possible to manufacture Invented volume hologram stack. Therefore, according to the present invention, it is possible to obtain a volume hologram laminate that can be produced in a simple process. Accordingly, the present invention can provide a volume hologram laminate that can control the reproduction wavelength, reproduce a bright hologram image, and can be produced in a simple process.

In the present invention, it is preferable that the period of the interference fringes formed in the volume hologram layer is different from the period of the interference fringes formed in the resin layer. The reason for this is that the holographic image can be reproduced by light having a wavelength consistent with any one of the periods of the interference fringes formed on the resin layer and the volume hologram layer, so that the holographic image can be reproduced with multiple reproduction wavelengths, making the present invention The inventive volume hologram stack reproduces brighter holographic images.

In addition, in the present invention, it is preferable that the transmittance in the visible light region shows two or more minimum transmission wavelengths. The reason for this is that a brighter hologram can be reproduced by the volume hologram laminate of the present invention.

The present invention also provides a volume hologram transfer foil comprising the volume hologram laminate of the present invention, and a film formed on the volume hologram laminate portion of the volume hologram laminate and containing a thermoplastic resin. heat seal layer.

According to the present invention, it is possible to obtain a volume hologram transfer foil which can be transferred by using the above-mentioned volume hologram laminate of the present invention and which can be transferred by arbitrarily controlling the volume formed on the above-mentioned volume hologram laminate. The period of the interference fringes of the volume hologram layer and the resin layer can reproduce a volume hologram of a bright hologram image at an arbitrary wavelength.

In the volume hologram transfer foil of the present invention, it is preferable that a release layer is formed between the volume hologram laminated portion of the volume hologram laminate and the base material. The reason for this is that, by forming the release layer, the adhesion between the substrate and the volume hologram lamination can be adjusted. As a result, when the volume hologram lamination is transferred from the volume hologram transfer foil of the present invention, , the peelability of the volume hologram lamination can be improved.

The present invention also provides a volume hologram label comprising the volume hologram laminate of the present invention and an adhesive layer formed on the volume hologram laminate portion of the volume hologram laminate.

According to the present invention, it is possible to obtain a volume hologram label that can be pasted by using the above-mentioned volume hologram laminate of the present invention and arbitrarily controlling the above-mentioned volume hologram layer and the above-mentioned volume hologram formed on the above-mentioned volume hologram laminate. The periodicity of the interference fringes of the resin layer enables volume holograms to reproduce bright holographic images at arbitrary wavelengths.

The volume hologram laminate of the present invention is a volume hologram laminate in which a resin layer is partially provided on a base material, and a volume hologram layer is laminated on the base material adjacent to the resin layer, and is characterized in that This is because the volume hologram is formed on the above-mentioned resin layer, and the reproduction center wavelength is different between the portion provided with the resin layer and the portion not provided with the resin layer in the volume hologram laminate.

It is characterized in that the above-mentioned resin layer is adjacent to the above-mentioned base material. In addition, it is characterized in that an undercoat layer is formed between the resin layer and the substrate.

It is characterized in that the volume hologram layer is a volume hologram layer derived from a volume hologram recording material containing a radically polymerizable monomer and a cationic polymerizable monomer, and at the same time, a volume hologram layer is formed on the resin layer based on a volume hologram recorded from an adjacent volume hologram. A moving volume hologram of the polymerizable monomer of the material.

It is characterized in that the resin layer contains a resin selected from polymethyl methacrylate resin, polyvinyl acetate, and polyester resin, and at the same time, the reproduction center wavelength of the part of the volume hologram laminate with the resin layer is the same as that without the resin layer. The reproduction center wavelength of the part is on the longer wavelength side than that.

It is characterized in that the resin layer contains a resin selected from polyvinyl butyral resin and polyvinyl acetal resin, and at the same time, the reproduction center wavelength of the part of the volume hologram laminate with the resin layer is the same as that without the resin layer. Part of the reproduction center wavelength is on the shorter wavelength side.

The volume hologram laminate is characterized in that the difference between the reproduction center wavelength of the part where the resin layer is provided and the reproduction center wavelength of the part where the resin layer is not provided in the volume hologram laminate is at least 10 nm or more.

The method for producing a volume hologram laminate according to the present invention is characterized in that, after partially coating a resin layer on a base material to form a resin layer, the resin layer is adjacent to the resin layer and coated on the base material to form a A volume hologram recording material layer of a body and a cationic polymerizable monomer, and then the following steps are sequentially performed on the obtained laminate:

(1) performing an etching process to move the polymerizable monomer in the volume hologram recording material layer to the resin layer;

(2) A hologram exposure process using laser exposure from the substrate side;

(3) performing heat treatment and ultraviolet irradiation treatment to move the above-mentioned polymerizable monomer between the resin layer and the volume hologram recording material layer, and simultaneously fix the hologram,

The volume hologram based on the polymerizable monomer moved from the adjacent volume hologram recording material layer is formed on the above-mentioned resin layer, and at the same time, the reproduction center at the part where the resin layer is provided and the part where the resin layer is not provided in the above-mentioned laminated body is adjusted. The wavelengths are different.

The first sheet for volume hologram transfer of the present invention is characterized in that an adhesive layer is provided on the volume hologram layer of the volume hologram laminate of the present invention.

The second volume hologram transfer sheet of the present invention is characterized in that a peelable second substrate is provided on the volume hologram layer of the volume hologram laminate of the present invention, An adhesive layer is provided on the resin layer and the volume hologram layer exposed by peeling off the base material. Alternatively, the volume hologram laminate of the present invention is characterized in that a peelable second substrate is provided on the volume hologram layer of the volume hologram laminate, and an adhesive layer is provided on the peelable substrate surface of the volume hologram laminate.

The first or second volume hologram transfer sheet is a volume hologram transfer foil in which the adhesive layer is a heat-sealing layer, or a volume hologram in which the adhesive layer is an adhesive layer. Figure transfer label.

The volume hologram bonded body of the present invention is characterized in that the base material is peeled off or remains as a volume hologram layer while being attached to the covering body from the adhesive layer side of the first volume hologram transfer sheet. protective layer.

The volume hologram bonded body of the present invention is characterized in that the second base material is peeled off or remains as a volume at the same time as the adhesive layer side of the second volume hologram transfer sheet is attached to the covering body. A protective layer for the holographic layer.

The effect of the invention

The method for producing a volume hologram laminate of the present invention has the effect that a volume hologram laminate capable of reproducing a hologram image at an arbitrary wavelength can be produced in a simple process. In addition, the volume hologram laminate of the present invention has the effect that a bright hologram image can be reproduced by controlling the reproduction wavelength, and can be produced in a simple process. In the volume hologram laminated body and the volume hologram bonded body of the present invention, the interference fringe period of the volume hologram layer adjacent to the partially disposed resin layer in the layer direction is different from that of the portion not adjacent to the resin layer in the layer direction Compared with the interference fringe period of the volume hologram layer, since the volume hologram with the enlarged or reduced interference fringe period is formed, the reproduction center of the part with the resin layer and the part without the resin layer of the volume hologram can be made The wavelength is different, and the design is also unprecedented. In addition, using the volume hologram laminate of the present invention as a master plate, a volume hologram recording material layer was bonded thereon, and contact replication was attempted using a single-wavelength laser for the purpose of replicating the volume hologram of the portion where the resin layer was not provided. , Since the resin layer is provided, the part where the reproduction center wavelength is different becomes dark and cannot be reproduced beautifully, so it becomes a volume hologram laminate with excellent anti-counterfeiting. In addition, the method for producing a volume hologram laminate of the present invention can produce a volume hologram laminate excellent in design and anti-counterfeiting in a simple process, and when the volume hologram transfer sheet of the present invention is used, it can be obtained by Volume hologram laminates can be easily produced by transfer printing.

Description of drawings

Fig. 1 is a schematic diagram showing an example of a method for producing a volume hologram laminate of the present invention.

Fig. 2 is a schematic diagram illustrating a method of calculating diffraction efficiency, half width, and reproduction center wavelength from spectral transmittance curves.

3 is an electron micrograph showing an example of spherical regions formed in a volume hologram layer and a resin layer in a volume hologram laminate produced by the volume hologram laminate production method of the present invention.

4 is an electron micrograph showing another example of spherical regions formed in a volume hologram layer and a resin layer in a volume hologram laminate produced by the volume hologram laminate production method of the present invention.

5 is an electron micrograph showing another example of spherical regions formed in a volume hologram layer and a resin layer in a volume hologram laminate produced by the volume hologram laminate production method of the present invention.

Fig. 6 is a schematic view showing an example of a volume hologram laminate (first embodiment) of the present invention.

Fig. 7 is a schematic cross-sectional view showing an example of the volume hologram transfer foil of the present invention.

Fig. 8 is a schematic cross-sectional view showing an example of the volume hologram label of the present invention.

Fig. 9 is a cross-sectional view showing a volume hologram laminate (second embodiment) of the present invention.

Fig. 10 is a cross-sectional view showing a first sheet for transferring a volume hologram according to the present invention.

Fig. 11 is a cross-sectional view showing a volume hologram laminate produced using the first volume hologram transfer sheet of the present invention.

Fig. 12 is a cross-sectional view showing a second sheet for transferring a volume hologram according to the present invention.

Fig. 13 is a cross-sectional view of a volume hologram laminate produced using the second volume hologram transfer sheet of the present invention.

14 is a graph showing spectral transmittance curves of volume hologram laminates of Examples and Comparative Examples.

Fig. 15 is a 70% reduced replica of a scanning electron micrograph (15,000 times) of a longitudinal section of a resin layer laminate in the volume hologram laminate (second embodiment) of the present invention.

Fig. 16 shows spectral transmittance curves of the patterned and unpatterned portions of the resin layer of the volume hologram laminate (second embodiment) of the present invention.

Fig. 17 shows spectral transmittance curves of the patterned and unpatterned portions of the resin layer of the volume hologram laminate (second embodiment) of the present invention.

Symbol Description

11...Substrate

12…resin layer

13…Volume Holographic Layers

110… volume hologram stack

110'...Substrate for volume hologram formation

21...Substrate

22...Volume hologram lamination department

22a...Volume Holographic Layer

22b...resin layer

210…volume hologram stack

220…Volume Hologram Transfer Foil

221...Heat seal layer

230…Volume Hologram Labels

231...joint layer

1…Substrate

2…resin layer

3…volumetric holographic layer

4…Adhesive layer

5...Releasable sheet

6…Covered body

7...Second substrate

8…Undercoat

Detailed ways

Each invention of the present invention will be described in detail below.

A. Method of Manufacturing a Volume Hologram Laminate

First, the method for producing the volume hologram laminate of the present invention will be described. As described above, the method for producing a volume hologram laminate of the present invention is characterized by comprising the steps of: using a volume hologram forming substrate, a hologram imaging step of recording a volume hologram on a volume hologram layer; The forming substrate has a base material, a volume hologram layer formed on the base material and containing a photopolymerizable material, and a resin-containing and polymerizable layer formed on the base material and in contact with the volume hologram layer. a resin layer of the compound; and a substance transfer step of moving the polymerizable compound to the volume hologram layer; and a post-treatment step of polymerizing the polymerizable compound.

A method for producing such a volume hologram laminate of the present invention will be described with reference to the drawings. Fig. 1 is a schematic view showing an example of a method for producing a volume hologram laminate of the present invention. As shown in FIG. 1 , the method of manufacturing a volume hologram laminate of the present invention is characterized in that it includes the following steps: using a volume hologram forming substrate 110 ′ ( FIG. 1( a )), recording In the hologram imaging process of a volume hologram (FIG. 1*(b)), the volume hologram forming substrate has a substrate 11, a resin layer 12 formed on the substrate 11 and containing a resin and a polymerizable compound, and A volume hologram layer 13 containing a photopolymerizable material formed adjacent to the above-mentioned resin layer 12; a substance transfer process of moving the polymerizable compound contained in the above-mentioned resin layer 12 to the above-mentioned volume hologram layer 13 (FIG. 1 (c)); a post-treatment process (FIG. 1(d)) of polymerizing the polymerizable compound transferred to the volume hologram layer 13 to produce a volume hologram having a resin layer 12 on at least the substrate 11 and recording a volume hologram. Volume hologram layer 110 of volume hologram layer 13 (FIG. 1(e)).

According to the present invention, as the substrate for forming the volume hologram, a substrate laminated such that the resin layer and the volume hologram layer are in contact is used, and the volume hologram is recorded on the volume hologram layer in the hologram imaging step. The period of the interference fringes constituting the volume hologram can be changed afterwards by transferring the polymerizable compound from the resin layer to the volume hologram layer in the substance transfer step. The reason for this is that, since the reproduction wavelength of the volume hologram coincides with the period of the interference fringes constituting it, by moving the above-mentioned polymerizable compound into the volume hologram layer on which the volume hologram is recorded, it is possible to enlarge the existing hologram. The direction of the period of the interference fringes formed on the volume hologram layer is changed. In the present invention, the period of the interference fringes can be arbitrarily increased by adjusting the migration amount of the polymerizable compound. Therefore, by appropriately adjusting the wavelength of light used for recording a volume hologram in the hologram imaging step and the polymerization The migration amount of the active compound can be adjusted afterwards, so that the volume hologram recorded on the volume hologram layer can reproduce the hologram image at any wavelength. In addition, in the present invention, by selecting the type of the above-mentioned resin layer, the period of the above-mentioned interference fringes can also be shortened to an arbitrary degree.

Therefore, in the present invention, a volume hologram laminate capable of reproducing a hologram image at an arbitrary wavelength can be produced in a simple process.

The method for producing a volume hologram laminate of the present invention includes at least a hologram imaging step, a substance transfer step, and a post-processing step, and may include other arbitrary steps as necessary.

Each step used in the present invention will be described in order below.

1. Hologram shooting process

First, the hologram imaging process of the present invention will be described. This step is a step of recording a volume-type hologram on the volume hologram layer using a volume hologram-forming substrate, wherein the volume hologram-forming substrate has a base material, is formed on the base material, and contains a photopolymerizable material. A volume hologram layer, a resin layer containing a resin and a polymerizable compound formed on the substrate and adjacent to the volume hologram layer.

Hereinafter, such a hologram imaging step will be described in detail.

(1) Substrate for volume hologram formation

First, the substrate for forming a volume hologram used in this step will be described. The volume hologram forming substrate used in this step has at least a volume hologram layer, a resin layer, and a base material.

a. Resin layer

The resin used in the present invention will be described. The resin layer used in the present invention contains at least a polymerizable compound and a resin. In the present invention, by using such a resin, the above-mentioned polymerizable compound is transferred to the volume hologram layer in a substance transfer step described later, whereby a volume hologram laminate capable of reproducing a hologram image at an arbitrary wavelength can be produced.

(polymeric compound)

The aforementioned polymerizable compound is not particularly limited as long as it is a substance that can move to the volume hologram layer in a substance moving step described later. Therefore, the polymerizable compound used in the present invention can be appropriately selected and used according to the resin, the composition of the volume hologram layer, the embodiment of the substance transfer step, and the like described later. Among them, the above-mentioned polymerizable compound in the present invention is preferably a substance that migrates from the above-mentioned volume hologram layer. The reason is that, after laminating a resin layer composed of only the above-mentioned resin on the above-mentioned volume hologram layer, the polymerizable compound contained in the above-mentioned volume hologram layer is moved to the resin layer, and the volume hologram used in the present invention can be produced. patterning substrate, so the present invention can be practiced in a simpler way. Another reason for this is that since the polymerizable compound is a substance that migrates from the hologram layer, it may easily migrate to the volume hologram layer in a substance transfer step described later.

In addition, the polymerizable compound used in the present invention is preferably a substance that is not photopolymerized by irradiating the volume hologram layer when the volume hologram is recorded in this step. This is because, when the above-mentioned polymerizable compound is photopolymerized to be used for recording a volume hologram in this step, it is difficult to transfer the above-mentioned polymerizable compound to the volume hologram layer in a substance transfer step described later.

Examples of the polymerizable compound used in the present invention include thermally polymerizable compounds and photopolymerizable compounds, and any of these compounds can be preferably used in the present invention. In addition, the polymerizable compound used in this invention may be only 1 type, or may be 2 or more types. Among them, it is preferable to use the above-mentioned polymerizable compound in the present invention that is contained in the photopolymerizable material contained in the volume hologram layer described later. The resin layer can be easily formed by using a common substance for the photopolymerizable material contained in the volume hologram layer as the polymerizable compound. That is, since the substrate for forming a volume hologram used in the present invention is laminated with a resin layer and a volume hologram layer in contact with each other, for example, when forming a resin layer on the volume hologram layer after forming the volume hologram layer, the volume hologram layer The photopolymerizable compound contained in the layer migrates to the resin layer, and the resin layer containing the polymerizable compound can be easily formed.

In addition, when the photopolymerizable material contained in the volume hologram layer described later contains a radically polymerizable compound and a cationically polymerizable compound, the polymerizable compound contained in the resin layer is preferably the same compound as the aforementioned cationically polymerizable compound. The reason for this is as follows.

That is, in the present invention, by using a radically polymerizable compound and a cationic polymerizable compound as the photopolymerizable material, it is possible to record a costly volume type hologram. In this case, the radically polymerizable compound is selectively polymerized in this step. . Therefore, by using a cationic polymerizable compound as the polymerizable compound, the polymerizable compound is polymerized in this step, and the migration of the polymerizable compound to the volume hologram layer is rarely hindered in the later-described substance transfer step.

In addition, since the above-mentioned cationically polymerizable compound will be described in detail in "b. Volume hologram layer" mentioned later, the description is abbreviate|omitted here.

The amount of the polymerizable compound contained in the resin layer is not particularly limited as long as a desired amount of the polymerizable compound can be transferred to the volume hologram layer in a substance transfer step described later. The specific content depends on various factors such as the type of resin used for the resin layer, the composition of the volume hologram layer, and the thickness of the resin layer. Among them, in the present invention, it is preferably in the range of 0.1% by mass to 30% by mass, and particularly preferably 0.1% by mass. It exists in the range of mass % - 20 mass %, More preferably, it exists in the range of 1 mass % - 10 mass %.

(resin)

Next, the resin used for the resin layer will be described. The resin used in the present invention is not particularly limited as long as it has desired transparency. Among them, the resin used in the present invention preferably has a relatively high molecular weight. The reason for this is that since the resin with a large molecular weight is likely to move the polymerizable compound to the volume hologram layer in the substance transfer process described later, it is possible to change the reproduction wavelength of the holographic image from that of the light used to record the volume hologram in this process. The wavelength is shifted to the longer wavelength side. More specifically, the molecular weight of the resin used in the present invention is preferably in the range of 5,000 to 1,000,000, more preferably in the range of 5,000 to 500,000, particularly preferably in the range of 10,000 to 300,000.

Specific examples of the resin used in the present invention include, for example, acrylic resins, styrene resins, polyester resins, polyurethane resins, polyethylene resins, cellulose resins, alkyd resins, petroleum resins, Various synthetic resins such as ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins, or mixtures of two or more of them, copolymers, etc. Resin, melamine resin, phenolic resin, urea resin, epoxy resin, unsaturated polyester resin, diallyl phthalate resin, polyurethane resin, amino alkyd resin, etc. Curable resins or acrylate resins, urethane acrylate resins, ester-based acrylate resins, epoxy-based acrylate resins, etc., which are cured by irradiation with ultraviolet rays or electron rays, etc. resin etc.

In addition, when a polyvinyl butyral resin or a polyvinyl acetal resin is used as the resin, the reproduction center wavelength can be shifted to the shorter wavelength side.

In addition, the resin used in this invention may be only 1 type, or may be 2 or more types.

(any compound)

The resin layer used in the present invention may contain other arbitrary compounds in addition to the above-mentioned resin and the above-mentioned polymerizable compound. The arbitrary compounds mentioned above are not particularly limited, and compounds that can impart desired functions to the resin layer can be arbitrarily selected according to the application of the volume hologram laminate produced by the present invention. Examples of such arbitrary compounds include antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, plasticizers, lubricants, antistatic agents, flame retardants, fillers, and the like. In the present invention, these compounds may be used alone or in combination of two or more.

(resin layer)

The thickness of the resin layer used in the present invention is not particularly limited as long as it is within a range that can contain a required amount of a polymerizable compound depending on the type of resin. Here, the greater the thickness of the above-mentioned resin layer, the more likely it is to contain a large amount of polymerizable compound in the resin layer, which can be moved to the volume hologram layer. Therefore, the greater the thickness of the resin layer, the greater the amount of shift in reproduction wavelength. The larger the adjustment is. Therefore, the thickness of the above-mentioned resin layer can be appropriately adjusted so that the reproduction wavelength falls within a desired range. Among them, the thickness of the above-mentioned resin layer in the present invention is preferably in the range of 0.1 μm to 10 μm, particularly preferably in the range of 0.5 μm to 5 μm, and more preferably in the range of 0.5 μm to 3 μm.

b. Volume hologram layer

Next, the volume hologram layer used in the present invention will be described. The volume hologram layer used in the present invention contains a photopolymerizable material, and a volume hologram can be recorded by forming interference fringes in a hologram imaging step described later.

Such a volume hologram layer is explained in detail below.

(photopolymerizable material)

First, the photopolymerizable material used in the present invention will be described. The photopolymerizable material used in the present invention is not particularly limited as long as it can undergo a polymerization reaction by irradiating desired light and can form interference fringes on the volume hologram layer. Among them, in the present invention, it is preferable to use at least one of a radically polymerizable compound or a cationically polymerizable compound, and it is particularly preferable to use a radically polymerizable compound and a cationically polymerizable compound in combination from the viewpoint that a holographic image with high contrast can be recorded.

Furthermore, when using a radically polymerizable compound as the said photopolymerizable material, in order to initiate the polymerization reaction of this radically polymerizable compound, it is preferable to use a photoradical polymerization initiator. On the other hand, when using a cationically polymerizable compound as a photopolymerizable material, it is preferable to use a photocationic polymerization initiator system from the same reason.

Moreover, when using a radical polymerizable compound and a cationic polymerizable compound as the said photopolymerizable material, it is preferable to use a photoradical polymerization initiator type and a photocationic polymerization initiator type.

In the volume hologram forming substrate, since the volume hologram is in a state before recording the volume type hologram, the photopolymerizable material is present in the volume hologram layer in an unpolymerized state.

The radically polymerizable compound, the cationically polymerizable compound, the photoradical polymerization initiator system, and the photocationic polymerization initiator system used in the present invention will be described in order below.

First, the cationically polymerizable compound used in the present invention will be described. The cationically polymerizable compound used in the present invention is a compound that cationically polymerizes with Brunstedt's acid or Lewis acid produced by decomposition of the photocationic polymerization initiator system described later upon receiving energy irradiation.

Here, when a radically polymerizable compound and a cationically polymerizable compound are used as the above-mentioned photopolymerizable material, the recording of the volume hologram in this step is usually carried out as follows: After polymerizing the base polymerizable compound, uncured substances such as the cation polymerizable compound are polymerized by irradiating energy over the entire surface. At this time, the wavelengths of laser light and the like used to form a holographic image are generally different from the energy used to irradiate the entire surface. Therefore, the cationically polymerizable compound used in the present invention is preferably a compound that does not polymerize at the wavelength of the light source used to form a holographic image. .

In addition, the cationically polymerizable compound used in the present invention is preferably liquid at normal temperature from the viewpoint that the polymerization of the above-mentioned radically polymerizable compound is preferably carried out in a relatively low-viscosity composition.

Examples of such cationic polymerizable compounds include Chemtec.Oct.J.V.Crivello, p. 624 (1980), Japanese Patent Application Laid-Open No. 62-149784, Journal of the Japanese Society of Splicing (Volume 26, No.5, 179- 187 (1990)), and compounds described in JP-A-5-107999, JP-A-2002-236439, JP-A-2002-236440 and the like.

In the present invention, any of these cationically polymerizable compounds can be preferably used, and among them, a cationically polymerizable compound having three or more functional polymerizable functional groups per molecule is preferably used. Thereby, the foil cuttability of the volume hologram layer can be optimized since the crosslink density in the volume hologram layer can be increased.

In addition, the cationically polymerizable compound used in this invention may be only 1 type, or may be 2 or more types.

Next, the radically polymerizable compound used in the present invention will be described. The radically polymerizable compound used in the present invention is not particularly limited as long as it is polymerized by the action of active radicals generated by the photoradical polymerization initiator described later, for example, by laser irradiation when forming the volume hologram layer. As a limitation, in the present invention, it is preferable to have at least one ethylenically unsaturated double bond in the molecule.

Here, in the volume hologram layer, for example, a radically polymerizable compound is polymerized by laser light or light with excellent coherence to form interference fringes, thereby forming a holographic image. Therefore, radically polymerizable compounds and cationically polymerizable compounds are usually selected from those having different diffraction indices. The relationship between the diffraction index of the radical polymerizable compound and the cationic polymerizable compound used in the present invention is not particularly limited, wherein from the aspect of material selectivity, it is preferable that the average diffraction index of the radical polymerizable compound is larger than the above-mentioned cationic polymerizable compound, Specifically, it is preferable that the difference in average diffraction index is 0.20 or more. This is because when the difference in average diffraction index between the radically polymerizable compound and the cationically polymerizable compound is less than the above value, modulation of the diffraction index becomes insufficient, making it difficult to form a high-definition hologram.

In addition, the average diffraction rate mentioned here means the average value of the diffraction rate measured about the polymer after polymerizing a cationically polymerizable compound or a radically polymerizable compound. In addition, the average diffraction rate in this invention means the value measured with the Abbe diffractometer.

Examples of the radically polymerizable compound used in the present invention include compounds described in JP-A-5-107999, JP-A-2002-236439, JP-A-2002-236440, and the like. In the present invention, one type or two or more types may be used in combination.

Next, the photoradical polymerization initiator system used in this invention is demonstrated. The photoradical polymerization initiator used in the present invention is a substance capable of generating active radicals by irradiated light when recording a volume hologram on a volume hologram layer in this step, and polymerizing the above-mentioned radical polymerizable compound. There is no particular limitation. Examples of such radical photopolymerization initiators include U.S. Patent No. 4,766,055, U.S. Patent No. 4,868,092, U.S. Patent No. 4,965,171, JP-A-54-151024, JP-A-58-15503 , JP-A-58-29803, JP-A-59-189340, JP-A-60-76735, JP-1-28715, JP-3-5569 and PROCEEDING OF CONFERENCE Initiator systems described in ON RADIATION CURING ASIA (P.461-477, 1988), etc.

Next, the photocationic polymerization initiator used in this invention is demonstrated. The photocationic polymerization initiator used in the present invention is not particularly limited as long as it can generate Brunsted's acid or Lewis acid by energy irradiation to polymerize the above-mentioned cationically polymerizable compound. Among them, in the present invention, a low-sensitivity substance that does not react with laser light or light with excellent coherence to polymerize the above-mentioned radically polymerizable compound, and is subsequently sensitized by the energy of overall irradiation is preferred. The reason for this is that since the cationically polymerizable compound can remain substantially without reaction when the radically polymerizable compound is polymerized thereby, a large diffraction index modulation can be obtained in the volume hologram layer.

Here, the photocationic polymerization initiator having low photosensitivity to laser light or light with excellent coherence refers to the DSC value due to photopolymerization initiated by the photocationic polymerization initiator when thermal analysis is performed under the following conditions: The maximum value is 500 mW or less (including 0 mW) per 1 mg of a measurement sample.

(measurement conditions)

Measuring device: A differential scanning calorimeter DSC220 and a light source device UV-1 were used in the SSC5200H thermal analysis system manufactured by Seiko Instruments Co., Ltd.

Measurement sample: Prepared by dissolving the photocationic polymerization initiator system of the object in UVR-6110 (cationic polymerizable compound) manufactured by Union Calcium Co., Ltd. 3% by mass (the organic solvent may be evaporated after adding an organic solvent to dissolve it) .

Irradiation light: Using an interference filter (half-maximum width about 10 nm), irradiate 200 mJ/cm ² of light adjusted to the same level as laser light or light with excellent coherence.

Such a photocationic polymerization initiator can be used, for example, "UV Curing; Science and Technology" pp. 23-76, edited by S.Peter Pappss, A Technology Marketing Publication and Coments Inorg.Chem, B.Klingert, M.Riediker and A . Roloff, Vol. 7, No. 3, pp. 109-138 (1988), JP-A-5-107999, JP-2002-236439 and JP-2002-236440 substance. In the present invention, one type or two or more types may be used.

(any compound)

The volume hologram layer used in the present invention may contain arbitrary compounds in addition to the photopolymerizable material described above. Any compound used in the present invention is not particularly limited as long as it can impart desired functions to the volume hologram layer according to the application of the volume hologram laminate produced by the present invention. Examples of such arbitrary compounds include sensitizing dyes, fine particles, thermal polymerization inhibitors, silane coupling agents, plasticizers, colorants, and polymer binders. Among them, in the present invention, it is particularly preferable to use a bonding resin, fine particles, and a sensitizing dye. By using the bonding resin, the volume hologram layer can be made uniform, and the hologram image formed by the polymerization of the above-mentioned radically polymerizable compound can be easily maintained.

In addition, the reason is that by using fine particles, it is possible to easily impart the desired foil cuttability to the volume hologram layer.

Furthermore, the reason for this is that many of the photopolymerizable materials described above are active against ultraviolet light, but they are also active against visible light by using a sensitizing dye, and volume holograms can be recorded using visible laser light.

Examples of the bonding resin include polymethacrylate or its partial hydrolyzate, polyvinyl acetate or its hydrolyzate, polyvinyl alcohol or its partial acetalate, triacetyl cellulose, polyisoprene, Polybutadiene, polychloroprene, silicone rubber, polystyrene, polyvinyl butyral, polyvinyl chloride, polyacrylate, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinyl Carbazole or derivatives thereof, poly-N-vinylpyrrolidone or derivatives thereof, copolymers of styrene and maleic anhydride or half esters thereof, and the like. In addition, it is also possible to polymerize at least one monomer selected from polymerizable monomers such as acrylic acid, acrylate, methacrylic acid, methacrylate, acrylamide, acrylonitrile, ethylene, propylene, vinyl chloride, vinyl acetate, etc. formed copolymers. Furthermore, in the present invention, one type or two or more types of these bonding resins can also be used.

In addition, in the present invention, an oligomer type curable resin can also be used as the above-mentioned bonding resin. Examples of such resins include those produced by the condensation reaction of various phenolic compounds such as bisphenol A, bisphenol S, novolac, o-cresol novolak resin, and p-alkylphenol novolak resin with dichloroepihydrin. epoxy compounds, etc.

(Volume Hologram Layer)

The volume hologram layer used in the present invention preferably has a glass transition temperature of 100° C. or higher. The reason for this is that a stable product can be obtained even when heat is applied to the volume hologram layer, and the volume hologram layer can be transferred by a thermal transfer method.

In addition, the thickness of the volume hologram layer used in the present invention is not particularly limited as long as the desired hologram image can be recorded, but it is usually in the range of 1 μm to 50 μm, more preferably in the range of 3 μm to 40 μm, and still more preferably 5 μm. ~30μm range.

c. Substrate

Next, the substrate used in the present invention will be described. The substrate used in the present invention has the function of supporting the above-mentioned resin layer and volume hologram layer.

The substrate used in the present invention is not particularly limited as long as it can support the above-mentioned resin layer and volume hologram layer. For example, general substrates such as polyester films such as polyethylene terephthalate films can be used.

In addition, the thickness of the base material used in the present invention is appropriately selected according to the use and type of the volume hologram laminate produced in the present invention, and is usually in the range of 2 μm to 200 μm, more preferably in the range of 10 μm to 50 μm.

In addition, when the adhesiveness of the substrate used in the present invention and the resin layer or the volume hologram layer is insufficient, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, or dichromic acid treatment may be performed on the surface of the substrate. Surface treatment such as anchoring or primer treatment can improve the adhesion between the substrate and the resin layer or volume hologram layer. Various primers such as polyurethane-based, acrylic-based, ethylene-vinyl acetate copolymer-based, and vinyl chloride-vinyl acetate copolymer-based primers are known, and can be selected from among them to suit the substrate.

d. Substrate for volume hologram formation

The substrate for forming a volume hologram used in this step has the above-mentioned base material, resin layer, and volume hologram layer, and their formation method is not particularly limited as long as the above-mentioned resin layer and volume hologram layer are laminated in contact with each other. Therefore, the substrate for forming a volume hologram used in the present invention may be a form in which a resin layer and a volume hologram layer are sequentially laminated on a substrate, or a form in which a volume hologram layer and a resin layer are sequentially laminated on a substrate. The form of the volume hologram forming substrate used in the present invention can be appropriately selected according to the method used for recording the volume hologram in the hologram imaging step described later. For example, in the method of recording a volume hologram using a hologram master in the hologram photographing process, it is preferable to arrange the hologram master so as to be in contact with the volume hologram layer, so the volume hologram forming substrate used in the present invention is preferably a substrate A resin layer and a volume hologram layer are sequentially laminated on the material.

The substrate for forming a volume hologram used in the present invention has at least the above-mentioned resin layer, volume hologram layer, and substrate, and may have other arbitrary configurations as necessary. Arbitrary configurations used in the present invention are not particularly limited, and configurations having desired functions can be used depending on the application of the volume hologram laminate produced in the present invention. Such other configurations include, for example, a hard coat layer, an antistatic layer, a printing layer, an ink receiving layer, a release layer, and the like.

e. Manufacturing method of substrate for volume hologram formation

Next, a method of producing a volume hologram forming substrate used in the present invention will be described. The substrate for forming a volume hologram used in the present invention can be produced by sequentially forming a resin layer and a volume hologram layer on a base material. However, from the standpoint of being able to produce in a simpler process, it is preferable to form a volume hologram layer on the resin layer after forming a resin layer not containing a polymerizable compound on the base material, and further make the volume hologram layer contained in the volume hologram layer A method in which a part of the photopolymerizable material is transferred to the above-mentioned resin layer; or after forming a volume hologram layer on a base material, a resin layer not containing a polymerizable compound is formed on the above-mentioned volume hologram layer, and then the above-mentioned volume hologram A method in which a part of the polymeric material contained in the layer is transferred to the above-mentioned resin layer.

Hereinafter, this method will be described as an example of a method for producing a volume hologram forming substrate used in the present invention.

First, a method of forming a resin layer not containing a polymerizable compound on the above substrate will be described. As a method of forming a resin layer not containing a polymerizable compound on the above-mentioned base material, generally known methods can be used as a method of forming a layer containing a resin material. Examples of such a method include a method of applying a resin melt or a coating liquid obtained by dissolving a resin in a solvent to the substrate; or a method of affixing a film made of a resin to the substrate. In the present invention, any method can be preferably used depending on the kind of resin used for the above-mentioned resin layer.

Next, a method for forming a volume hologram layer on the above resin layer will be described. As a method of forming a volume hologram layer on the above-mentioned resin layer, for example, a method of applying a coating solution in which a photopolymerizable material is dissolved in a solvent to the above-mentioned resin layer, coating a film containing a photopolymerizable material The method of pasting on the above-mentioned resin layer.

Next, a method for transferring the photopolymerizable material contained in the volume hologram layer to the resin layer will be described. By laminating the resin layer and the volume hologram layer so that they are in contact with each other, the resin layer and the volume hologram layer are usually heated together, so that the photopolymerizable material can be moved to the resin layer by the principle of equilibrium movement. At this time, the movement amount of the photopolymerizable material can be adjusted arbitrarily by controlling the heating time or heating temperature.

It should be noted that, as a method of forming a volume hologram layer on the above-mentioned resin layer, when using a method of applying a coating liquid in which a photopolymerizable material is dissolved in a solvent to the above-mentioned resin layer, since the coating liquid When coating on a resin layer, since the coating liquid penetrates into the resin layer, the photopolymerizable material can be moved to the resin layer, so it may not be necessary to additionally perform the above-mentioned heating and other treatments.

On the other hand, when a volume hologram layer is formed on a substrate, a resin layer not containing a polymerizable compound is formed on the volume hologram layer, and a part of the polymerizable material contained in the volume hologram layer is removed. When producing a volume hologram-forming substrate by the above-mentioned method on the resin layer, the volume hologram-forming substrate can be produced by the above-mentioned method except that the order of forming the resin layer and the volume hologram is reversed.

(2) Shooting method of volumetric hologram

Next, a method for recording a volume type hologram on the volume hologram layer included in the volume hologram forming substrate in this step will be described.

In the volume hologram, a photopolymerizable material is fixed to record a holographic image by using interference fringes generated by light interference as fringes with different refractive indices. Therefore, the method for recording the volume hologram in this step is not particularly limited as long as it is a method capable of recording predetermined interference fringes on the volume hologram layer. Such a method includes, for example, a method in which reference light is irradiated from the substrate side of the volume hologram forming substrate, object light is incident from the volume hologram layer side, and these lights are interfered in the volume hologram layer; A hologram master is placed on the layer, and light is incident from the substrate side, and the incident light and the reflected light reflected by the hologram master interfere in the volume hologram layer, etc. Any process can be preferably used in this step, and among them, the method of using the above-mentioned hologram original plate is preferable. By this method, volume type holograms can be recorded simply.

In addition, when the method of using the above-mentioned hologram original plate is adopted in this step, as the substrate for forming a volume hologram used in this step, a substrate having a structure in which a resin layer and a volume hologram layer are sequentially laminated on a base material is used. .

When the photopolymerizable material used for the volume hologram layer contains a single photopolymerizable compound, the volume hologram is recorded by polymerizing the photopolymerizable compound in this step. However, when two or more photopolymerizable compounds are used as the photopolymerizable material, the volume hologram can be recorded by polymerizing at least one photopolymerizable compound in this step.

When a material containing the above-mentioned radically polymerizable compound and cationically polymerizable compound is used as the above-mentioned photopolymerizable material, the volume type hologram is usually recorded by polymerizing the radically polymerizable compound in this step.

2. Material movement process

Next, the substance transfer step of the present invention will be described. This step is a step of moving the polymerizable compound contained in the resin layer to the volume hologram layer on which the volume hologram was recorded in the above-mentioned hologram imaging step. In addition, in this step, by transferring the polymerizable compound from the resin layer to the volume hologram layer, the period of the interference fringes recorded on the volume hologram layer can be arbitrarily increased, and the fringes recorded on the volume hologram layer can be reproduced at any wavelength. The process of layering volume holograms.

In this step, as the method of moving the polymerizable compound from the resin layer to the volume hologram layer, any method that moves the required amount of the polymerizable compound so as to keep the period of the interference fringes recorded on the volume hologram layer within a fixed range There is no particular limitation. Examples of such a method include a method of leaving the resin layer and the volume hologram layer in contact with each other for a predetermined time, a method of heating the resin layer and the volume hologram layer together, and the like. Any of these methods can be preferably used in this step, and among them, the method of heating the above-mentioned resin layer and the above-mentioned volume hologram layer together is preferable. By this method, by controlling the heating time, heating temperature, etc., the migration amount of the above-mentioned polymerizable compound can be easily and arbitrarily adjusted.

3. Post-processing process

Next, the post-processing step of the present invention will be described. This step is a step of polymerizing the aforementioned polymerizable compound.

The method for polymerizing the polymerizable compound in this step is appropriately selected according to the type of the polymerizable compound. That is, when the above-mentioned polymerizable compound is a photopolymerizable compound, a method of irradiating light capable of inducing a polymerization reaction is used depending on the type of photopolymerizable functional group that the photopolymerizable compound has. On the other hand, when the above-mentioned polymerizable compound is a thermally polymerizable compound, a heat treatment method is used to the extent that the polymerization reaction of the thermally polymerizable functional group possessed by the thermally polymerizable compound can be induced.

Here, since the polymerizable compound migrates to the volume hologram layer in the substance transfer step, the polymerizable compound is contained in both the resin layer and the volume hologram layer when this step is performed. Therefore, in this step, the resin layer and the polymerizable compound contained in the volume hologram layer are usually polymerized at the same time.

In addition, since the polymerizable compound contained in a resin layer and a volume hologram layer is polymerized and solidified in this process, it will not move later. Therefore, in this step, the reproduction wavelength of the volume hologram is fixed.

4. Volume hologram stack

Next, the volume hologram laminate produced by the present invention will be described. The volume hologram laminate produced by the present invention uses the above-mentioned substrate for forming a volume type hologram, so the volume hologram laminate produced by the present invention has a base material, a resin layer formed on the base material, and a resin layer formed on the base material. And the volume hologram layer formed adjacent to the resin layer.

In addition, since the volume hologram laminate produced by the present invention has a volume type hologram layer recorded on the volume hologram layer, interference fringes are recorded on at least the volume hologram layer, but due to the polymer content contained in the resin layer, Depending on the type of reactive compound, interference fringes may also be formed on the resin layer. At this time, when the period of the interference fringes formed on the volume hologram layer is different from the period of the interference fringes formed on the resin layer, the hologram image can be reproduced at a plurality of wavelengths, so that a bright hologram image can be reproduced. Volume hologram overlay.

Here, the volume hologram laminate produced by the present invention is characterized by being produced by the volume hologram production method of the present invention. That is, the volume hologram laminate produced by the present invention is characterized in that a spherical region is formed on at least one of the volume hologram layer and the resin layer.

In the volume hologram laminate produced by the present invention, an example of the spherical region formed in the volume hologram layer and the resin layer will be specifically described. 3 to 5 are electron micrographs showing an example of spherical regions formed in the volume hologram layer and the resin layer in the volume hologram laminate produced in the present invention. As shown in FIGS. 3 to 5 , the volume hologram laminate produced by the present invention has spherical regions formed on the volume hologram layer and the resin layer.

Thus, the volume hologram laminate produced by the present invention is characterized in that spherical regions are formed on the volume hologram layer and the resin layer. In other words, it can be easily judged by confirming the presence or absence of the above-mentioned spherical region. The presence or absence of the spherical regions can be clearly confirmed by observing the cross-sections of the hologram layer and the resin layer with a transmission electron microscope.

B. Volume hologram laminate (first embodiment)

Next, the volume hologram laminate according to the first aspect of the present invention will be described.

The volume hologram laminate of the present invention has a base material and a volume hologram laminate part having a volume formed on the base material, containing a photopolymerizable compound, and recording a volume hologram by forming interference fringes. The hologram layer and the resin layer containing a transparent resin formed adjacent to the volume hologram layer are characterized in that interference fringes are formed on the resin layer.

Such a volume hologram laminate of the present invention will be described with reference to the drawings. Fig. 6 is a schematic view showing an example of a volume hologram laminate of the present invention. As shown in FIG. 6, the volume hologram laminate 210 of the present invention has a base material 21 and a volume hologram laminate part 22 having a volume hologram layer 22a formed on the base material 21 and a corresponding volume hologram layer 22a. A resin layer 22b containing a transparent resin is formed adjacent to the volume hologram layer 22a. Here, the volume hologram layer 22a contains a photopolymerizable compound, and forms a volume hologram by forming interference fringes. In this example, the volume hologram laminate 210 of the present invention is characterized in that interference fringes are formed on the resin layer 22b. In other words, the volume hologram laminate 210 of the present invention is characterized in that interference fringes are formed on both the volume hologram layer 22a and the resin layer 22b.

Here, the aforementioned FIG. 6 shows an example in which the volume hologram laminate of the present invention has a structure in which a volume hologram layer and a resin layer are sequentially laminated on a substrate, but the volume hologram laminate of the present invention is not limited to this structure. Therefore, the volume hologram laminate of the present invention may have a configuration in which a resin layer and a volume hologram layer are sequentially laminated on a substrate.

According to the present invention, by forming interference fringes also on the resin layer, a volume hologram capable of reproducing a hologram image at an arbitrary wavelength can be obtained by arbitrarily controlling the periods of the interference fringes formed on the volume hologram layer and the resin layer respectively. laminated body. In addition, according to the present invention, by forming the above-mentioned resin layer in contact with the above-mentioned volume hologram layer, for example, by directly forming a volume hologram layer on the above-mentioned resin layer, and then simultaneously recording interference fringes on these layers, the present invention can be manufactured. Invented volume hologram stack. Therefore, according to the present invention, it is possible to obtain a volume hologram laminate that can be produced by a simple process. Thus, according to the present invention, it is possible to provide a volume hologram laminate which can reproduce a bright hologram image by controlling the reproduction wavelength and which can be produced through a simple process.

The volume hologram laminate of the present invention has at least a substrate and a volume hologram laminate, and may have other configurations as necessary. Each configuration used in the present invention will be described in order below.

1. Volume hologram lamination section

First, the volume hologram lamination unit used in the present invention will be described. The volume hologram lamination unit used in the present invention is formed by laminating a volume hologram layer on which a volume hologram is recorded and a resin layer containing a transparent resin so as to be in contact with each other.

1-1: Resin layer

First, the resin layer used in the present invention will be described. The resin layer used in the present invention is characterized by containing a transparent resin and forming interference fringes. Such a resin layer will be described below.

(1) Interference fringes

As described above, the resin layer used in the present invention is characterized in that interference fringes are formed, and the period of the interference fringes formed in the above-mentioned resin layer is not particularly limited, and the period of the interference fringes formed in the volume hologram layer described later can be We decide arbitrarily.

Here, the formation of interference fringes in the resin layer used in the present invention can be confirmed by observing a section obtained by cutting the resin layer in the thickness direction with a transmission electron microscope (TEM).

In addition, the "period of interference fringes" in the present invention refers to the distance between adjacent bright fringes or between adjacent dark fringes. The period of the interference fringes can be obtained by measuring the wavelength dependence of the transmittance of the resin layer, in addition to the method obtained from the interference fringes taken in a transmission electron microscope (TEM) photograph of the cross section by TEM magnification. That is, among the light incident on the resin layer from a certain angle, since the light of the wavelength satisfying the Bragg condition determined by the interference fringe period is diffracted in the resin layer, the wavelength dependence of the transmittance of the resin layer satisfies the interference Minimum values are shown at wavelengths determined by the Bragg conditions of the fringe period. Therefore, by obtaining the minimum transmission wavelength of the wavelength dependence of the transmittance, the period of the above-mentioned interference fringes can be obtained. In the method of obtaining the period using the above-mentioned transmission electron microscope, the average period of the part where the regular period is clearly photographed among the photographed interference fringes represents the period of the interference fringes of the resin layer.

The period of the interference fringes formed in the resin layer used in the present invention may be constant or different throughout the resin layer. When the interference fringes have a plurality of different periods, the interference fringes of different periods may be formed by continuously changing the periods of the interference fringes, or the interference fringes of different periods may be intermittently formed.

In addition, the period of the interference fringes formed on the resin layer used in the present invention may be the same as or different from the period of the interference fringes formed on the volume hologram layer described later. Among them, in the present invention, it is preferable that the period of the interference fringes formed on the resin layer is different from the period of the interference fringes formed on the volume hologram layer described later. The reason is that since the holographic image can be reproduced by light having a wavelength consistent with the period of the interference fringes formed in the above-mentioned resin layer and the volume hologram layer, the holographic image can be reproduced using a plurality of reproduction wavelengths. Therefore, the volume hologram laminate of the present invention can reproduce brighter holographic images.

When the period of the interference fringes formed on the above-mentioned resin layer is different from the period of the interference fringes formed on the volume hologram layer described later, the period of the interference fringes formed on the resin layer may be larger or smaller than the period of the interference fringes formed on the above-mentioned volume hologram layer. cycle.

Here, in the present invention, "different" in the period of the interference fringes formed on the resin layer and the period of the interference fringes formed on the volume hologram layer described later means that there is a difference of 3 nm or more in the periods of the interference fringes of at least two layers.

(2) Transparent resin

Next, the transparent resin of the present invention will be described. The transparent resin used in the present invention is not particularly limited as long as it has desired transparency. Here, since the transparent resin used in the present invention is the same as that described above in the section "A. Method for producing a volume hologram laminate", description thereof is omitted here.

(3) Any compound

In addition to the above-mentioned transparent resin, the resin layer used in the present invention may contain other arbitrary compounds. The arbitrary compounds mentioned above are not particularly limited, and those capable of imparting desired functions to the resin layer can be arbitrarily selected and used according to the application of the volume hologram laminate of the present invention. Here, since the above arbitrary compounds are the same as those described in the section "A. Method for producing a volume hologram laminate" above, description thereof will be omitted here.

(4) Resin layer

The thickness of the resin layer used in the present invention is not particularly limited as long as the volume hologram laminate of the present invention can reproduce a hologram image at a desired wavelength according to the type of transparent resin and the like described above.

1-2: Volume Holographic Layer

Next, the volume hologram layer used in the present invention will be described. The volume hologram layer used in the present invention is characterized by containing a photopolymerizable compound and recording a volume hologram by forming interference fringes.

Such a volume hologram layer will be described below.

(1) Interference fringes

As described above, the volume hologram layer used in the present invention has interference fringes formed therein, and the period of the interference fringes formed in the volume hologram layer may be constant or different throughout the volume hologram layer. When the interference fringes have a plurality of different periods, the interference fringes of different periods may be formed continuously according to the period of the interference fringes, or the interference fringes of different periods may be intermittently formed.

The period of the interference fringes formed in the volume hologram layer used in the present invention may be the same as or different from the period of the interference fringes formed in the resin layer. Among them, in the present invention, it is preferable that the period of the interference fringes formed in the resin layer is different from the period of the interference fringes formed in the volume hologram layer. Thus, a hologram image can be reproduced by light having a wavelength that matches the period of any one of the interference fringes formed in the resin layer and the volume hologram layer. Therefore, a holographic image can be reproduced using a plurality of reproduction wavelengths, so that the volume hologram laminate of the present invention can reproduce a brighter holographic image. It should be noted that the aspect in which the period of the interference fringes formed on the resin layer is different from the period of the interference fringes formed on the volume hologram layer is the same as that formed on the resin layer in the above item "1-1. Resin layer". The way of the interference fringes is the same, so the description is omitted here.

It should be noted that the specific period of the interference fringes formed in the volume hologram layer used in the present invention corresponds to the wavelength in the visible light region.

(2) Photopolymerizable compound

Next, the photopolymerizable compound contained in the volume hologram layer will be described. The photopolymerizable compound used in the present invention is not particularly limited as long as it can undergo a polymerization reaction by irradiation with predetermined light and can form interference fringes on the volume hologram layer. Here, the photopolymerizable compound used in the present invention is the same as that described in the section "A. Method for producing a volume hologram laminate" above, so the description is omitted here.

In addition, since the volume hologram layer of this invention has already recorded the volume hologram, the said photopolymerizable compound is contained in a volume hologram layer as a polymer.

(3) any compound

The volume hologram layer used in the present invention may contain arbitrary compounds other than the photopolymerizable compound described above. Arbitrary compounds used in the present invention can be appropriately selected according to the application of the volume hologram laminate of the present invention. Here, arbitrary compounds used in the volume hologram layer of the present invention are the same as those described above as arbitrary compounds used in the volume hologram layer in the section "A. Production method of volume hologram laminate", and thus description thereof is omitted here.

1-3. Volume hologram lamination section

The volume hologram lamination part used in the present invention is formed on the base material described later. In the present invention, as an aspect in which the volume hologram lamination part is formed on the above base material, the volume hologram layer side may be arranged on the above base material. The form formed on the side of the material, or the form formed by arranging the side of the resin layer on the side of the base material.

2. Substrate

Next, the substrate used in the present invention will be described. The base material used in the present invention has a function of supporting the volume hologram layered portion described above. Here, the base material used in the present invention is the same as that described in the section "A. Method for producing a volume hologram laminate" above, so the description is omitted here.

3. Arbitrary composition

The volume hologram laminate of the present invention has at least the volume hologram laminate portion and the base material described above, and may have other arbitrary configurations as necessary. Arbitrary configurations used in the present invention are not particularly limited, and configurations having desired functions corresponding to the application of the volume hologram laminate of the present invention can be used.

4. Volume hologram stack

The volume hologram laminate of the present invention preferably exhibits two or more minimum projection wavelengths in the visible light region. The reason for this is that bright hologram images can be reproduced by the volume hologram laminate of the present invention.

C. Volume Hologram Transfer Foil

Next, the volume hologram transfer foil of the present invention will be described. As described above, the volume hologram transfer foil of the present invention is characterized by comprising the above-mentioned volume hologram laminate of the present invention, a thermoplastic resin formed on the volume hologram laminate portion of the volume hologram laminate and containing a thermoplastic resin. seal layer.

Such a volume hologram transfer foil of the present invention will be described with reference to the drawings. Fig. 7 is a schematic cross-sectional view showing an example of the volume hologram transfer foil of the present invention. As shown in FIG. 7 , the volume hologram transfer foil 220 of the present invention is characterized by comprising the volume hologram laminate 210 of the present invention described above, formed on the volume hologram layer 22 of the volume hologram laminate 210 and containing Heat seal layer 221 of thermoplastic resin.

According to the present invention, by using the above-mentioned volume hologram laminate of the present invention, the period of interference fringes that can be transferred by arbitrarily controlling the volume hologram layer and the above-mentioned resin layer formed on the above-mentioned volume hologram laminate can be obtained, Volume hologram transfer foil capable of reproducing volume holograms of holographic images at any wavelength.

The volume hologram transfer foil of the present invention has at least the volume hologram laminate and the heat seal layer.

Each structure used for the volume hologram transfer foil of this invention is demonstrated sequentially below.

1. Volume hologram stack

First, the volume hologram laminate used in the present invention will be described. The volume hologram laminate used in the present invention is the above-mentioned volume hologram laminate according to the present invention. Therefore, the volume hologram laminate used in the present invention is the same as that described in the section "B. Volume hologram laminate" above.

Here, the volume hologram laminate used in the present invention has at least a substrate and a volume hologram laminate as described above. In the present invention, it is preferable to have other configurations than the above in view of the application of the volume hologram transfer foil. As other configurations used in the above-mentioned volume hologram laminate, a mold release layer and a protective layer are mentioned as configurations preferably used in the present invention.

2. Heat seal layer

Next, the heat-sealing layer used in the present invention will be described. The heat-sealing layer used in the present invention contains a thermoplastic resin, and when the volume hologram laminated part is transferred to the transferred body using the volume hologram transfer foil of the present invention, the volume hologram laminated part and the transferred body have Engagement function. The heat-sealing layer used in the present invention will be described in detail below.

As long as the thermoplastic resin used in the present invention is compatible with the type of the transfer target on which the volume hologram lamination is transferred from the volume hologram transfer foil of the present invention, the volume hologram lamination and the transfer target can be bonded together. No particular limitation. A specific example is the same as that described in the section "E. Volume hologram laminate (second embodiment)" described later, and therefore description thereof will be omitted here.

In addition, the thermoplastic resin used in this invention may be only 1 type, or may be 2 or more types.

The heat-sealing layer used in the present invention may contain other additives in addition to the aforementioned thermoplastic resins. The additives used in the present invention include, for example, dispersants, fillers, plasticizers, antistatic agents, and the like.

The thickness of the heat-sealing layer used in the present invention is not particularly limited, and is appropriately selected according to the type of the transfer object on which the volume hologram lamination is transferred using the volume hologram transfer foil of the present invention, and is usually preferably 0.3 μm to 50 μm. The range of 0.5 μm to 25 μm is preferred. The reason for this is that, when the thickness is thinner than the above-mentioned range, there is a possibility that the bondability with the transfer target body is insufficient. When the thickness is greater than the above range, when the volume hologram lamination is transferred from the volume hologram transfer foil of the present invention, the temperature of heating the heat-sealing layer becomes too high, and the base material and the like may be damaged.

In addition, the heat-sealing layer used in the present invention may be only one layer, or may be two or more layers. In the present invention, as an aspect of using two or more heat-sealing layers, heat-sealing layers of the same composition may be laminated, or heat-sealing layers of different compositions may be laminated.

3. Arbitrary composition

The volume hologram transfer foil of the present invention has at least the above-described volume type hologram laminate and a heat-sealing layer, and other arbitrary configurations may be used as needed. Any configuration used in the present invention can be used in accordance with the application of the volume hologram transfer foil of the present invention, and a configuration having a desired function can be appropriately selected and used. Among them, examples of arbitrary configurations preferably used in the present invention include spacers, printed layers (pattern layers) or printed layers (individual information numbers, etc.).

D. Volume Hologram Labels

Next, the volume hologram label used in the present invention will be described. As described above, the volume hologram label of the present invention is characterized by comprising the above volume hologram laminate of the present invention, and an adhesive layer formed on the volume hologram laminate portion of the volume hologram laminate.

Such a volume hologram label of the present invention will be described with reference to the drawings. Fig. 8 is a schematic diagram showing an example of the volume hologram label of the present invention. As shown in FIG. 8 , the volume hologram label 230 of the present invention is characterized by comprising the volume hologram laminate 210 of the present invention described above, and the volume hologram laminate 22 formed on the volume hologram laminate 210 of the above-mentioned volume hologram. Layer 231.

According to the present invention, by using the above-mentioned volume hologram laminate of the present invention, it is possible to affix the periods of interference fringes that can be affixed by arbitrarily controlling the volume hologram layer and the above-mentioned resin layer formed on the volume hologram laminate. Volume hologram label for volume holograms that reproduce bright holographic images at any wavelength.

The volume hologram label of the present invention has at least the above-mentioned volume hologram laminate and the above-mentioned bonding layer, and may have other configurations as required. Each configuration used in the volume hologram label of the present invention will be described in order below.

1. Volume hologram stack

First, the volume hologram laminate used in the present invention will be described. The volume hologram laminate used in the present invention is the above-mentioned volume hologram laminate according to the present invention. Therefore, the volume hologram layer laminate used in the present invention is the same as that described in the section "B. Volume hologram layer laminate" above.

2. Bonding layer

Next, the bonding layer used in the present invention will be described. The adhesive constituting the bonding layer used in the present invention may be a heat-sealing agent or a general pressure-sensitive adhesive. Here, as the bonding agent used in the present invention, those described in the section "E. Volume Hologram Laminate (Second Embodiment)" described later can be used, so the description is omitted here.

The thickness of the bonding layer is preferably within a range of 4 μm to 200 μm, more preferably within a range of 5 μm to 100 μm.

E. Volume hologram laminate (second mode)

Next, the volume hologram laminate according to the second aspect of the present invention will be described.

The volume hologram laminate of this aspect is a volume hologram laminate in which a resin layer is partially provided on a substrate, and a volume hologram layer is laminated on the substrate adjacent to the resin layer, and is characterized in that: While the volume hologram is formed on the above-mentioned resin layer, the reproduction center wavelength of the volume hologram laminate is different between the part provided with the resin layer and the part not provided with the resin layer.

9 is a schematic cross-sectional view of a volume hologram laminate of the present invention, which is laminated with a resin layer 2 partially provided on a base material 1, and adjacent to the above-mentioned base material 1 and resin layer 2 based on the base material containing a radically polymerizable monomer. A volume hologram layer 3 of a volume hologram recording material of volume and cationic polymerizable monomers (FIG. 9(a)).

Here, in the above-mentioned FIG. 9( a ), an example in which the base material 1 and the resin 2 are adjacent to each other is illustrated, but the volume hologram laminate of the present invention is not limited to this correspondence. The manner in which the undercoat layer 8 is formed between the layers 2 ( FIG. 1( b )).

As the substrate 1, polyethylene terephthalate or the like capable of supporting the resin layer 2 and the volume hologram layer 3 can be used. The thickness of the substrate is usually within a range of 2 μm to 200 μm, preferably within a range of 10 μm to 50 μm.

In addition, in the volume hologram bonded body described later, the substrate can be made to function as a protective film, and can also be peeled and removed. When functioning as a protective film, the adhesion between the base material and the resin layer or the volume hologram recording material layer is necessary, and the surface of the base material can be subjected to corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, gravity treatment, etc. Surface treatment such as chromate treatment, anchoring or primer treatment. Examples of the anchoring agent or primer include urethane-based, acrylic-based, ethylene-vinyl acetate copolymer-based, vinyl chloride-vinyl acetate copolymer-based, and the like. In addition, when peeling and removing, the substrate may be subjected to a release treatment, and a resin layer and a volume hologram layer may be provided with or without a protective layer.

Next, the resin layer 2 is a transparent resin layer, and is obtained by coating a part of the base material with a resin solution to form a pattern such as a movable type. The resin forming the resin layer includes those described above in the section "A. Method for producing a volume hologram laminate", and particularly polymethyl methacrylate (PMMA) resin and the like are mentioned.

When the resin forming the resin layer is polymethyl methacrylate resin, polyvinyl acetate resin, polyester resin, etc., the detailed reason is unclear, but it can be seen that the part where the resin layer 2 is laminated in the volume hologram laminate The reproduction center wavelength of (substrate 1/resin layer 2/volume hologram layer 3') is different on the longer wavelength side than the reproduction center wavelength of the part where the resin layer is not laminated (substrate/volume hologram layer 3") Different degrees are affected by the weight average molecular weight of the resin. When the weight average molecular weight is 5,000 to 1,000,000, preferably 5,000 to 500,000, and particularly preferably 10,000 to 300,000, the reproduction center wavelength can be different on the longer wavelength side. Explain , The molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

The difference between the reproduction center wavelength of the portion provided with the resin layer and the reproduction center wavelength of the portion not provided with the resin layer is at least 10 nm or more, preferably 15 nm or more. It should be noted that the difference is at most 100 nm.

In addition, when the resin forming the resin layer is a resin such as polyvinyl butyral resin or polyvinyl acetal resin, the detailed reason is not clear, but different from the above, it can be seen that the reproduction center of the part where the resin layer is provided The wavelength is seen to be different on the shorter wavelength side than the reproduction center wavelength of the part where the resin layer is not laminated. The degree of difference is affected by the weight average molecular weight of the resin as above, and when the weight average molecular weight is 5,000 to 1,000,000, preferably 5,000 to 500,000, and particularly preferably 10,000 to 300,000, the reproduction center wavelength can be varied on the shorter wavelength side.

The difference between the reproduction center wavelength of the portion provided with the resin layer and the reproduction center wavelength of the portion not provided with the resin layer is at least 10 nm or more, preferably 15 nm or more. It should be noted that the difference is at most 100 nm.

Each reproduction center wavelength of the part provided with the resin layer and the part not provided with the resin layer is obtained by measuring the transmittance using a spectrophotometer (UV-2450 (manufactured by Shimadzu Corporation)) to obtain a spectral transmittance curve. The ratio curve is obtained by the following method together with the diffraction efficiency and the half width, and will be described with reference to FIG. 4 .

(diffraction efficiency)

The peak transmittance A and valley transmittance B of the spectral transmittance were obtained, and |B-A|/B (%) was calculated.

(half width)

Find the left end (C) and right end (D) of the spectral transmittance curve at the peak transmittance A plus the half of the difference between the valley transmittance A and the peak transmittance B (A+|B-A|/2), and calculate the half Peak width = |D-C| (nm).

(reproduction center wavelength)

A wavelength (=C+|D-C|/2) at which half of the half-width is added to C obtained when calculating the half-width is taken as the reproduction center wavelength.

In the resin layer 2, for example, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, plasticizers, lubricants, antistatic agents, flame retardants, fillers, etc. agent etc.

The resin layer 2 is formed by partially coating a resin solution in which the above-mentioned resin and other components are dissolved in methyl ethyl ketone, toluene, ethyl acetate, etc., on the base material by gravure printing, screen printing, etc., to reach the dry film thickness on the base material. It is 0.1 μm to 10 μm, preferably 0.5 μm to 5 μm, particularly preferably 0.5 μm to 3 μm.

In addition, the resin layer 2 may be formed adjacent to the base material 1 mentioned above, or may be formed as another layer formed adjacent to the base material 1, such as a primer layer.

The undercoat layer used in the present invention can be appropriately selected from a substance having a desired function according to the application of the volume hologram laminate of the present invention, and is not particularly limited.

Next, as shown in FIG. 9 , a volume hologram recording material layer is formed by coating directly on the resin layer 2 formed on the base material 1 without an intermediate layer.

The volume hologram recording material layer used in the present invention contains a photopolymerizable material and can record a holographic image with high contrast. It is preferable to use a radically polymerizable monomer and a cationically polymerizable monomer in combination with a photoradical polymerization initiator. , photocationic polymerization initiator used together.

Here, the radically polymerizable compound, the photoradical polymerization initiator, the cationic polymerizable compound, and the photocationic polymerization initiator used in the present invention are different from the above-mentioned "A. Method for producing a volume hologram laminate". The substances that have been described are the same, so descriptions are omitted here.

Next, a method for producing the volume hologram laminate of the present invention will be described.

In the volume hologram laminate of the present invention, first, a resin layer is partially coated on a base material, and then the base material and the resin layer are respectively adjacently coated to form a resin layer containing a radically polymerizable monomer and a cationically polymerizable monomer. The volume hologram of the volume is recorded on the material layer to form a laminated body.

(1) Etching treatment is performed on the obtained laminated body. The etching treatment is performed by leaving the laminate at room temperature or heating the laminate at 40 to 80° C. for 1 to 48 hours. By this treatment, in the layer constitution of substrate/resin layer/volume hologram recording material layer, monomers and the like in the volume hologram recording material layer move into the resin layer. As described in Example 1, when the resin layer after the etching treatment was subjected to IR analysis, it was confirmed that the radical polymerizable monomer or cation polymerizable monomer in the volume hologram recording material layer migrated into the resin layer.

(2) Next, after performing an etching process on the laminated body, after adhering the hologram original plate on the side of the volume hologram recording material layer, and exposing the hologram by laser irradiation from the base material side of the laminated body, a hologram is produced. The volume holographic layer of the graph.

In the volume hologram, interference fringes generated by light interference are used as fringes with different diffraction indices, and a photopolymerizable material is immobilized to record a holographic image. Therefore, as a method for recording a volume hologram in this step, for example, reference light is incident from the base material side of the volume hologram forming substrate, object light is incident from the volume hologram layer side, and the volume hologram layer is irradiated within the above-mentioned volume hologram layer. A method of interfering these lights; a method of arranging a hologram master on a volume hologram layer, injecting light from the substrate side, and causing the incident light and reflected light reflected by the hologram master to interfere in the volume hologram layer wait. Among them, the above-mentioned method using a hologram master is preferable, whereby a volume type hologram can be easily recorded.

(3) After exposing the hologram, the original hologram is peeled off, and a PET film is laminated on the peeled surface. Then, after heating the laminated body at 50° C. to 150° C. for 5 minutes to 120 minutes, ultraviolet rays are irradiated at 500 mJ/cm ² to 5000 mJ/cm ² . The heat treatment process is considered to be a process of re-diffusing a part of the remaining polymerizable monomers after exposure of the hologram, and immobilizing other monomers by heat treatment-ultraviolet irradiation treatment to form a stable hologram.

In the present invention, when polymethyl methacrylate resin or polyvinyl acetate resin is used to form the resin layer, compared with the portion where the resin layer is not provided in the volume hologram laminate, the difference between the base material/resin layer/volume hologram layer In the laminated portion, it can be seen that the reproduction center wavelength is different on the longer wavelength side. The detailed reason is not clear, but it is thought that the interference fringe period (interference fringe interval) of the volume hologram layer is shorter than the interference fringe period (interference fringe period) of the resin layer as observed from the electron microscope cross-sectional photograph of Example 1 described later. In order to re-move the monomer from the resin layer to the volume hologram layer by the heating process of (3) after amplification, the reproduction center wavelength of the laminated part of the base material/resin layer/volume hologram layer is different from that not provided. The reproduction center wavelength of the lamination portion of the base resin layer/volume hologram layer of the resin layer is different on the longer wavelength side.

In addition, when polyvinyl butyral resin or polyvinyl acetal resin is used to form the resin layer, the reproduction center wavelength and the unset The portion of the resin layer is different on the short-wavelength side. The detailed reason is not clear, but it is considered that polyvinyl butyral resin and polyvinyl acetal resin move monomers different from the PMMA resin layer through the heating process of (3) above, and the substrate/resin layer/ The reproduction center wavelength of the laminated portion of the volume hologram layer is different from the reproduction center wavelength of the laminated portion of the substrate resin layer/volume hologram layer without the resin layer on the shorter wavelength side.

In this way, the volume hologram stack of the present invention can be made into a volume hologram stack partially having a portion where the reproduction center wavelength is different. In addition, the obtained volume hologram laminate is used as a master plate, and a volume hologram recording material layer is bonded to it, and contact copying is attempted using a single-wavelength laser, but parts with different reproduction center wavelengths become dark and cannot be reproduced perfectly. A volume hologram laminate with excellent anti-counterfeiting.

Next, the sheet for volume hologram transfer of the present invention will be described with reference to FIGS. 10 and 12 . FIG. 10 shows a first sheet for volume hologram transfer, in which an adhesive layer 4 is provided on the volume hologram layer 3 of the volume hologram laminate in FIG. 9 . The adhesive layer 4 is an adhesive layer or a heat-sealing layer. In particular, FIG. 10 shows the case where a peelable sheet 5 is further laminated to form an adhesive layer to form a volume hologram transfer label. When making a heat-sealing layer, the peelable sheet 5 can be omitted to make a volume hologram transfer foil.

Fig. 12 is a sheet for transferring a second volume hologram, in which a peelable second base material 7 is provided on the volume hologram layer of the volume hologram laminate of Fig. 9, and the volume hologram laminate of Fig. 9 is peeled off simultaneously. An adhesive layer 4 is provided on the resin layer 2 and the volume hologram layer 3 exposed from the substrate 1 . The adhesive 4 is an adhesive layer or a heat-sealing layer, and Fig. 12 shows a case in which a release sheet 5 is further laminated to form a volume hologram transfer label when the adhesive layer is formed. When making a heat-sealing layer, the peelable sheet 5 can be omitted to make a volume hologram transfer foil.

Acrylic resin can be used as an adhesive for the volume hologram transfer label. Adhesive can use ethyl acetate, toluene, methyl ethyl ketone, butyl acetate, etc. The permanent sheets are laminated together on the volume hologram layer 3. As the release sheet, in addition to the commonly used release paper, polyethylene terephthalate resin film, polypropylene resin film, etc. using fluorine-based release agent, silicone-based release agent, etc. can also be used. A film obtained by performing a release treatment.

In addition, as the heat-sealing agent for the volume hologram transfer foil, it is a thermoplastic resin and a substance having heat-sealing properties. As the resin that can be made into an organic solvent solution to form a heat-sealing layer, ethylene-vinyl acetate copolymer resin, poly Amide resin, polyester resin, polyethylene resin, ethylene-isobutyl acrylate copolymer resin, butyral resin, polyvinyl acetate resin, vinyl chloride vinyl acetate copolymer resin, cellulose derivatives, polymethyl methacrylate resin Such as acrylic resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin, polypropylene resin, epoxy resin, phenolic resin, SBS, SIS, SEBS, SEPS and other thermoplastic elastomers or reactive hot-melt resins, etc. Examples of organic solvents include toluene and methyl ethyl ketone, which can be formed on the volume hologram layer 3 by coating with a dry film thickness of 2 to 10 μm using a comma coater, die coater, or gravure coater.

The volume hologram bonded body of the present invention will be described using FIGS. 11 and 13 . As shown in FIG. 11 , the volume hologram bonded body of the present invention is bonded to the covered body from the adhesive layer 4 side after peeling off the release sheet 5 of the volume hologram transfer sheet shown in FIG. 10 . 6, the substrate 1 is peeled off or remains as a protective layer of the volume hologram layer.

In addition, another volume hologram bonded body of the present invention shown in FIG. 13 is bonded to the covered body from the adhesive layer 4 side after peeling off the release sheet 5 of the volume hologram transfer sheet shown in FIG. 12 . 6, the second substrate 7 is peeled off or remains as a protective layer of the volume hologram layer.

Examples of the covering body 6 of the volume hologram bonded body of the present invention include transparent or opaque materials such as glass and plastic. Plastics include vinyl chloride resin, acrylic resin, polystyrene resin, polyester resin such as polyethylene terephthalate, polycarbonate resin, etc., and are particularly suitable for making cards and sheets made of polyester resin. Materials and membranes. The sheet for volume hologram transfer can be pasted on a sheet such as an ID card, a ticket, a card such as an ID card, or a booklet such as a passport. In addition, it is also suitable for making security, disinfection, or fire protection, etc. certificate of sanitation or the certificate used to carry out this treatment. In addition, for the purpose of pasting paper certificates for sealing, if the object is transparent and basically flat or two-dimensional, it can be replaced with a certificate in principle. Furthermore, as objects to which volume hologram transfer sheets are pasted, films or sheets made of paper, synthetic paper, synthetic resin, metal, or articles with parts made of glass or the like can be widely used. In addition, volume holograms can also be used as labels that are pasted on newspapers such as books or saddle stitch weekly magazines, windows of automobiles, high-quality products, etc., by taking advantage of the unique characteristics of volume holograms that can express three-dimensionality.

In addition, this invention is not limited to the said embodiment. The above-described embodiments are examples, and those having the same technical idea and substance as described in the scope of the claims of the present invention and having the same functions and effects are also included in the technical scope of the present invention.

Example

The following examples will be given to describe the present invention concretely, but the present invention is not limited to the following examples.

1-1. Embodiment 1

(1) Preparation of substrate for volume hologram formation

A polyethylene terephthalate (PET) film (Lumirror-50T60, manufactured by Toray Co., Ltd.) with a thickness of 50 μm was used as the base material, and a weight solution dissolved in a solvent was coated on the base material using a bar coater. The coating solution for forming a resin layer of polymethyl methacrylate having an average molecular weight of 15,000 was dried to form a resin layer so as to have a coating film thickness of 2 μm.

Next, a coating solution for forming a volume hologram layer having the following composition was directly applied on the resin layer using a dispenser to a dry film thickness of 10 μm to form a volume hologram layer.

(Coating solution for volume hologram layer formation)

·Polyvinyl acetate 35 parts by weight

(Denka SAKNOHOLSN-08H: degree of polymerization 800; manufactured by Denka Kogyo Co., Ltd.)

1,6-hexanediol diglycidyl ether 25 parts by weight

(Denacol EX-212; manufactured by Nagase ChemteX Co., Ltd.)

Diphenoxyethanol fluorene diacrylate 35 parts by weight

(BPEFA: manufactured by Osaka Gas Chemical Co., Ltd.)

Diaryliodonium salt 4 parts by weight

(PI2074; manufactured by Rhodia)

2,5-bis(4-diethylaminobenzylidene)cyclopentanone 1 part by weight

Methyl isobutyl ketone 100 parts by weight

1-butanol 100 parts by weight

(2) Hologram shooting process

Next, a hologram master was laminated on the volume hologram layer, and a 532 nm laser beam of 80 mJ/cm ² was incident from the substrate side to record a volume hologram. After recording, the original volume hologram was peeled off, and a PET film with a thickness of 50 μm was laminated on the volume hologram layer.

(3) Material transfer process

Next, the resin layer and the volume hologram layer are heated. At this time, the heating condition was 100° C. for 10 minutes.

(4) Post-processing process

Next, the volume hologram layer was immobilized by irradiating the entire surface of the ultraviolet ray to obtain a volume hologram stack.

1-2. Embodiment 2

A volume hologram laminate was produced in the same manner as in Example 1 except that a polymethyl methacrylate having a weight average molecular weight of 35,000 was used.

1-3. Embodiment 3

A volume hologram laminate was produced by the same method as in Example 1 except that polymethyl methacrylate having a weight average molecular weight of 100,000 was used.

1-4. Embodiment 4

A volume hologram laminate was produced in the same manner as in Example 1 except that a polyester resin with a weight average molecular weight of 40,000 (Vylon 270, manufactured by Toyobo Co., Ltd.) was used instead of polymethyl methacrylate.

1-5. Comparative example 1

A volume hologram laminate was fabricated by the same method as in Example 1 except that the volume hologram layer was directly formed on the substrate without forming a resin layer.

1-6. Evaluation of hologram recording characteristics

The transmittances of the volume hologram laminates obtained in Examples and Comparative Examples were measured with a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation), and the diffraction efficiency, half-peak width, and reproduction center were calculated from the spectral transmittance curves wavelength. The results are shown in Table 1 below

The spectral transmittance curves of Examples 1 to 3 and Comparative Example 1 are shown in FIG. 14 .

Table 1

Width at half maximum (nm) Diffraction efficiency (%) Reproduced central wavelength (nm) Example 1 twenty four 80 532 Example 2 27 81 539 Example 3 twenty four 74 544 Example 4 28 74 556 Comparative example 1 28 88 527

2-1. Embodiment 5

(1) Fabrication of volume hologram stacks

A polyethylene terephthalate (PET) film (Lumirror-50T60, manufactured by Toray Co., Ltd.) with a thickness of 50 μm was used as a base material, and polymethyl methacrylate with a weight average molecular weight of 100,000 was used for dissolving by gravure printing. The coating solution for forming a resin layer in a methyl ethyl ketone solvent was applied on the substrate to form a patterned resin layer to form a patterned resin layer with a dry film thickness of 2 μm.

Next, a coating solution for forming a volume hologram layer having the following composition was directly applied to the above-mentioned resin layer using a dispenser to a dry film thickness of 10 μm to form a volume hologram layer.

(Coating solution for volume hologram layer formation)

・Polyvinyl acetate (Denka SAKNOHOL SN-08H: degree of polymerization 800; manufactured by Denka Kogyo Co., Ltd.) 35 parts by weight

1,6-hexanediol diglycidyl ether (Denacol EX-212; manufactured by Nagase ChemteX Co., Ltd.) 25 parts by weight

· Diphenoxyethanol fluorene diacrylate (BPEFA: manufactured by Osaka Gas Chemical Co., Ltd.) 35 parts by weight

・Diaryliodonium salt (PI2074; manufactured by Rhodia) 4 parts by weight

2,5-bis(4-diethylaminobenzylidene)cyclopentanone 1 part by weight

Methyl isobutyl ketone 100 parts by weight

1-butanol 100 parts by weight

(2) Etching process

The obtained volume hologram laminate was left at room temperature for 24 hours to perform etching treatment. After the etching treatment, the resin layer was analyzed with an IR analyzer (FT/IR-610 manufactured by JASCO Corporation), and it was confirmed that 1,6-hexanediol diglycidyl ether and diphenoxyethanol fluorene diacrylate were contained.

(3) Hologram shooting process

A hologram original plate was laminated on the volume hologram layer of the volume hologram laminate, and a 532 nm laser beam of 80 mJ/cm ² was incident from the substrate side to record a volume hologram. After recording, the original volume hologram was peeled off, and a PET film with a thickness of 50 μm was laminated on the volume hologram layer.

(4) Heat treatment - ultraviolet irradiation treatment process

After heating the volume hologram stack after hologram recording at 100° C. for 10 minutes, the entire surface was irradiated with ultraviolet light (3000 mJ/cm ² ) to fix the hologram to obtain a volume hologram layer.

Fig. 15 is a 70% reduced facsimile of a vertical cross-sectional scanning electron micrograph (15,000 times) of the position where the resin layer was laminated in the obtained volume hologram laminate. 15, 1 is the substrate, 2 is the resin layer, and 3 is the volume hologram layer. Interference fringes are recorded on the resin layer 2 at intervals of 116 nm, and interference fringes are recorded on the volume hologram layer 3 at intervals of 186 nm.

The transmittance was measured with a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) for the patterned portion and the unpatterned portion of the resin layer, and the results are shown in FIG. 16 as a spectral transmittance curve. .

The reproduction center wavelength of the spectral transmittance curve (A) of the patterned part of the resin layer was 544 nm, and the reproduction center wavelength of the spectral transmittance curve (B) of the unpatterned part was 527 nm.

(for security)

The coating solution for forming a volume hologram layer described above was applied on a PET film with a film thickness of 50 μm using a feeder to obtain a laminated body with a dry film thickness of 10 μm, and the above-mentioned recording material layer was coated from the side of the volume hologram recording material layer. After the volume hologram laminate with the volume hologram was pasted on the PET film as the original plate, the volume hologram was taken with a 532nm laser, and the patterned part of the resin layer became dark, making it impossible to take a good hologram.

2-2. Embodiment 6

Except for using a methyl ethyl ketone solution of polyvinyl acetal resin (S-LEC BH-6: about 92000 in weight average molecular weight, manufactured by Sekisui Chemical Co., Ltd.) as the coating solution for the resin layer, it was carried out in the same manner as in Example 5, A volume hologram stack in which volume holograms are recorded is obtained.

A spectrophotometer (UV-2450: manufactured by Shimadzu Corporation) was used to measure the transmittance of the patterned and unpatterned portions of the resin layer. FIG. 17 shows a spectral transmittance curve.

The reproduction center wavelength of the spectral transmittance curve (C) of the patterned part of the resin layer was 490 nm, and the reproduction center wavelength of the spectral transmittance curve (D) of the unpatterned part was 527 nm.

In addition, regarding anti-counterfeiting, as in Example 5, when a volume hologram was captured using the volume hologram laminate recorded thereon as a master, the patterned portion of the resin layer became dark, and the hologram could not be captured satisfactorily.

2-3. Embodiment 7

A volume hologram laminate on which a volume hologram was recorded was obtained in the same manner as in Example 5, except that a methyl ethyl ketone solution of polyvinyl acetate resin (weight average molecular weight: about 500,000, manufactured by ALDRICH) was used as the coating liquid for the resin layer. .

The transmittance was measured using a spectrophotometer (UV-2450: manufactured by Shimadzu Corporation) for the patterned portion and the non-patterned portion of the resin layer, and the reproduction center wavelength of the patterned portion of the resin layer was The reproduction center wavelength of the spectral transmittance curve of the 554 nm and non-patterned portion is 527 nm.

In addition, regarding anti-counterfeiting, as in Example 5, when a volume hologram was captured using the volume hologram laminate recorded thereon as a master, the patterned portion of the resin layer became dark, and the hologram could not be captured satisfactorily.

2-4. Embodiment 8

Except for using a methyl ethyl ketone solution of polyester resin (Vylon 270: weight average molecular weight 40,000, manufactured by Toyobo Co., Ltd.) as the coating liquid for the resin layer, it was carried out in the same manner as in Example 5, and a volume hologram in which a volume hologram was recorded was obtained. laminated body.

The transmittance was measured using a spectrophotometer (UV-2450: manufactured by Shimadzu Corporation) for the patterned portion and the non-patterned portion of the resin layer, and the reproduction center wavelength of the patterned portion of the resin layer was The reproduction center wavelength of the spectral transmittance curve of the 556 nm and non-patterned portion is 527 nm.

In addition, regarding anti-counterfeiting, as in Example 5, when a volume hologram was captured using the volume hologram laminate recorded thereon as a master, the patterned portion of the resin layer became dark, and the hologram could not be captured satisfactorily.

2-5. Embodiment 9

On the volume hologram layer of the volume hologram laminate produced in Example 5, apply an adhesive solution of the following composition with a feeder to a film thickness of 20 μm after drying, and dry it in an oven to form an adhesive layer. Then, a release sheet (SPPET (75 μm), manufactured by TOHCELLO Co., Ltd.) was laminated on the adhesive layer to obtain a volume hologram transfer label as the first volume hologram transfer sheet of the present invention.

Acrylic adhesive (Nissetsu PE-118; manufactured by Nippon Calcium Industry Co., Ltd.) 100 parts by mass

・Isocyanate-based crosslinking agent (Nissetsu CK-101; manufactured by Nippon Calcium Industry Co., Ltd.) 2 parts by mass

Solvent (methyl ethyl ketone/toluene/ethyl acetate=2/1/1 (mass ratio)) 60 parts by mass

After peeling off the release sheet of the label for volume hologram transfer, it was pasted on the PVC card as the covering body from the adhesive layer side using a manual laminator to obtain the volume hologram bonded body of the present invention. A volume hologram obtained in which the center wavelength of reproduction is patterned differently between the portion where the resin layer is provided and the portion where the resin layer is not provided is excellent in design.

2-6. Embodiment 10

Coat an untreated PET film {Lumirror-T60 (25 μm); manufactured by Toray Co., Ltd.} with a bar coater to form a peelable protective layer with the following composition to a film thickness of 1 μm after drying, and dry it in an oven , A laminate of PET film/peelable protective layer was obtained.

97 parts by mass of polymethyl methacrylate (weight average molecular weight: 100,000)

· Polyethylene wax (weight average molecular weight 10000) 3 parts by weight

Solvent (methyl ethyl ketone/toluene/ethyl acetate=2/1/1 (mass ratio)) 60 parts by mass

Using the volume hologram laminate (PET film/resin layer/volume hologram layer/PET film) before treatment in (4) heat treatment-ultraviolet irradiation treatment step of the volume hologram laminate production method of Example 5, the The PET film on the side of the volume hologram layer was peeled off, and the peelable protective layer of the PET film/peelable protective layer laminate obtained above was aligned from the volume hologram layer side, passed to a drum at 80° C., and the entire surface was irradiated with ultraviolet rays. A volume hologram laminate composed of PET film/peelable protective layer/volume hologram layer/resin layer/PET film was obtained.

After peeling off the PET film on the resin layer side of the obtained volume hologram laminate, a heat seal layer of the following composition was applied on the volume hologram layer and the partly provided resin layer using a bar coater so that the film thickness after drying was 4 μm , dried in an oven to obtain a volume hologram transfer foil as the second volume hologram transfer sheet of the present invention consisting of a PET film/peelable protective layer/volume hologram layer/resin layer/heat seal layer .

・Polyester resin (Vylonal MD1985; manufactured by Toyobo Co., Ltd.) …100 parts by mass

・Solvent (water/isopropanol=1/1 (mass ratio)) …100 parts by mass

Using a heat press (V-08: manufactured by Navitas Co., Ltd.), the obtained volume hologram transfer foil is superimposed from the heat-sealing layer side as a coating at a transfer temperature of 150° C., a transfer time of 0.5 seconds, and a pressure of 125 kgf/cm ^{2 .} After that, the PET film is peeled off to obtain a volume hologram laminated body consisting of a peelable protective layer/volume hologram layer/resin layer/heat seal layer/PVC card. A volume hologram obtained in which the center wavelength of reproduction is patterned differently between the portion where the resin layer is provided and the portion where the resin layer is not provided is excellent in design.

Claims (21)

1. A method of manufacturing a volume hologram laminate, characterized in that, Including the following procedures: A hologram photographing step of recording a volume hologram on a volume hologram layer using a volume hologram forming substrate having a base material and containing a photopolymerizable material formed on the base material a volume hologram layer, and a resin layer comprising a resin and a polymerizable compound formed on said substrate and in contact with said volume hologram layer; a mass transfer process of moving said polymerizable compound towards said volume hologram layer; A post-treatment step of polymerizing the polymerizable compound. 2. The method for manufacturing a volume hologram laminate according to claim 1, wherein: The polymerizable compound is transferred from the volume hologram layer. 3. The method for producing a volume hologram laminate according to claim 1 or 2, wherein the photopolymerizable material contains a radical polymerizable compound and a cationic polymerizable compound, and the polymerizable compound is the Cationic polymerizable compound. 4. A volume hologram laminate comprising a base material and a volume hologram laminate part comprising a photopolymerizable compound formed on the base material and recorded by forming interference fringes The volume hologram layer of the volume hologram, and the resin layer containing a transparent resin formed so as to be in contact with the volume hologram layer, are characterized in that interference fringes are formed on the resin layer. 5. The volume hologram laminate according to claim 4, wherein the period of the interference fringes formed on the volume hologram layer is different from the period of the interference fringes formed on the resin layer. 6. The volume hologram laminate according to claim 4 or 5, wherein the transmittance in the visible light region shows two or more minimum transmittance wavelengths. 7. A volume hologram transfer foil, comprising the volume hologram laminate according to any one of claims 4 to 6, and the volume hologram formed on the volume hologram laminate A heat-sealing layer containing a thermoplastic resin on the laminated part. 8. A volume hologram label, comprising the volume hologram laminate according to any one of claims 4 to 6, and the volume hologram laminate portion formed on the volume hologram laminate bonding layer on top. 9. A volume hologram laminate, which is partially provided with a resin layer on a base material, and a volume hologram layer is stacked adjacent to the resin layer and on the base material, characterized in that, A volume hologram is formed on the resin layer, and the center wavelength of reproduction differs between a portion provided with the resin layer and a portion not provided with the resin layer in the volume hologram stack. 10. The volume hologram laminate according to claim 9, wherein the resin layer is adjacent to the substrate. 11. The volume hologram laminate according to claim 9, wherein an undercoat layer is formed between the resin layer and the substrate. 12. The volume hologram laminate according to any one of claims 9 to 11, wherein the volume hologram is derived from a volume hologram recording material containing a radically polymerizable monomer and a cationically polymerizable monomer In addition, in the volume hologram laminated body, a volume hologram based on migration of a polymerizable monomer from an adjacent volume hologram recording material is formed on the resin layer. 13. The volume hologram laminate according to any one of claims 9 to 12, wherein the resin layer contains a resin selected from polymethyl methacrylate, polyvinyl acetate, polyester resin, and the volume The reproduction center wavelength of the part where the resin layer is provided in the hologram laminate is on the longer wavelength side than the reproduction center wavelength of the part where the resin layer is not provided. 14. The volume hologram laminate according to any one of claims 9 to 12, wherein the resin layer contains a resin selected from polyvinyl butyral resins and polyvinyl acetal resins, and the volume The reproduction center wavelength of the part where the resin layer is provided in the hologram laminate is on the shorter wavelength side than the reproduction center wavelength of the part where the resin layer is not provided. 15. The volume hologram laminate according to claim 13 or 14, wherein the difference between the reproduction center wavelength of the part of the volume hologram laminate with the resin layer and the reproduction center wavelength of the part without the resin layer At least 10nm or more. 16. A method for producing a volume hologram laminate, characterized in that: After partially coating the substrate to form a resin layer, coating adjacent to the resin layer and on the substrate to form a volume hologram recording material containing a radically polymerizable monomer and a cationically polymerizable monomer layer, and then carry out the following steps sequentially on the resulting laminated body: (1) performing an etching process to move the polymerizable monomer in the volume hologram recording material layer to the resin layer; (2) A hologram exposure process using laser exposure from the substrate side; (3) performing heat treatment and ultraviolet irradiation treatment, moving the polymerizable monomer between the resin layer and the volume hologram recording material layer, and simultaneously immobilizing the hologram, A volume hologram based on a polymerizable monomer moved from an adjacent volume hologram recording material layer is formed on the resin layer, and the difference between the portion provided with the resin layer and the portion not provided with the resin layer in the laminated body is adjusted. The reproduction center wavelengths are different. 17. A sheet for transferring a volume hologram, wherein an adhesive layer is provided on the volume hologram layer of the volume hologram laminate according to any one of claims 9 to 11. 18. A sheet for volume hologram transfer, characterized in that a peelable second substrate is provided on the volume hologram layer of the volume hologram laminate according to claim 9 or 11, and at the same time An adhesive layer is provided on the surface of the volume hologram laminate described above after the substrate is peeled off. 19. The sheet for transferring a volume hologram layer according to claim 9 or 10, wherein the sheet for transferring a volume hologram is a volume hologram transfer foil whose adhesive layer is a heat-sealing layer , or a volume hologram transfer label whose adhesive layer is an adhesive layer. 20. A volume hologram bonded body, characterized in that the volume hologram transfer sheet according to claim 17 is stuck to the covering body from the adhesive layer side, and the base material is peeled off or remains to form a Protective layer for the volume hologram layer. 21. A volume hologram bonded body, characterized in that the volume hologram transfer sheet according to claim 18 is stuck to the covering body from the adhesive layer side, and the second base material is peeled off or remains And become the protective layer of the volume hologram layer.

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