JPS63284586A - Transfer type hologram - Google Patents

Abstract

PURPOSE:To facilitate application of a hologram to various materials by providing a peelable volume phase type hologram film on a base material. CONSTITUTION:A hologram film 2 where a prescribed image is recorded is peelably laminated on a base material 1 and prescribed exposure and development processings are performed, or a peeling layer 3 is provided between the base material 1 and the film 2. In this transfer type hologram, the exposed surface of film 2 is put on the surface of a material to be transferred and is pressed to it, the film 2 is transferred to another desired material to be transferred. A transparent base material consisting of glass or various resins is preferable as the base material 1, and the base material is subjected to the surface treatment on demand to improve the peelability. Various film-shaped volume phase type holograms where a desired image is recorded can be used as the film 2. An adhesive layer (or layer for adhesion) 4 may be provided on the film 2.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a volume phase hologram that allows a three-dimensional image to be observed on, for example, a flat film. The present invention relates to a transfer hologram that can be easily provided.

[Conventional technology]

In holography, an object is irradiated with light waves with good coherence, such as a laser, and the reflected or transmitted light, whose amplitude and phase are modulated according to the shape of the object, is received and recorded using a sensitive material. , is a technique for reproducing an optical image of an object recorded using light irradiated onto a formed hologram. For example, it is possible to observe a stereoscopic optical image on a flat film.

With the progress of research on holography, the requirements for sensitizers have become quite clear. Many materials are known as sensitive materials that can be used in holography, such as bleached silver salts, photoresists, thermoplastics, dichromate gelatin, inorganic glass materials, and ferroelectric materials.
The suitability for this is being further studied.

Characteristics that a sensitizer for forming holograms should have include, for example, (1) laser sensitivity, especially laser sensitivity in the visible light region, and high sensitivity; (2) high resolution; (3) The obtained hologram has high diffraction efficiency, (4) hologram noise is low, (5) hologram is stable, and (6) recording and reproducing operations are easy. can.

On the other hand, with the advancement of holography technology, it is becoming possible to form holograms that can withstand practical use, and holograms are being used in a variety of ways, such as enjoying the image itself and using it to decorate various items. As the world continues to expand, holograms are also being required to take on a variety of shapes.

For example, a type of hologram that reproduces an image by forming unevenness corresponding to the image on the surface of the sensitive layer and utilizing the reflection or transmission of light on the unevenness can be used as a wooden cover, or for counterfeiting or alteration of magnetic cards. It is used on the hem as a preventive mark.

[Problem that the invention seeks to solve]

However, in terms of both the characteristics of the hologram-forming sensitizer mentioned above and the form of the hologram itself, no hologram has been provided that can fully meet the various demands associated with the expansion of applications as described above. The current situation is that there is no such thing.

For example, a technique for easily applying a hologram to various desired objects with simple operations and a suitable hologram form have not yet been provided.

The present invention was made in consideration of the various demands accompanying the expansion of the uses of holograms, and its purpose is to provide a technology that facilitates the application of holograms to various objects. do.

[Means for solving problems]

The above object can be achieved by the following invention.

That is, the present invention is a transfer-type hologram characterized by having a base material and a volume phase-type hologram film on which a desired image is recorded and is removable from the base material.

By using the transfer hologram of the present invention having such a configuration, a desired holographic image can be transferred to paper, metal, plastic, etc. by a simple operation of transferring a hologram film held on a base material to a desired article. It can be easily applied to desired portions of various objects (hereinafter referred to as transferred materials) made of ceramic or the like. Further, for example, by using a suitable mount as the transfer material and transferring the hologram film thereon, the hologram film can be enjoyed in the same way as a picture or photograph.

In addition, with the above-mentioned type using an uneven surface, when the hologram is directly adhered to various transfer materials by pressure bonding or adhesion, the unevenness formed on the surface is unavoidably affected by deformation or damage. Since the transfer type hologram uses a volume phase type hologram film, such a problem does not occur during transfer.

Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic side view showing the configuration of an example of a transfer hologram of the present invention.

This transfer type hologram includes a base material 1 and a hologram film 2 removably provided on the base material 1.

As the base material 1, one that has enough strength to support the hologram film 2 and has characteristics that facilitate the transfer operation of the hologram film can be suitably used.

The base material 1 may be made of any material as long as it satisfies these characteristics. Specifically, materials such as resins, metals, ceramics, paper, and cloth can be mentioned, and materials with appropriate flexibility are convenient because the hologram film 2 can be easily peeled off during the transfer operation. is good.

The substrate 1 has optical properties that do not affect the image exposure operation, that is, it has transparency to the extent that the exposure operation can be performed satisfactorily at the wavelength or wavelength range of the light used for exposure (hereinafter referred to as transparent material). If a hologram-forming sensitive layer is laminated on a base material having such characteristics so as to be transferable at least after exposure and development, the image is exposed and developed to form a hologram. is formed on a base material, and the resulting laminate can be used as it is as a transfer hologram of the present invention, which is convenient in terms of production efficiency.

Base materials used for this purpose include glass,
Or, for example, it is mainly composed of crystalline polymers such as polyesters such as polyethylene, polypropylene, poly(4-methyl)pentene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, and polyethylene terephthalate, and polyamide, and Accordingly, materials made transparent by stretching in biaxial directions during molding to cause oriented crystals: polymethyl methacrylate, polycarbonate, polyarylate, polyether ether ketone, polysulfone, styrene-methyl methacrylate copolymer, Acrylic acid polyhydric alcohol ester (CR, -39)
Examples of transparent substrates include those mainly composed of amorphous polymers such as .

The thickness of the base material 1 may be appropriately selected depending on the material of the base material used within a range that satisfies the above characteristics. For example, when using a base material made of resin, the thickness may be approximately 5μ1 or more. When used as a transparent base material made of resin, for example, from the viewpoint of mechanical strength and transparency, a material having a molecular weight of about 20 to 100 is preferably used.

Furthermore, on the surface of the base material 1 on the hologram film 2 side, in order to improve the transfer performance of the hologram film 2 or to adjust the lamination properties with the hologram film 2, a peeling film as described below may be applied. In order to improve compatibility with the layer, physical treatments such as discharge treatment and flame treatment using corona, plasma, etc.; surface treatments such as chemical treatments with sulfuric acid, nitric acid, fluoride compounds, alkalis, silane compounds, etc. may be applied.

However, when using a transparent base material as described above as the base material 1, it is desirable that these surface treatments be carried out within a range that does not impair the above-mentioned optical properties required of the transparent base material. .

As the hologram film 2, various volume phase type holograms in the form of a film on which a desired image is recorded can be used.

Among these, volume-phase holograms using vinylcarbazole polymers as a sensitizer satisfy the performance requirements listed above for sensitizers, and the resulting hologram itself has excellent moisture resistance and storage stability. It also has excellent stability against various operations during hologram formation or transfer, and is therefore suitable for use in the transfer type hologram of the present invention.

The vinylcarbazole polymer refers to polyvinylcarbazole, alkyl-substituted polyvinylcarbazole, halogen-substituted derivatives of polyvinylcarbazole, and polymers mainly composed of these.
More than one species may be used.

Specifically, for example, polyvinylcarbazole, 3-chlorovinylcarbazole polymer, 3-plumvinylcarbazole polymer, 3-iodovinylcarbazole polymer, 3-methylvinylcarbazole polymer, 3-ethylvinylcarbazole polymer, Chlorinated polyvinyl carbazole, brominated polyvinyl carbazole, etc. can be used.

Among these, unsubstituted polyvinylcarbazole is suitable for practical use because it is easy to use and the performance of the resulting hologram is particularly excellent.

The vinyl carbazole polymer may be copolymerized with other monomers as necessary, for example, in order to control properties such as strength and flexibility when formed into a film. Other polymers that can be used for such purposes include, for example, in addition to the above-mentioned vinyl carbazoles, vinyl esters such as vinyl acetate, esters of acrylic acid and methacrylic acid, styrene and styrene derivatives, etc., are produced by radical polymerization. Examples include vinyl monomers that can be copolymerized. Further, for such purposes, other polymers such as polystyrene, styrene-butadiene copolymer, styrene-hydrogenated butadiene copolymer, etc. may be blended to the extent that a hologram image can be recorded.

Incidentally, the addition ratio of these materials is selected so as to obtain the desired characteristics.

The stretched vinylcarbazole polymers mentioned above are used in holography in a state in which they are activated by radiation with an iodine compound.

Examples of such iodine compounds include carbon tetraiodide, iodoform, ethylene tetraiodide, triiodoethane, tetraiodoethane, bentayodoethane, and hexaiodoethane, which coexist in polymer components and provide sufficient protection against visible light wavelengths. A material capable of forming a sensitive layer having sensitivity is used.

The sensitive layer using a vinyl carbazole polymer with such a structure exhibits sensitivity to visible light up to 560 nm, and the two beams of object light and reference light with appropriate wavelengths within such a wavelength range can be coherent. A volume phase type hologram with high resolution and high diffraction efficiency can be formed by exposing an interference pattern to an optical laser and then performing a development process using swelling and shrinkage phenomena caused by a solvent.

Note that the hologram film used in the present invention is not limited to its material or image recording method, and may be made of any material or formed by any recording method.

In order to provide the hologram film 2 on the base material 1, for example, a hologram film on which a desired image has already been recorded is used as the hologram film 2, and it is laminated on the base material 1 in a peelable manner, or the base material A method can be used in which the above-mentioned transparent base material is used as 1, a sensitive layer for forming a hologram is laminated on the transparent base material so as to be removable, and predetermined exposure and development treatments are performed.

In the transfer type hologram having such a configuration, the exposed surface of the hologram film 2 is superimposed on the surface of the transfer material to which it is to be transferred, and the hologram film 2 is pressed into contact with the surface of the material to which it is to be transferred. It can be transferred onto a material to be transferred.

That is, the term "peelable" as used in the present invention means that the hologram film 2 can be peeled off from the base material 1 without any change in its shape or image recording state during the above-described transfer operation. .

Therefore, the base material 1 and the hologram film 2 are as follows:
It is preferable to select each material in a combination that allows a good transfer operation.

However, in the configuration shown in FIG. 1, if the hologram film 2 is difficult to peel off from the base material 1, or if the hologram film 2 is thin and has low strength, the hologram film 2 and the base material 1 may not be able to be transferred properly. When using a combination of films, a good transfer operation can be achieved by providing a release layer 3 between the base material 1 and the hologram film 2, as shown in FIG. 2, for example.

The release layer 3 used for this purpose is used during the transfer operation.
It is sufficient to use a material and a layer thickness that has a function of facilitating peeling between the base material 1 and the hologram film 2.

The type of release layer 3 may be one that remains on the base material 1 side after the transfer operation, or one that adheres to the hologram film 2 side and is transferred together with it.

For example, the peeling layer 3 used for this purpose has a surface tension of the hologram film 2 (30 to 35 dyne/cm when vinyl carbazole polymer is used).
For example, a layer made of a polymer or a low-molecular surface modifier called a silane coupling agent or a titanium coupling agent, which has a surface tension sufficiently large or small to obtain a good peeling condition. A layer consisting of can be used.

Specific examples of materials that can constitute the release layer 3 include polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyfluorinated ethylene-propylene, and polyorganosiloxane; and silanes such as γ-glycidoxypropyltrimethoxysilane and vinyltrimethoxysilane. Coupling agents; titanium coupling agents such as isopropyl tristearoyl titanate and isopropyl trioctyl titanate; and the like.

However, when the release layer 3 is transferred together with the hologram film 2 and is left on the hologram film 2 after the transfer operation, the release layer 3 is It must be such that it does not interfere with

In addition, when using a type of release layer that is left on the hologram film 2, the release layer may be made of a material that functions as a protective layer for the hologram film, or various additives may be added that can provide the release layer with a protective function. If the peeling layer 3 is provided with a function as a protective layer, the protective layer can be automatically provided on the hologram film after transfer.

Materials for forming a release layer that can also function as a protective layer include:
Examples include polyethylene terephthalate, polyetheretherketone ethylene-propylene, polyvinylidene fluoride, polyvinyl alcohol, and the like.

Further, as additives that can be added to provide a function as a protective layer, for example, as an ultraviolet absorber, 2-
Examples include triazole derivatives such as (hydroxyphenyl)benzotriazole, triazine derivatives such as 1,3,5-tris(2'-hydroxyphenyl)triazine, and benzophenone derivatives such as resorcyl monobenzoate.

Note that when a transparent base material is used as the base material 1 for the purpose described above, the peeling layer 3 is also required to have the same transparency as the base material 1.

The release layer 3 can be provided by laminating, for example, a layer made of the above polymer on the base material 1, or by treating the surface of the base material 1 with a solution containing a silane coupling agent or a titanium coupling agent.

On the other hand, on the exposed surface of the hologram film 2, in order to improve the transfer operation or to improve the fixation of the hologram film on the transferred material after transfer, as shown in FIG. An adhesive or adhesive layer 4 may also be provided.

The material that can be used for the layer 4 is one that has a good adhesion or adhesive effect, does not adversely affect the hologram film 2 in the adhesion or adhesion process using this layer, and is chemically compatible with the hologram film 2. Depending on the configuration of the desired transfer hologram, the material may be appropriately selected and used from materials that do not react physically or physically and cause harm to the material.

For example, select and use an acrylic ester polymer, vinyl acetate polymer, α-cyanoacrylate ester, urethane adhesive, rubber adhesive, epoxy adhesive, etc. that satisfies the above characteristics. For example, when using polyester, the copolymer composition of acrylic ester, butyl acrylate, 2-ethylhexyl acrylate, and ethylene can be changed as appropriate to adjust its properties to the target object to obtain the desired effect. Since it is adjusted accordingly, it can be used selectively.

Note that the layer 4 may be pretreated with a brimer if necessary.

In addition, the form of the adhesive or pressure-sensitive adhesive may be one-component type, two-component type, water-based latex, oil-based latex, hot melt type (powder form, sheet form), heat Any form such as a seal type may be used.

The layer 4 can be formed by coating it directly on the hologram film 2 (or recording material for forming a hologram), by gluing it onto the hologram film 2 after it has been formed into a film by casting, etc., depending on its form. What is necessary is to select and use the method of adhesion as appropriate.

Note that when layer 4 is provided as an adhesive layer, for example, 10
An adhesive layer that can be bonded under conditions of 0 to 120° C. and several kg/cm 2 can be suitably used.

In addition, the adhesion and adhesive strength of layer 4 is, for example, 200 g.
A length of about 725 mm or more is sufficient.

Furthermore, when a transparent base material is used as the base material 1 for the purpose described above, and when the layer 4 is previously provided on the recording material for hologram formation before the exposure process, the layer 4 may also be transparent. Although the same transparency as the base material is required, this is not the case if the layer 4 is provided on a hologram film formed after exposure and development.

In the transfer type hologram of the present invention, as shown in FIG. 4, a metal or metal oxide layer 5 may be provided on the exposed surface of the hologram film 2.

The layer 5 can make up the variation in the image observed on the film when the hologram film 2 is transferred to the transfer material, and the material, color, shape, layer thickness, and position where it is provided are determined by the layer 5. By making an appropriate selection, the holographic image can be made clearer and more visually appealing.

Particularly when the color of the transferred material impairs the image observed on the hologram film, by providing this layer as an opaque layer, good image observation is always possible.

The layer 5 used for such purpose is, for example, In01AI2
03, AI, An, etc. for 50 to 500 people
It can be laminated and provided on a predetermined portion of the upper surface of the hologram film 2 by a method such as a vapor deposition method with a layer thickness of about 0.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Poly(N-vinylcarbazole) was applied in the dark onto a 504 polyethylene terephthalate film as a substrate.
A solution of 2.5 g of carbon tetraiodide and 0.2 g of carbon tetraiodide dissolved in 30 g of monochlorobenzene was placed in a spinner (Mikasas Biner, I
H-2) was applied and dried to a layer thickness of 5. A raw sensitive layer for forming a hologram was obtained.

The absorbance of the obtained sensitive layer was measured with a spectrophotometer UV'lDE [Nie 650 (manufactured by JASCO), and it was found to be 560n.
It had an absorption edge of up to m.

Using an Ar laser (514.6 nm) for this sensitive layer, an offset angle of 70° and a light intensity ratio of 1:1 (the sum of the light intensities of both beams is 3 mW/cm2 immediately before incidence) were used according to Denishuk's method. An image corresponding to the desired object was recorded.

After exposure, the sensitive layer is sequentially processed through the following steps 1 to 2 to record a desired image on the substrate.The Lippmann type reflection hologram is transferably provided on the substrate. A transfer hologram was obtained.

After soaking in acetone for 2 minutes at 020°C, dry at 30°C.
After soaking in xylene for 3 minutes, dry at 25°C for 3 minutes.
After dipping in hebutane and drying, the resulting hologram was 514
．． It was a volume phase type with a spatial frequency of about 3000 lines/mm for light with a wavelength of 6 nm, a diffraction efficiency of 88% at 40 mJ/cm2, and a transmittance of 90%.

The transfer hologram obtained in this way is superimposed on a transfer material made of Kent paper coated with Polysol AB-4128N (manufactured by Showa Kobunshi ■) via the hologram film surface, and a pressure of about 2 kg/cm2 is applied with a roller. By doing this, we were able to transfer the hologram film onto Kent paper.

The characteristics of the transferred hologram were the same as those immediately after its formation, and a good holographic image could be observed there.

Example 2 A release layer was formed by coating polyvinyl alcohol with a degree of polymerization of 1200 (degree of saponification 86%) to a thickness of 5 μs on a 50 μm polyethylene terephthalate film as a base material, and further coated with Example 2 on the release layer. A sensitive layer was provided in the same manner as in 1, followed by exposure and development to obtain a transfer hologram of the present invention.

When the obtained transfer hologram was transferred onto Kent paper in the same manner as in Example 1, a good peeling effect was obtained by the release layer, and the hologram film could be easily transferred onto Kent paper.

The characteristics of the transferred hologram were the same as those immediately after its formation, and although a peeling layer remained in the state where it was laminated on the top surface of the hologram film, a good holographic image could be observed.

Furthermore, the release layer sufficiently functioned as a protective layer for the transferred hologram.

Example 3 A film (about 10 scales thick) of vinylol EA-300 (manufactured by Showa Kobunshi ■), an acrylic solution-based adhesive, was formed on a Teflon plate, and the resulting adhesive film was used in Example 1. 2 on the hologram film of the obtained transfer hologram.
A transfer type hologram with an adhesive layer was obtained by pressing with a roller at a pressure of 1 kg.

The obtained transfer type hologram was superimposed on a vinyl chloride sheet via an adhesive layer and pressed under the conditions of 70° C. and 10 kg/cm 2 , and the base material was peeled off from the vinyl chloride sheet to transfer the hologram film.

The characteristics of the transferred hologram were the same as those immediately after its formation, and a good holographic image could be observed there. Moreover, by using the adhesive layer, a better transfer operation could be performed, and the adhesion of the hologram film onto the vinyl chloride sheet was also more reliable.

Example 4 Aluminum was deposited to a thickness of 150 mm on the exposed surface of the hologram film of the transfer hologram obtained in Example 1.

Further, the adhesive film obtained in Example 3 was pressure-bonded onto the vapor deposited layer in the same manner as in Example 3 to obtain a transfer hologram.

Using the obtained transfer hologram, a transfer operation was carried out in the same manner as in Example 3, and a good transfer operation was achieved.

Furthermore, due to the effect of the vapor deposited film provided on the lower surface of the transferred hologram film, the image was clearer and more visually appealing.

Example 5 7 A solution of 2.5 g of poly(N-vinylcarbazole) and 0.2 g of carbon tetraiodide dissolved in 30 g of monochlorobenzene was placed on a glass substrate in a dark place using a spinner (Mikasa spinner, IH-2). After coating with
A sensitive layer for forming a bolt hologram was obtained.

When the absorbance of the obtained sensitive layer was measured in the same manner as in Example 1, it was found to have an absorption edge up to 560 nm.

An image corresponding to a desired object was recorded on this sensitive layer in the same manner as in Example 1.

After exposure, the same immersion treatment in an organic solvent as in Example 1 was performed to obtain a hologram film on which a desired image was recorded on a glass substrate.

The obtained hologram is a volume phase type with a spatial frequency of approximately 3000 lines/mm for light with a wavelength of 514.6 nm, a diffraction efficiency of 88% at 40 mJ/cm2, and a transmittance of 90%. there were.

Next, the hologram film was peeled off from the glass substrate by immersing it in water, and then it was coated with a polypropylene film (55 scales thick, Turfan BO #55 T2500).
The transferred hologram of the present invention was obtained by transferring the hologram onto a hologram (manufactured by Toshi, Inc.) and drying it.

When the transfer hologram thus obtained was transferred onto Ghent paper in the same manner as in Example 1, the transfer operation was successful, and the characteristics of the transferred hologram were the same as when it was formed. A good holographic image could be observed.

Example 6 The hologram film obtained in Example 5 was laminated on high-quality paper whose surface was coated with methylhydrogen polysiloxane, and then applied to vinyl roll E as an adhesive layer.-300 was used as a film in the same manner as in Example 3. A transfer hologram was obtained by laminating it on a hologram film.

This transfer type hologram was bonded to a polyethylene sheet via an adhesive layer at 50° C. by applying a pressure of 2 kg/cm 2 with a roller, and the base material was peeled off from the polyethylene sheet to transfer the hologram film.

The characteristics of the transferred hologram were the same as when it was formed, and a good holographic image could be observed.

〔Effect of the invention〕

The transfer type hologram of the present invention has a structure in which a hologram film is provided on a suitable base material and is removable from the base material, and the hologram film held on the base material can be easily transferred to a desired object. With simple operations, a desired holographic image can be easily and easily applied to desired parts of various objects. Also, for example, the hologram film can be transferred onto a suitable mount and enjoyed in the same way as a picture or photograph.

In addition, with the above-mentioned type that uses an uneven surface, when holograms are directly laminated onto various objects by pressure bonding or adhesion, the unevenness formed on the surface is unavoidably affected by deformation or damage. Since a volume phase type hologram film is used in the type hologram, such a problem does not occur during transfer.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 to 4 are schematic side views showing typical configuration examples of the transfer hologram of the present invention. 1: Base material 2: Hologram film 3: Peeling layer 4: Adhesive or adhesive layer 5: Layer made of metal and/or metal oxide

Claims (1)

[Scope of Claims] 1) A transfer hologram comprising a base material and a volume phase type hologram film on which a desired image is recorded and is removable from the base material. 2) The transfer type hologram according to claim 1, wherein the hologram film is provided on the base material with a release layer interposed therebetween. 3) The transfer type hologram according to claim 1 or 2, further comprising an adhesive or adhesive layer provided on a side of the hologram film opposite to the base material side. 4) The hologram film according to any one of claims 1 to 3, wherein a layer made of one or more of metals and metal oxides is provided on a side of the hologram film opposite to the base material side. Transfer hologram. 5) Claims 1 to 4, wherein the base material is transparent.
The transfer type hologram according to any one of paragraphs. 6) A transfer hologram comprising a base material and a vinyl carbazole polymer film on which a volume phase hologram is recorded and is removable from the base material. 7) The transfer type hologram according to claim 6, wherein the polymer film is provided on the base material with a release layer interposed therebetween. 8) The transfer hologram according to claim 6 or 7, further comprising an adhesion or adhesive layer provided on a side of the polymer film opposite to the base material side. 9) A layer made of one or more metals and metal oxides is provided on a side of the polymer film opposite to the base material side, according to any one of claims 6 to 8. Transfer type hologram. 10) The transfer hologram according to any one of claims 6 to 9, wherein the base material is transparent.