JPS63287877A - Transfer type hologram - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 already used 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 provides a base material and a 400 to 800
A transfer characterized in that it has a volume phase type hologram film on which a desired image is recorded and is removable from the base material provided via a peeling layer that does not have a specific absorption band in the nm wavelength range. It is a type hologram.

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 that uses an uneven surface, when a 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, a hologram film 2 removably provided on the base material 1, and a release layer 3 therebetween.

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 a transparent substrate). If a hologram-forming material is used, a hologram-forming sensitive layer is laminated on a base material having such characteristics so that it can be transferred at least after exposure and development, and then the image is exposed and developed to form a hologram. The laminate formed on the base material can be used as it is as the 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 Polymethyl methacrylate, polycarbonate, polyarylate, polyether ether ketone, polysulfone, styrene-methyl methacrylate copolymer, Examples include transparent substrates mainly composed of amorphous polymers such as acrylic acid polyhydric alcohol ester (CR-39).

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, a thickness of about 5- or more When used as a transparent substrate made of resin, for example, from the viewpoint of mechanical strength and transparency, a material having a diameter of about 20 to 100 μj is preferably used.

Furthermore, if necessary, the surface of the base material 1 on the hologram film 2 side may be coated with, for example, corona, plasma, etc., in order to enhance the transfer performance of the hologram film 2 or to improve compatibility with a release layer as described later. Physical treatments such as electric discharge treatment and flame treatment; surface treatments such as chemical treatments with sulfuric acid, nitric acid, fluoride compounds, alkalis, silane compounds, etc. may also be performed.

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-bromvinylcarbazole 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 polymers, if necessary, in order to control properties such as strength and flexibility when formed into a film. Other monomers that can be used for such purposes include, for example, in addition to the vinyl carbazoles mentioned above, vinyl esters such as vinyl acetate, esters of acrylic acid and methacrylic acid, styrene and styrene derivatives, etc. can be copolymerized by radical polymerization. Examples include vinyl monomers that can be used. 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.

This vinyl carbazole polymer is used in holography after being activated by radiation with an iodine compound.

Examples of this iodine compound include carbon tetraiodide, iodoform, ethylene tetraiodide, triiodoethane, tetraiodoethane, pentayodoethane, and hexaiodoethane, which coexist in polymer components and have sufficient resistance to 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 560r++n, and it is possible to make two beams of light, the object beam and the reference beam, of an appropriate wavelength within such a wavelength range 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.

To provide the hologram film 2 on the base material 1, for example, a hologram film on which a desired image is already recorded is used as the hologram film 2, and it is releasably laminated on the base material 1 via a release layer. Alternatively, using the transparent base material described above as the base material 1, a sensitive layer for forming a hologram is laminated on top of the transparent film through a release layer so as to be removable, and then subjected to prescribed exposure and development treatment. There are methods available to do this.

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. .

In the present invention, a good transfer operation can be achieved by providing a release layer 3 between the base material 1 and the hologram film 2.

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.

As the peeling layer 3 used for this purpose, for example, the 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.

Furthermore, since the release layer of the present invention does not have a specific absorption band in the wavelength range of 400 to 800 nm, even if the release layer remains on the hologram after the transfer operation, it will clearly show the unique coloration of the hologram. can be shown.

Note that the release layer 3 may be made of a material that functions as a protective layer for the hologram film, or various additives capable of imparting a protective function to the release layer may be added to provide the release layer 3 with the function of a protective layer. By doing so, a 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, polyperfluoroethylene-propylene, polyvinylidene fluoride, and polyvinyl alcohol.

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, and when a peeling layer 3 is present during exposure to form a hologram, the peeling layer 3 is also made of a transparent material similar to the base material 1. sexuality is required.

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 primer 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.

To provide the layer 4, depending on its form, it may be applied directly to the hologram film 2 (or a sensitive layer for forming a hologram), or it may be formed into a film by casting or the like and then applied onto the hologram film 2. Adhesion or pasting methods may be selected and used 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.
/25II1m 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. Transparency similar to that of the base material is required, but this is not the case if layer 4 is provided on a hologram film formed after exposure and development.

In the transfer hologram of the present invention, as shown in FIG. 3, a metal or metal oxide layer 5 may be provided on the exposed surface of the hologram film 2.

The layer 5 can constitute the back of the image observed on the hologram film 2 when it is transferred to the transfer material, and its material, color, shape, layer thickness, and position can be adjusted as appropriate. Depending on the 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, A1, An, etc., 50A to 500
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 Polyvinyl alcohol having a degree of polymerization of 1200 (degree of saponification 86%) was coated as a release layer to a thickness of 5 mm on a 50 μj polyethylene terephthalate film as a base material. The transmittance of the thus obtained laminate was measured using a spectrophotometer UVIDEC-650, and the results are shown in FIG. 4A.

Next, 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 the above laminate in a dark place using a spinner (Mikasa spinner, IH-2). The film was coated using a method of drying and dried to obtain a sensitive layer for forming a hologram with a layer thickness of 7 μm.

The absorbance of the obtained sensitive layer was measured using a spectrophotometer UVIDEC-6.
50 (manufactured by JASCO Corporation), it had an absorption edge up to 560 nm.

Using an Ar laser (514.5 nm) for this sensitive layer, the desired object is irradiated according to Denisyuk's method under the conditions of a light intensity ratio of 1:1 (the sum of the light intensities of both beams is 15 mJ/cm2 immediately before the incidence). The corresponding images were 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.

Immersed in toluene for 2 minutes at 020°C ■ Immersed in xylene for 3 minutes at 30°C ■ Immersed in n-hebutane for 3 minutes at 25°C, then dried The obtained hologram was resistant to light with a wavelength of 514.5 r++n. It was a volume phase type hologram with a spatial frequency of about 3000 wood/mm, a diffraction efficiency of 88%, 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 First, a glass substrate was cleaned, and then the glass substrate was placed in a closed container filled with trimethylchlorosilane gas, and 2.5 g of poly(N-vinylcarbazole) was added between the surface of the glass substrate and the gas. A solution prepared by dissolving 0.2 g of carbon tetraiodide in 30 g of monochlorobenzene was applied using a spinner (Mikasa spinner, IH-2) and dried to obtain a sensitive layer for forming a hologram with a layer thickness of 7 μm.

The absorbance of the obtained sensitive layer was measured using a spectrophotometer UVIDEO-8.
50 (manufactured by JASCO Corporation), it had an absorption edge up to 560 nm.

Using an Ar laser (514.5 nm) for this sensitive layer, the desired object is irradiated according to Denishuk's method under the conditions of a light intensity ratio of 1:l (the sum of the light intensities of both beams is 15 mJ/cm2 immediately before the incidence). The corresponding images were 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.

Immersed in toluene for 2 minutes at 020°C ■ Immersed in xylene for 3 minutes at 30°C ■ Immersed in n-hebutane for 3 minutes at 25°C, then dried The obtained hologram was resistant to light with a wavelength of 514.5 nm. It has a spatial frequency of about 3000 wood/mm and a diffraction efficiency of 88
%, and it was a volume phase type hologram with a transmittance of 90%.

Indium tin oxide (ITO) was sputtered on the vinyl carbazole film surface of the transfer hologram thus obtained to form a film having a surface resistance of 200 Ω/c12. The absorption spectrum is shown in FIG. 4B. Next, this was immersed in water and peeled off to obtain a hologram film having an ITO film on the surface.

The hologram film obtained in this way is superimposed on a transfer material made of Kent paper coated with Polysol AB-412ON (manufactured by Showa Kobunshi ■) via the hologram film surface, and a pressure of about 2 kg/cm2 is applied with a roller. Using this method, we were able to transfer a 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.

(Effects of the Invention) The transfer type hologram of the present invention has a configuration in which a hologram film is provided on a suitable base material through a release layer so that it can be peeled off from the base material, and the hologram film is held on the base material. By simply transferring a hologram film to a desired object, a desired holographic image can be easily and conveniently applied to a desired part of various objects.Also, for example, a hologram film can be placed on a suitable mount. You can also transfer it and enjoy it in the same way as a painting 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.

Furthermore, since the release layer does not have a specific absorption band in the wavelength range of 400 to 800 nm, even if the release layer remains on the hologram after the transfer operation, the unique coloring of the hologram can be clearly displayed. Can be done.

[Brief explanation of drawings]

Figures 1 to 3 are schematic side views showing typical configuration examples of the transfer hologram of the present invention, and Figure 4 shows the absorption spectrum of the base material or hologram provided with a release layer in an example of the present invention. FIG. 1: Base material 2: Hologram film 3: Peeling layer 4: Adhesive or adhesive layer 5: Layer made of metal and/or metal oxide A: Absorption spectrum of the laminate in Example 1 B: Absorption spectrum of the hologram in Example 2 absorption spectrum

Claims (1)

[Scope of Claims] 1) A base material, and a desired material that is releasable from the base material and is provided on the base material via a release layer that does not have a specific absorption band in the wavelength range of 400 to 800 nm. A transfer hologram comprising a volume phase hologram film on which an image is recorded. 2) The transfer type hologram according to claim 1, further comprising an adhesion or adhesive layer provided on a side of the hologram film opposite to the base material side. 3) The transfer type hologram according to claim 1 or 2, wherein a layer made of one or more metals and metal oxides is provided on the side of the hologram film opposite to the base material side. . 4) Claims 1 to 3, wherein the base material is transparent.
The transfer type hologram according to any one of paragraphs. 5) A vinyl recorder having a base material and a volume phase hologram recorded thereon, which is releasable from the base material and is provided on the base material via a release layer that does not have a specific absorption band in the wavelength range of 400 to 800 nm. A transfer hologram comprising a carbazole polymer film. 6) The transfer type hologram according to claim 5, further comprising an adhesion or adhesive layer provided on a side of the polymer film opposite to the base material side. 7) The transfer mold according to claim 5 or 6, wherein a layer made of one or more metals and metal oxides is provided on the side of the polymer film opposite to the base material side. hologram. 8) Claims 5 to 7, wherein the base material is transparent.
The transfer type hologram according to any one of paragraphs.