JP4663430B2 - Hologram observation card - Google Patents

Description

  The present invention relates to a hologram observation card that can be used for cards such as business cards and membership cards, toys, etc., can be printed on demand, and has a hologram observation section.

  In recent years, various things such as glasses and fan using a transmission hologram have been proposed (for example, Patent Document 1 and Patent Document 2). However, in any of these, it is difficult to integrally form a transmission hologram and another member, and only the transmission hologram portion is prepared in advance, and then the transmission hologram is sandwiched between other members. It was manufactured by dripping. Therefore, there are problems that the manufacturing process is complicated and difficult to use for various purposes.

  In addition, the user cannot print individual information on a card or the like using this transmission hologram, or process and print a digital image taken with a mobile phone or a digital camera. There is also a problem that it is difficult to use for various purposes.

JP 2004-126535 A Japanese Patent Laid-Open No. 2004-77548

  Therefore, it is desired to provide a hologram observation card that can be printed on demand and integrated with a transmission hologram.

  The present invention has a transparent substrate, a transmission Fourier transform hologram region formed on the transparent substrate and having a function as a Fourier transform lens, and a function as a Fourier transform lens other than the transmission Fourier transform hologram region. A hologram observation card having an image conversion layer made of a non-hologram area, and the surface of the transparent substrate opposite to the side on which the image conversion layer is formed, or the non-hologram area of the image conversion layer A hologram observation card characterized in that a printable receiving layer is formed thereon is provided.

  According to the present invention, since the receiving layer is formed, a hologram observation card capable of printing various information, images, and the like by various printers can be obtained. Further, in the present invention, since the image conversion layer having the transmission Fourier transform hologram region is formed, it is not necessary to separately attach or sandwich the transmission Fourier transform hologram, and it is efficiently manufactured. It can be set as a hologram observation card.

  In the said invention, it is preferable that the primer layer is formed between the said transparent base material and the said receiving layer. In this case, the adhesiveness between the transparent substrate and the receiving layer can be improved, and a higher quality hologram observation card can be obtained.

  Moreover, in the said invention, the said primer layer may contain the white pigment. In this case, the image printed on the receiving layer can be more easily observed.

  Further, the present invention provides a transparent base material, a transmission Fourier transform hologram region formed on the transparent base material and having a function as a Fourier transform lens, and a function as a Fourier transform lens other than the transmission Fourier transform hologram region. A hologram observation card having an image conversion layer composed of a non-hologram area that does not include a protective layer formed on the transmission Fourier transform hologram area of the image conversion layer, and is printable on the protective layer Provided is a hologram observation card characterized in that a receptive layer is formed.

  According to the present invention, since the receiving layer is formed, a hologram observation card capable of printing various information, images, and the like by various printers can be obtained. In the present invention, since the protective layer is formed and the receiving layer is formed on the protective layer, the Fourier transform of the transmission Fourier transform hologram region is also formed on the transmission Fourier transform hologram region. Printing can be performed without impairing the function as a lens. Furthermore, according to the present invention, since the image conversion layer having the transmission Fourier transform hologram region is formed, the transmission Fourier transform hologram can be efficiently manufactured without being separately attached or sandwiched. Hologram observation card.

  In the said invention, the image may be printed on the said receiving layer by the sublimation type thermal transfer system. An image may be printed on the receiving layer by an ink jet method. Furthermore, an image may be printed on the receiving layer by a melt type thermal transfer method, and an image may be printed on the receiving layer by an intermediate transfer method. This is because the formation of such a receiving layer makes it possible to print various images on the hologram observation card surface by various printing methods.

  Moreover, in the said invention, the said image conversion layer can be made into the surface phase type | mold diffractive optical element layer which has an uneven structure in the surface of the said transmission type Fourier-transform hologram area. This is because the transmission type Fourier transform hologram region can be formed by using the image conversion layer as such a layer.

  According to the present invention, a hologram observation card capable of printing various information, images, and the like by various printers can be obtained. In addition, the present invention also has an effect that a hologram observation card manufactured efficiently can be obtained without performing a step of separately attaching or sandwiching a transmission Fourier transform hologram.

  The present invention relates to a hologram observation card that can be used for cards such as business cards and membership cards, toys, etc., can be printed on demand, and has a hologram observation section. The hologram observation card of the present invention has two embodiments. Hereinafter, it explains for every embodiment.

A. First Embodiment First, a first embodiment of the hologram observation card of the present invention will be described. The hologram observation card in this embodiment includes a transparent base material, a transmission type Fourier transform hologram region formed on the transparent base material and having a function as a Fourier transform lens, and a Fourier transform lens other than the transmission type Fourier transform hologram region. A hologram observation card comprising an image conversion layer having a non-hologram area that does not have a function as a surface of the transparent substrate opposite to the side on which the image conversion layer is formed, or the image conversion layer A printable receiving layer is formed on the non-hologram region.

  For example, as shown in FIG. 1, the hologram observation sheet of this embodiment is an image conversion layer that is formed on a transparent substrate 1 and has a transmission Fourier transform hologram region a and a non-hologram region b. 2 and the receiving layer 3 formed on the surface of the transparent substrate 1 opposite to the side on which the image conversion layer 2 is formed. Alternatively, for example, as shown in FIG. 2, a transparent base material 1, an image conversion layer 2 formed on the transparent base material 1 and having a transmission type Fourier transform hologram region a and a non-hologram region b, and the image conversion layer 2 and the receiving layer 3 formed on the non-hologram region b.

  In this embodiment, for example, as shown in FIG. 3, the receiving layer 3 is formed on the surface of the transparent substrate 1 opposite to the side where the image conversion layer 2 is formed, and on the image conversion layer 2. It may be formed on both surfaces of the non-hologram area b.

  According to the present embodiment, since the printable receiving layer is formed, the user himself / herself can print various images or the like such as individual information on the receiving layer. At this time, the receiving layer is formed on the surface of the transparent substrate opposite to the side where the image conversion layer is formed, or on the non-hologram area of the image conversion layer. Therefore, the image printed on the receiving layer or the like can prevent the optical image formation in the transmission type Fourier transform hologram region from being hindered.

In this embodiment, since the transmission type Fourier transform hologram region is formed in the image conversion layer, a member having the function of the transmission type Fourier transform hologram is separately attached or sandwiched. Therefore, the hologram observation card can be efficiently manufactured.
Hereinafter, the hologram observation card of this embodiment will be described in detail for each member.

1. Receiving layer First, the receiving layer used in this embodiment will be described. The receiving layer used in the present embodiment is a printable layer and functions as a surface of the transparent substrate, which will be described later, on the side opposite to the side on which the image conversion layer is formed, or the Fourier transform lens of the image conversion layer. It is formed on a non-hologram area that does not have any.

  In this embodiment, the receiving layer may be formed on the entire surface of the transparent substrate or non-hologram region, or may be formed only on a partial region of the transparent substrate or non-hologram region. The shape and range of the region where the receiving layer is formed are appropriately selected according to the type and application of the hologram observation card.

  The receiving layer is not particularly limited as long as it is printable by a general method. In this embodiment, it is particularly preferable that the hologram observation card can be printed on demand, and it is preferable that the hologram observation card can be printed by a sublimation thermal transfer method, an ink jet method, a melt type thermal transfer method, or an intermediate transfer method. Hereinafter, the receiving layer that can be printed by these methods will be described separately.

(Receptive layer printable by sublimation thermal transfer method)
The receiving layer that can be printed by the sublimation thermal transfer method is not particularly limited as long as it can receive the sublimation thermal transfer ink. Examples of such a receiving layer include a resin having an ester bond such as a polyester resin, a polyacrylate resin, a polycarbonate resin, a polyvinyl acetate resin, a styrene acrylate resin, and a vinyl toluene acrylate resin; a urethane bond such as a polyurethane resin. Resin; Resin having amide bond such as polyamide resin (nylon); Resin having urea bond such as urea resin; Resin having highly polar bond such as polycaprolactone resin, polystyrene resin, polyvinyl chloride resin, polyacrylonitrile resin It can be set as the layer which contains 1 type, or 2 or more types. Alternatively, a layer made of a mixed resin of saturated polyester and vinyl chloride-vinyl acetate copolymer may be used. Specific examples of the saturated polyester include Byron 200, Byron 290, Byron 600 and the like (manufactured by Toyobo), KA-10380 (manufactured by Arakawa Chemical), TP220 and TP235 (manufactured by Nippon Synthetic Chemical Industry). The vinyl chloride-vinyl acetate copolymer preferably has a vinyl chloride component content of 85 to 98 wt% and a polymerization degree of about 200 to 800. The vinyl chloride-vinyl acetate copolymer may contain a vinyl alcohol component, a maleic acid component, and the like.

  Further, for example, it may be a layer containing a polystyrene-based resin. For example, a polystyrene-based resin composed of a styrene monomer alone or a copolymer such as styrene, α-methylstyrene, vinyltoluene, etc. A layer containing a monomer, for example, an acrylic or methacrylic monomer such as acrylic ester, methacrylic ester, acrylonitrile, methacrylonitrile, or a styrene copolymer resin that is a copolymer with maleic anhydride, etc. it can.

  As a method of forming a receiving layer printable by the sublimation type thermal transfer method, the resin is appropriately mixed with an additive such as an ultraviolet absorber, a solvent or the like as necessary, and then applied on a transparent substrate by a known method. Or by applying or printing on the image conversion layer. In addition, it is preferable that the film thickness of the said receiving layer shall be about 0.5 micrometer-50 micrometers, especially about 1 micrometer-20 micrometers.

(Receiving layer printable by inkjet method)
In addition, the receiving layer that can be printed by the inkjet method is not particularly limited as long as it is a layer that can favorably receive the ink-jet ink. Such a receiving layer is, for example, a porous layer made of alumina hydrate. It can be a layer or the like. The alumina hydrate porous layer preferably has a structure in which alumina hydrate is bonded with a binder. As alumina hydrate, what is called boehmite or boehmite (Al ₂ O ₃ .nH ₂ O, n = 1 to 1.5) has good absorbability and selectively adsorbs pigments well. However, it is preferably used because a clear image having a high color density can be obtained.

  The alumina hydrate porous layer has a pore structure substantially consisting of pores having a radius of 1 to 15 nm and a pore volume of 0.3 to 1.0 cc / g. It is preferable because it has absorptivity and transparency. The average pore radius of the alumina hydrate porous layer is more preferably in the range of 3 to 7 nm.

  Examples of the binder used for the alumina hydrate porous layer include starch and modified products thereof, polyvinyl alcohol and modified products thereof, SBR (butadiene styrene rubber) latex, NBR (butadiene acrylonitrile rubber) latex, hydroxycellulose, polyvinylpyrrolidone and the like. Of organic substances. If the amount of the binder used is small, the strength of the alumina hydrate porous layer may be insufficient. Conversely, if the amount is too large, the amount of ink absorbed or the amount of dye supported may be low. It is preferable to set it as about 5-50 mass% of a Japanese thing.

  Another example of the receiving layer that can be printed by the inkjet method is a layer containing amorphous fine silica. Amorphous fine silica is silica obtained by precipitation by a wet method or a dry method, and is known as white carbon, anhydrous silicic acid, hydrous silicic acid or the like. The average particle size of the amorphous fine silica is preferably 0.5 to 15 μm. This is because the oil absorption can be increased. In addition to the amorphous silica, the receiving layer containing amorphous finely divided silica, if necessary, other pigments such as zeolite, calcium carbonate, diatomaceous earth, kaolin, calcined clay, talc, It is also possible to use together a pigment generally used for paper coating such as aluminum hydroxide. The blending amount of such a pigment is preferably 30 to 80% by mass of the solid content of the receiving layer. If the amount exceeds 80% by mass, the strength of the receiving layer may be lowered, and printing becomes difficult due to scratches, rubbing, and the like.

  The binder resin used in the receiving layer containing the above amorphous fine powder silica includes polyvinyl alcohol and modified products thereof, proteins such as casein, starch and modified products thereof, styrene-butadiene copolymer, methyl methacrylate-butadiene. Latex such as copolymer, polymer or copolymer latex of acrylate ester and methacrylate ester, vinyl polymer latex such as ethylene-vinyl acetate copolymer, polyvinyl butyral, unsaturated polyester resin, alkyd resin And polymers such as those of the system. By using these resins, the adhesiveness between the binder resin and the pigment can be improved. The usage ratio of the binder resin in the receiving layer is 20 to 70% by mass, preferably 25 to 60% by mass, based on the solid content of the receiving layer. If it is less than 20% by mass, the adhesive strength becomes insufficient, and the strength of the receiving layer may be lowered, and defects in the recording layer due to scratches, rubbing, etc. are likely to occur. On the other hand, if it exceeds 70% by mass, the adhesiveness increases, but the use ratio of the pigment decreases, which may cause a problem in ink absorbability.

  As the method for forming the receiving layer, for example, the above materials are appropriately mixed with an additive such as an ultraviolet absorber or a solvent as required, and applied on a transparent substrate or an image conversion layer by a known method. It can be formed by printing or printing. The thickness of the receiving layer that can be printed by the inkjet method is preferably about 1 μm to 50 μm, and more preferably about 10 μm to 40 μm.

(Receivable layer printable by melt-type thermal transfer method)
The receiving layer that can be printed by the melt-type thermal transfer method is not particularly limited as long as it is a layer that can receive heat-melted ink. For example, the layer can be a layer made of a thermoplastic resin. . Examples of the resin constituting the receptor layer include various polyester resins, vinyl chloride-vinyl acetate copolymer resins, polycarbonate resins, polyurethane resins, polyether resins, polyamide resins, acrylic resins, and cellulose derivatives. Moreover, it is preferable that a crosslinking agent, a lubricant, a release agent and the like are appropriately added to the receiving layer. By adding these, it is possible to prevent the ink ribbon and the receiving layer from fusing when the ink ribbon is heated by the thermal head and printed on the receiving layer. Moreover, additives such as an antioxidant, a pigment, and an ultraviolet absorber may be added to the receiving layer as necessary. These various additives may be mixed with the resin in advance before forming the receiving layer, or a coating layer made of various additives may be formed on the receiving layer.

  In addition, as a method for forming the receiving layer, for example, the resin may be appropriately mixed with an additive, a solvent, or the like as necessary, and applied to a transparent substrate or the image conversion layer by a known method. It can be formed by printing or the like. The film thickness of the receiving layer is preferably about 0.5 to 50 μm, more preferably about 1 to 20 μm.

(Receptive layer printable by intermediate transfer method)
The receiving layer that can be printed by the intermediate transfer method is not particularly limited as long as it can receive ink transferred by the intermediate transfer method. For example, the receiving layer that can be printed by the above-described melt-type thermal transfer method. And can be similar. Also in this case, the thickness of the receiving layer is preferably about 0.5 μm to 50 μm, and more preferably about 1 μm to 20 μm.

2. Image Conversion Layer Next, the image conversion layer used in this embodiment will be described. The image conversion layer used in the present embodiment is formed on a transparent substrate to be described later, and has a transmission Fourier transform hologram region having a function as a Fourier transform lens, and other than the transmission Fourier transform hologram region. It consists of a non-hologram area that does not have a function as a Fourier transform lens. The shape, range, and the like of the transmission type Fourier transform hologram region are appropriately selected according to the type and use of the hologram observation card.

  The Fourier transform lens function of the transmission type Fourier transform hologram region will be described with reference to FIG. FIG. 4A is a schematic diagram for explaining a case where an image is visually observed through a normal lens, and FIG. 4B is a diagram through a Fourier transform lens in the transmission type Fourier transform hologram region of the image transform layer in the present embodiment. It is the schematic explaining the case where the image is visually observed. As shown in FIG. 4A, when a desired image 31 is observed with a human eye 33 through a lens 32, an observation image 34 similar to the image 31 is observed.

  On the other hand, as shown in FIG. 4B, when the point light source 35 is viewed through the transmission Fourier transform hologram area of the image conversion layer 2 and visually observed by the human eye 33, the transmission Fourier transform hologram of the image conversion layer 2 is obtained. The optical image 36 corresponding to the data recorded in the area will be observed. For example, if a concavo-convex shape for reproducing a heart image as shown in FIG. 4B is provided in the transmission Fourier transform hologram area of the image conversion layer 2, the point light source 35 is visually observed through the image conversion layer 2. Thus, the light image 36 of the heart is visually recognized. As described above, the Fourier transform lens function of the image conversion layer in this embodiment refers to a function of converting light incident from a point light source into a desired light image.

  The wavelength of the point light source in which the transmission type Fourier transform hologram region of the image conversion layer in this embodiment can exhibit the function as a Fourier transform lens is not particularly limited, and a desired wavelength can be targeted. Further, the wavelength of the point light source is not limited to monochromatic light of one wavelength, but may be light including multiple wavelengths, and may be white light.

  Here, the type of the image conversion layer is not particularly limited as long as a transmission type Fourier transform hologram region having a function as a Fourier transform lens is formed. For example, it may be a surface phase type diffractive optical element layer having a concavo-convex structure on the surface of the transmission type Fourier transform hologram region, or an internal phase type diffraction having a refractive index distribution inside the image conversion layer in the transmission type Fourier transform hologram region. It may be an optical element layer. Furthermore, an amplitude type diffractive optical element layer having a transmittance distribution in the transmission type Fourier transform hologram region may be used. Hereinafter, each case will be described separately.

(Surface phase type diffractive optical element layer)
When the image conversion layer is a surface phase type diffractive optical element layer, irregularities are formed on the surface in the transmission Fourier transform hologram region of the image conversion layer. In the present embodiment, the image conversion layer may be transparent or colored.

  As a method for forming such an image conversion layer, for example, the following method can be used. First, data of an image to be displayed by the transmission type Fourier transform hologram area is converted into Fourier transform data by calculation, and the Fourier transform data is binarized or binarized. Furthermore, this data is converted into rectangular data for electron beam drawing, and this rectangular data is drawn on a resist surface applied to a glass plate or the like by an electron beam drawing apparatus used for drawing a semiconductor circuit mask or the like, Make the original. At this time, the portion to be the non-hologram region is a flat plate. Thereafter, for example, by forming a layer in which the irregularities of the original plate are duplicated by 2P method (Photo Polymerization method), injection molding method, sol-gel method, hard embossing method, soft embossing method, semi-dry embossing method, various nanoimprinting methods, etc. An image conversion layer can be formed. In the present embodiment, the 2P method is preferably used because the image conversion layer can be efficiently formed, among the above.

  In the formation of the image conversion layer by the 2P method, for example, an ionizing radiation curable resin composition is dropped on the original plate, and a transparent substrate is placed on the ionizing radiation curable resin composition and pressed. Next, after irradiating ionizing radiation such as ultraviolet rays from the original plate side or the transparent substrate side to cure the ionizing radiation curable resin composition, the ionizing radiation curable resin composition and the transparent substrate are transferred to the original plate side. It can carry out by the method of peeling from.

  Here, for the formation of the image conversion layer, any of various resin materials such as thermosetting resins, thermoplastic resins, ionizing radiation curable resins, which have been conventionally used as materials for relief hologram forming layers can be used. There is no particular limitation.

  Examples of the thermosetting resin include unsaturated polyester resins, acrylic modified urethane resins, epoxy modified acrylic resins, epoxy modified unsaturated polyester resins, alkyd resins, and phenol resins. Examples of the thermoplastic resin include acrylate resin, acrylamide resin, nitrocellulose resin, polystyrene resin, and the like.

  These resins may be homopolymers or copolymers composed of two or more components. These resins can be used alone or in combination of two or more. These resins include various isocyanate compounds, metal soaps such as cobalt naphthenate and zinc naphthenate, organic peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide, benzophenone, acetophenone, anthraquinone, naphthoquinone, azobisisobutyronitrile. In addition, a heat or ultraviolet curing agent such as diphenyl sulfide can be appropriately selected and blended.

  Examples of the ionizing radiation curable resin include an epoxy-modified acrylate resin, a urethane-modified acrylate resin, and an acrylic-modified polyester. Among these, a urethane-modified acrylate resin is particularly preferable, and a urethane-modified acrylic resin represented by the following formula is particularly preferable.

(In the formula, five R ^{1 s} each independently represent a hydrogen atom or a methyl group, R ² represents a C _{1 to} C ₁₆ hydrocarbon group, and X and Y are linear or branched. Represents an alkylene group, where (a + b + c + d) is 100, a is an integer from 20 to 90, b is from 0 to 50, c is from 10 to 80, and d is an integer from 0 to 20.

  As a preferred example, the urethane-modified acrylic resin represented by the above formula is obtained by copolymerizing 20 to 90 mol of methyl methacrylate, 0 to 50 mol of methacrylic acid, and 10 to 80 mol of 2-hydroxyethyl methacrylate. The resulting acrylic copolymer is a resin obtained by reacting methacryloyloxyethyl isocyanate (2-isocyanate ethyl methacrylate) with a hydroxyl group present in the copolymer. Therefore, it is not necessary that the methacryloyloxyethyl isocyanate reacts with all the hydroxyl groups present in the copolymer, preferably at least 10 mol% or more of the hydroxyl groups of 2-hydroxyethyl methacrylate units in the copolymer. It is sufficient that 50 mol% or more is reacted with methacryloyloxyethyl isocyanate. Instead of or in combination with the above 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Monomers having a hydroxyl group such as 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate can also be used.

The urethane-modified acrylic resin represented by the above formula is dissolved in a solvent capable of dissolving the copolymer, for example, a solvent such as toluene, ketone, cellosolve acetate, dimethyl sulfoxide, and the like while stirring. By dropping and reacting methacryloyloxyethyl isocyanate, the isocyanate group reacts with the hydroxyl group of the acrylic resin to form a urethane bond, and the methacryloyl group can be introduced into the resin through the urethane bond. The amount of methacryloyloxyethyl isocyanate used in this case is in the range of 0.1 to 5 moles, preferably 0.5 to 3 moles of isocyanate groups per mole of hydroxyl groups based on the ratio of hydroxyl groups to isocyanate groups of the acrylic resin. Amount. When methacryloyloxyethyl isocyanate having an equivalent amount or more than the hydroxyl group in the resin is used, the methacryloyloxyethyl isocyanate also reacts with a carboxyl group in the resin to form a —CONH—CH ₂ CH ₂ — linkage. It can happen.

The above example is a case where in the above formula, all R ¹ and R ² are methyl groups, and X and Y are ethylene groups, but this embodiment is not limited to these, and 5 R ¹ may independently be a hydrogen atom or a methyl group, and specific examples of R ² include, for example, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert- Examples thereof include a butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and specific examples of X and Y include an ethylene group, a propylene group, a diethylene group, and a dipropylene group. The urethane-modified acrylic resin thus obtained has an overall molecular weight of 10,000 to 200,000, more preferably 20 to 40,000 in terms of standard polystyrene equivalent weight average molecular weight measured by GPC.

  When curing the ionizing radiation curable resin as described above, the following monofunctional or polyfunctional monomers and oligomers may be used in combination with the above monomers for the purpose of adjusting the cross-linked structure and viscosity. it can.

  Examples of the monofunctional monomer include mono (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, (meth) acryloyloxyethyl succinate, and (meth) acryloyloxyethyl phthalate. As a bifunctional or higher monomer, polyol (meth) acrylate (for example, epoxy-modified polyol (meth) acrylate, lactone-modified polyol (meth) acrylate, etc.), polyester (meth) acrylate, epoxy (Meth) acrylates, urethane (meth) acrylates, other polybutadiene-based, isocyanuric acid-based, hydantoin-based, melamine-based, phosphoric acid-based, imide-based, phosphazene-based poly (meth) ) Acrylate and the like, can be used ultraviolet, various monomers is an electron beam curable, oligomers, polymers.

  More specifically, examples of the bifunctional monomer and oligomer include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth). ) Acrylates, etc., and examples of trifunctional monomers, oligomers and polymers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, aliphatic tri (meth) acrylate, etc. Examples of tetrafunctional monomers and oligomers include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and aliphatic tetra (meth) acrylate. Examples of pentafunctional or higher functional monomers and oligomers include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and (meth) acrylates having a polyester skeleton, urethane skeleton, and phosphazene skeleton. Etc. The number of functional groups is not particularly limited, but if the number of functional groups is less than 3, the heat resistance tends to decrease, and if it exceeds 20, the flexibility tends to decrease. The thing of 3-20 is preferable.

  The amount of the monofunctional or polyfunctional monomer or oligomer as described above may be arbitrarily determined according to the production method of the image conversion layer, etc., but is usually 100 parts by weight of the ionizing radiation curable resin. The amount is preferably 50 parts by weight or less, and particularly preferably in the range of 0.5 to 20 parts by weight.

  Furthermore, in the image conversion layer in this embodiment, a photopolymerization initiator, a polymerization inhibitor, an anti-degradation agent, a plasticizer, a lubricant, a colorant such as a dye or a pigment, an extender pigment such as an increase or an anti-blocking agent, if necessary. Additives such as fillers such as and resins, surfactants, antifoaming agents, leveling agents, thixotropic agents, and the like may be added as appropriate.

(Internal phase type diffractive optical element layer)
When the image conversion layer is an internal phase type diffractive optical element layer, interference fringes of object light and reference light are recorded in the transmission Fourier transform hologram area of the image conversion layer. The optical image can be observed by the difference in refractive index between the interference fringes and the component forming the interference fringes.

  As a material for forming such an image conversion layer, a photosensitive composition can be used, and generally known materials such as a silver salt material, a dichromated gelatin emulsion, a photopolymerizable resin, and a photocrosslinkable resin are used. Although a photosensitive composition can be used, in the present embodiment, a photosensitive composition containing the following materials (i) and (ii) is particularly preferably used from the viewpoint of production efficiency. Each of such photosensitive compositions will be described below.

(I) About photosensitive composition containing binder resin, photopolymerizable compound, photopolymerization initiator and sensitizing dye First, it contains a binder resin, a photopolymerizable compound, a photopolymerization initiator and a sensitizing dye. The photosensitive composition will be described. The binder resin used in such a photosensitive composition can be copolymerized with poly (meth) acrylic acid ester, or a partially hydrolyzed product thereof, polyvinyl acetate or hydrolyzed product thereof, acrylic acid, acrylic acid ester, etc. Copolymers containing at least one monomer group as a polymerization component, or a mixture thereof, polyisoprene, polybutadiene, polychloroprene, polyvinyl acetal which is a partial acetalization product of polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, chloride Examples thereof include a vinyl-vinyl acetate copolymer or a mixture thereof. Here, when the image conversion layer is formed, there is a step of moving the monomer by heating in order to stabilize the hologram recorded in the transmission Fourier transform hologram region. For this purpose, it is preferable that the binder resin has a relatively low glass transition temperature and can easily move the monomer.

  The photopolymerizable compound contained in the photosensitive composition includes photopolymerization having at least one ethylenically unsaturated bond in one molecule as described later, photocrosslinkable monomer, oligomer, and prepolymer. And unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amide compounds of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and the like. It is done.

  Specific examples of unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc., and monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids. Specific examples of the acrylic acid ester include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, and trimethylol. Examples include propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate and the like.

  Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolethane trimethacrylate. Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, and 1,3-butanediol diitaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of the halogenated unsaturated carboxylic acid include 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and the like. Can be mentioned. Specific examples of amide monomers of unsaturated carboxylic acids and aliphatic polyvalent amine compounds include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, and 1,6-hexamethylene bismethacrylamide. Etc.

  Examples of the photopolymerization initiator used include 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, and N-phenylglycine. 2,4,6-tris (trichloromethyl) -s-triazine, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, imidazole dimers and the like. The photopolymerization initiator is preferably decomposed after hologram recording from the viewpoint of stabilization of the recorded hologram. For example, organic peroxides are preferable because they are easily decomposed by irradiation with ultraviolet rays.

  As sensitizing dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes having absorption light at 350 to 600 nm. And cyanine dyes, rhodamine dyes, thiopyrylium salt dyes, pyrylium ion dyes, diphenyliodonium ion dyes, and the like. A sensitizing dye having absorption light in a wavelength region of 350 nm or less or 600 nm or more may be used.

  The blending ratio of the photosensitive composition comprising the binder resin, the photopolymerizable compound, the photopolymerization initiator, and the sensitizing dye is as follows. The photopolymerizable compound is used in a proportion of 10 parts by mass to 1000 parts by mass, preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the binder resin. A photoinitiator is used in the ratio of 1-10 mass parts with respect to 100 mass parts of binder resin, Preferably it is 5-10 mass parts. The sensitizing dye is used in a proportion of 0.01 to 1 part by mass, preferably 0.01 to 0.5 part by mass, with respect to 100 parts by mass of the binder resin. In addition, examples of the components of the photosensitive composition include plasticizers, glycerin, diethylene glycol, triethylene glycol, and various nonionic surfactants, cationic surfactants, anionic surfactants, and the like.

  The photosensitive composition usually uses methyl ethyl ketone, cyclohexanone, xylene, tetrahydrofuran, ethyl cellosolve, methyl cellosolve acetate, ethyl acetate, isopropanol or the like alone or a mixed solvent thereof and has a solid content of 10% to 25%. It will be used as a coating solution. The image conversion layer is formed by coating by bar coating, spin coating, dipping or the like using the diluted photosensitive composition if the transparent substrate is in a state of a single sheet (each sheet). The In addition, if the transparent base material is applied in a roll-like long state, the photosensitive composition diluted by gravure coating, roll coating, die coating, or comma coating is applied, dried and / or necessary The image conversion layer is formed by curing according to the above. The image conversion layer thus obtained has a thickness of 0.1 μm to 50 μm, preferably 5 μm to 20 μm, and a protective film may be attached as necessary. As the protective film, a resin film having high transparency and high smoothness such as a polyethylene terephthalate film, a polypropylene film, and a polyvinyl chloride film having a thickness of about 10 μm to 100 μm may be bonded with a rubber roller or the like. In addition, as the photosensitive composition, for example, a commercial product “Omnidex 801” manufactured by DuPont may be used.

  In such a transmission type Fourier transform hologram area of the image conversion layer, interference light fringes are recorded by using two light beams of laser light. Examples of the laser light include wavelength light of 633 nm in a helium-neon laser that is a visible light amount range, light of 514.5 nm, 488 nm, and 457.9 nm in an argon laser, and 647.1 nm and 568.2 nm in a krypton laser. , 520.8 nm wavelength light, 337.5 nm, 350.7 nm, 356.4 nm wavelength light in krypton laser (1.5 W), and 351.1 nm, 368.8 nm wavelength in argon laser (40 mW) Light, 332.4 nm wavelength light in a neon laser (50 mW), 325.0 nm wavelength light in a cadmium laser (15 mW), and the like can be applied.

  Take out one of these wavelengths and record the interference fringes using the wavelength that allows excitation of the photopolymerization initiator, record the interference light between the object light and the reference light, or peel off the protective film Then, the hologram original plate is brought into close contact with the image conversion layer, a laser is incident from the image conversion layer side, and the reflected light from the original plate and the interference fringes of the incident light are recorded to give hologram information.

Then, ultra-high pressure mercury lamp, high pressure mercury lamp, carbon arc, xenon arc, from a light source such as a metal halide lamp, 0.1~10,000mJ / cm ^2, preferably, photopolymerization by ultraviolet irradiation of 10~1,000mJ / cm ² A stable image conversion layer is obtained through a step of decomposing the initiator and a heat treatment step of diffusing and moving the photopolymerizable compound by heating at 120 ° C. for 120 minutes, for example.

(Ii) a cationically polymerizable compound, a radically polymerizable compound, a photoradical polymerization initiator system that polymerizes a radically polymerizable compound by exposure to light of a specific wavelength, and low sensitivity to light of a specific wavelength; Photosensitive composition containing a photo-cationic polymerization initiator system that polymerizes a cationically polymerizable compound in response to light of another wavelength Next, it is exposed to a cationically polymerizable compound, a radically polymerizable compound, and light of a specific wavelength. Photo-radical polymerization initiator system that polymerizes radically polymerizable compounds and photocationic polymerization that is low-sensitivity to light of a specific wavelength and that is sensitive to light of another wavelength to polymerize cationically polymerizable compounds The photosensitive composition containing an agent system will be described.

  When this photosensitive composition is used, after applying the photosensitive composition on the transparent substrate, the photo radical polymerization initiator system is irradiated with light such as laser light, and then photocation polymerization is initiated. By irradiating light having a wavelength different from that of the laser beam to which the agent system is exposed, an image conversion layer in which a hologram is recorded in the transmission type Fourier transform hologram region is formed. Specifically, the radically polymerizable compound is polymerized by irradiation with light such as laser light (hereinafter referred to as first exposure). Thereafter, the cationically polymerizable compound is subjected to cationic polymerization with Bronsted acid or Lewis acid generated by decomposition of the photocationic polymerization initiator system by subsequent overall exposure (hereinafter referred to as post-exposure). A conversion layer is formed.

  As the cationically polymerizable compound, those which are liquid at room temperature are used from the viewpoint that the polymerization of the radically polymerizable compound is preferably performed in a composition having a relatively low viscosity. Examples of such cationically polymerizable compounds include diglycerol diether, pentaerythritol polydiglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, and 1,6-hexanediol. Examples thereof include glycidyl ether, polyethylene glycol diglycidyl ether, and phenyl glycidyl ether.

  Moreover, as a radically polymerizable compound, what has at least 1 ethylenically unsaturated double bond in a molecule | numerator is preferable. Moreover, it is preferable that the average refractive index of a radically polymerizable compound is larger than the average refractive index of the said cation polymeric compound, and it is preferable that it is larger 0.02 or more especially. This is because a hologram is formed by the difference in refractive index between the radical polymerizable compound and the cationic polymerizable compound. Therefore, when the average refractive index difference is not more than the above value, the refractive index modulation becomes insufficient. The refractive index can be measured with a spectroscopic ellipsometer. Examples of the radical polymerizable compound include acrylamide, methacrylamide, styrene, 2-bromostyrene, phenyl acrylate, 2-phenoxyethyl acrylate, 2,3-naphthalenedicarboxylic acid (acryloxyethyl) monoester, methylphenoxyethyl acrylate, Nonylphenoxyethyl acrylate, β-acryloxyethyl hydrogen phthalate and the like can be mentioned.

  The radical photopolymerization initiator system may be an initiator system that generates active radicals by the first exposure for producing a hologram, and the active radicals polymerize radical polymerizable compounds, and generally absorbs light. A combination of a sensitizer, which is an active component, and an active radical generating compound or acid generating compound may be used. A sensitizer in such a radical photopolymerization initiator system often uses a colored compound such as a dye to absorb visible laser light, but in the case of a colorless transparent hologram, a cyanine dye is used. Is preferred. Since cyanine dyes are generally easily decomposed by light, the dyes in the hologram are decomposed and absorbed in the visible region by being left exposed for several hours to several days under post-exposure or indoor light or sunlight in this embodiment. This is because a colorless and transparent hologram can be obtained.

  Specific examples of the cyanine dye include anhydro-3,3′-dicarboxymethyl-9-ethyl-2,2′thiacarbocyanine betaine, anhydro-3-carboxymethyl-3 ′, 9′-diethyl-2, 2 'thiacarbocyanine betaine, 3,3', 9-triethyl-2,2'-thiacarbocyanine iodine salt, 3,9-diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine iodine Salt, 3,3 ′, 9-triethyl-2,2 ′-(4,5,4 ′, 5′-dibenzo) thiacarbocyanine iodine salt, 2- [3- (3-ethyl-2-benzothia Zolidene) -1-propenyl] -6- [2- (3-ethyl-2-benzothiazolidene) ethylideneimino] -3-ethyl-1,3,5-thiadiazolium iodine salt, 2- [ [3-Allyl-4-oxo-5- (3-n-propyl-5,6-dimethyl) Ru-2-benzothiazolidene) -ethylidene-2-thiazolinylidene] methyl] 3-ethyl-4,5-diphenylthiazolinium-iodine salt, 1,1 ′, 3,3,3 ′, 3′-hexamethyl -2,2'-Indotricarbocyanine iodine salt, 3,3'-diethyl-2,2'-thiatricarbocyanine perchlorate, anhydro-1-ethyl-4-methoxy-3'-carboxy And methyl-5'-chloro-2,2'-quinothiocyanine betaine, anhydro-5,5'-diphenyl-9-ethyl-3,3'-disulfopropyloxacarbocyanine hydroxide, triethylamine salt, and the like. These can be used alone or in combination of two or more.

  Examples of the active radical generating compound that may be used in combination with a cyanine dye include diaryliodonium salts and 2,4,6-substituted-1,3,5-triazines. The use of diaryliodonium salts is particularly preferred when high photosensitivity is required. Specific examples of the diaryl iodonium salts include diphenyl iodonium, 4,4′-dichlorodiphenyl iodonium, 4,4′-dimethoxydiphenyl iodonium, 4,4′-ditertiary butyl diphenyl iodonium, and 3,3′-dinitrodiphenyl iodonium. Such as chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, and the like. Specific examples of 2,4,6-substituted-1,3,5-triazines include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6. -Tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( p-methoxyphenylvinyl) -1,3,5-triazine, 2- (4′-methoxy-1′-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like. .

  The above cationic photopolymerization initiator system has low photosensitivity for the first exposure, and after exposure to light having a wavelength different from that of the first exposure, it generates a Bronsted acid or a Lewis acid upon exposure to light. It is preferable to use an initiator system that polymerizes the polymerizable compound, and those that do not polymerize the cationic polymerizable compound during the first exposure are particularly preferable. Examples of the cationic photopolymerization initiator system include diaryliodonium salts, triarylsulfonium salts, iron allene complexes, and the like. Preferable diaryliodonium salts include iodonium tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like shown in the radical photopolymerization initiator system described above. Preferable triarylsulfonium salts include triphenylsulfonium, 4-tertiarybutyltriphenylsulfonium, and the like.

  In the photosensitive composition, a binder resin, a thermal polymerization inhibitor, a silane coupling agent, a plasticizer, a colorant and the like may be used in combination as necessary. The binder resin is used to improve the film formability and film thickness uniformity of the composition before hologram formation, and to stabilize interference fringes formed by polymerization by irradiation with light such as laser light until post-exposure. Used to make it exist. The binder resin only needs to be compatible with the cationic polymerizable compound or the radical polymerizable compound. For example, a copolymer of chlorinated polyethylene, polymethyl methacrylate, methyl methacrylate and other alkyl (meth) acrylates. And a copolymer of vinyl chloride and acrylonitrile, polyvinyl acetate, and the like. The binder resin may have reactivity such as a cationic polymerizable group in its side chain or main chain.

  The composition of the photosensitive composition is 2% by mass to 70% by mass, preferably 10% by mass to 50% by mass, and 30% by mass of the radical polymerizable compound, based on the total mass of the photosensitive composition. ~ 90 wt%, preferably 40 wt% to 70 wt%, cationic polymerization initiator system is 0.3 wt% to 8 wt%, preferably 1 wt% to 5 wt%, radical polymerization initiator system is 0.3 wt% The content is 8% by mass to 8% by mass, preferably 1% by mass to 5% by mass. The above-mentioned photosensitive composition may be prepared by using essential components and optional components as they are or as necessary, for example, a ketone solvent such as methyl ethyl ketone, an ester solvent such as ethyl acetate, an aromatic solvent such as toluene, and a cellosolve such as methyl cellosolve. It can be prepared by blending with a system solvent, an alcohol solvent such as methanol, an ether solvent such as tetrahydrofuran or dioxane, or a halogen solvent such as dichloromethane or chloroform and mixing in a cool and dark place using, for example, a high-speed stirrer.

  The image conversion layer comprising such a photosensitive composition can be formed by applying the above-mentioned photosensitive composition by the same application method as the photosensitive composition of (i) and drying. The coating amount is appropriately selected, and for example, the film thickness after drying can be 1 μm to 50 μm.

  Interference fringes are recorded in the image conversion layer thus produced by polymerizing a radical polymerizable compound using, for example, laser light having a wavelength of 300 to 1200 nm. At this stage, diffracted light by the recorded interference fringes is obtained and a hologram is formed, but in order to further polymerize the cation polymerizable compound remaining unreacted, a photocation polymerization initiator is used as a post-exposure. It is preferable to form a hologram by irradiating the entire surface with light having a wavelength of 200 nm to 700 nm which is sensitive to the system. Note that the diffraction efficiency, the peak wavelength of diffracted light, the half-value width, and the like can be changed by treating the image conversion layer with heat or infrared rays before post-exposure.

(Amplitude type diffractive optical element layer)
When the image conversion layer is an amplitude type diffractive optical element layer, a light and dark intensity distribution such as black and white is recorded in the transmission Fourier transform hologram area of the image conversion layer. In such an image conversion layer, an image conversion layer is formed using a photosensitive material such as a silver salt photosensitive material, and an object beam and a reference beam are formed by a laser light source on a portion of the image conversion layer which becomes a transmission type Fourier transform hologram region. Exposure to interference light. Thereafter, development and fixing can be performed to form a hologram in the transmission Fourier transform hologram region.

  Examples of the material used for such an image conversion layer include a silver salt photographic light-sensitive material such as a silver halide photographic light-sensitive material, gelatin processed with dichromic acid, and a light-sensitive material using a photosensitive resin. In the present embodiment, among the above, the silver salt photosensitive material is preferable because it can form an image conversion layer having high sensitivity, wide spectral sensitivity distribution, and higher diffraction efficiency.

3. Transparent base material Next, the transparent base material used for this embodiment is demonstrated. The transparent substrate used in this embodiment is capable of forming the image conversion layer and has a light transmission property capable of transmitting a light image formed in the transmission type Fourier transform hologram region of the image conversion layer. If it does not specifically limit. Among them, the transparent substrate in this embodiment preferably has a transmittance in the visible light region of 80% or more, and more preferably 90% or more. This is because if the transmittance is low, the optical image obtained by the transmission type Fourier transform hologram region of this embodiment may be disturbed. Here, the transmittance of the transparent substrate can be measured by JIS K7361-1 (Testing method for total light transmittance of plastic-transparent material).

  In addition, the transparent base material used in this embodiment is preferably as the haze value is low, specifically, the haze value is preferably in the range of 0.01% to 5%, particularly 0.01% to 3%. %, Preferably within the range of 0.01% to 1.5%. Here, as the haze value, a value measured in accordance with JIS K7105 is used.

  The material which comprises the transparent base material used for this embodiment will not be specifically limited if it has the said characteristic, For example, a plastic resin film and a glass plate can be used. In this embodiment, it is preferable to use a plastic resin film as the transparent substrate. This is because the plastic resin film is lightweight and has a low risk of breakage like glass.

  The resin constituting the plastic resin film is not particularly limited as long as it has rigidity capable of supporting the image conversion layer. Examples of such plastic resins include polyethylene terephthalate, polycarbonate, acrylic resin, cycloolefin resin, polyester resin, polystyrene resin, and acrylic styrene resin. Of these, polycarbonate is most suitable in terms of birefringence. The thickness is preferably about 0.05 to 5 mm, preferably 0.1 to 3 mm from the viewpoint of handleability.

4). Hologram Observation Card Next, the hologram observation card of this embodiment will be described. The hologram observation card of this embodiment is not particularly limited as long as it has the transparent substrate, the image conversion layer, and the receiving layer, and is formed in a card shape. The hologram observation card of this embodiment can be used for various purposes such as business cards, membership cards, and toys.

  In addition, the hologram observation card of this embodiment may be one in which various printing is performed on a transparent substrate or an image conversion layer. In addition, an image may be formed on the receiving layer by, for example, a sublimation type thermal transfer method, an ink jet method, a melt type thermal transfer method, an intermediate transfer method, or the like.

  Here, in this embodiment, when the said receiving layer is formed on the transparent base material, it is preferable that the primer layer is formed between the said transparent base material and a receiving layer. Thereby, the adhesiveness between the transparent substrate and the receiving layer can be improved, and a higher quality hologram observation card can be obtained.

  The primer layer is not particularly limited as long as it can improve the adhesion between the receptor layer and the transparent substrate. For example, the primer layer may be transparent to visible light. For example, it may be colored white. When the primer layer is white, there is an advantage that the printed surface can be more easily observed when printing is performed on the receiving layer. In addition, it is preferable that a primer layer has transparency about the part laminated | stacked with the transmission type Fourier-transform hologram area | region of the said image conversion layer. This is because the optical image formed by the transmission Fourier transform hologram region can be easily observed.

  Examples of such a primer layer include polyurethane, polyester, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, ethylene and acetic acid. It can be set as the layer containing a copolymer with vinyl or acrylic acid, an epoxy resin, or the like.

  The primer layer can be formed by appropriately dissolving or dispersing the resin in a solvent to form a coating solution, and applying and drying by a known coating method. As a coating solution, monomers, oligomers, prepolymers and the like may be combined with the above resin, a reaction initiator, a curing agent, a crosslinking agent, a coloring agent such as a dye or a pigment, or a combination of a main agent and a curing agent, You may make it react by apply | coating, drying, and performing an aging process as needed. Moreover, as a white pigment used for the said primer layer, a titanium oxide, a zinc oxide, kaolin clay, a calcium carbonate, fine powder silica etc. are mentioned, for example, These can be used in mixture of 2 or more types.

  The thickness of the primer layer is usually about 0.05 to 10 μm, and preferably about 0.1 to 5 μm.

  Also in this embodiment, a protective layer as described in the second embodiment to be described later may be formed on the transmission type Fourier transform hologram region of the image conversion layer.

B. Second Embodiment Next, a second embodiment of the hologram observation card of the present invention will be described. The hologram observation card of the present embodiment includes a transparent base material, a transmission Fourier transform hologram region formed on the transparent base material and having a function as a Fourier transform lens, and a Fourier transform lens other than the transmission Fourier transform hologram region. A hologram observation card having an image conversion layer having a non-hologram area not functioning as a protective layer formed on the transmission Fourier transform hologram area of the image conversion layer, A printable receiving layer is formed.

  For example, as shown in FIG. 5, the hologram observation card of this embodiment is an image conversion formed on a transparent base material 1 and at least a transmission type Fourier transform hologram area a and a non-hologram area b. It has a layer 2, a protective layer 4 formed on the transmission Fourier transform hologram region a of the image conversion layer 2, and a printable receiving layer 3 formed on the protective layer 4.

  According to this embodiment, since the receiving layer is formed, a hologram observation card capable of printing various information, images and the like by various printers can be obtained. In general, when printing is performed on a layer having a Fourier transform lens function, a difference in refractive index of the layer having a Fourier transform lens function changes, and optical image formation becomes difficult. However, according to this embodiment, since the protective layer is formed and the receiving layer is formed on the protective layer, the receiving layer is received without changing the refractive index difference in the transmission Fourier transform hologram region. Printing can be performed on the layer, and a hologram observation card used for various applications can be obtained.

  Furthermore, according to the present embodiment, since the image conversion layer having the transmission Fourier transform hologram region is formed, the transmission Fourier transform hologram is efficiently manufactured without being separately bonded or sandwiched. There is also an advantage that the hologram observation card can be made. Hereinafter, each configuration of the hologram observation card of the present embodiment will be described. Note that the transparent substrate and the image conversion layer are the same as those in the first embodiment described above, and a description thereof will be omitted here.

1. Receiving layer First, the receiving layer used in this embodiment will be described. The receiving layer used in this embodiment is not particularly limited as long as it is formed on a protective layer described later and can be printed. In this embodiment, it suffices to be formed on at least the protective layer. For example, it may be formed in a pattern on the protective layer, or may be formed on the entire surface of the protective layer. Moreover, you may form not only on a protective layer but on the surface on the opposite side to the side in which the image conversion layer of the transparent base material was formed, for example.

  Such a receiving layer is not particularly limited as long as it can be printed, and the type of printing is not particularly limited. In this embodiment, it is particularly preferable that the hologram observation card can be printed on demand, and it is preferable that the hologram observation card can be printed by a sublimation thermal transfer method, an ink jet method, a melt type thermal transfer method, or an intermediate transfer method. Since such a receiving layer can be the same as that of the first embodiment described above, detailed description thereof is omitted here.

2. Next, the protective layer used in this embodiment will be described. The protective layer used in this embodiment is formed on at least the transmission type Fourier transform hologram region of the image conversion layer, prevents contamination of the transmission type Fourier transform hologram region of the image conversion layer, and the like. There is no particular limitation as long as it has a function of preventing a change in the refractive index difference in the transmission type Fourier transform hologram region. In the present embodiment, the protective layer may be formed only on the transmission Fourier transform hologram region in the image conversion layer, but may be formed on the entire surface of the image conversion layer, for example.

  In addition, the protective layer used in this embodiment transmits light diffracted by the image conversion layer, and preferably has excellent light transmittance. The protective layer in this embodiment preferably has a transmittance in the visible light region of 80% or more, and more preferably 90% or more. This is because if the light transmittance is low, the optical image obtained by the transmission type Fourier transform hologram region of this embodiment may be disturbed. Here, the transmittance of the protective layer can be measured by JIS K7361-1 (Testing method for total light transmittance of plastic-transparent material).

  Further, the protective layer in this embodiment is preferably as the haze is low, specifically, the haze value is preferably in the range of 0.01% to 5%, particularly in the range of 0.01% to 3%. Is preferably within the range of 0.01% to 1.5%. Here, as the haze value, a value measured in accordance with JIS K7105 is used.

  The material constituting the protective layer used in this embodiment is not particularly limited as long as it has the above characteristics. As such a material, a rigid material such as glass or a flexible material can be used. However, in the present embodiment, it is preferable to use a flexible material. This is because, by using a flexible material, for example, the manufacturing process of the hologram observation card of this embodiment can be a roll-to-roll process, and the hologram observation card of this embodiment can be made highly productive.

  Examples of the flexible material include those made of a thermoplastic resin. Examples of these materials include olefins such as polyethylene resins, polypropylene resins, cyclic polyolefin resins, fluorine resins, and silicone resins. Based resins and the like. Specific examples of such thermoplastic resins include poly (meth) acrylic acid esters or partial hydrolysates thereof, polyvinyl acetate or hydrolysates thereof, polyvinyl alcohol or partial acetalized products thereof, triacetyl cellulose, polyisoprene. , Polybutadiene, polychloroprene, silicone rubber, polystyrene, polyvinyl butyral, polyvinyl chloride, polyarylate, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinylcarbazole or derivatives thereof, poly-N-vinylpyrrolidone or derivatives thereof, styrene And at least a copolymerizable monomer group such as a copolymer of maleic anhydride or a half ester thereof, acrylic acid, acrylic ester, acrylamide, acrylonitrile, ethylene, propylene, vinyl chloride, vinyl acetate, etc. Copolymers of one polymerization component, and the like. In this embodiment, only one type of these thermoplastic resins may be used, or a mixture of two or more types may be used.

  The protective layer used in this embodiment may contain an additive within a range that does not impair the purpose of the present embodiment and the haze value. The additive is not particularly limited, and may be appropriately selected according to the use of the hologram observation sheet of the present embodiment. Examples of such additives include an ultraviolet absorber, an infrared absorber, a water repellent function imparting agent, and a fluorescent brightening agent.

  The thickness of the protective layer used in this embodiment is not particularly limited as long as the protective layer has a rigidity that does not damage the saddle shape of the image conversion layer described later due to deformation caused by external factors. . Such a thickness may be appropriately determined according to the type of the constituent material of the protective layer, but is usually preferably in the range of 0.5 μm to 10 mm, and particularly preferably in the range of 1 μm to 5 mm.

  Further, the method for forming the protective layer is not particularly limited. For example, the image conversion layer is provided with a spacer or the like so that an air layer is formed between the transmission hologram region of the image conversion layer and the protective layer. And the protective layer may be bonded. For example, when the protective layer has a certain refractive index difference from the image conversion layer, the protective layer is formed by coating the resin material on the image conversion layer. May be.

3. Hologram Observation Card Next, the hologram observation card of this embodiment will be described. The hologram observation card of this embodiment has the above-mentioned transparent substrate, the above-mentioned image conversion layer, the above-mentioned protective layer, and the above-mentioned receiving layer, and is particularly limited as long as it is formed in a card shape. Instead, for example, the primer layer described in the first embodiment may be formed. The hologram observation card of this embodiment can be used for various purposes such as business cards, membership cards, and toys.

  Moreover, the hologram observation card of this embodiment may be one in which various printings are performed on a transparent substrate or an image conversion layer. In addition, an image may be formed on the receiving layer by, for example, a sublimation type thermal transfer method, an ink jet method, a melt type thermal transfer method, an intermediate transfer method, or the like.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has the same configuration as the technical idea described in the claims of the present invention. It is included in the technical scope of the invention.

[Example 1]
<Formation of image conversion layer>
A dry etching resist was spin-coated with a spinner on a chromium thin film of a photomask blank plate in which a surface low-reflection chromium thin film was laminated on a synthetic quartz substrate. As a resist for dry etching, ZEP7000 manufactured by Nippon Zeon Co., Ltd. was used and formed to have a thickness of 400 nm. The resist layer was exposed to a pattern prepared in advance by a computer using an electron beam drawing apparatus (MEBES4500: manufactured by ETEC), and the exposed portion of the resist resin was easily dissolved. Thereafter, the developer was sprayed (spray development) to remove the easily soluble portion, and a resist pattern was formed.
Subsequently, by using the formed resist pattern, a portion of the chromium thin film not covered with the resist was etched away by dry etching to expose the quartz substrate. Next, the exposed quartz substrate was etched to form a recess in the quartz substrate. Thereafter, the resist thin film was dissolved and removed to obtain an original plate having a concave portion formed by etching the quartz substrate and a convex portion in which the quartz substrate and the chromium thin film remained without being etched.
A composition for forming an image conversion layer (UV curable acrylate resin: refractive index 1.52, measurement wavelength: 633 nm) is dropped on the uneven master, and a polycarbonate substrate (transparent substrate) having a thickness of 0.5 mm is stacked thereon. Placed and pressed. Next, the composition for forming an image conversion layer was cured by irradiating actinic radiation and then peeled off to prepare a transparent substrate with an image conversion layer having a concavo-convex image obtained by inverting the concavo-convex pattern of the original. In addition, the part used as a non-hologram area | region was made into planar shape.

<Formation of protective layer>
Acrylic plate (product name: Paraglass thickness 2 mm: manufactured by Kuraray Co., Ltd.) as a spacer and adhesive (coating solution CAT-1300S: manufactured by Teikoku Ink Co., Ltd.) is screen-printed in a pattern and a release paper is pasted on the printed surface. Prepared as forming member. Note that the spacer / adhesive was formed in a pattern in a portion to be a non-hologram region.
Subsequently, the release paper of the protective layer forming member was peeled off, and pressed and bonded to the side on which the uneven surface of the transparent substrate with the image conversion layer was formed. The bonded material was extracted to a predetermined size (5 cm × 5 cm) and processed.

<Formation of receiving layer that can be printed by sublimation thermal transfer method>
(Composition of receiving layer forming ink)
・ Polyester resin (Byron 200 manufactured by TOYOBO) ... 100 parts by weight-Hydroxyl-modified silicone resin (X-62-1421B, manufactured by Shin-Etsu Silicone) ... 4 parts by weight-Isocyanate curing agent (Takenate A14, manufactured by Mitsui Takeda Chemical) ... 4 weights Parts / solvent (toluene / methylethylketone = 1/1): 100 parts by weight The receiving layer-forming ink having the above composition is the entire surface of the transparent substrate opposite to the side where the image conversion layer is formed. Then, coating was performed with a bar coater, and drying was performed at 110 ° C. for 3 minutes. At this time, the film thickness of the receiving layer after drying was 5 μm.

<Evaluation>
When an image was printed on the obtained hologram observation card with a sublimation card printer DTC300 (FARGO), the image was clearly formed. Further, when the point light source was observed through the transmission type Fourier transform hologram region, a converted image was observed.

[Example 2]
<Formation of image conversion layer and protective layer>
In the same manner as in Example 1, an image conversion layer and a protective layer were formed on a transparent substrate.

<Formation of primer layer and receiving layer printable by sublimation thermal transfer method>
(Composition of primer layer forming ink)
・ Polyurethane resin (N-5247 manufactured by Nippon Polyurethane Co., Ltd.) ... 100 parts by weightTitanium oxide particles (A-150, manufactured by Sakai Chemical Co., Ltd.) ... 150 parts by weightSolvent (toluene / methyl ethyl ketone / IPA = 1/1/1) ... 100 Part by weight The primer layer-forming ink having the above composition was applied to the entire surface of the transparent substrate opposite to the side on which the image conversion layer was formed with a bar coater. Let dry for minutes. The film thickness after drying was 3 μm. Subsequently, as in Example 1, a receiving layer printable by a sublimation thermal transfer method was formed on the primer layer to obtain a hologram observation card.

<Evaluation>
When an image was printed on the obtained hologram observation card with a sublimation card printer DTC300 (FARGO), the image was observed more clearly than in Example 1. Further, when the point light source was observed through the transmission type Fourier transform hologram region, a converted image was observed.

[Example 3]
<Formation of image conversion layer and protective layer>
In the same manner as in Example 1, an image conversion layer and a protective layer were formed on a transparent substrate.

<Formation of receiving layer printable by melt-type thermal transfer method and intermediate transfer method>
(Composition of receiving layer forming ink)
-Polyester resin (byron 200 manufactured by TOYOBO) ... 100 parts by weight-Solvent (toluene / methyl ethyl ketone = 1/1) ... 100 parts by weight The receiving layer-forming ink having the above composition is composed of the transparent substrate and the image conversion layer is The whole surface on the side opposite to the formed side was coated with a bar coater and dried at 110 ° C. for 3 minutes. The film thickness after drying was 5 μm.

<Evaluation>
Images were printed on the obtained hologram observation card by a hot-melt card printer CP400 (letter printing) and an intermediate transfer card printer CX-210 (Dainippon Printing). Each of the images was clearly formed, and when the point light source was observed through the Fourier transform hologram region, the converted image was observed.

[Example 4]
<Formation of image conversion layer and protective layer>
In the same manner as in Example 1, an image conversion layer and a protective layer were formed on a transparent substrate.

<Formation of receiving layer printable by inkjet method>
(Composition of receiving layer forming ink)
-Pateracol IJ2 (manufactured by Dainippon Ink & Co., Ltd.) ... 100 parts by weight · Solvent (water) ... 30 parts by weight The ink for forming the receiving layer having the above composition is the side of the transparent substrate on which the image conversion layer is formed. The entire surface on the opposite side was coated with a bar coater and dried at 110 ° C. for 3 minutes. The film thickness after drying was 20 μm.

<Evaluation>
An image was printed on the obtained hologram observation card with an ink jet printer PM-900 (EPSON). The image was clearly formed, and when the point light source was observed through the Fourier transform hologram region, the converted image was observed.

It is a schematic sectional drawing which shows an example of the hologram observation card | curd of this invention. It is a schematic sectional drawing which shows the other example of the hologram observation card | curd of this invention. It is a schematic sectional drawing which shows the other example of the hologram observation card | curd of this invention. It is the schematic explaining a Fourier-transform lens function. It is a schematic sectional drawing which shows the other example of the hologram observation card | curd of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent base material 2 ... Image conversion layer 3 ... Receptive layer 4 ... Protective layer a ... Transmission type Fourier-transform hologram area b ... Non-hologram area

Claims (9)

A transparent base material, a transmission type Fourier transform hologram region formed on the transparent base material and having a function as a Fourier transform lens, and a non-hologram region having no function as a Fourier transform lens other than the transmission type Fourier transform hologram region A hologram observation card having an image conversion layer comprising:
A hologram having a printable receiving layer formed on a surface of the transparent substrate opposite to the side on which the image conversion layer is formed, or on the non-hologram region of the image conversion layer. Observation card.   The hologram observation card according to claim 1, wherein a primer layer is formed between the transparent substrate and the receiving layer.   The hologram observation card according to claim 2, wherein the primer layer contains a white pigment. A transparent base material, a transmission type Fourier transform hologram region formed on the transparent base material and having a function as a Fourier transform lens, and a non-hologram region having no function as a Fourier transform lens other than the transmission type Fourier transform hologram region A hologram observation card comprising: an image conversion layer comprising: a protective layer formed on the transmission Fourier transform hologram region of the image conversion layer;
A hologram observation card, wherein a printable receiving layer is formed on the protective layer.   The hologram observation card according to any one of claims 1 to 4, wherein an image is printed on the receiving layer by a sublimation thermal transfer method.   The hologram observation card according to any one of claims 1 to 4, wherein an image is printed on the receiving layer by an ink jet method.   The hologram observation card according to any one of claims 1 to 4, wherein an image is printed on the receiving layer by a melt-type thermal transfer method.   The hologram observation card according to claim 1, wherein an image is printed on the receiving layer by an intermediate transfer method. The said image conversion layer is a surface phase type | mold diffractive optical element layer which has an uneven | corrugated structure in the surface of the said transmission type Fourier-transform hologram area, The claim in any one of Claim 1-8 characterized by the above-mentioned. Hologram observation card.

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