JP2012194206A - Coating material for hologram, hologram formation body, packaging material, and manufacturing method of hologram formation body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a coating material for holograms capable of forming a reflective layer excellent in reflectance and abrasion resistance; a hologram formation body with a reflective layer formed using the coating material; a packaging material; and a manufacturing method of the hologram formation body.SOLUTION: The coating material for holograms contains a hydrolysis polycondensable organometallic compound, an organometallic compound and a solvent, and the content of the metal oxide fine particles to the total amount of solid content is 0.1-50 mass%. The hologram formation body comprises a relief member with a relief formation surface, and a transparent reflection layer covering the relief formation surface of the relief member and formed using the coating material for holograms. The packaging material consists of the hologram formation body.

Description

  The present invention relates to a hologram coating material, a hologram forming body and a packaging material using the same, and a method for producing the hologram forming body.

  Conventionally, a photocurable resin composition is applied onto a support to form a photocurable resin layer (relief material layer), and an uneven pattern (relief) is imparted to the surface of the photocurable resin layer. After that, the photocurable resin layer is cured by exposure to active energy rays such as ultraviolet rays and electron beams to form a relief layer, and a reflective layer made of a metal thin film is laminated on the concavo-convex pattern surface formed on the relief layer. Thus, an optical article such as a diffraction grating or a relief hologram is formed (for example, Patent Document 1).

As such a metal thin film, a thin film such as a metal oxide or a metal sulfide is often used. As a method for forming the metal thin film, a general thin film forming method such as vacuum deposition or sputtering is used.
However, in a film forming method that requires a vacuum apparatus such as vacuum deposition or sputtering, a large-scale apparatus is required, the manufacturing cost becomes very high, or the base material is damaged due to thermal damage from the sprayed heat from the deposition source. There are problems such as deformation and thermal sag.

  On the other hand, for example, Patent Document 2 proposes a method of applying a solution containing an organometallic compound to the surface of a base resin to form a transparent reflective layer made of an oxide of an organometallic compound.

However, in the method of Patent Document 2, the reflectance of the relief layer provided with the transparent reflection layer does not sufficiently increase, and thus the glitter (visual feeling that feels bright) is insufficient.
In order to obtain a hologram that is superior in design and brightness (visual feeling that makes you feel brilliant) than before, it is required to further improve the light reflectivity and light transparency of the transparent reflective film.

JP 2005-10230 A JP 2001-75462 A

  The present invention has been made to solve the above-mentioned problems, and is formed by using the coating material for hologram capable of forming a transparent reflective layer excellent in reflectance and wear resistance on the relief forming surface. It is an object of the present invention to provide a hologram forming body, a packaging material, and a method for manufacturing the hologram forming body, each including the formed reflection layer.

  In order to increase the reflectance of the transparent reflective layer made of an oxide of an organometallic compound, it is conceivable that metal fine particles are mixed in a coating solution containing the organometallic compound. However, as a result of studies by the present inventors, if the amount of metal oxide fine particles contained in the coating solution is too large, the reflectance of the transparent reflective layer is improved, but the wear resistance is lowered, and the desired hologram is formed by the wear. There is a problem that it cannot be reproduced (the hologram disappears), or in some cases, the reflectance of the core is not sufficiently increased, and only the wear resistance is lowered.

  The hologram coating material according to the present invention has been completed based on the above knowledge, and includes the hydrolyzed polycondensable organometallic compound, the metal oxide fine particles, and the solvent, and the hydrolyzed polycondensation based on the total solid content. The content ratio of the conductive organic metal compound is 50 to 99.9% by mass, and the content ratio of the metal oxide fine particles is 0.1 to 50% by mass.

  In the hologram coating material according to the present invention, the content ratio of the hydrolytic polycondensable organometallic compound is preferably larger than the content ratio of the metal oxide fine particles.

  In the hologram coating material according to the present invention, the hydrolyzable polycondensable organometallic compound is preferably a metal alkoxide, and the alkoxyl group preferably has 1 to 10 carbon atoms.

  A hologram forming body according to the present invention includes a relief member having a relief forming surface and a transparent reflecting layer covering the relief forming surface of the relief member, and the transparent reflecting layer is formed using the above-described hologram coating material. It is characterized by being made.

  The hologram forming body according to the present invention is excellent in reflectance and wear resistance because the transparent reflection layer is formed using the above-mentioned hologram coating material.

  In the hologram forming body according to the present invention, it is preferable that the unevenness of the fine uneven structure on the relief forming surface is 10 to 2000 nm, and the film thickness of the transparent reflective layer is 1 to 200 nm.

  In a preferred embodiment of the hologram formed body according to the present invention, the reflectance of the hologram formed body based on JIS-K0115 may be 5 to 20%.

  In a preferred embodiment of the hologram forming body according to the present invention, the haze based on JIS-K7105 of the transparent reflective layer may be 0.1 to 2%.

  The packaging material which concerns on this invention consists of the said hologram formation body, It is characterized by the above-mentioned.

  In the method for producing a hologram forming body according to the present invention, (i) a relief forming composition containing a thermoplastic resin and / or a thermosetting resin is applied to one side of a flexible sheet-like substrate, and a relief is formed. Forming a material layer; (ii) preparing a relief member by forming a fine relief structure on the surface of the relief material layer and recording a hologram; and (iii) hydrolyzing the relief forming surface of the relief member. And applying a hologram coating material containing a condensable organometallic compound, metal oxide fine particles, and a solvent, followed by drying to form a transparent reflective layer.

The hologram coating material according to the present invention is excellent in reflectivity and wear resistance, exhibits excellent glitter and has surface rubbing when a transparent reflective layer is formed on the relief forming surface using the coating material. A hologram can be obtained in which the disappearance of the hologram is difficult.
Since the hologram forming body and the packaging material according to the present invention are formed with the transparent reflective layer using the above-mentioned hologram coating material, the hologram forming body and the packaging material have a hologram with high design properties excellent in glitter and abrasion resistance. .
The method for producing a hologram forming body according to the present invention is excellent in the brightness and abrasion resistance of a hologram, and a flexible hologram forming body can be easily produced at a lower cost than when a dry film forming process is used. Can be produced.

FIG. 1 is a cross-sectional view schematically showing an example of a layer configuration in the first aspect of the hologram forming body according to the present invention. FIG. 2 is a cross-sectional view schematically showing an example of a layer configuration in the second embodiment of the hologram forming body according to the present invention. FIG. 3 is a cross-sectional view schematically showing an example of a layer configuration in the third aspect of the hologram forming body according to the present invention. FIG. 4 is a cross-sectional view schematically showing an example of a layer configuration in the fourth aspect of the hologram forming body according to the present invention. FIG. 5 is a cross-sectional view schematically showing another example of the layer configuration in the first aspect of the hologram forming body. FIG. 6 is a cross-sectional view schematically showing another example of the layer configuration in the first aspect of the hologram forming body. FIG. 7 is a cross-sectional view schematically showing another example of the layer configuration in the first aspect of the hologram forming body. FIG. 8 is a diagram schematically showing an example of a flow of a method for producing a hologram forming body according to the present invention.

In the present invention, (meth) acrylate represents acrylate and / or methacrylate.
In the present invention, the resin is a concept including a polymer in addition to a monomer and an oligomer.
In the present invention, the molecular weight means a weight average molecular weight which is a polystyrene equivalent value measured by gel permeation chromatography (GPC) in a THF solvent when having a molecular weight distribution, and when having no molecular weight distribution, It means the molecular weight of the compound itself.
According to the definition of film and sheet in JIS K6900, the sheet is thin and generally refers to a flat product whose thickness is small relative to the length and width, and the film is extremely small compared to the length and width. A thin, flat product with an arbitrarily limited maximum thickness, usually supplied in the form of a roll. Therefore, it can be said that a film with a particularly thin thickness among the sheets is a film, but the boundary between the sheet and the film is not clear and is difficult to distinguish clearly. Is defined as “sheet”.
The light of the present invention includes not only electromagnetic waves having wavelengths in the visible region and invisible region, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.

  Hereinafter, the hologram coating material according to the present invention will be described first, and then the hologram forming body, the packaging material, and the method for producing the hologram forming body will be described.

(Hologram coating material)
The hologram coating material according to the present invention includes a hydrolyzable polycondensable organometallic compound, metal oxide fine particles, and a solvent.
A hydrolyzable polycondensable organometallic compound and metal oxide fine particles are used in combination, and the content ratio of the hydrolyzed polycondensable organometallic compound with respect to the total solid content is 50 to 99.9% by mass, and the metal oxide fine particles By setting the content ratio to 0.1 to 50% by mass, the reflectance of the transparent reflective layer formed of the hologram coating material according to the present invention is improved, and excellent wear resistance is also obtained. Therefore, the hologram formed body having the transparent reflection layer formed of the hologram coating material according to the present invention is excellent in radiance, and the hologram is not easily lost due to wear.

  Hereinafter, the hydrolyzable polycondensable organometallic compound, the metal oxide fine particles and the solvent, which are essential components of the hologram coating material according to the present invention, and other components which may be appropriately contained as necessary will be described.

(Hydrolyzed polycondensable organometallic compound)
The hydrolyzable polycondensable organometallic compound is a component that functions as a binder when the transparent reflective layer is formed using the coating material of the present invention.
For example, by using a hydrolyzable polycondensable organometallic compound as a binder compared to the case of using an organic polymer binder such as polyester resin and acrylic resin, the reflectance of the hologram formed body is increased, and the design of the hologram formed body is improved. And brightness can be improved.

As a hydrolysis polycondensable organometallic compound used in the present invention, for example, a metal alkoxide used in a conventionally known reflective layer can be used. For example, the metal compound described in Patent Document 2 can be used.
In addition, as the hydrolytic polycondensable organometallic compound, an organometallic complex such as acetylacetonate or a chelate complex may be used.

Examples of the metal alkoxide include those represented by the following general formula (1) or (2).
_{R m M (OR ') n1} ··· formula (1)
_{R m (R'O) n2 M-} O-MR m (OR ') n2 ··· formula (2)
(In the general formulas (1) and (2), each R is independently an alkyl group having 1 to 10 carbon atoms, a vinyl group, a (meth) acryloyl group, an epoxy-containing group, an amide group, a sulfonyl-containing group, a hydroxyl group, or Each of the carboxyl group and R ′ is independently an alkyl group having 1 to 10 carbon atoms, M is a metal atom, m + n1 is a valence of the metal atom M, and m + n2 is a number obtained by subtracting 1 from the valence of the metal atom M. Yes, m may be 0.)

Examples of the metal atom M include silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), tin (Sn), copper (Cu), magnesium (Mg), potassium (K), sodium ( Na), iron (Fe), cobalt (Co), chromium (Cr), nickel (Ni) and the like. Titanium and zirconium are particularly preferable from the viewpoints of reflectance, transparency, and safety.
Examples of R include an alkyl group having 1 to 10 carbon atoms, a vinyl group, a (meth) acryloyl group, an epoxy-containing group, an amide group, a sulfonyl-containing group, a hydroxyl group, or a carboxyl group. In particular, when a vinyl group or a (meth) acryloyl group is used, it can react with a binder having a photopolymerizable group by light irradiation, so that a transparent reflective layer having higher durability and heat resistance is obtained.
R ′ is preferably an alkyl group having 1 to 10 carbon atoms. The bulkiness of the OR ′ group in the metal alkoxide, that is, the alkoxyl group, increases the film stability and coating suitability of the transparent reflective layer.

A commercial item may be used for the metal alkoxide. Such commercially available products include, Ltd. Matsumoto交商trade name ORGATIX TA-22 (titanium butoxide _{dimer; (n-C 4 H 9} O) 3 Ti-O-Ti (O-n- C ₄ H ₉ ) ₃ ), TA-30 (titanium tetra-2-ethylhexoxide; Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] ₄ ) and other organics (titanium alkoxide) series, TC-100 (titanium diisopropoxy bis _{(acetylacetonate); (i-C 3 H} 7 O) 2 Ti (C 5 H 7 O 2) 2), TC-200 ( titanium dioctyloxy b carboxymethyl bis (octylene glycolate Rate); titanium chelate series such as (C ₈ H ₁₇ O) ₂ Ti (O ₂ C ₈ H ₁₇ ) ₂ ), ZA-40 (zirconium tetranormal propoxide; Zr (On) -C ₃ H ₇ ) ₄ ), ZA-65 (zirconium tetranormal butoxide; Zr (On-C ₄ H ₉ ) ₄ ) and other zirconium alkoxide series, ZC-150 (zirconium tetraacetylacetonate; Zr _{(C 5 H 7 O 2)} 4), ZC-540 ( zirconium tributoxy _{monoacetylacetonate; Zr (O-n-C} 4 H 9) 3 (C 5 H 7 O 2)) zirconium chelate series such as Is mentioned. Of these, ORGATICS TA-22 and TA-30 are preferable.

In the present invention, other binders may be used in addition to the hydrolyzable polycondensable organometallic compound in order to impart coating suitability and the like to the transparent reflective layer without departing from the spirit of the present invention.
Examples of other binders include tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, vinyl pyrrolidone, (meth) acryloyloxyethyl succinate, (meth) acryloyloxyethyl phthalate, isobornyl (meth) acrylate, cyclohexyl Monofunctional monomers such as (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate may be mentioned.
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, aliphatic tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, aliphatic tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Polyfunctional monomers and oligomers such as erythritol hexa (meth) acrylate may be used.
In addition, vinyl compounds such as styrene, vinyl toluene, chlorostyrene, bromostyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene, N-vinylpyrrolidone, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl, diallyl phthalate, di Allyl compounds such as methacryl phthalate and diallyl isophthalate may be used.

  When using the hydrolyzable polycondensable organometallic compound and other binders in combination, the content ratio of the other binder is based on the total mass of the hydrolyzed polycondensable organometallic compound and the other binder from the viewpoint of adhesion. It is preferable to set it as 0.1-5 mass% or less. However, from the viewpoint of reflectance, it is preferable not to use other binders.

In the hologram coating material according to the present invention, the content ratio of the hydrolyzable polycondensable organometallic compound with respect to the total solid content of the hologram coating material is 50 to 99.9% by mass, and the inclusion of metal oxide fine particles described later By setting the ratio to 0.1 to 50% by mass, a high reflectance is imparted to the transparent reflective layer, and at the same time, excellent wear resistance (hologram disappearance preventing performance) is imparted.
When the content ratio of the metal oxide fine particles is too small, the reflectivity of the transparent reflective film is not sufficiently increased, so that the excellent glitter of the hologram cannot be obtained. Further, when the content ratio of the metal oxide fine particles is increased from zero to 100% by mass, excellent reflectance is obtained from zero to 50% by mass, but when it exceeds 50% by mass, the wear resistance is deteriorated. In addition, the reflectivity once dropped, and when approaching 100% by mass, the reflectivity increases again, but the wear resistance remains poor.
Therefore, in order to provide a high reflectance to the transparent reflective layer and at the same time to provide excellent wear resistance (hologram disappearance prevention performance), the content ratio of the metal oxide fine particles is 0.1 to 50% by mass. There is a need to.

In the hologram coating material according to the present invention, the content ratio of the hydrolytic polycondensable organometallic compound is preferably larger than the content ratio of the metal oxide fine particles described later from the viewpoint of the abrasion resistance of the transparent reflective layer. .
In particular, the hologram coating is such that the ratio (a / b) of the content ratio (a) of the hydrolyzable polycondensable organometallic compound to the content ratio (b) of the metal oxide fine particles described later is 1 to 250. It is preferable from the viewpoint of the coating property of the material (coating uniformity), the glitter of the resulting hologram (visual feeling that glitters), abrasion resistance (hologram disappearance prevention performance), and transparency, and the ratio (a / B) is more preferably 1 to 25, and further preferably 2 to 10.

  As the hydrolysis polycondensable organometallic compound, those described above may be used alone or in combination of two or more.

(Metal oxide fine particles)
The metal oxide fine particles are components for increasing the reflectivity of the hologram forming body and enhancing the design and brightness of the hologram forming body.
As the metal oxide fine particles, for example, TiO ₂ , ZrO ₂ , SnO ₂ , Al ₂ O ₃ described in Patent Document 1 can be used. In addition, ITO, ZnO, CeO, or the like can be used.

  The shape of the metal oxide fine particles is not particularly limited, and may be a conventionally known shape such as a substantially spherical shape, a spheroid shape, a polyhedron shape, a disk shape, a fiber shape, and a needle shape. Of these, the shape of the metal oxide fine particles is preferably substantially spherical. In the present invention, a substantially spherical shape is a concept including a true sphere.

The average primary particle size of the metal oxide fine particles may be appropriately adjusted according to the application of the hologram forming body and the required performance, but is preferably 1 to 300 nm, and preferably 5 to 100 nm from the viewpoint of reflectance and transparency. More preferred.
As the metal oxide fine particles, those described above may be used alone or in combination of two or more.

Since the hologram coating material according to the present invention contains the hydrolyzable polycondensable organometallic compound and metal oxide fine particles, the refractive index can be increased to 1.5 to 2.5. Therefore, a hologram forming body in which a transparent reflective layer is formed on a relief forming surface of a relief layer having a refractive index of about 1.4 to 1.6 using a hologram coating material has a high reflectance of 5 to 20%. Cheap. For this reason, high designability and glitter are imparted to the hologram formed body.
In order to increase the reflectivity of the hologram forming body, the relief coating surface of the relief layer faces the viewer side, and the transparent coating layer is formed on the viewer side of the relief forming surface. The material composition may be higher than that of the relief layer.
In addition, the reflectance of a hologram formation body is the maximum value of the reflectance in the wavelength of 450-600 nm of the hologram display surface measured based on JIS-K0115 using the brand name UV-2200 made from Shimadzu Corporation. Say.

(solvent)
As the solvent, a conventionally used solvent for a composition for forming a reflective layer or a relief layer can be used.
For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, hexane, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4-dioxane, 1, 2-Dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol, n-propanol and the like can be used.
A solvent may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the solvent may be appropriately adjusted according to the composition of the coating material, the coating property such as the viscosity required for the coating material, and the method for producing the hologram forming body. It is about -99 mass%.

(Other ingredients)
In addition to the above essential components, the hologram coating material of the present invention may contain other conventionally known components used in the composition for forming a transparent reflective layer in order to impart or improve various performances.
Examples of other components include a photopolymerization initiator, a polymerization inhibitor, a release agent, and an organometallic coupling agent described in Patent Document 1.
Hereinafter, these other components will be described.

(Photopolymerization initiator)
As the photopolymerization initiator, those that generate appropriate active species according to the functional group of the hydrolyzable polycondensable organometallic compound or other binder are used.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, anthraquinone, methylanthraquinone, acetophenone, 2,2-diethoxyacetophenone, 2, 2-dimethoxy-2-phenylacetone, benzyldiacetylacetophenone, benzophenone, p-chlorobenzophenone, 2-hydroxy-2-methylpropiophenone, diphenyldisulfide, tetramethylthiuram sulfide, α-chloromethylnaphthalene, anthracene, hexachlorobutadiene, Pentachlorobutadiene, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-hydroxy-2-methyl-1- And phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and the like.
A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

  When using a photoinitiator, it is normally used in a ratio of about 0.1 to 10% by mass with respect to the total solid content of the hologram coating material.

(Polymerization inhibitor)
The hologram coating material of the present invention may contain a polymerization inhibitor in order to improve storage stability.
Examples of the polymerization inhibitor include phenols such as hydroquinone, t-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; coppers and the like.
When a polymerization inhibitor is used, it is usually used at a ratio of about 0.1 to 10% by mass with respect to the total solid content of the hologram coating material.
A polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type.

(Release agent)
When producing a hologram forming body, when a hologram coating material is applied before giving a fine relief structure (relief structure) to the relief forming surface, it is preferable that a release agent is contained in the hologram coating material. By including a release agent, it is possible to prevent the material forming the relief layer from being removed when the stamper pressed against the relief forming surface is removed, and to use the stamper continuously for a long time (repetitive embossing). become able to.

As the release agent, conventionally known release agents, for example, waxes such as polyethylene wax, paraffin wax, microcrystalline wax, amide wax, montanic acid wax, oil-based wax; fluorine-based and phosphate-based surface activity Agents: Silicone release agents such as silicone oils and silicone resins; Fluorine release agents such as fluorine compounds and fluorine resins such as vinylidene fluoride; and the like can be used.
A mold release agent may be used individually by 1 type, and may be used in combination of 2 or more type.
When using a mold release agent, it is normally used at a ratio of about 0.1 to 10% by mass with respect to the total solid content of the hologram coating material.

(Organic metal coupling agent)
The organometallic coupling agent has a function of improving the heat resistance and strength of the transparent reflective layer.
As the organometallic coupling agent, for example, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.
An organometallic coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.
When using an organometallic coupling agent, it is normally used at a ratio of about 0.1 to 10% by mass with respect to the total solid content of the hologram coating material.

(Hologram formation)
A hologram forming body according to the present invention includes a relief member having a relief forming surface and a transparent reflecting layer covering the relief forming surface of the relief member, and the transparent reflecting layer is formed using the above-described hologram coating material. It is characterized by being made.
The hologram forming body according to the present invention is excellent in wear resistance because the transparent reflection layer is formed using the above-mentioned hologram coating material.

FIG. 1 is a cross-sectional view schematically showing an example of a layer configuration in the first aspect of the hologram forming body according to the present invention.
In the hologram forming body 1 of the first aspect of FIG. 1, the relief forming surface 20 of the relief member 10 is covered with a transparent reflection layer 30 formed using the above-mentioned hologram coating material. In the relief member 10, a relief layer 50 is provided on one surface side of the sheet-like substrate 40.
In FIG. 1 and the subsequent drawings, for convenience of explanation, the vertical and horizontal dimension ratios and the dimension ratios between the layers and the members are exaggerated as appropriate instead of the actual dimensions. Further, in the drawings after FIG. 1, unless otherwise specified, the upper side of the drawing is the viewer side of the hologram formed body.

FIG. 2 is a cross-sectional view schematically showing an example of a layer configuration in the second embodiment of the hologram forming body according to the present invention.
In the hologram forming body 1 of the second embodiment in FIG. 2, the relief forming surface 20 of the relief member 11 is covered with the transparent reflection layer 30 formed using the above-mentioned hologram coating material. In the relief member 11 of FIG. 2, the sheet-like base material also serves as the relief layer 50.

FIG. 3 is a cross-sectional view schematically showing an example of a layer configuration in the third aspect of the hologram forming body according to the present invention.
In the hologram forming body 2 of the third embodiment in FIG. 3, the relief forming surface 20 of the relief member 12 is covered with a transparent reflecting layer 30 formed using the above-mentioned hologram coating material.
In the relief member 12, a relief layer 50 is provided on the surface of the support 60.

FIG. 4 is a cross-sectional view schematically showing an example of a layer configuration in the fourth aspect of the hologram forming body according to the present invention.
In the hologram forming body 2 of the fourth embodiment in FIG. 4, the relief forming surface 20 of the relief member 13 is covered with the transparent reflecting layer 30 formed using the above-mentioned hologram coating material. In the relief member 13 of FIG. 4, the support also serves as the relief layer 50.

  Hereinafter, the relief member, the transparent reflection layer, and other layers that can be appropriately provided as necessary, constituting the hologram forming body according to the present invention will be described in order.

(Relief member)
The relief member is a member having a relief forming surface, in which a relief layer having a fine concavo-convex structure for reproducing a hologram and a base material (support) are integrated, and the relief layer and the base material (support) are separately provided. It is a concept that includes both those that are formed.
As an aspect in which the relief layer and the substrate (support) are separately formed, for example, relief members 10 and 12 as shown in FIGS.
Examples of an embodiment in which the relief layer and the base material (support) are integrated include relief members 11 and 13 as shown in FIGS.

In an embodiment in which the relief layer and the substrate (support) are formed separately, a conventionally known relief hologram substrate can be used as the substrate. For example, a flexible resin sheet may be used as the substrate. In addition, metal, paper, or the like may be used as the base material. In the case of using an impregnated base material such as paper, it may be formed in a state in which the relief layer is impregnated in the base material. Even in such a state, one of the relief layers provided on the base material may be formed. Included in the form.
The resin sheet may be a continuous belt or may be a sheet.

Examples of the resin sheet include a stretched polyethylene terephthalate sheet, a stretched nylon sheet, a stretched polypropylene sheet, a stretched polyethylene sheet, a polyvinyl alcohol sheet, a polyvinyl alcohol-coated stretched polypropylene sheet, a nylon 6 / metaxylylenediamine nylon 6 co-extrusion co-stretched sheet, Polypropylene / ethylene / vinyl alcohol copolymer coextrusion co-stretched sheet, cellophane, polyvinylidene chloride sheet, polyvinylidene chloride coated stretched polyethylene terephthalate sheet, polyvinylidene chloride coated stretched nylon sheet, polyvinylidene chloride coated stretched polypropylene sheet, polyvinylidene chloride Coated cellophane, ethylene / vinyl alcohol copolymer sheet, polycarbonate sheet, polystyrene sheet, poly Acrylonitrile copolymer sheet and the like.
In addition, aluminum vapor-deposited stretched polyethylene terephthalate sheet, silica vapor-deposited stretched polyethylene terephthalate sheet, alumina vapor-deposited stretched polyethylene terephthalate sheet, aluminum vapor-deposited stretched nylon sheet, silica-deposited stretched nylon sheet, alumina vapor-deposited stretched nylon sheet, aluminum vapor-deposited stretched polypropylene sheet, aluminum vapor-deposited sheet A sheet obtained by depositing an inorganic oxide or an organic metal oxide on a resin sheet such as a stretched polypropylene sheet may be used.
In addition, the material of the resin sheet may be, for example, a cyclic polyolefin resin described in JP-A-2009-285863.

  The formation method of a resin sheet is not specifically limited, A conventionally well-known method can be used. For example, it can be formed by an extrusion lamination method or a casting method described in JP-A-2009-285863.

  The thickness of the sheet-like base material such as a resin sheet or paper is not particularly limited, and may be appropriately adjusted according to the application, required performance, and the like. Usually, the thickness of a sheet-like base material is about 5-200 micrometers.

  Paper base materials include high-quality paper, pure white roll paper, kraft paper, imitation paper, coated paper, aluminum vapor-deposited paper, synthetic paper, water-resistant paper, coated ball, Manila ball paper, card paper, ivory paper, milk carton paper A cup base paper or the like can be used.

  The base material (support) other than the sheet shape as shown in FIG. 3 is not particularly limited, and the above resin, ceramic, metal, or the like can be used. Moreover, the shape is not particularly limited, and may be any shape having a flat surface, a curved surface, or the like.

  The relief layer and the base material (support) are integrally formed, and the relief layer in which the relief layer and the base material (support) are separately formed are usually thermoplastic resins suitable for embossing. It consists of a thermosetting resin or a photocurable resin. What is necessary is just to select the material of a relief layer suitably according to the use of the hologram formation body which concerns on this invention. For example, in the case of packaging materials, the material of the relief layer is acrylic resin, polyvinyl chloride resin, vinyl acetate resin, vinyl acetate resin, nitrification that does not have a photocurable group such as (meth) acryloyl group. Preferred are thermoplastic resins such as cotton resins, polycarbonates, urethane resins, and polyester resins, thermosetting resins such as unsaturated polyester resins, melamine resins, and epoxy resins, and resins obtained by mixing these resins.

  As the relief member, those described above may be used singly or in combination of two or more by lamination or the like.

The fine concavo-convex structure formed on the relief forming surface of the relief member may be appropriately selected from conventionally known relief shapes depending on the application, the hologram to be recorded, and the like. For example, the hologram described in Patent Document 2 can be used.
The height difference of the unevenness of the fine uneven structure may be appropriately adjusted according to the application, the hologram to be recorded, etc., but is usually about 10 to 2000 nm.

  In the first aspect of the hologram formed body, the relief layer 50 and the transparent reflective layer 30 are laminated on one side of the flexible sheet-like base material by using a resin sheet having flexibility, as a whole. It is also possible to obtain the hologram forming body 1 in the form of a flexible sheet.

  FIG. 5 is a cross-sectional view schematically showing another example of the layer configuration in the first aspect of the hologram forming body. In FIG. 5, a printing layer 70 is provided between the sheet-like substrate 40 and the relief layer 50.

  FIG. 6 is a cross-sectional view schematically showing another example of the layer configuration in the first aspect of the hologram forming body. In FIG. 6, the printing layer 70 is provided in the surface on the opposite side to the relief layer 50 of the transparent resin sheet-like base material 41. As shown in FIG.

  FIG. 7 is a cross-sectional view schematically showing another example of the layer configuration in the first aspect of the hologram forming body. In FIG. 7, the printed layer 70, the relief layer 50, and the transparent reflective layer 30 are provided in this order on the surface of the transparent resin sheet-like substrate 41 opposite to the viewer side.

As shown in FIGS. 5 to 7, the relief member may include a printed layer 70.
The printing layer 70 is a known gravure printing, offset printing, screen printing, flexographic printing, or other printing method using a known gravure ink, offset ink, screen ink, flexographic ink or the like in which a dye or pigment is dissolved or dispersed. The layer may be a layer printed with arbitrary information such as characters and figures. A fluorescent ink containing a fluorescent pigment or a fluorescent dye may be used.

  As shown in FIG. 6 and FIG. 7, when the printed layer 70 is present on the back side of the substrate when viewed from the viewer side, the substrate is a transparent resin sheet in order to ensure the visibility of the printed layer 70. A substrate 41 is used. The transparency of the transparent resin sheet-like base material 41 may be appropriately adjusted depending on the application and reproducibility of the required hologram. For example, in the visible light region of 380 to 780 nm, the average light transmittance is 50% or more. 70% or more is preferable, and 80% or more is more preferable. In the present invention, the light transmittance is a value measured in the atmosphere at room temperature using an ultraviolet-visible spectrophotometer (for example, trade name UV-3100PC manufactured by Shimadzu Corporation).

In addition to the print layer 70, although not shown, the relief member may have an anchor layer on the relief forming surface 20 of the relief layer 50 in order to improve the adhesion between the relief layer 50 and the transparent reflective layer 30. .
As a material of the anchor layer, for example, a polyurethane resin, a polyester resin, a polyamide resin, an epoxy resin, a phenol resin, a polyvinyl chloride resin, a polyvinyl acetate resin without departing from the spirit of the present invention. , Vinyl chloride-vinyl acetate copolymer, acid-modified polyolefin resin, copolymer of ethylene and vinyl acetate, acrylic acid, (meth) acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polybutadiene resin, Rubber compounds, petroleum resins, alkyl titanate compounds, polyethyleneimine compounds, isocyanate compounds, starch, casein, gum arabic, cellulose derivatives, waxes and the like can be used.

(Transparent reflective layer)
The transparent reflection layer is formed using the hologram coating material according to the present invention, and has a high reflectance, high transparency, and excellent wear resistance. By coating, it is possible to impart excellent glitter, transparency, design, and durability to the hologram formed body.

  In the hologram forming body according to the present invention, from the viewpoint of reflectivity, the unevenness of the fine uneven structure on the relief forming surface is 10 to 2000 nm, and the film thickness of the transparent reflective layer is 1 to 200 nm. It is preferable.

The transparency of the transparent reflective layer of the present invention may be appropriately adjusted depending on the application and required hologram reproducibility. For example, in the visible light region of 380 to 780 nm, the average light transmittance is 50% or more. 70% or more is preferable, and 80% or more is more preferable.
Moreover, in the hologram formation body which concerns on this invention, it is also possible to make the haze of the said transparent reflection layer into 0.1 to 2%. In order to do this, for example, the particle size of the oxide fine particles may be 300 nm or less, more preferably 100 nm or less.
In addition, haze is taken as the value measured based on JIS-K7105 using the Nippon Denshoku Industries Co., Ltd. brand name NDH2000 type | mold.

Since the coating material for forming the transparent reflective layer has been described above, description thereof is omitted here.
As a method for forming the transparent reflective layer, a conventionally known coating method or extrusion method other than the dry film forming method can be used. For example, a method using a roll coater or a gravure coater described in Patent Document 1 can be used.

Since the transparent reflective layer in the hologram formed body of the present invention uses a hydrolyzed polycondensable organometallic compound as a binder as compared with the case of using a binder such as an acrylic resin, the relief layer has a refractive index of 1.4 to Even if it is a material like 1.6, the reflectance of a hologram formation body is high, and the designability and glitter of a hologram formation body can be improved.
In a mode in which the transparent reflective layer is positioned closer to the viewer side than the relief forming surface as in the hologram forming body of FIGS. 1 to 6, the relief layer has a refractive index of 1.4 to 1.6. Due to the difference in refractive index between the (relief forming surface) and the transparent reflective layer, the reflectivity of the hologram formed body in accordance with JIS-K0115 is easily set to 5 to 20%.
Further, as in the hologram forming body of FIG. 7, it is possible to adopt a mode in which the relief forming surface is located closer to the viewer side than the transparent reflective layer.

The application of the hologram formed body according to the present invention is not particularly limited as long as it can utilize the design and brightness of the hologram. Such uses include, for example, packaging materials including pillow bags, standing pouches, pouches such as 4-way pouches, 3-way pouches, various label materials, lid materials, sheet molded products, laminate tubes, and polypropylene. An overlap etc. are mentioned.
The hologram formed body is excellent in glitter, transparency, design and durability, and is excellent in wear resistance, and is therefore suitably used for packaging materials.

(Method for producing hologram forming body)
The method for producing the hologram formed body is not particularly limited, and any method may be used as long as the transparent reflection layer is formed using the above-described hologram coating material in a conventionally known hologram method.
For example, a relief material layer is formed by applying an acrylic resin, which is a thermoplastic resin, on a resin sheet substrate such as a stretched polyethylene terephthalate sheet, and a relief having a desired fine uneven structure on the surface of the relief material layer. Is formed by embossing or the like to form a relief layer, and then the hologram coating material is applied to the relief forming surface and dried to form a transparent reflective layer, whereby a hologram formed body can be obtained.
The hologram coating material may be applied to the relief forming surface after the formation of the fine uneven structure as described above or before the formation of the fine uneven structure.

  In particular, the method for producing a hologram-forming body according to the present invention that is flexible and suitable for a packaging material includes: (i) a thermoplastic resin and / or thermosetting resin on one side of a flexible sheet-like substrate. Applying a relief-forming composition containing a resin to form a relief material layer; (ii) forming a relief structure by forming a fine relief structure on the surface of the relief material layer and recording a hologram; A step, (iii) applying a coating material for hologram containing a hydrolyzable polycondensable organometallic compound, metal oxide fine particles and a solvent to the relief forming surface of the relief member, and drying to form a transparent reflective layer; It is characterized by having.

FIG. 8 is a diagram schematically showing an example of a flow of a method for producing a hologram forming body according to the present invention.
First, as shown to (A) of FIG. 8, the flexible sheet-like base material 42 is prepared.
Next, as shown in FIG. 8 (B), a relief forming composition containing a thermoplastic resin and / or a thermosetting resin is applied to one side of the flexible sheet-like base material 42, and a relief material is formed. Layer 50 'is formed.
Next, as shown in FIG. 8C, a relief structure 10 having a relief layer 50 on which a hologram is recorded is prepared by forming a fine relief structure on the surface (formation surface 20) of the relief material layer 50 ′. .
Next, as shown in FIG. 8D, a hologram coating material is applied to the relief forming surface 20 and dried to form a transparent reflective layer 30 to obtain the hologram forming body 1.

  Hereinafter, each process of the manufacturing method of the hologram formation body which concerns on this invention is demonstrated in order.

(Process i)
In the step (i), a relief forming composition containing a thermoplastic resin and / or a thermosetting resin is applied to one surface side of the flexible sheet-like base material 42 to form a relief material layer 50 ′. .
The flexible sheet-like base material 42 should just be flexible in the material quoted by the said relief member.
As the thermoplastic resin and / or thermosetting resin contained in the relief forming composition, the materials mentioned in the relief layer may be used.
The coating method of the relief forming composition is not particularly limited, and a conventionally known coating method can be used. For example, what is necessary is just to apply | coat using the gravure coater described in patent document 1, a roll coater, etc.
Depending on the application, the relief forming composition may contain a photocurable resin in addition to the thermoplastic resin and the thermosetting resin. The resin contained in the object is preferably a thermoplastic resin and / or a thermosetting resin.

(Step ii)
In the step (ii), a relief structure 10 is prepared by forming a fine relief structure on the surface of the relief material layer 50 'and recording a hologram.
The formation method of the fine concavo-convex structure is not particularly limited, and a method used for a conventionally known relief hologram can be used. For example, the fine concavo-convex structure may be formed by pressing a stamper on the surface of the relief material layer 50 ′ and performing embossing. Further, if necessary, when the thermosetting resin is included in the relief forming composition in step (i), after forming the fine uneven structure by embossing, the thermosetting resin is cured by heating to form fine unevenness. The structure may be fixed or the strength may be increased.
In addition, when embossing is performed by pressing the stamper and the relief material layer 50 ′ is further cured, the relief material layer 50 ′ may be cured after removing the stamper as described in Patent Document 1. Alternatively, the relief material layer 50 ′ may be cured in a state where the stamper is in pressure contact with the relief material layer 50 ′.

(Iii process)
In the step (iii), a coating material for hologram containing a hydrolyzable polycondensable organometallic compound, metal oxide fine particles and a solvent is applied to the relief forming surface 20 of the relief member 10 and dried to form the transparent reflective layer 30. To do.
Since the hologram coating material has been described above, its description is omitted here.
The application method of the hologram coating material is not particularly limited, and a conventionally known method can be used. For example, what is necessary is just to apply | coat using the gravure coater described in patent document 1, a roll coater, etc.
The drying may be appropriately adjusted according to the type of coating material for hologram and the amount of coating. For example, it can be dried at a temperature of 70 to 80 ° C. for about 30 to 120 seconds.

When providing the printed layer 70 etc. in the hologram formation body 1, you may add another process to the said process suitably, or may change the said process.
For example, when the printing layer 70 is located between the sheet-like base material and the relief layer 50 as shown in FIGS. 5 and 7, it is not shown, but it is possible between the steps (A) and (B) in FIG. What is necessary is just to add the process of providing the printing layer 70 in the surface in which the relief layer 50 of the flexible sheet-like base material 42 is provided.
Further, for example, when the printing layer 70 is located on the surface opposite to the surface on which the relief layer 50 of the sheet-like substrate as shown in FIG. 6 is provided, although not shown, it is replaced with the step (A) in FIG. The step of preparing the flexible sheet-like base material 42 provided with the printing layer 70 on the surface opposite to the surface on which the relief layer 50 of the flexible sheet-like base material 42 is provided.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and this embodiment has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.

(Preparation of hologram coating materials A to E)
The following materials were mixed and stirred to prepare hologram coating materials A to E, respectively.
Table 1 shows a summary of the content ratios of the hydrolyzable polycondensable organometallic compound and metal oxide fine particles in each hologram coating material.

(Hologram coating material A)
Hydrolyzed polycondensable organometallic compound (trade name: Orgatics TA-30, manufactured by Matsumoto Kosho Co., Ltd., and solvent IPA (isopropanol) mixed at a mass ratio TA-30: IPA = 1: 6) : 70 parts by mass in terms of solid content Metal oxide fine particles (TiO ₂ slurry liquid of Teika Co., Ltd., trade name ND134 and IPA mixed at a mass ratio ND134: IPA = 1: 5.8): 30 mass in terms of solid content Part

(Hologram coating material B)
The same hydrolyzable polycondensable organometallic compound as used in the hologram coating material A: 50 parts by mass in terms of solid content The same metal oxide fine particles as used in the coating material A for hologram: 50 parts by mass in terms of solid content

(Hologram coating material C)
The same hydrolyzable polycondensable organometallic compound as used in hologram coating material A: 33.4 parts by mass in terms of solid content The same metal oxide fine particles as used in hologram coating material A: 66.6 in terms of solid content Parts by mass

(Hologram coating material D)
Same metal oxide fine particles as used in hologram coating material A: 100 parts by mass in terms of solid content

(Hologram coating material E)
Hydrolyzed polycondensable organometallic compound same as that used in hologram coating material A: 100 parts by mass in terms of solid content

(Preparation of resin composition for low refractive index layer)
Pentaerythritol (acrylic monomer manufactured by Nippon Kayaku Co., Ltd., product name PET30) is diluted to 50% by weight with a solvent MEK (methyl ethyl ketone), 99.5 parts thereof, and a curing agent (product name Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.). ) Was added and stirred to prepare a resin composition for a low refractive index layer.

Example 1
As a transparent flexible sheet-like substrate, a TAC (triacetylcellulose) substrate (trade name, Fujitac, manufactured by Fuji Film) having a thickness of 80 μm was used. On the TAC substrate, the resin composition for a low refractive index layer is applied by a gravure coating method, and after drying, a low refractive index layer having a thickness of 5 μm is formed by irradiation with 500 mJ / cm ² using a UV light source. A prepared substrate (hereinafter referred to as “optical adjustment film substrate”) was prepared.
And the acrylic resin (Brand name LG-OX anchor agent A, Tokyo Ink Co., Ltd. product) was apply | coated by the gravure coating with the film thickness of 2 micrometers on the surface of the said optical adjustment film base material, and the material layer for relief was formed. .
A hologram having a relief with a fine unevenness of 100 nm was recorded on the surface of the relief material layer (surface to be a relief forming surface) by fine embossing.
Next, the hologram coating material A was applied to the relief forming surface with a thickness of 50 nm by gravure coating and dried at 50 ° C. for 3 days to form a transparent reflective layer, whereby a hologram formed body was obtained.

(Example 2)
In Example 1, a hologram formed body was obtained in the same manner as in Example 1 except that the hologram coating material B was used instead of the hologram coating material A.

(Comparative Examples 1-3)
In Example 1, a hologram formed body was obtained in the same manner as in Example 1 except that the hologram coating material C, D, or E was used instead of the hologram coating material A.

(Evaluation and measurement)
About the hologram formation body obtained in Examples 1-2 and Comparative Examples 1-3, the reflectance, haze, and abrasion resistance were evaluated as follows. The results are summarized in Table 1.

(Reflectance)
Using the product name UV-2200 manufactured by Shimadzu Corporation, the maximum value of the reflectance at a wavelength of 450 to 600 nm on the target hologram display surface was determined in accordance with JIS-K0115.

(Haze)
The haze of the hologram formed body was measured according to JIS-K7105, using a trade name NDH2000 type manufactured by Nippon Denshoku Industries Co., Ltd.

(Abrasion resistance)
Using the Gakushin Friction Tester brand name FR-II manufactured by Suga Test Instruments Co., Ltd., in accordance with JIS L-0849, black fine paper (contact area of about 100 mm ² ) is attached to the tip of the friction element. It was rubbed back and forth 100 times with a load of 2N between the length of 12 cm on the surface of the transparent reflecting layer of the hologram formed body fixed on the tester. After reciprocating friction, whether the surface of the transparent reflective layer was rubbed or scratched was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
Good (O): The surface of the transparent reflective layer is rubbed and there is no scratch.
Defect (x): The surface of the transparent reflective layer was rubbed and scratched.

(Summary of results)
The coating material A of Example 1 and the coating material B of Example 2 contain a hydrolyzed polycondensable organometallic compound and metal oxide fine particles, and the content of the hydrolyzed polycondensable organometallic compound is 50 in terms of solid content. The content of the metal oxide fine particles is 50% by mass or less.
In Example 1 and Example 2, the reflectance of the obtained hologram surface was very high. Further, the haze was low and the wear resistance was good.
On the other hand, in the comparative example 3, when the coating material E which consists only of a hydrolysis polycondensable organometallic compound was used, the reflectance of the obtained hologram surface was inferior compared with Examples 1,2.
In Comparative Example 2, when the coating material D consisting only of metal oxide fine particles was used, the resulting hologram surface had a reflectance similar to that in Examples 1 and 2, but the wear resistance was poor.
In Comparative Example 1, the hydrolyzed polycondensable organometallic compound and the metal oxide fine particles were contained, and the content of the hydrolyzed polycondensable organometallic compound was 33.4% by mass of the solid content. When the coating material C having a solid content of 66.6% by mass was used, the reflectance of the obtained hologram surface was lower than those of Examples 1 and 2, and the wear resistance was poor. .

1, 2, 3 Hologram forming body 10, 11, 12, 13 Relief member 20 Relief forming surface 30 Transparent reflection layer 40 Sheet-like substrate 41 Transparent resin sheet-like substrate 42 Flexible sheet-like substrate 50 Relief layer 50 ′ Relief material layer 60 Support 70 Printing layer

Claims (10)

  A hydrolyzable polycondensable organometallic compound, metal oxide fine particles and a solvent are contained, the content of the hydrolyzed polycondensable organometallic compound is 50 to 99.9% by mass with respect to the total solid content, and the metal oxidation A hologram coating material, wherein the content of the fine particles is 0.1 to 50% by mass.   The hologram coating material according to claim 1, wherein a content ratio of the hydrolyzable polycondensable organometallic compound is higher than a content ratio of the metal oxide fine particles.   The hologram coating material according to claim 1 or 2, wherein the hydrolyzable polycondensable organometallic compound is a metal alkoxide, and the alkoxyl group thereof has 1 to 10 carbon atoms. A relief member having a relief forming surface, and a transparent reflective layer covering the relief forming surface of the relief member,
The said transparent reflection layer is formed using the hologram coating material in any one of the said Claim 1 thru | or 3, The hologram formation body characterized by the above-mentioned.   5. The hologram forming body according to claim 4, wherein the unevenness of the fine uneven structure on the relief forming surface is 10 to 2000 nm, and the film thickness of the transparent reflective layer is 1 to 200 nm. .   6. The hologram forming body according to claim 4, wherein the hologram forming body has a reflectivity of 5 to 20% in accordance with JIS-K0115.   The hologram forming body according to any one of claims 4 to 6, wherein the transparent reflective layer has a haze of 0.1 to 2% in accordance with JIS-K7105.   The relief sheet as the relief member and the transparent reflection layer are laminated on one surface side of a flexible sheet-like base material, and the whole is in the form of a flexible sheet. The hologram formation body as described in any one of these.   A packaging material comprising the hologram forming body according to claim 8. (I) A step of applying a relief forming composition containing a thermoplastic resin and / or a thermosetting resin to one surface side of a flexible sheet-like substrate to form a relief material layer;
(Ii) preparing a relief member by forming a fine relief structure on the surface of the relief material layer and recording a hologram;
(Iii) applying a coating material for hologram containing a hydrolyzable polycondensable organometallic compound, metal oxide fine particles and a solvent to the relief forming surface of the relief member, followed by drying to form a transparent reflective layer A method for producing a hologram formed body.