JP6314476B2 - Transfer laminated media and printed matter - Google Patents

Description

  The present invention relates to a transfer laminate medium and a printed matter, and more particularly to a transfer laminate medium used for thermally transferring a printed matter having a transfer laminate containing a fine concavo-convex structure with a hot stamp.

Conventionally, as a typical technique used for continuous and mass replication of a fine uneven pattern on a transfer laminated medium, a “pressing method” described in Patent Document 1 and a “casting method” described in Patent Document 2 are used. And “photopolymer method” described in Patent Document 3.
When manufacturing a fine concavo-convex structure by the “press method”, the fine concavo-convex structure is formed by heating the resin layer on the side where the fine concavo-convex structure is formed above the softening point and pressing it onto a relief mold (reproduction mold of the fine concavo-convex structure). The shape is transferred. As another method, there is a method in which a relief pattern itself heated to a temperature higher than the softening point of the resin layer is pressed against the resin layer to transfer the shape of the fine concavo-convex structure. In either method, it is necessary to set the processing temperature of the resin layer on the side where the fine concavo-convex structure is formed to a temperature equal to or higher than the softening point. Further, the heat-resistant temperature of the molded fine concavo-convex structure is substantially equal to the minimum processing temperature.

As described above, in order to obtain a fine concavo-convex structure having high heat resistance, the pressing method needs to use a resin having a softening point equal to or higher than a desired heat resistance temperature and to be molded at a processing temperature higher than the desired heat resistance temperature. There is. For this reason, a high amount of heat is required, the processing speed is low, and the productivity is lowered.
In addition, when manufacturing a fine concavo-convex structure by the “casting method”, the resin for forming the fine concavo-convex structure is heated to the melting point or higher and melt-extruded onto a relief mold (reproduction mold of the fine concavo-convex structure) to form a fine concavo-convex structure Transfer the shape of. And after cooling resin and reducing fluidity, it peels off from a relief type | mold and manufactures.

Even in this case, a processing temperature equal to or higher than the melting point of the resin forming the fine uneven structure is required. Further, the heat-resistant temperature of the molded fine concavo-convex structure is substantially equal to the minimum processing temperature.
“Photopolymer method” (2P method, photosensitive resin method) is described in, for example, Patent Document 3, and radiation curable resins are classified into “relief type (reproduction type of fine relief pattern)” and “flat substrate”. This is a method in which the cured film is peeled off from the “relief mold” together with the base material after pouring between the “material (plastic film, etc.)” and cured by radiation, and a high-definition fine relief pattern can be obtained. .

An optical element obtained by such a photopolymer method has a better precision in forming a concavo-convex pattern and is excellent in heat resistance and chemical resistance than the “press method” and “casting method” using a thermoplastic resin. In addition, since a liquid radiation curable resin is used, no heat is required during processing.
However, any of the “pressing method”, “casting method”, and “photopolymer method” has the following problems. The problem will be described with reference to FIG.

In FIG. 5, reference numeral 101 denotes a transfer laminated medium. The transfer laminated medium 101 has a structure in which a bonding layer 103, a fine uneven structure forming layer 104, a reflective layer 105, and an adhesive layer 106 are laminated in this order on a support base material 102.
In such a molding method using the transfer laminated medium 101, the fine concavo-convex structure forming layer 104 made of a resin for forming a transfer region including the fine concavo-convex structure in the transfer target is formed by “pressing method”, “casting”. In any molding method of “method” or “photopolymer method”, the mold must be releasable with respect to the relief mold. If a resin having high adhesion to metal or a resin with high viscosity is used, the resin will be transferred to the relief mold during molding. Adhering “plate removal” occurs, leading to a decrease in the yield rate.

  Furthermore, as shown in FIG. 5, the fine uneven structure forming layer 104 is adjacent to the reflective layer 105. For this reason, when the transfer laminated medium 101 is transferred to the surface of the substrate by hot stamping, delamination occurs between the fine concavo-convex structure forming layer 104 and the reflective layer 105 formed of a resin having high releasability with respect to the relief type. In addition, the yield rate decreases.

Japanese Patent No. 4194073 Utility Model Registration No. 2524092 Japanese Patent No. 4088884

  It is an object of the present invention to provide a transfer laminated medium that can be molded without being affected by the performance such as the viscosity of a resin used for a fine concavo-convex structure and has good adhesion to a reflective layer. To do.

  In order to solve the above problems, one embodiment of the present invention is a transfer laminated medium for forming a transfer laminate including a fine uneven structure portion having a fine uneven shape by hot stamping on a transfer object. A supporting substrate, a bonding layer formed on the supporting substrate, and a fine concavo-convex structure portion having a fine concavo-convex shape formed individually in a region to be transferred on the bonding layer, An adhesive layer formed on the fine concavo-convex structure portion, and the fine concavo-convex structure portion is formed by being divided into a plurality along the surface of the bonding layer. The transfer laminate, wherein the transfer layer is arranged so as to be spaced apart via an embedded portion having no uneven shape, and the embedded portion is formed by the adhesive layer entering a space between adjacent fine uneven structure portions. It is a medium.

  According to one aspect of the present invention, a fine concavo-convex structure portion is included in a region to be transferred, is formed independently, and is favorable without being affected by adhesion performance such as viscosity of a resin used for the fine concavo-convex structure portion. To improve the yield of non-defective products that have excellent formability, prevent "plate removal" from occurring during molding, and prevent delamination between the microstructure and the reflective layer after transfer Therefore, it is possible to provide a transfer laminated medium capable of satisfying the requirements.

1 is a conceptual cross-sectional view showing a transfer laminated medium according to an embodiment. It is a cross-sectional conceptual diagram which shows another laminated medium for transfer which concerns on embodiment. It is a cross-sectional conceptual diagram which shows an example of the manufacturing method of the fine grooving | roughness structure part of the lamination | stacking medium for transfer which concerns on embodiment. It is a principal part cross-sectional conceptual diagram of FIG. It is a cross-sectional conceptual diagram in order to explain the problem of the conventional transfer laminated medium. FIG. 4 is a conceptual cross-sectional view for explaining a transfer mode of a transfer laminated medium.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
(Configuration of the first embodiment)
FIG. 1 is a conceptual cross-sectional view illustrating a configuration of a transfer laminated medium according to an embodiment.
The transfer laminated medium 1 includes a bonding layer 3 on a support substrate 2, a fine concavo-convex structure portion 4 having a fine concavo-convex shape formed individually in a region to be transferred, a reflective layer 5 and an adhesive layer 6. It has the form provided in this order.

That is, the fine concavo-convex structure portion 4 is not a layer formed continuously on the surface of the bonding layer 3 but a plurality of fine concavo-convex structure portions having a desired interval independently formed as final fine concavo-convex structure portions. That is, the fine concavo-convex structure portion 4 is formed by being divided into a plurality along the surface of the bonding layer 3, and the adjacent fine concavo-convex structure portions 4 are separated from each other via the embedded portion 7 having no fine concavo-convex shape. The interval between adjacent fine concavo-convex structure portions 4 arranged in this manner need not be constant.
Further, the fine concavo-convex structure portion 4 is included in the region to be transferred, and the outer peripheral edge of the structure portion 4 is located inside the outer peripheral edge of the region to be transferred.

Here, in this specification, “enclose in the region to be transferred” means that, for example, when the region (R) shown in FIG. It means a state that exists only inside the end (broken line).
An embedded portion 7 is provided between the fine concavo-convex structure portions 4. The embedded portion 7 is made of the same material as the adhesive layer 6. The embedded portion 7 does not need to be made of the same material as the adhesive layer 6, but is easier to manufacture if it is made of the same material as the adhesive layer 6.
The reflective layer 5 is formed on the surface of the fine concavo-convex structure portion 4 and on the concave surface where the embedded portion 7 is formed continuously with the surface. The reflection layer 5 may be formed between the surface of the concavo-convex shape (uneven surface) of the fine concavo-convex structure portion 4 and the bonding layer 3 and the embedded portion 7.

(Configuration of Second Embodiment)
FIG. 2 is a conceptual cross-sectional view showing the configuration of another transfer laminated medium according to the embodiment.
The transfer laminated medium 1 includes a bonding layer 3 on a support substrate 2, a fine concavo-convex structure portion 4 having a fine concavo-convex shape formed individually in a region to be transferred, a reflective layer 5, a mask layer 8, and The adhesive layer 6 is provided in this order.
The reflection layer 5 is formed on the uneven surface of the fine uneven structure portion 4, and the mask layer 8 is formed on the reflection layer 5. That is, in the reflection layer 5 shown in FIG. 1 described above, the mask layer 8 is formed on the reflection layer 5 corresponding to the uneven surface of the fine uneven structure portion 4 as shown in FIG. The layer 5 portion is selectively removed. Thereby, the reflective layer 5 and the mask layer 8 in the arrangement state shown in FIG. 2 can be formed.
Hereinafter, each layer according to FIGS. 1 and 2 described above will be described in detail.

(Supporting substrate)
In FIG. 1 and FIG. 2, it is preferable that the support base material 2 is a film base material. As the film substrate, for example, a plastic film such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PP (polypropylene) can be used. In particular, it is preferable to use a material having heat resistance that is not deformed or altered by the amount of heat applied during curing and transfer.
The surface of the support base 2 on the side of the bonding layer 3 is preferably subjected to a treatment for improving the peelability.

(Laminated layer)
1 and 2, the bonding layer 3 is used for smoothly transferring the fine concavo-convex structure portion 4 during thermal transfer. The bonding layer 3 is preferably made from an adhesive resin. Adhesive resins include, for example, polyester resins, acrylic resins, vinyl chloride resins, vinyl resins, polyamide resins, polyvinyl acetate resins, rubber resins, ethylene-vinyl acetate polymerization resins, and vinyl chloride acetate copolymers. A thermoplastic resin such as a resin can be used. The bonding layer 3 preferably has a thickness of 1 μm or more and 20 μm or less.
Note that the bonding layer 3 may be formed of a material that also functions as a release layer during transfer.

(Fine relief structure)
1 and 2, the fine concavo-convex structure 4 includes a relief hologram, a diffraction grating, a sub-wavelength grating, a microlens, a polarizing element, a screen, a Fresnel lens plate or a lenticular plate, a backlight or a diffusion plate of a liquid crystal device, Examples thereof include an antireflection film.
For the fine concavo-convex structure portion 4, a thermoplastic resin, a thermosetting resin, an oxidation polymerizable resin, a reactive curable resin, an ultraviolet ray, an electron beam curable resin, or the like can be used. For example, examples of the thermoplastic resin include acrylic resins, epoxy resins, cellulose resins, polyester resins, vinyl resins, rubber resins, polyamide resins, polyimide resins, polycarbonate resins, and liquid crystals.

(Formation of fine uneven structure)
The fine concavo-convex structure can be formed by the following methods (1) and (2), for example.
(1) A metal base plate having a concave portion corresponding to the fine concavo-convex structure portion and a support base material on which a bonding layer is formed are prepared. Using this original plate, the resin coating liquid can be printed so as to be included in the region to be transferred of the bonding layer of the supporting base material to form a fine concavo-convex structure portion.

(2) A metal base plate having a concave portion corresponding to the fine concavo-convex structure portion and a support base material on which a bonding layer is formed are prepared. A resin layer in which a molding structure having a shape inverted with respect to the fine concavo-convex structure portion is formed on the support base material for transfer using the original plate and the first resin coating solution is formed. Subsequently, the second resin coating solution is transferred to the resin layer of the transfer support substrate to form a fine concavo-convex structure portion. Thereafter, the fine concavo-convex structure portion of the transfer support base material is transferred so that the fine concavo-convex structure portion is included in the region to be transferred of the bonding layer of the support base material.
In the molding methods (1) and (2), the resin used for the fine concavo-convex structure is preferably a urethane resin or an epoxy resin that gradually cures at room temperature.
The urethane resin is usually synthesized by reacting an “isocyanate-reactive compound” with a diisocyanate, which is mainly a bifunctional “isocyanate”. Functional groups such as a carboxy group and an amino group can also be used in combination, and products with very diverse properties can be made.

  The term “isocyanate-reactive compound” as used herein includes any organic compound having at least two isocyanate-reactive moieties, such as a compound containing an active hydrogen component, or an imino functional compound. The active hydrogen-containing portion refers to a portion containing a hydrogen atom, and the hydrogen molecule is determined according to the position in the molecule according to Wohler in “Journal of the American Chemical Society, Vol. 49, p. 3181 (1927)”. Shows remarkable activity according to the described Zerewitnoff test. Illustrative examples of such active hydrogen moieties are -COOH, -OH, -NH2, -NH-, -CONH2, -SH, and -CONH-. Preferred active hydrogen-containing compounds include polyols, polyamines, polymercaptans and polyacids. Suitable imino functional compounds are those having at least one terminal imino group per molecule. Preferably, the isocyanate-reactive compound is a polyol, more preferably a polyether polyol.

  Suitable polyols include compounds containing at least two hydroxyl groups. These can be monomers, oligomers, polymers, and mixtures thereof. Examples of hydroxy functional oligomers and monomers are castor oil, trimethylolpropane, and diol. Also included are branched diols such as those described in WO 98/053013, such as 2-butylethyl-1,3-propanediol.

  Examples of suitable polymers include polyester polyols, polyacrylate polyols, polycarbonate polyols, polyurethane polyols, melamine polyols, and mixtures and hybrids thereof. Such polymers are generally known to those skilled in the art and are commercially available. Suitable polyester polyols, polyacrylate polyols, and mixtures thereof are described, for example, in WO 96/20968 and EP 0688840. Examples of suitable polyurethane polyols are described in WO 96/040813.

  Hydroxy-functional epoxy resins, alkyds, and dendrimeric polyols include, for example, those described in International Patent Application Publication No. 93/17060. The coating composition may comprise a latent hydroxy functional compound, such as a compound comprising a bicyclic orthoester, spiroorthoester, spiroorthosilicate group, or a bicyclic amide acetal. These compounds and their methods of use are described in WO 97/31073, WO 2004/031256, and WO 2005/035613, respectively.

  The fine relief structure may include a metal-based catalyst for the addition reaction between an isocyanate group and an isocyanate-reactive compound. Such catalysts are known to those skilled in the art. Calculated per non-volatile material of the coating composition, generally 0.001% to 10% by weight, preferably 0.002% to 5% by weight, more preferably 0.01% to 1% by weight. The catalyst is used in an amount in the range of% or less. Suitable metals in the metal based catalyst include zinc, cobalt, manganese, zirconium, bismuth, and tin. The coating composition preferably comprises a tin based catalyst. Well known examples of tin based catalysts are dimethyltin dilaurate, dimethyltin diversate, dimethyltin dioleate, dibutyltin dilaurate, dioctyltin dilaurate, and tin octoate.

On the other hand, an epoxy resin is a general term for thermosetting resins that can be cured by graft polymerization with an epoxy group remaining in a polymer. A prepolymer before graft polymerization and a curing agent are mixed and obtained by heat curing.
There are various prepolymer compositions, but the most typical one is a copolymer of bisphenol A and epichlorohydrin. As the curing agent, various polyamines and acid anhydrides are used.

  Examples of alicyclic epoxy compounds are 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxycyclohexyl-3 ′, 4. '-Epoxycyclohexanecarboxylate (EECH), 3,4-epoxycyclohexylalkyl-3', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl, 3 ', 4-epoxy-6' -Methylcyclohexanecarboxylate, vinylcyclohexane dioxide, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, exo-exobis (2,3-epoxycyclopentyl) Ether, endo-exobis (2,3- Xycyclopentyl) ether, 2,2-bis (4- (2,3-epoxypropoxy) cyclohexyl) propane, 2,6-bis (2,3-epoxypropoxycyclohexyl-p-dioxane), 2,6- Bis (2,3-epoxypropoxy) norbornene, diglycidyl ether of linoleic acid dimer, limonene dioxide, 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene dioxide, 1,2 -Epoxy-6- (2,3-epoxypropoxy) hexahydro-4,7-methanoindane, p- (2,3-epoxy) cyclopentylphenyl-2,3-epoxypropyl ether, 1- (2,3-epoxypropoxy ) Phenyl-5,6-epoxyhexahydro-4,7-methanoindane, o- (2,3-epoxy) Lopentylphenyl-2,3-epoxypropyl ether), 1,2-bis [5- (1,2-epoxy) -4,7-hexahydromethanoindanoxyl] ethane, cyclopentenylphenyl glycidyl ether, cyclohexanediol Including but not limited to diglycidyl ether, diglycidyl hexahydrophthalate, and mixtures thereof.

  Examples of aromatic epoxy resins are bisphenol-A epoxy resin, bisphenol-F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenol epoxy resin, biphenyl epoxy resin, 4,4'-biphenyl epoxy resin, divinylbenzene di Including, but not limited to, oxide resins, 2-glycidyl phenyl glycidyl ether resins, and the like, and mixtures thereof.

  Examples of the curing agent that cures with the epoxy prepolymer include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as dicyanodiamide, phenol compounds such as phenol novolac and cresol novolac, and the like. Not. Moreover, you may use the hardening accelerator of an epoxy resin, For example, although imidazoles and its derivative (s), tertiary amines, a quaternary ammonium salt, etc. are mentioned, it is not this limitation.

(Formation of fine uneven structure using photo-curing material)
The fine concavo-convex structure portion can be formed of a resin that is cured by radiation.
As an example of the radiation curable resin, a monomer, oligomer, polymer or the like having an ethylenically unsaturated bond can be used. Examples of the monomer include 1,6-hexanediol, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. . Examples of the oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate. Examples of the polymer include urethane-modified acrylic resins and epoxy-modified acrylic resins.

  Examples of other photocurable resins are described in JP-A Nos. 61-98751, 63-23909, 63-23910, and 2007-118563. And a photocurable resin. Polymers such as an acrylic resin, a polyester resin, a urethane resin, and an epoxy resin having no reactivity can be added in order to accurately form a fine relief pattern.

  When using photocationic polymerization, an epoxy group-containing monomer, oligomer, polymer, oxetane skeleton-containing compound, or vinyl ether can be used. When the ionizing radiation curable resin is cured by light such as ultraviolet rays, a photopolymerization initiator can be added. Depending on the resin, a radical photopolymerization initiator, a cationic photopolymerization initiator, or a combination thereof (hybrid type) can be selected.

  Examples of photo radical polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether and benzoin ethyl ether, anthraquinone compounds such as anthraquinone and methylanthraquinone, acetophenone, diethoxyacetophenone, benzophenone, hydroxyacetophenone, 1-hydroxycyclohexylphenyl Examples include ketones, phenyl ketone compounds such as α-aminoacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, benzyldimethyl ketal, thioxanthone, acylphosphine oxide, Michler's ketone, etc. Can do.

  When using a compound capable of photocationic polymerization, the photocationic polymerization initiator may be an aromatic diazonium salt, aromatic iodonium salt, aromatic sulfonium salt, aromatic phosphonium salt, mixed ligand metal salt, or the like. it can. In the case of so-called hybrid materials that use both radical photopolymerization and cationic photopolymerization, the respective polymerization initiators can be mixed and used. Aromatic iodonium salts and aromatic sulfonium salts having a function of initiating polymerization of both with a kind of initiator can also be used.

  A fine concavo-convex structure part is obtained by mix | blending 0.1 to 15 mass% of photoinitiators with respect to radiation curable resin. A sensitizing dye may be used in combination with the photopolymerization initiator in the resin composition. If necessary, dyes, pigments, various additives (polymerization inhibitors, leveling agents, antifoaming agents, sagging inhibitors, adhesion improvers, coating surface modifiers, plasticizers, nitrogen-containing compounds, etc.), crosslinking agents ( For example, an epoxy resin or the like may be included. A non-reactive resin may be added to improve moldability.

What is necessary is just to select suitably the thickness of a fine concavo-convex structure part in the range of 0.1 micrometer or more and 10 micrometers or less.
Although depending on the viscosity (fluidity) of the uncured coating film, if the thickness of the fine concavo-convex structure portion exceeds 10 μm, the resin of the uncured coating film protrudes or wrinkles during press processing. When the thickness of the fine concavo-convex structure is extremely thin, sufficient molding becomes difficult.
Since the formability changes depending on the shape of the fine uneven structure of the original plate, it is preferable to provide a fine uneven structure portion having a thickness of 3 to 10 times the desired depth of the uneven surface.

When forming the fine concavo-convex structure forming portion, a coating method may be used. In particular, wet coating can be applied at low cost. Moreover, in order to adjust a coating film thickness, you may apply | coat and dry what was diluted with the solvent.
In addition, urethane resin, melamine resin, phenolic resin and the like obtained by adding polyisocyanate as a crosslinking agent to an acrylic polyol or polyester polyol having a reactive hydroxyl group and crosslinking can be used for forming the fine concavo-convex structure portion. As the ultraviolet or electron beam curable resin, epoxy (meth) acryl, urethane (meth) acrylate, or the like can be used, and the thickness is preferably 0.5 μm or more and 5.0 μm or less.
In addition to the resin described above, a resin material containing a metal such as aluminum or silver, an inorganic oxide such as silica or mica, a magnetic material such as magnetite, or the like may be used for forming the fine concavo-convex structure portion.

(Embedded part)
1 and 2, an embedded portion 7 is provided between the fine concavo-convex structure portions 4. When only the pressure-bonded part is peeled off from the support base material by thermocompression bonding, the embedded part 7 is provided to suppress the generation of burrs even if the fine concavo-convex structure part 4 is formed of a rigid and low breakable material. Have. Physically, the breakability can be improved by preventing the presence of a rigid material in the cross section.

(Reflective layer)
1 and 2, examples of the material for the reflective layer 5 include metals such as Al, Sn, Cr, Ni, Cu, Au, and Ag, or metal compounds. A single metal material as the “metal” and an oxide, sulfide, and fluoride of the metal as the “metal compound” are preferable because of their high polarity and good adhesion to the resin of the relief forming layer. The thickness of the reflective layer is preferably 100 to 3000 mm.

The reflective layer 5 can use a transparent material made of a metal compound, examples of which are given below. The numerical value in parentheses following the chemical formula or compound name shown below indicates the refractive index n. Metal compounds include Sb ₂ O ₃ (3.0), Fe ₂ O ₃ (2.7), TiO ₂ (2.6), CdS (2.6), CeO _{2 (} 2.3), ZnS (2 .3), PbCl ₂ (2.3), CdO (2.2), Sb ₂ O ₃ (5), WO ₃ (5), SiO (5), Si ₂ O ₃ (2.5), In ₂ O ₃ (2.0), PbO (2.6), Ta ₂ O ₃ (2.4), ZnO (2.1), ZrO ₂ (5), MgO (1), Si ₂ O ₂ (10) MgF ₂ (4), CeF ₃ (1), CaF ₂ (1.3 to 1.4), AlF ₃ (1), Al ₂ O ₃ (1), GaO (2) and the like. These materials are appropriately selected based on optical characteristics such as refractive index, reflectance, and transmittance, weather resistance, interlayer adhesion, and the like, and are formed in the form of a thin film.

As a method for forming the reflective layer 5, a known method such as a vacuum deposition method, a sputtering method, a CVD method, or the like that can control the film thickness, the film formation speed, the number of stacked layers, the optical film thickness, and the like can be used as appropriate. It is also possible to apply high glitter ink in which fine particles of these materials are dispersed in various solvents.
High-brightness light reflecting ink obtained by dispersing fine powder, sol or metal nanoparticle of metal, metal compound or organic polymer in organic polymer resin, organic polymer or organic polymer fine particles can also be used. . In this case, care must be taken not to attack the fine concavo-convex structure portion 4 with a solvent, but it can be formed by a known printing method such as a gravure printing method, a flexographic printing method, or a screen printing method. When the reflective layer 5 is provided by such a printing method, the thickness after drying may be adjusted to be about 0.001 to 10 μm.

The reflective layer 5 may be partially provided. In this case, pasta processing, water-washed celite processing, laser processing, etc. can be mentioned as examples, and it is also possible to provide a fine sea-island-like reflective layer by, for example, vacuum deposition of tin or the like.
In the case where a transparent reflective layer is provided, if the transmittance is 20% or more in the wavelength region of 400 nm or more and 700 nm or less, the effect of the optical element in transmission can be used. In addition, it is possible to confirm information arranged under the reflective layer, for example, print information such as a face photograph, characters, and patterns.

(Mask layer)
In FIG. 2, a mask layer 8 that covers the reflective layer 5 may be provided between the reflective layer 5 and the adhesive layer 6, and immersed in an alkaline solution, for example, and the reflective layer 6 may be partially etched away.
For the mask layer 7, for example, a thermoplastic resin such as a polyamide resin, a polyimide resin, or a vinyl resin, or a resist that is cured by ultraviolet rays can be used.

(Adhesive layer)
1 and 2, the adhesive layer 6 includes, for example, a polyester resin, an acrylic resin, a vinyl chloride resin, a vinyl resin, a polyamide resin, a polyvinyl acetate resin, a rubber resin, and an ethylene-vinyl acetate copolymer system. A thermoplastic resin such as a resin or a vinyl chloride acetic acid copolymer resin can be used. The thickness of the adhesive layer 6 is preferably 1 μm or more and 20 μm or less.

Even if a dye or pigment is added to any one of the film substrate 2, the bonding layer 3, the fine concavo-convex structure portion 4, the reflective layer 5, the mask layer 8, and the adhesive layer 6, coloring processing may be performed in the visible region. Good. Further, by adding a material excited by ultraviolet rays or infrared rays, an effect that can be visually recognized in a specific wavelength region by visual observation or mechanical detection may be imparted.
Next, an example of the manufacturing method of the fine concavo-convex structure portion according to the embodiment will be described with reference to the conceptual cross-sectional views shown in FIGS.

  The forming film 56 for forming the fine concavo-convex structure portion is unwound from the forming film unwinding roll 51. On one surface (lower surface) of the molding film 56, as shown in FIG. 4, a resin layer is formed by molding a molding structure having a shape inverted with respect to the fine concavo-convex structure portion shown in FIGS. ing. The molding film 56 is passed between the molding resin ink coating cylinder 52 and the molding resin ink pressurizing cylinder 53 so that the lower surface thereof is located on the coating cylinder 52 side. At this time, as shown in FIG. 3, the coating cylinder 52 rotates while being immersed in the molding resin ink 55 of the molding resin ink holding container 54, so that the molding resin ink is formed in a pattern on the peripheral surface as shown in FIG. To be attached to. For this reason, as shown in FIG. 4, the molding resin ink attached to the coating cylinder 52 is transferred to the resin layer of the molding film 56 to form an uncured fine uneven structure portion. Thereafter, the film 57 for forming the fine concavo-convex structure portion is conveyed to the molded resin ink curing portion 58, where the uncured molded resin ink of the fine concavo-convex structure portion is cured and formed to form the fine concavo-convex structure portion.

  On the other hand, a bonding film 66 for transferring the fine concavo-convex structure portion is unwound from the bonding film unwinding roll 61 and passed between the bonding ink coating cylinder 62 and the bonding ink pressurizing cylinder 63. At this time, the coating cylinder 62 rotates while being immersed in the bonding ink 65 of the bonding ink holding container 64, and the bonding ink adheres to the entire peripheral surface. For this reason, the bonding ink 65 is transferred from the coating cylinder 62 to the bonding film 66, and a bonding ink layer is formed on the bonding film 66. Thereafter, the bonded ink layer forming bonded film 67 is conveyed to a bonded ink curing unit 68 where the bonded ink layer is cured to form a film.

Next, the fine concavo-convex structure portion forming film 57 and the laminated ink layer forming laminated film 67 are brought into contact with each other by a pair of bonding cylinders 59 and 69 and heated as necessary. The uneven structure portion is transferred to the bonding ink layer of the bonding film 67. Thereafter, the molding film 56 having a resin layer obtained by molding the molding structure at the film peeling portion 71 in FIG. 3 is peeled off and wound around the take-up roll 60. On the other hand, the laminated film 67 having the fine concavo-convex structure portion transferred to the laminated ink layer is wound around a winding roll 70.
In the following, the materials used in the manufacturing method of FIGS. 3 and 4 and the molding of the fine concavo-convex structure will be described in detail.

(Film for molding)
In FIG. 3, a molding film 56 for molding a fine concavo-convex structure is a “press method” or “casting” for plastic films such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PP (polypropylene). A film having a resin layer formed by molding a molding structure by a known method such as “method” or “photopolymer method” can be used. In addition, the resin layer obtained by molding the molding structure is used only in molding the molding resin ink in the present invention and does not impart metals by vapor deposition or the like. For example, a silicon compound or a fluorine compound is applied to the resin layer. In addition, an inorganic filler or the like may be added to perform a mold release treatment. For the resin layer in which the molding structure is molded, a material that does not require adhesion to metals can be used.

(Ink curing part)
In FIG. 3, the molded resin ink curing unit 58 and the bonding ink curing unit 68 can use, for example, an oven by heating and blowing, an ultraviolet or electron beam irradiation device, or the like.
(Ink for bonding)
As the bonding ink, a laminating agent by heat pressure, a resin material that is cured by ultraviolet rays or an electron beam and loses its adhesive force, and the like can be used.

According to the transfer laminated medium according to the embodiment described above, the fine concavo-convex structure portion is included in the region to be transferred and is independently formed, which affects the adhesion performance such as the viscosity of the resin used for the fine concavo-convex structure portion. It has good formability without being subjected to, and prevents the “plate removal” from occurring at the time of molding, and prevents delamination between the microstructure and the reflective layer after transfer Can do.
Further, according to the transfer laminated medium according to the embodiment, a pattern including a fine concavo-convex structure formed by molding a resin containing metals, silicon dioxide, a magnetic material, an inorganic metal oxide, liquid crystal, or the like is transferred to a transfer target. It becomes possible to do.

Hereinafter, an embodiment of the present invention will be described with reference to FIG.
Example 1
A urethane-based resin was applied onto a PET substrate and dried, and a molding film 56 was obtained by a “press method”. A molding resin in which a molding resin 56 is unwound from a molding film unwinding roll 51, and a polyurethane resin is filled in a molding resin ink holding container 54 as a molding resin ink 55 for forming a fine concavo-convex structure portion. The ink coating cylinder 52 was aligned with the molding film 56 and pressurized and transferred by the molding resin ink pressurizing cylinder 53, and the molding resin ink curing portion 58 was dried using a hot air oven.

  On the other hand, a PET base material coated with a release layer made of an acrylic resin is used as the bonding film 66, the bonding film 66 is unwound from the bonding film unwinding roll 61, and the acrylic adhesive resin is used as the bonding ink. Filled in the ink holding container 64 for bonding used as 65, transferred from the bonding ink application cylinder 62 to the bonding film 66 by the pressure of the bonding ink pressurizing cylinder 63, and transferred and cured. The part 68 was dried using a hot air oven.

  At the contact point between the molding film laminating cylinder 59 and the laminating film laminating cylinder 69, the micro uneven structure portion forming molding film 57 and the laminating ink layer forming laminating film 67 are pressed and joined to form a micro asperity. The structure is transferred to the laminated film side, the film for molding 56 and the laminated film 66 are peeled off at the film peeling portion 71, and the laminated film provided with the fine concavo-convex structure portion is applied to the laminated film winding roll 70. Winded up. On the other hand, the forming film 56 separated from the fine concavo-convex structure portion was wound around a forming film take-up roll 60.

  Subsequently, aluminum metal was vapor-deposited with a thickness of 550 mm on the fine concavo-convex structure portion side of the laminated film 66 to form a reflective layer. Subsequently, a mask layer made of polyamideimide resin is applied only to a desired position of the reflective layer 5 and immersed in a sodium hydroxide solution to selectively remove the reflective layer to form a patterned reflective layer. did. After removal by etching, the film was washed with a hydrochloric acid solution and water, and the laminated film 66 was dried with hot air. Thereafter, the dried laminated film 66 was coated with an adhesive layer 6 made of an acrylic resin to produce the transfer laminated medium 1 shown in FIG.

The obtained laminate medium for transfer was subjected to thermocompression bonding using an up-down type thermal transfer apparatus provided with a hot stamp on a polypropylene substrate, and the bonded film 66 was peeled and removed.
Thereafter, cello tape (registered trademark) CT-24 (manufactured by Nichiban) was applied to the transfer laminate including the relief forming layer, which is a fine uneven structure portion on the polypropylene base material, and horizontally 20 cm per second at an angle of 180 degrees. An adhesion test for peeling at a speed was performed. As a result, the relief forming layer made of polyurethane resin did not peel from the reflective layer made of aluminum and maintained the laminated structure.

  As the relief forming layer, polyurethane resin is preferable because of its good adhesion to the reflective layer. In particular, among polyurethane resins, if it is tack-free at normal temperature and has tackiness when heated at 60 ° C. to 200 ° C., the adhesion to the reflective layer can be further enhanced, while being conveyed. And at the time of storage, it is more preferable because the relief forming layer can be prevented from blocking due to sticking to the overlapped film in a wound state. As such a polyurethane resin, a thermoplastic resin can be used. If the relief structure layer requires hardness, a reactive polyurethane resin can be used.

  In Example 1, the mechanism for maintaining the adhesion without causing the relief forming layer made of polyurethane resin to peel off from the reflective layer made of aluminum is not exactly clear, but when the heat pressure by the “press method” is applied. The same phenomenon as “plate removal” where the resin adheres to the metal plate, the polyurethane resin tackiness can be improved in an atmosphere heated by vapor deposition on the surface of the vapor deposited metal by using a polyurethane resin with strong viscosity. This is thought to be because the adhesion between the resin and the metal was improved.

(Comparative Example 1-1)
An acrylic resin was applied to the surface of the release layer of the PET substrate, and a fine concavo-convex structure layer was formed by the “photopolymer method”. Aluminum was vapor-deposited on the fine concavo-convex structure layer to provide a reflective layer, and a mask layer made of polyamide-imide resin was applied to a desired position and dried. Subsequently, the reflective layer was selectively etched away with a sodium hydroxide solution to form a patterned reflective layer. Thereafter, a laminated medium for transfer coated with an acrylic resin adhesive was produced.

The obtained transfer laminated medium was thermally transferred using an up-down type thermal transfer machine equipped with a hot stamp on a polypropylene substrate.
Thereafter, cello tape CT-24 (manufactured by Nichiban) is applied to the transfer laminate including the relief forming layer which is a fine uneven structure portion on the polypropylene substrate, and peeled horizontally at a speed of 20 cm per second at an angle of 180 degrees. An adhesion test was performed. As a result, the relief forming layer made of acrylic resin was peeled off from the reflective layer made of aluminum, and the laminated structure was separated on the cello tape and the PET substrate.

(Comparative Example 1-2)
The surface of the release layer of the PET substrate was coated with a polyurethane resin, and was molded by the “press method”. As a result, since the polyurethane resin is a resin with high metal adhesion, “plate removal” occurs in which the resin adheres to the relief mold at a molding temperature of 140 ° C. or higher. For this reason, the molding temperature was lowered to 150 ° C. or lower, and molding by the “press method” was performed to form a fine concavo-convex structure forming layer on the polyurethane resin. However, since the softening point of the polyurethane resin is 140 ° C. or higher, it is difficult to stably form a fine uneven structure.

  As mentioned above, although the details of each member were explained based on the example, the purpose of use such as printing on the surface or between layers, or overcoating that makes the step of any layer placed in a pattern inconspicuous Can be used as appropriate. Moreover, in view of the adhesiveness of each layer, it is also possible to provide an adhesion anchor layer between each layer, and to perform various easy adhesion treatments such as corona discharge treatment, plasma treatment, and frame treatment.

  INDUSTRIAL APPLICABILITY According to the present invention, it can be used for a Fresnel lens plate and a lenticular plate used for relief holograms, diffraction gratings, sub-wavelength gratings, microlenses, polarizing elements, screens, etc., backlights of liquid crystal devices, diffusion plates, antireflection films, etc. Thus, it is possible to provide a transfer laminated medium in which a fine concavo-convex structure portion is made of a material that is difficult to be molded by the “press method”, “casting method”, and “photopolymer method”, and is encapsulated in an area to be transferred.

  In addition, the transfer laminated medium according to the present invention is thermally transferred to a transfer object using a hot stamp, thereby producing a printed material useful for various industries having a transfer laminate including fine concavo-convex structure portions free of burrs. It becomes possible to obtain at a rate. It can be used as a fine concavo-convex structure for industrial use.

DESCRIPTION OF SYMBOLS 1 ... Transfer lamination medium, 2 ... Support base material, 3 ... Laminate layer, 4 ... Fine uneven structure part, 5 ... Reflective layer, 6 ... Adhesive layer, 7 ... Embedded part, 8 ... Mask layer, 51 ... Molding film Unwinding roll, 52 ... Cylinder for molding resin ink application, 53 ... Cylinder for molding resin ink pressurization, 54 ... Molding resin ink holding container, 55 ... Molding resin ink, 56 ... Film for molding, 57 ... Formation of fine uneven structure Molding film, 58 ... molding resin ink curing part, 59 ... molding film laminating cylinder, 60 ... molding film winding roll, 61 ... laminating film unwinding roll, 62 ... laminating ink coating cylinder 63 ... Cylinder for pressurizing ink for bonding, 64 ... Ink holding container for laminating, 65 ... Ink for laminating, 66 ... Laminating film, 67 ... Laminating ink layer forming Laminated film, 68 ... Laminated ink curing section, 69 ... Laminated film laminating cylinder, 70 ... Laminated film winding roll, 71 ... Film peeling section, 101 ... Laminating medium for transfer, 102 ... Support substrate, 103 DESCRIPTION OF SYMBOLS: Laminated layer, 104 ... Fine uneven structure forming layer, 105 ... Reflective layer, 106 ... Adhesive layer.

Claims (3)

A transfer laminated medium for forming a transfer laminate containing a fine uneven structure portion having a fine uneven shape by hot stamping on a transfer object, comprising a support base material and a paste formed on the support base material A laminated layer, a fine concavo-convex structure portion having a fine concavo-convex shape formed individually in a region to be transferred on the bonding layer, and an adhesive layer formed on the fine concavo-convex structure portion,
The fine concavo-convex structure portion is formed by being divided into a plurality along the surface of the bonding layer, and the adjacent fine concavo-convex structure portions are arranged apart via an embedded portion having no fine concavo-convex shape, The embedded portion is formed by the adhesive layer entering the space between adjacent fine concavo-convex structure portions ,
Each fine concavo-convex structure portion is included in each region to be transferred that is transferred by hot stamping, and the outer peripheral edge of the fine concavo-convex structure portion is located inside the outer peripheral edge of the region to be transferred. Laminated media for transfer. 2. The laminated medium for transfer according to claim 1, wherein the fine concavo-convex structure portion is made of a polyurethane resin having high adhesion to metals and metal compounds.   A transfer laminate including a fine concavo-convex structure having a fine concavo-convex shape is formed on the transfer medium by hot stamping the transfer laminate medium according to any one of claims 1 to 2. Characteristic printed matter.

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