JP4712663B2 - Resin duplication plate and method for producing the same - Google Patents

Description

  The present invention generally relates to a replica plate made of resin. In particular, the present invention relates to a resin replication plate used for replicating a large number of fine uneven patterns on which relief holograms, diffraction gratings and the like are recorded, and a method for manufacturing the same.

In the relief hologram and diffraction grating, interference fringes generated by interference of laser light are recorded as a fine uneven pattern. The fine concavo-convex pattern is formed as hundreds to thousands of fine convex shapes per 1 mm length.
When replicating such a fine concavo-convex pattern, a duplicate plate is produced from an original plate on which laser light interference fringes are directly recorded, and the concavo-convex pattern of the duplicate plate is molded into a resin material to duplicate the fine concavo-convex pattern. be able to.

  Conventionally, as the above-mentioned replica plate, a metal pattern obtained by forming a concavo-convex pattern by a photo process on the surface of a photoresist layer provided on a glass substrate, and molding the surface of the concavo-convex pattern by metal plating, electroforming or the like. A so-called electroforming plate was used. By using this replication mold and hot pressing the thermoplastic resin applied on the substrate, the concavo-convex pattern can be replicated in large quantities. However, such a replication method using a metal replication mold has a problem that the plate itself is very expensive and the storage place is bulky, and the handling is inconvenient.

  Therefore, a method has been proposed in which a concavo-convex pattern is replicated using a resin replica plate in which a fine concavo-convex layer is formed on a resin base material from an ionizing radiation curable resin or a thermoplastic resin instead of a metal replica mold. (Patent Document 1 and Patent Document 2).

  In Patent Document 1, a resin layer comprising a mixture of an electron beam or ultraviolet curable acrylate resin and a polymerizable monomer containing a fluorine atom in the molecule is applied on a sheet-like support, and then the resin A method is disclosed in which a hologram original plate having a fine relief pattern is brought into close contact with the surface of a layer, and the resin layer is cured by irradiation with an electron beam or ultraviolet rays to produce a resin replica.

  Patent Document 2 discloses a resin duplication plate in which a concavo-convex pattern is formed by irradiating an ionizing radiation curable resin composition containing silicone as a wetting regulator with ionizing radiation.

When using a replica plate made of resin, compared with a replica plate made of metal (electroforming plate) manufactured by electroforming, (1) manufacturing cost is very low, and (2) suitable for production of small lots of various products. (3) Convenient for storage without taking up space, (4) Since resin is used, it is easy to connect the plate cylinder, (5) It is advantageous for hologram pattern replication on the surface of a very thin resin film There is an advantage that it is.
More specifically, regarding the advantage (5), in the case of an electroforming plate, it is necessary to store the cylinder to which the electroforming plate is attached, and the cylinder is bulky (the cylinder circumference is about several tens of centimeters and the width is several). 10 cm or more) In addition, a sufficient buffer space must be secured so as not to damage the fine hologram pattern of the electroformed plate on the cylinder surface. In the case of resin replica plates, it is a sheet-like laminate, so if you cover the hologram pattern on the surface with a protective film, you can stack multiple resin replica plates, and it has excellent storage properties Yes. With regard to the advantage (4), an endless plate can be manufactured by connecting processing, which is difficult to achieve with an electroformed plate. As for the advantage (5), since the resin duplication plate is made of a softer material than the metal duplication plate, when the resin film is hot embossed into an extremely thin resin film having a thickness of about several microns. There is an advantage that duplication is possible without cutting.

  On the other hand, the resin duplication plate has the following problems compared to the metal duplication plate produced by electroforming.

In order to accurately reproduce fine uneven patterns, it is important that the resin applied to the surface of the duplicate plate easily enters the recesses, and when the resin is peeled from the duplicate plate, it is important that the resin is easily removed from the duplicate plate. It is.
When the resin for duplication is difficult to come off from the duplication plate, there is a so-called “plate removal” phenomenon where separation of the plate worsens and a part of the resin adheres to the concave portion of the duplication plate and peels in a clogged state. It tends to occur. When the phenomenon of being taken off occurs, the resin remains clogged in the concave portion of the duplicated plate, so that the concave / convex pattern cannot be accurately shaped and cannot be used as the duplicated plate. Thus, when the resin for duplication is difficult to come off from the duplication plate, there is a problem that the plate life is shortened and printing durability is lowered, and high printing durability cannot be expected.
Therefore, in replicating a resin replica plate, it is required that the release property between the surface of the replica plate of the previous generation and the ionizing radiation curable resin after shaping is good.

  In a metal replication plate manufactured by conventional electroforming, it has been common to perform a fluorine surface treatment in order to improve releasability. However, since the conventional fluorine surface treatment requires a baking step at about 500 ° C., it has been considered that such fluorine surface treatment is impossible in the case of resin duplication plates in terms of heat resistance.

In Patent Document 1, by adding a monomer containing a fluorine atom to an ionizing radiation curable resin that forms a replica plate surface and polymerizing it, the heat resistance and mold release of the resin replica plate are improved. As shown, since the ionizing radiation curable resin contains fluorine atoms, there is a problem that the adhesion to the base material (the support for the duplicate plate) is lowered.
In addition, the fluorine-containing compound and the resin are generally low in compatibility, and when the fluorine-containing compound is added, phase separation is easy. Depending on the combination of the fluorine-containing compound and the resin, it will not be separated if the fluorine-containing compound is added to a small amount, but in that case, the amount of addition of the fluorine-containing compound is limited and there is a major drawback that it is difficult to exhibit releasability. .

  Patent Document 3 discloses a technique for adding a fluorine-containing compound having a polar group such as a hydroxyl group to the fluorine-containing resin for the purpose of improving adhesion to a coating target of a thin film coating made of a fluorine-containing resin having a fluorine-containing ring structure. It is disclosed. However, the coating object disclosed here is limited to a material having a substrate surface with a large polarity, such as glass, and it has been difficult to laminate the material on a substrate with a small polarity.

  On the other hand, in Patent Document 2, in order to improve the releasability, specifically, to prevent “plate removal”, wetting of silicone or the like in the ionizing radiation curable resin that forms the surface of the resin replica plate A technique is disclosed in which a conditioner is added so that the concentration of the wetting conditioner on the surface of the duplicate plate is higher than the inside of the duplicate plate. However, since the silicone used as a wetting conditioner is a non-reactive silicone, it was initially present on the surface of the duplicate plate when it was repeated using a resin-made duplicate plate obtained by this technique. There is a problem in that the silicone is gradually detached and transferred to the replica, and the releasability of the surface of the replica plate is gradually lowered, that is, the releasability is not maintained. Furthermore, silicone as a wetting adjuster also has a situation in which release properties cannot be improved as much as fluorine compounds.

  In addition, a method has been proposed in which reactive silicone, not non-reactive silicone, is added to the ionizing radiation curable resin that forms the surface of the resin replication plate. This method is also used when a fluorine compound is used. Compared to the release effect.

Japanese Patent Laid-Open No. 2-111988 JP 2005-91596 A JP 2004-115622 A

The present invention seeks to solve the above-mentioned drawbacks of the prior art, and in a resin replica plate having advantages that are industrially advantageous compared to a metal replica plate, the adhesiveness to the substrate, and the replica An object of the present invention is to provide a resin-made replica plate having good releasability from the replica plate.
In particular, in the present invention, the improvement of the releasability of the surface of the replica plate made of resin and the conflicting problem of not impairing the adhesion between the replica plate made of resin and the base material that is the support thereof, An object of the present invention is to prevent release of a release agent that has been observed when silicone is conventionally used as a wetting regulator.
It is another object of the present invention to improve printing durability, which has been a drawback of conventional resin duplication plates, by preventing the phenomenon of “taken off the plate”.
Another object of the present invention is to provide a method for producing the above-mentioned duplicate plate.
Another object of the present invention is to provide a mold release treatment method for a surface formed of a resin.

A silica thin film obtained by baking a polysilazane thin film in the air to convert the polysilazane to silica has been conventionally used as a dense film having excellent durability, such as a film for a semiconductor substrate.
In recent years, techniques capable of converting silica in a normal temperature environment have been proposed (Japanese Patent Laid-Open Nos. 11-116815 and 2003-347294).
As a result of earnest research, the present inventor has applied and dried a specific polysilazane solution on the concavo-convex pattern surface of the resin concavo-convex pattern layer having a fine concavo-convex pattern formed on the surface, thereby along the geometric surface shape of the concavo-convex pattern. The present invention pays attention to the fact that a thin silica thin film is formed on the surface of the concavo-convex pattern, and the resin layer surface having a low polarity that has been conventionally used as the concavo-convex pattern layer can have the same polarity as the surface of the conventional glass substrate. It came to complete.

  That is, the resin duplication plate provided by the present invention has a silica thin film and a fluorine-containing thin film on the concave / convex pattern surface of the concave / convex pattern layer having a surface on which a concave / convex pattern made of resin is formed on a base material. Is a resin duplication plate characterized by being laminated in this order.

In the present invention, the silica thin film is preferably an amorphous silica thin film.
The amorphous silica thin film can be formed by applying a solution containing a silica precursor to the uneven pattern surface and allowing it to react with water.
As the silica precursor, polysilazane is preferably used.

In the present invention, the fluorine-containing thin film is preferably formed of a fluorine-containing resin.
The fluorine-containing resin preferably contains a fluorine-containing polymer having a fluorine-containing ring.
Moreover, it is preferable that the said fluorine-containing resin contains the fluorine-containing compound which has a polar group.

In the present invention, the fluorine-containing thin film may be formed by applying a coating liquid for a fluorine-containing thin film obtained by dissolving the fluorine-containing resin in a fluorine-based solvent on the surface of the silica thin film. preferable.
It is preferable that the coating liquid for the fluorine-containing thin film contains a fluorine-containing resin and a fluorine-containing compound having a polar group.

  In this invention, it is preferable that the said uneven | corrugated pattern layer is formed with the hardened | cured material of a photocurable and / or thermosetting resin composition.

  In addition, the method for producing a resin replica plate provided by the present invention comprises forming a silica thin film on the concavo-convex pattern surface of the concavo-convex pattern layer on which the concavo-convex pattern to be the parent of the replica is formed, and fluorine-containing on the surface of the silica thin film. A method for producing a resin duplication plate characterized by forming a thin film.

  In the production method of the present invention, it is preferable that the silica thin film is formed by applying a solution containing a silica precursor, preferably polysilazane as a silica precursor, to the surface of the uneven pattern and reacting with water.

It is preferable to form the fluorine-containing thin film by applying a coating liquid for a fluorine-containing thin film in which a fluorine-containing resin is dissolved in a fluorine-based solvent on the surface of the silica thin film.
As the coating liquid for the fluorine-containing thin film, one containing a fluorine-containing resin and a fluorine-containing compound having a polar group is preferably used.

  In the manufacturing method of this invention, it is preferable to use what the resin-made base material layers are laminated | stacked on the surface on the opposite side to the uneven | corrugated pattern surface of the said uneven | corrugated pattern layer.

ADVANTAGE OF THE INVENTION According to this invention, the release property and the adhesiveness with a board | substrate can be improved in the resin duplication plate, and the printing durability which was the subject of the resin duplication plate conventionally can be aimed at.
Further, according to the present invention, since it is not necessary to make the resin layer itself for forming the uneven pattern a highly releasable resin such as a fluorine-containing resin, the moldability capable of accurately forming a fine uneven pattern, It is possible to solve the problems of the prior art, in which it has been difficult to select a resin material that has a mold release property that prevents “plate removal”. That is, according to the present invention, there is an advantage that the range of selection of the resin material for forming the uneven pattern layer is widened.

The resin replication plate provided by the present invention has a silica thin film and a fluorine-containing thin film on the concavo-convex pattern surface of the concavo-convex pattern layer that has a surface on which a concavo-convex pattern that is made of a resin and is a parent of a replica is formed. It is characterized by being laminated in this order.
FIG. 1 is a schematic diagram showing an embodiment of a resin replica according to the present invention. The resin duplication plate shown in FIG. 1 is supported by laminating a concavo-convex pattern layer 3 having a surface on which a concavo-convex pattern made of resin and formed as a parent of a replica is formed on a substrate 2. That is, the base material 2 is a support that assists the self-supporting property of the uneven pattern layer 3 when the resin uneven pattern layer 3 is very thin. And the silica thin film 4 and the fluorine-containing thin film 5 are laminated | stacked on the uneven | corrugated pattern surface 3a of the said uneven | corrugated pattern layer 3 in this order.
Hereinafter, each layer shown in FIG. 1 will be described in order.

(Base material)
As the base material 2 of the resin duplication plate 1, a resin material such as a plastic sheet is usually used. In particular, a plastic sheet that can be used by being wound around a cylindrical plate cylinder is preferable from the viewpoint of efficient mass production by a roll-to-roll method described later. However, as long as the concavo-convex pattern layer is formed of a resin, the substrate that is the support may not be made of a resin material.
Examples of plastic sheets include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, and polyethylene terephthalate / polyethylene naphthalate coextruded film. Polyester resins such as nylon 6, nylon 66 and nylon 610, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, polyacrylate, polymethacrylate and poly Acrylic resins such as methyl methacrylate, imide resins, polyarylate, polysulfone, polyethers Engineering plastics such as phon, polyphenylene ether, polyphenylene sulfide (PPS), polyaramide, polyether ketone, polyether nitrile, polyether ether ketone, polyether sulfite and polycarbonate, styrene resins such as ABS resin, cellophane, cellulose There are cellulosic films such as triacetate, cellulose diacetate and nitrocellulose.
The plastic sheet may be a copolymer resin containing the resin as a main component, a mixture (including a polymer alloy), or a laminate including a plurality of layers. The plastic sheet may be a stretched sheet or an unstretched sheet, but a sheet stretched in a uniaxial direction or a biaxial direction is preferable from the viewpoint of improving strength.
As the substrate 2, polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used since they have heat resistance, dimensional stability, and resistance to ionizing radiation, and polyethylene terephthalate is particularly suitable. Moreover, you may add additives, such as a filler, a plasticizer, a coloring agent, and an antistatic agent, to a base material as needed. The thickness of the base material 2 can usually use about 25-2000 micrometers, and 50-200 micrometers is suitable.
Prior to forming the concavo-convex pattern layer on the surface of the substrate 2, corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also called an anchor coat, adhesion promoter, or easy adhesive) coating treatment, pretreatment Easy adhesion treatment such as heat treatment, dust removal treatment, vapor deposition treatment, and alkali treatment may be performed.
(Uneven pattern layer)

The fine concavo-convex pattern (relief) formed on the surface of the concavo-convex pattern layer 3 functions as a parent mold for replicating various concavo-convex patterns, and is particularly preferably used for replicating holograms and diffraction gratings. .
As an image of a hologram, symbols, letters, numbers, illustrations, etc. can be used in addition to an image obtained by photographing the actual object. The hologram image itself can be obtained by calculating a hologram diffraction grating, calculating a hologram diffraction grating, using a digital camera, 2D or 3D image data obtained from computer graphics, holographic stereogram, etc. It can also be created by an appropriate means. The diffraction grating can express an image such as a character by its outline.

  As the relief hologram, a hologram or diffraction grating in which the intensity distribution of the interference fringe light due to the interference between the object beam and the reference beam is recorded in a concavo-convex pattern can be applied. Examples of the relief hologram include Fresnel holograms, Fraunhofer holograms, lensless Fourier transform holograms, laser reproduction holograms such as image holograms, and white light reproduction holograms such as rainbow holograms, color holograms utilizing these principles, computer holograms, There are hologram displays, multiplex holograms, holographic stereograms, holographic diffraction gratings, and the like.

  Diffraction gratings can be obtained based on calculations by creating holographic diffraction gratings using hologram recording means, as well as mechanical and drawing diffraction gratings using precision lathes and electron beam drawing devices. For example, a lattice. Specific examples of the diffraction grating include a blazed holographic grating (BHG) with a sawtooth groove, a holographic grating (HG) with a sinusoidal groove, and a laminar grating with a rectangular groove.

  These holograms, diffraction gratings, etc. may be recorded singly, in multiple recordings, or in combination. The diffraction grating may be an aggregate having a plurality of regions in which the direction of the ridges and / or the interval between the ridges and / or the shape of the unevenness and / or the height of the unevenness are different. When a plurality of regions having different diffraction directions are combined regularly or randomly, a visual effect of shining the surface, a so-called eye catching effect is obtained.

(Method for forming uneven pattern layer)
The concavo-convex pattern layer 3 in the present invention is a concavo-convex pattern forming layer made of a resin, and a relief pattern is formed by molding a fine concavo-convex pattern having a specific shape on the surface. Therefore, a resin capable of forming a fine uneven pattern on the surface is used.
The resin used as the material for the uneven pattern forming layer contains a photocurable resin composition such as an ionizing radiation curable resin composition, a thermosetting resin composition, and both a photocurable resin and a thermosetting resin. Examples of the resin composition and thermoplastic resin composition include photocurable resin compositions, thermosetting resin compositions, and curable reactive resin compositions such as light and thermosetting resin compositions, and particularly ionization. A radiation curable resin composition is preferred.
The uneven pattern layer 3 is preferably formed by curing an ionizing radiation curable resin composition with ionizing radiation. The ionizing radiation curable resin composition contains, as an essential component, a curable component having at least one functional group that undergoes polymerization (also referred to as curing) reaction with ionizing radiation. As the ionizing radiation curable resin, one or two or more kinds can be arbitrarily selected from relatively low molecular weight monomers and oligomers and high molecular weight binder polymers as long as they have ionizing radiation curability.
As the ionizing radiation curable component, a compound having a radical polymerizable functional group can be applied, and examples thereof include a monofunctional monomer, a bifunctional or higher polyfunctional monomer, a functional oligomer, and a functional polymer. Examples of the radical polymerizable functional group include a functional group having an ethylenically unsaturated bond such as a vinyl group, an acrylic group, a methacryl group, an acryloyl group, a methacryloyl group or an allyl group, and an oxirane structure such as an epoxy group or a glycidyl group. There are groups that have.

Examples of the monofunctional monomer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, -2-ethylhexyl acrylate, isobutyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2 (Meth) acrylic acid such as 2-hydroxypropyl acrylate, nonylphenol EO adduct acrylate (DNPA), 2-hydroxy-3-phenoxypropyl acrylate (HPPA), 3-ethyl-3-hydroxymethyloxetane, or alkyl or aryl esters thereof , Styrene, methylstyrene, styrene acrylonitrile, n-vinylpyrrolidone and the like can be applied.
Moreover, in this specification, (meth) acrylic acid means acrylic acid or methacrylic acid. (Meth) acrylate means acrylate or methacrylate, and the same notation applies to this.

  Examples of the bifunctional monomer include 1,6-hexanediol acrylate (HDDA), hexamethylene diacrylate, diethylene glycol diacrylate (DEGDA), neopentyl glycol diacrylate (NPGDA), tripropylene glycol diacrylate (TPGDA), Polyethylene glycol 400 diacrylate (PEG400DA), hydroxypivalate ester neopentyl glycol diacrylate (HPNDA), bisphenol AEO modified diacrylate, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, etc. are applicable it can.

  As a bifunctional or higher polyfunctional monomer, a bifunctional or higher (meth) obtained by reacting two or more molecules of (meth) acrylic acid or a derivative thereof with a bifunctional or higher compound such as ethylene glycol, glycerin or pentaerythritol. An acryloyl monomer etc. can be applied, for example, trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (PEHA), dipentaerythritol pentaacrylate, trimethylolpropane EO modified triacrylate, di- Examples thereof include methylolpropane tetraacrylate.

  As the polymerizable oligomer (also referred to as prepolymer), a polyurethane system or polyester having a weight average molecular weight of about 300 to 5000 and having a radically polymerizable double bond such as a (meth) acryloyl group or an allyl group in the molecule. System, polyether system, polycarbonate system, poly (meth) acrylic acid ester system can be applied, for example, urethane (meth) acrylate, isocyanurate (meth) acrylate, polyester (meth) acrylate, polyester-urethane (meth) acrylate, Examples thereof include epoxy (meth) acrylate, amino-modified triacrylate, fatty acid acrylate and the like.

As the polymerizable polymer, urethane (meth) acrylate, isocyanurate (meth) acrylate having a weight average molecular weight of about 1000 to 300,000 and having a radical polymerizable double bond such as (meth) acryloyl group or allyl group, Polyester-urethane (meth) acrylate and epoxy (meth) acrylate can be applied.
When the surface of the concavo-convex pattern forming layer is subjected to continuous embossing by a roll-to-roll method to form a fine concavo-convex pattern, the concavo-convex pattern forming layer needs to be in a semi-solid or solid state before being cured. When such a semi-solid or solid state is required, the ionizing radiation curable resin composition for forming the concavo-convex pattern forming layer includes a polymerizable polymer, a non-polymerization reactive thermoplastic polymer, etc. It is preferable to blend these polymers.

The ionizing radiation curable component is contained in the solid content of the ionizing radiation curable resin composition in an amount of 5% by mass or more, preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.
The ionizing radiation curable resin composition may contain a monomer called a reactive diluent. The reactive diluent is a monomer having only one polymerizable functional group in one molecule such as a (meth) acryl group, a (meth) acryloyl group, an allyl group, or an epoxy group, that is, a monofunctional monomer described above. is there. Since the reactive diluent has a low molecular weight, it has the effect of lowering the viscosity of the ionizing radiation curable resin composition. However, unlike an organic solvent such as toluene, it becomes part of the matrix after the curing reaction. Usually, the ionizing radiation curable resin composition has a high viscosity, and cannot be applied unless it is adjusted to reduce the viscosity with an organic solvent. However, when the reactive diluent is contained in the ionizing radiation curable resin composition, the viscosity is lowered, and it is not necessary to use a solvent, and it can be used in a non-solvent (no solvent). An oligomer having a relatively small molecular weight is also used as a reactive diluent.

  Furthermore, the monomer or oligomer improves the speed of the polymerization reaction, and the oligomer or polymer can adjust the crosslinking density, cohesive force and the like of the concavo-convex pattern layer after curing. For this reason, the performance of the ionizing radiation curable resin composition can be adjusted according to the application and purpose by appropriately combining monomers and / or oligomers and / or polymers and changing the compounding ratio.

The ionizing radiation curable resin composition can be used as necessary, such as a photo radical polymerization initiator, a crosslinking agent, a polymerization inhibitor, a plasticizer, a lubricant, an anti-aging agent, a colorant such as a dye or a pigment, an increase or an anti-blocking agent, etc. May contain additives such as extender pigments, fillers, surfactants, antifoaming agents, leveling agents, thixotropy imparting agents, thermosetting resins and non-polymerizable thermoplastics A binder component other than an ionizing radiation curable resin such as a resin may be contained.
When an appropriate thermosetting catalyst is blended in the ionizing radiation curable resin composition, a thermosetting treatment is performed after the shaping process and ionizing radiation irradiation are performed on the concavo-convex pattern forming layer made of the resin composition. It is also possible to cure completely.

  The ionizing radiation curable resin composition can be sufficiently cured by an electron beam, but when cured by ultraviolet irradiation, a photopolymerization initiator such as acetophenones, benzophenones, Michler benzoylbenzoate, α-amino A photopolymerization initiator such as oxime ester, tetramethylthiuram monosulfide, or thioxanthone, and a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine are added as necessary.

  When forming a concavo-convex pattern forming layer using an ionizing radiation curable resin composition, the concavo-convex pattern forming layer provided with the concavo-convex pattern is irradiated with ionizing radiation to be cured. Although ionizing radiation may be classified by the quantum energy of electromagnetic waves, in this specification, ionizing radiation refers to all ultraviolet rays (UV-A, UV-B, UV-C), visible light, gamma rays, It is defined as including X-rays and electron beams. Accordingly, the ionizing radiation includes ultraviolet rays (UV), visible rays, gamma rays, X-rays, electron beams, etc., among which ultraviolet rays and electron beams are preferable.

  In the electron beam irradiation, an electron beam generated by an electron beam accelerator is irradiated. As an electron beam irradiation device, for example, an electron beam accelerator such as a Cockloft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, or a linear type, a dynamitron type, a high frequency type, etc. The electron beam is irradiated by the Tron curtain method, the beam scanning method, etc. An apparatus “Electro Curtain” (trade name) that can irradiate a uniform electron beam in the form of a curtain from a linear filament is preferable. The electron beam is irradiated with electrons having an energy of 100 to 1000 keV, preferably 100 to 300 keV, with an irradiation amount of about 0.5 to 20 Mrad. If the irradiation amount is less than 0.5 Mrad, unreacted monomers may remain and curing may be insufficient, and if the irradiation amount exceeds 20 Mrad, the crosslinking density increases and the cured binder or substrate There is a risk of damage. Moreover, the atmosphere at the time of hardening is performed at an oxygen concentration of 500 ppm or less, and it is usually preferable to carry out at about 200 ppm.

  As an ultraviolet (UV) lamp used for ultraviolet curing, a high-pressure mercury lamp or a metal halide lamp can be applied, and the wavelength of the ultraviolet light is about 200 to 400 nm, and the wavelength may be selected according to the adhesive composition. The irradiation amount may be irradiated according to the material and amount of the composition, the output of the UV lamp, and the processing speed.

As a method for forming the concavo-convex pattern layer, first, an original having a fine concavo-convex pattern such as a relief hologram or a diffraction grating is prepared. Because the original master is difficult to produce, it is generally used only when creating a limited number of master plates, that is, replicas (primary intermediate plate materials) directly copied from the original, and should be stored carefully. It is.
Then, using the master plate (primary intermediate plate material) or a duplicate (secondary or subsequent intermediate plate material) obtained by further duplicating from the master plate, a resin uneven pattern is formed. By forming a fine uneven pattern on the surface of the layer, the resin replica of the present invention is produced.

As a method for forming the concave / convex pattern of the original plate for replication plate on the concave / convex pattern forming layer comprising the ionizing radiation curable resin composition, a known method such as a photopolymerization method (abbreviated as 2P method) or a roll-to-roll method is known. A method can be mentioned.
In the case of the 2P method, as shown in FIG. 2, the concavo-convex pattern forming layer is formed by applying the liquid ionizing radiation curable resin composition 7 on the master plate 6 for duplication so that the basic principle is shown in FIG. The substrate 8 is pressed from above, the substrate 8 and the ionizing radiation curable resin composition 7 are brought into close contact with each other, and the ionizing radiation curable resin composition is cured or semi-cured by irradiating with ionizing radiation, and the uneven pattern is transferred. The cured or semi-cured ionizing radiation curable resin composition 7 ′ is peeled off from the original plate for the replica plate together with the substrate 8 to obtain a resin replica plate 9.

  The intermediate product formed by integrating the base material and the concave / convex pattern forming layer is apparently formed in a dry-to-touch state even when the concave / convex pattern forming layer is not completely cured. If it exists, it can be made to harden completely by peeling from the original plate 6 for replication plates in such a temporary hardening state, and further irradiating an ultraviolet-ray or an electron beam after peeling. In that case, the unevenness pattern forming layer can be sufficiently cured to further improve the hardness, heat resistance, solvent resistance, and the like of the duplicate plate.

  When the resin replica plate 9 is produced by the roll-to-roll method, a solid or semi-solid uneven pattern forming layer made of an ionizing radiation curable resin composition is formed on a long continuous substrate. A film for forming a hologram and an embossing roller having a roll-shaped side surface provided with an original plate for a replication plate are prepared, and the embossing is continuously performed while supplying the film for forming a long hologram to the embossing roller.

The concavo-convex pattern forming layer of the hologram forming film is formed by applying an ionizing radiation curable resin composition on a substrate by a known coating method such as spin coating, knife coating, roll coating, bar coating, or the like. It can be formed by drying the coating film. When it is intended to partially form the concavo-convex pattern layer on the substrate, a general printing technique such as screen printing or gravure printing can be used, or a transfer method can be used.
For example, when a relief hologram is duplicated as a concavo-convex pattern, the concavo-convex pattern forming layer on the substrate is usually formed with a film thickness of 0.1 to 50 μm, preferably 0.5 to 20 μm. This film thickness can be appropriately selected depending on the purpose of use of the uneven pattern to be replicated.

  FIG. 3 is a diagram showing an example of a hologram duplicating device, and FIG. 4 is an enlarged view showing the vicinity of the transfer device of the device of FIG. In the hologram duplicating device 10, a supply device 20, a transfer device 30, an irradiation device 50, and a winding device 60 are sequentially disposed on a pair of main body frames 12 fixed to a bed 13.

  The supply device 20 includes a shaft 22 rotatably supported by a roller 23 fixed to the main body frame 12, and a winding roll 21 for the hologram forming film 1 serving as a resin replica is mounted on the shaft 22. The tip is connected to a bower brake (not shown).

  The transfer device 30 includes an embossing roller 31 in which a shaft 32 is rotatably supported by a bearing fixed to the central portion of the main body frame 12, a pressing roller 40 that is rotatably supported by a pair of arms 42, and a pressure mechanism. 38. The pressurizing mechanism 38 includes a pair of arms 42 and an air cylinder 45, and an attachment 47 is attached to the tip of the piston rod 46 of the air cylinder 45, and the attachment 47 is connected to the lower center of the arm 42 via a pin 48. The air cylinder 45 is rotatably supported by a pin 49 fixed to the main body frame 12. The pair of arms 42 is fixedly connected by a rod 44 and is rotatably supported by pins 43 fixed to the main body frame 12.

  Accordingly, the operation of the piston rod 46 of the air cylinder 45 causes the arm 42 to rotate about the pin 43 and the pressing roller 40 is pressed against the embossing roller 31. The pressing roller 40 is equipped with a heating device (not shown) so as to heat the surface of the pressing roller 40.

  As shown in FIG. 4, the embossing roller 31 is provided with a replica plate master 34 on its peripheral surface, and a roller plate with a replica plate master attached to the peripheral surface of a cylinder is usually used. . Multiple copies may be made by arranging two or more duplicate master plates side by side. A driving side tip of the shaft 32 of the embossing roller 31 is connected to driving means (not shown). The embossing roller 31 is equipped with a cooling device (not shown), and cools the roller surface.

  The irradiation device 50 is fixed to the main body frame 12 via a support member (not shown) at a position facing the winding roller 51 rotatably supported by the main body frame 12 at a distance. The hologram forming film 1 wound around is irradiated with ultraviolet rays or electron beams.

  The winding device 60 includes a shaft 62 rotatably supported by a roller 63 fixed to the main body frame 12 and a powder clutch (not shown). The shaft 62 is configured to wind the hologram forming film 1. It has become.

  Further, guide rollers 71 and 72 rotatably supported by the main body frame 12 are provided between the embossing roller 31 and the supply device 20, and between the embossing roller 31 and the winding roller 51, A guide roller 73 is provided in the vicinity of the roller 31.

  Next, the operation of the hologram duplicating apparatus 10 described above will be described. First, the hologram forming film 1 fed from the supply device 20 is guided to the embossing roller 31 via the guide rollers 71 and 72. At this time, the hologram forming film 1 ′ is adjusted to an appropriate tension by the bower brake.

  Next, the film 1 is pressed against the embossing roller 31 with a constant pressure by the pressing roller 40 by the operation of the air cylinder 45. Since the surface of the pressing roller 40 is heated, the concavo-convex pattern forming layer 3 ′ is softened, and as shown in FIG. 4, the concavo-convex pattern of the replica plate precursor 34 is transferred to the concavo-convex pattern forming layer 3 ′. The embossing roller 31 is rotated by a drive motor in a state where the concave / convex pattern forming layer 3 ′ is in close contact with the replica plate original plate 34, and the concave / convex pattern forming layer 3 ′ in which the concave / convex pattern is formed from the replica plate original plate 34 in the vicinity of the guide roller 73. Is peeled off.

  At this time, since the surface of the embossing roller 31 is cooled, the concavo-convex pattern forming layer 3 ′ in a softened state is hardened to some extent, and even if the concavo-convex pattern forming layer 3 ′ is peeled off from the original plate 34 for copying, Is guided to the winding roller 51. The film 1 wound around the winding roller 51 is irradiated with ultraviolet rays or an electron beam from the irradiation device 50, and the uneven pattern forming layer 3 'is cured. Here, since the winding roller 51 is cooled, the film 1 can be prevented from being heated and thermally contracted by irradiation with ultraviolet rays or an electron beam.

  Thereafter, the hologram forming film 1 ′ is wound around a shaft 62 connected to the drive motor 14. At this time, since the film 1 is adjusted to an appropriate tension by the powder clutch, the film 1 is wound without causing wrinkles or the like.

(Silica thin film)
The silica thin film in the present invention functions as an anchor layer that enhances the adhesion between the resin-made concave / convex pattern layer on which a fine concave / convex pattern is formed and the fluorine-containing thin film.
Silica thin film is a variety of wet film forming methods in which a solution containing a silica precursor is applied to the concavo-convex pattern surface of the concavo-convex pattern layer to form a coating film, and then the precursor in the coating film is changed to silica by a chemical reaction. Further, physical vapor deposition method (PVD method), chemical vapor deposition method (CVD method), etc. in which silica or its precursor is gasified and deposited on the concave / convex pattern surface of the concave / convex pattern layer, and the deposit is chemically changed as necessary. These can be formed using various vapor deposition methods.
In particular, according to the wet film forming method using the silica precursor solution, a uniform amorphous silica thin film having high adhesion to the concavo-convex pattern surface can be formed.

As the silica precursor, polysilazane is very preferable. By applying and drying a polysilazane solution on the concavo-convex pattern surface of the concavo-convex pattern layer, a thin silica thin film can be formed on the concavo-convex pattern surface along the geometric surface shape of the concavo-convex pattern. As a result, it is possible to impart the same polarity as the surface of the conventional glass substrate to the surface of the resin layer having a low polarity that has been conventionally used as the uneven pattern layer.
According to the wet film forming method using such a polysilazane solution, it is not necessary to form the concavo-convex pattern layer itself with a highly releasable resin such as a fluorine-containing resin, so selection of a resin material for forming the concavo-convex pattern layer There is an advantage that the width of.
That is, according to the present invention, it has been difficult to select a resin material that has both moldability capable of accurately forming a fine concavo-convex pattern and releasability that prevents “plate removal”. It is possible to achieve a very excellent effect that the technical problem can be solved.

As a method for forming a silica thin film by a wet film forming method using a polysilazane solution, methods as described in JP-A-11-116815 and JP-A-2003-347294 can be applied.
More specifically, a polysilazane composition composed of polysilazane, an appropriate organic solvent and a catalyst is applied along a concavo-convex pattern shape by a known application method such as spray coating, roll coater, flow coating, and left in the atmosphere. Thus, polysilazane is converted to silica in a normal temperature environment.
According to this method, a sufficiently dense silica thin film can be formed on the concavo-convex pattern surface without baking the coating film of the silica precursor in a high temperature environment of several hundred degrees or more. Further, it is preferable to carry out in a high humidity environment as much as possible (for example, a relative humidity of 90% at a room temperature of 27 degrees) from the viewpoint of accelerating the reaction between polysilazane and water.

  Various polysilazanes are known, but from the point of denseness of the thin film obtained, “Perhydropolysilazane” (for example, “AQUAMICA” manufactured by Clariant) and the atmosphere It is preferable to obtain a silica thin film by reacting with water in the mixture and converting the silica as shown in the following formula.

  As a catalyst for converting silica of polysilazane at room temperature, N-heterocyclic compounds are preferable, and specifically, piperidine, piperazine, pyrrolidine, imidazolidine, pyrazolidine, pyrazoline, pyrroline, pyrazine, indole, imidazole, triazine and the like. In addition, heterocyclic bridged ring compounds such as 1,4-diazabicyclo [2.2.2] octane and 7-azabicyclo [2.2.1] heptane, 1,3-di-4-piperidylpropane, 4,4 Examples thereof include ring-assembled heterocyclic compounds such as' -trimethylenebis (1-methylpiperidine) and 2,2-dipyridylamine. These catalysts are preferably added in an amount of 0.1 to 10 wt% with respect to polysilazane.

  As an organic solvent for dissolving perhydropolysilazane, an organic solvent composed of 91.0 to 98.8% dibutyl ether and 0.2 to 9.0% anisole is preferable.

Since silica is a polar molecule, when a fluorine-containing thin film is formed on the surface of a silica thin film, the adhesion of the fluorine-containing thin film to the substrate is lower than when a fluorine-containing thin film is directly formed on the surface of a resin concavo-convex pattern layer. improves.
When the fluorine compound constituting the fluorine-containing thin film has a functional group capable of forming a chemical or physicochemical bond such as a covalent bond or a hydrogen bond with a silanol group (Si-OH), the silica thin film These bonds are formed between the fluorine-containing thin film and the silica thin film by the interaction with the silanol groups that are present, and a stronger adhesion can be obtained.

  As a standard indicating the polarity of the silica thin film, a water contact angle (contact angle with water) which is a hydrophilic parameter can be used. In the present invention, the water contact angle of the concavo-convex surface of the concavo-convex pattern layer before the formation of the silica thin film is approximately 60 to 90 degrees although it depends on the components contained in the resin composition forming the concavo-convex pattern layer and its content. is there. And the water contact angle of the uneven | corrugated surface after a silica thin film formation becomes a value lower than the measured value before formation. Specifically, the measurement method involves dropping pure water on the surface to be measured and measuring the contact angle one minute after the dropping. As a measuring machine, a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd. can be used.

  Moreover, although the thickness of the silica thin film formed on the uneven | corrugated pattern surface can be adjusted according to a use, in the use of this invention, it is preferable to set it as 0.05-0.2 micrometer. More preferably, the thickness is set to 05 to 0.1 μm. If the thickness of the silica thin film is less than 0.05 μm, sufficient adhesion to the fluorine-containing thin film may not be obtained. On the other hand, when the thickness of the silica thin film exceeds 0.2 μm, the shape of the concavo-convex pattern surface may not be accurately raised on the silica thin film.

(Fluorine-containing thin film)
The fluorine-containing thin film in the present invention is a thin film containing a fluorine compound, and excellent releasability is imparted to the surface of the concavo-convex pattern layer by the action of the fluorine-containing compound. As the fluorine-containing compound, a fluorine-containing resin is preferably used from the viewpoint of excellent thin film forming ability. Here, the fluorine-containing resin is a fluorine-containing polymer having or not having non-polymerization reactivity, or a fluorine-containing monomer or fluorine-containing oligomer having a polymerization reactivity or a crosslinking reactivity that can be finally polymerized (relatively low). Molecular weight polymer).
Preferably, the fluorine-containing thin film comprises a fluorine-containing polymer having a fluorine-containing ring structure (referred to as a fluorine-containing ring structure in the present invention) as disclosed in JP-A No. 2004-115622, and a polar group. It is obtained by applying and drying on a silica thin film a solution prepared by dissolving a composition comprising a fluorine-containing compound that is provided and soluble in a fluorine-based solvent in a fluorine-based solvent.

The fluorinated polymer having a fluorinated cyclic structure, the repeating unit (a) _-CF 2 -CF 2 _- and can be used a polymer comprising a repeating unit (b) represented by the following formula.

(In the formula, X 1 and X 2 are each independently —F or —CF ₃ , Y is —F, —ORf, and Rf is a C 1-5 perfluoroalkyl group.)

  The molecular weight of the fluorinated polymer having a fluorinated ring structure is preferably from 5,000 to 1,000,000. If the molecular weight is less than 5,000, the film-forming ability may be inferior. On the other hand, if the molecular weight exceeds 1,000,000, the solubility in a fluorinated solvent may be reduced, and coating may be difficult.

The fluorine-containing compound having a polar group and soluble in a fluorine-based solvent may be either a fluorine-based monomer or a fluorine-based polymer which may be an oligomer.
Specifically, a compound containing a polyfluoroalkyl group or a polyfluoroether group having 4 to 21 carbon atoms can be used. Moreover, as a polar group, a hydroxyl group, a carboxyl group, an amino group, a silanol group, a phosphoric acid group, an alkoxyl silyl group, etc. can be used. In the present invention, the polar group means a functional group that imparts polarity to the molecule. This polar group improves the adhesion to the silica thin film.

Examples of the fluorine-containing compound include compounds represented by the general formula C _n F _{2n + 1} RX ³ (in the case of less than 4, ≦ n ≦ 21, R represents an alkylene group, and X ³ represents a polar group). . _{Among, C 6 F 13 C 2 H} 4 COOH, C 7 F 15 C 2 H 4 COOH, C 8 F 17 C 2 H 4 COOH, C 9 F 19 C 2 H 4 COOH, C 10 F 21 C 2 H _{4 COOH, C 11 F 23 C} 2 H 4 COOH, C 12 F 25 C 2 H 4 COOH, C 13 F 27 C 2 H 4 COOH, C 14 F 29 C 2 H 4 COOH, C 15 F 31 C 2 H ₄ COOH, C ₁₆ F ₃₃ C ₂ H ₄ COOH, C ₁₇ F ₃₅ C ₂ H ₄ COOH, C ₁₈ F ₃₇ C ₂ H ₄ COOH, C ₁₉ F ₃₉ C ₂ H ₄ COOH, C ₂₀ F ₄₁ C ₂ H _{4 COOH, C 21 F 43 C} 2 perfluoroalkylethyl acids such as _{H 4 COOH, C 6 F 13} C 2 H 4 Si (OCH 3) 3, C 7 F _{5 C 2 H 4 Si (OCH} 3) 3, C 8 F 17 C 2 H 4 Si (OCH 3) 3, C 9 F 19 C 2 H 4 Si (OCH 3) 3, C 10 F 21 C 2 H 4 Si (OCH ₃ ) ₃ , C ₁₁ F ₂₃ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₁₂ F ₂₅ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₁₃ F ₂₇ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₁₄ F ₂₉ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₁₅ F ₃₁ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₁₆ F ₃₃ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₁₇ F ₃₅ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₁₈ F ₃₇ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₁₉ F ₃₉ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₂₀ F ₄₁ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₂₁ F Perfluoroalkylethyltrimethoxysilanes such as ₄₃ C ₂ H ₄ Si (OCH ₃ ) ₃ are preferred.

  Moreover, as said fluorine-containing compound, the copolymer of the unsaturated compound which has a C4-C21 polyfluoroalkyl group or polyfluoroether group, and the unsaturated compound provided with the polar group can also be used. The copolymerization ratio of the unsaturated compound having a polar group is preferably 50% by weight or less based on the entire copolymer. If it exceeds 50% by weight, the solubility of the copolymer in the fluorinated solvent is lowered, which is not preferable. In particular, 10% by weight or less is preferable.

Examples of the copolymer as the fluorine-containing compound include a general formula C _m F _{2m + 1} SO ₂ N (CH ₃ ) C ₂ H ₄ OCOCH═CH ₂ (where 4 ≦ m ≦ 21) and HOC ₄ H ₈ OCOCH = it can be exemplified a copolymer of CH _{2. Further,} mention may be made also like the _{(CF 3) 2 C 6 F} 12 C 2 H 4 OCOC (CH 3) = CH 2, (OH) 3 SiC 2 H 4 copolymer of OCOCH = CH _2.

  The copolymer as the fluorine-containing compound is prepared by dissolving the corresponding monomer in a suitable organic solvent, and a polymerization initiator (peroxide, azo compound, etc. soluble in the organic solvent to be used) or ionizing radiation. It can be obtained by solution polymerization, for example, by the action of As a solvent suitable for solution polymerization, toluene, ethyl acetate, isopropyl alcohol, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachlorodifluoroethane, methyl chloroform, and the like can be used.

  The above-mentioned fluorine-containing compounds having a polar group and soluble in a fluorine-based solvent may be used alone or in combination of two or more.

Examples of the fluorine-based solvent for dissolving the fluorine-containing polymer and fluorine-containing compound having a fluorine-containing ring structure include perfluorocarbons such as perfluoropentane, perfluorohexane, perfluorooctane, and perfluorononane, and a general formula CF ₃ [(OCF (CF ₃ ) CF ₂ ) _p (OCF ₂ ) _q ] OCF ₃ (where 0 ≦ p ≦ 14, 0 ≦ q ≦ 14), perfluoropolyethers represented by the general formula HCF ₂ [OCF (CF ₃ ) CF ₂ ) _r (OCF ₂ ) _s ] OCF ₂ H (where 0 ≦ r ≦ 14, 0 ≦ s ≦ 14), hydrofluoropolyethers, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, etc. Hydrofluoroethers such as 2,3-dihydroperfluoropentane Fluorocarbons such as fluorocarbons and 1,1-dichloro-2,2,3,3,3-pentafluoropropane can be used. The said fluorine-type solvent may be used independently, and 2 or more types may be mixed and used for it.

  A fluorine-containing polymer having a fluorine-containing ring structure and a fluorine-containing compound are dissolved in different fluorine-based solvents to prepare a fluorine-containing polymer solution and a fluorine-containing compound solution, respectively. A solution containing a fluoropolymer and a fluorine-containing compound (fluorine-containing thin film coating solution) may be prepared.

  As a method for applying the coating liquid for fluorine-containing thin film, the same application / drying process as that for forming a silica thin film can be used.

  When the fluorine-containing resin has a fluorine-containing ring structure, it can be sufficiently dissolved by using a fluorine-based solvent, and a coating solution suitable for forming a thin film can be prepared. In the present invention, by setting the solid content concentration of the coating liquid for fluorine-containing thin film to about 0.1% by weight or less, the thickness of 10 to 20 nm is very thin along the unevenness of the relief pattern in the submicron order. A fluorine-containing thin film can be formed, and the fluorine treatment can be performed without burying the unevenness of the hologram pattern.

  Moreover, although the thickness of the fluorine-containing thin film formed on a silica thin film can be adjusted according to a use, it is preferable to set it as 10-20 nm in this invention use. If the thickness of the fluorine-containing thin film is less than 10 nm, sufficient adhesion to the silica thin film and sufficient release properties may not be obtained. On the other hand, even if the thickness of the fluorine-containing thin film becomes thicker than 20 nm, the adhesion and releasability are not improved so much, so that it is not desirable that the thickness exceeds 20 nm in consideration of accurate coating along the uneven shape.

  In addition, the fluorine-containing thin film in the present invention may contain components other than the fluorine-containing resin and fluorine-containing compound, for example, a non-fluorine resin.

(Reproduction method of uneven pattern)
According to the present invention, as described above, it is possible to obtain a resin duplication plate having good adhesion to the substrate and good releasability between the duplicate and the duplication plate.
The resin replication plate of the present invention is suitably used for replicating a fine uneven pattern such as a relief hologram or a diffraction grating on a resin surface using a 2P method or a roll-to-roll method.
In particular, even when high-speed embossing by the roll-to-roll method is performed, excellent release properties are maintained for a long period of time, so that continuous mass production is possible without causing the material resin of the replica to be taken off.
Further, the resin replica of the present invention is more elastic than the metal replica. Therefore, an embossing process using the resin-made replication plate of the present invention on a replica forming sheet provided with a very thin uneven pattern forming layer made of resin on a substrate, for example, an uneven pattern forming layer having a thickness of 2 μm or less. When forming a fine concavo-convex pattern by performing the above, there is an advantage that cutting of the concavo-convex pattern forming layer is less likely to occur than when using a metal replica.

  When replicating a relief hologram by the roll-to-roll method using the resin replication plate of the present invention, a solid or semi-solid uneven pattern forming layer made of a resin composition is formed on a long continuous substrate. Prepare the formed long replica forming sheet and an embossing roller with the roll-shaped side surface of the resin replica of the present invention attached, and continuously feed the long replica forming sheet to the embossing roller. Embossing.

  The replica forming sheet is obtained by providing an uneven pattern forming layer made of an embossable resin composition on a substrate. As a material of the concave-convex pattern forming layer of the duplicate, it contains a photocurable resin composition such as an ionizing radiation curable resin composition, a thermosetting resin composition, and both a photocurable resin and a thermosetting resin. Examples of the resin composition and thermoplastic resin composition include photocurable resin compositions, thermosetting resin compositions, and curable reactive resin compositions such as light and thermosetting resin compositions, and particularly ionization. A radiation curable resin composition is preferred.

  The material of the concavo-convex pattern forming layer of the replica-forming sheet is to contain a component that causes, accelerates or adjusts a curing reaction such as photo-curing property or thermosetting property and other components in the binder polymer as necessary. It is prepared by.

  As the binder polymer, either one having curable property itself or one having no curable property may be used, or two or more binder polymers may be used in combination. When the binder polymer does not have curability, curability can be imparted to the resin composition by using at least one monomer or oligomer having curability.

  The binder polymer has a film-forming property that can be formed into a film having a thickness sufficient to shape a fine uneven pattern when coated on a support such as a base film, and is an optical article after photocuring. Depending on the application, the surface structure of fine uneven patterns satisfying general properties such as transparency, strength, scratch resistance, heat resistance, water resistance, chemical resistance, adhesion to substrates and flexibility Which can be used.

  For example, acrylic resin, polyester, epoxy resin, polyolefin, styrene resin, polyamide, polyimide, polyamideimide, polyurethane, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polycarbonate, melamine resin, urea resin, alkyd resin, phenol resin, cellulose resin , Diallyl phthalate resin, silicone resin, polyarylate resin, polyacetal resin, and the like, but are not limited thereto.

Suitable binder polymers include acrylic resins; urethane acrylates, polyester acrylates, epoxy acrylates, polyether acrylates and other acrylates; and hard and soft segments as described in JP-B-4-5681. The resin or the like possessed by
Among the above, acrylic resin, urethane acrylate, and polyester acrylate are particularly preferable.

  The roll-to-roll method for producing a duplicate by embossing the duplicate-forming sheet can be performed with the same procedure and apparatus as the roll-to-roll method for producing the above-described resin-made duplicate plate. it can.

(Release surface release method)
The method of mold release treatment applied to the concavo-convex pattern surface of the resin replica plate of the present invention can be widely applied as a mold release treatment method for a surface formed of resin. That is, by forming a silica thin film on the resin surface and forming a fluorine-containing thin film on the surface of the silica thin film, a release surface that exhibits excellent releasability when contacting with the resin material can be obtained.
In particular, even when the resin surface is shaped into a concavo-convex pattern, excellent releasability is exhibited.

In the release treatment method of the present invention, it is preferable to form a silica thin film by applying a silica precursor, preferably a solution containing polysilazane as a silica precursor, to the resin surface and reacting with water.
In the mold release treatment method of the present invention, the fluorine-containing thin film is formed by applying a coating liquid for a fluorine-containing thin film in which a fluorine-containing resin is dissolved in a fluorine-based solvent to the surface of the silica thin film. It is preferable.
Moreover, it is preferable that the coating liquid for a fluorine-containing thin film contains a fluorine-containing resin and a fluorine-containing compound having a polar group.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention. In the examples, parts represent parts by weight unless otherwise specified.

<Example 1>
(Reproduction of uneven pattern)
A concavo-convex pattern forming layer composed of an ultraviolet curable resin composition of the following composition A is formed on a polycarbonate substrate, and the fine concavo-convex pattern of the relief hologram master is copied and cured on the surface of the concavo-convex pattern forming layer by a roll-to-roll method. Then, an uneven pattern layer made of an ultraviolet curable resin (cured product of the ultraviolet curable resin composition) was formed. That is, a relief surface composed of a fine concavo-convex pattern was duplicated on the duplicate plate surface.
(Composition A)
Bisphenol A epoxy acrylate 28 parts by weight Polyester acrylate 1 20 parts by weight Polyester acrylate 2 part 35 parts by weight Special acrylate (polyfunctional acrylate) A 10 parts by weight Special acrylate (polyfunctional acrylate) B 3 parts by weight Irgacure 184 (trade name) 5 parts by weight

(Formation of silica thin film)
To a solution obtained by dissolving perhydropolysilazane in a dibutyl ether / anisole (95: 4) mixed solvent, 1 wt% of 1,3-di-4-piperidylpropane (DPP) as a room temperature silica conversion catalyst was added to perhydropolysilazane. A solution for forming a silica thin film (also referred to as primer ink) was obtained.
The primer ink obtained as described above was applied to the relief surface comprising a fine uneven pattern formed on the surface of the duplicate plate, and then allowed to stand for 90 minutes in an atmosphere at a temperature of 27 ° C. and a relative humidity of 90%.

(Formation of fluorine-containing thin film)
A fluorine coating agent (trade name: FG-5010S135-0.1, manufactured by Fluoro Technology Co., Ltd.) in which a fluorine-containing resin having a fluorine ring structure and a hydroxyl group introduced is dissolved in a nonflammable fluorine-based solvent to form a solution. This was prepared and used as a coating solution for a fluorine-containing thin film.

  The coating liquid for fluorine-containing thin film prepared as described above was applied on the silica thin film formed on the surface of the concavo-convex pattern, and then heated and dried at a temperature of 60 ° C. for 90 minutes.

<Comparative Example 1>
(Reproduction of uneven pattern)
A concavo-convex pattern forming layer made of an ultraviolet curable resin composition of the following composition B is formed on a polyethylene terephthalate (PET) base material, and is made of an ultraviolet curable resin in the same procedure as in Example 1 and is a relief hologram. A concavo-convex pattern layer having the following pattern was formed.
(Composition B)
Bisphenol A epoxy acrylate 28 parts by weight Polyester acrylate 1 20 parts by weight Polyester acrylate 2 part 35 parts by weight Special acrylate (polyfunctional acrylate) A 10 parts by weight Special acrylate (polyfunctional acrylate) B 3 parts by weight Irgacure 184 (trade name) 5 parts by weight Non-reactive polyether-modified polydimethylsiloxane 2.5 parts by weight

<Comparative Example 2>
(Reproduction of uneven pattern)
A concavo-convex pattern forming layer made of an ultraviolet curable resin composition of the following composition C is formed on a polyethylene terephthalate (PET) substrate, and thereafter, made of an ultraviolet curable resin in the same procedure as in Example 1, and a relief hologram A concavo-convex pattern layer having the following pattern was formed.
(Composition C)
Bisphenol A epoxy acrylate 28 parts by weight Polyester acrylate 1 20 parts by weight Polyester acrylate 2 part 35 parts by weight Special acrylate (polyfunctional acrylate) A 10 parts by weight Special acrylate (polyfunctional acrylate) B 3 parts by weight Irgacure 184 (trade name) 5 parts by weight Reactive polyether-modified polydimethylsiloxane 17.8 parts by weight

<Evaluation of releasability>
As an index for evaluating the releasability of the replica plate surface, the contact angle of pure water on the surface of the concavo-convex pattern on which the fluorine-containing thin film was formed was measured. The results are shown in Table 1. The value of the contact angle in the table is an average value of measured values obtained by repeating the dropping and measurement three times for the measured value of the contact angle one minute after dropping pure water.

  Comparative Example 2 has been conventionally used as a resin replica of a hologram. Compared with the conventional product, it can be seen that the resin duplication plate according to the present invention has remarkably improved releasability.

<Evaluation of printing durability>
Next, a printing durability test was performed when the duplicate plates produced in the above-described examples and comparative examples were used in an actual hologram duplicating apparatus.
The printing durability test was performed using a duplicating apparatus based on the roll-to-roll method illustrated in FIG.
The duplicate plates produced in the above examples and comparative examples were used by being wound around the peripheral surface of the embossing roller 31 of the transfer device 30 in the above apparatus.

As a copy-forming sheet (raw material for testing) to which the concavo-convex pattern is transferred, a UV-curable resin composition for hologram formation coated on a PET substrate was used. For the purpose, no particular treatment is performed to improve the adhesion between the substrate and the resin.
Table 2 shows the length of the original web that was supplied from the start of the supply of the test web to the time when “plate removal” occurred.

<Comparative Example 3>
To composition A used in Example 1, 1 part by weight of V-3F (2,2,2-trifluoroethyl acrylate), which is a fluorine acrylic monomer, manufactured by Osaka Organic Chemical Industry Co., Ltd. was added, and a resin composition having the following composition D was added. A product was prepared.
(Composition D)
Bisphenol A epoxy acrylate 28 parts by weight Polyester acrylate 1 20 parts by weight Polyester acrylate 2 part 35 parts by weight Special acrylate (polyfunctional acrylate) A 10 parts by weight Special acrylate (polyfunctional acrylate) B 3 parts by weight Irgacure 184 (trade name) 5 parts by weight 2,2,2-trifluoroethyl acrylate (trade name V-3F) 1 part by weight

However, the fluorine acrylic monomer has been separated without being compatible with the ultraviolet curable resin. Since the fluorine additive, which is a mold release component, is unevenly distributed in the resin composition, if a concave / convex pattern layer is formed using this resin composition, there will be a mixture of parts with excellent mold release and extremely poor mold release characteristics. The plate is removed at the part where the releasability is inferior. This cannot be used for an actual copy.
Therefore, when the added amount of V-3F (2,2,2-trifluoroethyl acrylate) was 0.3 parts by weight, it was dissolved in the ultraviolet curable resin, but the contact angle one minute after the addition of pure water was 60.2. It was almost the same as the contact angle 60.0 ° of the UV curable resin without additives. In other words, no improvement in mold releasability was observed when the addition amount was such that the fluorine additive was not separated.

<Comparative example 4>
To composition A used in Example 1, 0.5 part by weight of V-4F (2,2,3,3-tetrafluoropropyl acrylate), which is a fluorine acrylic monomer, manufactured by Osaka Organic Chemical Industry Co., Ltd. was added and the following composition was added: A resin composition of E was prepared.
(Composition E)
Bisphenol A epoxy acrylate 28 parts by weight Polyester acrylate 1 20 parts by weight Polyester acrylate 2 part 35 parts by weight Special acrylate (polyfunctional acrylate) A 10 parts by weight Special acrylate (polyfunctional acrylate) B 3 parts by weight Irgacure 184 (trade name) 5 parts by weight 2,2,3,3-tetrafluoropropyl acrylate (trade name V-4F) 0.5 parts by weight

However, the fluorine acrylic monomer has been separated without being compatible with the ultraviolet curable resin. Since the fluorine additive, which is a mold release component, is unevenly distributed in the resin composition, if a concave / convex pattern layer is formed using this resin composition, there will be a mixture of parts with excellent mold release and extremely poor mold release characteristics. The plate is removed at the part where the releasability is inferior. This cannot be used for an actual copy.
Therefore, when the addition amount of V-4F (2,2,3,3-tetrafluoropropyl acrylate) was 0.1 parts by weight, it was dissolved in the ultraviolet curable resin, but the contact angle one minute after dropping pure water. Was 60.5 °, almost the same as the contact angle of 60.0 ° for the UV curable resin without additives. In other words, no improvement in mold releasability was observed when the addition amount was such that the fluorine additive was not separated.

(Test results)
In Comparative Example 1, the release treatment was performed by adding a non-reactive silicone compound to the concavo-convex pattern layer, but the plate was taken off when 300 m of the original test material was supplied. In Comparative Example 1, since the mold release treatment was performed by adding a non-reactive silicone compound to the concavo-convex pattern forming layer, the detachment property of the concavo-convex pattern layer lasted more than Comparative Example 1, The plate was taken out when 8,000 m was supplied.
Further, when the fluorine-based additive was used in Comparative Example 3 and Comparative Example 4, the releasability is very excellent as compared with the silicone system, but the releasability is exhibited because the compatibility with the resin is extremely poor. There was a major drawback that a sufficient amount of additive could not be added to the resin.
On the other hand, the resin replica of the present invention used in Example 1 has a releasability of the uneven pattern layer that is remarkably long compared to Comparative Example 1 and Comparative Example 2, and the test original fabric is 20, The plate was not taken out until 000 m was supplied. As described above, the resin replica plate of the present invention has a significantly improved printing durability as compared with the conventional product, and peeling of the concavo-convex pattern layer from the substrate through a long working time until the plate is taken off. Did not occur. From this result, it can be seen that the life of the duplicate plate has been dramatically improved.

  INDUSTRIAL APPLICABILITY The present invention can be used to further improve production efficiency, production cost, lifetime of a duplicated plate, and the like in the field of industrially producing printing materials that can exhibit visual effects such as holograms and diffraction gratings.

It is a schematic sectional drawing which shows the basic composition of the resin replication plate which concerns on this invention. It is a conceptual diagram explaining 2P method. It is a figure which shows an example of a hologram replication apparatus. FIG. 4 is an enlarged view showing the vicinity of a transfer device in the apparatus of FIG. 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin replication plate 1 'Hologram formation film 2 Base material 3 Unevenness pattern layer 3a Unevenness pattern surface 3' Unevenness pattern layer formation layer 4 Silica thin film 5 Fluorine-containing thin film 6 Original for replication plate 7 Ionizing radiation curable resin 8 Base material DESCRIPTION OF SYMBOLS 9 Resin replication plate 10 Hologram replication apparatus 12 Main body frame 13 Bed 14 Drive motor 20 Supply apparatus 21 Winding roll 22 Shaft 23 Roller 30 Transfer apparatus 31 Embossing roller 32 Axis 34 Hologram master 38 Pressing mechanism 40 Pressing roller 42 Arm 44 Rod 45 Air cylinder 46 Piston rod 47 Attachment 48 Pin 50 Irradiation device 51 Brazing roller 60 Winding device 62 Shaft 63 Roller 71, 72, 73 Guide roller

Claims (16)

  A silica thin film and a fluorine-containing thin film are laminated in this order on a concavo-convex pattern surface of a concavo-convex pattern layer that has a surface on which a concavo-convex pattern that is made of a resin and serves as a parent of a replica is formed. Resin replica version.   The resin replica plate according to claim 1, wherein the silica thin film is an amorphous silica thin film.   The resin-made replica plate according to claim 2, wherein the amorphous silica thin film is formed by applying a solution containing a silica precursor to the surface of the concavo-convex pattern and reacting with water.   The resin replica plate according to claim 3, wherein the silica precursor is polysilazane.   The resin-made replica plate according to any one of claims 1 to 4, wherein the fluorine-containing thin film is formed of a fluorine-containing resin.   The resin-made replica plate according to claim 5, wherein the fluorine-containing resin contains a fluorine-containing polymer having a fluorine-containing ring.   The resin-made replica plate according to claim 5 or 6, wherein the fluorine-containing resin contains a fluorine-containing compound having a polar group.   The fluorine-containing thin film is formed by applying a coating liquid for a fluorine-containing thin film obtained by dissolving the fluorine-containing resin in a fluorine-based solvent on the surface of the silica thin film. The resin replica plate according to any one of the above.   The resin-made replica plate according to claim 8, wherein the coating liquid for a fluorine-containing thin film contains a fluorine-containing resin and a fluorine-containing compound having a polar group.   10. The resin duplication plate according to claim 1, wherein the uneven pattern layer is formed of a cured product of a photocurable and / or thermosetting resin composition.   A method for producing a resin-made duplication plate, comprising: forming a silica thin film on a concavo-convex pattern surface of a concavo-convex pattern layer on which a concavo-convex pattern serving as a parent of replication is formed; and forming a fluorine-containing thin film on the surface of the silica thin film.   12. The method for producing a resin replica according to claim 11, wherein the silica thin film is formed by applying a solution containing a silica precursor to the surface of the concavo-convex pattern and reacting with water.   The method for producing a resin replica according to claim 12, wherein the silica precursor is polysilazane.   14. The fluorine-containing thin film is formed by applying a coating liquid for a fluorine-containing thin film in which a fluorine-containing resin is dissolved in a fluorine-based solvent on the surface of the silica thin film. A method for producing a resin replica plate according to claim 1.   The method for producing a resin-made replica plate according to claim 14, wherein the coating liquid for a fluorine-containing thin film contains a fluorine-containing resin and a fluorine-containing compound having a polar group.   The method for producing a resin replica plate according to any one of claims 11 to 15, wherein a resin substrate layer is laminated on a surface of the uneven pattern layer opposite to the surface of the uneven pattern.

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