JPH02281285A - Hologram reproducing matrix, production thereof and production of hologram - Google Patents

Abstract

PURPOSE:To shorten stages for producing a hologram reproducing matrix and to stabilize the quality of the matrix by forming a resin layer of specified acrylate resin on a filmlike or sheetlike support transmitting electron beams and forming a fine relief pattern on the surface of the resin layer. CONSTITUTION:A filmlike or sheetlike support 1 is coated with acrylate resin curable with electron beams and having >=35dyn/cm surface tension to form a resin layer 2 and this resin layer 2 is adhered to the rugged surface of the photoresist 3 of a hologram master A, cured by irradiation with electron beams from support 1 side and released from the surface of the master A to form a hologram reproducing matrix B consisting of the support 1 and the cured resin layer 2. Stages for producing the matrix B can be considerably shortened, time can be saved and the quality of the matrix is stabilized.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to the production of holograms, and more particularly to a replication mold for relief-type holograms, a method for producing the same, and an effective method for producing bolograms. It is.

Since holograms reproduce three-dimensional images, they are preferred for their excellent design and are used for covers of books, magazines, etc., POP displays, gifts, and the like.

Furthermore, since holograms are equivalent to recording information on the submicron order, they are also used to prevent counterfeiting of securities, credit cards, and the like.

<Conventional technology> Conventionally, when mass-producing relief-type holograms, a photoresist on which an uneven relief pattern is formed is used as a mother plate, and a mold is formed by metal plating, etc., and the hologram is coated onto a base material. A commonly used method is to perform mass duplication of holograms by thermoforming thermoplastic resin.

However, this method requires a large number of steps to produce the mold, making quality control difficult, and requires a large amount of time and labor, leading to a problem of higher product prices.

Therefore, as a method to solve the above problem, a method of using electron beam or ultraviolet curable resin, thermoplastic resin, and thermosetting resin as multiple molds instead of a mold was proposed in JP-A-58-
It is shown in Japanese Patent No. 184986.

However, in the method described in the above publication, when producing a replicated hologram using a resin replication mold, an electron beam or ultraviolet curable resin is brought into close contact with the resin mold, and the resin is cured and imprinted by electron beam or ultraviolet irradiation. Because of the molding process, the resin mold itself may be deformed and deteriorated by irradiation with high-energy rays, which could pose a problem in ensuring stable quality.

In addition, when making a replica mold using thermosetting resin alone, heat is also applied to the photopolymer, which is a hologram, at the same time as the thermosetting resin is heated, making it difficult to peel off due to the increased adhesive force between the thermosetting resin and photopolymer. There is a possibility that
Furthermore, there are other problems such as curing shrinkage of the thermosetting resin, which damages the relief pattern of the hologram original, making it impossible to reuse the hologram original.

<Problems to be solved by the invention> The problems to be solved by the present invention are as described above. By making it easy to separate from the mother mold and using this as a replication mold, the manufacturing process of the replication mold can be shortened and the manufacturing quality can be stabilized.

Another objective is to provide a replication mold that enables mass replication of holograms with stable quality using a replication device that uses heat and pressure, which is simple in principle, through heating and pressure embossing of thermoplastic resin in the post-process. It is something to do.

Means for Solving the Problems> That is, the present invention provides an electron beam-curable film or sheet-like support having a surface tension of 35 dyn.
A resin layer made of an acrylate resin having a particle size of /cm or more is provided, and then it is brought into close contact with a hologram original plate having a fine relief pattern on the surface, and after the resin layer is cured by irradiation with an electron beam, it is peeled off. This is a hologram replication type manufacturing method. The hologram manufacturing method is characterized in that the hologram replica mold is bonded under heat and pressure onto a thermoplastic resin layer and then separated.

Here, in the present invention, the electron beam curable acrylate resin used is ester acrylate, epoxy acrylate, or urethane acrylate containing at least two or more acryloyl groups in one molecule. When the resin layer is cured, an electron beam is irradiated from the support side to produce a hologram replica mold.

<Detailed description of the invention> Hereinafter, the present invention will be explained in detail using the drawings.

First, FIGS. 1 to 3 show a method for manufacturing a hologram duplication type according to the present invention, and FIGS. 4 to 5 show a method for mass-producing holograms.

First, the constituent materials will be explained, and then the manufacturing process will be explained.

In Figure 1, (1) is a film or sheet-like support, and (2) is an electron beam curable material with a surface tension of 35 dyn/
A resin layer made of an acrylate resin having a cut or higher
3) is a photoresist layer on which a relief pattern is formed, which is the hologram original A; and (4) is a base material for the photoresist, which is usually a glass plate.

The film or sheet-like support (1) having electron beam transparency described in the present invention has appropriate heat resistance to withstand the heating of the thermoplastic resin of the resin mold for hologram duplication in the subsequent process and the heating during pressure embossing molding. , mechanical strength, surface smoothness, etc. are required. Specifically, polyester, polycarbonate, polyetherimide, borephenylene sulfide, polyimide, polyether thyl ketone, glass, etc. can be used, and the thickness is 20~ The thickness is preferably about 200 μm.

Further, as the electron beam curable acrylate with a surface tension of 35 dyn/cm or more used in the resin layer (2), general ester acrylates, epoxy acrylates, and urethane acrylates can be used. Those that give a highly cured film are preferred; specifically, trimethylolpropane triacrylate, ECH-modified ethylene glycol dimethacrylate,
PO, EO modified bisphenol A diacrylate, EO
Modified bisphenol A dimethacrylate, pentaerythritol triacrylate, EO modified phosphoric acid diacrylate, ECH modified glycerol triacrylate, EC
H-modified glycerol triacrylate, ECH-modified phthalic acid diacrylate, triallyl isocyanurate, etc. can be used. Moreover, these may be used in combination.

As the photoresist layer (3) on which the relief pattern of the hologram original plate A is formed, generally widely used resists for semiconductors can be used, but positive resists with particularly excellent resolution are preferred, and are available under the trade name AZ- 13
50, AZ-2400 (manufactured by Shipley), 0FP
R800 (manufactured by Tokyo Ohkasha), IABy coat H
It is commercially available as PR (manufactured by Hunt). As the photoresist base material (4), since smoothness is required, a glass plate is usually used.

In FIG. 4, (5) is a thermoplastic resin layer, and (6) is a thermoplastic resin base material.

The thermoplastic resin layer (5) is made of polyester resin, polystyrene, styrene-acrylic copolymer, polyvinyl chloride,
Polyvinyl acetate, vinyl chloride/vinyl acetate copolymer polyvinyl acecool, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyketone, etc. can be used.

As the thermoplastic resin base material (6), polyester polypropylene, polycarbonate, cellophane, etc. can be used, and the electron beam transparent film described above can also be used. A film or sheet having a thickness of about 10 to 100 μm is preferable.

Next, the manufacturing process will be explained.

First, in FIG. 1, on the film or sheet-like support (1), an electron beam curable material with a surface tension of 35 dyn is placed.
/cm or more of acrylate resin is applied by a known method such as knife coat spin cord or roll coating to form a resin layer (2), and then it is brought into close contact with the surface of the photoresist (3) having an uneven shape of the hologram master A. .

The photoresist (3) is applied to a glass plate with a thickness of 2 to 3 cylinders using a spin cord so that the film thickness is approximately 1 to 3 μm, exposed to an argon laser, and then developed with a prescribed developer. This is a relief image created.

Next, as shown in FIG. 2, the resin layer (2) is cured by irradiating an electron beam from the support (1) side.

Next, by peeling from the surface of the hologram original A, a hologram replica mold B consisting of a support and a cured resin layer is obtained. In this case, in order to carry out a sufficient curing reaction,
The electron beam irradiation amount is 1. It is preferable that it is OMrad or more.

Next, as shown in FIG. 4, the hologram replica mold B obtained by the above method is brought into close contact with the thermoplastic resin layer (5), and at the same time, heat and pressure embossing molding is performed, and then peeled off. As shown in the figure, a final hologram replica C is obtained.

Hereinafter, the present invention will be explained in more detail using Examples.

<Example-1> Using Microposit 1350 (manufactured by Shipley) as a photoresist, a photoresist layer with a film thickness of approximately 1.5 μm was prepared on a substrate consisting of a glass plate with a thickness of 3 mm, and an argon Laser (wavelength 457, 9 nm,
After exposing the interference fringes of the three-dimensional object for about 10 minutes at an intensity of 50 mJ/cdl, a relief hologram was produced by alkaline development, and this was used as a hologram original.

Next, an electron beam curable film with a surface tension of 41.4 dyn/
cm of ECH-modified ethylene glycol dimethacrylate (Bunacol DM-811, manufactured by Nagase Sangyo Co., Ltd.) was coated with a wire bar to a thickness of about 5 μm to form a resin liquid layer. Surface tension was measured using an automatic surface tension meter (C
BVP-A3 model, manufactured by Kyowa Interface Science Co., Ltd.). Next, after the resin liquid layer is brought into close contact with the relief surface of the hologram master, a 200 KeV electron beam is irradiated from the support side at an absorbed dose of 5 Mrad, and then peeled from the hologram master, thereby forming the support. A hologram replica mold consisting of a hardened resin layer was fabricated. The peeling between the cured resin layer and the photoresist, which is the hologram master plate, is good.
The 90 degree peel strength was 5.2 g/cm.

Next, a thermoplastic resin layer having the following composition was coated to a thickness of about 15 μm on a base material made of a polyester film having a thickness of 50 μm using a wire bar, thereby producing a film for a replicated hologram.

Next, about 25 kg of the relief surface of the hologram replication mold was placed on the thermoplastic resin layer surface of the replication hologram film.
/Cl11 pressure, heating was performed from the support surface of the hologram replication mold at 130° C. for 15 seconds, and then the thermoplastic resin layer surface and the hologram replication mold were peeled off to obtain a replica Boro Durum product. When peeled off, there was no blocking and a hologram was obtained that gave a good, sharp and clear image.

<Example-2> Electron beam curable surface with a force of 37.0 dyn/c+++
Trimethylolpropane triacrylate (KA
YARAD TMPTA (manufactured by Japan Tohoku Co., Ltd.) with a thickness of 75μ
on a support consisting of a polyimide film (Corpilex 753, corona treated clade, manufactured by Ube Industries, Ltd.) of
Coat with a wire bar to a film thickness of approximately 5 μm,
After forming the resin layer, a hologram replica mold was produced under the same conditions as in Example-1. Peeling between the cured resin layer and the photoresist was good, and the 90 degree peel strength was 3.5 g/pulse.

Next, a relief pattern was produced on the same thermoplastic resin layer as in Example-1 using the same method and conditions as in Example-1 to obtain a replicated hologram product. A clear hologram similar to that in Example-1 was obtained.

<Example 3> As an electron beam curable resin, the surface tension is 4s, eayn
A hologram replica mold was produced using the same method and conditions as in Example-1, except that PO, EO-modified bisphenol A diacrylate (NK ester A-BPE-4, manufactured by Shin-Nakamura Chemical Co., Ltd.) of /cm was used. did. Good peeling from photoresist original plate, 90 degree peel strength of 10.8g/c+n
Met. Furthermore, the thermoplastic resin had excellent suitability for hot-pressure embossing, and a good replicated hologram product similar to that of Example-1 was obtained.

<Comparative Example-1> As an electron beam curable resin, the surface tension is 32.8 dyn.
/cm neopentyl glycol diacrylate)
(KAYARAD NPGDA, manufactured by Nippon Tohoku Co., Ltd.) was used, but electron beam irradiation and peeling were performed in the same manner and under the same conditions as in Example 1. The adhesive force was strong, and only the polyester film that served as the support was peeled off.

<Comparative Example-2> Hydroxypivalic acid ester neopentyl glycol diacrylate (KAYARAD MANDA, manufactured by Nippon Tohoku Co., Ltd.), which is electron beam curable and has a surface tension of 34.2 dyn/cm, was coated with a 75 μm thick polyimide film (Tubiretsu Ube Industries, Ltd.). on a support consisting of a
Coat with a wire bar to a film thickness of approximately 5 μm,
Electron beam irradiation was performed under the same conditions as in Example-1, and then peeling was performed, but as in Comparative Example-1, the adhesive force between the cured resin and the photoresist was strong, and the photoresist was peeled from the glass surface of the substrate.

The above results are shown in Table-1.

Table 1 <Effects of the Invention> As described above, the hologram replication mold according to the present invention can significantly shorten the steps in producing the hologram replication mold and save time accordingly.

In addition, when producing a hologram replica mold, by using an electron beam, the curable resin is cured without applying heat, and the surface tension of the curable resin liquid is reduced to 35 dyn.
/cm or more and by reducing the affinity with the photopolymer matrix, the relief pattern can be peeled and replicated without damaging the matrix.

Furthermore, by using the hologram replica mold obtained by the above method, a hologram with a clear image and stable quality can be produced on thermoplastic resin using a therapeutically simple method of heating and pressure embossing. This has the great effect of making mass replication possible in a short period of time.

[Brief explanation of drawings]

FIGS. 1, 2, and 3 are cross-sectional views showing a method for manufacturing a resin mold for replicating BOLO 2 and RAM, and FIGS. 4 and 5 are cross-sectional views showing a method for mass-reproducing holograms. 1...Support 2...Resin layer 3...Photoresist 4.6...Base material 5...Thermoplastic resin layer A...Hologram original plate B...Replication plate C...Hologram Written amendment for reproduction procedures (voluntary)

Claims (5)

[Claims] (1) A resin layer made of an acrylate resin that can be cured by electron beams and has a surface tension of 35 dyn/cm or more is provided on an electron beam transparent film or sheet support, and a fine relief pattern is formed on the surface of the resin layer. A hologram replica mold formed by forming. (2) A resin layer made of an acrylate resin or monomer that can be cured by electron beams and has a surface tension of 35 dyn/cm or more is provided on an electron beam-transparent film or sheet-like support, and then fine particles are formed on the surface. A method for manufacturing a hologram duplication type, in which the resin layer is brought into close contact with a hologram master having a relief pattern, irradiated with an electron beam to cure the resin layer, and then peeled off from the hologram master. (3) The method for manufacturing a hologram duplication type according to claim (2), wherein the electron beam is irradiated from the support side. (4) A claim in which the resin layer is made of ester acrylate, epoxy acrylate, or urethane acrylate containing at least two or more acryloyl groups in one molecule (
2) or (3) the method for manufacturing a hologram duplication type. (5) A method for producing a hologram, in which the replication mold according to claim (1) is bonded under heat and pressure onto a thermoplastic resin layer of a base material having a thermoplastic resin layer, and then the replication mold is removed.