JP2007210271A - Duplicate impression for forming optical diffraction structure, manufacturing method of duplicate impression of it and method of manufacturing duplication for transcription of optical diffraction structure using duplicative impression - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a duplicating impression capable of making a satisfied mold releasability sure by adding a large amount of a mold releasing agent to a resin as a raw material of an optical diffraction structure layer and also able to suppress separation of the mold releasing agent from the duplicating impression. <P>SOLUTION: An ultraviolet ray curable resin 3A loaded with a reactive silicone made by modifying a polyether modified silicone by acrylic modification as a mold releasing agent is interposed between an original impression 4 having the optical diffraction structure and a substrate 2 of the duplicate impression 1 where the optical diffraction structure is to be copied. The silicone and the ultraviolet ray curable resin 3A are cross-linking bonded under curing the ultraviolet ray curable resin 3A by irradiating the ultraviolet ray curable resin 3A with an ultraviolet ray UV. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a replica plate made of resin for shaping an optical diffraction structure.

As a method for producing a transfer replica (hereinafter sometimes abbreviated as a replica) such as a transfer foil and a transfer ribbon having an optical diffraction structure, a replica layer provided on the replica is used as an optical diffraction structure of a replica plate. A method is known in which a light-diffractive structure of a replicated plate is replicated in a replica by closely contacting the layers and heating them. In such a manufacturing method, when the duplicate is peeled from the duplicate plate, a so-called plate removal phenomenon may occur in which the duplicate layer peels off from the substrate together with a part of the peeling layer behind the duplicate plate and adheres to the duplicate plate. . Therefore, as a countermeasure against plate removal, a technique has been proposed in which a release agent made of silicone is added to the light diffraction structure layer of the duplicate (see, for example, Patent Document 1).
JP 2004-258455 A

  A coating layer, such as a reflective layer made of a metal such as aluminum, is further formed on the surface of the replica with the optical diffraction structure, but if a release agent is added to the replica layer of the replica, the release layer There is a possibility that the adhesion between the coating layer and the light diffraction structure layer is lowered by the mold action. In spite of such concerns, one of the reasons for adding a mold release agent to the replica is that an electroforming plate is used for the replica plate for forming the light diffraction structure, and the mold is released on the plate side. There is a situation that it is difficult to put the agent. In recent years, however, resin-made duplication plates are sometimes used for the purpose of dealing with high-mix low-volume production and reducing the storage cost of duplication plates. It is also possible to secure release properties by adding a release agent.

  However, the conventional silicone used as a release agent has good compatibility with the resin, but has the property of being easily separated from the resin. For this reason, when a large amount of silicone is added to the replication plate in order to ensure releasability, the release agent is separated from the replication plate and transferred to the replica, and the transferred release agent provides adhesion to the reflective layer and the like. There is a risk of damage. In addition, since the duplicate plate is used repeatedly, the release property gradually decreases with the release of the release agent, and there is a possibility that the life of the duplicate plate may be exhausted early. In order to avoid such an inconvenience, it is desirable to use, as a mold release agent, silicone that is reactive with the resin used for the light diffraction structure layer of the replication plate. However, since the conventional reactive silicone has low compatibility with the resin, it can be added only in a small amount to the resin, and it has been difficult to ensure sufficient releasability.

  The present invention has been made in view of the above-mentioned circumstances, and a sufficient amount of release agent can be added to the resin as the material of the light diffraction structure layer to ensure sufficient release properties. It is an object of the present invention to provide a replica plate capable of suppressing the separation of the release agent from the resin, a manufacturing method thereof, and a manufacturing method of a replica for optical diffraction structure transfer using the replica plate.

  The replication plate of the present invention is a reactive silicone obtained by acrylic-modifying a polyether-modified silicone in the optical diffraction structure layer in the replication plate (1) having a resin optical diffraction structure layer (3) formed on the surface. Is cross-linked as a release agent to solve the above-mentioned problems.

  Polyether-modified silicone exhibits good compatibility with the resin constituting the light diffraction structure layer of the replication plate, and by further modifying this with acrylic, the reactivity with the resin is changed to silicone without impairing compatibility. It can be applied to crosslink the resin and silicone. Therefore, according to the replication plate of the present invention, silicone is added to the resin of the light diffractive structure layer while a sufficient amount of silicone is added to the resin constituting the light diffractive structure layer to ensure sufficient releasability. Crosslinking can be used to prevent separation of the silicone from the replica.

  In the production method of the duplicate plate of the present invention, between the original plate (4) having a light diffraction structure and the base material (2) of the duplicate plate (1) to which the light diffraction structure is to be duplicated, An electromagnetic radiation curable resin (3A) to which a reactive silicone formed by acrylic modification of polyether-modified silicone is added as a release agent is interposed, and the electromagnetic radiation curable resin is irradiated with electromagnetic radiation to thereby provide the electromagnetic radiation curable resin. The above-mentioned problem is solved by crosslinking the silicone and the electromagnetic radiation curable resin while being cured.

  According to the method for producing a replication plate of the present invention, the electromagnetic radiation curable resin is cured by irradiation of electromagnetic radiation to the electromagnetic radiation curable resin, and the light diffractive structure of the original plate is molded thereon, and the resin and Silicone is cross-linked and silicone is taken into the electromagnetic radiation curable resin. Thereby, it is difficult to separate the silicone from the duplicate, and it is possible to produce a duplicate plate having excellent releasability.

  In the method for producing a replica for optical diffraction structure transfer according to the present invention, a resin-made optical diffraction structure layer (3) in which a reactive silicone obtained by acrylic modification of a polyether-modified silicone is crosslinked as a release agent is used. Adhering the duplicate plate (1) and the resin duplication layer (23) provided on the substrate (21) of the transfer duplicate, and applying heat to the adhering portion to soften the duplication layer Thus, the above-described problem is solved by replicating the optical diffraction structure of the replica plate on the replica layer.

  According to the method for producing a duplicate for optical diffraction structure transfer of the present invention, since the reactive silicone as a release agent is cross-linked to the resin constituting the optical diffraction structure layer of the duplicate plate, the plate is taken off. The replication layer on the replica substrate can be easily released from the replication plate. In addition, there is no possibility that the release agent of the duplicate plate is transferred to the duplicate, and a coating layer such as a reflective layer can be satisfactorily adhered to the light diffraction structure formed on the duplicate layer.

  In a preferred embodiment of the present invention, the reactive silicone may be formed by polyether-modifying both ends of the siloxane skeleton structure and further acrylic-modifying the polyether structure at both ends.

  In addition, in the above description, in order to make an understanding of this invention easy, the reference sign of the accompanying drawing was attached in parenthesis, but this invention is not limited to the form of illustration by it.

  As described above, according to the present invention, as a silicone to be added as a release agent to the resin of the light diffraction structure layer, by using a reactive silicone obtained by acrylic modification of a polyether-modified silicone, The reactivity with the resin can be imparted to the silicone without impairing the compatibility of the silicone with the resin of the light diffraction structure layer. Therefore, a large amount of silicone is added to the resin of the optical diffraction structure layer to ensure sufficient release properties between the duplicate plate and the replica, and the resin of the optical diffraction structure layer and the silicone of the release agent are cross-linked. Thus preventing the separation of the silicone from the replica, thereby improving the lifetime of the replica. In addition, since the release agent does not adhere to the replication layer of the transfer replica in which the optical diffraction structure is replicated using the replication plate of the present invention, a coating layer such as a reflective layer is favorably applied to the replication layer. It can be adhered.

[Replication version structure]
FIG. 1 shows a partial cross section of a duplicate plate according to an embodiment of the present invention. The duplicate plate 1 has a configuration in which a light diffractive structure layer 3 is provided on a resin substrate 2. The resin base material 2 includes various polyester resins such as polyethylene terephthalate, polyamide resins such as nylon 6, polyolefin resins such as polymethylpentene, vinyl resins such as polyvinyl chloride, and acrylic resins such as polyacrylate. The resin base material can be used. The light diffractive structure layer 3 is formed with fine irregularities forming a light diffractive structure such as a diffraction grating and a hologram on the surface. In FIG. 1, the light diffraction structure is drawn in a simple uneven shape, but the shape may be appropriate. In FIG. 1, the resin base material 2 and the light diffraction structure layer 3 are exaggerated for convenience of explanation, and the dimensional relationship does not reflect an actual product. The layer configuration in FIG. 1 is an example, and the resin substrate 2 may be composed of a plurality of layers, or other layers such as a primer layer may be interposed between the resin substrate 2 and the light diffraction structure layer 3. Good.

  The light diffractive structure layer 3 is made of an ultraviolet curable resin, which is a kind of electromagnetic radiation curable resin, and a reactive silicone is added to the light diffractive structure layer 3 as a release agent. As an example, the ultraviolet curable resin is configured by adding a photopolymerization initiator to an acrylate monomer or an acrylate resin composed of bisphenol A-based epoxy acrylate, polyester acrylate, or special acrylate having a few functional groups. Examples of the resin constituting the light diffraction structure layer 3 include ultraviolet curable resins having the composition described below (hereinafter referred to as composition A).

Bisphenol A-based epoxy acrylate 27 parts by weight Polyester acrylate A 19 parts by weight Polyester acrylate B 34 parts by weight Special acrylate (polyfunctional acrylate) A 9.7 parts by weight Special acrylate (polyfunctional acrylate) B 2.9 parts by weight Irgacure 184 9 parts by weight Polyether-modified polydimethylsiloxane (non-reactive) 2.5 parts by weight

  As the reactive silicone as the release agent, silicone obtained by further acrylic modification of polyether-modified silicone is used. The polyether-modified silicone is obtained by modifying the silicone skeleton having a basic structure of polydimethylsiloxane and adding a polyether group to the dimethyl group, thereby improving the compatibility of the silicone with the resin. Its structural formula is as shown in the following formula (1).

  A release agent to be added to the light diffraction structure layer 3 is obtained by adding an acryloyl group as an organic group (modified group) for further imparting reactivity to the polyether-modified silicone described above. The structural formula of an acryloyl group that can be used as an organic group is shown in Formula (2). The addition position of these organic groups may be the side chain of polysiloxane, the terminal on one side or both sides, or the side chain and both terminals.

  The ultraviolet curable resin to which the reactive silicone as described above is added, for example, excludes the silicone component from the ultraviolet curable resin having the composition A, and instead of this, Shin-Etsu Chemical Co., Ltd. has trade name X- It is obtained by adding the reactive silicone provided with 22-1602. The reactive silicone under the trade name X-22-1602 is obtained by polyether-modifying both ends of the siloxane skeleton structure and further acrylic-modifying the polyether structure at both ends. The same effect can be obtained by adding polydimethylsiloxane having a polyether-modified acrylic group, which is provided by the trade names BYK-UV3500 and BYK-UV3530 provided by Big Chemie Japan Co., Ltd., respectively.

  The reactive silicone to be added to the light diffractive structure layer 3 as a release agent is not limited to the above, and has a structure in which polyether-modified silicone is acrylic-modified, and undergoes a crosslinking reaction with an ultraviolet curable resin by irradiation with ultraviolet rays. As long as it shows, you may select suitably.

  The amount of reactive silicone to be added to the light diffractive structure layer 3 may be appropriately set according to the releasability required for the replication plate 1 and the compatibility of the reactive silicone with the ultraviolet curable resin. However, as much as possible, it is desirable to add a reactive silicone in the range of 0.2 to 20% as an additive to the total formulation, and further in a range of 2 to 15% as an additive to the total formulation. Reactive silicone may be added.

[Manufacturing method of duplicate plate]
With reference to FIGS. 2A to 2C, an embodiment of a method for manufacturing the duplicate plate 1 will be described. Here, a method of manufacturing the duplicate plate 1 by the so-called 2P method (abbreviation of Photo Polymerization method) will be described. In order to manufacture the duplicate plate 1 by the 2P method, first, as shown in FIG. 2A, the replica plate 1 having an uneven portion having a shape complementary to the optical diffraction structure to be formed on the duplicate plate 1 is formed. A plate 4 is prepared, and an uncured ultraviolet curable resin 3A is coated on the surface thereof. An appropriate amount of a release agent made of reactive silicone is previously added to the ultraviolet curable resin 3A. Various known coating methods may be used for coating the ultraviolet curable resin 3A. The original plate 4 may be a so-called original plate obtained by photographing or drawing a pattern for forming a light diffraction structure on a hard substrate such as a glass substrate, or an intermediate plate duplicated from the original plate.

  Next, as shown in FIG. 2B, the resin substrate 2 is placed on the surface of the ultraviolet curable resin 3A, and the ultraviolet curable resin 3A is sandwiched between the plate 4 and the resin substrate 2 by pressing it. In addition, by laminating the plate 4 and the resin base material 2 via the ultraviolet curable resin 3A, the state shown in FIG. 2B may be obtained immediately without applying the ultraviolet curable resin 3A. Subsequently, as shown in FIG. 2C, ultraviolet rays UV are irradiated toward the ultraviolet curable resin 3A. Thereby, the ultraviolet curable resin 3A is cured, and the light diffraction structure having a shape complementary to the plate 4 is replicated on the surface of the cured product to form the light diffraction structure layer 3. At the time of irradiation with ultraviolet rays UV, the reactive silicone added to the ultraviolet curable resin 3A causes a crosslinking reaction with the ultraviolet curable resin 3A and is taken into the resin. Thereby, the reactive silicone is firmly fixed to the light diffractive structure layer 3, and it becomes difficult to separate the release agent from the light diffractive structure layer 3. The ultraviolet ray UV may be irradiated from the resin substrate 2 side or from the plate 4 side. After curing the ultraviolet curable resin 3A, the resin base material 2 and the light diffraction structure layer 3 are peeled off from the plate 4, and then the ultraviolet curable resin 3A is further cured by further irradiating with ultraviolet rays, whereby the duplicate plate 1 can be obtained. .

[Production method of duplicate]
Next, a method for producing a duplicate using the duplicate plate 1 will be described. Here, a method for producing a duplicate by a so-called semi-dry method will be described. FIG. 3 shows an outline of the replication apparatus 10 by the semi-dry method. The duplicating apparatus 10 embosses a film 20 to be duplicated at a predetermined speed, an embossing roller 12 around which the film 20 is wound, a take-up roller 13 that winds up the film 20, and an embossing of the film 20 at a crimping point α. A pressure roller 14 for pressure bonding to the roller 12, a peeling roller 15 provided at a peeling point β for peeling the film 20 from the embossing roller 12, a guide roller 16 for appropriately guiding the film 20, and heating for heating the embossing roller 12. A device 17 and a cooling device 18 for cooling the peeling roller 15 are provided. The replica plate 1 shown in FIG. 1 is wound around the outer periphery of the embossing roller 12 and fixed so as to be integrally rotatable. Further, the duplicating apparatus 10 is provided with an ultraviolet irradiation device 19 for irradiating the film 20 formed by the embossing roller 12 with ultraviolet UV.

  An example of the cross-sectional structure of the film 20 is shown as shown in FIG. This example is one form of a film for forming a transfer foil having a light diffraction structure as a replica. The film 20 is formed by sequentially forming a release layer 22 and a replication layer 23 on a resin base material 21. The resin base material 21 is made of various resins such as polyethylene terephthalate, polyethylene naphthalate, and polypropylene. The release layer 22 is provided to peel the resin base material 21 and the replication layer 23 when transferring the light diffraction structure formed on the replication layer 23 to another article. An acrylic resin, a melamine resin, a styrene resin, or the like can be used as the material for the release layer 22. The replication layer 23 is made of an ultraviolet curable resin. The ultraviolet curable resin used here may be appropriately selected in the same manner as that used as the base material of the light diffraction structure layer 3 of the replication plate 1.

  The duplication procedure of the light diffraction structure using the duplication apparatus 10 and the film 20 described above is as follows. First, the film 20 is mounted on the duplication device 10 in such a direction that the duplication layer 23 is in close contact with the duplication plate 1 on the surface of the embossing roller 12. The embossing roller 12 of the duplicating apparatus 10 is heated by the heating device 17 to the softening point temperature of the duplicating layer 23 (for example, about 60 ° C.) or higher, and the peeling roller 15 is heated by the cooling device 18 to the softening point of the duplicating layer 23. The temperature is kept lower than the temperature. In this state, the embossing roller 12 is rotationally driven in the direction of the arrow in the drawing, and in parallel therewith, the film 20 is continuously fed from the feeding roller 11 to the winding roller 13. Therefore, the duplication layer 23 of the film 20 pressed against the embossing roller 12 by the pressure roller 14 is softened, and the light diffraction structure of the duplication plate 1 is duplicated (molded) on the surface thereof.

  Then, the film 20 is further cooled by the peeling roller 15 and the replication layer 23 is cured, and the film 20 is peeled from the duplicate plate 1 on the embossing roller 12 at the peeling point β. At this time, since the release agent is added to the duplicate plate 1 as described above, the duplicate layer 23 peels off from the resin base material 21 together with a part of the peeling layer 22 on the back and adheres to the duplicate plate 1. It will not be taken. Thereafter, the film 20 is completely cured by being irradiated with ultraviolet rays from the ultraviolet irradiation device 19.

  As shown in FIG. 5, a reflective layer 24 is formed as a coating layer on the duplicate layer 23 of the film 20 on which the optical diffraction structure is duplicated as described above. The reflective layer 24 is provided to reflect visible light on the light diffraction structure, and a metal or an alloy such as aluminum, silver, or gold, or a high refractive index ceramic is suitably used as the material thereof. The reflective layer 24 is formed by forming these materials with a substantially uniform film thickness on the surface of the replication layer 23 using a thin film forming technique such as vapor deposition, sputtering, or ion plating. In this embodiment, since no release agent is added to the replication layer 23 and the release agent is not separated from the replication plate 1 and does not adhere to the replication layer 23, the reflective layer 24 is attached to the replication layer 23. On the other hand, it can be satisfactorily adhered.

  Further, an adhesive layer 25 is formed on the surface of the reflective layer 24, thereby forming a transfer foil 20A having a light diffraction structure. The adhesive layer 25 is for fixing the duplication layer 23 and the reflective layer 24 to a transfer target to which the light diffraction structure of the transfer foil 20A is to be transferred. As an example, a heat-sensitive adhesive is used. However, the layer configuration of the transfer foil 20A is an example, and the front and back of the replication layer 23 are not limited to the illustrated layers, and appropriate layers may be provided.

  The present invention is not limited to the above form and may be implemented in an appropriate form. For example, the production method of the duplicate plate 1 is not limited to the 2P method described above, and the duplicate plate may be produced by the same semi-dry method as exemplified as the duplicate production method. In this case, an ultraviolet curable resin layer to which reactive silicone is added is provided on the base of the film to be pressure-bonded to the embossing roller, and the ultraviolet curable resin layer is pressed against the replica plate on the embossing roller to soften the ultraviolet ray. Irradiation may cause a crosslinking reaction. The 2P method is appropriate when producing a duplicate plate from an original plate using a hard substrate such as a glass substrate, but the semi-dry method is preferably used when producing a further duplicate plate from a resin-made duplicate plate. Can do. In any case, an ultraviolet curable resin containing the above-described reactive silicone added as a release agent is interposed between the original plate having a light diffraction structure to be formed on the replica plate and the base material of the replica plate. In this state, it is only necessary that the ultraviolet curable resin is irradiated with ultraviolet rays to cure and cure the release agent silicone and the ultraviolet curable resin. Furthermore, in the above-mentioned form, an ultraviolet curable resin is used as a material for the replication plate. Various electromagnetic radiation curable resins that cause a curing reaction may be selected as a material for the replication plate, and the reactive silicone to be added to the resin may be appropriately adjusted according to the type of electromagnetic radiation and the irradiation dose.

  In the above-described method for producing a duplicate, ultraviolet rays are irradiated in parallel with the heating of the film. However, after the heating, electromagnetic waves such as ultraviolet rays may be irradiated to cure the duplicate layer. In the above, the transfer foil is taken as an example of the duplicate, but the duplicate is not limited to this, and may be a transfer ribbon or the like. The product names mentioned in the above description are trademarks or registered trademarks of each company.

  Next, examples of the present invention will be described. The table below shows the release agent by adding the reactive silicones described in Examples 1 and 2 and Comparative Examples 1 to 7 as a release agent to the ultraviolet curable resin whose composition has been specified in the embodiment described above. The results show that the compatibility is evaluated, the resin after the addition of the release agent is completely cured by irradiation with ultraviolet rays, and the release properties of the obtained samples are evaluated. The weight ratio of reactive silicone to UV curable resin was 5:95. The compatibility was shown as “◎”, △, which was somewhat better than the conventional one, but still not enough as a release agent for the replication plate, and “×” as the same level of compatibility as before. For releasability, pure water is dropped on the surface of the cured sample, and the contact angle θ (see FIG. 6) of the water drop after 1 minute has been measured. However, since the contact angle θ varies depending on the surface state, the surface state of each example is unified by bringing the surface of the resin before curing into contact with the raw glass. In Examples 1 to 3, it can be seen that the mold release agent exhibits good compatibility, and the mold releasability is equal to or higher than that of the comparative example. In addition, the silicone name of Example 2 is a brand name of Big Chemie Japan Co., Ltd., and the other silicone names are brand names of Shin-Etsu Chemical Co., Ltd. These trade names are trademarks or registered trademarks of the respective companies.

The fragmentary sectional view of the replication plate which concerns on one form of this invention. The figure which shows one form in the case of manufacturing a duplicate plate by 2P manufacturing method. The figure which shows the procedure following FIG. 2A. The figure which shows the procedure following FIG. 2B. The figure which shows the replication apparatus for replicating a light diffraction structure from a replication plate to a transfer foil base material. The figure which shows an example of the laminated constitution of the film for manufacturing transfer foil. The figure which shows the transfer foil which covered the light diffraction structure layer with the reflection layer and the contact bonding layer. The figure which shows the contact angle of the water droplet used as a standard of mold release evaluation in an Example and a comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Duplicating plate 2 Resin base material 3 Light diffraction structure layer 3A Ultraviolet curable resin 4 Duplicating original plate 10 Duplicating device 12 Embossing roller 19 Ultraviolet irradiation device 20 Film 20A Transfer foil 21 Resin base material 22 Peeling layer 23 Duplicating layer 24 Reflecting layer 25 Adhesive layer

Claims (6)

  In the replica plate having a resin-made light diffraction structure layer formed on the surface, a reactive silicone obtained by acrylic modification of polyether-modified silicone is cross-linked to the light diffraction structure layer as a release agent. A replicated version of the light diffraction structure.   2. The replication plate according to claim 1, wherein the reactive silicone is obtained by polyether-modifying both ends of a siloxane skeleton structure and further acrylic-modifying the polyether structure at both ends.   A reactive silicone formed by acrylic modification of polyether-modified silicone is added as a mold release agent between a replication source plate having a light diffraction structure and a base plate of the replication plate on which the light diffraction structure is to be replicated. A duplication plate characterized in that the electromagnetic radiation curable resin is interposed, the electromagnetic radiation curable resin is irradiated with electromagnetic radiation to cure the electromagnetic radiation curable resin, and the silicone and the electromagnetic radiation curable resin are cross-linked. Manufacturing method.   4. The method for producing a duplicated plate according to claim 3, wherein the reactive silicone is obtained by modifying both ends of a siloxane skeleton structure with polyether and further modifying the polyether structure at both ends with acrylic.   A replication plate having a light diffraction structure layer made of a resin in which a reactive silicone obtained by acrylic modification of a polyether-modified silicone is cross-linked as a release agent, and a resin provided on a substrate of a copy for transfer A replica for optical diffraction structure transfer, wherein the optical diffraction structure of the replica plate is replicated on the replica layer by applying heat to the adhesive layer and softening the replica layer. Manufacturing method.   6. The optically diffractive structure transfer replica according to claim 5, wherein the reactive silicone is obtained by polyether-modifying both ends of a siloxane skeleton structure and further acrylic-modifying the polyether structure at both ends. Production method.

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