KR100503498B1 - Structured surface bearing articles and method of making - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure comprising a structured surface and a method of manufacturing the same, in which contact between the master and the ultraviolet curable resin inevitably occurs, and transfer residues from the ultraviolet curable resin to the master molding surface accumulate on the master molding surface. It is aimed to provide a master and manufacturing method which can make continuous production difficult and effectively overcome the problems of the conventionally provided technology, which makes it difficult to accurately duplicate a product, generates product defects and ultimately produces continuous products. .

In order to achieve the above object, the present invention provides a structure including a structured surface, the step of applying a master mold material on the surface of the structure to be replicated, and after curing the applied master mold material to remove the ultraviolet curable resin Depositing on the structured surface of the master; exposing the ultraviolet curable resin to ultraviolet rays; curing; and desorbing the ultraviolet curable resin from the master, wherein the master mold material comprises a silicone or a fluorine component. Method for producing a structure provided by, and characterized in that the structure comprising a structured surface produced by this method.

Description

STRUCTURED SURFACE BEARING ARTICLES AND METHOD OF MAKING}

The present invention relates to a structure including a structured surface and a method of manufacturing the same, and in particular, UV-curable resin is transferred to the master molding surface so that it does not remain and is effectively capable of continuous production as well as excellent products without defects duplicated products. It relates to a manufacturing method for providing.

Such a structure and a method of manufacturing the same may be used for a light-controlled structure having a surface structure, a Fresnel lens, retroreflective cube-corner sheeting, an optical film for improving brightness, and the like. In particular, the representative prior arts that present optical films used for the purpose of increasing luminance in liquid crystal display devices are US Patent No. 4,542,449 and Korean Patent Application No. 1986-0009868.

A method of manufacturing a structure comprising such a structured surface is described in detail in US Pat. No. 3,689,346, US Pat. No. 4,576,850, US Pat. No. 4,374,077, and Korean Patent Publication No. 1990-012750.

US Pat. No. 3,689,346 discloses a retroreflective cube-corner sheeting by applying a crosslinkable, partially polymerized resin to the master intaglio molding surface and depositing it, curing the resin to replicate the intaglio molding surface. ), US Pat. No. 4,576,850 discloses a product consisting of a crosslinked polymer having a microstructured surface, and US Pat. No. 4,374,077 discloses a fresnel lens on the surface. It is proposed a method of replicating a microstructure such as.

Korean Patent Publication No. 1990-012750 also discloses microstructures such as retroreflective cube-corner sheeting, fresnel lenses, complete internal reflective films, occlusal members, and information transfer disks. Discloses a method for producing plastic products

However, in such a prior art, the resin generally used exhibits relatively high shrinkage when solidified or cured, and thus the microstructure provided by such a method has optical defects.

As described above, in the method of manufacturing a structure including most structured surfaces, contact between the master and the ultraviolet curable resin inevitably occurs. The transfer product generated at this time accumulates on the surface of the master molding, making it difficult to accurately duplicate the product, and causes defects in the product, which ultimately makes it difficult to produce continuous products.

Accordingly, the present invention to solve this problem is a invention comprising a structure including a structured surface and a method for manufacturing the same, while the contact between the master and the ultraviolet curable resin inevitably occurs transfer material from the ultraviolet curable resin to the master molding surface ( Residue) accumulates on the surface of the master molding, making it difficult to accurately reproduce the product, overcoming the problems of the conventionally provided technology that causes product defects and ultimately continuous product production, and enables continuous production. It is an object to provide a method.

In order to achieve the above object, the present invention provides a structure including a structured surface and a method of manufacturing the same, wherein the manufacturing method includes applying a master mold material to a surface of a structure to be replicated and curing the applied master mold material. And desorption to deposit the ultraviolet curable resin on the structured surface of the master, the ultraviolet curable resin is exposed to ultraviolet rays to cure, and the ultraviolet curable resin is detached from the master. Provided are a process for the manufacture of a structure comprising a resin comprising silicone or a fluorine-based fingerprint, and a structure comprising a structured surface produced by such a method.

Here, in order to manufacture a replica of the structure, the master mold material applied in the manufacturing method of the structure is cured and then desorbed and the UV-curable resin is deposited on the structured surface of the master, and then the detached master mold material is used as the master. Step may be included.

The present invention, in particular, by using a master made of a polymer material with a low surface energy including silicon, UV-curable resin is easily deposited to prevent bubbles from forming on the structured master molding surface, and exposed to ultraviolet rays to cure and detachable The present invention relates to a structure including a structured surface for providing an excellent product free from defects as well as a continuous product by preventing the ultraviolet curable resin from being transferred to and remaining on the master molding surface.

Specifically, the manufacturing method according to the present invention has a depth of the structured surface of the structure of 10㎛ to 10,000㎛, in the manufacturing method for continuously producing a relatively large plastic product or polymer structure from the microstructure, the structure of the product It is characterized in that the silicon rubber is excellent in heat resistance, chemical resistance, low surface energy of the surface material of the master mold or master mold structured intaglio. Rubber mold materials are classified according to the components, but any chemical component that can be cured can be used.

More specifically, the resin containing the silicon component is preferably characterized in that it comprises a combination of silicon (Si) and oxygen (O). Particularly, the resin containing the silicone component is preferably polysiloxane in which Si atoms and O atoms are alternately arranged, because of the inorganic nature of the siloxane bonds, which are nonflammable and endurable at high temperatures, and have chemical resistance, oxidation resistance, and electrical insulation. And because it has excellent water repellency and non-adhesive properties, hardly accumulates transfer materials on the surface of the master mold material.

For the above reason, in the present invention, the resin containing the silicon component may further include a vinyl group in the combination of silicon (Si) and carbon (C). This reinforces the mechanical strength of the silicone rubber to make it durable against the pressure applied to the master. However, it is preferable that a vinyl group has a value of 30 mol% or less. If it has a value of 30 mol% or more, it takes a long time to duplicate the master having a micrometer-sized microstructure and has the disadvantage of increasing surface energy.

In addition, the resin containing the fluorine component is polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), hexafluoropropylene-based compound , Teflon (Teflon) is preferably characterized in that it is a resin mixed with one or more kinds. This is because the resin containing the fluorine component is excellent in chemical resistance, oxidation resistance, electrical insulation and water repellency, and very excellent in non-tacky properties, so that almost no transfer material accumulates on the surface of the master mold material.

Usually, the most important property for rubber mold materials is viscosity, which is affected by the material, temperature, time after mixing with other components, and mixing speed. When the rubber mold material has a low viscosity, the flow characteristics are good, and thus the reproducibility is excellent after replicating a minute part of the structure. The viscosity of the master mold material and the ultraviolet curable resin used in the present invention is preferably 300cps to 30,000cps at room temperature. The reason is that if the viscosity is lower than 300 cps, it is difficult to replicate the structure because it flows out before curing, and if it is higher than 30,000 cps, the microstructure is very difficult to replicate. For this reason, the viscosity of the resin is preferably 5,000 to 20,000 cps.

In addition, when the structure is manufactured for use in optical applications, the UV curable resin is typically transparent and preferably a single or a mixture of resins having a refractive index of at least 1.40. In order to more effectively express the optically designed structural features of the structure, it is more preferable to apply a single or a mixture of resins of 1.55 to 1.75. Applying a resin of 1.55 or less is because the performance of the product is weak and the resin of 1.75 or more is very expensive and the economic efficiency is insufficient.

However, in the rubber mold material for forming the master mold, the viscosity is only a main characteristic for manufacturing the master, and the release force between the ultraviolet curable resin and the master mold material is very important in the step of replicating the structure through the ultraviolet curable resin.

Therefore, in the present invention, a rubber containing a silicon or fluorine component was used as the master mold material or surface treatment material of the master mold, and even in the step of forming the master mold, the resin containing the component has excellent flowability and replicates the structure. Even better than other components, the releasability is excellent, which is very effective for replica reproduction and continuous productivity. In addition, when providing a master through a rubber containing a silicon or fluorine component, the life of the master that engraved the original is prolonged, which is very economical in producing the structure of the present invention.

On the other hand, if the components of the rubber mold material is adhesive to the commonly used UV-curable resin is not detachable it is impossible to replicate the structure through the master mold material. As a result, the use of a material with low surface energy in terms of adhesion improves the release force between the master mold material and the UV curable resin and facilitates the replication of the structure.

Here, surface energy is generated from the forces acting between molecules in the presence of liquid and gas phases, and the forces attracting molecules in all directions between liquid molecules are called cohesion and the forces attracting other molecules. It is called adhesion. At this time, the force generated by the difference between cohesion and adhesion is called surface tension. Cohesion, adhesion, and surface tension defined in this way can not be applied as it is in the case of solid non-liquid, but can be applied conceptually to those who are engaged in the industry in the case of solid.

Therefore, the master mold material applied to the master in the liquid state and the ultraviolet curable resin applied to replicate the structure on the master mold material are initially in the liquid state, but are cured and solid at the time of desorption. It is possible to find and use a resin having As a method, it is possible to measure the surface energy by measuring the contact angle of distilled water through a specimen in a solid state. In general, the larger the contact angle, the higher the surface tension, while the lower the surface energy.

As a result of the measurement by this method, the most preferable physical property is to use silicone rubber as described above. Herein, the value of the surface energy is preferably 50 dyne / cm or less. If the surface energy value exceeds 50 dyne / cm, the adhesive strength at the interface with the curable resin is strong, it is not easy to detach, it is difficult to manufacture a precise structure of the micrometer size. For this reason, the surface energy value is preferably low, and more preferably, 25 dyne / cm or less is used as the master mold material.

Moreover, the method of mixing and using curable resin compatible with silicone resin is also possible. For example, it is possible to lower the surface energy by mixing components containing silicon or fluorine groups with thermosetting resins such as epoxy resins, phenol resins, and acrylic resins.

The silicone resins that may be used in the present invention include addition polymerization type and condensation polymerization type. The addition polymerization type silicone resin has a polymer having a vinyl group (-CH = CH2) at the end, a platinum salt catalyst, and a silane group (Si-) at the end. It is obtained by mixing and curing the crosslinking agent having H) and the reaction formula is shown in the following formula (1).

[Equation 1]

In addition, the condensation-polymerization type silicone resin that can be used as the master mold material of the present invention is a polysiloxane having a hydroxyl group at the end (polysiloxane, provided by Ciba) and a crosslinking agent is mixed with ethyl silicate (ethyl silicate) and organo tin activator that is tin octane It can obtain by hardening, and general reaction formula is as following Formula 2. Condensation polymerization type silicone resins can be divided into one-component type and two-component type, the curing reaction of the one-component type is the same as the following formula 3, the following formula 2 is a two-component type curing reaction.

[Equation 2]

[Equation 3]

On the other hand, the structure produced by the above method is an optical film for light control, having a first surface structured on one side, a second surface on the other side, the structured surface is at least one of the smooth surface of the cross-section One or more inclined polygonal shapes may be arranged and included.

In the case where the shape of the structured surface is formed of a plurality of triangular prisms, it is preferable that they are linear arrays of small isosceles prisms arranged side by side. At this time, the angle between the two oblique planes of the prism in the upper structure of the optical structure layer 4 has a value of 20 to 140 degrees.

In the case of the triangular prism, the characteristics of the brightness and the wide viewing angle change greatly depending on the angle of the vertex of the prism, and the angle of the vertex of the triangular prism is preferably 80 to 100 degrees. When the angle of the vertex of the triangular prism is 80 degrees or less, the brightness due to condensation is good, but the optical viewing angle is poor, and it is difficult to apply. When the angle is 100 degrees or more, the optical viewing angle characteristic is good but the luminance is low. Considering this point, the angle of the vertex is particularly preferably used in the range of 85 to 95 degrees. In the present invention, the cross-sectional shape of the structured surface is preferably an isosceles triangle composed of two inclinations inclined 45 degrees with respect to the smooth surface. Do.

Herein, the structured surface is preferably arranged in the same structure having an inclined surface, the spacing between the vertices of the structure is 10 to 200 micrometers. This is because, if it is smaller than 10 micrometers, the master fabrication of the microstructure is difficult, and if it is larger than 200 micrometers, the product becomes thick and does not meet the needs of consumers.

The manufacturing method of the structure may be characterized by providing a brightness enhancement film, a prism film, a Fresnel lens, a retroreflective cube-corner sheeting, etc., having optical properties, and the present invention. The structure of also includes such optical films.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The method for producing a surface structured structure provided in the present invention is applied as shown in FIGS. 4, 5 and 6. 4 and 5 show an example in which a flat plate master is used. However, the master applied to the present invention is not necessarily limited to the plate type. 4 shows that the UV curable resin 41 is applied to the master, the base film 43 is provided, and the UV curable resin and the master are brought into close contact with the contact mechanism 46. At this time, the ultraviolet curable resin is present between the master and the base film, the ultraviolet curable resin is cured by the ultraviolet light provided from the ultraviolet lamp 45, desorbed from the master to produce a structure having a shape 47 to be replicated The method is presented.

5 shows that the UV curable resin 56 is applied to the base films 54 and 55 through the coating mechanisms 52 and 53 and adhered to the master 51 and the adhesion mechanism 57. At this time, the ultraviolet curable resin is present between the base film and the master, the ultraviolet curable resin is cured by the ultraviolet light provided from the ultraviolet lamp 45, the method of manufacturing a structure having a shape 47 to be detached from the master to replicate. Presented.

6 shows an example in which the master is provided as a roll. After the ultraviolet curable resin 73 is applied and rotated in one direction, the ultraviolet curable resin applied to the master roll 80 and rotated is brought into close contact with the base film 71 (72), and the master roll and the ultraviolet curable resin and the base material. When the film is integrated, it is exposed to ultraviolet rays 75. That is, it is an example of the manufacturing method which manufactures the film 88 by which the surface was structured by the method which transfers the ultraviolet curable resin hardened | cured from the master roll to a base film after ultraviolet-curable resin is exposed to ultraviolet-ray hardening. The method shown in FIG. 6 may be applied to the base film to be in close contact with the master as applied in FIG. 5.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The following examples are intended to illustrate the invention, but are not limited to these.

 Example 1

A master polymer was prepared by adding and curing a polymerized silicone resin on a linear array structure of a right-sided isosceles triangular prism having a surface structure of 30 X 15 micrometers (base X height) used for a back light fixture of a liquid crystal display device. .

The addition-polymerization type silicone resin used in the present invention used US 3M brand name Express (code EP), Japan GC brand name Examix (code EM), US Kerr brand name Extrude (code ET). The addition polymerization type silicone resin used in the evaluation took 6 to 30 minutes to cure as much as possible after being mixed with the polymer, the crosslinking agent and the catalyst, and no bubble was found. The silicone resin cured and detached from the surface structure of the right isosceles triangle was an elastomer but slightly hard. Contact angle and contact angle of the distilled water for each material (Fig. 7) and the surface energy is shown in Table 1 below.

Applying the master mold material to the surface of the structure to be replicated using the resin as a master mold material, and replicating the master mold material prepared by the step of removing the removable by curing the applied master mold material When used as a master for producing a structure, the structure comprising the step of depositing an ultraviolet curable resin on the structured surface of the master, the ultraviolet curable resin is exposed to ultraviolet light to cure, and the step of detaching the ultraviolet curable resin from the master Was prepared in the same manner as in FIGS. 4, 5 and 6.

The process corresponding to FIG. 4 is carried out by closely contacting the base film 43 on the UV curable resin 41 applied to the master 42, exposing the base film 43 to ultraviolet rays through the UV lamp 45, and then detaching and removing the 47 from the master. It is a process.

FIG. 5 shows that the UV curable resin 56 applied to the base film 54 through the comma coating heads 52 and 53 is in close contact with the master 51 and exposed to ultraviolet rays through the UV lamp 56. It is a process of detaching (59) from the master. FIG. 6 applies a manufacturing method as shown in FIG. 4 by integrating a master 81 made of a master mold material on a roll 80 and may be applied as shown in FIG. 5.

SEM image of the structure thus prepared is shown in Figure 8 (e).

Example 2

The same master as in Example 1 was prepared except that a condensation polymerization type silicone resin was used. The condensation polymerization type silicone resin was prepared by mixing Ciba's polysiloxane and a crosslinking agent to cure by mixing ethyl silicate and organo tin activator, that is, tin octane.

Here, the contact angle and contact angle (Fig. 7) and the surface energy of the silicone resin are shown as code name PE in Table 1 below. In addition, a structure was manufactured by the same manufacturing method as Example 1 using the thus prepared master, and the SEM image of the structure at that time is as shown in FIG.

TABLE 1

code Distilled water contact angle (degrees) Surface energy (dyne / cm) Contact angle picture (Fig. 7) EP 101.01 23.42 a EM 76.05 29.44 b ET 58.95 45.79 d PE 65.00 36.91 c

Example 3

     The polysulfide resins (KCC, PS9210PTA) were mixed with metal peroxides (KCC, PS9210PTB) and vinylidene fluoride, and coated on a substrate on which the partition wall of the plasma display device was formed, cured, and detached to prepare a master.

     Here, the master mold material mainly containing polysulfide has a one-component type and a two-component type. The one-component type is a moisture curing type that reacts with moisture in the air to cure from the surface, and the two-component type is a reaction curing type wherein the polysulfide, which is the main component of the substrate, reacts with the curing material to cure. In this example, the second component type was followed. At this time, the contact angle of the resin with distilled water was 59 degrees.

In addition, a structure was manufactured by the same manufacturing method as Example 1 using the thus prepared master, and the SEM image of the structure at that time is as shown in FIG.

Comparative Example 1

A structure was prepared in the same manner as in Example 1 except that the polyethylene mold material was used as the master mold material. Here, the surface energy of the polyethylene mold material was 60 dyne / cm.

The SEM image of the structure including the structured surface thus prepared is shown in FIG.

 Comparative Example 2

   A structure was manufactured in the same manner as in Example 1, except that an epoxy mold material having a surface energy of 72 dyne / cm was used as the master mold material. The epoxy mold material could not be used as a master because it was not detached or damaged from the structure to be replicated.

As shown in the above embodiment, the resin containing silicon or fluorine to be used in the present invention has a surface energy value of 50 dyne / cm or less, and when the structure is manufactured using the same, as shown in FIG. It can be seen that the structure is easily detached and little damage occurs. However, in the comparative example using the conventional material as it is, damage occurred or the state was severe as shown in FIG.

Method for producing a structure and the structure according to the present invention can be modified and applied in various forms within the scope of the technical idea of the present invention is not limited to the above preferred embodiment. The present invention described above is capable of various substitutions, modifications, and changes without departing from the technical spirit of the present invention for those skilled in the art to which the present invention pertains. It is a matter of course that it is not limited, and should be determined including not only the claims described below but also the claims and equivalents.

The present invention relates to a structure including a structured surface and a method for manufacturing the same, wherein a master is manufactured from a resin containing silicon and a fluorine compound, thereby mastering from an ultraviolet curable resin in which contact between the master and the ultraviolet curable resin inevitably occurs. Residues on the molding surface do not accumulate on the master molding surface, so that the product can be accurately reproduced.

Therefore, the present invention overcomes the problems of the conventionally provided technology which causes the defect of the product and ultimately the continuous production of the product is difficult, and provides a manufacturing method and a structure by such a method that can be continuously produced effectively.

Figure 1 shows the structure of a representative light control film provided in the prior art.

Figure 2 shows a path for adjusting the cross section and the light ray of a typical light control film provided in the prior art.

3 illustrates a light conditioning structure in which the pattern of the structured surface is curved.

4 illustrates a method of making a structure that includes a structured surface.

FIG. 5 illustrates an example of using a plate-shaped master for a method of making a structure that includes a structured surface.

6 shows an example in which a master is provided as a roll for a method of making a structure including a structured surface.

Fig. 7 shows the results of contact angle test on distilled water of the resin used as the master mold material.

8 shows an SEM image of the manufactured structure.

[Description of main part of drawing]

41: UV curable resin 42, 51: master

43, 56: base film 45: UV lamp

46: contact mechanism 47: structure shape

Claims (18)

In a method of making a structure comprising a structured surface, Applying a master mold material to the surface of the structure to be replicated; Curing the applied master mold material and then detaching and depositing the master mold material on the structured surface of the master; Curing the master mold material by exposure to ultraviolet rays; And Detaching a master mold material from the master; Including Wherein said master mold material is a resin comprising a silicon or fluorine component. The method of claim 1, The method of manufacturing the structure after the step of curing the applied master mold material and then detaching the master mold material on the structured surface of the master, Using the detached master mold material as a master for producing a replica manufacturing method of a structure. The method of claim 1, Resin comprising the silicon component is a method for producing a structure, characterized in that it comprises a combination of silicon (Si) and oxygen (O). The method of claim 3, wherein Resin comprising the silicone component is a method for producing a structure, characterized in that the polysiloxane. The method of claim 1, Resin comprising the silicon component is a method for producing a structure, characterized in that containing a vinyl group in the bonding of silicon (Si) and carbon (C). The method of claim 1, The resin containing the fluorine component Polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), hexafluoropropylene-based compound, Teflon (Teflon) Method for producing a structure, characterized in that the resin is a mixture of at least one of any one selected material. The method of claim 1, The master mold material is a method of producing a structure, characterized in that it comprises a material with a distilled water contact angle of 58 degrees or more. The method of claim 1, The master mold material of the structure is characterized in that the viscosity of 300cps to 30,000cps at room temperature. The method of claim 1, The master mold material is a manufacturing method of the structure, characterized in that the viscosity of the ultraviolet curable resin is 300cps to 30,000cps at room temperature. The method of claim 1, The structure to be replicated is a manufacturing method characterized in that the structure having optical properties such as brightness enhancement film, prism film, Fresnel lens, retroreflective corner sheet material. In a structure comprising a structured surface, Applying a master mold material to the surface of the structure to be replicated; Curing the applied master mold material and then desorbing to deposit an ultraviolet curable resin on the structured surface of the master; Curing the ultraviolet curable resin by exposure to ultraviolet rays; And Detaching the ultraviolet curable resin from the master; Including; The master mold material is a structure produced by the method for producing a structure, characterized in that the resin containing silicon or fluorine. The method of claim 11, The structure is cured after the applied master mold material and then detached to deposit an ultraviolet curable resin on the structured surface of the master, Structure for producing a structure comprising the step of using the detached master mold material for the production of the replica as a master. The method of claim 11, The master mold material, characterized in that the viscosity of the ultraviolet curable resin is 300cps to 30,000cps at room temperature. The method of claim 11, The master mold material, characterized in that the refractive index of the ultraviolet curable resin is 1.40 to 1.75. The method of claim 11 or 12, The structure is an optical film for light control, Having a first surface structured on one side and a second surface on the other side, the structured surface comprising at least one shape of at least one inclined polygon with respect to the side of which the shape of the cross section is smooth; Structure characterized in that. The method of claim 15, Wherein the cross-sectional shape of the structured surface is an isosceles triangle consisting of two slopes tilted at 45 degrees with respect to the smooth surface. The method of claim 15, The structured surface of the structure is a structure, characterized in that the same structure is repeatedly arranged with an inclined surface, the spacing between the vertices of the structure is 10 ~ 200 micrometers. The method of claim 1, The structure to be duplicated is a structure characterized in that it is used as an optical enhancement film, a prism film, a Fresnel lens (Fresnel lens), retroreflective cube-corner sheeting (retroreflective cube-corner sheeting).