JP2014051013A - Method for manufacturing transparent shaped film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a transparent shaped film having good formativeness and exhibiting weathering performance and self-cleaning properties.SOLUTION: A method for manufacturing a transparent shaped film includes the steps of: preparing a plastic substrate 1, a shaping plate 24, and an electron beam curable resin composition 6; setting the electron beam curable resin composition 6 between the plastic substrate 1 and the shaping plate 24; forming a shaped layer 2 by irradiating the electron beam curable resin composition 6 with an electron beam; peeling off the plastic substrate 1 and the shaped layer 2 from the shaping plate 24; and forming an inorganic layer 3 having hydrophilicity on the shaped layer 2 by an ion plating method or a plasma chemical vapor phase growth method. The electron beam curable resin composition 6 contains urethane acrylate and an ultraviolet absorber. The urethane acrylate has a glass transition temperature of 17°C or higher or has no glass transition temperature, and has a viscosity at 60°C of not less than 2,000 mPa s and not more than 24,000 mPa s.

Description

  The present invention relates to a method for producing a transparent shaped film, and more particularly, to a method for producing a transparent shaped film exhibiting good weather resistance and self-cleaning properties.

  The transparent shaped film has a shaped shape as an optical element, and is used in devices such as organic electroluminescence elements (organic EL elements), liquid crystal display elements, thin film transistors, solar cells, touch panels, electronic paper, It is used for films to be attached to windows of buildings and cars. When such a transparent shaped film is used outdoors, high weather resistance is required.

  Various techniques relating to transparent shaped films exhibiting weather resistance have been proposed. For example, Patent Document 1 proposes a laminate excellent in weather resistance that does not yellow and does not crack or detach from a layer provided on a substrate when the laminate is used for an outdoor structure. Yes. Specifically, it is a laminate formed by laminating at least a primer layer and a surface protective layer on a substrate, and either or both of the primer layer and the surface protective layer are white or transparent, and the surface A protective layer is obtained by crosslinking and curing an ionizing radiation curable resin composition containing an ionizing radiation curable resin and a hindered amine light stabilizer having reactivity with the ionizing radiation curable resin or a hindered amine light stabilizer solid at room temperature. A laminate is proposed.

  Patent Document 2 proposes a resin base material having weather resistance against heat, light and moisture. Specifically, it has at least one ceramic layer mainly composed of an oxide, nitride oxide or nitride containing Si or Al on at least one surface of a resin substrate containing a light stabilizer, and water vapor. A weather resistant resin base material having a transmittance (JIS K7129-1992 method B, 40 ° C., 90% RH condition) of 0.01 g / m 2/24 hours or less has been proposed.

  Patent Document 3 proposes an optical functional film having an uneven antiglare layer with a fine surface. Specifically, an optical functional property in which an uneven antiglare layer having a fine surface is formed directly or via another layer on a transparent substrate film, and a silicon oxide film is further formed thereon. There has been proposed an optical functional film in which the silicon oxide film is a SiOx film (x is 1.50 ≦ x ≦ 4.00) having a surface contact angle with water of 40 ° to 180 °. .

JP 2011-207183 A WO2009 / 150992A1 JP 2004-341541 A

  By the way, recent transparent shaped films have not only good shapeability and transparency, but also self-cleaning properties as well as a requirement for weather resistance. Therefore, in some transparent shaped films in which a shaping layer made of an organic material is provided on a plastic substrate, a hydrophilic inorganic layer is laminated on the shaping layer. The transparent shaped film provided with such a hydrophilic inorganic layer has an advantage that the self-cleaning property is improved.

  However, although the laminated body proposed in Patent Document 1 has good weather resistance, it is considered that the shaped layer cannot be formed with good formability with the polyurethane acrylate resin used therein. Further, even if a shaping layer is formed with the resin material, when the inorganic layer for imparting self-cleaning properties is formed on the shaping layer, it is imparted by heat or plasma during film formation. The shape layer may be discolored.

  In addition, although the resin base material proposed in Patent Document 2 includes a UV absorber and has good weather resistance, the pentaerythritol polyfunctional acrylate resin used therein has a shaping layer. It is thought that it cannot be formed well.

  Moreover, it is thought that the optical functional film proposed by patent document 3 cannot form a shaping layer with sufficient shaping property with the binder resin which has the polyester acrylate and polyurethane acrylate currently used there. Further, even if a shaping layer is formed with the resin material, when the inorganic layer for imparting self-cleaning properties is formed on the shaping layer, it is imparted by heat or plasma during film formation. The shape layer may be discolored and transparency may be lowered.

  The present invention has been made in order to solve the above-described problems, and an object of the present invention is to provide a method for producing a transparent shaped film that has good shapeability and exhibits weather resistance and self-cleaning properties.

  The method for producing a transparent shaped film according to the present invention for solving the above problems includes a step of preparing a plastic substrate, a shaped plate, and an electron beam curable resin composition, the plastic substrate and the shaping A step of providing the electron beam curable resin composition between the plate, a step of irradiating the electron beam curable resin composition with an electron beam to form a shaping layer, the plastic substrate and the shaping Separating the layer from the shaping plate, and forming a hydrophilic inorganic layer on the shaping layer by an ion plating method or a plasma chemical vapor deposition method, and the electron The linear curable resin composition contains a urethane acrylate and an ultraviolet absorber, and the urethane acrylate has a glass transition temperature of 17 ° C. or higher or a glass transition temperature, and a viscosity at 60 ° C. of 2000 mPa · s or higher. 2400 Characterized in that it is less than or equal to mPa · s.

  In the method for producing a transparent shaped film according to the present invention, the electron beam curable resin composition may contain a light stabilizer.

  In the method for producing a transparent shaped film according to the present invention, the electron beam curable resin composition may contain a release agent.

  According to the present invention, the shapeability is good, the weather resistance and self-cleaning properties can be shown, and a transparent shaped film can be produced.

It is a typical perspective view which shows an example of the transparent shaping film obtained with the manufacturing method which concerns on this invention. It is typical sectional drawing which shows the example of a transparent shaping film. It is a schematic diagram for demonstrating the manufacturing method of the transparent shaping film which concerns on this invention.

  Hereinafter, the manufacturing method of the transparent shaped film which concerns on this invention is demonstrated in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

[Method for producing transparent shaped film]
As shown in FIG.1 and FIG.2, the manufacturing method of the transparent shaping film 10 which concerns on this invention is the plastic base material 1, the shaping layer 2 provided on the plastic base material 1, and the shaping layer 2 top. It is a method for manufacturing the transparent shaping film 10 which has the inorganic layer 3 provided in this.

  And the manufacturing method is as shown in FIG. 3, the process (preparation process) which prepares the plastic base material 1, the shaping plate 24, and the electron beam curable resin composition 6, and the plastic base material 1 and the shaping. A step of providing the electron beam curable resin composition 6 between the plate 24 (composition installing step) and a step of forming the shaping layer 2 by irradiating the electron beam curable resin composition 6 with an electron beam (imposition) Forming layer forming step), a step of peeling the plastic substrate 1 and the shaping layer 2 from the shaping plate 24 (peeling step), and an ion plating method or a plasma chemical vapor deposition method on the shaping layer 2 And the step of forming the hydrophilic inorganic layer 3 (inorganic layer forming step). In this production method, the electron beam curable resin composition 6 contains a urethane acrylate and an ultraviolet absorber, and the urethane acrylate has a glass transition temperature of 17 ° C. or higher or a glass transition temperature, and a viscosity at 60 ° C. Is 2000 mPa · s or more and 24000 mPa · s or less.

  According to such a method for producing the transparent shaped film 10, it is possible to produce a transparent shaped film that has good shapeability and can exhibit weather resistance and self-cleaning properties. More specifically, since the electron beam curable resin composition 6 contains urethane acrylate and an ultraviolet absorber, the shaping layer 2 formed with the electron beam curable resin composition 6 has good weather resistance against ultraviolet rays. Can show gender. Moreover, since the electron beam curable resin composition 6 contains a urethane acrylate having a viscosity at 60 ° C. of 2000 mPa · s or more and 24000 mPa · s or less, the shaping layer 2 can be formed with high shape accuracy. Moreover, since the electron beam curable resin composition 6 contains urethane acrylate having a glass transition temperature of 17 ° C. or higher or no glass transition temperature, the formed shaping layer 2 has increased heat resistance. As a result, when forming the hydrophilic inorganic layer 3 having self-cleaning properties by the ion plating method or the plasma chemical vapor deposition method, the shaping layer 2 is whitened by heat generated during plasma discharge, for example. Can be prevented.

  Hereinafter, each process of the manufacturing method of the transparent shaped film which concerns on this invention is demonstrated in detail.

<Preparation process>
The preparation step is a step of preparing the plastic substrate 1, the shaping plate 24, and the electron beam curable resin composition 6. In addition, about the electron beam curable resin composition 6, it explains in detail in the description column of the following composition installation process.

(Plastic substrate)
The plastic substrate 1 is not particularly limited as long as it has transparency and can form the shaping layer 2 thereon. From the standpoint of actual use, a plastic substrate 1 made of a polyester resin, a cycloolefin polymer, triacetyl cellulose (TAC), or the like can be given. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), copolymers thereof, and polycyclohexanedimethylene terephthalate (PCT). Among the polyester resins, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and copolymers thereof are preferable, and polyethylene naphthalate and polyethylene terephthalate are particularly preferable. Examples of the cycloolefin polymer include a norbornene polymer, a cyclopentene polymer, a cyclobutene polymer, and the like. Among these, a norbornene polymer can be preferably exemplified.

  When a polyester resin is applied as the material of the plastic substrate 1, the plastic substrate 1 may be entirely made of a polyester resin, or the surface S1 on the side on which the shaping layer 2 is formed (see FIG. 1 and FIG. 1). A laminated plastic substrate 1 in which at least a polyester resin layer is formed may be used (see FIG. 2). In this laminated plastic substrate 1, layers other than the polyester resin layer on which the shaping layer 2 is formed may not be a polyester resin layer. As a layer other than the polyester resin layer, various resin layers can be selected in consideration of heat resistance, thermal expansion, light transmittance, and the like.

  Although the thickness of the plastic base material 1 is not specifically limited, It is preferable that it is a grade of 10 micrometers or more and 500 micrometers or less. The plastic substrate 1 may be called a film shape or a sheet shape depending on its thickness. The plastic substrate 1 preferably has a total light transmittance of 80% or more. By setting the total light transmittance to 80% or more, the transparent shaped film 10 can be preferably used for applications requiring transparency.

  Such a plastic substrate 1 may be prepared by purchasing a commercially available product, or may be prepared by producing it on its own. As a manufacturing method of the plastic substrate 1, a conventionally known manufacturing method can be applied, and examples thereof include a solution casting method, a melt extrusion method, and a calendar method. The surface of the plastic substrate 1 may be any one or two selected from corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, heat treatment, chemical treatment, and easy adhesion treatment as necessary. The above surface treatment may be performed. As a specific method of such surface treatment, a conventionally known method can be appropriately used.

(Primer layer)
The primer layer may be provided as a base layer of the shaping layer 2 on the plastic substrate 1 on the side where the shaping layer 2 is provided, if necessary. The primer layer is not an essential component, but it can improve the weather resistance of the transparent shaped film 10 by adding a weathering agent such as an ultraviolet absorber, or improve the adhesion between the plastic substrate 1 and the shaped layer 2. It is preferably provided for the purpose.

  The primer layer-forming resin composition for forming the primer layer is not particularly limited as long as it contains a resin that can form the primer layer that can achieve the above-described purpose. Among these, from the viewpoint of adhesion to the shaping layer 2, it is preferable to include a resin having a radical polymerizable unsaturated group. Examples of the resin having a radical polymerizable unsaturated group include resins similar to various monomers, oligomers and prepolymers used as a material for forming the shaping layer 2 described later. The polymer which the polymer polymerized can be mentioned. Among these, urethane acrylate resins can be preferably used in terms of adhesion to the shaping layer 2 and weather resistance. Preferred examples of the urethane acrylate resin include a polycarbonate urethane-acrylic copolymer resin.

  Depending on the type of resin contained in the primer layer forming resin composition, it is desirable that the primer layer forming resin contain a curing agent or the like. For example, by using a urethane-based resin and an isocyanate-based curing agent, a urethane bond can be generated to cure the primer layer forming resin composition. As an example, when a polycarbonate urethane-acrylic copolymer resin is used as the resin composition for forming a primer layer, for example, it is preferable to cause a curing reaction using an isocyanate curing agent such as hexamethylene diisocyanate.

  The primer layer forming resin composition preferably contains the same ultraviolet absorber as that contained in the shaping layer 2 as a weathering agent. Moreover, other weathering agents, such as a reactive weathering agent and a light stabilizer, may be contained as needed. The primer layer formed of the resin composition for forming a primer layer containing a weathering agent can cause photo-oxidative degradation of the primer layer even when the transparent shaped film 10 is in an environment exposed to ultraviolet rays. Can be suppressed. Furthermore, when the primer layer is provided on the side irradiated with ultraviolet rays from the shaping layer 2, the primer layer functions as an ultraviolet absorbing layer and absorbs ultraviolet rays. Reaching can be reduced. As a result, the shaping layer 2 can be prevented from being photooxidatively deteriorated by ultraviolet rays due to the presence of the primer layer, and good weather resistance can be imparted to the transparent shaped film 10. For these weathering agents such as ultraviolet absorbers, reactive weathering agents, and light stabilizers, photooxidation deterioration is the same as that explained in the explanation section of the shaping layer 2 described later.

  Examples of ultraviolet absorbers include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, acrylonitrile-based ultraviolet absorbers, and among them, triazine-based ultraviolet absorbers are preferred. Moreover, the ultraviolet absorber which has reactive functional groups, such as an acryloyl group, in a molecule | numerator can also be used. Examples of the ultraviolet absorber having a reactive functional group include (2-hydroxy-4- (methacryloyloxyethoxy) benzophenone) methyl methacrylate copolymer.

  The content of the UV absorber contained in the primer layer forming resin composition is arbitrarily set according to the UV absorbing ability of the UV absorber, but is 0 with respect to the resin constituting the primer layer forming resin composition. It is preferably 1% by mass or more and 30% by mass or less. When the primer layer-forming resin composition contains an ultraviolet absorber in this range, the transparent shaped film 10 is provided with good weather resistance even under an environment where ultraviolet rays reach the formed primer layer. Can do. The content of the ultraviolet absorber is more preferably 0.1% by mass or more and 15% by mass or less. In addition, the ultraviolet absorber contained in the resin composition for primer layer formation may be used individually by 1 type, and may be used in combination of 2 or more type. The content when two or more ultraviolet absorbers are combined is the total content thereof.

  The primer layer forming resin composition may contain a light stabilizer as another weathering agent. Since the light stabilizer acts to trap radicals generated when the primer layer formed with the primer layer-forming resin composition, for example, is irradiated with ultraviolet rays, the resin composition for forming the primer layer is combined with the above-described ultraviolet absorber. It is preferable to make it contain. As the light stabilizer, for example, a hindered amine light stabilizer is preferable, and a hindered amine light stabilizer having a reactive functional group is particularly preferably used. Specific examples include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate.

  The content of the light stabilizer contained in the primer layer forming resin composition is arbitrarily set according to the radical scavenging ability of the light stabilizer, but for the resin constituting the primer layer forming resin composition, It is preferable that it is 0.1 mass% or more and 20 mass% or less. When the primer layer forming resin composition contains a light stabilizer in this range, the transparent shaped film 10 has good weather resistance even under an environment where ultraviolet rays reach the primer layer formed with the resin composition. Sex can be imparted. In addition, the light stabilizer contained in the resin composition for primer layer formation may be used individually by 1 type, and may be used in combination of 2 or more type. The content when two or more light stabilizers are combined is the total content thereof.

  In the ultraviolet absorber having a reactive functional group or the light stabilizer having a reactive functional group, the reactive functional group is bonded to a resin component constituting the primer layer. Therefore, the ultraviolet absorber or light stabilizer having a reactive functional group can be prevented from bleeding out to the surface of the primer layer after it is formed, and the ultraviolet absorber or light stabilizer in the primer layer can be prevented by bleeding out. It can be prevented from decreasing with time. Further, it is possible to prevent the adhesion between the primer layer and the shaping layer 2 due to the deposition of the ultraviolet absorber or the light stabilizer between the primer layer and the shaping layer 2.

  The primer layer can be formed by applying the primer layer forming resin composition onto the plastic substrate 1 by a conventionally known method and then curing the applied primer layer forming resin composition. Examples of such coating methods include roll coating, gravure roll coating, kiss roll coating, reverse roll coating, Miya bar coating, gravure coating, spin coating, dip coating, spray coating, and curtain coating. And various printing methods such as a method, a flow coating method, a die coating method, screen printing, and gravure printing. The thickness of the primer layer is not particularly limited, and is usually 1 μm or more and 10 μm or less.

(Shaped version)
The shaping plate 24 is not particularly limited as long as it has various uneven shapes and can impart the intended shaping shape to the shaping layer 2. Such a shaped plate 24 can usually include a plate-shaped plate or a cylindrical plate. The uneven | corrugated shape provided in the shaping plate 24 is not specifically limited, For example, what is necessary is just to become the inversion shape of the shaping shape of the above-mentioned transparent shaping film 10. FIG.

  The shape provided on the shaping plate 24 is appropriately designed in consideration of the optical characteristics of the shaping shape to be formed on the shaping layer 2 as shown in FIGS. 2 (A) to (C), for example. The As the shaping shape to be provided in the shaping layer 2, for example, the prism 5A shown in FIG. 2 (A), the Fresnel lens 5B shown in FIG. 2 (B), or the lenticular lens 5C shown in FIG. 2 (C). Etc.

  When the prism 5A shown in FIG. 2A is formed on the shaping layer 2, the prism 5A has a main cut surface (a cross section orthogonal to the ridge line) in a triangular or substantially triangular shape and has a ridge line at the top. An example is one in which a large number of unit prisms 4 are arranged in parallel in a direction perpendicular to the ridgeline. The cross-sectional shape of the unit prism 4 is not limited to a triangle or a substantially triangular shape, and may be a polygon such as a quadrangle, a pentagon, a hexagon, or an octagon, or a shape having a curvature in the vicinity of the apex of a sector or a triangle. The combination shape of a straight line and a curve may be used. The angle at the top of the unit prism 4 is not particularly limited, and is, for example, about 80 ° to 110 °. Further, the pitch of the unit prisms 4 arranged is not particularly limited, and is, for example, about 10 μm or more and 300 μm or less.

  When the Fresnel lens 5B shown in FIG. 2B is formed on the shaping layer 2, examples of the Fresnel lens 5B include a general Fresnel lens shape in which convex lenses are divided and arranged in a plane. The Fresnel center of the Fresnel lens 5B may be in the plane of the transparent shaped film 10B or out of the plane.

  When the lenticular lens 5C shown in FIG. 2C is formed on the shaping layer 2, the lenticular lens 5C may have a semi-cylindrical shape (also referred to as “kamaboko shape”) or a hemispherical lens shape. (It is also referred to as “a moth-eye shape” or “moth-eye shape”). The semi-cylindrical lenticular lens 5C has a one-dimensional array (linear array) structure in which kamaboko shapes are arranged in a one-dimensional direction, and the hemispherical lens-shaped lenticular lens 5C has a two-dimensional direction (vertical and horizontal directions). It is an arrayed two-dimensional array structure. A polyhedral cylindrical shape may be used instead of the semicylindrical shape, and a polyhedral lens shape may be used instead of the hemispherical lens shape.

<Composition installation process>
The composition installation step is a step of providing the electron beam curable resin composition 6 between the plastic substrate 1 and the shaping plate 24. In this step, as shown in FIG. 3, the electron beam curable resin composition 6 is brought into direct contact with the shaping plate 24 and the plastic substrate 1 and the shaping plate are interposed via the electron beam curable resin composition 6. 24, and is not particularly limited as long as it is such a step.

  For example, as shown in FIG. 3, the electron beam curable resin composition 6 is applied from the T-die nozzle 21 to the shaping plate 24 on the surface of the molding drum 23, and then applied. The plastic substrate 1 is pressed against 6 and pressed by the pressing roll 22. By doing so, the electron beam curable resin composition 6 can be provided between the plastic substrate 1 and the shaping plate 24. Although not shown, the electron beam curable resin composition 6 may be applied on the plastic substrate 1, and then the shaping plate 24 may be pressed against the applied electron beam curable resin composition 6, The plastic substrate 1 and the shaping plate 24 may be disposed so as to face each other, and the electron beam curable resin composition 6 may be supplied therebetween. Moreover, you may apply the means which does not press the plastic base material 1 or the shaping plate 24 to the electron beam curable resin composition 6. FIG. For example, the plastic base material 1, the shaping plate 24, and the electron beam curable resin composition 6 may be arbitrarily stacked, stacked, or bonded together.

  As a method of applying the electron beam curable resin composition 6 onto the shaping plate 24 or the plastic substrate 1, a conventionally known application method can be applied. Examples of the coating method include a roll coating method, a gravure roll coating method, a kiss roll coating method, a reverse roll coating method, a Miya bar coating method, a gravure coating method, a spin coating method, a dip coating method, a spray coating method, and a curtain coating method. And various printing methods such as a flow coating method, a die coating method, screen printing, and gravure printing.

  The electron beam curable resin composition 6 is a resin composition for forming the shaping layer 2. And the electron beam curable resin composition 6 contains at least urethane acrylate and an ultraviolet absorber.

(Urethane acrylate)
Urethane acrylate has a glass transition temperature (Tg) of 17 ° C. or higher or no glass transition temperature, and a viscosity at 60 ° C. of 2000 mPa · s to 24000 mPa · s. Urethane acrylate having such characteristics is a monomer, oligomer or prepolymer of urethane acrylate. For example, commercially available products include UV-7000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), UV-7650B (Nippon Synthetic Chemical Industry Co., Ltd.) Company), UV-7600B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), UV-7630B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), UV-7630B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), UV-7640B (manufactured by Nippon Synthetic Chemical Industry) Kogyo Co., Ltd.), EBECRYL284 (Daicel Cytec Co., Ltd.), EBECRYL8701 (Daicel Cytec Co., Ltd.), and the like can be preferably exemplified. Further, other urethane acrylates having the same or similar characteristics as these and exhibiting the same or similar functions and effects may be used. These urethane acrylates may be used singly or in combination of two or more. In addition, as for the urethane acrylate, it is desirable for the hardened | cured material to have transparency, and can comprise a transparent shaping film.

  In the present application, “acrylate” such as urethane acrylate and epoxy acrylate includes methacrylate such as urethane methacrylate and epoxy methacrylate, and “acryloyl group” includes methacryloyl group.

  Urethane acrylate has a glass transition temperature (Tg) of 17 ° C. or higher or does not exhibit a glass transition temperature. The shaping layer 2 formed of the electron beam curable resin composition 6 containing a urethane acrylate having a glass transition temperature of 17 ° C. or higher or a urethane acrylate not exhibiting a glass transition temperature can be seen from the results of Examples described later. Even after the inorganic layer 3 was formed, no whitening occurred. This is probably because the heat resistance of urethane acrylate has been improved. More specifically, the phenomenon in which whitening occurs in the transparent shaped film 10 is caused by heat at the time of plasma discharge that occurs when the inorganic layer 3 is formed by ion plating or plasma chemical vapor deposition (plasma CVD). It is considered that the structure derived from the urethane acrylate of the shaping layer 2 becomes fluid and causes fine distortion and deformation on the surface and inside of the shaping layer 2. Therefore, the visible light irradiated on the transparent shaped film 10 may be scattered at the interface between the shaped layer 2 and the inorganic layer 3 where fine distortion or deformation has occurred, or may be scattered at the surface of the inorganic layer 3. Thus, it is considered that the transparent shaped film 10 is whitened. Urethane acrylate having a glass transition temperature (Tg) of 17 ° C. or higher or not exhibiting a glass transition temperature can be said to have high heat resistance. By using such urethane acrylate, plasma discharge during film formation of the inorganic layer 3 is achieved. It is considered that fine distortion and deformation were prevented from occurring in the shaping layer 2 due to the heat generated from the above and the whitening was solved. As a result, since the transparency of the shaping layer 2 can be maintained, the transparent shaping film 10 having high transparency in which whitening is suppressed can be produced.

  The glass transition temperature of urethane acrylate should just be 17 degreeC or more. Depending on the measuring method or measuring apparatus of the glass transition temperature, it may not be possible to measure the glass transition temperature within the measurement temperature range. In the present application, a urethane acrylate having a glass transition temperature of 17 ° C. or higher and a glass transition temperature that cannot be measured is referred to as “a urethane acrylate that does not exhibit a glass transition temperature”. When the glass transition temperature is measured in a temperature range of, for example, −50 ° C. to 100 ° C., urethane acrylate that does not show the glass transition temperature in this measurement temperature range can be said to have a glass transition temperature of 100 ° C. or higher. It can be said that the glass transition temperature is not shown within the measurement temperature range, and can be applied as the urethane acrylate constituting the present invention. The upper limit of the glass transition temperature is not particularly limited because it depends on the measuring method or measuring apparatus of the glass transition temperature, but for example, about 220 ° C. can be mentioned. In addition, glass transition temperature (Tg) can be calculated | required with the measuring method based on JISK7121, for example using a suggestive calorimeter (DSC, Shimadzu Corporation make, model number: DSC-60).

  The viscosity of urethane acrylate is 2000 mPa · s or more and 24000 mPa · s or less at 60 ° C. The electron beam curable resin composition 6 containing urethane acrylate having such a viscosity range can form the shaping layer 2 having a desired shaping shape with the shaping plate 24 with high accuracy. The viscosity of urethane acrylate is measured using a BL adapter and M4 rotor using a B-type viscometer (for example, manufactured by Toki Sangyo Co., Ltd., trade name: VISCOMETER) according to JIS K7117-1. It can be determined by measuring for 1 minute after 30 seconds.

  When the viscosity of urethane acrylate at 60 ° C. is less than 2000 mPa · s, the shapeability of the formed shaping layer 2 deteriorates, for example, the shape of the top of the unit prism 4 is rounded, and the shaping layer 2 However, the shape may not be the same as that of the shaping plate 24. The reason for this is that urethane acrylate having a viscosity at 60 ° C. of less than 2000 mPa · s is a relatively low molecular weight, so that the urethane acrylate cure shrinkage when urethane acrylate is cured in the shaping layer forming step described later. It is thought that it is to become.

  When the viscosity of urethane acrylate at 60 ° C. exceeds 24,000 mPa · s, the releasability of the formed shaping layer 2 may be deteriorated. Specifically, the adhesion between the shaping layer 2 and the shaping plate 24 becomes too high, and the shaping layer 2 cannot be peeled off from the shaping plate 24 in the peeling step described later, or the shaping layer 2 is shaped. When the shaping layer 2 is peeled off from the plate 24, the intended shaping shape may not be formed in the shaping layer 2. The reason why the adhesion between the shaping layer 2 and the shaping plate 24 becomes too high is that the urethane acrylate having a viscosity at 60 ° C. exceeding 24,000 mPa · s has a relatively large molecular weight, and therefore the electron beam curability containing the urethane acrylate. This is considered to be because the adhesion between the shaping layer 2 formed with the resin composition 6 and the shaping plate 24 is increased.

  Urethane acrylate has an acryloyl group, but the number of acryloyl groups is not particularly limited. The number of acryloyl groups is usually 2 or more and 8 or less. When the number of acryloyl groups exceeds 8, there is a possibility that the curing shrinkage of the shaping layer 2 becomes large, and the shaping property may be deteriorated.

  The number average molecular weight of the urethane acrylate is not particularly limited, but is preferably 500 or more and 10,000 or less, and more preferably 1000 or more and 5000 or less. When the number average molecular weight of the urethane acrylate is less than 1000, the crosslinking density after curing is usually likely to be high, so that the curing shrinkage of the urethane acrylate when the urethane acrylate is cured in the shaping layer forming step described later increases. It is easy and the shaping property of the shaping layer 2 may deteriorate. On the other hand, when the number average molecular weight of the urethane acrylate exceeds 10,000, the adhesiveness between the formed shaping layer 2 and the shaping plate 24 is increased, so that the releasability may be deteriorated. In addition, the value of polystyrene conversion by gel permeation chromatography (GPC) can be used for the number average molecular weight.

  Such urethane acrylate is preferably contained in the electron beam curable resin composition 6 by 50% by mass or more, more preferably 65% by mass or more, and further preferably 80% by mass or more. That is, if the urethane acrylate is contained in the electron beam curable resin composition 6 at least half or more, the above-described effect of the urethane acrylate can be obtained, and as the content increases as described above, This is preferable because the effect of the urethane acrylate can be exhibited more. Further, since urethane acrylate has a flexible skeleton structure, the electron beam curable resin composition 6 is formed of the electron beam curable resin composition 6 by including such urethane acrylate in the above content. The shaping layer 2 has an advantage that it is difficult to become brittle. On the other hand, although different from the present invention, a shaping layer formed of an acrylic resin tends to be hard and brittle. In addition, the urethane acrylate contained in the electron beam curable resin composition 6 may be used individually by 1 type, and may be used in combination of 2 or more type. The content when two or more urethane acrylates are combined is the total content thereof.

(UV absorber)
The ultraviolet absorber is contained in the electron beam curable resin composition 6 as one of weathering agents for enhancing the weather resistance of the transparent shaped film 10. Since the electron beam curable resin composition 6 contains an ultraviolet absorber, even if the shaping layer 2 formed of the electron beam curable resin composition 6 is irradiated with ultraviolet rays or the like from the outside, The shape layer 2 can be prevented from being colored or fragile. The phenomenon that the shaping layer 2 is colored or becomes brittle is also called “photooxidation degradation”. If the shaped layer 2 subjected to photooxidation degradation is further exposed to ultraviolet rays, photooxidation degradation may be further promoted. In the present invention, the electron beam curable resin composition 6 for forming the shaping layer 2 is at least Since it contains an ultraviolet absorber and further preferably includes other weathering agents such as a hindered amine light stabilizer as necessary, even if the shaping layer 2 composed of the electron beam curable resin composition 6 is exposed to ultraviolet rays. The weathering agent such as an ultraviolet absorber contained in the shaping layer 2 acts to suppress the progress of photo-oxidative deterioration.

  The ultraviolet absorber is for absorbing ultraviolet rays contained in natural light or the like. The ultraviolet absorber is not particularly limited as long as such an object can be achieved, and conventionally known ones can be used. For example, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, a salicylate ultraviolet absorber, an acrylonitrile ultraviolet absorber, and the like can be given.

  Of these, triazine-based ultraviolet absorbers are preferred. Triazine-based ultraviolet absorbers have the advantage that they have a high ultraviolet-absorbing ability and are not easily deteriorated by high energy such as ultraviolet rays. Specific examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tri [{3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl} methyl], And benzotriazole-based ultraviolet absorbers. Specific examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, Examples include 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol.

  As the ultraviolet absorber, an ultraviolet absorber having a reactive functional group such as an acryloyl group in the molecule can be used. Examples of the ultraviolet absorber having a reactive functional group include (2-hydroxy-4- (methacryloyloxyethoxy) benzophenone) methyl methacrylate copolymer.

  Such an ultraviolet absorber may be contained alone in the electron beam curable resin composition 6 as a weathering agent, or other weathering agents such as an ultraviolet absorber having the following reactive functional group and a light stabilizer. It may be included with the agent. The content of the ultraviolet absorber contained in the electron beam curable resin composition 6 is arbitrarily set according to the ultraviolet absorbing ability of the ultraviolet absorber, but is 0. It is preferable that they are 1 mass% or more and 20 mass% or less. When the shaping layer 2 contains the ultraviolet absorber within this range, the transparent shaping film 10 is provided with good weather resistance even under the environment where ultraviolet rays reach the shaping layer 2 after being formed. can do. The content of the ultraviolet absorber is more preferably 0.1% by mass or more and 15% by mass or less, and particularly preferably 0.1% by mass or more and 10% by mass. By forming the shaping layer 2 using the electron beam curable resin composition 6 containing the ultraviolet absorber in such a range, the transparent shaped film 10 showing better weather resistance can be produced. In addition, the ultraviolet absorber contained in the electron beam curable resin composition 6 may be used individually by 1 type, and may be used in combination of 2 or more type. The content when two or more ultraviolet absorbers are combined is the total content thereof.

  The electron beam curable resin composition 6 may contain a light stabilizer as another weathering agent. Even if the light stabilizer is a case where radicals are generated by applying ultraviolet rays to the shaping layer 2 after being formed, the light stabilizer can capture the radicals. As a result, deterioration of the shaped layer due to radicals can be suppressed, and weather resistance can be further improved. It is preferable that the light stabilizer is contained in the electron beam curable resin composition 6 together with the ultraviolet absorber described above. As the light stabilizer, for example, a hindered amine light stabilizer (HALS) is preferable, and when a free radical that causes an oxidation reaction is generated in the shaped layer 2 after it is formed, the free radical is captured and stabilized. It can be made.

  Specific examples of hindered amine light stabilizers include bis (1,2,2,6,2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate). 6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4 -Yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- Butante La carboxylate, can be mentioned 1,2,2,6,6-pentamethyl-4-piperidinyloxy methacrylate. Further, a hindered amine light stabilizer having a reactive functional group may be used, and specific examples include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate.

  The content of the light stabilizer contained in the electron beam curable resin composition 6 is arbitrarily set according to the radical scavenging ability of the light stabilizer. For example, the hindered amine light stabilizer is an electron beam curable resin composition. It is preferable to contain 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more, It is particularly preferable to contain 10% by mass or less. When the electron beam curable resin composition 6 contains a hindered amine light stabilizer in this range, the transparent shaping film 10 is good even in an environment where ultraviolet rays reach the shaping layer 2 after being formed. Weather resistance can be imparted. In addition, the light stabilizer contained in the electron beam curable resin composition 6 may be used individually by 1 type, and may be used in combination of 2 or more type. The content when two or more light stabilizers are combined is the total content thereof.

  In the ultraviolet absorber having a reactive functional group or the light stabilizer having a reactive functional group, the reactive functional group is bonded to the resin component constituting the shaping layer 2. Therefore, it is possible to prevent the ultraviolet absorber or light stabilizer having a reactive functional group from bleeding out on the surface of the shaping layer 2, and the ultraviolet absorber or the light stabilizer in the shaping layer 2 is deteriorated by bleed-out. Therefore, it is preferable to use it as necessary. Furthermore, it is possible to prevent the adhesion between the shaping layer 2 and the inorganic layer 3 due to precipitation of an ultraviolet absorber or a light stabilizer between the shaping layer 2 and the inorganic layer 3. Further, when the primer layer is provided, it is possible to prevent the adhesive property between the primer layer and the shaping layer 2 from being lowered due to the deposition of the ultraviolet absorber or the light stabilizer between the primer layer and the shaping layer 2. be able to.

  As described above, the electron beam curable resin composition 6 includes an ultraviolet absorber as an essential weathering agent, and the light stabilizer is included as a preferable weathering agent in combination with the ultraviolet absorber. Other weathering agents may be contained within a range not impairing the gist of the present invention.

(Release agent)
A mold release agent is contained in the electron beam curable resin composition 6 as needed. By including this release agent in the electron beam curable resin composition 6, the mold release property at the time of the peeling process of peeling the shaping layer 2 formed of the electron beam curable resin composition 6 from the shaping plate 24. Can be improved. As a result, it is possible to prevent the occurrence of cracks and cracks that may occur when the shaping layer 2 is peeled off. The release agent is not particularly limited as long as this object can be achieved, and examples thereof include silicone release agents, fluorine release agents, and phosphoric acid release agents. Among these, from the viewpoint of releasability, a phosphoric acid type release agent can be preferably mentioned. Examples of the phosphoric acid release agent include a phosphoric acid release agent and a phosphate ester release agent. Examples of the phosphoric acid type release agent include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 3-methyl-1 -Phenyl-2-phospholene-1-oxide, and phospholene oxides such as these 3-phospholene isomers; triphenylphosphine, tris- (2,4-di-t-butylphenyl) phosphite, brominated tetraethylphosphine And one or more selected from chlorinated tetraethylphosphine and the like. Examples of the phosphoric acid ester release agent include di-2-ethylhexyl hydrogen phosphite, dilauryl hydrogen phosphite, dialkyl hydrogen phosphite, dioleyl hydrogen phosphite, triisooctyl phosphite, diphenyl iso phosphite. 1 selected from decyl phosphite, phenyl diisodecyl phosphite, triisodecyl phosphite, trialkyl phosphite, trioleyl phosphite, tristearyl phosphite, trilauryl trithiophosphite, methyl acid phosphate and ethyl acid phosphate A seed | species or 2 or more types can be mentioned.

  The release agent is preferably contained in an amount of 0.01% by mass or more and 20% by mass or less, and preferably 0.01% by mass or more and 10% by mass or less with respect to the electron beam curable resin composition 6. The content is more preferably 0.01% by mass or more and 5% by mass or less. When the electron beam curable resin composition 6 contains a release agent in such a range, the release property of the shaping layer 2 after being formed can be further improved. The content of the release agent can be appropriately changed according to the release ability. In addition, as a quantification method of the weathering agent and mold release agent in the electron beam curable resin composition 6, it can obtain | require by a gas chromatography mass spectrometry, for example.

(Other ingredients)
The electron beam curable resin composition 6 may contain other resins in addition to the urethane acrylate. Such a resin is not particularly limited as long as it is a radically polymerizable compound that can be crosslinked by irradiation with an electron beam. For example, radically polymerizable compounds such as an acryloyl group, a vinyl group, an allyl group, and an isopropenyl group. One type or two or more types selected from monomers having an unsaturated group (monomers), oligomers and prepolymers can be mentioned. Examples of such oligomers and prepolymers include pentaerythritol acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, polyethylene acrylate, polybutadiene acrylate, silicone acrylate, and polyol acrylate. These may be used alone or in combination of two or more.

  Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers and polyfunctional monomers. Although it does not specifically limit as a monofunctional monomer, For example, vinyl monomers, such as N-vinyl pyrrolidone, N-vinyl caprolactone, vinyl imidazole, vinyl pyridine, styrene; Phenoxyethyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, Ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxydipropylene glycol acrylate, balacyl phenoxyethyl acrylate, nonylphenoxy polyethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isooctyl acrylate, cyclohexyl acrylate, Benzyl Acryl , Ortho-phenyl phenoxyethyl acrylate, N, N-dimethylacrylamide, N, N-dimethylaminopropyl acrylate, acrylate monomers such as acryloyl morpholine; and the like can be given; acrylamide derivatives. Polyfunctional monomers include pentaerythritol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, butane Diol diacrylate, hexanediol diacrylate, nonanediol diacrylate, pentanediol diacrylate, neopentyl glycol diacrylate, dimethylol-tricyclodecane diacrylate, hydroxypivalate neopentyl glycol diacrylate, bisphenol A polyethoxydiol diacrylate Bisphenol A Ripropoxydiol diacrylate, trimethylolpropane triacrylate, glyceryl triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexa Examples thereof include acrylates and the like, ethylene oxide-modified products, propylene oxide-modified products, and caprolactan-modified products. These monomers may be used alone or in combination of two or more. Moreover, the oligomer produced | generated by combining such a monomer may be sufficient.

  Moreover, you may add an additive to the electron beam curable resin composition 6 as needed within the range which does not inhibit the effect of this invention. Examples of the additive include a heat stabilizer, an antifoaming agent, a leveling agent, a plasticizer, a surfactant, an antistatic agent, an antioxidant, an ultraviolet absorber, an infrared absorber, a pigment (colored dye, colored pigment), Examples include extender pigments, light diffusing agents, and coupling agents. In addition, since the electron beam curable resin composition 6 is a resin composition that is cured by an electron beam, photopolymerization initiation of an acetophenone compound, an acyl phosphooxide compound, and the like added to the resin composition that is cured by an ultraviolet ray is started. The agent is not included.

<Shaping layer forming process>
The shaping layer forming step is a step of forming the shaping layer 2 by irradiating an electron beam to cure the electron beam curable resin composition 6. In this step, for example, as shown in FIG. 3, the electron beam curable resin composition provided between the shaping plate 24 and the plastic substrate 1 and in contact with the shaping plate 24 and the plastic substrate 1. 6 is irradiated with an electron beam. In the example of FIG. 3, the electron beam source 27 of the electron beam irradiation apparatus 26 is used as the electron beam source, and the electron beam is irradiated from the plastic substrate 1 side.

  As the electron beam source 27, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type are used. The electron beam is an electron beam, an electromagnetic wave such as an X-ray or a γ-ray, a charged particle beam such as an α-ray, and the electron beam curable resin composition 6 is irradiated with an electron beam. It is a resin composition containing a resin that is cured by crosslinking.

  The formed shaping layer 2 may be a single layer or two or more layers, and in any case, it is formed by irradiation with an electron beam. Since the shaping layer 2 formed by irradiating the electron beam is considered to be more closely cross-linked, the transparent shaped film 10 having better weather resistance can be produced.

  The thickness of the shaping layer 2 is not particularly limited, and may be arbitrarily formed within a range of 0.01 μm or more and 500 μm or less, regardless of whether it is a single layer or two or more layers, and is usually 0.1 μm or more and 200 μm or less. Degree. In addition, the thickness of the shaping layer 2 means the value of the location where the thickness of the shaping layer 2 becomes the maximum.

  In the present invention, as described above, since the viscosity of the urethane acrylate contained in the electron beam curable resin composition 6 at 60 ° C. is 2000 mPa · s or more, the shaped layer 2 after being formed has a good shape. Can show shape. Therefore, the formed shaping layer 2 does not have a problem that the shape of the top of the unit prism 4 is rounded or the shaping layer 2 does not have the same shape as the shaping plate 24. The shaping layer 2 can be formed with high accuracy.

<Peeling process>
The peeling step is a step of peeling the plastic substrate 1 and the shaping layer 2 from the shaping plate 24. In the example of FIG. 3, the plastic substrate 1 and the shaping layer 2 are peeled from the shaping plate 24 by the peeling roll 25. As a result, a laminate in which the shaping layer 2 is provided on the plastic substrate 1 can be obtained.

  In the present invention, as described above, since the urethane acrylate contained in the electron beam curable resin composition 6 has a viscosity at 60 ° C. of 24000 mPa · s or less, the releasability of the shaping layer 2 after it is formed. Can be improved. Therefore, the formed shaping layer 2 has a problem that the shaping layer 2 cannot be peeled off from the shaping plate 24, or the shaping layer 2 may break when the shaping layer 2 is peeled off from the shaping plate 24. Thus, the problem that the desired shaped shape cannot be formed does not occur, so that the shaped layer 2 having the desired shape can be formed with high accuracy.

<Inorganic layer forming step>
The inorganic layer forming step is a step of forming the inorganic layer 3 on the shaping layer 2. The inorganic layer 3 is formed on the shaping layer 2 as a functional layer that improves the self-cleaning property of the transparent shaping film 10. The self-cleaning property is preferably exhibited when the inorganic layer 3 has hydrophilicity.

  Examples of the material for forming the inorganic layer 3 include one or more inorganic compounds selected from oxides, oxynitrides, nitrides, oxycarbides, oxycarbonitrides, and the like. Specific examples include inorganic compounds containing one or more elements selected from silicon, aluminum, magnesium, titanium, tin, indium, cerium, and zinc, and more specifically, oxidation. Examples include oxides such as silicon, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, silicon zinc oxide, and indium alloy, nitrides such as silicon nitride, aluminum nitride, and titanium nitride, and oxynitrides such as silicon oxynitride. be able to. Particularly preferably, the inorganic layer 3 is an inorganic compound layer composed of one or more selected from silicon oxide, silicon nitride, silicon oxynitride, and silicon zinc oxide. The inorganic layer 3 may use the said material independently, and may mix and use the said material in arbitrary ratios within the range of the summary of this invention.

  Although the thickness of the inorganic layer 3 varies depending on the inorganic compound to be used, it is usually 5 nm or more, preferably 10 nm or more, and is usually 5000 nm or less, preferably 500 nm or less, from the viewpoint of suppressing the occurrence of cracks and the like. More preferably, it is 300 nm or less. The inorganic layer 3 may be a single layer or two or more inorganic layers 3 having a total thickness within the above range. In the case of two or more inorganic layers 3, the same materials may be combined or different materials may be combined.

  The inorganic layer 3 is formed by an ion plating method or a plasma chemical vapor deposition method (plasma CVD method). In the ion plating method and the plasma CVD method, when the inorganic layer 3 is formed on the shaping layer 2 by the film forming means in which plasma discharge occurs during film formation and heat is generated during the plasma discharge, the conventional shaping is performed. Layer 2 was whitened due to the heat. However, in the present application, since a characteristic urethane acrylate having a glass transition temperature of 17 ° C. or higher or not exhibiting a glass transition temperature is used as a constituent material of the electron beam curable resin composition 6, film forming means for generating heat during plasma discharge is used. Even so, whitening caused by heat during the plasma discharge could be suppressed. Therefore, in the present invention, there is a remarkable effect when the inorganic layer 3 is formed by an ion plating method or a plasma CVD method. Moreover, even if it is a case where plasma discharge is performed in order to impart more hydrophilicity to the inorganic layer 3, the above-described whitening can be suppressed. Even in other PVD methods, when heat is generated at the time of film formation, whitening due to the heat may occur. The film forming conditions in these various forming methods may be adjusted by appropriately adjusting conventionally known film forming conditions in consideration of the physical properties and thickness of the inorganic layer 3 to be obtained.

  More specifically, the material is heated by a plasma beam generated by a plasma gun and deposited on a substrate, or an ion plating method in which the material is deposited on a substrate, or plasma in which a silicon oxide film is deposited on a substrate using an organosilicon compound or the like as a material. Chemical vapor deposition can be preferably used. In particular, plasma chemical vapor deposition is preferably applied from the viewpoint of the shape-following property of uniformly forming the inorganic layer 3 on the shape of the shaping layer 2.

<Other processes>
The method for producing the transparent shaped film 10 may include, for example, a step of forming an arbitrary functional layer on the inorganic layer 3 or the surface S2 on the side where the shaped layer 2 is not provided. As an optional functional layer, a conventionally known mat layer, protective layer, antistatic layer, smoothing layer, adhesion improving layer, light shielding layer, antireflection layer, hard coat layer, stress, as long as the features of the present invention are not impaired. Examples include a relaxation layer, an antifogging layer, an antifouling layer, a printing layer, and an easy adhesion layer. A conventionally well-known formation method can be applied to the formation process of such a functional layer.

  As shown in FIG. 1, the transparent shaped film 10 produced by such a production method includes at least a plastic substrate 1, a shaped layer 2, and an inorganic layer 3. Moreover, the transparent shaped film 10 may have the above-described functional layer.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.

[Example 1]
As a plastic substrate 1, a polyethylene terephthalate film (trade name: Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm was used, and a plastic substrate 1 provided with a primer layer on one side thereof was prepared. As the shaping plate 24, a die plate was prepared in which the cross-section of the shaping shape was an isosceles triangle, the groove depth was 20 μm, and parallel lines with a pitch width of 50 μm were carved. For the plastic substrate 1 provided with a primer layer (not shown) on one side S1, a primer layer forming resin composition having the following composition is applied to one side S1 of the plastic substrate 1 with a Miyabar, and then 30 ° C. at 30 ° C. It was dried for 2 seconds, and a primer layer having a thickness of 3 μm was provided. After the electron beam curable resin composition A having the following composition is applied to the above-mentioned shaping plate 24 with an applicator, the applied electron beam curable resin composition A and the primer layer of the plastic substrate 1 described above are applied. The surface S1 provided with was bonded with a roller. Then, using an electron beam irradiator (trade name: low acceleration energy irradiator manufactured by Iwasaki Electric Co., Ltd.) from the plastic substrate side, the electron beam is irradiated under the conditions of 165 keV, 10 Mrad (100 kGy), and an electron beam curable resin. Composition A was cured to form shaping layer 2 having a thickness of 30 μm.

(Composition of primer layer forming resin composition)
Polycarbonate urethane-acrylic copolymer resin (mass ratio of polycarbonate urethane urethane component to acrylic component = 50: 50): 100 parts by mass Hydroxyphenyltriazine ultraviolet absorber (manufactured by BASF Japan Ltd., trade name: Tinuvin 479): 1.5 parts by mass Hindered amine light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd., trade name: Sanol LS-3410): 3 parts by mass Curing agent (hexane methylene diisocyanate): 6 parts by mass

(Composition of electron beam curable resin composition A)
Urethane acrylate (number of acryloyl groups per molecule: 2-3, number average molecular weight: 3500, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-7000B): 100 parts by mass Ultraviolet absorber (hydroxyphenyltriazine, BASF Japan Co., Ltd., trade name: Tinuvin 479): 2 parts by mass Phosphate ester release agent (SC Organic Chemicals, trade name: Chelex H-18D): 1 part by mass

  Next, the inorganic layer 3 was formed by the plasma CVD method. Specifically, it is set in a plasma CVD apparatus in a direction to form the shaping layer side of the plastic substrate 1 on which the shaping layer 2 is formed, and hexamethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a raw material gas. Oxygen gas and argon gas were prepared. The conditions of the plasma CVD method are a film formation pressure of 0.4 Torr, a film formation time of 1 minute, a discharge power of 200 W, and each gas is octamethylcyclotetrasiloxane: oxygen gas: argon gas = 1 sccm: 50 sccm: A silicon oxide layer having a thickness of 80 nm was formed as the inorganic layer 3 by supplying 5 sccm. In addition, as a result of measuring the composition ratio of the inorganic layer 3 of Example 1 by X-ray photoelectron spectroscopy using an X-ray photoelectron spectrometer (model number: ESCA-5600, manufactured by ULVAC-PHI), Si: O: C = 25:57:18 (unit: mol%). Further, sccm is an abbreviation for standard cubic centimeter per minute, and the same applies to the following examples and comparative examples.

[Example 2]
A hindered amine light stabilizer having a reactive functional group in the electron beam curable resin composition A (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd., trade name: Sanol A transparent shaped film of Example 2 was produced in the same manner as Example 1 except that 3 parts by mass of LS-3410) was blended.

[Example 3]
A transparent shaped film of Example 3 was produced in the same manner as in Example 1 except that the electron beam curable resin composition B prepared in the following composition was used. The electron beam curable resin composition B is the same as the electron beam curable resin composition A except that the types of ultraviolet absorbers are increased.

(Composition of electron beam curable resin composition B)
Urethane acrylate (number of acryloyl groups per molecule: 2-3, number average molecular weight: 3500, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-7000B): 100 parts by mass Hydroxyphenyltriazine-based ultraviolet absorber (BASF Made by Japan Co., Ltd., trade name: Tinuvin 479): 1 part by mass ・ Hydroxyphenyl triazine ultraviolet absorber (BASF Japan Ltd., trade name: Tinuvin 400): 1 part by mass ・ Hydroxyphenyl triazine ultraviolet absorber (BASF) Made by Japan Co., Ltd., trade name: Tinuvin 477): 1 part by mass • Hindered amine light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, Japan Emulsifier Stock Product name: Sanol LS-3410): 3 parts by mass Phosphate ester-based mold release agent (SC Organic Chemical Co., Ltd., trade name: Chelex H-18D): 1 part by weight

[Example 4]
The conditions of the plasma CVD method for forming the inorganic layer 3 are as follows: the film forming pressure is 0.1 Torr; the film forming time is 4 minutes; the discharge power is 200 W; each gas is replaced with octamethylcyclotetrasiloxane; Using methyldisiloxane, hexamethyldisiloxane: oxygen gas: argon gas = 1 sccm: 50 sccm: 3 sccm was supplied to form an 80 nm thick silicon oxide layer as the inorganic layer 3. Otherwise, the transparent shaped film of Example 4 was produced in the same manner as Example 1. In addition, as a result of measuring the composition ratio of the inorganic layer 3 in the same manner as in Example 1, it was Si: O: C = 24: 62: 14 (unit: mol%).

[Example 5]
Except for changing the urethane acrylate of the electron beam curable resin composition A to urethane acrylate (number of acryloyl groups per molecule: 2, number average molecular weight: 1200, manufactured by Daicel-Cytec Co., Ltd., trade name: EBECRYL284), A transparent shaped film of Example 5 was produced in the same manner as Example 1.

[Example 6]
Except for changing the urethane acrylate of the electron beam curable resin composition A to urethane acrylate (number of acryloyl groups per molecule: 3, number average molecular weight: 2000, manufactured by Daicel-Cytec Co., Ltd., trade name: EBECRYL8701), A transparent shaped film of Example 6 was produced in the same manner as Example 1.

[Example 7]
The urethane acrylate of the electron beam curable resin composition A is changed to urethane acrylate (number of acryloyl groups per molecule: 4 to 5, number average molecular weight: 2300, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-7650B). A transparent shaped film of Example 7 was produced in the same manner as Example 2 except that.

[Example 8]
The urethane acrylate of the electron beam curable resin composition A was changed to urethane acrylate (number of acryloyl groups per molecule: 6, number average molecular weight: 1400, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-7600B). A transparent shaped film of Example 8 was produced in the same manner as Example 2 except for the above.

[Example 9]
The urethane acrylate of the electron beam curable resin composition A is changed to urethane acrylate (number of acryloyl groups per molecule: 6 to 7, number average molecular weight: 2200, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-7630B). A transparent shaped film of Example 9 was produced in the same manner as Example 2 except that.

[Example 10]
The urethane acrylate of the electron beam curable resin composition A is changed to urethane acrylate (number of acryloyl groups per molecule: 6 to 7, number average molecular weight: 1500, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-7640B). A transparent shaped film of Example 10 was produced in the same manner as Example 2 except that.

[Example 11]
The transparent of Example 11 is the same as Example 2 except that the urethane acrylate of the electron beam curable resin composition A is changed to urethane acrylate (number of acryloyl groups per molecule: 6, number average molecular weight: 1000). A shaped film was produced.

[Example 12]
A transparent shaped film of Example 12 was produced in the same manner as in Example 1 except that the primer layer was not provided on the plastic substrate.

[Example 13]
A transparent shaped film of Example 13 was produced in the same manner as in Example 6 except that the primer layer was not provided on the plastic substrate.

[Example 14]
A transparent shaped film of Example 14 was produced in the same manner as in Example 2 except that the inorganic layer 3 was formed by an ion plating method using silicon oxide (SiO 2) as a deposition raw material. The ion plating method was performed using Ar gas as a process gas, a film forming pressure of 1.2 × 10 −2 Pa, and a film forming power of 9 kW. In addition, as a result of measuring the composition ratio of the inorganic layer in the same manner as in Example 1, it was Si: O: C = 29: 57: 14 (unit: mol%).

[Comparative Example 1]
The urethane acrylate of the electron beam curable resin composition A was changed to urethane acrylate (number of acryloyl groups per molecule: 2, number average molecular weight: 18000, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-3000B). Except for the above, a transparent shaped film of Comparative Example 1 was produced in the same manner as Example 1.

[Comparative Example 2]
Other than changing the urethane acrylate of the electron beam curable resin composition A to urethane acrylate (number of acryloyl groups per molecule: 1, number average molecular weight: 236, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: AMP-20GY) Produced the transparent shaped film of Comparative Example 2 in the same manner as in Example 1.

[Comparative Example 3]
The urethane acrylate of the electron beam curable resin composition A was changed to urethane acrylate (number of acryloyl groups per molecule: 2, number average molecular weight: 18000, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-7605B). Except for the above, a transparent shaped film of Comparative Example 3 was produced in the same manner as in Example 1.

[Comparative Example 4]
The urethane acrylate of the electron beam curable resin composition A was changed to urethane acrylate (number of acryloyl groups per molecule: 3, number average molecular weight: 3500, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV-7650B). Except for the above, a transparent shaped film of Comparative Example 4 was produced in the same manner as in Example 1.

[Measurement and evaluation]
For the urethane acrylates of Examples 1 to 13 and Comparative Examples 1 to 4, (a) measurement of glass transition temperature and (b) measurement of viscosity at 60 ° C were performed. Moreover, about the shaping layer 2 of Examples 1-13 and Comparative Examples 1-4, (c) evaluation of shaping property and (d) evaluation of mold release property were performed. Moreover, about the transparent shaped film of Examples 1-13 and Comparative Examples 1-4, (o) Observation of external appearance, (f) Measurement of hardness, (G) What passed 24 hours at normal temperature after manufacture, Exposure test Evaluation of self-cleaning properties after 6 months and after 250 hours of weather resistance test, (K) Color difference measurement between 24 hours at room temperature after manufacturing and 500 hours of weather resistance test And (g) The shape stability of the one subjected to the weather resistance test for 500 hours was evaluated.

  The measurement of the glass transition temperature of urethane acrylate is a measurement method based on JIS K7121, using a suggested calorimetric analyzer (DSC, manufactured by Shimadzu Corporation, model number: DSC-60). The temperature was measured at a temperature rise rate of 10 ° C./min.

  The viscosity of urethane acrylate at 60 ° C. is measured using a BL adapter and M4 rotor using a B-type viscometer (trade name: VISCOMETER, manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K7117-1. It was determined by measuring for 1 minute 30 seconds after the start of measurement.

  The evaluation of the shapeability of the shaping layer 2 is performed by cutting the obtained plastic substrate 1 and the shaping layer 2 so that the cross section can be observed, and carbon paste (manufactured by Ted Pella, Pasted with colloidal carbon) and pretreated by sputtering using an alloy of palladium and platinum as a target, and then observed with a scanning electron microscope (manufactured by Shimadzu Corporation, model number: S-8000). And evaluated. Because the shaping shape of the shaping layer 2 is not missing and the desired shaping shape has been formed over the entire test piece is defined as “good” and the top of the shaping shape is rounded or not symmetrical A case where there was a defect in the shaped shape was regarded as “bad”.

  In order to quantitatively measure the ease of peeling, the mold release layer 2 was evaluated using a tensile tester (manufactured by Orientec Co., Ltd., model number: Tensilon STA-1150), and a tensile speed of 10 mm / Tensile strength was measured by pulling a 15 mm wide plastic substrate and shaping layer from the shaping plate at an angle of 180 °. The tensile strength is less than 1.0 N / 15 mm, and those that were easily peeled off from the shaping plate were regarded as “good”, and the tensile strength was 1.0 N / 15 mm or more, and peeling from the shaping plate was difficult Those that were or could not be peeled off from the shaped plate were regarded as “bad”.

  The appearance of the transparent shaped film was observed visually and with an optical microscope. Those that had no change in appearance and had high transparency were evaluated as “good”, and those that were whitened and reduced in transparency were evaluated as “bad”.

  The hardness of the transparent shaped film is evaluated by a pencil scratch hardness tester (NB type, manufactured by Toyo Seiki Seisakusho Co., Ltd.) using a pencil having a hardness of 3B to 4H and a test method based on JIS K5400. The presence or absence of was evaluated by visual observation and observation with an optical microscope. The pencil hardness has a measurement limit of 4H, and the pencil hardness test was performed with a load of 500 g applied.

The weather resistance test is performed using a super accelerated weathering tester (manufactured by Iwasaki Electric Co., Ltd., trade name: iSuper UV tester, model number: SUV-W23), and the following (A), (B) , (C) was taken as one cycle, and this cycle was repeated. For example, when the weather resistance test was performed for 250 hours, this cycle was repeated 10 times, and when the weather resistance test was performed for 500 hours, this cycle was repeated 21 times.
(A) Irradiation with ultraviolet rays having an illuminance of 60 mW / cm ² and a peak wavelength of 365 nm in an atmosphere of temperature: 63 ° C. and humidity: 50% RH for 20 hours.
(B) Watering treatment (shower) is performed for 30 seconds.
(C) Hold for 4 hours in an atmosphere of temperature: 63 ° C. and humidity: 98% RH (no UV irradiation).

  The exposure test was performed by leaving the transparent shaped film to stand outdoors for 6 months.

  The self-cleaning property of the transparent shaped film was evaluated by a self-cleaning property evaluation test and contact angle measurement with water. In the self-cleaning evaluation test, a colored oil mixed with oleic acid and a red colorant is dropped on the inorganic layer, and then water is dropped from above the dropped colored oil. Was visually observed and evaluated. The contact angle for water was measured by dropping water on the flat inorganic layer of the transparent shaped film and measuring with a contact angle meter (model number: CA-X, manufactured by Kyowa Interface Science Co., Ltd.). These results were used as indicators of self-cleanliness. According to the self-cleaning evaluation test, the colored oil dropped on the transparent shaped film floats in the water, and the contact angle measurement with the water having a contact angle of less than 60 ° is “good”. did. In addition, the self-cleaning evaluation test showed that the colored oil dropped on the transparent shaped film did not float on the water, or the contact angle measurement determined that the contact angle with water was 60 ° or more as “bad”. . The flat inorganic layer 3 of the transparent shaped film is formed by, for example, applying the electron beam curable resin compositions of the examples and comparative examples to the plastic substrate 1 with an applicator. It can be prepared by curing the composition to form a flat organic layer and forming the inorganic layer 3 on the organic layer.

For the color difference measurement of the transparent shaped film, a spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3100PC) was used, and the ΔE * ab value was measured by the transmission method according to the description of JIS-K7105. The ΔE * ab value is a color difference formula according to the CIE 1976 standard (L *, a *, b *) space color system: ΔE * ab = {(ΔL *) ² + (Δa *) ² + (Δb *) ² } Value obtained from ^1/2 . A case where the ΔE * ab value was less than 1 and the appearance was not changed at all was regarded as “very good”, and a case where the ΔE * ab value was 1 or more and less than 3 was regarded as “good”. A ΔE * ab value of less than 3 indicates good weather resistance, and a ΔE * ab value of 3 causes a practical problem in terms of weather resistance.

For the evaluation of the shape stability of the transparent shaped film, the transparent shaped film was cut into 5 cm × 5 cm to obtain a measurement sample, and five sheets were placed so that the inorganic layer having the shaped shape was on top. This inorganic layer was weighed with a constant load compression tester (manufactured by A & D Co., Ltd., product name: Tensilon Universal Material Tester, Model No .: RTG-1210) at a diameter of 2.5 mm under an environment of 40 ° C. A so-called “mountain collapse” test in which a load of 26 kg / cm ² was applied for 24 hours with a 1.27 kg stainless steel material was performed, and then the appearance was visually observed. In addition, a transparent shaped film cut so that the cross section can be observed is attached to a pedestal for a measurement sample with a carbon paste, a pretreatment is performed by sputtering using an alloy of palladium and platinum as a target, and then a scanning electron microscope (Shimadzu Corporation, product number: S-8000) was used for cross-sectional observation and evaluation. A shaped shape with no crushing and almost no collapse of the shape was judged as “good”, and a shaped shape with cresting and a shape collapsed was judged as “bad”.

[result]
Table 1 shows the evaluation results of the urethane acrylates and shaping layers of Examples 1 to 13 and Comparative Examples 1 to 4. Table 2 shows the evaluation results of the transparent shaped films of Examples 1 to 13 and Comparative Examples 1 to 4. In addition, "-" does not show a glass transition temperature (Tg), and Tg is a thing of 100 degreeC or more. “*” Indicates that no measurement was performed.

  From the results of Tables 1 and 2, since the shaping layers of the transparent shaping films of Examples 1 to 13 had good shaping properties and releasability, the desired shaping shapes could be produced with high accuracy. . Moreover, since the transparent shaped film of Examples 1-13 did not whiten even if the inorganic layer was formed, it had favorable transparency. Moreover, since all of the weather resistance were “very good” or “good”, they had good weather resistance. Moreover, it had a good self-cleaning property. Further, the hardness was 2H or more, and good shape stability was exhibited.

  The shaped layer of the transparent shaped film of Comparative Example 1 had poor release properties and could not produce a transparent shaped film having the intended shaped shape. Moreover, the shaping layer of the transparent shaping film of Comparative Examples 2-4 had bad shaping property, and could not manufacture the transparent shaping film which has the target shaping shape.

  According to the present invention, a transparent shaped film showing good weather resistance can be produced. This transparent shaped film can be applied mainly to applications that require high weather resistance, and particularly to applications that are used in environments exposed to ultraviolet rays for a long period of time such as outdoors. Examples of such applications include concentrating sheets for solar cells, backsheets for solar cells, antireflection sheets for liquid crystal displays, films for electronic paper, electromagnetic wave shielding films for plasma displays, and films for organic electroluminescence. It is preferably used as a film for use in electronic devices such as. In addition, overlay films for the purpose of surface protection of marking films used on the surfaces of railway vehicles, automobiles, vending machines, etc., surface protection films for exterior signage, outdoor windows in buildings, automobile windows, etc. As a transparent film that can be used outdoors for a long period of time, such as film for window pasting for lighting, light guiding, heat ray reflection, heat ray control, etc., housing window members, and agricultural greenhouse films. Preferably used.

DESCRIPTION OF SYMBOLS 1 Plastic base material 2 Shaped layer 3 Inorganic layer 4 Unit prism 5A Prism 5B Fresnel lens 5C Lenticular lens 6 Electron beam curable resin composition 10, 10A, 10B, 10C Transparent shaped film 20 Shaped layer forming device 21 T die Mold nozzle 22 Press roll 23 Molding drum 24 Shaping plate 25 Peeling roll 26 Electron beam irradiation device 27 Electron beam source S1 One side of plastic substrate S2 Other side of plastic substrate

Claims (3)

Preparing a plastic substrate, a shaping plate and an electron beam curable resin composition;
Providing the electron beam curable resin composition between the plastic substrate and the shaping plate;
Irradiating the electron beam curable resin composition with an electron beam to form a shaping layer;
Peeling the plastic substrate and the shaping layer from the shaping plate;
Forming an inorganic layer having hydrophilicity by ion plating or plasma chemical vapor deposition on the shaping layer, and
The electron beam curable resin composition contains a urethane acrylate and an ultraviolet absorber, and the urethane acrylate has a glass transition temperature of 17 ° C. or higher or a glass transition temperature, and a viscosity at 60 ° C. of 2000 mPa · s. The method for producing a transparent shaped film, which is 24000 mPa · s or less.   The method for producing a transparent shaped film according to claim 1, wherein the electron beam curable resin composition contains a light stabilizer.   The manufacturing method of the transparent shaped film of Claim 1 or 2 with which the said electron beam curable resin composition contains a mold release agent.

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